The preparation method of catalyst for sulfur from hydrogen sulfide

 

(57) Abstract:

Usage: in catalytic chemistry, in particular in the preparation method of catalyst for sulfur from hydrogen sulfide. The inventive method provides for the plasticization of aluminium hydroxide with the introduction of plasticized mass of 5 - 15% of the active component. The latter corresponds to the ratio of titanium, vanadium and tungsten, equal(55 - 85) : (10 - 30) : (5 - 15). Of the plasticized mass is formed into spherical granules, which are then subjected to heat treatment at 110 - 1200°C. 9 table.

The invention relates to the field of chemistry, namely, catalytic methods of disposal of various gases from hydrogen sulfide to produce elementary sulfur, the content of hydrogen sulfide in the gas can be up to about 50.

Recently, processes and cleaning methods of different gases from hydrogen sulfide, based on the reaction of direct oxidation of hydrogen sulfide (1), widespread

H2S + 1/2 O2___ Sg+ H2O (1)

There are various oxide catalysts based on TiO2, SiO2or on the basis of their mixed alumbramiento oxides. The most active, stable/SUB> and SiO2the paste of aluminum oxide before the hydrocarbon-ammonia formation, can be operated in a fluidized bed at a temperature of 250-550aboutC. the Use of this catalyst allows to reduce energy consumption and eliminate waste carrier by eliminating the stage of introduction of the active component by impregnation of a spherical-alumina.

Know the use of compounds of W and V as active ingredients for obtaining sulfur from hydrogen sulfide. However, for effective catalysts for the content of these components should be 15% to the total mass of the catalyst. The known method involves the production of catalysts containing 5% V2O5aluminum oxide. The method includes mixing an aqueous solution of NH4VO3powder of aluminum hydroxide (Owner.= 25,8%), drying, molding in the form of extrudates and subsequent heat treatment. As carriers can also be TiO2, SiO2the aluminosilicate, zeolites, etc. and as active components use the oxides or sulfides of chromium, molybdenum, tungsten, niobium and tantalum.

The disadvantage of this method is the inability to obtain spherical granules (1-3 mm), including with you what they layer. In addition, in the description of the way data is missing for the preparation of catalysts containing both oxides of aluminum, titanium, vanadium and tungsten.

It should also be noted that to the best known catalysts for activity 95-98% of the contact time should be at least 1 second

The objective of the invention is to increase the efficiency of the catalyst, reducing 50-70aboutWith the process temperature (direct oxidation of N2S to elemental sulfur) and in reducing the contact time of 0.1 s at maintaining high activity and selectivity of the catalyst by introducing active components (TiO2WO3V2O5in a certain ratio.

This objective is achieved in that the aforementioned mixture of active components administered in a plasticized mass of aluminum hydroxide before forming. The mass is stirred and formed into spherical granules of hydrocarbon-ammonia method. The obtained pellets are dried and calcined.

The catalysts obtained by the proposed method have the following advantages:

the increase in flow rate (up to 18000 h-1) the reaction flow while maintaining high activity and selective behaviour is the decrease in the content of active components.

It should be noted that the known oxide catalysts that operate at a flow rate of 15,000 h-1and the temperature of 120-300aboutS, i.e. at conditions close to the claimed, however, these catalysts are applied when the content of hydrogen sulfide in the gas is not more than about 3. The specific productivity of the catalyst does not exceed 0.8 g S/1 g cat h

Distinctive features of the prototype features are:

pre-plasticization of aluminum hydroxide;

introduction active components in the form of a paste, containing both compounds of titanium, tungsten and vanadium;

forming a spherical granules hydrocarbon-ammonia method.

Practically the method is as follows. In plasticized aluminum hydroxide pseudoboehmite patterns obtained either from an amorphous hydroxide, or from industrial hydroxide, add 5-15% of a mixture of active components in the form of pastes with a total moisture content (determined by weight loss on ignition of from 20 to 800aboutC)Owner.59-66 wt. The content of active components in these pastes (in terms of dry substance) is: 55-85% Ti; 10-30% W; 5-15% V.

