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Combination catalyst for diesel hydrodesulfurization and method for diesel hydrodesulfurization

A hydrodesulfurization and catalyst technology, applied in molecular sieve catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problems of decreased pore volume and specific surface area, blocked pores, and decreased activity.

Active Publication Date: 2015-07-29
BC P INC CHINA NAT PETROLEUM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The catalyst prepared by this method plays the role of HY and phosphorus respectively, without combining the two, the treatment of HY molecular sieve is limited to the pretreatment of its surface, the control degree of its acidity is limited, and the surface impregnation of P It is also easy to cause the pore blockage of the catalyst, the decrease of pore volume and specific surface area, and the decrease of activity, etc.

Method used

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  • Combination catalyst for diesel hydrodesulfurization and method for diesel hydrodesulfurization
  • Combination catalyst for diesel hydrodesulfurization and method for diesel hydrodesulfurization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Example 1TiO 2 -SiO 2 (TiO 2 Mass fraction is 20%) preparation of composite oxide

[0042] In this example, TiO was prepared by sol-gel method 2 -SiO 2 Composite oxides:

[0043] Add 400mL of ethanol, 277.3g of ethyl orthosilicate and 85g of tetrabutyl titanate in sequence to a constant temperature reactor at 36°C, stir and mix uniformly to obtain solution A; prepare mixed solution B of deionized water, acetic acid and ethanol, in which : Acetic acid: ethanol = 4:2:4 (volume ratio); add solution B dropwise to A, control the dropping time, and obtain a light yellow sol after a certain period of hydrolysis reaction; the sol turns into a gel at room temperature , gel at 40 ℃, 9.0 ~ 12.0MPa conditions, with CO 2 The drying medium was supercritically dried for 3 hours, and then the dried sample was calcined in a muffle furnace at 500°C for 3 hours to obtain a TiO-containing 2 TiO with a mass fraction of 20% 2 -SiO 2 composite oxides. After molding, it is ground int...

Embodiment 2

[0044] Example 2TiO 2 -Al 2 o 3 (Al 2 o 3 Mass fraction is 75%) preparation of composite oxide

[0045] In this example, the precipitation method is used to prepare TiO 2 -Al 2 o 3 Composite oxides:

[0046] Prepare 1.562mol / L of Ti(SO 4 ) 2 Solution 0.2L, denoted as solution A, prepared 0.24L of 3.523mol / L sodium metaaluminate solution and 0.16L of 1.934mol / L aluminum sulfate solution, denoted as solutions B and C, and placed solution A at a constant temperature of 70°C In the reactor, use the parallel flow method to drop the two solutions of B and C into A at the same time at a constant speed, control the dropping speed at 2-2.5mL / min, keep the pH value in the reactor at 8.0±0.3, and react at a constant temperature for 30 minutes after titration After the reaction, the resulting suspension was filtered with suction, and the precipitate was washed until the filtrate was neutral. Afterwards, the obtained filter cake was dried at 110-120°C for 4 hours, and roasted at...

Embodiment 3

[0047] The preparation of embodiment 3PY molecular sieve

[0048] First, weigh 4.24g solid NaOH, 2.09g solid NaAlO 2 with 19.95gH 2 Mix the O solution in a 50ml plastic bottle, stir until dissolved; then add 22.72g of water glass solution (modulus 3.3) to mix, stir vigorously until a transparent gel-like liquid is formed, and leave it to age at room temperature for 24 hours to obtain a directing agent .

[0049] Secondly, weigh 0.15gNaOH, 13.09gNaAlO 2 , 130.97gH 2 O, mix and place in a 500ml plastic beaker, stir well; then add 142.43g of water glass solution (modulus 3.3), stir vigorously until gel is formed to obtain mother liquor; then add 2.74g of ammonium dihydrogen phosphate, and stir evenly , to obtain phosphorus-containing mother liquor.

[0050] After the phosphorus-containing mother liquor is prepared, add the directing agent dropwise into the phosphorus-containing mother liquor, stir well, and continue vigorously stirring for 20 minutes. The obtained material ...

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Abstract

The invention provides a combination catalyst for diesel hydrodesulfurization and a diesel deep hydrodesulfurization method. The combination catalyst comprises a first catalyst CAT-1 and a second catalyst CAT-2, wherein the first catalyst CAT-1 is prepared by drying and roasting after carrying an active component on a first support, and the first support is selected from a composite of two or three of TiO2, SiO2 and Al2O3; the second catalyst CAT-2 is prepared by carrying an active component on a second support, and the second support is selected from a composite of two or three of TiO2, SiO2 and Al2O3; and the active components of the two catalysts are selected from a combination of two or three of Co, Mo, Ni and W. The two catalysts are combined and filled according to a certain proportion; and the temperature gradient variation or step-by-step temperature control in the reaction process is utilized to fully display the characteristics of the two catalysts, so that the sulfur content in the diesel is reduced to 10 mu g / g below.

Description

technical field [0001] The invention relates to a combined catalyst for deep hydrodesulfurization of diesel oil and a method for deep hydrodesulfurization of diesel oil, in particular to a combined catalyst applied to deep hydrodesulfurization of diesel oil and the deep hydrodesulfurization of diesel oil using the combined catalyst Methods. Background technique [0002] With the continuous improvement of environmental protection regulations on the sulfur content index requirements of clean diesel, the production of ultra-low sulfur diesel has become a major technical problem faced by refineries. Straight-run diesel, catalytic cracking diesel and coker diesel are the main blending components of finished diesel, which are characterized by high sulfur content, and it is difficult to remove sulfur compounds in depth. [0003] At present, hydrodesulfurization is the leading technology in the deep desulfurization technology of diesel oil, and the requirement for desulfurization d...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/888B01J23/883B01J29/16C10G45/08C10G45/12
Inventor 周亚松陶秀娟魏强丁思佳张涛刘亭亭刘京罗秀娟蒋淑娇
Owner BC P INC CHINA NAT PETROLEUM CORP
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