The catalyst for sulfur by the claus process and the method of its preparation

 

(57) Abstract:

The invention relates to catalysts for sulfur by the Claus process and ways of cooking. Describes a catalyst for sulfur by the Claus process containing oxide component and connection alkaline earth element, which additionally contains aluminum compounds, as compounds of alkaline earth element it contains calcium, as well as the oxide component solid solution of titanium dioxide and niobium pentoxide, niobium at the following content, wt.%: calcium 1,0-5,0, aluminum compounds 20,0-55,0, solid solution of titanium dioxide and niobium pentoxide, niobium else. Describes the method of preparation of the catalyst for sulfur by the Claus process, including the processing of titanium tetrachloride aqueous solution or suspension of alkali agent, molding, drying and calcination to obtain a catalyst, characterized in that together with the titanium tetrachloride are processed pentachloride niobium aqueous solution or suspension of an alkaline agent with obtaining oxyhydroxides titanium and niobium, sediment oxyhydroxides titanium and niobium mixed with calcium compounds, udaetsya in higher activity of the proposed catalyst in the hydrolysis of organo-sulfur compounds and mechanical strength, lower bulk weight compared to the prototype, the simplified preparation method of the catalyst by reducing the number of technological operations and the exclusion of emissions of nitrogen oxides into the environment. 2 S. and 11 C.p. f-crystals, 2 tab.

The invention relates to the field of inorganic chemistry, in particular to catalysts based on titanium dioxide and methods for their preparation, and can be used in the gas processing industry at facilities Claus.

The Claus process is designed to produce elemental sulfur by oxidation of hydrogen sulfide with sulfur dioxide by the reaction:

2H2S + SO2---> 3/nSn+ 2H2O (1)

In gases arriving at the installation Claus, along with hydrogen sulfide and sulfur dioxide typically contain one organo-sulfur compounds - CS2and COS.

One of the requirements for the catalysts of the Claus process is their activity in the reactions of hydrolysis of organo-sulfur compounds:

CS2+ 2H2O ---> CO2+ 2H2S (2)

CS2+ H2O ---> COS + H2S (3)

COS + H2O ---> CO2+ H2S (4)

The result of reactions (2-4), hydrogen is formed, which on the

At low hydrolytic activity of the catalyst organo-sulfur compounds (CS2and COS) whose concentration in the source gas mixture is 0.5 - 2. % pass through the entire chain of devices installations Klaus-Suffren and come with tail gases in the furnace thermal treatment, where it is burned with the formation of SO2. At high hydrolytic activity of the catalyst CS2and COS converted into hydrogen sulfide, and then into elemental sulfur. Thereby is achieved a higher yield of the target product and reduces the emission of sulphur dioxide into the environment.

Currently, installations Claus used alumina oxide and dioxide based catalysts. Alumina catalysts quickly sulfatide and lose their hydrolytic activity. Dioxide based catalysts have a much more stable catalytic activity in the hydrolysis of CS2and COS than aluminum oxide. Therefore, to increase the recovery of sulfur and reduce emissions of SO2in the atmosphere due to the hydrolysis of organo-sulfur compounds, it is advisable to use at facilities Claus dioxide based catalysts.

Known dioxide based catalyst Claus process, recip is arid, coal, aluminum oxide or sodium silicate. The disadvantage of this catalyst is low activity in the reactions of hydrolysis of organo-sulfur compounds. Thus, the degree of transformation CS2and COS at 340oC and contact time 4 does not exceed 66% [1].

Known catalyst for Claus process, containing oxides of titanium and aluminum (60: 40) obtained by mixing and agglomeration of the active alumina powder and titanium dioxide. The disadvantage of this catalyst is relatively low activity in the reaction of hydrolysis of organo-sulfur compounds at low contact times. Thus, the degree of transformation CS2at a temperature of 335oC and a contact time of 2.0 with is 62% [2].

