A kind of heavy petroleum distillate hydrogenation treatment catalyst and preparation method thereof

Abstract

The invention relates to a highly active heavy petroleum fraction hydrotreating catalyst and a preparation method thereof. It proposes a method for preparing a catalyst using titanium-modified silicon-aluminum composite oxide as a carrier, in which mesoporous silicon prepared by a co-precipitation method is used. Aluminum composite oxide is the matrix material, and titanium oxide, titanium sulfate, titanium tetrachloride, titanium n-propoxide, titanium isopropoxide, or Isobutyl titanate, etc., to obtain a titanium modified carrier with a large specific surface area and pore volume. The specific surface area of ​​the carrier is 200~310m 2 / g, pore volume is 0.5~1.2ml / g. The metal active components are loaded on the carrier using solution impregnation technology. The catalyst of the invention has good hydrodesulfurization and hydrodenitrification activities for heavy petroleum fractions.

Description

technical field

[0001] The present invention relates to a heavy petroleum distillate hydrotreating catalyst with a silicon-aluminum composite oxide (ASA) as a carrier, in particular to a heavy petroleum distillate hydrotreating catalyst with a titanium-modified silicon-aluminum composite oxide as a carrier and its Preparation. Background technique

[0002] With the intensification of the trend of heavy and inferior crude oil in the world, the proportion of inferior heavy oil continues to increase, and it is more important to effectively process heavy distillate oil, and hydrotreating is the most effective processing of heavy distillate oil One of the techniques.

[0003] The key to hydroprocessing technology is the catalyst, and the basis for improving the performance of the catalyst is the development of new catalytic materials. As we all know, the carrier material needs to have a large specific surface area, pore volume and pore size to increase the metal loading and dis...

Examples

Embodiment 1

[0034] Example 1 Preparation of titanium-modified silicon-aluminum composite oxide carrier by synchronous method

[0035] Dissolve 24.0g of aluminum nitrate and 28g of water glass in water and mix uniformly to obtain solution A; mix 19ml of water, 30ml of ammonia water and 20ml of absolute ethanol to obtain solution B. Under strong stirring, add 3g of titanium oxide powder into solution A, stir evenly, drop solution B into solution A drop by drop to react to obtain sol, and the sol is aged under natural conditions for a certain period of time to obtain gel; the drying of the gel The conditions are: the temperature is 160°C, and the time is 2 hours to obtain a white powder; the white powder is roasted in a muffle furnace at 600°C for 3 hours to obtain a titanium oxide-modified silicon-aluminum composite oxide carrier prepared by a simultaneous method. It is C1, and the specific surface area, pore volume and average pore diameter of the carrier measured by BET method are: 332m ...

Embodiment 2

[0036] Example 2 Preparation of titanium-modified silicon-aluminum composite oxide carrier by step-by-step method

[0037]Dissolve 24.0g of aluminum nitrate and 28g of water glass in water and mix uniformly to obtain solution A; mix 19ml of water, 30ml of ammonia water and 20ml of absolute ethanol to obtain solution B. Under strong stirring, drop solution B into solution A for reaction; add 3g of titanium oxide powder after 30 minutes of reaction, and then react to obtain a sol. Other processes and conditions are the same as in Example 1, and titanium oxide prepared by a step-by-step method is obtained. Modified silicon-aluminum composite oxide carrier, denoted as C2, the specific surface area, pore volume and average pore diameter of the carrier measured by the BET method are: 280m 2 / g, 0.73ml / g, 12.8nm.

Embodiment 3

[0038] Example 3 Preparation of titanium sulfate modified silicon-aluminum composite oxide carrier by synchronous method

[0039] Replace the titanium oxide in Example 1 with 18g of titanium sulfate, and keep the rest of the steps and reaction conditions unchanged to obtain a silicon-aluminum composite oxide carrier modified by the simultaneous method of titanium nitrate, which is denoted as C3, and the BET method is used to measure the content of the carrier. The specific surface area, pore volume and average pore diameter are respectively: 304m 2 / g, 0.76ml / g, 10.5nm.

technical field

[0001] The present invention relates to a heavy petroleum distillate hydrotreating catalyst with a silicon-aluminum composite oxide (ASA) as a carrier, in particular to a heavy petroleum distillate hydrotreating catalyst with a titanium-modified silicon-aluminum composite oxide as a carrier and its Preparation. Background technique

[0002] With the intensification of the trend of heavy and inferior crude oil in the world, the proportion of inferior heavy oil continues to increase, and it is more important to effectively process heavy distillate oil, and hydrotreating is the most effective processing of heavy distillate oil One of the techniques.

[0003] The key to hydroprocessing technology is the catalyst, and the basis for improving the performance of the catalyst is the development of new catalytic materials. As we all know, the carrier material needs to have a large specific surface area, pore volume and pore size to increase the metal loading and dis...

Examples

Embodiment 1

[0034] Example 1 Preparation of titanium-modified silicon-aluminum composite oxide carrier by synchronous method

[0035] Dissolve 24.0g of aluminum nitrate and 28g of water glass in water and mix uniformly to obtain solution A; mix 19ml of water, 30ml of ammonia water and 20ml of absolute ethanol to obtain solution B. Under strong stirring, add 3g of titanium oxide powder into solution A, stir evenly, drop solution B into solution A drop by drop to react to obtain sol, and the sol is aged under natural conditions for a certain period of time to obtain gel; the drying of the gel The conditions are: the temperature is 160°C, and the time is 2 hours to obtain a white powder; the white powder is roasted in a muffle furnace at 600°C for 3 hours to obtain a titanium oxide-modified silicon-aluminum composite oxide carrier prepared by a simultaneous method. It is C1, and the specific surface area, pore volume and average pore diameter of the carrier measured by BET method are: 332m ...

Embodiment 2

[0036] Example 2 Preparation of titanium-modified silicon-aluminum composite oxide carrier by step-by-step method

[0037]Dissolve 24.0g of aluminum nitrate and 28g of water glass in water and mix uniformly to obtain solution A; mix 19ml of water, 30ml of ammonia water and 20ml of absolute ethanol to obtain solution B. Under strong stirring, drop solution B into solution A for reaction; add 3g of titanium oxide powder after 30 minutes of reaction, and then react to obtain a sol. Other processes and conditions are the same as in Example 1, and titanium oxide prepared by a step-by-step method is obtained. Modified silicon-aluminum composite oxide carrier, denoted as C2, the specific surface area, pore volume and average pore diameter of the carrier measured by the BET method are: 280m 2 / g, 0.73ml / g, 12.8nm.

Embodiment 3

[0038] Example 3 Preparation of titanium sulfate modified silicon-aluminum composite oxide carrier by synchronous method

[0039] Replace the titanium oxide in Example 1 with 18g of titanium sulfate, and keep the rest of the steps and reaction conditions unchanged to obtain a silicon-aluminum composite oxide carrier modified by the simultaneous method of titanium nitrate, which is denoted as C3, and the BET method is used to measure the content of the carrier. The specific surface area, pore volume and average pore diameter are respectively: 304m 2 / g, 0.76ml / g, 10.5nm.