The catalyst for reforming of gasoline fractions

 

(57) Abstract:

Usage: in catalytic chemistry, in particular in the composition of the catalyst for petrochemical and refining. The inventive catalyst contains 0.2 to 1.2 wt. titanium or a mixture of platinum with a promoter selected from the group of rhenium, iridium, rhodium, tungsten, molybdenum in a weight ratio of platinum and a promoter, is equal to (0.5 to 12) 1, 50 to 75 wt. high zeolite ZSM-5, ZSM-8 or ZSM-11 with silicate module 25 100, of 0.4 to 6.8 wt. oxide of alkaline metal is lithium or sodium, or potassium, and the remainder alumina. The catalyst in the process riformista gasoline fractions provides the resultant catalysate after 24 h to 86% after 240 h to 85.8% octane catalyzate to 104,3. 1 C.p. f-crystals, 1 table.

The invention relates to a catalyst for reforming of gasoline fractions and can be used at the enterprises of oil refining and petrochemical industries.

A known catalyst for the reforming of hydrocarbons, containing platinum, chlorine, mordenite with a molar ratio of silicon oxide to aluminum oxide 19-45 and aluminum oxide [1,2]

The disadvantage of this catalyst is its low stability. So, when reforming a gasoline FR,8 chlorine and aluminum oxide, at 480aboutWith the pressure of 1.4 MPa, molar ratio hydrogen:feedstock 7:1 and flow rate of feed of 1.5 h-1receive produce octane on the research method 95 points at the exit 65.2 wt. and after 240 hours of work output is reduced to 60,4 wt.

The closest in technical essence of the present invention is a reforming catalyst containing 1-15 wt. zeolite ZSM-5 in the protonated form, platinum or a mixture of platinum and rhenium on alumina [3]

The disadvantage of this catalyst is its low stability. So, when reforming FR. 85-180aboutWith the catalyst containing of 0.35 wt. platinum on aluminum oxide and 2 wt. zeolite ZSM-5 in the protonated form with silicate module 80, 480aboutWith the pressure of 1.4 MPa, molar ratio hydrogen:feedstock 7: 1 and flow rate of feed of 1.5 h-1get produce with an octane number according to research method 103 points at the exit of 40.5 wt. and after 240 hours of work output is reduced to 38.0 wt.

The aim of the invention is to increase the stability of the catalyst.

The objective is achieved by the fact that in contrast to the known proposed catalyst contains 50-75 wt. zeolite ZSM, 0.2 to 1.2 wt. platinum or platinum with PDFs as promoter contains rhenium, or iridium, or rhodium, or tungsten or molybdenum in the ratio of platinum and a promoter (0.5 to 12):1.

Distinctive features of the proposed catalyst is that it additionally contains an alkali metal oxide from among lithium, sodium or potassium and the ratio of the components.

The catalyst is prepared as follows.

Aluminum hydroxide is mixed with high zeolite in the sodium form, add nitric acid as patinator, formed into extrudates, dried and calcined in air flow. The catalyst is immersed in a solution of emmakate platinum or a mixture of emmakate platinum compound promoter. The impregnation is carried out at 80-90aboutC and pH 10 for 3 h, the excess solution is drained and the catalyst is immersed in an aqueous solution of salts of alkaline metal and are impregnated for 1 h at 80-90aboutWith, the excess solution is drained, the catalyst is dried and calcined in air flow at a temperature of 500aboutC.

P R I m e R 1. 47.9 g of a paste of aluminum hydroxide is mixed with 70 g of zeolite ZSM-5 with module 25 in the sodium form and 1 ml of 57% nitric acid, formed into extrudates, dried and calcined in air flow at 500aboutC. 100 g of the extrudates are immersed in 200 ml of solution steriade the RA is drained, and extrudates in 200 ml of a solution containing 86,5 g of potassium chloride and process them for 1 h at 90aboutC. the Excess solution is drained, the catalyst is dried and calcined in air flow at a temperature of 500aboutC. the Composition of the finished catalyst shown in the table.