Known catalyst for Claus process, containing oxides of titanium and cerium (40:60) obtained by the mixture of metal hydroxides in the presence of nitric acid with subsequent extrusion of the mass, drying and calcination of the extrudates. The disadvantage of this catalyst is relatively low activity in the reactions of hydrolysis of organo-sulfur compounds at low contact times. Thus, the degree of transformation CS2at a temperature of 340oC and the contact time between 0.5 and 1.0 is 63 and 88% within the Oia and cerium in the ratio of 62.3:23,2:14,5. The catalyst was prepared separate deposition oxyhydroxides titanium, zirconium and cerium by interaction of the basic sulfates of titanium, zirconium and cerium nitrate with an alkaline agent, mixing, processing wet catalyst weight nitric acid at a ratio of (oxihydroxide metals): (H2O):(HNO3) = 69:23:8 with subsequent stages of forming, drying and calcination. The catalyst provides an output of sulfur according to reaction (1), close to thermodynamic equilibrium. Conversion CS2at a temperature of 340oC and the contact time between 0.5 and 1.0 is 63 and 95%, respectively [4].

The disadvantage of this catalyst is relatively low activity in the reactions of hydrolysis of organo-sulfur compounds at low contact times.

The disadvantages of the method of preparation of the catalyst is separate the three precipitation oxyhydroxides titanium, zirconium and cerium, leading to complication of the technology; introduction to catalyst weight nitric acid, and therefore require expensive corrosion-resistant equipment; emissions of significant quantities of nitrogen oxides resulting from the decomposition of nitric acid in prochema technical solution is the catalyst, containing 65 to 98.5% of titanium dioxide and 1.5 to 35% of calcium sulfate, strontium or barium (connection alkaline earth element).

The method of its preparation is getting oxyhydroxide titanium processing of titanium tetrachloride aqueous solution of an alkaline agent, separating the precipitate, washing with water (with or without rinsing, drying at 110oC for 24 h, and stirring the obtained powder for 30 min with water and carboxymethyl cellulose, extruding the mixture, drying the extrudate at 110oC for 8 h and annealed at 450 - 500oC for 2 to 7 hours, the impregnated product with a solution of ammonium sulfate or sulfuric acid, drying for 4 h at 110oC, the subsequent impregnation of the nitrate of the alkaline earth element, drying at 110oC for 4 to 12 h and calcination at 450oC for 1 - 2 hours

The catalyst provides an output of sulfur according to reaction (1), close to thermodynamic equilibrium. Conversion CS2at a temperature of 260oC and a contact time of 1 s is 72% at a temperature of 340oC and a contact time of 3 seconds - 99% [5] - (prototype).

The disadvantage of this catalyst is relatively low activity in the reactions of hydrolysis of organo-sulfur socializaton is a multi-stage and complexity of technology, large energy costs of multiple stage drying and calcination of a catalyst mass, the presence of atmospheric emissions of nitrogen oxides (about 100 kg per 1 ton of catalyst).

Comparison of data on activity in the oxidation reaction of hydrogen sulfide with sulfur dioxide and hydrolysis of organo-sulfur compounds shows that the catalysts obtained according to the patent [4] and [5], almost the same. Choice as a prototype of the catalyst according to the patent [5] due to the fact that the proposed catalyst, as well as the prototype contains an oxide component and connection alkaline earth element. In addition, the production of the catalyst of the prototype developed in industry (catalyst CRS-31, the firm Rhone-Poulenc), it can be used for experimental determination of catalytic activity of the prototype and the proposed catalyst.

The technical task of the invention is to create a catalyst for sulfur by the Claus process, with increased activity in the reactions of hydrolysis of organo-sulfur compounds, and a method of its preparation, allowing to improve the textural characteristics of the catalyst, to increase the mechanical strength and to eliminate emissions of nitrogen oxides in the UNT and compounds of rare-earth element, which is characterized in that it additionally introduced aluminum compounds, as compounds of alkaline-earth element, calcium, and as the oxide of the component it contains a solid solution of titanium dioxide and niobium pentoxide, niobium at the following content, wt.%:

Calcium - 1,0 - 5,0

Aluminum compounds - 20,0 - 55,0

Solid solution of titanium dioxide and niobium pentoxide, niobium - Rest

The problem is solved also by the fact that the content of titanium dioxide in the solid solution is 90,0 - a 99.0 wt.%, and also the fact that it contains in its composition of solid solution of titanium dioxide and niobium pentoxide, niobium following composition:

Ti(Nb)xO(2+2.5 x)where 0,006 x 0,06.

