RU2004321C1 - Method of catalyst making for hydrodeparaffination of oily fractions - Google Patents

Abstract

SUMMARY OF THE INVENTION: Ammonium hydroxide is added to a suspension of pseudoboehmite to a pH of 7.1-7.4. Freshly formed washed balls of aluminosilicate are treated with a solution of magnesium nitrate. Magnesium-exchange aluminosilicate of the composition silicon dioxide 862% SiO, alumina 9.8% BF AI O is obtained. sodium oxide 0.6% Na O, magnesium 3.4% Bf Mg. It is triturated to a homogeneous mass and added to a pseudoboehmite suspension. A pentasil type high silica zeolite in ammonium form with a cobalt content of 1.5% is added to the resulting suspension. Mass ratio aluminosilicate: pentasil: pseudoboehmite (5-15): (45-60): (35-40). Mixed. A solution of silicic tungsten acid is added to the suspension, followed by a solution of nickel nitrate. The mass is evaporated. Molded into extrudates. Dried and calcined. 1 tabd

Description

The alleged invention relates to the field of oil refining, in particular, to the preparation of catalysts for the hydrogenation processing of oil fractions.

, One of the most valuable products obtained during oil refining is residual oil refined refining with selective solvents (N-MP, phenol, furfural), residue-hydrocracking deasphalting agent having a boiling point above 450 ° C and a pour point above + 50 ° C. Lubricating oils with a pour point below minus 12 ° C can be obtained from this feedstock by subsequent catalytic hydrodewaxing.

A known method 1 is the preparation of a hydrodewaxing catalyst for a paraffinic hydrocarbon fraction boiling in the range of 232-566 ° C in a hydrogen medium, which consists in the dispersion of a noble metal (platinum) in high silica zeolite (VCC) and alumina.

The process allows the preparation of a catalyst to eliminate a high pour point and improve color by hydrodeparaffin, lowering the heavy oil fraction.

The disadvantage of this method. is the preparation of a catalyst with low stability in the processing of residual sulfur feed and insufficient hydrodeparaffinizing activity (the solidification temperature of hydroparaffinisate is not lower than minus 3-5 ° C), as well as the use of expensive platinum in the preparation of the catalyst.

The prototype of the invention is a process for preparing a catalyst for producing oils by hydrodeparaffinization of residual oil fractions. The catalyst contains hydrogenating components (metal compounds of a secondary subgroup of groups VI and VIII) on a support made of porous refractory oxide and crystalline silicon dioxide and high-silica zeolite ZSM-5, hydrogenated metals in dispersed form are mixed with silicon oxide in alumina, dried and calcined.

The disadvantage of the method adopted for the prototype is the insufficient activity of the catalyst in the processing of raw materials with a high pour point: after dewaxing, the pour point does not drop below minus 6-7 ° C.

The aim of the invention is to increase the activity of the catalyst during hydrodeparaffinization of residual oil fractions boiling at temperatures above 450 ° C.

The goal is achieved that

pseudo-bitumen is used as AI oxide, from which a suspension is prepared containing additional aluminate in a magnesium-exchange form, followed by the introduction of MH4-VK zeolite dentasil,

0 containing 0.5-2% of May. cobalt or nickel (on dry zeolite), with a mass ratio (% on dry carrier) of pentasil, aluminosilicate and pseudoboehmite 45-60: 5-15: the rest (until May 100%), followed by

5 by introducing hydrogenating components from solutions of silicic tungsten acid into the resulting composition; and

Nickel nitrate.

The significant difference between the claimed

A method known from the prior art is the introduction of a hydrodeparaffinization aluminosilicate catalyst in a magnesium-exchange form and pseudoboehmite in a mass ratio of components (aluminosilicate,

5 pentasil, pseudoboehmite) 5-15: 45-60: the rest is up to 100 wt.% (On a calcined carrier).

The catalyst according to the proposed method is prepared as follows.

0 to the suspension of pseudoboehmite are added ground balls of magnesium-exchanged aluminosilicate and NI- or Co-MSC-VK zeolite pentasil. The mass ratio of the components: aluminum 5 licate-pentasil-pseudoboehmite 5-15: 45-60 - the rest is up to 100 wt.%. After stirring, solutions of silicic tungsten acid and nickel nitrate are added to the suspension to formulate

0 catalyst for oxides of nickel and tungsten. The resulting mass is evaporated, formed into extrudates, dried and calcined.

