SU891143A1 - Catalyst for vapour conversion of direct-distillation petrols - Google Patents

Description

This invention relates to the manufacture of catalysts for the steam reforming of liquid hydrocarbons. A known catalyst for steam reforming of light gasoline, containing, by weight. %: nickel oxide 24.0; oxy sodium 3,5} kashti oxide 11.3; magnesium oxide 19.1; alumina 22.9; silica 12.6 and iron oxide 7.2 1J. The catalyst in the reforming process at 115 ° C, a pressure of 20 bar and an atomic ratio of steam: hydrocarbon of 3: 1 is characterized by the absence of coke formation and the gas yield (161), which is predominantly hydrogen. However, the transition to a straight-run gasoline leads to the carbonization of the catalyst and the loss of its activity. The closest to the proposed technical essence and the achieved effect is a catalyst for steam reforming of straight race gasoline G23 containing oxides of nickel, magnesium, calcium and aluminum in the following ratio, weight. %: Nickel oxide 12-15 Calcium oxide 1-4 Magnesium oxide 1-3 Alumina Rest While a well-known catalyst and has an initial high activity in the process of conversion of gasoline, but it is unstable, quickly loses activity after 2-3 hours of work; and the conversion rate after 8 hours of operation is 79%. In addition, the catalyst is carbonized during operation: after 35 hours, the amount of deposited coke is 9.8% at 500-600 ° C, pressure of 30 atm, gasoline volume velocity 2 and steam: gasoline ratio of 3: 1. The catalyst carrier has a small specific surface area of 2.5 MVr and water absorption of 24.5%. The purpose of the invention is to increase the stable activity and decrease the coal yield on the catalyst. This goal is achieved by using a catalyst for steam reforming of straight race gasolines containing nickel, magnesium, calcium and aluminum oxides in the following ratio, weight. %: Nickel oxide 5-10 Calcium oxide 0.47-0.9

Magnesium oxide 9.0-18.5 Alumina rest The proposed catalyst has a stable activity, for 50 hours the degree of conversion of gasoline does not decrease and amounts to 100%, the carbon deposition on the catalyst decreases to 0.24-0.55%, and the surface area increases to 4.5-8.0.

PRI and 1 ER 1. To prepare 66.6 kg of catalyst composition, wt. %: N10 10; MDO 9; SEO 0.9; 80.1 take 53.5 kg of ground alumina brand HA-85 or G-00, b kg of magnesium oxide, 3 kg of wood flour brand 560. All three components are mixed in the mixer in a dry form for 15 minutes, after which 23 l of calcium nitrate solution prepared by dissolving 2.5 kg of calcium nitrate rCa (NOj) 2 in a 25% solution of nitric acid. All contents in the mixer are kneaded for -45 to 60 minutes. The finished dough with loss on ignition - 31.5% of the SPT is formed on an automatic screw into cylinders with a diameter and height of 16 mm. The carrier is subjected to treatment for 48 h, then loaded into a quenching bin, where it is calcined continuously. The maximum temperature zone is 1380 ° C. As it unloads, the carrier enters the zone of ever higher temperatures. The calcining process, including cooling to, ends within 18-20 hours.

The carrier has the following composition, weight. %: MDO.DO; .СаО 1; - residual and physicochemical characteristics:

Bulk weight, kg / l 1.0-1.2 Mechanical crushing strength from the end face of the granule, kg / cm2. 200-220 Water absorption,% 28.3 Specific surface, m Vr4, 5 The carrier is impregnated with an aqueous solution of nickel nitrate, prepared by dissolving 25.7 g of nickel nitrate in 20 liters of distilled water. It is calcined at a temperature, cooled, re-impregnated with the remaining solution, dried and calcined. After three-time impregnation, the carrier absorbs nickel nitrate in the calculation of 10% weight. N iO from the weight of the carrier.

The catalyst worked stably for 50 hours, the carbon deposition was 0, 24%.

Example 2. The catalyst is prepared as in example 1, only 49.75 kg of alumina and 9 kg of magnesium oxide are taken to prepare the carrier. , 3 kg of wood flour and 1.25 kg of calcium nitrate.

Get the media composition, weight. %: MDO 15; CaO 0.5; AljiGj and the following physico-chemical characteristics

Bulk weight, kg / l 1.0-1.2 Mechanical crushing strength from the end face of the granule, kg / cm. 150-170 Water absorption,% 29.5 Specific surface, MVr5.8 The treatment of the carrier is carried out analogously to Example 1, only 12.9 kg of calcium nitrate are taken for the pickle.

Get the catalyst of the following composition, weight,%: N10 5; MDO 14.25; -SaO 0.47; 80.28.

The catalyst worked stably (the degree of conversion of gasoline - 100%) for 40 hours, carbon deposition 0, 40%,

Example 3 A catalyst is prepared analogously to example 1, only for the preparation of the carrier, 46.15 kg of alumina, 12. kg of magnesium oxide, 3 kg of 400 type wood flour and 1.85 kg of calcium nitrate are taken.

Get a carrier with the composition, ve%: MDO 20; CaO 0.75; the rest with the following physical and chemical characteristics:

Bulk weight, kg / l

1.0-1.1 Mechanical crushing strength from the end of the granule, kg / cm

130-150 Water absorption,% 31 Specific surface, Mvr The treatment of the carrier is carried out analogously to example 1, only taking 19.35 kg of nickel nitrate.

Get the catalyst of the following composition, weight,%: N10 7,5; MDO 18.5; CaO 0.7; A1 Q 0 73.3,

The catalyst worked stably (the degree of conversion of gasoline - 100%) for 45 hours, carbon deposition 0, 55%,

Comparative tests are known and the proposed catalysts were carried out at 500 BOOC C {500 ° C at the inlet and at the bed exit of the catalyst. The volumetric rate for gasoline was 2 h, the pressure was 30 atm, and the volume ratio of steam: gasoline was 3: 1.

The test results of the conversion of straight-run gasoline (B5-190s) containing 0.5 ppm total sulfur are presented in the table.

After 2 hours of work on a known catalyst, the degree of gasoline conversion began to decrease, and after 8 hours, the amount of gasoline in the steam condensate was 21% of the missed

Due to significant coal deposition, it was destroyed when the catalyst was unloaded after 35 hours of operation.

For catalyst 46-1 of Example 1, the degree of gasoline conversion began to decrease after 15 hours of operation, when traces of gasoline appeared in the steam condensate and the amount of deposited coke after 20 hours of operation was 0.95%.

A suitable catalyst was stably working for 50 hours of tests with insignificant carbon formation.

The catalyst during unloading did not destroy with. Structural and chemical composition has not changed. The samples of the proposed catalysts have the following characteristics:

Bulk weight, kg / l 1.0-1.2 Mechanical crushing strength from the end face of the granule, kg / cm2-130-220

Water absorption,% 28.3-31.0 Specific surface area, m2- / g4.5-8.0

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Claims (2)

1.Patent of France No. 1433595, cl. C 10 d, B 013, published 1966. 2. Authors certificate of the USSR (223063, cl. In 013 21/04, 1965 (prototype).