The problem is solved also by the fact that as calcium compounds, the catalyst contains an oxide and calcium carbonate.

The problem is solved also by the fact that in its composition it contains 0.5 - 2.5 wt. % of calcium oxide, and aluminum compounds it contains calcium aluminate or calcium aluminate and alumina.

The problem is solved and the fact that the catalyst consists of the following components, wt%:

Calcium oxide is 0.5 to 2.5

Calcium carbonate is 0.5 to 2.5

The calcium aluminate - 20,0 - 25,0

Calcium oxide is 0.5 to 2.5

Calcium carbonate is 0.5 to 2.5

The calcium aluminate - 20,0 - 25,0

Aluminum oxide is Not more than 30,0

Solid solution of titanium dioxide and niobium pentoxide, niobium - Rest

The problem is solved by creating a method of preparation of the catalyst for sulfur by the Claus process, including the processing of titanium tetrachloride aqueous solution or suspension of alkali agent, molding, drying and calcination to obtain a catalyst which is characterized by the fact that together with the titanium tetrachloride are processed pentachloride niobium aqueous solution or suspension of an alkaline agent with obtaining oxyhydroxides titanium and niobium, sediment oxyhydroxides titanium and niobium mixed with calcium compounds and lead the process under conditions that provide a catalyst containing aluminum compounds, as compounds of alkaline-earth element, calcium, and as the oxide component solid solution of titanium dioxide and niobium pentoxide, niobium at the following content, wt.%:

Calcium - 1,0 - 5,0

Aluminum compounds - 20,0 - 55,0

Solid solution of titanium dioxide and niobium pentoxide, niobium - Rest

The problem is solved agent with obtaining oxyhydroxides titanium and niobium precipitates of oxyhydroxides titanium and niobium mixed additionally with calcium compounds and aluminum compounds, which take calcium oxide, calcium carbonate, oxyhydroxide aluminum and calcium aluminate and lead the process under conditions that provide a catalyst containing aluminum compounds, as compounds of alkaline-earth element, calcium, and as the oxide component solid solution of titanium dioxide and niobium pentoxide, niobium at the following content, wt.%:

Calcium oxide is 0.5 to 2.5

Calcium carbonate is 0.5 to 2.5

The calcium aluminate - 20,0 - 25,0

Solid solution of titanium dioxide and niobium pentoxide, niobium - Rest

The task is also solved by the creation of a method in which after processing pentachloride niobium aqueous solution or suspension of an alkaline agent with obtaining oxyhydroxides titanium and niobium, sediment oxyhydroxides titanium and niobium mixed additionally with calcium compounds and aluminum compounds, which take calcium oxide, calcium carbonate, oxyhydroxide aluminum and calcium aluminate and lead the process under conditions that provide a catalyst containing aluminum compounds, as compounds of alkaline-earth element, calcium, and as the oxide component is solid rest is,5

Calcium carbonate is 0.5 to 2.5

The calcium aluminate - 20,0 - 25,0

The alumina - To 30.0

Solid solution of titanium dioxide and niobium pentoxide, niobium - Rest

While the number of titanium tetrachloride and pentachloride niobium take from the calculation that the ratio of titanium oxide and niobium in solid solution was within (90-99): (1-10) and in addition the process is conducted under conditions providing a catalyst containing a solid solution of titanium dioxide and niobium pentoxide, niobium following composition: Ti(Nb)xO(2+2.5 x)where 0,006 x 0,06.

Distinctive features of the process of preparation of the catalyst are:

- simultaneous receiving oxyhydroxides titanium and niobium by joint processing of titanium tetrachloride and pentachloride niobium aqueous solution or suspension of alkali agent;

- pre-treatment with compounds of calcium oxide and calcium carbonate) in the precipitate of oxyhydroxides titanium and niobium;

- mix the wet mass of oxyhydroxides titanium and niobium and compounds of calcium aluminate calcium and oxyhydrates aluminium;

hydrothermal processing of dried extrudates.

