A regenerative lubricating oil deacidifier and a method of making the same

Abstract

The application discloses a regenerative lubricating oil deacidification agent and a preparation method thereof, and relates to the technical field of lubricating oil deacidification agents.The application first prepares macroporous spherical activated carbon, carries out hydroxylation treatment on the macroporous spherical activated carbon by using sodium zincate, embeds anion resin into the acid-treated spherical activated carbon, retains the hollow structure of the activated carbon, and increases the contact surface area of the resin to improve the adsorption efficiency; after adsorption, the resin expands to fill the pores of the activated carbon, and the adsorption effect is further improved.Secondly, long-chain polyvinyl alcohol is bonded to the surface of silica gel to obtain silica gel with a multi-hydroxyl group, a hybrid deacidification agent of silica gel embedding metal nanoparticles and activated carbon is prepared by using a sol-gel method, and the deacidification agent contains a certain magnetism by using ferric oxide, and the deacidification agent is still an integral whole after deacidification, so that the subsequent recycling and regeneration are facilitated.The deacidification agent prepared by the application has the effects of efficient deacidification adsorption and recycling regeneration.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of lubricating oil deacidification agent, in particular to a regenerated lubricating oil deacidification agent and a preparation method thereof. BACKGROUND

[0002] The presence of acidic components in the lubricating oil base oil will reduce the quality of the lubricating oil base oil, affect its performance, and cause the corrosion of engine parts to increase. Although hydrogenation refining can effectively remove petroleum acids in the lubricating oil base oil, it successfully solves the problem of high acid value of the lubricating oil base oil, but the hydrogenation device requires large investment, high operating cost and a large amount of hydrogen source, and the hydrogenated base oil has poor light stability. Under this background, the lubricating oil base oil refining of many refineries in China still mainly uses non-hydrogenation solvent refining process.

[0003] However, the processes such as propane deasphalting, furfural refining, ketone benzene dewaxing and clay supplementary refining in the solvent refining combined device cannot efficiently remove the acidic components in the lubricating oil base oil raw material, thereby making the lubricating oil base oil product unable to meet the standard and be out of the factory due to the high acid value. The alkali washing deacidification has problems such as easy emulsification of oil, need for strong acid neutralization and water washing of oil after alkali washing, and serious pollution. The use of alcohol ammonia method or alkali washing method to remove and produce petroleum acids requires the construction of a separate deacidification device, and the construction of a separate deacidification device is not economical due to the sometimes not very high acid value of the lubricating oil raw material. The physical adsorption means is a research direction, but the addition of the physical deacidification agent is easy to cause secondary pollution to the raw material due to the difficulty in recovery, and the deacidification effect is not satisfactory. In view of the above problems, the present application provides a regenerated lubricating oil deacidification agent and a preparation method thereof. SUMMARY

[0004] The present application aims to provide a regenerated lubricating oil deacidification agent and a preparation method thereof to solve the problems in the prior art.

[0005] In order to solve the above technical problems, the present application provides the following technical scheme: a regenerated lubricating oil deacidification agent, which is prepared from modified silica gel embedded with iron trioxide particles and spherical modified activated carbon embedded with anion exchange resin.

[0006] Further, the modified silica gel embedding is to bond long-chain polyvinyl alcohol to the surface of silica gel to obtain silica gel with multi-hydroxyl groups, and then a silica gel embedded deacidification agent is prepared by sol-gel method.

[0007] Further, the spherical modified activated carbon is prepared by carbonizing resin to obtain macroporous spherical activated carbon, which is then hydroxylated by sodium zincate and mixed with anion exchange resin for embedding.

[0008] Further, a preparation method of the regenerated lubricating oil deacidification agent comprises the following preparation steps:

[0009] (1) In a sealed reactor, spherical resin is mixed with dichloroethane at a weight ratio of 1:1-1.5, heated to 60-80°C with stirring at a speed of 60 rpm for 30 min; then 2-10 times the weight of concentrated sulfuric acid is added to the reactor, and heating is continued to a sulfonation temperature of 150-200°C for 120-420 min; the temperature is allowed to cool naturally to room temperature, and the acid liquid is drained to obtain sulfonated resin; the sulfonated resin spheres are washed once with 85% concentrated sulfuric acid solution, then once with 60% concentrated sulfuric acid solution, again once with 40% sulfuric acid solution, then once with 20% sulfuric acid solution, and finally washed to neutral with deionized water, and dried at room temperature for 5 h; the solidified spherical resin is carbonized at a temperature of 700-1000°C for 1-2 h under a helium gas atmosphere, and then activated by passing in 1 ml / min of water vapor for 30 min to obtain spherical activated carbon; the spherical activated carbon is treated with 5% nitric acid at a temperature of 75-85°C for 1.8-2.2 h, and washed to neutral; a sodium zincate solution is prepared by mixing 0.1-2 parts of sodium hydroxide per 100 parts of deionized water, and adding 10-12 parts of zinc powder, and reacting at a temperature of 38-42°C for 0.8-1.2 h, and then filtering to remove insoluble matter to obtain a clear filtrate; the treated spherical activated carbon is mixed with the sodium zincate solution to form a slurry, and stirred at a temperature of 55-65°C for 15-25 min at a speed of 60 rpm, and then filtered, and the stirring and filtering is repeated 2-5 times, and finally washed 3 times with deionized water to neutral to obtain modified spherical activated carbon;

