The catalyst for dehydroisomerization n-butane catalytic system for dehydroisomerization n-butane and a method of producing isobutene

 

(57) Abstract:

Usage: petrochemicals, the production of catalysts for dehydroisomerization n-butane, obtaining isobutene. The inventive catalyst contains 0.1 to 1.0 wt. platinum and solid granular porous media gamma-alumina with a specific surface area 100-420 m2/g and total pore volume of 0.5 to 1.5 ml/g in the form of granules with a size of 0.4 to 5 mm are deposited on the surface of the silicon dioxide in the amount of 0.5 to 5 wt. preferably 1 to 2.5 wt. The catalyst preferably contains tin in an amount of 0.1 to 1 wt. and indium in the amount of 0,0501,0 wt. moreover, the mass ratio of platinum and tin (0.5 to 2) 1 and platinum and India (0,3 1,5) 1. The catalytic system contains a catalyst of the composition and socialization representing a porous gamma-alumina with precipitated on the surface of 0.5 to 5 wt. silicon dioxide, when the mass ratio of the catalyst and socializaton from 20 to 80 to 80 to 20, preferably 70 to 30. The catalytic system contains a catalyst of the composition and socialization moralit In, having in the dry and calcined as the following molar composition C2/nO B2O3(5-50)SiO2where C is a metal cation of valency n, H+NH+4or Antichiral at 450 to 600°C With a fixed bed catalytic system in the presence of hydrogen at a molar ratio of n-butane hydrogen from 1 1 to 5 1, the pressure from 200 mm RT.article up to 5 kg/cm2and volume rate of n-butane 0,50 5 hours 3 C. and 18 h.p. f-crystals, 1 table.

The invention relates to a catalyst obtain isobutene by dehydroisomerization n-butane, the method of its production and method of use of this catalyst.

Isobutene is a valuable intermediate product used in various chemical processes, in particular in the form of a monomer in the polymerization and copolymerization, in the form of an alkylating agent upon receipt of methyl tert-butyl ether (interaction with methanol), and upon receipt of isoprene (interaction with formaldehyde).

Isobutan usually obtained as a by-product of the processes of refining, such as thermal or catalytic cracking, or two-stage process, the first stage of which is the catalytic isomerization of n-butane in isobutene, and the second last catalytically dehidrirana education isobutene.

Have recently been described catalytic processes, allowing one-stage conversion of n-alkanes in isoolefine. In particular, it is getting isobutene by dehydroisomerization n-butane in the presence also of media with low pH [1] is Known, that dehydroisomerization n-alkane to the corresponding otoolefan carried out on the catalyst obtained by impregnation of a porous crystalline borosilicate called AMS-18, a noble metal [2] Such processes dehydroisomerization not give fully satisfactory results from the point of view, in particular, the limited output of the desired product. Also known catalysts for the dehydrogenation process that represents the media on which the deposited platinum or another noble metal. These catalysts may contain promoters, which are usually chosen tin, indium, thallium, or one of the alkaline earth metals. They are commonly used in processes for the dehydrogenation of paraffins with long-chain [4]

Known crystalline borosilicate called Baralic, also causing the isomerization of n-paraffin.

There is a method of isomerization of alkanes in isoalkane that uses a catalyst based on oxides of aluminum deposited on the surface oxide of silicon [3]

It is also known that n-butane can be converted into isobutene by dehydroisomerization in one stage using a two-component catalytic system, one component kotorsta platinum and perhaps one or more promoters, and the other component may be an aluminum oxide on the surface of which is deposited catalytically effective amounts of oxide silicon or Moralit Century

Currently found a new catalyst comprising an oxide of aluminum, on the surface of which is deposited platinum, silicon oxide and, in a preferred implementation, one or more promoters, which when conducting the reaction in suitable conditions, allows dehydroisomerization n-butane in isobutene in one stage with a high yield of the desired useful product.

Thus, the object of the invention is a catalyst (a) providing a solid support made of porous gamma-alumina on the surface of which the besieged provide the catalytic effect of the number of platinum, silicon oxide and, in the preferred implementation, tin and/or indium as promoters.

