The method of obtaining low-sulfur waxy diesel fuels

 

(57) Abstract:

Usage: petrochemistry. The inventive diesel fraction is subjected to pre-treatment in the presence of a catalyst based on oxides of aluminum, cobalt or Nickel and molybdenum. Then the product will podvergaut re hydrobromide in the presence of a catalyst containing, wt.%: the oxide of cobalt or Nickel 4,0 - 6,0; molybdenum oxide 10,0 - 12,0; oxides of rare earth elements 0,5 - 1,5; fluoride of 0.5 - 1.5; boron oxide 0.5 to 1.5; pentasil ZSM-8 module 30 40,0 - 60,0; - aluminum oxide - rest. table 1.

The invention relates to a method for producing waxy diesel fuels and can be used in the refining industry.

The known method [1] of receipt of distillate with initial boiling point 163aboutWith and end boiling 346aboutWith at a temperature of 320aboutWith a pressure of 4.0 MPa, the space velocity of the raw material 1 h-1and the ratio of hydrogen:the raw material is equal to 1000 m3/m3catalyst consisting of a modified zeolite (60-70%), hydrogenating metal VI or VIII groups of the periodic system usually Pt, Pd, Ni in an amount of 0.1-10% of the oxides of molybdenum or tungsten in the amount of 2-10% or a combination of Ni (Co), c Mo (W), and swazey the

The disadvantage of this method is the low volumetric feed rate, the poisoning of platinum in the catalyst in the processing of high-sulphur raw materials and relatively low yield of waxy diesel fuel (82-83 wt.).

The closest in technical essence and the achieved effect is the way [2] obtain the waxy diesel fuels.

Diesel fraction with temperature 183-363aboutWith hydroabrasive at a temperature of 350-400aboutC, pressure 3 MPa, the space velocity of the raw materials 3 h-1circulation of hydrogen 250 m3/m3raw material while a double-layer loading catalysts (in the ratio 1: 1) top downloaded the Hydrotreating catalyst composition, wt. NiO 4,0; MoO313,0; zeolite So 5,0; stop-Al2O3up to 100% Below the hydrodewaxing catalyst composition, wt.

Moo310; NiO 5,4; zeolite DCM 65,3; -Al2O3the rest, up to 100%

Prototype method [2] allows to obtain a diesel fuel with a pour point of minus 46-50aboutWith residual sulfur content of 0.06% cetane number 45-55.

The disadvantage of this method is the low feed rate, increasing the freezing temperature of from -50 to -23aboutWhen essentialine fuel in the winter, you can only get at a temperature of 370-400aboutC and a flow rate not exceeding 2 h-1.

The aim of the invention is to increase the volumetric feed rate of the raw material, the cetane number of diesel fuels with a low freezing point and a low content of sulphur.

The objective is achieved by the fact that sulfur diesel fraction 200-360 (200-380about(C) with a sulfur content of 0.5-1.8 wt. with a pour point of minus 10aboutWith, cetane number 45-47 points previously in contact with a hydrogen-containing gas in the presence of a catalyst based on oxides of aluminum, cobalt or Nickel, molybdenum, and then on broad porous catalyst Hydrotreating of hydroisomerization when the mass ratio of the catalyst is 1:1.

The composition of the isomerization catalyst, wt. the oxide of cobalt (Nickel) 4-6; molybdenum oxide 10-12; oxides of rare earth elements 0,5-1,5; boron oxide 0.5 to 1.5; a fluoride of 0.5-1.5; zeolite-pentasil ZSM-8 40-60; -Al2O3the rest of it.

Process temperature 320-390aboutWith the pressure of 2.5-3.0 MPa, the rate of circulation of the hydrogen-containing gas is between 250 and 450 Nm3/m3raw materials, the volumetric feed rate of 2.5-4 h-1.

The use of the proposed method turns out diesel is the first number 50-57 points.

A significant difference of the invention from the known analogs and prototypes is the use after a preliminary Hydrotreating raw material of the new catalyst hydroisomerization n-paraffin hydrocarbons containing additional fluorine, oxides of boron, REE and broad porous oxidability matrix.

The novelty of technical solutions of the present invention is the contacting of the feedstock with hydrogen in the presence of broad porous catalyst hydroisomerization (hydrobromide) diesel fractions containing along with zeolite Pancasila ZSM-8 M 30, cobalt (Nickel), mo, REE, also halogen-fluorine.