[0010] (2) The modified spherical activated carbon and anion exchange resin of type 205x7 are washed in deionized water under ultrasonic power of 35 kHz for 30 min, and then dried at room temperature for 2 h; then the dried activated carbon and anion exchange resin are mixed with anhydrous ethanol, and ultrasonically stirred at a speed of 100-200 rpm for 10-30 min under ultrasonic power of 20-40 kHz to fully disperse and dissolve the activated carbon in the anhydrous ethanol, and a polytetrafluoroethylene emulsion is added dropwise during this process, and ultrasonic stirring is continued for 15-30 min; the mixture is stirred in a water bath at 70°C for 60-120 min, and anhydrous ethanol is added to the mixture in an amount of 1.2 times the mass of the mixture to form a gel, and ultrasonic stirring is continued under the same conditions for 20-60 min, and then filtered to obtain a filtrate, which is washed twice with anhydrous ethanol, and dried at 50°C for 2-5 h to obtain activated carbon embedded with exchange resin;

[0011] (3) take 3-5 parts of silica gel, put it in a round bottom flask, add 20 parts of deionized water to disperse silica gel, add 15 parts of 15% mass fraction hydrochloric acid solution, 5-7 parts of 50% mass fraction glutaraldehyde solution in the flask at room temperature for 3h; then add 20 parts of 15% mass fraction polyvinyl alcohol solution, stir at 60rpm at 35℃ for 6h, wash the product with deionized water for 3 times, dry at room temperature for 2h to obtain polyhydroxy silica gel powder; add ferric oxide, modified silica gel powder, cosolvent, deionized water and 36.5% mass fraction concentrated hydrochloric acid in a three-necked flask in a 60-80℃ water bath, the volume ratio of ferric oxide, modified silica gel powder, cosolvent, deionized water and concentrated hydrochloric acid is 0.2-0.4:3-6:2-5:2-4:1; mix them uniformly by mechanical stirring, the stirring speed is 60-180rpm, add activated carbon powder during the stirring process, the mass ratio of ferric oxide and activated carbon powder is 1:0.5-4.5, stir for 2-4h until the formation of gel, then age at room temperature for 4-24h, and then dry at 120℃ under vacuum for 3-8h, the vacuum degree is -0.085Pa, to obtain the deacidification agent.

[0012] Further, the concentration of concentrated sulfuric acid in step (1) is 92.5%.

[0013] Further, the solid-liquid ratio of spherical activated carbon and sodium zincate solution in step (1) is 1:8-12.

[0014] Further, the mass ratio of activated carbon, anion exchange resin and polytetrafluoroethylene emulsion in step (2) is 5-7:1:1.

[0015] Further, the concentration of polytetrafluoroethylene emulsion in step (2) is 1.5g / mL.

[0016] Further, the degree of polymerization of polyvinyl alcohol in step (3) is 1700, and the alcoholysis rate is 99%.

[0017] Further, the cosolvent in step (3) is ethanol or diethylene glycol.

[0018] Compared with the prior art, the present application has the following beneficial effects:

[0019] The present application uses modified silica gel to embed ferric oxide particles and spherical modified activated carbon embedded with anion exchange resin as a deacidification agent to achieve the effects of deacidification adsorption and regeneration.

[0020] Firstly, macroporous spherical activated carbon is prepared by self-made spherical resin carbonization, then the spherical activated carbon is treated by sodium zincate to make the activated carbon surface have high concentration of hydroxyl groups, which provides more adsorption and attachment sites; the activated carbon after acid treatment is mixed with anion exchange resin, stirring to make the anion resin completely and fully embedded in the spherical activated carbon, forming a dough-like material with elasticity, then drying to make the anion exchange resin coated in the activated carbon pores, and the volume is still small due to the loss of water during drying, still retaining the hollow structure of the activated carbon, while increasing the contact surface area of the resin to improve the adsorption efficiency; the ion exchange resin containing tertiary amine groups is a kind of high molecular compound with ion exchange functional groups and network structure, the anion active groups in the resin are alkaline, which preferentially reacts with acidic groups in oil, when the acid-containing oil passes through the ion exchange resin, the petroleum acid is adsorbed on the resin within the capacity range of the resin, then the resin is washed with solvent to regenerate and recycle, so as to achieve the effect of regeneration; and when the anion exchange resin adsorbs the acidic substances in the lubricating oil, it expands to fill the pores of the activated carbon, extruding the acidic substances also adsorbed in the pores of the activated carbon, so as to form a whole, and the adsorbed acidic substances are not easy to fall off, further improving the adsorption effect.