These distinctive features make it possible to get kutadanta sulfur dioxide, high mechanical strength and relatively low bulk weight.

Obtaining catalysts is as follows.

In the reactor pour a certain amount of an aqueous solution or suspension of an alkaline agent and under stirring enter the calculated amount of titanium tetrachloride and pentachloride niobium, providing the neutralization of the alkaline agent.

In the interaction of titanium tetrachloride and pentachloride niobium with an alkaline agent to form a mixture of oxyhydroxides titanium and niobium, precipitated, and the chlorides of ammonium, alkali or alkaline earth element dissolved in the mother liquor. The number of TiCl4and NbCl5taken from the calculation that the ratio (TiO2):(Nb2O5in the solid solution was within (90-99):(1-10).

The precipitate containing oxyhydroxide titanium and niobium, is separated by filtration and washed with water to remove chlorides of ammonium, alkali or alkaline earth element. The washed precipitate oxyhydroxides titanium and niobium with a humidity of 75 5 wt.% mix in mixer with calcium carbonate and calcium oxide based, so that in the finished catalyst, the content was in the range of 1 to 5 wt.%, aluminate was within 20 - 25 wt.% or 20 to 55 wt.% respectively, and 1.0 wt.% per finished product plasticizer (polyvinyl alcohol or carboxymethylcellulose), molded in the form of extrudates, which are dried at 110 - 120oC for 2 h and subjected to hydrothermal treatment at a temperature of 85 - 95oC for 1 h the resulting extrudates are dried at 110 - 120oC for 2 h and calcined at 450oC for 4 h

When the joint deposition of oxyhydroxides titanium and niobium by the described method is a uniform distribution of oxyhydroxide niobium in oxihydroxide titanium. Subsequent stages of drying and calcination lead to the formation of a solid solution of oxides of titanium and niobium, with increased activity in the reactions of hydrolysis of organo-sulfur compounds.

The presence of 1 to 5 wt.% carbonate and calcium oxide in the catalyst enhances its basic properties, which also increases the activity in the reactions of hydrolysis CS2and COS.

The calcium aluminate refers to the quick-setting cements. Supplement it in catalyst mass can improve the mechanical strength of the catalyst molded in the form of extrudates. Additional hardening of the extrudates produced is the calcium in the catalyst mass is accompanied by the improvement of the porous structure of the catalyst by increasing the proportion of mesopores and macropores, leading to the intensification of mass transfer processes inside the granules of the catalyst and, consequently, to increase the velocity of the flowing reaction.

Oxyhydrate aluminum - AlO(OH), included in the catalyst mass, after calcination is converted into aluminum oxide: 2AlO(OH) ---> Al2O3+ H2O.

The aluminum oxide has a high surface area (200 - 250 m2/g) and therefore increases the activity of the catalyst in the Claus reaction (oxidation of hydrogen sulfide with sulfur dioxide), and the reactions of hydrolysis of COS and CS2. The activity of the synthesized samples of the catalyst determine the hydrolysis reaction of carbon disulfide and the Claus reaction on impulse installation chromatographic analysis of the products. For testing certain amount of the catalyst grain size of 0.25 - 0.50 mm is placed in a steel microreactor (length 70 mm, diameter 3 mm) and heated in a stream of helium for 1 h

In determining the activity of the catalysts in the reaction of hydrolysis of organo-sulfur compounds in the microreactor place of 0.05 cm3catalyst and Microstream introducing the fluid mixture in a molar ratio of CS2:H2O = 1:2.

Catalase activity in S:SO2= 2:1.

The contact time of the reactants with the catalyst is 0.05 and 0.01 s, the temperature in the reaction zone 300oC and 220oC, respectively, for the reactions of hydrolysis of carbon disulphide and oxidation of hydrogen sulfide with sulfur dioxide. Catalytic activity expressed in the form of the reaction rate constants are calculated by the equation Habgood and Basset /J. Phys. Chem., 1960, v. 64, p. 769/. The value of the reaction rate constants are calculated as the average of five measurements.