In a preferred embodiment of the invention described catalyst is used in combination with a second catalyst (b), which can be manufactured from Moralita Into or out of solid granular porous media gamma form of alumina, on which surface the tel represents the alumina in the gamma crystallographic form, with a specific surface area of from 100 to 400 m2/g and total pore volume of from 0.5 to 1.2 ml/g, in the form of granules, extrusion or pellets, useful size which is suitable for use in the process with a fixed bed of the catalyst and is typically 0.4 to 5 mm

The catalyst (a) necessary to achieve the purposes of the invention, consists of the gamma form of alumina with the described characteristics, which is deposited platinum in an amount of 0.1-1 wt. and silicon oxide in the amount of 0.5-5 wt. preferably 1-2,5%

The catalyst (a) preferably contains as promoters tin in an amount of 0.1-1 wt. and/or indium in the amount of 0.05-1-% In this case seems convenient to withstand the following mass ratios: platinum indium from 0.3:1 to 1.5:1 and platinum tin from 0.5:1 to 2:1. All the above percentages refer to the total weight of the catalyst. The catalyst (a) receive a two-step process, including:

1) thermal decomposition of alkalitolerant in the presence of the gamma form of alumina and processing of the product at high temperature, first in an inert atmosphere and then in an oxidizing;

2) impregnation obtained at the previous stage selectonemenu okiem, followed by drying and calcination.

In the first stage related to obtaining selectonemenu aluminum oxide are provided in contact with the appropriate number of gamma form of alumina and alkalitolerant, preferably of atlantogenata, at a temperature of 100-400aboutC, a pressure of 10-30 kg/cm2and contact time of from about 1 to 20 hours, Similar processing is carried out in the absence of oxygen and moisture, which is provided with an inert gas, preferably nitrogen, at a temperature of 100-400aboutWith over a period of time, the duration of which varies from 2 to 8 h, and then in a stream of air at a temperature of 400-600aboutC for 2-8 hours for the second stage, the impregnation is used, in particular, soluble in water and decomposing at high temperature platinum compounds and, possibly, tin and indium, such as chloroplatinate acid, tin chloride (IV) and nitrate India.

Drying the impregnated carrier is best done at a temperature of about 100-130aboutWith the current of air, and the annealing at 400-600aboutWith the current of air during the period of time from 2 to 8 o'clock

Thus prepared catalyst before use in the reaction of dehydroisomerization, for example, the systems, usually carried out in a stream of hydrogen at high temperatures (approx.450-650about(C) during the period of time of the order 1-5 PM

This catalyst is used for dehydroisomerization n-butane in isobutan preferably together with the second catalyst (b), which is a granular solid media of porous gamma-alumina or moralita In, the surface of which is deposited providing a catalytic effect of the number of silicon oxide.

In cases where the catalyst (b) is silicatization gamma form of alumina, it is received by applying the method similar to that described previously for stage 1) preparation of the catalyst (a). Thus obtained catalyst (b) is subjected to recovery processing before use in the reaction of dehydroisomerization. In the most preferred embodiment, the catalysts (a) and (b), subject to such recovery processing at a time. The catalyst (b) may also be Moralit Century Moralit represents a zeolite. In dehydrated and calcined form it has the following molar composition (if the components are present as oxides):

C2/nOB2O3 is alit get In a known manner, the reaction under hydrothermal conditions with a derivative of silicon, boron derivative, a hydroxide of alkaline metal salt of tetraethylammonium. In particular, a derivative of silicon, which is selected, for example, colloidal silica, silica gel or sodium silicate, a derivative of boron, for example, selected from boric acid, alkali borates or trialkylborane, hydroxide of alkaline metal salt of tetraethylammonium, preferably a hydroxide of tetraethylammonium, is heated in an autoclave at self-regulating pressure and temperature between 90 and 160aboutTo achieve complete crystallization. Thus obtained crystalline product is then filtered off, dried and calcined.

Preferably, in particular, to carry out the crystallization in the presence of grains of Moralita, taken in an amount of 1 to 60 wt. that reduces required for the synthesis time.

Such seeds are putting in the autoclave derivative of silicon, a derivative of boron, alkali metal hydroxide and a salt of a tetraalkylammonium taken in known proportions, and conducting the reaction under hydrothermal conditions for at least one day.