[0021] Secondly, polyvinyl alcohol long chain is bonded to the surface of silica gel to obtain silica gel with multi-hydroxyl groups, which can react with the carboxyl groups on the surface of naphthenic acid to be adsorbed, and then a hybrid deacidification agent of silica gel embedded metal nanoparticles and activated carbon is prepared by sol-gel method, which uses ferric oxide to be adsorbed on the surface of spherical activated carbon, so that the deacidification agent contains a certain magnetism, improving the subsequent recovery and regeneration efficiency; as a metal oxide, it can also react with naphthenic acid to replace the salt of acidic substances, which is still adsorbed by silica gel after the reaction, which can improve the adsorption efficiency and make the deacidification agent still be a whole after deacidification, which is convenient for subsequent recovery and regeneration. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0023] In order to more clearly illustrate the method provided by the present application, the following examples are used for detailed description, and the test methods of various indexes of a regenerated lubricating oil deacidification agent prepared in the following examples are as follows:

[0024] Deacidification rate: The deacidifier prepared in the examples and comparative examples was used as an additive, the ratio of the deacidifier to oil was 1:50, and the oil was treated by dewaxing, furaldehyde refining, denitrification, and deacidifier adsorption. The oil acid value before and after deacidification was measured at 100°C for 30 min. The deacidification rate was calculated as (solvent refined raw material oil acid value - solvent refined oil acid value x solvent refined oil yield) / raw material oil acid value x 100%.

[0025] Example 1

[0026] (1) In a sealed reactor, spherical resin was mixed with dichloroethane at a weight ratio of 1:1, stirred at a speed of 60 rpm, and heated to 60°C for 30 min; then 2 times the weight of concentrated sulfuric acid with a concentration of 92.5% was added to the reactor, and the temperature was continuously heated to 150°C for sulfonation, and the sulfonation time was 120 min; naturally cooled to room temperature, and the acid liquid was drained to obtain the sulfonated resin; the sulfonated resin spheres were washed once with 85% concentrated sulfuric acid solution, then washed once with 60% concentrated sulfuric acid solution, then washed once with 40% sulfuric acid solution, then washed once with 20% sulfuric acid solution, and finally washed with deionized water until neutral, and dried at room temperature for 5 h; the solidified spherical resin was carbonized at 700°C for 1 h under helium gas protection, and then activated for 30 min by passing in 1 ml / min of water vapor to obtain spherical activated carbon; the spherical activated carbon was treated with 5% nitric acid at a temperature of 75°C for 1.8 h, and washed to neutral; a sodium zincate solution was prepared, mixed with 0.1 parts of sodium hydroxide per 100 parts of deionized water, and 10 parts of zinc powder was added, and reacted at a temperature of 38°C for 0.8 h, then filtered to remove insoluble substances to obtain a clear filtrate; the treated spherical activated carbon was mixed with the sodium zincate solution at a solid-liquid ratio of 1:8 to form a slurry, and stirred at a temperature of 55°C for 15 min at a speed of 60 rpm, then filtered, and the stirring and filtering were repeated twice, and finally washed with deionized water until neutral to obtain modified spherical activated carbon;

[0027] (2) The modified spherical activated carbon and the anion exchange resin of model 205x7 are washed in deionized water at 35 kHz power for 30 min, and then dried at room temperature for 2 h. Then the dried activated carbon, anion exchange resin and anhydrous ethanol are mixed, and ultrasonic stirring is carried out at 20 kHz and 100 rpm for 10 min to make the activated carbon fully dispersed and dissolved in the anhydrous ethanol. In this process, the polytetrafluoroethylene emulsion is added dropwise, and the concentration of the polytetrafluoroethylene emulsion is 1.5 g / mL. The ultrasonic stirring is continued for 15 min, and the mass ratio of the activated carbon, anion exchange resin and polytetrafluoroethylene emulsion is 5:1:1. The mixture is stirred in a water bath at 70°C for 60 min, and 1.2 times the mass of anhydrous ethanol is added to make it into a colloidal state. The ultrasonic stirring is continued under the same conditions for 20 min, and then the filtrate is obtained by filtration, washed twice with anhydrous ethanol, and dried at 50°C for 2 h to obtain the activated carbon embedded with the exchange resin;

[0028] (3) 3 parts of silica gel are weighed and placed in a round-bottom flask, and 20 parts of deionized water is added to disperse the silica gel. A constant pressure dropping funnel is used to add 15 parts of 15% mass fraction hydrochloric acid aqueous solution and 5 parts of 50% mass fraction glutaraldehyde aqueous solution to the flask at room temperature for 3 h. Then 20 parts of 15% mass fraction polyvinyl alcohol aqueous solution is added dropwise, the degree of polymerization of the polyvinyl alcohol is 1700, and the alcoholysis rate is 99%. The reaction is carried out at 35°C and 60 rpm for 6 h. The product is washed with deionized water for 3 times, and dried at room temperature for 2 h to obtain a polyhydroxyl-tipped silica gel powder. In a three-necked flask, ferric trioxide, modified silica gel powder, ethanol cosolvent, deionized water and 36.5% mass fraction concentrated hydrochloric acid are added in a volume ratio of ferric trioxide: modified silica gel powder: ethanol cosolvent: deionized water: concentrated hydrochloric acid = 0.2:3:2:2:1. The mixture is uniformly mixed by mechanical stirring at a stirring speed of 60 rpm. Activated carbon powder is added during the stirring process, and the mass ratio of ferric trioxide: activated carbon powder is 1:0.5. The stirring is carried out for 2 h until the formation of a gel, and then the gel is aged at room temperature for 4 h. The gel is dried at 120°C under vacuum for 3 h, and the vacuum degree is -0.085 Pa. The deacidification agent is obtained.

