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A preparing method of a mercaptan etherification catalyst

A catalyst, etherification technology, applied in physical/chemical process catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc. Divided into the problems of easy loss of phosphoric acid and polyphosphoric acid, and high catalyst carbon deposition, to achieve good hydrogenation effect, improve the ability and stability of carbon deposition resistance, and weaken the effect of interaction

Inactive Publication Date: 2015-04-15
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The catalyst is used to remove mercaptans and dienes in full-fraction catalytic cracking gasoline. The removal efficiency of mercaptans is very high, and there is no alkali residue discharge, but the disadvantage is that the removal rate of dienes needs to be further improved.
The reaction conditions are room temperature ~ 140 ℃, pressure 0.5 ~ 1MPa, agent oil ratio is 1:10 ~ 20; the catalyst is made of SiO 2 -Al 2 o 3 or SiO 2 -ZrO 2 As the carrier, phosphoric acid and polyphosphoric acid are the active components, phosphoric acid and polyphosphoric acid account for 10-80% of the catalyst weight, and the rest is the carrier; in SiO 2 -Al 2 o 3 Middle Al 2 o 3 18-50% by weight, SiO 2 50-82% by weight; in SiO 2 -ZrO 2 Medium SiO 2 and ZrO 2 The molar ratio is 1:1; silica hydrogel prepared by sodium silicate and alumina hydrogel prepared by ammonium nitrate precipitation or Zr(SO 4 ) 2 The hydrolyzate is mixed, and the active components of phosphoric acid and polyphosphoric acid are loaded on the carrier. The transfer rate of mercaptan and thiophene in this method is over 90%, but the disadvantage is that the active components of phosphoric acid and polyphosphoric acid are easy to lose
The hydrodemercaptan process provided by the invention is carried out under the condition of dissolving hydrogen, which significantly reduces energy consumption and hydrogen consumption, but the disadvantage is that the cost of precious metals is relatively high, and they are easily poisoned by sulfides
At a reaction temperature of 120 °C, a pressure of 1.0 MPa, and a space velocity of 10 h -1 And under the condition of hydrogen, the conversion rate of mercaptan can reach 94.9%, but the disadvantage is that the carbon deposition of the catalyst is relatively high, and the stability needs to be further improved

Method used

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  • A preparing method of a mercaptan etherification catalyst
  • A preparing method of a mercaptan etherification catalyst
  • A preparing method of a mercaptan etherification catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] (1) Set the specific surface area to 100 m 2 / g, the pore volume is 0.5 cm 3 / g, spherical Al with an average pore size of 50 nm 2 o 3 K 2 O / Al 2 o 3 carrier;

[0031] (2) Add ammonium molybdate, nickel nitrate, and citric acid and phosphoric acid into deionized water, stir well, and make an impregnation solution; the amount of compound additive is 0.5 times the mass of ammonium molybdate and nickel nitrate , the mass content of citric acid in the composite auxiliary agent is 60%, and the mass content of phosphoric acid is 40%;

[0032] (3) K obtained in step (1) 2 O / Al 2 o 3 The impregnating solution in the carrier impregnation step (2) was 0.5 h, dried at 100 °C for 10 h and calcined at 300 °C for 4 h to obtain NiO-MoO 3 -K 2 O / Al 2 o 3 catalyst.

[0033] The mass content of each component in the catalyst that present embodiment obtains is: NiO is 15%, MoO 3 5%, K 2 O is 0.5%, the rest is Al 2 o 3 , the activity of the catalyst is shown in Table 1. ...