In this invention Moralit In use in the form of Gran the layer and ranges from 0.4 to 5 mm

Another object of the invention is a method of obtaining isobutene by dehydroisomerization n-butane using the above-mentioned catalyst (a), where the catalyst is used alone or in conjunction with the described catalyst (b).

The proposed method is that the gaseous mixture of n-butane and hydrogen, possibly diluted with an inert gas, is fed into the fixed bed of catalyst comprising a catalyst (a) itself or, preferably, in a mixture with a catalyst (b).

In the feed gas stream should support the molar ratio between hydrogen and n-butanone at the level of from 1:1 to 5:1, preferably from 1: 1 to 3:1. If the gas stream is diluted, for example, nitrogen, the molar ratio between hydrogen and n-butane will be in the range from 1:1 to 5:1, and between nitrogen and n-butane in the range from 1:1 to 5:1 and preferably in the range from 1:1 to 3:1.

The reaction dehydroisomerization carried out in the temperature range 450-600aboutC, at a pressure of from 200 mm RT.article up to 5 kg/cm2and flow rate from 0.5 to 5-1(mass of n-butane/mass of catalyst.h). In a preferred implementation, the temperature fluctuates between 500-580aboutWho in those cases, when the catalyst (a) is used together with the catalyst (b), these catalysts (b) and (C) uniformly distributed in the layer or placed as two contiguous layers. In this second case, the layer of catalyst (a) is located in the reactor for dehydroisomerization so that he first came into contact with the incoming gas stream. The catalyst layer contains a catalyst (a) and (b) mass ratio of from 20:80 to 80:20, preferably about 70:30.

When carrying out the process according to the invention achieve high conversion of the supplied n-butane at high yields and selectivity for useful reaction product.

P R I m e R 1. Obtaining a catalyst (a).

In this and subsequent examples, the receiving selectonemenu aluminum oxide is carried out in accordance with U.S. patent 4013590. To obtain a catalyst (a) used commercially aluminum oxide of the gamma form with a specific surface area of 196 m2/g and total pore volume of 0.75 mg/l, in the form of granules with 0.5% -0,8 mm In the autoclave was placed 20 g of this gamma-alumina together with 1.5 g of atlantogenata. The mixture was incubated for 2 h, and then the autoclave is emptied, udala, finally, is brought to a pressure of 5 kg/cm2why use nitrogen, the Autoclave is heated to 200aboutC and maintained at this temperature for 4 hours, after this period of time the pressure was lowered after cooling, remove the solid product which is then subjected to an additional heat treatment for 2 h at 200aboutC in an atmosphere of nitrogen and probalily in air at 500aboutC for 4 h, After cooling, was selected solid product, representing the aluminum oxide of the gamma form, which on the surface is a layer of silicon oxide, in the amount of 1.5 wt. To 20 g of this solid product was added slowly with stirring to 1.9 g chloroplatinic acid (4,21 wt. platinum). After contacting at room temperature for 12 h mass was heated at 120aboutWith the current of air for 1 h prior to drying of the sample. The resulting dry solid product was probalily in a muffle furnace at 500aboutC for 4 h in air flow. Finally, the autoclave was cooled and the obtained catalyst (a) containing 0.4 wt. platinum.

P R I m m e R 2. Obtaining a catalyst (a) promoters.

Used commercially aluminum oxide of the gamma form with a specific surface 196 of aluminum together with 1.5 g of atlantogenata. The mixture was left for 2 h, and then the autoclave was emptied in order to remove excess unreacted of atlantogenata, washed with nitrogen to exclude the presence of oxygen and, finally, brought pressure to a value of 5 kg/cm2using nitrogen. The autoclave was heated to 200aboutC and kept at this temperature for 4 hours, after this period of time the pressure triggered after cooling, the selected solid product was then subjected to an additional heat treatment for 2 h at 200aboutWith in a stream of nitrogen, after which he probalily in air for 4 h at 500aboutC. Allocated after cooling, the solid product which consisted of aluminum oxide of the gamma form, which on the surface was a layer of silicon oxide, in the amount of 1.5 wt. To 20 g of the aluminum oxide of the gamma form slowly added with stirring to 30 ml of an aqueous solution obtained from 0.25 g of nitrate India pentahydrate, 0.2 g of tin chloride, 0,47 g chloroplatinic acid (up to 16 wt. platinum) and 1.3 g of 65% nitric acid. After contact for 1 h at room temperature (about 25about(C) under continuous stirring the mass was heated for 1 h at 120aboutWith the current of air, to evaporate excess water rastvoritelya. Then the autoclave was cooled and the obtained catalyst (a) containing and 0.37 wt. platinum, 0.50 wt. tin and 0.36 wt. India.