[0029] Example 2

[0030] (1) In a sealed reactor, spherical resin was mixed with dichloroethane at a weight ratio of 1:1.25, stirred at a speed of 60 rpm, heated to 70°C, and kept at this temperature for 30 min; then 6 times the weight of concentrated sulfuric acid with a concentration of 92.5% was added to the reactor, and heating was continued to a sulfonation temperature of 175°C, and the sulfonation time was 270 min; natural cooling to room temperature, and the acid liquid was drained to obtain the sulfonated resin; the sulfonated resin spheres were washed once with 85% concentrated sulfuric acid solution, then once with 60% concentrated sulfuric acid solution, and then once with 40% sulfuric acid solution, followed by washing once with 20% sulfuric acid solution, and finally washed with deionized water until neutral, and dried at room temperature for 5 h; the solidified spherical resin was carbonized at 850°C for 1.5 h under helium gas protection, and then activated for 30 min by passing in 1 ml / min of water vapor, to obtain spherical activated carbon; the spherical activated carbon was treated with 5% nitric acid at a temperature of 80°C for 2 h, and washed to neutral; a sodium zincate solution was prepared, 1 part of sodium hydroxide was mixed per 100 parts of deionized water, and 11 parts of zinc powder was added, and reacted at a temperature of 40°C for 1 h, and then filtered to remove insoluble substances to obtain a clear filtrate; the treated spherical activated carbon was mixed with the sodium zincate solution at a solid-liquid ratio of 1:10 to form a slurry, and stirred at a temperature of 60°C for 20 min at a speed of 60 rpm, and then filtered, and the stirring and filtering were repeated 3 times, and finally washed with deionized water 3 times until neutral to obtain modified spherical activated carbon;

[0031] (2) The modified spherical activated carbon and the type 205x7 anion exchange resin were washed with deionized water under ultrasonic power of 35 kHz for 30 min, and then dried at room temperature for 2 h; then the dried activated carbon, anion exchange resin, and anhydrous ethanol were mixed, and ultrasonically stirred at a speed of 150 rpm for 20 min under a power of 30 kHz to make the activated carbon fully dispersed and dissolved in the anhydrous ethanol, and in this process, polytetrafluoroethylene emulsion was added dropwise, the concentration of the polytetrafluoroethylene emulsion was 1.5 g / mL, and the ultrasonic stirring was continued for 22 min, and the mass ratio of the activated carbon: anion exchange resin: polytetrafluoroethylene emulsion was 6:1:1; the mixture was stirred in a water bath at 70°C for 90 min, 1.2 times the mass of the mixture of anhydrous ethanol was added to make it into a colloidal state, and the ultrasonic stirring was continued under the same conditions for 40 min, and then filtered to obtain the filtrate, which was washed with anhydrous ethanol 2 times, and then dried at 50°C for 3.5 h to obtain the exchange resin-embedded activated carbon;

[0032] (3) Take 4 parts of silica gel and put it in a round bottom flask, disperse the silica gel with 20 parts of deionized water, then add 15 parts of 15% mass fraction hydrochloric acid aqueous solution and 6 parts of 50% mass fraction glutaraldehyde aqueous solution into the flask by constant pressure dropping funnel at room temperature for 3 hours; then add 20 parts of 15% mass fraction polyvinyl alcohol aqueous solution into the flask, the polyvinyl alcohol has a polymerization degree of 1700 and an alcoholysis rate of 99%, and the reaction is carried out at 35°C for 6 hours with stirring at a speed of 60 rpm; the product is washed with deionized water for 3 times and dried at room temperature for 2 hours to obtain a multi-hydroxyl tipped silica gel powder; add ferric trioxide into a three-necked flask in a water bath at 70°C, then add the modified silica gel powder, ethanol cosolvent, deionized water and 36.5% mass fraction concentrated hydrochloric acid, and mix them uniformly by mechanical stirring at a speed of 120 rpm; add activated carbon powder during the stirring process, and the mass ratio of ferric trioxide to activated carbon powder is 1:2.5; stir for 3 hours until the formation of a gel, then age at room temperature for 14 hours, and finally dry at 120°C under vacuum for 5.5 hours with a vacuum degree of -0.085 Pa to obtain a deacidification agent.

[0033] Example 3

[0034] (1) Mix the spherical resin with dichloroethane in a sealed reactor at a weight ratio of 1:1.5, and stir at a speed of 60 rpm to heat to 80°C for 30 min; then add 10 times the weight of concentrated sulfuric acid with a concentration of 92.5% into the reactor, continue to heat to a sulfonation temperature of 200°C, and sulfonate for 420 min; naturally cool to room temperature, drain the acid liquid to obtain sulfonated resin; wash the sulfonated resin spheres with 85% concentrated sulfuric acid solution once, then with 60% concentrated sulfuric acid solution once, then with 40% sulfuric acid solution once, then with 20% sulfuric acid solution once, and finally wash with deionized water until neutral, and dry at room temperature for 5 h; carbonize the solidified spherical resin under helium gas protection at a temperature of 1000°C for 2 h, and then activate for 30 min by passing in 1 ml / min of water vapor to obtain spherical activated carbon; treat the spherical activated carbon with 5% mass fraction nitric acid at a temperature of 85°C for 2.2 h, and wash to neutral; prepare a sodium zincate solution by mixing 2 parts of sodium hydroxide per 100 parts of deionized water, and adding 12 parts of zinc powder, and react at a temperature of 42°C for 1.2 h, and then filter to remove insoluble substances to obtain a clear filtrate; mix the treated spherical activated carbon with the sodium zincate solution at a solid-liquid ratio of 1:12 to prepare a slurry, and stir at a temperature of 65°C for 25 min at a speed of 60 rpm, then filter, repeat the stirring and filtering for 5 times, and finally wash with deionized water until neutral to obtain modified spherical activated carbon;

