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Supported composite sulfur phosphide hydrotreatment catalyst, preparation and applications thereof

A hydrotreating and catalyst technology, applied in catalyst activation/preparation, physical/chemical process catalyst, molecular sieve catalyst, etc., can solve the problem that the improvement of oil hydrodesulfurization activity is not obvious, and achieve low cost and operation process. Simple and good hydrodesulfurization effect

Active Publication Date: 2013-03-27
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Complicated steps such as high temperature, high pressure, and temperature program are not required. Similar patents include CN 101671009 and CN10658795, etc., but these methods are only simple phosphide catalysts, which are not combined with traditional methods. The improvement is not obvious

Method used

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  • Supported composite sulfur phosphide hydrotreatment catalyst, preparation and applications thereof
  • Supported composite sulfur phosphide hydrotreatment catalyst, preparation and applications thereof
  • Supported composite sulfur phosphide hydrotreatment catalyst, preparation and applications thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Weigh 1000g of industrial pseudo-boehmite, extrude it into a clover shape with a circumscribed circle diameter of 1.8mm on an extruder, dry at 120°C for 6 hours, and calcinate at 550°C for 4 hours to obtain catalyst carrier S1.

[0028] Using S1 as the carrier, weigh 9g of nickel nitrate, 5.2g of ammonium phosphomolybdate, 15.4g of ammonium tungstate, 2.3g of ethylenediamine, and 2g of diammonium hydrogen phosphate to prepare a mixed solution, set the volume to 42ml, and impregnate on 50g of carrier S1 4 hours, drying at 120°C, then vulcanization, vulcanization conditions: containing CS 2 2.5% (mass content) straight-run gasoline, pressure: 6MPa; temperature rise program: rise from room temperature to 230°C at a rate of 1°C / h, keep the temperature constant for 8 hours, and then rise to 360°C, constant temperature for 6 hours; hydrogen-oil ratio: 600:1; space velocity: 1.5h -1 . The obtained catalyst is denoted as C1.

Embodiment 2

[0030] Dissolve 9g of nickel nitrate in 100ml of deionized water, add dropwise 2mol / L NaOH solution, stir until all precipitate, filter the above precipitate with suction, and wash the filter cake with deionized water for several times until no 8O is detected. 4 2- and Na + the presence of plasma. The resulting filter cake was placed in 20 ml of deionized water, then stirred and added dropwise with 30 wt% H 3 PO 2 solution until the precipitate is completely dissolved. Then add 3.6g of ammonium molybdate, 15.4g of ammonium tungstate and 8.3g of citric acid into the solution to dissolve, and finally make up 42ml of the solution, impregnate it on 50g of carrier S1 for 4 hours, dry it at 120°C, and then vulcanize it. : with CS 2 2.5% (mass content) straight-run gasoline, pressure: 6MPa; temperature rise program: rise from room temperature to 230°C at a rate of 1°C / h, keep the temperature constant for 8 hours, and then rise to 360°C, constant temperature for 6 hours; hydroge...

Embodiment 3

[0032] The catalyst precursor in Example 2 was vulcanized at an end point temperature of 380° C. to obtain a catalyst, which was denoted as C3.

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PUM

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Abstract

The present invention relates to a supported composite sulfur phosphide hydrotreatment catalyst, preparation and applications thereof. The preparation comprises: respectively dissolving a soluble transition metal salt and a soluble alkali in water, and mixing the obtained two solutions; placing the obtained filter cake in deionized water, adding H3PO2 or a H3PO2 solution in a dropwise manner until precipitate is completely dissolved, and adding a complexing agent and a transition metal salt to the obtained solution; or dissolving a transition metal salt, a phosphorus source and a complexing agent in water; or dissolving a transition metal salt, ammonium phosphomolybdate or ammonium phosphotungstate, and a complexing agent in water; or dissolving hypophosphite containing Ni or Co, a transition metal salt and a complexing agent in water; adding the prepared clear solution to a carrier, and drying to obtain a precursor; and carrying out pre-sulfurization on the precursor to obtain the catalyst. The catalyst has good performances of hydrogenation desulfurization, denitrification and dearomatization, and has characteristics of simple operation process, low cost and no requirement of high temperature. In addition, the catalyst can be combined with the traditional catalyst to effectively use the existing equipment so as to achieve industrialization.

Description

technical field [0001] The invention relates to a catalyst for the hydrogenation of a supported composite sulfur and phosphide, as well as its preparation and application. Background technique [0002] In recent years, with the increasing environmental protection standards, countries have increasingly stringent requirements for fuel oil standards. In order to meet this standard, the traditional Co-Mo and Ni-Mo catalysts must be used. The catalyst loading must be increased and the hydrotreating conditions more harsh. For this reason, experts in the field try to make the oil meet the stringent standard requirements by developing new high-efficiency hydrotreating catalysts. In the 1990s, Oyama et al. proposed a new metal phosphide material and applied it in the field of hydrogenation treatment, and found that the new metal phosphide material showed better performance than traditional hydrogenation catalysts. Subsequently, the new material of metal phosphide was extensively st...

Claims

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Application Information

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IPC IPC(8): B01J27/19B01J29/78B01J37/20C10G45/08C10G45/12C10G45/50C10G45/54C10G49/04C10G49/08
Inventor 葛少辉刘坤红兰玲马安侯远东刘岩吴平易赵秦峰鞠雅娜张鹏吴培钟海军孙洪磊王鹏吕忠武何皓马健波王书芹王春燕
Owner PETROCHINA CO LTD
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