Adsorbent for refining lubricating oil base oil and method for preparing the same

Abstract

The application discloses an adsorbent for lubricating oil base oil refining and a preparation method thereof. The preparation method comprises the following steps: mixing 2-amino terephthalic acid, cerium chloride, DMF and water, and then performing a hydrothermal reaction to obtain material A; activating montmorillonite by using sulfuric acid as a modifier, and then performing calcination to obtain material B; adding the material A into dichloroethane, adding acyl chloride graphene oxide and DMF, and then performing reaction at 80-110 DEG C for 30-45 h, and then performing separation to obtain material C; modifying the material B by using hexadecyl trimethyl ammonium bromide as a modifier to obtain material D; adding the material C into ethanol, uniformly performing ultrasonic dispersion, adding the material D, and then performing stirring at 35-55 DEG C for 5-12 h, and then performing suction filtration and drying, and then uniformly mixing the obtained solid product with activated carbon to obtain the adsorbent for lubricating oil base oil refining. The preparation method is simple, the obtained adsorbent has a large specific surface area, many adsorption sites and good adsorption performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adsorbent, in particular to an adsorbent for refining lubricating oil base oil and a preparation method thereof. BACKGROUND

[0002] Base oil is the main component of lubricating oil, which is generally processed from the vacuum distillate oil or light deasphalted oil of vacuum residue. Base oil contains impurities such as azo, asphalt gum, organic pigment, naphthenic acid and trace metal decomposed from additives, which have a negative effect on the oxidation stability of oil products. The presence of these impurities will deteriorate the oxidation stability of oil products, thereby affecting the service life of lubricating oil. Clay supplemental refining of lubricating oil can further remove impurities and residual solvents in oil products, reduce the content of basic nitrogen compounds in oil products, and improve the oxidation stability of oil products. At present, clay supplemental refining of lubricating oil is widely used in China. However, the adsorption performance of the existing clay is poor, which limits its application in the refining of lubricating oil base oil. SUMMARY

[0003] Based on the technical problems existing in the background technology, the present application provides an adsorbent for refining lubricating oil base oil and a preparation method thereof. The preparation method is simple, the obtained adsorbent has a large specific surface area and many adsorption sites, and has good adsorption performance for the refining of lubricating oil base oil.

[0004] The preparation method of the adsorbent for refining lubricating oil base oil provided by the present application comprises the following steps:

[0005] S1, uniformly mix 2-amino terephthalic acid, cerium chloride, DMF and water, and place them in a hydrothermal reaction kettle for hydrothermal reaction at 110-135 DEG C for 50-80 h. After the reaction is completed, filter, wash and dry to obtain material A. Add montmorillonite to dilute sulfuric acid with a mass concentration of 15-20%, activate in a boiling water bath for 3-5 h, and then perform suction filtration, water washing and drying, and then calcine to obtain material B;

[0006] S2, obtain acyl chloride of graphene oxide by acyl chloride of graphene oxide; add material A to dichloroethane, add acyl chloride of graphene oxide and DMF, and react at 80-110 DEG C for 30-45 h. After the reaction is completed, separate to obtain material C;

[0007] S3, mix material B with water, stir at 45-55 DEG C for 30-50 min, then add cetyltrimethylammonium bromide, and stir at 45-55 DEG C for 100-200 min. After water washing, filtration and drying, material D is obtained;

[0008] S4, adding material C into ethanol, uniformly dispersing by ultrasonic, then adding material D, stirring at 35-55℃ for 5-12h, suction filtering, drying, uniformly mixing the obtained solid product with activated carbon to obtain the adsorbent for refining lubricating oil base oil.

[0009] Preferably, in S1, the molar volume ratio of the 2-amino terephthalic acid, cerium chloride and DMF is 1mmol:0.3-1mmol:3-5ml.

[0010] Preferably, in S1, the volume ratio of the DMF and water is 1:2-5.

[0011] Preferably, in S1, the mass concentration of the dilute sulfuric acid is 18%; the mass volume ratio of the montmorillonite and dilute sulfuric acid is 1g:3-5ml.

[0012] Preferably, in S1, the temperature of the calcination is 150-180℃, and the time is 80-200min.

[0013] Preferably, in S2, the weight ratio of the material A and acylated graphene oxide is 1:1-2.5.

[0014] Preferably, in S3, the weight of the material B is 2-3% of the weight of water; the weight of the cetyltrimethylammonium bromide is 0.3-0.8 times of the weight of the material B.