[0035] (2) The modified spherical activated carbon and the anion exchange resin of model 205x7 were washed in deionized water at 35 kHz power for 30 min, and then dried at room temperature for 2 h. Then the dried activated carbon and anion exchange resin were mixed with anhydrous ethanol, and ultrasonic stirring was carried out at 40 kHz and 200 rpm for 30 min to make the activated carbon fully dispersed and dissolved in the anhydrous ethanol. In this process, the polytetrafluoroethylene emulsion was added dropwise, and the concentration of the polytetrafluoroethylene emulsion was 1.5 g / mL. The ultrasonic stirring was continued for another 30 min, and the mass ratio of the activated carbon, anion exchange resin and polytetrafluoroethylene emulsion was 7:1:1. The mixture was stirred in a water bath at 70°C for 120 min, and anhydrous ethanol was added to the mixture in an amount of 1.2 times the mass of the mixture to make it into a colloidal state. The ultrasonic stirring was continued under the same conditions for 60 min, and then the filtrate was obtained by filtration, washed twice with anhydrous ethanol, and dried at 50°C for 5 h to obtain the activated carbon embedded with the exchange resin;

[0036] (3) 5 parts of silica gel were placed in a round-bottom flask, and 20 parts of deionized water was added to disperse the silica gel. A constant-pressure dropping funnel was used to add 15 parts of 15% by mass hydrochloric acid aqueous solution and 7 parts of 50% by mass glutaraldehyde aqueous solution to the flask at room temperature for reaction for 3 h. Then, 20 parts of 15% by mass polyvinyl alcohol aqueous solution was added dropwise, the polyvinyl alcohol had a degree of polymerization of 1700 and an alcoholysis rate of 99%, and the reaction was carried out at 35°C with stirring at a speed of 60 rpm for 6 h. The product was washed with deionized water for 3 times, and dried at room temperature for 2 h to obtain a polyhydroxyl-tipped silica gel powder. In a three-necked flask, ferric sesquioxide, modified silica gel powder, diethylene glycol cosolvent, deionized water and 36.5% by mass concentrated hydrochloric acid were added in a volume ratio of ferric sesquioxide: modified silica gel powder: diethylene glycol cosolvent: deionized water: concentrated hydrochloric acid = 0.4:6:5:4:1, and mechanical stirring was used to make them uniformly mixed, and the stirring speed was 180 rpm. Activated carbon powder was added during the stirring process, and the mass ratio of ferric sesquioxide: activated carbon powder was 1:4.5, and the stirring was carried out for 4 h until the formation of a gel. Then, the gel was aged at room temperature for 24 h, and then dried at 120°C under vacuum for 8 h, and the vacuum degree was -0.085 Pa, to obtain the deacidification agent.

[0037] Comparative Example 1

[0038] Comparative Example 1 and Example 2 differ in steps (1) (2), which are changed to: (1) coal-based activated carbon with a particle size of 80 mesh is treated with 5% nitric acid at a temperature of 80°C for 2h, and washed to neutral; a sodium zincate solution is prepared, 1 part of sodium hydroxide is mixed per 100 parts of deionized water, and 11 parts of zinc powder is added, and reacted at a temperature of 40°C for 1h, and then filtered to remove insoluble substances to obtain a clear filtrate; the treated activated carbon and the sodium zincate solution are mixed at a solid-liquid ratio of 1:10 to prepare a slurry, stirred at a temperature of 60°C and a speed of 60 rpm for 20 min, then filtered, and the stirring and filtering are repeated 3 times, and finally washed with deionized water 3 times to neutral, to obtain modified activated carbon;

[0039] (2) The modified activated carbon and the type 205x7 anion exchange resin are washed with deionized water under ultrasonic power of 35 kHz for 30 min, and then dried at room temperature for 2h; then the dried activated carbon, anion exchange resin and anhydrous ethanol are mixed, ultrasonically stirred at a speed of 150 rpm for 20 min under 30 kHz to make the activated carbon fully dispersed and dissolved in anhydrous ethanol, and polytetrafluoroethylene emulsion is added dropwise in the process, the concentration of the polytetrafluoroethylene emulsion is 1.5g / mL, and the ultrasonic stirring is continued for 22 min, in which the mass ratio of activated carbon: anion exchange resin: polytetrafluoroethylene emulsion is 6:1:1; the mixture is stirred in a water bath at 70°C for 90 min, 1.2 times the mass of anhydrous ethanol is added to make it into a colloidal state, and the ultrasonic stirring is continued for 40 min under the same conditions, then the filtrate is obtained by filtration, washed with anhydrous ethanol 2 times, and dried at 50°C for 3.5h to obtain activated carbon embedded with exchange resin; the remaining steps are the same as in Example 2.

