Multistage pore molecular sieve-supported heteropolyacid alkylation desulfurization catalyst and preparation method thereof

An alkylation desulfurization and molecular sieve technology, applied in molecular sieve catalysts, catalyst activation/preparation, physical/chemical process catalysts, etc. Transalkylation ability, improved accessibility and diffusivity, effect of high acid strength

Active Publication Date: 2018-06-08
CNOOC TIANJIN CHEM RES & DESIGN INST +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The technical problem to be solved by the present invention is to solve the problem of poor selectivity and poor stability of the alkylation desulfurization catalyst in the prior art, and to provide a sulfide alkylation transfer ability, good catalyst stability, easy regeneration, and recyclable Utilized gasoline alkylation desulfurization hierarchical porous molecular sieve loaded heteropolyacid solid catalyst, and preparation method of said catalyst

Method used

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  • Multistage pore molecular sieve-supported heteropolyacid alkylation desulfurization catalyst and preparation method thereof
  • Multistage pore molecular sieve-supported heteropolyacid alkylation desulfurization catalyst and preparation method thereof

Examples

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Effect test

Embodiment 1

[0026] 100g SiO 2 / Al 2 o 3 NaY molecular sieve with a molar ratio of 10 was placed in 800 mL of hydrochloric acid and ammonium chloride mixed solution, wherein the concentration of hydrochloric acid and ammonium chloride solution was 1.2 mol / L, and the molar ratio of hydrochloric acid to ammonium chloride was 1.5. Stand at room temperature for 12 hours, filter, wash, dry, and roast to obtain acid-treated Y molecular sieve.

[0027] Mix the molecular sieve obtained above with 0.9mol / L tetramethylammonium hydroxide solution, the solid-to-liquid ratio of the molecular sieve to the lye is 1:5, treat it in a polytetrafluoroethylene-lined synthesis kettle at 80°C for 12h, and filter , washing, drying, and roasting to prepare a multi-level porous Y molecular sieve containing a mesoporous composite structure.

[0028] Put the above multi-stage molecular sieve into the mixed solution of sodium tungstate and ammonium dihydrogen phosphate, wherein the weight ratio of sodium tungstate...

Embodiment 2

[0030] Put 100g of NaY molecular sieve with SiO2 / Al2O3 molar ratio of 10 in 800mL hydrochloric acid and ammonium chloride mixed solution, wherein the concentration of hydrochloric acid and ammonium chloride solution is 1.2mol / L, and the molar ratio of hydrochloric acid to ammonium chloride is 1.5. Stand at room temperature for 12 hours, filter, wash, dry, and roast to obtain acid-treated Y molecular sieve.

[0031] Mix the molecular sieve obtained above with 0.9mol / L tetramethylammonium hydroxide solution, the solid-to-liquid ratio of the molecular sieve to the lye is 1:5, treat it in a polytetrafluoroethylene-lined synthesis kettle at 80°C for 12 hours, and filter , washing, drying, and roasting to prepare a multi-level porous Y molecular sieve containing a mesoporous composite structure.

[0032] Put the above-mentioned multi-stage porous molecular sieve into the mixed solution of ammonium molybdate and ammonium dihydrogen phosphate, wherein the weight ratio of ammonium moly...

Embodiment 3

[0034] 100g SiO 2 / Al 2 o 3 NaY molecular sieve with a molar ratio of 10 was placed in 800 mL of hydrochloric acid and ammonium chloride mixed solution, wherein the concentration of hydrochloric acid and ammonium chloride solution was 1.2 mol / L, and the molar ratio of hydrochloric acid to ammonium chloride was 1.5. Stand at room temperature for 12 hours, filter, wash, dry, and roast to obtain acid-treated Y molecular sieve.

[0035] Mix the molecular sieve obtained above with 0.9mol / L tetramethylammonium hydroxide solution, the solid-to-liquid ratio of the molecular sieve to the lye is 1:5, treat it in a polytetrafluoroethylene-lined synthesis kettle at 80°C for 12 hours, and filter , washing, drying, and roasting to prepare a multi-level porous Y molecular sieve containing a mesoporous composite structure.

[0036]Put the above-mentioned multi-stage molecular sieve into the mixed solution of sodium silicate and sodium tungstate, wherein the weight ratio of sodium silicate ...

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Abstract

The invention discloses a multistage pore molecular sieve-supported heteropolyacid alkylation desulfurization catalyst and a preparation method thereof. A multistage pore molecular sieve prepared by acid-base compound treatment is taken as a carrier, and with the aid of microwaves, a supported heteropolyacid catalyst is subjected to in-situ synthesis through a hydrothermal dispersion method. A specific synthesis method of the catalyst comprises the following steps: firstly preparing the molecular sieve carrier with multistage pore channels by adopting acid-base hydro-thermal treatment and thenperforming in-situ synthesis on the supported heteropolyacid catalyst by adopting a hydrothermal dispersion method with the aid of the microwaves. Measured by 100 percent by weight of multistage poremolecular sieve, the catalyst comprises 5-40 percent by weight of heteropolyacid; in the multistage pore molecular sieve, the molar ratio of SiO2 to Al2O3 is 10:60; the specific surface area is 200-700 m<2> / g; the pore volume is 0.3-0.8 m<3> / g. The multistage pore molecular sieve-supported heteropolyacid catalyst disclosed by the invention has the characteristics of firm active component supporting and good reusability and has the advantages of high thiophene sulfide conversion rate, good stability and high selectivity and the like when being used in the gasoline sulfide alkylation conversionprocess especially.

Description

technical field [0001] The invention relates to the field of catalysts and their preparation, in particular to a method for preparing a multi-stage porous molecular sieve-supported heteropolyacid alkylation desulfurization catalyst. Background technique [0002] At present, the fuel oil desulfurization technology is mainly hydrodesulfurization, but in addition to the removal of sulfur-containing compounds in the hydrodesulfurization process, olefins in gasoline are inevitably hydrogenated and saturated, and saturated hydrocarbons with relatively low octane numbers are generated, resulting in a decrease in the octane number of gasoline. And hydrodesulfurization investment and operating costs are high. Non-hydrogenation desulfurization methods include adsorption desulfurization, oxidative desulfurization, extractive distillation, and alkylation desulfurization. Among them, the alkylation desulfurization technology has the advantages of mild reaction conditions, no loss of octa...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/18B01J27/188B01J27/19B01J23/30B01J37/34B01J37/10C10G29/00
CPCB01J23/30B01J27/188B01J27/19B01J29/166B01J37/10B01J37/346B01J2229/14B01J2229/186B01J2229/37B01J2229/38C10G29/00C10G2300/202C10G2400/02
Inventor 靳凤英臧甲忠刘艳范景新李健于海斌李滨赵闯马明超王梦迪
Owner CNOOC TIANJIN CHEM RES & DESIGN INST
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