A method of processing gasoline secondary processes

 

(57) Abstract:

Usage: petrochemistry. The inventive gasoline secondary processes are hydrobromide in two stages. The catalyst of the first stage contains, by weight. platinum 0,5 0,65; fluorine 0,5 2,5; aluminium oxide - rest. The catalyst of the second stage contains, by weight. platinum or a mixture of platinum promoter 0,3 1,2; high-silica zeolite ZSM in the Na-form 50,0 75,0; alumina rest. The ratio of the catalysts (0,3 2,5) 1. As the promoter used rhenium, iridium, bear, tungsten or molybdenum at a mass ratio of platinum and a promoter (0,15 12) 1. 2 C.p. f-crystals, 1 table.

The invention relates to a method of catalytic hydrofining gasoline secondary processes and can be used in oil refining, petrochemical and chemical industry for producing high quality components for automotive fuels.

Known way catalytic hydrofining gasoline secondary processes by hydrogenation on lookbetteronline.com catalyst at temperatures 260-420aboutC and a pressure of 2.6 and 2.9 MPa. The disadvantage of this method is the low octane number catalyzate (50-55 points on m is in two stages on lookbetteronline.com the catalyst under the following conditions: stage I: temperature 350-420aboutWith a pressure of 3.5-5 MPa; stage II: the temperature of 380-400aboutC, pressure 3 MPa.

The product of the two-stage refining contains not more of 0.003 wt. sulfur. The disadvantage of this method is the low octane number of the product (50-52 point by the motor method).

The aim of the invention is to increase the octane number of the resulting product.

This goal is achieved by the described method of processing gasoline secondary processes by hydrobromide in two stages with the first stage catalyst composition, wt. Platinum 0,5-0,65 Fluorine 0,5-2,5 alumina Rest. at the second stage catalyst composition, wt. Platinum or a mixture of platinum promoter 0,3-1,2 high-silica zeolite ZSM in Na form 50,0-75,0 alumina Rest when the mass ratio of the catalysts of the first and second stages (from 0.3 to 2.5):1.

Preferably hydrobromide carried out at a temperature of 460-530aboutC, a pressure of 2.5-3.5 MPa.

On the second step using the catalyst containing the promoter of the rhenium, iridium, rhodium, tungsten or molybdenum at a mass ratio of platinum and a promoter (0.5 to 12):1.

Distinctive features of the method are that on stage using the catalyst, optionally containing platinum or a mixture of platinum promoter, high-silica zeolite ZSM in PA the form of said composition, in that the catalysts used in the mass ratio of 0.3 to 2.5):1 and in the preferred process conditions.

The first stage of the process flow of the reaction of dehydrogenation of naphthenic hydrocarbons. The second stage is the transformation malorazmernyj paraffin hydrocarbons into aromatic hydrocarbons. Adverse reaction is the hydrocracking of hydrocarbons with the formation of mainly propane and butane.

Catalysts I and stage II are characterized by resistance to the action of sulphur and moisture, and the zeolite catalyst has a higher compared to aluminium oxide-platinum catalysts selectivity in the conversion of paraffin hydrocarbons. Because of this, when the ratio indicated catalysts receive high-octane produce with octanoyl number by the motor method in its pure form 81-85 points at a high yield.

The hydrofining hydrotreated gasoline secondary processes carried out in a flow type reactor under hydrogen pressure. Download fluorinated aluminium oxide-platinum cathalifaud the catalyst in a stream of hydrogen and served raw.

P R I m e R 1. Raw materials, representing the hydrotreated mixture with a mass ratio of 1:1 petrol thermal cracking fractions 62-180aboutAnd straight-run gasoline fraction 62-180aboutWith, and has the following characteristics: Density, g/cm30,733 Fractional composition,aboutWith NC 58 10% 97 50% 123 95% 160 QC 182 Octane number by the motor method in its pure form 50,5 Sulfur, h/min 125 served on the bi-reactor pilot plant. The catalyst of the I-th level contains 0.5 wt. platinum and 1.5 wt. fluoride on alumina, the catalyst of the second stage contains 0.6. platinum, 0.6. rhenium, 60 wt. NaZSM and alumina rest, the mass ratio of catalyst 1:1. At a temperature of 480aboutC, pressure 3 MPa, the space velocity of the raw material 2 h-1and circulation SIV 1200 m3/m3get produce with an octane number (pure motor method) 83 points at exit 82 wt. The results are presented in the table.

P R I m m e R 2. The method is carried out as in example 1 with the difference that the conditions for the process: temperature 490aboutWith the pressure of 3.0 MPa, the volumetric feed rate 2 h-1and the circulation of the SIVs 1500 m3/m3. The catalyst composition I: 0,3 wt. platinum and 2.5 wt. fluorine aluminum oxide, the composition of the AC, the new ratio of 0.3:1. The results are presented in the table.

P R I m e R 3. The method is carried out as in example 1 with the difference that the conditions for the process: temperature 450aboutWith the pressure of 2.0 MPa, the volumetric feed rate of 1.5 h-1the circulation SIV 1500 m3/m3. The compositions of catalysts: step I: to 0.65 wt. platinum and 0.5. fluorine aluminum oxide; grade II: to 0.35 wt. platinum, 0.03 wt. molybdenum, 75 wt. NaZSM, alumina rest. The catalysts used in a mass ratio of 2.5:1. The results are presented in the table.