The stability of the catalysts to sulfate crystallization is determined by comparison of their activity in the hydrolysis of CS2before and after treatment with a gas mixture containing, vol.%: SO225, a pair of water 25 and the air 50. Sulfation is carried out in a flow glass reactor, in which loads a portion of the catalyst, raising the temperature to 400oC and serves gas mixture at a speed of 10 cm3/Ming catalyst.

The invention is illustrated by the following examples.

Example 1. Charged to the reactor 1386 ml of 10% suspension of calcium hydroxide and with stirring was added 1.52 g of pentachloride niobium and 176,3 g (101,9 cm3) of titanium tetrachloride. After addition of TiCl4stirring is continued for 30 min to complete the reaction of neutralia. The washed precipitate oxyhydroxides titanium and niobium mixed with 2.5 g of CaO, 2.5 g of CaCO3, 20 g of calcium aluminate and 1 g of plasticizer (polyvinyl alcohol or carboxymethyl cellulose in the form of a 10% aqueous solution). The catalyst mass is stirred for 30 min, then formed by extrusion. The resulting extrudates are dried at 110 - 120oC for 2 h, then subjected to hydrothermal treatment for 1 h, placing them in water heated to 85 - 95oC, and then dried at 110 - 120oC for 2 h and calcined at 450oC for 4 h to Receive the catalyst containing wt.%: 2,5 CaCO3, 2,5 CaO, 20.0 calcium aluminate and 75.0 solid solution of metal oxides composition TiNb0,006O2,02when the mass ratio of titanium oxide and niobium equal to 99:1.

Example 2. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 1307 ml of 10% suspension of calcium hydroxide is injected under stirring 4.26 deaths g pentachloride niobium and 163,6 g (94,6 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with 1.5 g of CaCO3and 25 g of calcium aluminate.

Get the catalyst containing wt.%: 2,5 CaO, 1,5 CaCO3, 25.0 calcium aluminate and 71.0 solid solution of oxides m/P> Example 3. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 1333 ml of 10% ammonium hydroxide solution and injected under stirring 10,35 g pentachloride niobium and 161,3 g (93,2 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with 2.0 g of CaO, 2.0 g CaCO3and 23 g of calcium aluminate.

Get the catalyst containing wt.%: 2,0 CaO, 2,0 CaCO3, 23.0 calcium aluminate and 73.0 solid solution of metal oxides composition TiNb0,04O2,10when the mass ratio of titanium oxide and niobium, equal to 93:7.

Example 4. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 1397 ml of 10% suspension of calcium hydroxide and injected under stirring 15,63 g pentachloride niobium and 164,6 g (95,2 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with 0.5 g of CaO, 0.5 g CaCO3and 22 g of calcium aluminate.

Get the catalyst containing wt.%: 0,5 CaO, 0.5 to CaCO3, 22.0 calcium aluminate and 77,0 solid solution of metal oxides composition TiNb0,06O2,15when the mass ratio of titanium oxide and niobium equal to 90: 10.

Example 5. The catalyst is prepared analogously as described in Prienai to 9.66 g pentachloride niobium and 165,4 g (95,6 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with 0.3 g of CaO, 0.3 g CaCO3and 25.0 g of calcium aluminate.

Get the catalyst containing wt.%: 0,3 CaO, 0,3 CaCO3, 25.0 calcium aluminate and 74,4 solid solution of metal oxides composition TiNb0,04O2,10when the mass ratio of titanium oxide and niobium, equal 93,6: 6,4.

Example 6. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 1394 ml of 10% suspension of calcium hydroxide and injected under stirring and 17.2 g of pentachloride niobium and 162,8 g (94,1 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with 18.0 g of calcium aluminate.

Get the catalyst containing wt.%: 2,5 CaO, 2,5 CaCO3, 18.0 calcium aluminate and 77,0 solid solution of metal oxides composition TiNb0,074O2,19when the mass ratio of titanium oxide and niobium, equal to 89: 11.