P R I m m e R 2. The catalyst prepared according to example 1 with the difference that taking 70 g of paste of aluminum hydroxide and 60 g of zeolite ZSM-8 module 70, and an impregnating solutions contain:

first of 0.38 g of emmakate platinum

second 110,5 g of lithium chloride.

The composition of the finished catalyst shown in the table.

P R I m e R 3. The catalyst prepared according to example 1 with the difference that take 82.8 g of paste of aluminum hydroxide and 50 g of high modulus of zeolite ZSM-11, and impregnating solutions contain:

first of 1.15 g of emmakate platinum and 0,86 g renevating ammonium,

second 153 g of sodium chloride

The composition of the finished catalyst shown in the table.

P R I m e R 4. The catalyst prepared according to example 1 with the difference that we take for 61.9 g of paste of aluminum hydroxide and 65 g of zeolite with the module 100, and impregnating solutions contain:

first 0,19 g emmakate platinum and 0.18 g radiological ammonium, and the second is 34.2 g of sodium chloride.

The composition of gotovac the take and 31.7 g of paste of aluminum hydroxide and 75 g of zeolite module 35, and impregnating solutions contain:

first of 0.23 g of emmakate platinum and 0.34 g of ammonium tungstate, and the second 367,9 g of sodium carbonate.

The composition of the finished catalyst shown in the table.

P R I m e R 6. The catalyst prepared according to example 5 with the difference that take 68 g of paste of aluminum and 60 g of zeolite, and impregnating solutions contain: first of 1.15 g of emmakate platinum and 0.09 g of ammonium molybdate, and the second 177,5 g of sodium chloride.

The composition of the finished catalyst shown in the table.

P R I m e R 7. The catalyst prepared according to example 6 with the difference that they take and 63.3 g of paste of aluminum hydroxide, and impregnating solutions contain: first and 0.33 g of emmakate platinum and 0.24 g radiological ammonium, and the second 190.5 g of sodium chloride.

The composition of the finished catalyst shown in the table.

P R I m e R 8 (comparative). The catalyst prepared according to example 5 with the difference that take 71 g of paste of aluminum hydroxide, and impregnating solutions contain: first of 0.58 g of emmakate platinum and 0.38 g of ammonium tungstate, and the second of 10.2 g of sodium chloride.

The composition of the finished catalyst shown in the table.

P R I m e R 9 (comparative). The catalyst prepared according to example 8 with the difference that we bring to 58.2 g of paste of healither shown in the table.

P R I m e R 10 (comparative). The catalyst prepared according to example 8 with the difference that the second impregnation solution containing 7.6 g of potassium chloride.

The composition of the finished catalyst shown in the table.

P R I m e R 11 (comparative). The catalyst prepared according to example 9 with the difference that the second impregnation solution contains 278,9 g of potassium chloride.

The composition of the finished catalyst shown in the table.

P R I m e R 12 (comparative). The catalyst prepared according to example 8 with the difference that the second impregnation solution containing 12.3 g of lithium chloride.

The composition of the finished catalyst shown in the table.

P R I m e p 13 (comparative). The catalyst prepared according to example 9 with the difference that the second impregnation solution contains 442,8 g of lithium chloride.

The composition of the finished catalyst shown in the table.

P R I m e R 14 (comparative). The catalyst prepared according to example 6 with the difference that take 104,9 g of paste of aluminum hydroxide and 40 g of zeolite, and impregnating solutions contain: first of 0.58 g of emmakate platinum and 0.17 g of ammonium molybdate, and the second to 99.2 g of sodium chloride.

The composition of the finished catalyst shown in the table.

P R I m e R 15 (comparative). Catalizers of 0.13 g of emmakate of platinum and 0.05 g of ammonium molybdate, and second of 160.4 g of potassium chloride.

The composition of the finished catalyst shown in the table.

P R I m e R 16 (comparative). The catalyst prepared according to example 15 except that the impregnating solution contains: first 0,19 g emmakate platinum, and the second 213,6 g of sodium chloride.

The composition of the finished catalyst shown in the table.