Embodiment 2

[0035] (1) Set the specific surface area to 50 m 2 / g, the pore volume is 0.3 cm 3 / g, powdered Al with an average pore size of 100 nm 2 o 3 The carrier was impregnated with potassium nitrate solution, dried at 100 °C for 10 h and calcined at 300 °C for 4 h to obtain K 2 O / Al 2 o 3 carrier;

[0036] (2) Add ammonium molybdate and nickel chloride, and composite additives composed of citric acid and phosphoric acid into deionized water, stir evenly, and make an impregnation solution; the amount of composite additives is the quality of ammonium molybdate and nickel chloride 2 times, the mass content of citric acid in the compound additive is 10%, and the mass content of phosphoric acid is 90%;

[0037] (3) K obtained in step (1) 2 O / Al 2 o 3 The impregnation solution in the carrier impregnation step (2) was 0.1 h. After the impregnation, it was dried at 100 °C for 10 h and calcined at 200 °C for 4 h to obtain NiO-MoO 3 -K 2 O / Al 2 o 3 catalyst.

[0038] The mass co...

Embodiment 3

[0040] (1) Set the specific surface area to 200 m 2 / g, the pore volume is 1.0 cm 3 / g, flake Al with an average pore size of 10 nm 2 o 3 The carrier was impregnated with potassium hydroxide solution, dried at 100 °C for 10 h and calcined at 600 °C for 4 h to obtain K 2 O / Al 2 o 3 carrier;

[0041] (2) Add molybdenum oxide, nickel sulfate, and composite additives composed of citric acid and urea into deionized water, stir evenly, and make an impregnation solution; the amount of composite additives is 0.1 times the mass of molybdenum oxide and nickel sulfate, compound The mass content of citric acid in the auxiliary agent is 90%, and the mass content of urea is 10%;

[0042] (3) K obtained in step (1) 2 O / Al 2 o 3 The impregnation solution in the carrier impregnation step (2) was used for 1 h, dried at 100 °C for 10 h and calcined at 400 °C for 4 h to obtain NiO-MoO 3 -K 2 O / Al 2 o 3 catalyst.

[0043] The mass content of each component in the catalyst that presen...

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Abstract

A preparing method of a mercaptan etherification catalyst is disclosed. The method includes: (1) dipping an Al2O3 carrier with a potassium salt solution, drying, and calcinating at 300-600 DEG C to obtain a K2O / Al2O3 carrier; and (2) adding a molybdenum-containing compound, a nickel-containing compound and a composite auxiliary agent into deionized water to prepare a dipping solution; and (3) dipping the carrier obtained in the step (1), drying and calcinating at 200-400 DEG C to obtain a NiO-MoO3-K2O / Al2O3 catalyst. The Al2O3 carrier is modified by the K2O so as to enhance carbon deposit resistance and stability of the catalyst. The composite auxiliary agent, the molybdenum-containing compound and the nickel-containing compound form a complex, thus weakening interaction of NiO, MoO3 and the Al2O3 carrier, promoting dispersion of active components in the Al2O3 carrier, and enhancing activity of the catalyst. The catalyst is high in activity of removing mercaptan in gasoline, and has good hydrogenation effects for dienes.

Description

technical field [0001] The invention relates to a preparation method of a mercaptan etherification catalyst, in particular to a preparation method of a catalyst used for the reaction of mercaptans and diolefins in catalytic cracking gasoline to generate thioether compounds. Background technique [0002] Catalytic cracking (FCC) gasoline is currently the main source of gasoline. The output of FCC gasoline in my country accounts for more than 70% of the total gasoline output, and the total sulfur content and mercaptan content of FCC gasoline are very high. Generally, the total sulfur content is between 200 and 1000 μg / g, and the mercaptan content is 10-100 μg / g, so reducing the total sulfur and mercaptans in FCC gasoline is the key to producing high-standard clean gasoline. [0003] For the removal of mercaptans in catalytic cracked gasoline, there are mainly Merox deodorization process and non-caustic alkali deodorization process, but these two processes can only oxidize merca...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/887C10G45/38C10G45/08
Inventor 堵文斌王继元卞伯同许建文陈韶辉杨爱武柏基业朱庆奋庞焱
Owner CHINA PETROLEUM & CHEM CORP
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