Example 7. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 1253 ml of 10% suspension of calcium hydroxide and injected under stirring to 4.14 g pentachloride niobium and 156,7 g (90,6 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium smesi the CaCO3, 30.0 calcium aluminate and 68,0 solid solution of metal oxides composition TiNb0,018O2,05when the mass ratio of titanium oxide and niobium, equal to 97: 3.

Example 8. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 1270 ml of 10% suspension of calcium hydroxide and injected under stirring 4,20 g pentachloride niobium and 158,9 g (91,8 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with 3.0 g of CaO, 3.0 g CaCO3and 25.0 g of calcium aluminate.

Get the catalyst containing wt.%: 3,0 CaO, 3,0 CaCO3, 25.0 calcium aluminate and 69.0 solid solution of metal oxides composition TiNb0,019O2,05when the mass ratio of titanium oxide and niobium, equal to 97: 3.

Example 9. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 1204 ml of 10% suspension of calcium hydroxide and injected under stirring 0,61 g pentachloride niobium and 153,7 g (88,8 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with 30.0 g of calcium aluminate.

Get the catalyst containing wt.%: 2,5 CaO, 2,5 CaCO3, 30.0 calcium aluminate and 65,0 solid solution of metal oxides composition TiNb3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with 1.18 g of aluminum oxyhydrate.

Get the catalyst containing wt.%: 2,5 CaO, 2,5 CaCO3, 20.0 calcium aluminate, 1,0 Al2O3and 74.0 solid solution of metal oxides composition TiNb0,006O2,02when the mass ratio of titanium oxide and niobium equal to 99: 1.

Example 11. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 1294 ml of 10% suspension of calcium hydroxide and injected under stirring 1.42 g of pentachloride niobium and 164,6 g (95,1 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with 5,88 g of aluminum oxyhydrate.

Get the catalyst containing wt.%: 2,5 CaO, 2,5 CaCO3, 20.0 calcium aluminate, 5,0 Al2O3and 70.0 solid solution of metal oxides composition TiNb0,006O2,02when the mass ratio of titanium oxide and niobium equal to 99: 1.

Example 12. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 1203 ml of 10% suspension, hydro is the residue of oxyhydroxides titanium and niobium mixed with 11,76 g of aluminum oxyhydrate.

Get the catalyst containing wt.%: 2,5 CaO, 2,5 CaCO3, 20.0 calcium aluminate, 10,0 Al2O3and 65,0 solid solution of metal oxides composition TiNb0,006O2,02when the mass ratio of titanium oxide and niobium equal to 99: 1.

Example 13. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 1017 ml of 10% suspension of calcium hydroxide and injected under stirring 1.12 g of pentachloride niobium and is 129.3 g (74,7 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with 23,53 g of aluminum oxyhydrate.

Get the catalyst containing wt.%: 2,5 CaO, 2,5 CaCO3, 20.0 calcium aluminate, 20,0 Al2O3and 55.0 solid solution of metal oxides composition TiNb0,006O2,02when the mass ratio of titanium oxide and niobium equal to 99: 1.

Example 14. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 924 ml of 10% suspension of calcium hydroxide and injected under stirring 1,02 g pentachloride niobium and of 117.6 g (68,0 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with a 29.4 g of aluminum oxyhydrate.

Get the catalyst containing wt.%: 2,5 CaO, 2,5 CaCSUB>O2,02when the mass ratio of titanium oxide and niobium equal to 99: 1.

Example 15. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 832 ml of 10% suspension of calcium hydroxide and injected under stirring 0,91 g pentachloride niobium and 105,8 g (61,2 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with 35.2 g of aluminum oxyhydrate.

Get the catalyst containing wt.%: 2,5 CaO, 2,5 CaCO3, 20.0 calcium aluminate, 30,0 Al2O3and 45.0 solid solution of metal oxides composition TiNb0,006O2,02when the mass ratio of titanium oxide and niobium equal to 99: 1.

Example 16. The catalyst is prepared as described in example 1 with the difference that was charged to the reactor 740 ml of 10% suspension of calcium hydroxide and injected under stirring 0,81 g pentachloride niobium and 94,1 g (54,4 cm3) of titanium tetrachloride, and the residue of oxyhydroxides titanium and niobium mixed with a 41.3 g of aluminum oxyhydrate.