P R I m e R 4. The method is carried out as in example 1 with the difference that the conditions for the process: temperature 530aboutC, pressure 3 MPa, the volumetric feed rate of 4.5 h-1the circulation SIV 1500 m3/m3. The compositions of catalysts: I step: 0.5. platinum and 1.0 wt. fluorine aluminum oxide; grade II: 0.36 wt. platinum, 0.06 wt. iridium, 60 wt. NaZSM, alumina rest, when the mass ratio of catalyst 2:1. The results are presented in the table.

P R I m e R 5. The method is carried out as in example 1 with the difference that the conditions for the process: temperature 480aboutWith the pressure of 2.5 MPa, the volumetric feed rate of 2.0 h-1the circulation SIV 1000 m3. the Latino, 0.5. rhodium, 60 wt. NaZSM, alumina rest, when the mass ratio of catalyst 1:1. The results are presented in the table.

P R I m e R 6. The method is carried out as in example 1 with the difference that the circulation everything is 1500 m3/m3on stage I use a catalyst containing 0,6% Pt, 1.5% Of F, the second stage uses a catalyst of the following composition: platinum 0.6. NaZSM 60,0 wt. alumina rest. The results are presented in the table.

P R I m e R 7 (comparative). The method is carried out according to example 6 with the difference that the use of the catalyst of the second stage of the following composition: platinum of 0.15 wt. NaZSM 60,0 wt. alumina rest. The results are presented in the table.

P R I m e R 8 (comparative). The method is carried out according to example 6 with the difference that the use of the catalyst of the second stage of the following composition: platinum of 0.15 wt. rhenium 0.1 wt. NaZSM 60,0 wt. alumina rest. The results are presented in the table.

P R I m e R 9 (comparative). The method is carried out according to example 6 with the difference that the use of the catalyst of the second stage of the following composition: platinum 0.36 wt. molybdenum of 0.18 wt. NaZSM 60,0 wt. alumina rest, catalysts I and II of the steps taken in the ratio of 0.26 with the difference, using the catalyst of the second stage of the following composition: platinum of 0.35 wt. molybdenum 0.1 wt. NaZSM 60,0 wt. alumina rest, catalysts I and II of the steps taken in the ratio 3:1. The results are presented in the table.

P R I m e R 11 (comparative). The method is carried out according to example 6 with the difference that the use of the catalyst of the second stage of the following composition: platinum 0.7 wt. rhenium 0.7 wt. NaZSM 60,0 wt. alumina rest. The results are presented in the table.

P R I m e R 12 (comparative). The method is carried out according to example 6 with the difference that the use of the catalyst of the second stage of the following composition: platinum of 0.35 wt. molybdenum 0.1 wt. NaZSM 40.0 wt. alumina rest. The results are presented in the table.

P R I m e p 13 (comparative). The method is carried out according to example 6 with the difference that the use of the catalyst of the second stage of the following composition: platinum 1.4 wt. NaZSM 60,0 wt. alumina rest. The results are presented in the table.

P R I m e R 14 (comparative). The method is carried out according to example 6 with the difference that the use of the catalyst of the first stage of the following composition: platinum, 0.2 wt. fluoride of 1.5 wt. alumina rest. The results of the experiment are shown in table.

P R I m e R 15 (Crisostomo: platinum 0.7 wt. fluoride of 1.5 wt. alumina rest. The results of the experiment are shown in table.

P R I m e R 16 (comparative). The method is carried out according to example 6 with the difference that on stage I use a catalyst of the following composition: platinum 0.6. fluoride is 0.3 wt. alumina rest. The results of the experiment are shown in the table.

P R I m e R 17 (comparative). The method is carried out according to example 6 with the difference that on stage I use a catalyst of the following composition: platinum 0.6. fluorine 2.8 wt. alumina rest. The results of the experiment are shown in the table.

P R I m e R 18 (prototype). The method is carried out as in example 1 with the difference that the hydrotreated feedstock fed to the catalyst of the following composition, wt. zeolite NU 15; HZSM 30,0; Nickel oxide 3,0; molybdenum oxide 10,0; alumina rest. The results are presented in the table.

As follows from the results of examples 1-6 described method has a high efficiency. Liquid catalysate is the octane number by the motor method 81-85 points at the exit 79-83,5 wt. Mainegenealogy the period of the catalysts.

1. A METHOD of PROCESSING GASOLINE SECONDARY PROCESSES at elevated temperature and pressure by hydrobromide in any use of the catalyst, optionally containing platinum and fluorine, in the following ratio, wt.

Platinum 0,5 0,65

Fluorine 0,5 2,5

Alumina Rest

the second stage uses a catalyst, optionally containing platinum or a mixture of platinum promoter, high-silica zeolite ZSM in the Na-form in the following ratio, wt.

Platinum or a mixture of platinum promoter 0,3 1,2

The specified high-silica zeolite 50,0 75,0

Alumina Rest

and the process is carried out at a mass ratio of the catalysts in the first and second steps (0,3 2,5) 1.

2. The method according to p. 1, characterized in that hydrobromide carried out at a temperature of 460 530oC, a pressure of 2.5 to 3.5 MPa.

3. The method according to p. 1, characterized in that in the second stage using a catalyst containing a rhenium promoter, pride, rhodium, tungsten or molybdenum, at mass ratio of platinum promoter (0.5 to 12) 1.

 

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