SU1214195A1 - Method of preparing catalyst for hydrodemetallization of heavy hydrocarbon fractions - Google Patents

Description

The invention relates to the preparation of catalysts for the process of hydrotreatment of heavy metal and heavy metal fractions.

The purpose of the invention is to obtain a catalyst with increased activity and stability by mixing the hydride of an alloy of metals with aluminum hydroxide or silicon, followed by formation, drying, calcining at a certain temperature.

Example 1, 1 g of ZrNiH hydride is mixed with 20 g of aluminum hydroxide, molded, dried at 110 ° C, calcined at 550 ° C for 1 hour. The resulting catalyst has a composition of 10% ZrNiH / AlT Oj. 20 cm of catalyst 10% ZrNiH / AI is placed in the reactor ., 03 and the process of hydrodemetal of the back of the raw material - fuel oil is carried out at atmospheric pressure. Fuel oil is served in a stream of hydrogen. The consumption of hydrogen is 1500 nl / l of raw material, the feed rate of raw material is 1.0. The content of metals in raw materials, ppmrV 90, Ni 27, The content of metals in the reaction product ppm: V is absent; Ni is missing. The degree of hydrodemetallization 100%.

Example 2, 1 g of ZrNiH hydride is mixed with 20 g of silicon hydroxide, molded, dried at 110 ° C, calcined at 550 ° C for 1 hour. The resulting catalyst has a composition of 10% ZrNlH / SiOj. A 20 cm catalyst 10% ZrNiH / SiO is placed in the reactor and fuel oil is fed in a stream of hydrogen at 380 ° C and atmospheric pressure. The consumption of hydrogen is 1500 nl / l of raw material, the feed rate is 1.0 h. The content of metals in raw materials, ppm: V 90, i 27 o The content of metals in the reaction product, rrga: V is absent, i is absent. The degree of gi, chromatization is 100%.

Example 3. 3.0 ZrCoH is mixed with 20 g of aluminum hydroxide, formed .. dried at 120 ° C, calcined, at 500 ° C for 1 hour. The resulting catalysts; the additive has a composition of 30% ZrCoH / A1 0j.

Place 20 cm of a 30% ZrCoH / ACHOZ catalyst into the reactor and fuel oil is fed in a stream of hydrogen at 390 ° C and atmospheric pressure. The consumption of hydrogen is 1500 nl / l of raw material, the feed rate is 1.0 h. The content of metals in raw materials is ppm: V 90, Ni 27. The content of metals in products.

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reactions, ppm; V 1,8, Ni 4,6. The degree of demetallization: V 100%, Ni 83%.

Example 4. 20 cm of the catalyst 5 obtained under conditions of example 3 are placed in a reactor and fuel oil is fed in a stream of hydrogen. The process of hydrometallization of fuel oil is carried out at 420 C and atmospheric pressure, the flow rate of hydrogen is 1500 nl / l of raw material, the feed rate of the raw material is 1.0 h. Metal content in, ppm: V 90; Ni27; in the reaction product; V is absent, Ni 1,5. The degree of demetallization is 15%: V 100%, Ni 99.5.

Example 5. 3.0 g of ZrCOn is mixed with 20 g of silicon hydroxide, molded, dried at 120 ° C, calcined at 500 ° C for 1 hour. The resulting catalyst has a composition of 30% ZrCoH / SiO. 20 cm of catalyst 30% ZrCon / SiO, 2 are placed in the reactor. At a temperature of 390 ° C and atmospheric pressure, fuel oil is supplied. Consumption of 25 hydrogen 1500 nl / l of raw materials, feed rate of 1.0. The content of metals in raw materials, rrga: V 90J Ni 27, in the reaction product: V - absent, Ni 1,5. The degree of demobilization: V 100%, Ni 99.5%.

Example 6. 3.0 g of HfNi H hydride is mixed with 20 g of aluminum hydroxide, molded, dried, calcined at 500 ° C for 1 hour. The resulting catalyst has a composition of 30% HfNiH 70% A1,

A catalyst of 20 cm is placed in the reactor and fuel oil is fed in a stream of hydrogen at atmospheric pressure. The consumption of hydrogen is 1500 nl / l of raw materials, the feed rate of raw materials is 1.0. The content of metals in raw materials, ppm: V 90 ,, Ni 27. The content of metals in the reaction product, ppm: V is absent, Ni 4,4. Degree of deme35

45

thallization,% V 100, Ni 82/7.

Experiments have been carried out on the hydrodemetallization of fuel oil on the known ZrNiH, ZrCoH catalysts and on catalysts of the invention according to the invention 10% ZrNili, 90% A1., 0h and 30% ZrCoH, 70% A1 ,. A 20 cm catalyst was charged to the reactor and the feed was fed at 380 ° C and atmospheric pressure. Hydrogen flow rate 1500 nl / l feedstock, feed rate, 1.0. The data obtained are shown in the table.

Editor L-.Avramenko

Compiled by V.Teplkova

Tehred T. Dubinchak Proofreader A.ZimokoSov

Order 819/11 Circulation 527 Subscription

VNIIPI USSR State Committee

for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab, 4/5

Filial PPP Patent, g, Uzhgorod, st. Project, 4

Claims (1)

METHOD FOR PREPARING A CATALYST FOR HYDRODEMETALLIZATION OF HEAVY HYDROCARBON FRACTIONS based on a hydride of an alloy of metals of zirconium or hafnium and nickel or cobalt, characterized in that, in order to obtain a catalyst with increased activity and stability, the alloy hydride of these metals is mixed with or aluminum hydroxide dried and calcined at 500-550 ° C. " 1