Get the catalyst containing wt.%: 2,5 CaO, 2,5 CaCO3, 20.0 calcium aluminate, 35,0 Al2O3and 40.0 solid solution of metal oxides composition TiNb0,006O2,02when the mass ratio of titanium oxides and catalysts, prepared by the described method and the prototype (dioxide based catalyst brand CRS-31 the company rhône-Poulenc, France) show that the samples of the catalyst obtained by the proposed method have a significantly higher activity in the hydrolysis reaction of carbon disulphide in comparison with the prototype. Thus, the rate constant for the hydrolysis reaction of carbon disulphide on the proposed catalyst 2.1 - 2.8 times higher in comparison with the known catalyst: conversion of carbon disulfide at a temperature of 300oC and contact time of 0.25 s in examples 1 - 4 and 11 - 16 at the proposed catalyst is 57% and 65%, the catalyst prototype - 38%. In examples 5 to 9, the catalytic activity in the hydrolysis reaction of carbon disulphide is somewhat lower due to the fact that the samples obtained in examples 6 and 9, the ratio of the components in the solid solution (oxides of titanium and niobium) beyond the optimum, the catalysts obtained in examples 5 and 8, the contents of CaO and CaCO3beyond the optimum.

The catalyst obtained in example 6 and containing 18 wt. % of calcium aluminate, has relatively low mechanical strength, and a catalyst containing 30 wt.% the calcium aluminate (examples 7 and 9), mechanistically.

The catalyst obtained in example 16 and containing 35 wt.% aluminum oxide, the hydrolysis reaction of carbon disulphide is active, close to the activity of the catalyst of example 15, but after sulfate crystallization of its activity decreases to a greater extent than that of the prototype.

All catalyst samples prepared in the described manner, have a more developed surface in comparison with the prototype, thereby increasing their activity in the Claus reaction, providing a thermodynamically equilibrium yields of the target product, as well as high thermal stability (after calcination of the catalyst at a temperature of 600oC for 4 h activity is practically not reduced).

Prepared according to the procedure described in samples of catalyst pastes have high plasticity and in forming smooth extrudates.

The catalysts prepared by the described method have a relatively low bulk weight (of 0.68 - 0.72 kg/l) and high mechanical strength destructive force on the crushing is 0.6 - 0.8 kg/mm2for prototype - 0.3 kg/mm2.

The proposed method for the preparation of the catalyst in comparison with the prototype allows us to simplify the operations, in particular, reducing the number and duration of the stages of drying and calcination, associated with high costs of energy, as well as to exclude the formation and emission of oxides of nitrogen in the environment due to the fact that for the preparation of the catalyst is not used nitrates.

The use of the catalyst in the gas processing industry will allow due to the high activity in the reaction of hydrolysis of CS2and COS to increase the output of the gas sulfur and reduced sulfur dioxide emissions into the environment because of low activity of the catalyst part CS2and of COS, not subjected to hydrolysis, comes with tail gas installations Klaus-Suffren in a furnace thermal treatment where it is burned to form sulfur dioxide and is released into the atmosphere.

The above causes obtain a technical result, which includes the creation of catalyst and method of its preparation.

The technical result of the invention consists in a higher activity of the proposed catalyst in the reaction of hydrolysis of organo-sulfur compounds, higher mechanical strength and a relatively low bulk weight compared to the prototype, the simplification SP the AI of emissions of nitrogen oxides into the environment.

LITERATURE

1. French patent N 2481145, class B 01 J 21/06, 1981.

2. Patent Germany N 2417092, class B 01 D 53/36, 1977.

3. Patent EP N 0272979, class B 01 J 23/10, 1988.

4. French patent N 2598094, CL 01 D 53/36, 1987.

5. Patent USSR, N 1213976, CL 01 J 21/06, 1986.

1. The catalyst for sulfur by the Claus process containing oxide component and connection alkaline earth element, characterized in that it additionally contains aluminum compounds, as compounds of alkaline earth element it contains calcium, as well as the oxide of the component it contains a solid solution of titanium dioxide and niobium pentoxide, niobium at the following content, wt.%:

Calcium - 1,0-5,0

Aluminum compounds - 20,0-55,0

Solid solution of titanium dioxide and niobium pentoxide, niobium - Rest

2. The catalyst p. 1, characterized in that the content of titanium dioxide in the solid solution is 90,0-a 99.0 wt.%.

3. The catalyst p. 1, characterized in that it comprises a solid solution of titanium dioxide and niobium pentoxide, niobium following composition: TiNbxO(2+2.5 x)where 0,h,06.