P R I m e R 17 (comparative). The catalyst prepared according to example 15, except that take and 64.3 g of paste of aluminum hydroxide, and the first impregnation solution containing 1.42 g emmakate platinum and 1.07 g of ammonium tungstate.

The composition of the finished catalyst shown in the table.

P R I m e R 18 (comparative). The catalyst prepared according to example 15 with the difference that we bring to 64.6 g of paste of aluminum hydroxide, and the first impregnating solution contains 2,59 g emmakate platinum.

The composition of the finished catalyst shown in the table.

P R I m e R 19 (prototype). 100 g of the extrudates of alumina was immersed in 200 ml of a solution containing 1 g of acetic acid, 1 g of hydrochloric acid and 0.74 g of hexachloroplatinic acid and lead impregnation 2 h at 25aboutC and 1 h at 80aboutC. the Excess solution is drained, the catalyst is dried and calcined in air flow. Received ka is the first contact with hot 5% solution of ammonium chloride to reduce sodium in the zeolite to 0.01 wt. After each treatment the zeolite was filtered, after the last treatment, the zeolite in NH4the form is then washed from chloride ions, dried at 110aboutWith and progulivali for 10 hours at 538aboutC. 2 g of the obtained zeolite and 98 g milled in a ball mill 0,35 Pt/Al2O3the catalyst was ground in a ball mill for two hours, alloy preformed into pellets 3 mm in diameter, which had a density of 0.75 g/cm3.

The composition of the finished catalyst shown in the table.

Samples of the catalysts prepared in examples 1-19, experienced in the process of reforming of hydrotreated gasoline fraction, wikipeida within 85-180aboutWith and having the octane number of 48 points by the motor method. The reforming conditions: a pressure of 1.4 MPa, the volumetric feed rate of 1.5 h-1, the molar ratio of hydrogen:feedstock 7:1. The temperature was chosen so that to get the octane number catalyzate on the research method 103 points, but the test temperature should not exceed 510aboutC. During the test specified octane number maintained at the same level, changing the temperature, if needed. The resultant catalysate was calculated as the average of velterop, prepared according to examples 1 to 18, it is seen that the stability of the proposed catalyst is significantly higher than the catalyst of the prototype. While the importance of the ratio of the components. Thus, the reduction of the oxide of the alkali metal in the catalyst to a value of less than 0.4. decreasing its stability (examples 8, 10 and 12), while increasing its quantity over 6.8 wt. decreases the activity of the catalyst (examples 9, 11 and 13). When the content in the catalyst is less than 50 wt. zeolite (example 14) or less than 0.2 wt. platinum or platinum promoter (examples 15 and 16) also decreases the activity of the catalyst. The increase in the number of platinum or platinum promoter to more than 1.2 wt. (17, 18) or increasing the amount of zeolite is more than 75 wt. impractical because in the first case, a high amount of platinum, Doroga the catalyst does not improve its performance, and in the second case leads to a decrease in mechanical strength of the extrudates of catalyst.

1. The CATALYST FOR reforming of GASOLINE FRACTIONS containing platinum or a mixture of platinum promoter, high-silica zeolite ZSM and aluminum oxide, characterized in that it further contains an oxide of an alkali metal lithium, Il the rum 0,2 1,2

High-silica zeolite ZSM 50 75

The specified oxide of an alkali metal 0,4 6,8

The aluminum oxide To 100

2. The catalyst p. 1, characterized in that it contains a high-silica zeolite ZSM-5, ZSM-8 or ZSM-11 with silicate module 25 to 100, and as a promoter of the rhenium or iridium, or rhodium, or tungsten, or molybdenum in the ratio of platinum:promoter (0.5 to 12) 1.

 

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2 cl, 1 tbl, 25 ex

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30 cl, 3 dwg, 4 tbl, 2 ex

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6 cl, 4 ex, 6 tbl, 5 dwg

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7 cl, 42 ex, 4 tbl

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11 cl, 4 dwg, 3 tbl, 16 ex

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18 cl, 3 dwg, 9 ex

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