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Method for desulphurizing gasoline

A gasoline and removal technology, applied in chemical instruments and methods, refined hydrocarbon oil, petroleum industry, etc., to achieve the effects of strong controllability, refined gasoline desulfurization and high exchange degree

Active Publication Date: 2013-11-06
PETROCHINA CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The adsorbent belongs to the oxide carrier and is not suitable for fine desulfurization of gasoline and diesel

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0022] Preparation of ammonium and hydrogen molecular sieves: first configure the concentration to 1mol·L -1 Then mix the synthesized NaBeta molecular sieve with the ammonium chloride solution in a solid-liquid ratio of 1:15, stir in a water bath at 90°C for ammonium exchange for 1 hour, and then filter with suction and fully use deionized water After washing until no chloride ions can be detected in the washing liquid (which can be measured with silver chloride solution), the filter cake is dried at 393K for 2h, and the second exchange is performed under the same conditions. After the two exchanges, 393K is dried to obtain an ammonium Beta molecular sieve. Further, the ammonium type Beta molecular sieve was calcined in a muffle furnace at 823K for 3 hours to prepare the hydrogen type Beta molecular sieve (Hβ).

[0023] Adsorption desulfurization experiment: room temperature and normal pressure conditions, completed on a fixed bed adsorption device. The adsorption column uses a t...

Embodiment 1

[0026] Accurately weigh 10g of hydrogen-type Beta molecular sieve, add 1.5g CuCl and 1.0g of cerium nitrate metal salt, respectively, and mix the mixture uniformly, and then conduct sufficient grinding for 30 minutes, and then transfer the mixture to a quartz tube reactor. Under the protection of nitrogen, the temperature program is used for solid-phase ion exchange reaction. The specific heating procedure for preparing the adsorbent is as follows. The flow rate of nitrogen is 50ml / min and the heating rate is 10℃ / min: room temperature is raised to 120℃, 120℃ Keep it at 350℃ for 2h; then keep it at 350℃ for 2h; keep it at 450-650℃ for 6h, and get Cu after natural cooling + / Ce 2+ Beta molecular sieve adsorbent for ion exchange. For model compounds for adsorption desulfurization, the maximum saturated sulfur capacity is 0.550mmol·g -1 , And the breakthrough sulfur capacity is 0.2500mmol·g -1 .

Embodiment 2

[0028] Accurately weigh 5g of hydrogen type Beta molecular sieve and add 1.0g AgNO respectively 3 After mixing with 1.0 g of cerium nitrate metal salt, the mixture was thoroughly ground for 30 minutes, and then the mixture was transferred to a quartz tube reactor. Under the protection of nitrogen, the temperature program is used for solid-phase ion exchange reaction. The specific heating procedure for preparing the adsorbent is as follows. The flow rate of nitrogen is 50ml / min and the heating rate is 10℃ / min: room temperature is raised to 120℃, 120℃ Keep it under pressure for 2h; then keep it at 350℃ for 2h; keep it at 450-650℃ for 6h, and get Ag after automatic cooling + / Ce 2+ Beta molecular sieve adsorbent for ion exchange. The maximum penetration sulfur capacity for desulfurization of the model compound is 0.2625mmol·g -1 , The saturated sulfur capacity is 0.5250mmol·g -1 .

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Abstract

The invention relates to a method for desulphurizing gasoline. In the method, a beta molecular sieve serves as a carrier; a selective adsorbent is adopted to adsorb thiophene sulfides in the gasoline and remove the thiophene sulfides from the gasoline; a hydrogen type beta molecular sieve serves as the carrier of the adsorbent; the molecular sieve carries copper, silver, zinc, nickel or gallium metal ions and metal cerium ions; and the exchange amount of the metal ions is 0.001 to 15 percent based on the mass of the hydrogen type beta molecular sieve. The adsorbent is used to selectively adsorb the thiophene sulfides in the gasoline and deeply remove the thiophene sulfides from the gasoline. A result shows that: the bimetallic ions have a synergistic effect, improve the selectivity of adsorptive desulphurization and can reduce the content of the sulfides in the fluid catalytically cracked (FCC) gasoline to below 1mu g / g or zero from 200mu g / g. The reaction condition is mild; the equipment is simple; the activity of the adsorbent is high; and the adsorbent is easy to regenerate. At normal temperature and normal pressure, hydrogen is not consumed and the gasoline is finely desulphurized.

Description

Technical field: [0001] The invention relates to a method for deep desulfurization of model gasoline and actual FCC gasoline by adopting a bimetal ion modified Beta molecular sieve adsorbent under normal temperature and pressure. Background technique: [0002] Wardencki et al. reported earlier on the study of molecular sieve adsorption desulfurization [J.Chromatogr.91(1974)715-722], which used 13X molecular sieve to adsorb and remove thiophene compounds in n-hexane solution. Recently, several research groups reported the research results of ZSM-5 adsorption desulfurization [J.Chem.Soc., Chem.Commun.(1991)1133-1134; J.Phys.Chem.96(1992)2669-2675; Langmuir 20 (2004) 10982-10991]. They found that the use of ZSM-5 molecular sieve for desulfurization often brings about side effects such as polymerization and coking of thiophene compounds, so they believe that ZSM-5 molecular sieve is not suitable for the removal of thiophene compounds, especially alkyl-substituted thiophenes with lar...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J20/18B01J20/06C10G25/05
Inventor 巩雁军窦涛康善娇徐庆虎邢法猛
Owner PETROCHINA CO LTD
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