Plasticized mass with added active paste to the manual. Spherical granules are subjected to heat treatment at a temperature 110-1200aboutC for 2-4 h

Examples of 1.2 describe the receipt of the catalyst by a known method. Examples 3-8 of the proposed method.

P R I m e R 1 (known way). Aluminum hydroxide pseudoboehmite patternsVL. 72% is dried toVL. 23% then ground in a ball mill to a particle size of 10-50 μm. In the resulting powder containing 1000 g of Al2O3add water to the formation of the suspension, containing 28 wt. Al2O3and concentrated nitric acid in the amount of 0.07 mol per mol of Al2O3. In the plasticized mass is added 3440 g (50 wt. SiO2in terms of dry substance of Al2O3+ additive) sour Zola SiO2(pH 2-3) with a concentration of SiO228 wt. The mass is stirred for 15 min and added 53 g (5 wt. in terms of dry substance of Al2O3+ additive) powder of titanium concentrate with a particle size of 30 μm (based on the dry powder concentrate containing 95 TiO2and having a VL=0,006). This corresponds to the content of anhydrous TiO24.8 wt. The mass is stirred for 15 min and formed into spherical granules liquid method. Granules drying is Seva and calcining (5%) is 1935 The resulting catalyst has a granule size of 1.0 to 1.6; 1.4 to 2.0 and 2.0 to 3.0 mm

The catalyst granule size of 1.4-2.0 mm, consisting of aluminum oxide 48,65 wt. silicon dioxide 48,75 wt. titanium dioxide 2.6 wt. has indicators shown in the table.1.

P R I m m e R 2 (known way). Amorphous aluminum hydroxide (AH)VL. 10% milled to a particle size of 10-50 μm. The sample milled AG containing 1000 g of Al2O3, washed with a solution of NH4NO3(C=1 g/l) at 60aboutS and T:W 1:3. To the washed precipitate add water toowner.75% and nitric acid in the amount of 0.12 mol per mol of Al2O3and spend hydration when 130aboutWith over 7 hours In the resulting plasticized mass, containing 1000 g of Al2O3add 3440 g (50 wt. on SiO2in terms of dry substance of Al2O3+ additive) sour Zola SiO2(pH 2-3) with 28% of the Mass is stirred for 15 min and added 53 g (5% of Al2O3) powder of titanium concentrate (particle size 30 μm, WITH a 95%owner.=0,006%). This corresponds to the content of anhydrous TiO24.8 wt. The mass is stirred for 15 min and formed into spherical granules liquid method. The granules are dried at 110aboutC and calcined at 550, 1000 and 1200aboutWith. talization has a granule size of 1.0 to 1.6; 1.4 to 2.0 and 2.0 to 3.0 mm

The catalyst granule size of 1.4-2.0 mm, consisting of aluminum oxide 48,65 wt. silicon dioxide 48,75 wt. titanium dioxide 2.6 wt. has indicators shown in the table.2.

P R I m e R 3. In plasticized mass, obtained in example 1, containing 1000 g of Al2O3(25% Al2O3in weight) add a level of 121.8 g of a mixture of active componentsVL. 59% which is 5% of Al2O3The ratio of active ingredients in this weight is the following:

76% Ti + 11% W + 13%V Mass is stirred for 15 min and formed into spherical granules liquid method. The pellets are dried and calcined at 550, 1000 and 1200aboutC. the Exit of the catalyst losses during drying, sieving and calcining (5%) is 1935, the resulting catalyst has a granule size of 1.0 to 1.6; 1.4 to 2.0 and 2.0 to 3.0 mm

The catalyst granule size of 1.4-2.0 mm, consisting of aluminum oxide 95 wt. titanium 3.8 wt. tungsten of 0.55 wt. vanadium content of 0.65 wt. has the characteristics shown in the table.3.