[0015] Preferably, in S4, the weight ratio of the material C and material D is 1:3-6.

[0016] Preferably, in S4, the weight ratio of the solid product and activated carbon is 5-10:1-3.

[0017] The application further provides an adsorbent for refining lubricating oil base oil, which is prepared by the method.

[0018] The preparation method of the adsorbent for refining lubricating oil base oil provided by the application comprises the following steps: DETAILED DESCRIPTION

[0019] The technical scheme of the application will be described in detail below through specific examples.

[0020] Example 1

[0021] The preparation method of the adsorbent for refining lubricating oil base oil provided by the application comprises the following steps:

[0022] S1, 2-amino terephthalic acid, cerium chloride, DMF and water are uniformly mixed, wherein the molar volume ratio of the 2-amino terephthalic acid, cerium chloride and DMF is 1 mmol: 0.3 mmol: 5 ml, the volume ratio of the DMF and water is 1:2, and the mixture is placed in a hydrothermal reaction kettle and subjected to hydrothermal reaction at 135 DEG C for 50 h. After the reaction is completed, filtration, washing and drying are performed to obtain material A. Montmorillonite is added to 20% dilute sulfuric acid, wherein the mass-volume ratio of the montmorillonite and the dilute sulfuric acid is 1 g: 3 ml, and the mixture is activated in a boiling water bath for 3 h. After suction filtration, water washing and drying, the mixture is calcined at 170 DEG C for 80 min to obtain material B.

[0023] S2, acyl chloride of graphene oxide is obtained by acyl chlorination of graphene oxide. Material A is added to dichloroethane, and acyl chloride of graphene oxide and DMF are added, wherein the weight ratio of the material A and the acyl chloride of graphene oxide is 1:1. The mixture is reacted at 90 DEG C for 45 h. After the reaction is completed, material C is obtained by separation.

[0024] S3, material B is mixed with water, and the weight of the material B is 3% of the weight of the water. The mixture is stirred at 45 DEG C for 50 min. Then, cetyltrimethylammonium bromide is added, and the weight of the cetyltrimethylammonium bromide is 0.3 times the weight of the material B. The mixture is stirred at 45 DEG C for 200 min. After water washing, filtration and drying, material D is obtained.

[0025] S4, the material C is added to ethanol, ultrasonic dispersion is uniform, then material D is added, wherein the weight ratio of the material C, the material D is 1:6, stirring is carried out at 38 DEG C for 8h, extraction filtration, drying, the obtained solid product is mixed with activated carbon to obtain the adsorbent for lubricating oil base oil refining, wherein the weight ratio of the solid product and activated carbon is 5:2.

[0026] Example 2

[0027] The application provides a preparation method of the adsorbent for lubricating oil base oil refining.

[0028] S1, 2-amino terephthalic acid, cerium chloride, DMF and water are uniformly mixed, wherein the molar volume ratio of the 2-amino terephthalic acid, cerium chloride and DMF is 1 mmol: 1 mmol: 3 ml, the volume ratio of the DMF and water is 1:5, the mixture is placed in a hydrothermal reaction kettle, and hydrothermal reaction is carried out at 110 DEG C for 80h, then filtration, washing and drying are carried out to obtain material A; montmorillonite is added to dilute sulfuric acid with a mass concentration of 15%, wherein the mass-volume ratio of the montmorillonite and dilute sulfuric acid is 1g:5ml, activation is carried out in a boiling water bath for 5h, then extraction filtration, water washing and drying are carried out, and then calcination is carried out at 150 DEG C for 200min to obtain material B;

[0029] S2, acyl chloride is obtained by acyl chloride of graphene oxide; material A is added to dichloroethane, acyl chloride of graphene oxide and DMF are added, wherein the weight ratio of the material A and acyl chloride of graphene oxide is 1:2.5, reaction is carried out at 110 DEG C for 30h, then separation is carried out to obtain material C;

[0030] S3, material B is mixed with water, wherein the weight of the material B is 2% of the weight of water, stirring is carried out at 50 DEG C for 40min, then cetyltrimethylammonium bromide is added, wherein the weight of the cetyltrimethylammonium bromide is 0.8 times of the weight of the material B, stirring is carried out at 50 DEG C for 150min, then water washing, filtration and drying are carried out to obtain material D;

[0031] S4, the material C is added to ethanol, ultrasonic dispersion is uniform, then material D is added, wherein the weight ratio of the material C, the material D is 1:3, stirring is carried out at 35 DEG C for 12h, extraction filtration, drying, the obtained solid product is mixed with activated carbon to obtain the adsorbent for lubricating oil base oil refining, wherein the weight ratio of the solid product and activated carbon is 10:1.