4. The catalyst p. 1, characterized in that compounds of the AC is part of it contains oxide and calcium carbonate in the amount of 0.5-2.5 wt.% each.

6. The catalyst p. 1, characterized in that as the aluminum compounds it contains calcium aluminate or calcium aluminate and alumina.

7. The catalyst p. 1, characterized in that it consists of the following components, wt%:

Calcium oxide is 0.5 to 2.5

Calcium carbonate is 0.5 to 2.5

The calcium aluminate - 20,0-25,0

Solid solution of titanium dioxide and niobium pentoxide, niobium - Rest

8. The catalyst p. 1, characterized in that it consists of the following components, wt%:

Calcium oxide is 0.5 to 2.5

Calcium carbonate is 0.5 to 2.5

The calcium aluminate - 20,0-25,0

Aluminum oxide is Not more than 30,0

Solid solution of titanium dioxide and niobium pentoxide, niobium - Rest

9. The preparation method of catalyst for sulfur by the Claus process, including the processing of titanium tetrachloride aqueous solution or suspension of alkali agent, molding, drying and calcination to obtain a catalyst, characterized in that together with the titanium tetrachloride are processed pentachloride niobium aqueous solution or suspension of an alkaline agent with obtaining oxyhydroxides titanium and niobium, sediment oxyhydroxides titanium and niobium mixed with calcium compounds and lead the process when the service is zemelnogo element calcium, as well as the oxide component solid solution of titanium dioxide and niobium pentoxide, niobium at the following content, wt.%:

Calcium - 1,0-5,0

Aluminum compounds - 20,0-55,0

Solid solution of titanium dioxide and niobium pentoxide, niobium - Rest

10. The method according to p. 9, wherein after processing pentachloride niobium aqueous solution or suspension of an alkaline agent with obtaining oxyhydroxides titanium and niobium precipitates of oxyhydroxides titanium and niobium mixed additionally with calcium compounds, which take calcium oxide and calcium carbonate, with a compound of aluminum, which take calcium aluminate, and lead the process under conditions that provide a catalyst containing aluminum compounds, as compounds of alkaline-earth element, calcium, and as the oxide component solid solution of titanium dioxide and niobium pentoxide, niobium at the following content, wt.%:

Calcium oxide is 0.5 to 2.5

Calcium carbonate is 0.5 to 2.5

The calcium aluminate - 20,0-25,0

Solid solution of titanium dioxide and niobium pentoxide, niobium - Rest

11. The method according to p. 9, characterized in that after britana and niobium precipitates of oxyhydroxides titanium and niobium mixed additionally with calcium compounds, which take calcium oxide and calcium carbonate, aluminum compounds, which take oxyhydroxide aluminum and calcium aluminate, and lead the process under conditions that provide a catalyst containing aluminum compounds, as compounds of alkaline-earth element, calcium, and as the oxide component solid solution of titanium dioxide and niobium pentoxide, niobium at the following content, wt.%:

Calcium oxide is 0.5 to 2.5

Calcium carbonate is 0.5 to 2.5

The calcium aluminate - 20,0-25,0

Aluminum oxide is Not more than 30,0

Solid solution of titanium dioxide and niobium pentoxide, niobium - Rest

12. The method according to p. 9, characterized in that the amount of titanium tetrachloride and pentachloride niobium take from the calculation that the ratio of titanium oxide and niobium in solid solution was within (90-99):(1-10).

13. The method according to p. 9, wherein the process is conducted under conditions providing a catalyst containing a solid solution of titanium dioxide and niobium pentoxide, niobium following composition: TiNbxABOUT(2+2.5 x)where 0,h,06.

 

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