P R I m e R 3. To obtain a catalyst (b) used commercially aluminum oxide of the gamma form with a specific surface area of 196 m2/g and total pore volume 0.75 ml/g in the form of granules with a size of 0.5-0.8 mm. was Placed in the autoclave, 20 g of this gamma-alumina together with 1.5 g of atlantogenata. The mixture was left for 2 h, and then the autoclave was drained to remove excess atlantogenata, unreacted, washed with nitrogen in order to exclude the presence of oxygen and, finally, nitrogen brought pressure to a value of 5 kg/cm2. The autoclave was heated to 200aboutC and kept at this temperature for 4 hours, after this period of time the pressure is triggered, and the resulting solid product was subjected to additional heat treatment for 2 h at 200aboutIn nitrogen atmosphere, and then progulivali in air at 500aboutC for 4 h, After cooling, there was obtained a solid product that represents the aluminum oxide of the gamma form, which on the surface was a layer of silicon oxide, in the amount of 1.5 wt.

P R I m e R 4. Getting Moralita Century

In 28,12 g water 40%-but is then diluted with 30 g of distilled water and added to 51 g of silicon oxide trademark Ludox A. S, containing 30 wt. oxide of silicon. Obtained the suspension thus, the pH of which was equal to 12.2, was kept for 4 h at room temperature with stirring, and then placed for crystallization in an autoclave under static conditions, under autogenous pressure at 150aboutWith 5 days. Then the autoclave was cooled and took molokoobraznuyu suspension of grains Moralita Century, the Amount of suspension is equal to 15 wt. added to a mixture of the following composition, after the latter was kept at room temperature under stirring for about 4 h: 112,5 g Thea-HE's in the water up to 40% 25,5 g H3IN3; to 120.0 g of distilled water, 12.0 g of NaOH and 204 g of a 30% silica trademark Ludox A. S.

This mixture together with a suspension of grains placed for crystallization in a steel autoclave under static conditions, under autogenous pressure, temperature 150aboutWith 3 days. The autoclave was cooled, highlighted Moralit In filtration, washed it with distilled water, dried at 120aboutWith, progulivali for 5 h at 550aboutC and then transferred into acid form using known methods. Thus obtained Moralit In representing the crystal size of about 1 μm, sformovat into granules, the size of which example 1, quartz reactor with an internal diameter of 10 mm, the Catalyst was subjected to in situ recovery, passing a stream of hydrogen for 2 h at 550aboutC. After processing conducted the test on dehydroisomerization, feeding into the reactor a gaseous mixture containing n-butane, hydrogen and nitrogen at a molar ratio of hydrogen and n-butane 1:1 and the nitrogen n-butane 2:1. In addition, tests were carried out at a temperature of 553aboutWith atmospheric pressure and at a flow rate of 2 h-1(mass of n-butane/mass of Katalizator).

The results of the tests are given in the table.

P R I m e R 6. In a quartz reactor internal diameter of 10 mm was placed 0.34 g of catalyst (a) obtained as described in example 2. The catalyst was subjected to in situ recovery in hydrogen flow for 2 hours at a temperature of 550aboutC. After this treatment was tested on dehydroisomerization, feeding into the reactor a gaseous mixture containing n-butane, hydrogen and nitrogen at a molar ratio of hydrogen and n-butane 1:1 and the nitrogen n-butane 2:1. In addition, tests were conducted under the following conditions: temperature 563aboutC, atmospheric pressure, space velocity of 2 h-1(mass of n-butane/mass of Katalizator.).