Obtained according to the proposed method, the catalyst samples were tested in

5 hydrodeparaffinization process of residual raffinate (fr. 490 ° С-КК, Тzast. + 53 ° С) under the following conditions: temperature 370-410 ° С, pressure 3-8 MPa, space velocity 0.5-1.5 h 1 . Under the specified conditions

0 the basic components of dewaxed oil with a pour point of minus 15 - minus 18 C and a yield of 79.4-83.6 wt.% Were obtained.

EXAMPLE 1 NH40H (12% solution) was added to a pseudoboehmate suspension (90 g a.s.v. in 200 ml of NaO) until a pH of 7.1-7.4 was reached. The freshly formed washed balls of aluminosilicate are treated with a solution of magnesium nitrate to obtain a magnesium-exchange aluminosilicate composition (wt.%): Si02 86.2; ALOz 9.8; NaOa 0.6; Mg 3.4 and further triturated to a homogeneous mass and added to a suspension of pseudoboehmite in an amount of 30 g a.s. To the resulting suspension was added 1.5% Co-NHij-BK-zeolite pentasil (129 g per a.s.w.). The mass ratio of the components: aluminosilicate-pentasil-pseudoboehmite is 12.1: 51.8: 36.1.

After stirring, a solution of silicic tungsten acid (43.3 g in 150 ml of H20) is added to the suspension, to which 17 ml of a 12% solution of MCHON are added to bring the pH to 7.1-7.4, and then a solution of nitric acid nickel (60 g of salt + 33 ml of a 24% solution + 150 ml of NaO). The content of hydrogenating components (wt.% On dry matter): LUZ - 12.0; NiO - 5.0.

The composition is evaporated, formed into extrudates, dried at a temperature of 120 ° C for 4 hours and calcined at a temperature of 550 ° C for 5 hours

The test results of the catalyst are shown in the table.

Example 2. The catalyst is prepared according to the method described in example 1 (when the mass ratio of the components of the composition):

aluminosilicate in MD-ion exchange form - 2.0% Co-MH4-pentasil - pseudobeamite 5.0, 60.0: 35.0.

After adding tungsten silicic acid and nickel nitrate to the suspension (content% May. On dry matter: L / Oz - 10.0, NiO - 6.0), the mass is molded, dried and calcined.

The test results of the catalyst are shown in the table.

Example 3. The catalyst is prepared according to the method described in example 1, with a small ratio of the components of the composition:

Aluminosilicate in MD-ion exchange form: 0.5% M1-MH4-pentasil: pseudo-beate 15: 45: 40.

After adding tungsten silicic acid and nickel nitrate to the suspension (content, wt% on dry matter: L / Oz - 14.0; NiO - 4.0), the mass is molded, dried and calcined.

The test results of the catalyst are shown in the table.

Example 4. The catalyst is prepared according to the method described in example 1, with a mass ratio of the components of the composition:

aluminosilicate in MD-ion exchange form: 0.3% Co-NhU-pentasil: pseudo-bitumen 3: 33.3: 63.7.

After adding tungsten silicic acid and nickel nitrate to the suspension (content, wt% on dry matter: WOs - 8.0; NiO - 2.0), the mass is formed, dried and calcined.

The test results of the catalyst are shown in the table.

As can be seen from examples 1-3, the preparation of the catalyst according to the proposed method allows to obtain a catalyst with high activity in hydrodewaxing of residual oil fractions (depressurization pour point 68-71 ° C with a high yield of dewaxed oils (79.4-85, 1 wt.%) Preparation of the catalyst at a ratio of components outside the limits specified by the present method does not allow to obtain an active catalyst for hydrodeparaffinization of residual oil fractions (Example 4).

(56) U.S. Patent

N54476618,101. 208-111, published. 1984.

US patent No. 4743355, CL. 208-59, published.

The test results of samples of catalysts prepared according to the proposed method, in hydrodeparaffinization of residual raffinate of Shaim oil

Claims (1)

The claims A METHOD FOR PREPARING A BLOCK CATALY FOR HYDRODEPARAFINIZATION OF OIL FRACTIONS, including applying hydrogenating components - nickel and tungsten to a carrier, which is a mixture of alumina and high-silica zeolite, forming and calcining, which uses aluminum oxide as a suspension, , in which Table continuation 0 aluminum silicate in magnesium exchange form is additionally introduced; pentasil in ammonium form containing 0.5–2 wt% nickel or cobalt is used as a high-silica zeolite, while these components are taken in a weight ratio (calculated on a female carrier) aluminosilicate: pentasil: pseudoboehmite 5-15: 45-60: 35-40, and the hydrogenation components are applied from solutions of silicic tungsten acid and nickel nitrate.