Method for removing petroleum acid in hydrocarbon oil by using membrane dispersion extractor

Abstract

The present invention relates to a method of removing petroleum acid from hydrocarbon oil by a membrane dispersion extraction device. A continuous phase of the hydrocarbon oil is heated up to 10 DEG C to 150 DEG C; deacidification solvent dispersed phase is heated up to 10 DEG C to 90 DEG C; the cubage ratio of the continuous phase and the dispersed phase is 50 to 2 ®U 1; the pressure difference of the dispersed phase and the continuous phase is 0.05MPa to 0.4MPa; the flow velocity of the dispersed phase deacidification solvent is 0.5 to 5L / <2> per hour; membrane aperture is 0.01 to 60 microns; the dispersed phase deacidification solvent is dispersed into continuous phase oil through membrane micropores; clean oil after the deacidification is obtained after sedimentation and separation. The deacidification solvent is 1 percent to 15 percent of ammonia, 20 percent to 70 percent of alcohol or 0.02 percent to 5 percent of petroleum acid or 0.004 percent to 1 percent of demulsifier and the water with the rest quantity. The contacting time of the oil and the solvent is short; mass transfer efficiency is high; the disposal capability is large; the extraction course is not emulsified easily; the hydrocarbon oil contains little alkali liquid; the device operation is convenient.

Description

technical field [0001] The invention relates to a method for removing petroleum acid in hydrocarbon oil by using a membrane dispersion extractor. Background technique [0002] The acidic oxides in petroleum are collectively called petroleum acid, and its main component is petroleum carboxylic acid. Since more than 90% of petroleum acid is naphthenic acid, it is also called naphthenic acid. Naphthenic acid will cause equipment corrosion during petroleum processing and affect the quality of subsequent products, but it is also a valuable fine chemical raw material, so the research on naphthenic acid separation technology at home and abroad is very active, mainly focusing on distillate oil Petroleum acid separation technology. At present, the main deacidification methods researched are: (1) chemical and electrochemical deacidification method: this technology mainly uses lye, such as NaOH, KOH, Ca(OH)2, ammonia, etc. to compound with demulsifier or alcohol Naphthenic acids in ...

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Problems solved by technology

The principle of this technology is simple, and it can remove a certain amount of petroleum acid, but the ratio of agent to oil used is large, the energy consumption is high, and the recovery system is relatively complicated, so the application of this technology is limited

(3) Adsorption separation deacidification method: use selective adsorbents such as clay, natural silica gel, anion and cation resins, ion exchange resins, etc. to adsorb and deacidify raw materials containing petroleum acid, but the equipment investment is large and it is not suitable for high-density processing , high viscosity, high acid value hydrocarbon oil, and it is easy to increase the ash content of the oil after removing petroleum acid

This method is to keep crude oil at low pressure and petroleum acid decomposition temperature of 350°C to 400°C for a long enough time to decompose and convert petroleum acid. However, naphthenic acid is very corrosive at this temperature, causing corresponding equipment The investment is high, and the oil product is easy to crack and coke at this temperature, making industrial application difficult. In addition, the precious naphthenic acid resources are also destroyed

(5) Hydrodeacidification method: as US5897769, ZL9519522.8 discloses a method of hydrodeacidification using a selective catalyst and hydrogen under corresponding operating conditions, this method can avoid alkali slag pollution, but the refining cost is large and the process Complex, and naphthenic acid resources are destroyed

Among the above five deacidification methods, the deacidification solvent and the oil product are carried out in a mixer, an extraction tower or a fixed bed reactor. Generally speaking, after the oil product is deacidified, the oil and water are easy to emulsify and the phase separation is difficult. ; or affected by the chemical reaction balance, the reaction conversion rate is limited, so that the deacidification effect is not high; or the recovered naphthenic acid is low in purity, and the energy consumption of solvent recovery is large; or the equipment investment is large, and the process control and management technology requirements are high. Issues such as the need to equip a dedicated hydrogen production system hinder the economical operation of related technologies

(6) Biological deacidification method: use specially cultivated strains to decompose petroleum acid, but this method takes a long time to decompose, and petroleum acid resources cannot be utilized

JP10235102 discloses an effective and low-cost membrane extraction method for metal elements, which uses solvents such as diethylhexylphosphonic acid to extract petroleum acid in gasoline, and then uses ion exchange membranes for filtration to extract petroleum acid into an aqueous solution In the process of removing metal ions, this method requires the joint action of a mixed extractor and is only used in the process of gasoline alkali elution acid

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