The test results privadas is, is received in accordance with the description of example 2. The catalyst was subjected to in situ recovery, feeding a stream of hydrogen for 2 hours at a temperature of 550aboutC. After this treatment was tested on dehydroisomerization, feeding into the reactor a gaseous mixture containing n-butane, hydrogen and nitrogen at a molar relationship hydrogen, n-butane 1:1 and the nitrogen n-butane 2:1. In addition, the tests were carried out under the following conditions: a temperature of 560aboutWith atmospheric pressure, the volumetric rate of 4 h-1(mass of n-butane/mass of Katalizator.).

The results are given in the table.

P R I m e R 8. In a quartz reactor internal diameter of 10 mm was placed separately 0.33 g of catalyst (a) obtained as described in example 2, and 0.31 g of catalyst (b) obtained as described in example 3. The catalysts were subjected to in situ recovery, feeding a stream of hydrogen for 2 hours at a temperature of 550aboutC.

After treatment tested on dehydroisomerization, feeding into the reactor a gaseous mixture containing n-butane, hydrogen and nitrogen at a molar ratio of hydrogen and n-butane 1:1 and the nitrogen n-butane 2:1. In addition, the tests were carried out under the following conditions: temperature 563aboutWith, the atmosphere is Katalizator.).

The results are given in the table.

P R I m e R 0. 0.50 g of catalyst (a) obtained in example 2 and 0.25 g of catalyst (b) obtained in example 4 was mixed until homogeneous, after which the mixture was placed in a still layer in a quartz reactor of internal diameter 10 mm, the Catalysts were subjected to in situ recovery, feeding for 2 h in a current of hydrogen at a temperature of 550aboutC. After this treatment was tested on dehydroisomerization, feeding into the reactor a gaseous mixture containing n-butane, hydrogen and nitrogen at a molar ratio of hydrogen and n-butane 1: 1 and the nitrogen n-butane 2:1. The tests were carried out under the following conditions: temperature 564aboutC, atmospheric pressure, space velocity, calculated only for catalyst (a), 2 h-1(mass of n-butane/mass of Katalizator.).

The results are given in the table.

P R I m e R 10. 0,86 g of catalyst (a) obtained in example 2, and 0.33 g of the catalyst (b) obtained in example 4, was placed separately in a quartz reactor internal diameter of 10 mm and subjected to preliminary restoration in a stream of hydrogen at a temperature of 550aboutC for 2 h After recovery tested on dihydroethidium n-butane 1:1 and the nitrogen n-butane 2:1. The tests were carried out under the following conditions: at a temperature of 552aboutC, atmospheric pressure and volume velocity, the catalyst (a), 2 h-1(mass of n-butane/mass of Katalizator.).

The results are given in the table.

P R I m e R 11. 0,86 g of catalyst (a) obtained in example 2, and 0.33 g of the catalyst (b) obtained in example 4, was placed separately in a quartz reactor internal diameter of 10 mm and subjected to preliminary restoration in a stream of hydrogen at a temperature of 550aboutC for 2 h After recovery was tested on dehydroisomerization, feeding into the reactor a gaseous mixture containing hydrogen, n-butane and nitrogen, at molar ratios of hydrogen and n-butane 1:1 and the nitrogen n-butane 2:1. The tests were carried out at a temperature of 551aboutC, atmospheric pressure and volume velocity, the catalyst (a), 4 h-1(mass of n-butane/mass of Katalizator).

The results are given in the table.

P R I m e R 12 (comparative). In accordance with the description of example 1 of U.S. patent 4.269.813 received a crystalline borosilicate called AMS-18. More specifically, 10,5 g of boric acid and 67.2 per g of sodium hydroxide dissolved in 2653 g of water at continuous peremeshivaniya, 400 g of silicon oxide trademark Ludox. The solution was placed in an autoclave and left for crystallization at 165aboutWith 7 days. Thus obtained crystalline product was dried and probalily at 550aboutC for 5 h, was transferred to an acid form and again dried and probalily. A sample of this solid product weighing 4 g in the form of granules with a size of 0.5-0.8 mm was impregnable solution chloroplatinic acid concentration of 16 wt. so to get the content of metallic platinum of 0.55 wt. The solid product was dried and probalily for 12 h at 350aboutWith, resulting in a catalyst, 0.34 g obtained as described catalyst was placed in a quartz microreactor. The restoration was performed in a stream of hydrogen at 525aboutC for 2 hours After treatment was tested on dehydroisomerization. Into the reactor was fed a mixture of n-butane, hydrogen and nitrogen at a molar ratio of hydrogen and n-butane 1:1 and the nitrogen n-butane 2:1. The reaction was carried out at a temperature of 542aboutC, atmospheric pressure and volume rate of 8 h-1.