P R I m e R 4. In plasticized mass, obtained according to example 2, containing 1000 g of Al2O3(25% Al2O3in weight), add 138,8 g of a mixture of active componentsVL. 64% which is 5% of Al2O3. The ratio of the granules liquid method. The pellets are dried and calcined at 550, 1000 and 1200aboutC. the Exit of the catalyst losses during drying, sieving and calcining (5%) is 1935, the resulting catalyst has a granule size of 1.0 to 1.6; 1.4 to 2.0 and 2.0 to 3.0 mm

The catalyst granule size of 1.4-2.0 mm, consisting of aluminum oxide 95 wt. titanium 4.25 wt. tungsten 0.50 wt. vanadium 0,25. has the characteristics shown in the table.4.

P R I m e R 5. In plastifitsirovannyy mass obtained in example 1 or 2, containing 1000 g of Al2O3(25% Al2O3in weight), add 147,1 g of a mixture of active componentsowner.66% which is 5% of Al2O3. The ratio of active ingredients in this weight is the following: 70%Ti+20%W+10%V. Then get spherical granules of the catalyst according to example 3. The catalyst granule size, 1.4-2.0 mm, consisting of aluminum oxide 95 wt. titanium 3,5 wt. tungsten 1,0 wt. vanadium 0.50 wt. has the characteristics shown in the table.5.

P R I m e R 6. The catalyst is prepared analogously to examples 3-5, adding 5% of a mixture of active componentsVL. 65% and the following ratio of active components: 55% Ti + 30% W + 15% V. the Composition of the finished catalyst: 95 Al2O3+2,7% Ti + 1.5 W + 0,8 V Characteristics of the catalyst size Gras and active componentsVL. 64% and the following ratio of active ingredients: 85% Ti + 10% W + 5% V. Composition prepared Katalizator% Al2O3+ 8,5% Ti + 1,0% W+ 0,5% V. Characteristics of the catalyst grain size of 2-3 mm are given in table.7.

P R I m e R 8. The catalyst is prepared analogously to examples 3-7, adding 15% of a mixture of active componentsVL. 64% and the following ratio of active ingredients: 85% Ti + 10% W + 5% V. the Composition of the finished catalyst: 85% Al2O3+ 12,7% Ti + 1.5% W + 0,8% V. Characteristics of the catalyst grain size of 2-3 mm are given in table.8.

In the future, all the catalysts were studied in the target reaction (1), running on a laboratory setup with vibramicina catalyst layer. The original components of the gas mixture and the gaseous reaction products were analyzed using GC Color-530 m, and oxygen, nitrogen was separated on a column of molecular sieve NaX (column dimensions 1 m x 3 mm) at T 25aboutWith, and sulfur compounds, and water vapor were separated on a column of porapak Q (column dimensions 1 m x 3 mm), the carrier gas used was helium, the rate of carrier gas was 30 ml/min, and the detector current of 130 mA.

Conditions of test:

Vabout.,h-110000-18000

. the AK can be seen, the specific performance target product for the catalyst in examples 3-8 about 3-10 times higher than in the known method (examples 1,2) and at lower temperatures. For comparison in the table.9 presents tests of the known sample and with the same chemical composition (sample 9). It should be noted that according to the known method are cylindrical pellets, which are not suitable for use in the apparatus with fluidized bed. Therefore, for the comparative test sample of the catalyst (9) was fragmented with obtaining fractions of 1.4 to 2.0 mm, As can be seen from the table, this catalyst has a significantly lower activity (average conversion) and selectivity, the relative performance of sulfur, about 7 times lower than for the claimed catalysts.

1. The PREPARATION METHOD of CATALYST FOR SULFUR FROM hydrogen SULFIDE, including plasticization of aluminum hydroxide formed in the spherical granules and heat treated at 110 1200o, Characterized in that the plasticized mass injected 5 to 15% of the active component containing a mixture of oxides of titanium, vanadium and tungsten.

2. The method according to p. 1, characterized in that the composition of the active component

 

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FIELD: heterogeneous catalysts.

SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.

55 cl, 4 dwg

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