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Removal and recovery of naphthenic acid in oil based on ion switch principle

An ion switch, naphthenic acid technology, applied in the petroleum industry, refining hydrocarbon oil, refining with alkaline aqueous solution, etc., can solve the problems of no recycling, loss of naphthenic acid resources, etc.

Active Publication Date: 2007-10-24
INST OF PROCESS ENG CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the annual output of naphthenic acid in my country is only 60,000 to 8,000 tons, and 96% to 97% of naphthenic acid resources are lost without recycling.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0008] Take a refinery's regular fourth-line distillate oil, the acid value of which is 3.56 mgKOH / g, and tetramethylammonium hydroxide is formulated into 25% ethanol solution as a deacidification agent. Mix according to the agent-oil ratio of 1:15, and mix and react at 60°C for 10 minutes. After the reaction was completed, it was kept at 60° C. and kept at rest. The oil phase after deacidification and the ionic liquid phase generated after the reaction were quickly separated. The acid value was measured to be 0.15 mgKOH / g, and the deacidification rate was 95.8%. Dilute HCl is added to the ionic liquid phase of the lower layer, and the naphthenic acid is precipitated from the ionic liquid phase and recovered. Heating the ionic liquid phase reclaims HCl (absorbed with water), and the remaining tetramethylammonium hydroxide ethanol solution after heating can be recycled as a deacidification agent.

Embodiment 2

[0010] Take the second-line distillate from an oil refinery, the acid value of which is 2.65 mgKOH / g, and tetraethylammonium hydroxide is formulated into 25% isopropanol solution as a deacidification agent. Mix according to the agent-oil ratio of 1:10, and mix and react at 50°C. After the reaction was completed, it was kept at 50° C. and kept at rest. The oil phase after deacidification and the ionic liquid phase generated after the reaction were quickly separated. The acid value was measured to be 0.09 mgKOH / g, and the deacidification rate was 96.6%. Dilute HCl is added to the ionic liquid phase of the lower layer, and the naphthenic acid is precipitated from the ionic liquid phase and recovered. Heating the ionic liquid phase reclaims HCl (absorbed with water), and the remaining tetraethylammonium hydroxide isopropanol solution after heating can be recycled as a deacidifying agent.

Embodiment 3

[0012] Take the third-line distillate oil from a refinery, the acid value of which is 2.79mgKOH / g, and tetrapropylammonium hydroxide is formulated into 25% ethanol solution as a deacidification agent. Mix according to the agent-oil ratio of 1:5, and mix and react at 70°C for 10 minutes. After the reaction was completed, it was kept at 70° C. for standing. The oil phase after deacidification and the ionic liquid phase generated after the reaction were quickly separated. The acid value was measured to be 0.04 mgKOH / g, and the deacidification rate was 98.6%. Dilute HCl is added to the ionic liquid phase of the lower layer, and the naphthenic acid is precipitated from the ionic liquid phase and recovered. Heating the ionic liquid phase reclaims HCl (absorbed with water), and the remaining tetrapropylammonium hydroxide ethanol solution after heating can be recycled as a deacidifying agent.

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Abstract

The invention discloses a removing and recycling method of naphthenic acid in the oil based on ion-switch elementary, which comprising the following steps: choosing a mixture or a plurality of mixtures in ammonium hydroxide tetramethyl , ammonium hydroxide tetraethyl, ammonium hydroxide tetrapropyl quaternary ammonium hydroxide; regarding the homogeneous solution of the mixtures and a reacting agent as a deacidificator; reacting with the naphthenic acid in the oil according to 1:1-1:20 ratio of flux and oil at the temperature of 20-70Deg. C; getting an ion liquid phase; separating the ion liquid phase and the oil product reducing acid value efficiently owing to the great polarity difference; adding the volatile acid to the ion liquid phase; separating and recovering the naphthenic acid from the iron liquid phase; recovering separately the volatile acid and deacidificator with the vacuum distillation. The invention provides an efficient deacidifying technique, which saves the time, has a high recovering ratio.

Description

[0001] Field of the invention: the present invention relates to the removal and recovery of naphthenic acid in oil products in the field of petrochemical industry. Background of the invention: [0002] With the increase of oil production and the increase of heavy oil, the direct impact on the processing and use of oil products is the increase of naphthenic acid content in petroleum fractions. Naphthenic acid is a mixture of monocarboxylic acids with five-membered or six-membered rings. It is usually distributed in various petroleum products according to different fractions. Generally speaking, it is mostly distributed in the middle distillate, that is, a section with a distillation range of 250-350°C. in fractions. The molecular weight of naphthenic acid varies greatly, mostly between 200 and 700. The smaller the molecular weight, the larger the dissociation constant and the greater the acid strength. In addition to directly interacting with iron, naphthenic acid can also int...

Claims

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Application Information

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IPC IPC(8): C10G29/20C10G19/02C10G19/08C07C61/00
Inventor 张锁江于英豪罗忻刘龙
Owner INST OF PROCESS ENG CHINESE ACAD OF SCI
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