The results are given in the table.

P R I m e p 13 (comparative). A sample of the crystalline borosilicate AMS-18 obtained in example 7 was mixed with 16 g of gamma-alumina. With the Ohm chloroplatinic acid concentration of 4.1 wt. according to example 9 of U.S. patent 4.433.190. Impregnated solid product was dried and probalily for 12 h at 350aboutC. was Placed in a quartz reactor 0.3 g obtained in this way catalyst. After recovery processing conducted in a stream of hydrogen at a temperature of 525aboutC for 2 h, was tested on dehydroisomerization. Gave a mixture of n-butane, hydrogen and nitrogen at a molar ratio of hydrogen and n-butane 1:1 and the nitrogen n-butane 2: 1. The reaction was carried out at a temperature of 542aboutWith atmospheric davlenie and volume rate of 8 h-1.

The results are given in the table.

In the table conversion means mass percent of n-butane converted into isobutene, in relation to the original. Further, the selectivity and yield are respectively converted to the reagent and filed with the reagent. Finally, WITH1-C3and C5+denote paraffin and olefin products, respectively, containing from 1 to 3 carbon atoms and more than 5 carbon atoms.

P R I m e R 14. Use of gamma-alumina having a specific surface area equal to 394 m2/g and pore volume of 1.32 ml/g Using the method of example 2: using 2.6 g of atlantogenata NSCA add 30 ml of solution which contains of 0.68 g of nitrate pentahydrate India, of 0.43 g of tin tetrachloride, 1.2 g of hexachloroplatinic acid (16 wt. Pt) and 1.3 g of 66 wt. nitric acid. The catalyst (a) obtained by the method of example 2, containing 1 wt. Pt, 1 wt. In and 1 wt. Sn. This catalyst was tested under the conditions of example 7 and receive a conversion equal of 56.4% and the selectivity to isobutene 20,1%

P R I m e R 15. Use of gamma-alumina having a specific surface area equal to 110 m2/g and pore volume of 0.58 ml/g Using the method of example 2: using 0.9 g of atlantogenata 20 g of gamma-alumina and thus receive a sample containing 1.0 wt. silicon dioxide. To 20 g of this sample, add 30 ml of a solution containing 0.05 g of nitrate pentahydrate India, 0.05 g of tin tetrachloride, of 0.13 g of hexachloroplatinic acid (16 wt. Pt) and 1.3 g of 0.65 wt. nitric acid. The catalyst obtained by the method of example 2, containing 0.1 wt. Pt and 0.07 wt. In and 0.1 wt. Sn. This catalyst was tested under the conditions of example 7 and get the conversion rate of 50.4% and the selectivity to isobutene 20,4%

1. The catalyst for dehydroisomerization n-butane in isobutene, including an active metal and a solid granular porous media, aluminum oxide, different the specific surface area of 100 to 400 m2/l and total pore volume of 0.5 to 1.5 ml/g in the form of granules with a size of 0.4 to 5 mm, deposited on its surface as silicon dioxide in amounts of 0.5 to 5 wt. preferably 1 to 2.5 wt. and platinum in an amount of 0.1 to 1.0 wt.

2. The catalyst p. 1, characterized in that it further contains tin in an amount of 0.1 to 1 wt. and/or indium in the amount of 0.05 to 1.0 wt. moreover, the mass ratio of platinum to tin (0.5 to 2) 1, platinum, indium (0,3 1,5) 1.

3. Catalytic system for dehydroisomerization n-butane isobutane, characterized in that it contains a catalyst consisting of 0.1 to 1 wt. platinum and solid granular porous media g-alumina with a specific surface area of 100 to 400 m2/g and total pore volume of 0.5 to 1.5 ml/g in the form of granules with a size of 0.4 to 5 mm are deposited on the surface of the silicon dioxide in the amount of 0.5 to 5 wt. preferably 1 to 2.5 wt. and, if necessary, 0.1 to 1 wt. tin and/or 0.05 to 1.0 wt. in India, the mass ratio of platinum to tin (0.5 to 2) 1 and platinum indium (0.3 to 1.5) 1 and socialization representing porous g-alumina with precipitated on the surface of 0.5 to 5 wt. silicon oxide at a mass ratio of catalyst and socializaton from 20 to 80 to 80 to 20, preferably 70 to 30.