[0040] Comparative Example 2

[0041] Comparative Example 2 and Example 2 differ in steps (1) (2), which are changed to: (1) in a sealed reactor, spherical resin and dichloroethane are mixed at a weight ratio of 1:1.25, stirred at a speed of 60 rpm, heated to 70°C, and kept at a constant temperature for 30 min; then 6 times the weight of concentrated sulfuric acid with a concentration of 92.5% is added to the reactor, and heated to a sulfonation temperature of 175°C, and sulfonated for 270 min; naturally cooled to room temperature, and the acid liquid is drained to obtain sulfonated resin; the sulfonated resin spheres are washed once with 85% concentrated sulfuric acid solution, then once with 60% concentrated sulfuric acid solution, once with 40% sulfuric acid solution, once with 20% sulfuric acid solution, and finally washed with deionized water to neutral, and dried at room temperature for 5h; the solidified spherical resin is carbonized at 850°C for 1.5h under helium gas protection, and then activated for 30 min by passing in 1ml / min of water vapor, to obtain spherical activated carbon;

[0042] (2) The spherical activated carbon and the type 205x7 anion exchange resin were washed in deionized water at 35 kHz power for 30 min, then dried at room temperature for 2 h; then the dried activated carbon, anion exchange resin and anhydrous ethanol were mixed, and ultrasonic stirring was carried out at 30 kHz and 150 rpm for 20 min to make the activated carbon fully dispersed and dissolved in anhydrous ethanol; in this process, polytetrafluoroethylene emulsion was added dropwise, the concentration of the polytetrafluoroethylene emulsion was 1.5 g / mL, and ultrasonic stirring was continued for 22 min; the mass ratio of activated carbon: anion exchange resin: polytetrafluoroethylene emulsion was 6:1:1; the mixture was stirred in a 70°C water bath for 90 min, 1.2 times the mass of anhydrous ethanol was added to make it into a colloidal state, and ultrasonic stirring was continued under the same conditions for 40 min, then the filtrate was obtained by filtration, washed twice with anhydrous ethanol, and dried at 50°C for 3.5 h to obtain the exchange resin-embedded activated carbon; the remaining steps were the same as in Example 2.

[0043] Comparative Example 3

[0044] Comparative Example 3 differs from Example 2 in that there is no step (2), and step (3) is changed to: 4 parts of silica gel were placed in a round-bottom flask, 20 parts of deionized water was added to disperse the silica gel, and a constant-pressure dropping funnel was used to add 15 parts of 15% mass fraction hydrochloric acid aqueous solution, 6 parts of 50% mass fraction glutaraldehyde aqueous solution, and the mixture was reacted at room temperature for 3 h; then 20 parts of 15% mass fraction polyvinyl alcohol aqueous solution was added, the degree of polymerization of the polyvinyl alcohol was 1700, and the alcoholysis rate was 99%, and the mixture was stirred at 35°C and 60 rpm for 6 h; the product was washed with deionized water for 3 times, and dried at room temperature for 2 h to obtain a polyhydroxyl-tipped silica gel powder; in a 70°C water bath, ferric trioxide was added to a three-necked flask, and then modified silica gel powder, ethanol cosolvent, deionized water and 36.5% mass fraction concentrated hydrochloric acid were added, the volume ratio of ferric trioxide: modified silica gel powder: ethanol cosolvent: deionized water: concentrated hydrochloric acid was 0.3:4.5:3.5:3:1; the mixture was uniformly mixed by mechanical stirring at a stirring speed of 120 rpm, and modified spherical activated carbon powder was added during the stirring process, the mass ratio of ferric trioxide: modified spherical activated carbon powder was 1:2.5, and the stirring was continued for 3 h until the formation of a gel, then the gel was aged at room temperature for 14 h, and then dried at 120°C under vacuum for 5.5 h, the vacuum degree was -0.085 Pa, to obtain a deacidification agent; the remaining steps were the same as in Example 2.

[0045] Comparative Example 4

[0046] The difference between Comparative Example 4 and Example 2 is that step (3) is changed to: in a three-necked flask, add ferric trioxide, silica gel powder, ethanol co-solvent, deionized water and 36.5% concentrated hydrochloric acid by mass fraction, the volume ratio is ferric trioxide: silica gel powder: ethanol co-solvent: deionized water: concentrated hydrochloric acid = 0.3:4.5:3.5:3:1, mix them uniformly by mechanical stirring, the stirring speed is 120 rpm, add activated carbon powder during stirring, the mass ratio of ferric trioxide: activated carbon powder is 1:2.5, stir for 3 h until the formation of gel, then age for 14 h at room temperature, and then dry at 120 °C under vacuum for 5.5 h, the vacuum degree is -0.085 Pa, to obtain the deacidifier; the remaining steps are the same as those in Example 2.