P R I m e R 1. Diesel fraction 200-360aboutWith a pour point of minus 10aboutWith a sulfur content of 1.8% is subjected to a preliminary communication (hydrofining) with hydrogen, and then repeated the hydraulic control treatment (IPF of hydroisomerization) at a temperature of 320aboutC, a pressure of 2.5 MPa, the space velocity of the raw materials 2.5 h-1; circulation N2-containing gas 250 nm3/m3raw materials in the presence of a Hydrotreating catalyst GS-168 composition, wt. Nickel oxide 5; molybdenum oxide 15; -Al2O380 and catalyst hydroisomerization composition, 3 44,5.

The process is carried out at a mass ratio of catalyst 1:1. The hydrogenation product to stabilize the temperature of the flash 80aboutC. Characteristics and yield of the target product based on the examples presented in the table.

P R I m m e R 2. Diesel fraction in example 1 is subjected to Hydrotreating in AMN catalyst SKP-202, composition, wt. NiO 4,0; MoO313,5; CoO 0,5; Al2O382,0; then in the presence of isomerization catalyst composition, wt. NiO 6,0; MoO312.0, REE2ABOUT31,5; fluorine 1,5;2ABOUT31,5; pentasil ZSM-8 (M 30) 60,0-Al2O319,5; T 390aboutS; Vc4 h-1; P 4 MPa; VH2450 nm3/m3of raw materials. The ratio of the catalysts in the reactors of 1:1.

P R I m e R 3. Diesel fraction 200-380aboutWith a sulfur content of 1.5 wt. put first in the first hydrofining reactor at AMN-catalyst GM 85, composition, wt. NiO 4,0; MoO313,5; SiO20,1; B2O30,5; -Al2O3rest, then in the second reactor installation on the isomerization catalyst composition, wt. REE 1,0, fluorine 1,0,2ABOUT31,0, Soo 5,0 Moo311,07, ZSM-8 50, -Al2O331,0 when TaboutS; Vc3.5 h-1; P 3 MPa; VH2350 nm3/m3of raw materials.

The ratio of the Hydrotreating catalyst of example 3 and isomerization catalyst composition, wt. CoO 3,5; MoO39,5; REE2ABOUT30,3; fluorine 0,40;2ABOUT30,4; pentasil ZSM-8 38,0-Al2O347,9, at T 315aboutS; Vc2 h-1; P 2 MPa; VH2200 nm3/m3of raw materials. The mass ratio of catalysts for Hydrotreating and isomerization of 1:1

P R I m e R 5 (comparative).

The process is carried out on raw materials in example 3 in the presence of a catalyst preliminary Hydrotreating according to example 2, in the second reactor to the catalyst composition, wt. Soo 6,5;2ABOUT31,6; NGO312; REE2ABOUT31,6; fluorine 1,9; pentasil ZSM-8 65,0, - Al2O310,9; T 395aboutC; R 4.5 MPa; Vc4.5 h-1; VH2500 nm3/m3of raw materials.

The ratio of catalyst 1:1.

P R I m e R 6 (comparative). The process is carried out on raw materials in example 1 on the catalysts according to example 3, however, the isomerization catalyst has a composition, by weight. CoO 5,0; MoO311,0; REE2ABOUT31,0;2ABOUT31,0, ZSM-8 50,0, -Al2O332,0. The mass ratio of catalyst 1:1.

P R I m e R 7 (comparative). The process is conducted according to example 3, the isomerization catalyst has a composition, by weight. CoO 5,0; MoO311,0 REE2ABOUT31,0; fluorine 1,0, ZSM-8 50,0, -Al2O332,0.

P R I m e R 9 (comparative). The process is conducted as in example 1, the catalyst composition of example 1. The mass ratio of catalysts for Hydrotreating and isomerization of 1:2.

The table shows the data shown in the examples that characterize the quality improvement waxy diesel fuel at high space velocity of the raw material compared with the known method.

Thus, the use of the invention allows to improve the quality of the target product of low-sulphur waxy diesel fuel, to get winter and Arctic diesel clean fuel with a pour point below -35aboutand below 45aboutRespectively with a high cetane number 7-12 points compared with the known method and high selectivity 95-98% yield of the target product (FR. 180-360aboutC).

The METHOD of OBTAINING low-sulfur WAXY DIESEL fuel from the diesel fractions by preliminary hydrobromide feedstock in the presence of a catalyst based on oxides of aluminum, cobalt or Nickel, molybdenum and re hydrobromide in the presence of a catalyst containing the oxides of cobalt or Nickel oxide MT in the presence of a catalyst, containing as high zeolite pentasil ZSM-8 module 30, and optional oxides of rare earth elements, fluorine, boron oxide in the following ratio, wt.

The oxide of cobalt or Nickel 4,0 6,0

Molybdenum oxide 10,0 12,0

The oxides of rare earth elements 0,5 1,5

Fluorine 0,5 1,5

The boron oxide is 0.5 to 1.5

Pentasil ZSM-8 40,0 60,0

g alumina Rest

 

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