4. Catalytic systems is 1.0 mass. platinum and solid granular porous media g-alumina with a specific surface area of 100 to 400 m2/g and total pore volume of 0.5 to 1.5 ml/g in the form of granules with a size of 0.4 to 5 mm of deposition on the surface of the silicon dioxide in the amount of 0.5 to 5 wt. preferably 1 to 2.5 wt. and, if necessary, 0.1 to 1.0 wt. tin and/or 0.05 to 1.0 wt. in India, the mass ratio of platinum to tin (0.5 to 2) 1 and platinum indium (0.3 to 1.5) 1 and socialization representing moralit In, having in the dry and calcined as the following molar composition C2/n O B2O3(5 50)SiO2where the metal cation of valency n, H+, NH+4or their mixture at a mass ratio of catalyst socialization from 20 to 80 to 80 to 20, preferably 70 to 30.

5. The method of producing isobutene by dehydroisomerization n-butane when contacting the gaseous stream of n-butane with a porous layer at 450 - 600oWith a catalyst containing an active metal in an amount of 0.1 to 1.0 wt. solid granular porous media, aluminum oxide, characterized in that the use of a catalyst containing as the active metal is platinum and aluminum oxide-aluminum oxide with a specific surface area of 100 to 400 m2/g and total pore volume, preferably 1 to 2.5 wt. and the process is carried out in the presence of hydrogen at a molar ratio of hydrogen and n-butane from 1 1 to 5 1, at a pressure of from 200 mm RT.article up to 5 kg/cm2and volume rate of n-butane 0.5 to 5 h-1.

6. The method of producing isobutene by dehydroisomerization n-butane when contacting the gaseous stream of n-butane at 450 600oWith fixed bed catalytic system, wherein the use of a catalytic system containing a catalyst consisting of 0.1 to 1.0 wt. platinum and solid granular porous media g-alumina with a specific surface area of 100 to 400 m2/g and total pore volume of 0.5 to 1.5 ml/g and a grain size of 0.4 to 5 mm are deposited on the surface of the silicon dioxide in the amount of 0.5 to 5 wt. preferably 1 to 2.5 wt. and, if necessary, 0.1 to 1 wt. tin and/or 0.05 to 1.0 wt. in India, the mass ratio of platinum to tin (0.5 to 2) 1 and platinum indium (0,3 1,5) 1 and socialization representing porous g-alumina with precipitated on the surface of 0.5 to 5 wt. silicon oxide at a mass ratio of catalyst and socializaton from 20 to 80 to 80 to 20, preferably 70 to 30, and the process is carried out in the presence of hydrogen at a molar ratio of hydrogen and n-butane from 1 1 to 5 1, at a pressure of from 200 mm RT.article dem dehydroisomerization n-butane when contacting the gaseous stream of n-butane at 450 600oWith fixed bed catalytic system, wherein the use of a catalytic system containing a catalyst consisting of 0.1 to 1.0 wt. platinum and solid granular porous media g-alumina with a specific surface area of 100 to 400 m2/g and total pore volume of 0.5 to 1.5 ml/g and a grain size of 0.4 to 5 mm are deposited on the surface of the silicon dioxide in the amount of 0.5 to 5 wt. preferably 1 to 2.5 wt. and, if necessary, 0.1 to 1.0 wt. tin and/or 0.05 to 1.0 wt. in India, the mass ratio of platinum to tin (0.5 to 2) 1 and platinum indium (0,3 1,5) 1 and socialization representing moralit In, having in the dry and calcined as the following molar composition C2/nO B2O3(5 50)SiO2where the metal cation of valency n, N+, NH+4or their mixture at a mass ratio of catalyst socialization from 20 to 80 to 80 to 20, preferably 70 to 30, and the process is carried out in the presence of hydrogen at a molar ratio of hydrogen and n-butane from 1 1 to 5 1, at a pressure of from 200 mm RT.article up to 5 kg/cm2and volume rate of n-butane 0.5 to 5 h-1.

