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Modified aluminum oxide carrier and preparation method thereof

A technology of alumina carrier and nano-alumina, which is applied in the direction of catalyst carrier, chemical instrument and method, catalyst activation/preparation, etc. It can solve the problem that the continuity of large pores cannot be substantially changed, and the channels cannot be used for large residual oil. Molecular catalysis, limited diffusion of reactants and products, etc., to achieve the effect of prolonging the operation cycle, good pore penetration, and large pore openings

Active Publication Date: 2010-11-24
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the method of pore expansion is mainly physical pore-making method, which can obtain large pores from 30nm to micron, but this kind of channel is discontinuous, the channel is in a dispersed state, and the orifice is the type of ink bottle, which is sensitive to reactants and Limited diffusion of the product
Carbon black and polystyrene are used as templates to generate ordered macroporous materials. The pores belong to the type of ink bottle orifice, and most of the pores cannot be catalyzed by residual oil macromolecules.
[0007] In order to adjust the acidity of the alumina carrier, control the pore structure, and adjust the interaction between the metal and the carrier, some additives such as silicon, boron, titanium, zirconium, phosphorus or fluorine are usually added, such as CN1179356A, CN17655090A, CN1324691A, CN1765509A, CN1169336A, CN1872959A, but the current alumina is prepared by conventional precipitation method, even if the above-mentioned additives are added, the continuity of the macropore channel or the ink bottle-shaped orifice cannot be substantially changed

Method used

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  • Modified aluminum oxide carrier and preparation method thereof
  • Modified aluminum oxide carrier and preparation method thereof

Examples

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Effect test

Embodiment 1

[0047] Under stirring conditions, 750g of aluminum nitrate nonahydrate and 90g of urea were mixed and heated to 100°C, and added to a mixture of 32g of polyisobutylene maleate triethanolamine maleate and 88g of 150HVI neutral oil at the same temperature to form supersolubilizing micelles , and then reacted at 100°C for 3 hours to obtain nano-aluminum hydroxide gel. Wash three times with distilled water, add 235ml content to 150g B 2 o 3 / L boric acid aqueous solution mixed evenly, and dried at 120°C for 10 hours. Mix 70g of boron-containing nano-aluminum hydroxide gel dry powder with 30g of macroporous aluminum hydroxide, mix evenly with 6g of acetic acid, 60g of water and 5g of ethanol, and shape it in an extruder, controlling the pressure at 30MPa. The molded product was dried at 130°C for 10 hours, calcined at 200°C for 3 hours, and then calcined at 750°C for 20 hours with a heating rate of 5°C / min to obtain the boron-containing alumina carrier BA1 of the present inventio...

Embodiment 2

[0049] Under stirring conditions, 630g of aluminum nitrate nonahydrate and 240g of urea are mixed and heated to 100°C, and added to the mixture of 22g of polyisobutylene diglyceride maleate and 108g of third-line oil under the same temperature conditions to form supersolubilizing micelles. Then react at 100° C. for 3 hours to obtain nano-aluminum hydroxide gel. Wash three times with distilled water, add 35ml silica sol solution (weight concentration is 30% SiO 2 ) were mixed evenly, and dried at 120° C. for 10 hours. Mix 70g of silicon-containing nano-aluminum hydroxide gel dry powder with 30g of macroporous alumina, mix 6g of acetic acid, 60g of water and 5g of ethanol, and shape it in an extruder, controlling the pressure at 30MPa. The molded product was dried at 130°C for 10 hours, calcined at 200°C for 3 hours, and then calcined at 750°C for 20 hours with a heating rate of 5°C / min to obtain the silicon-containing alumina carrier BA2 of the present invention.

Embodiment 3

[0051] Mix 60g minus three-line dewaxed oil and 25g SP-80, heat to dissolve at 80°C, and mix well; heat 750g of aluminum nitrate nonahydrate to 80°C to melt, slowly add to the above mixture, and mix for 20 minutes to form a uniform supersolubilized colloid. 320 g of saturated ammonia water at 20° C. was added dropwise and aged for 3 hours to obtain a nano-aluminum hydroxide gel. Wash three times with distilled water, add 100 ml of zirconium oxychloride aqueous solution with a content of 600 g / L to the solid phase obtained through separation, mix evenly, and dry at 120° C. for 10 hours. Mix 90 g of zirconium-containing nano-aluminum hydroxide gel dry powder with 10 g of binder pseudo-boehmite; mix 2 g of dilute nitric acid (mass concentration 17%), 15 g of water and 25 g of cosolvent ethanol, and put Mix evenly, then shape in extruder, control pressure at 20MPa. The formed product was dried at 110°C for 15 hours, calcined at 220°C for 10 hours, and then calcined at 650°C for 1...

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Abstract

The invention discloses a modified aluminum oxide carrier and a preparation method thereof. The modified aluminum oxide carrier is prepared from aluminum hydroxide gel serving as a raw material by the steps of introducing an auxiliary agent before and / or after drying, and then forming, drying and roasting, wherein the aluminum hydroxide gel is prepared by a molten salt super-solubilizing micelle method. In the preparation process of the carrier, the aluminum hydroxide gel comprises a surfactant and a hydrocarbon component, so after the processes of forming and roasting, nano-aluminum oxide particles formed by dehydrating polymerized aluminum hydroxide still have bar-shaped basic structures and are stacked into a frame structure out of order; and the properties of a catalyst are further improved by adjusting the acidity of the carrier and the interaction between an active metal and the carrier through the auxiliary agent. The carrier has the advantages of large pore volume, large aperture, high porosity, larger orifice on the outer surface, high pore canal penetrability, favorability for increasing deposition of impurities and capacity of prolonging the running period of the catalyst.

Description

technical field [0001] The invention relates to a modified alumina carrier and a preparation method thereof, in particular to a modified alumina carrier with a large pore volume and a preparation method thereof, which can be used as a residual oil hydrogenation treatment desulfurization, hydrogenation denitrogenation or hydrogenation Remove carbon residue catalyst carrier. Background technique [0002] Hydrodesulfurization, hydrodenitrogenation and hydrodecarbonization are important processes in petroleum refining and synthetic ammonia production using petroleum as raw material, and have always been valued by people. However, in recent years, the quality of petroleum has become heavier and worse, while the requirements for product quality have become more stringent, and the requirements for feed materials in subsequent processes have become more and more stringent. In addition, since mankind entered the 21st century, people's awareness of environmental protection has been c...

Claims

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Application Information

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IPC IPC(8): B01J32/00B01J21/04B01J21/06B01J21/02B01J27/125B01J27/14B01J35/02B01J37/00B01J37/04B01J37/08C10G45/04
Inventor 王鼎聪刘纪端
Owner CHINA PETROLEUM & CHEM CORP
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