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Heavy petroleum fraction hydroprocessing catalyst and preparing method thereof

A technology for hydroprocessing and heavy petroleum, applied in the direction of physical/chemical process catalysts, catalyst carriers, chemical instruments and methods, etc., can solve problems such as easy to block pores, unfavorable active metal loading, small unit cell constant, etc., to achieve Good effect of hydrodesulfurization and hydrodenitrogenation performance

Active Publication Date: 2017-07-07
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the unit cell constant of the catalyst is small, and the rare earth, clay and molecular sieve are modified by binder, which is easy to block some pores, which is not conducive to the loading of active metals.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

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 24.0 g of aluminum nitrate and 28 g of water glass in water, respectively, and then uniformly mix to obtain solution A; mix 19 ml of water, 30 ml of ammonia water and 20 ml of absolute ethanol to obtain solution B. Under vigorous stirring, solution B was dropwise added to solution A for reaction; after 30 minutes of reaction, 3 g of titanium oxide powder was added, and then the sol was obtained by the reaction. The modified silicon-alumina composite oxide carrier, denoted as C2, the specific surface area, pore volume and average pore size of the carrier were determined by BET method: 280m 2 / g, 0.73ml / g, 12.8nm.

Embodiment 3

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

[0039] The titanium oxide in Example 1 was replaced with 18g of titanium sulfate, and the remaining steps and reaction conditions were unchanged to obtain a synchronous titanium nitrate modified silicon-aluminum composite oxide carrier, denoted as C3, and the BET method was used to determine the carrier's content. The specific surface area, pore volume and average pore diameter are: 304m 2 / g, 0.76ml / g, 10.5nm.

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Abstract

The invention relates to a high-activity heavy petroleum fraction hydroprocessing catalyst and a preparing method thereof. A method of using silica-alumina composite oxide modified by titanium as a carrier to prepare the catalyst is put forward, meso-porous silicon composite oxide prepared through a coprecipitation method is regarded as a substrate material, a synchronous method or a fractional step method is adopted to introduce titanium oxide, or titanium sulfate, or titanium tetrachloride, or N-propyl titanium, or isopropyl titanate or Tetraisobutyl Orthotitanate and the like into the silica-alumina composite oxide, so that a titanium-modified carrier which has a large specific area and a large pore volume is obtained, wherein the specific area of the carrier is 200-310 m<2> / g, and the pore volume is 0.5-1.2 ml / g. A solution impregnation technology is adopted in support of metal active components on the carrier, and the heavy petroleum fraction hydroprocessing catalyst has good hydro-desulfurization and hydro-denitrification activities in heavy petroleum fraction.

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...

Claims

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Application Information

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IPC IPC(8): B01J23/888B01J35/10B01J32/00B01J21/12C10G45/08
CPCC10G45/08B01J21/12B01J23/888B01J23/8885C10G2300/202B01J35/635B01J35/647B01J35/615
Inventor 王刚周亚松马守涛魏强葛冬梅张志华孙发民张文成郭金涛吴显军陆雪峰倪术荣靳丽丽郭立艳李凤铉谢方明夏恩冬李瑞峰徐铁钢孟祥彬王锐张铁珍
Owner PETROCHINA CO LTD