8. The method according to p. 6, characterized in that the catalyst and socialization contained in the catalytic system is homogeneous distributed sym comes into contact with the gas stream.

9. The method according to p. 7, characterized in that the catalyst and socialization contained in the catalytic system is homogeneous distributed in the layer of the catalytic system or are in the form of two contiguous layers, with the layer of the first catalyst comes into contact with the gas stream.

10. The method according to p. 5, wherein the process is carried out at a molar ratio of hydrogen and n-butane from 1 1 to 3 1.

11. The method according to p. 6, wherein the process is carried out at a molar ratio of hydrogen and n-butane from 1 1 to 3 1.

12. The method according to p. 7, wherein the process is carried out at a molar ratio of hydrogen and n-butane from 1 1 to 3 1.

13. The method according to p. 5, characterized in that the gas stream of n-butane and hydrogen diluted with nitrogen at a molar ratio of nitrogen n-butane from 1 1 to 5 1 before the stream comes into contact with a fixed bed of the catalyst.

14. The method according to p. 6, characterized in that the gas stream of n-butane and hydrogen diluted with nitrogen at a molar ratio of nitrogen n-butane from 1 1 to 5 1 before the stream comes into contact with a fixed bed catalyst system.

15. The method according to p. 7, characterized in that the gas stream of n-butane and hydrogen diluted with nitrogen at Moscou system.

16. The method according to p. 5, wherein the process is carried out at a molar ratio of hydrogen and n-butane from 1 1 1 to 5, preferably from 1 1 to 3 1, and a molar ratio of nitrogen n-butane from 1 1 to 3 1.

17. The method according to p. 6, wherein the process is carried out at a molar ratio of hydrogen and n-butane from 1 1 1 to 5, preferably from 1 1 to 3 1, and the molar ratio of the nitrogen n-butane from 1 1 to 3 1.

18. The method according to p. 7, wherein the process is carried out at a molar ratio of hydrogen and n-butane from 1 1 1 to 5, preferably from 1 1 to 3 1, and the molar ratio of the nitrogen n-butane from 1 1 to 3 1.

19. The method according to p. 5, wherein the process is carried out at a temperature of 500 580oC, a pressure of 400 mm RT.article up to 2 kg/cm2and volume rate of n-butane 2 4 h-1.

20. The method according to p. 6, wherein the process is carried out at a temperature of 500 580oC, a pressure of 400 mm RT.article up to 2 kg/cm2and volume rate of n-butane 2 4 h-1.

21. The method according to p. 7, wherein the process is carried out at a temperature of 500 580oC, a pressure of 400 mm RT.article up to 2 kg/cm2and volume rate of n-butane 2 4 h-1.

 

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FIELD: petroleum refining industry; production of engine fuels.

SUBSTANCE: the invention is pertaining to the field of petroleum refining industry, in particular, to production of engine fuels. Substance: the method provides for carrying out a catalytic cracking of petroleum fractions in presence of platinumzeolite-bearing rare-earth aluminum-silicate catalyst. The used catalyst consists of 5-20 mass % of "Y" zeolite with a molar ratio of silicon oxide to aluminum oxide within 4.5-9.5 and 80-95 mass % of the silica-alumina base in turn consisting of 40-95 mass % of amorphous aluminosilicate and 5-60 mass % of clay, and having a chemical composition, in mass %: aluminum oxide - 4.5-40.0, oxides of rare earths - 0.5-4.0, platinum - 0.0001-0.01, sodium oxide - 0.01-0.5, silicon oxide - the rest. The technical result: increased output of a gasoline fraction.

EFFECT: the invention ensures increased output of a gasoline fraction.

2 tbl, 8 ex

FIELD: organic synthesis catalysts.

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21 cl, 3 tbl

FIELD: structural chemistry and novel catalysts.

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EFFECT: improved activity and regeneration of catalyst.

41 cl, 3 dwg, 8 tbl, 10 ex

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2 cl, 6 ex

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EFFECT: achieved full oxidation of organics and intensified oxidation process.

21 cl, 23 ex

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