[0047] Comparative Example 5

[0048] The difference between Comparative Example 5 and Example 2 is that step (3) is changed to: weigh 4 parts of silica gel, put it in a round-bottom flask, add 20 parts of deionized water to disperse the silica gel, and then add 15 parts of 15% hydrochloric acid aqueous solution, 6 parts of 50% glutaraldehyde aqueous solution by mass fraction into the flask at room temperature for 3 h; then add 20 parts of 15% polyvinyl alcohol aqueous solution by mass fraction, the degree of polymerization of polyvinyl alcohol is 1700, and the alcoholysis rate is 99%, stir at 60 rpm at 35 °C for 6 h, wash the product with deionized water for 3 times, and dry at room temperature for 2 h to obtain the polyhydroxyl-tipped silica gel powder; in a three-necked flask, add the modified silica gel powder, ethanol co-solvent, deionized water and 36.5% concentrated hydrochloric acid by mass fraction, the volume ratio is modified silica gel powder: ethanol co-solvent: deionized water: concentrated hydrochloric acid = 4.5:3.5:3:1; mix them uniformly by mechanical stirring, the stirring speed is 120 rpm, add activated carbon powder during stirring, the mass ratio of modified silica gel powder: activated carbon powder is 6:1, stir for 3 h until the formation of gel, then age for 14 h at room temperature, and then dry at 120 °C under vacuum for 5.5 h, the vacuum degree is -0.085 Pa, to obtain the deacidifier; the remaining steps are the same as those in Example 2.

[0049] Effect Example

[0050] The performance analysis results of the deacidifier for a regenerated lubricating oil by using one of Examples 1 to 3 and Comparative Examples 1 to 5 of the present application are shown in Table 1 below.

[0051] Table 1

[0052] Deacidification rate (%) Recovery rate (%) Example 1 80.52 86.12 Example 2 81.56 86.25 Example 3 80.91 85.90 Comparative Example 1 77.25 82.65 Comparative Example 2 72.21 79.13 Comparative Example 3 65.03 78.89 Comparative Example 4 75.10 72.76 Comparative Example 5 70.45 60.51

[0053] From the experimental data comparison of the deacidification rate of the examples and the comparative examples, it can be found that the present application prepares the macroporous spherical activated carbon by carbonizing the self-made spherical resin, then the spherical activated carbon is treated by hydroxylation with sodium zincate, so that the activated carbon surface has a high concentration of hydroxyl groups, providing more adsorption and attachment sites; the activated carbon after acid treatment is mixed with anion exchange resin, and stirring makes the anion exchange resin completely and fully embedded in the spherical activated carbon, forming a dough-like material with elasticity, and then drying makes the anion exchange resin coated in the activated carbon pore, and the volume becomes smaller due to the loss of water during drying, still retaining the hollow structure of the activated carbon, while increasing the contact surface area of the resin to improve the adsorption efficiency; the ion exchange resin containing tertiary amine groups is a kind of network structure high molecular compound with ion exchange functional groups, the anion active groups in the resin are alkaline, which preferentially reacts with the acidic groups in the oil, when the acid-containing oil passes through the ion exchange resin, the petroleum acid is adsorbed on the resin within the capacity range of the resin. Secondly, the present application bonds the long chain of polyvinyl alcohol to the surface of silica gel to obtain silica gel with multi-hydroxyl groups, which can react with the carboxyl groups on the surface of naphthenic acid for adsorption, and then a hybrid deacidification agent of silica gel embedded metal nanoparticles and activated carbon is prepared by sol-gel method, and the ferric oxide is adsorbed on the surface of the spherical activated carbon, which can also react with naphthenic acid as a metal oxide to replace the salt of acidic substances, improving the overall adsorption effect of the deacidification agent. From the experimental data comparison of the recovery rate of the examples and the comparative examples, it can be found that when the anion exchange resin used in the present application adsorbs the acidic substances in the lubricating oil, it expands and fills the pores of the activated carbon, extruding the acidic substances also adsorbed in the pores of the activated carbon, so that it forms a whole, and the adsorbed acidic substances are not easy to fall off and are easy to recover. The ferric oxide makes the deacidification agent have a certain magnetic property, and it is still adsorbed by the silica gel after the reaction is completed, so that the deacidification agent is still a whole after deacidification, which is convenient for subsequent recovery and regeneration.

[0054] It is apparent for those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, but can be implemented in other concrete forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be considered in all aspects as exemplary and non-limiting, and the scope of the present application is defined by the appended claims rather than the above description, and therefore all changes falling within the meaning and range of the equivalent elements of the claims are intended to be encompassed in the present application. Any mark in the claims should not be considered as limiting the involved claims.

Claims

1. A deacidifying agent for regenerated lubricating oil, characterized in that, The deacidifying agent was prepared by embedding ferric oxide particles in modified silica gel and using modified spherical activated carbon embedded with anion exchange resin. The modified silica gel with polyhydroxy tentacles is obtained by reacting polyvinyl alcohol and silica gel. Then, the modified silica gel is used to embed ferric oxide particles and modified spherical activated carbon embedded with anion exchange resin to prepare a deacidifying agent. The method for preparing the modified spherical activated carbon embedded with anion exchange resin includes the following steps: carbonizing the spherical resin, performing hydroxylation treatment with sodium zincate, mixing with anion exchange resin to embed the anion exchange resin into the modified spherical activated carbon, and drying.

2. A method for preparing a deacidifying agent for regenerated lubricating oil, characterized in that, The preparation steps include the following: (1) In a sealed reactor, spherical resin and dichloroethane are mixed at a weight ratio of 1:1-1.5, stirred and heated at 60 rpm to 60-80℃, and kept at a constant temperature for 30 min; then 2-10 times the weight of concentrated sulfuric acid is added to the reactor, and the mixture is heated to a sulfonation temperature of 150-200℃ for 120-420 min; the mixture is cooled to room temperature naturally, and the acid solution is drained to obtain sulfonated spherical resin; the sulfonated spherical resin balls are washed once with 85% sulfuric acid aqueous solution, then once with 60% sulfuric acid aqueous solution, then once with 40% sulfuric acid aqueous solution, then once with 20% sulfuric acid aqueous solution, and finally washed with deionized water until neutral, and dried at room temperature for 5 h; the cured spherical resin is heated to 700-1000℃ under helium gas protection and carbonized for 1-2 h, and then activated with steam at 1 ml / min for 30 min to obtain spherical activated carbon; Spherical activated carbon was treated with 5% nitric acid at 75-85℃ for 1.8-2.2 h, and washed until neutral. A sodium zincate solution was prepared by mixing 0.1-2 parts sodium hydroxide with 100 parts deionized water and adding 10-12 parts zinc powder. The mixture was reacted at 38-42℃ for 0.8-1.2 h, and then filtered to remove insoluble matter, yielding a clear sodium zincate filtrate. The treated spherical activated carbon was mixed with the sodium zincate solution to form a slurry, and stirred at 60 rpm for 15-25 min at 55-65℃. The mixture was then filtered, and the stirring and filtration were repeated 2-5 times. Finally, the carbon was washed 3 times with deionized water until neutral to obtain modified spherical activated carbon. (2) The modified spherical activated carbon and the 205×7 anion exchange resin were washed in deionized water by ultrasonication at 35 kHz for 30 min and then dried at room temperature for 2 h. The dried modified spherical activated carbon, anion exchange resin and anhydrous ethanol were then mixed and ultrasonically stirred at 100-200 rpm at 20-40 kHz for 10-30 min so that the modified spherical activated carbon was fully dispersed and dissolved in anhydrous ethanol. During this process, polytetrafluoroethylene emulsion was added dropwise and ultrasonic stirring was continued for 15-30 min. The mixture was stirred in a 70℃ water bath for 60-120 min. Anhydrous ethanol with a mass of 1.2 times the mass of the mixture was added to make it into a flocculent. The mixture was ultrasonically stirred for 20-60 min under the same conditions. The filter was then collected and washed twice with anhydrous ethanol. The mixture was dried at 50℃ for 2-5 h to obtain modified spherical activated carbon embedded with anion exchange resin. (3) Weigh 3-5 parts of silica gel and place them in a round-bottom flask. Add 20 parts of deionized water to disperse the silica gel. Using a constant pressure dropping funnel, add 15 parts of 15% hydrochloric acid aqueous solution and 5-7 parts of 50% glutaraldehyde aqueous solution dropwise to the flask and react at room temperature for 3 hours. Then add 20 parts of 15% polyvinyl alcohol aqueous solution dropwise and stir at 60 rpm at 35°C for 6 hours. Wash the product three times with deionized water and dry it at room temperature for 2 hours to obtain modified silica gel powder with polyhydroxy tentacles. In a water bath at 60-80°C, add ferric oxide to a three-necked flask, then add the modified silica gel powder, co-solvent, deionized water and mass percentage of the solution. A 36.5% concentrated hydrochloric acid solution was prepared with a volume ratio of ferric oxide: modified silica gel powder: co-solvent: deionized water: concentrated hydrochloric acid = 0.2-0.4: 3-6: 2-5: 2-4:

1. The solution was mechanically stirred at 60-180 rpm until homogeneous. Modified spherical activated carbon embedded with anion exchange resin was added during stirring at a mass ratio of ferric oxide: modified spherical activated carbon embedded with anion exchange resin = 1: 0.5-4.

5. The mixture was stirred for 2-4 hours until gel formation, then aged at room temperature for 4-24 hours, followed by vacuum drying at 120℃ for 3-8 hours at a vacuum degree of -0.085 Pa to obtain the deacidifying agent.

3. The deacidifying agent for regenerated lubricating oil and its preparation method according to claim 2, characterized in that, The concentration of concentrated sulfuric acid in step (1) is 92.5%.

4. The method for preparing a regenerated lubricating oil deacidifying agent according to claim 2, characterized in that, In step (1), the solid-liquid ratio of spherical activated carbon to sodium zincate solution is 1:8-12.

5. The method for preparing a regenerated lubricating oil deacidifying agent according to claim 2, characterized in that, In step (2), the mass ratio of modified spherical activated carbon, anion exchange resin, and polytetrafluoroethylene emulsion is 5-7:1:

1.

6. The method for preparing a regenerated lubricating oil deacidifying agent according to claim 2, characterized in that, The concentration of the polytetrafluoroethylene emulsion in step (2) is 1.5 g / mL.

7. The method for preparing a regenerated lubricating oil deacidifying agent according to claim 2, characterized in that, The degree of polymerization of polyvinyl alcohol in step (3) is 1700, and the alcoholysis rate is 99%.

8. The method for preparing a regenerated lubricating oil deacidifying agent according to claim 2, characterized in that, In step (3), the co-solvent is ethanol or diethylene glycol.