[0032] Example 3

[0033] The application provides a preparation method of the adsorbent for lubricating oil base oil refining.

[0034] S1, 2-amino terephthalic acid, cerium chloride, DMF and water are uniformly mixed, wherein the molar volume ratio of 2-amino terephthalic acid, cerium chloride and DMF is 1 mmol: 0.5 mmol: 3 ml, the volume ratio of DMF and water is 1:4, placed in a hydrothermal reaction kettle, hydrothermal reaction is carried out at 130 DEG C for 60 h, after reaction, filtration, washing and drying to obtain material A; montmorillonite is added into dilute sulfuric acid with mass concentration of 18%, wherein the mass-volume ratio of montmorillonite and dilute sulfuric acid is 1g:3ml, activated in boiling water bath for 3h, after suction filtration, water washing and drying, calcination is carried out at 180 DEG C for 80 min to obtain material B;

[0035] S2, acyl chloride of graphene oxide is obtained by acyl chloride of graphene oxide; material A is added into dichloroethane, acyl chloride of graphene oxide and DMF are added, wherein the weight ratio of material A and acyl chloride of graphene oxide is 1:2.2, reaction is carried out at 95 DEG C for 40 h, after reaction, material C is obtained by separation;

[0036] S3, material B is mixed with water, wherein the weight of material B is 2.6% of the weight of water, stirred at 55 DEG C for 30 min, then cetyltrimethylammonium bromide is added, wherein the weight of cetyltrimethylammonium bromide is 0.7 times of the weight of material B, stirred at 52 DEG C for 120 min, water washing, filtration and drying to obtain material D;

[0037] S4, material C is added into ethanol, ultrasonic dispersion is carried out uniformly, then material D is added, wherein the weight ratio of material C and material D is 1:4, stirred at 55 DEG C for 5 h, suction filtration and drying, the obtained solid product is uniformly mixed with activated carbon to obtain the adsorbent for lubricating oil base oil refining; wherein the weight ratio of the solid product and activated carbon is 7:3.

[0038] Example 4

[0039] The preparation method of the adsorbent for lubricating oil base oil refining provided by the application comprises the following steps:

[0040] S1, 2-amino terephthalic acid, cerium chloride, DMF and water are uniformly mixed, wherein the molar volume ratio of 2-amino terephthalic acid, cerium chloride and DMF is 1 mmol: 0.7 mmol: 4 ml, the volume ratio of DMF and water is 1:3, placed in a hydrothermal reaction kettle, hydrothermal reaction is carried out at 118 DEG C for 70 h, after reaction, filtration, washing and drying to obtain material A; montmorillonite is added into dilute sulfuric acid with mass concentration of 16%, wherein the mass-volume ratio of montmorillonite and dilute sulfuric acid is 1g:4ml, activated in boiling water bath for 4h, after suction filtration, water washing and drying, calcination is carried out at 155 DEG C for 170 min to obtain material B;

[0041] S2, acyl chlorination of graphene oxide is obtained; material A is added into dichloroethane, acyl chlorinated graphene oxide and DMF are added, wherein the weight ratio of the material A, acyl chlorinated graphene oxide is 1:1.7, reaction is carried out at 105 DEG C for 38 h, and material C is obtained after separation;

[0042] S3, material B is mixed with water, wherein the weight of the material B is 2.5% of the weight of water, stirring is carried out at 48 DEG C for 38 min, then cetyltrimethylammonium bromide is added, wherein the weight of the cetyltrimethylammonium bromide is 0.4 times of the weight of the material B, stirring is carried out at 48 DEG C for 140 min, water washing, filtration and drying are carried out to obtain material D;

[0043] S4, material C is added into ethanol, ultrasonic dispersion is carried out uniformly, then material D is added, wherein the weight ratio of the material C, material D is 1:5, stirring is carried out at 43 DEG C for 7 h, suction filtration and drying are carried out, the obtained solid product is mixed with activated carbon uniformly to obtain the adsorbent for lubricating oil base oil refining; wherein the weight ratio of the solid product and activated carbon is 6:1.

[0044] Example 5

[0045] The application provides a preparation method of an adsorbent for lubricating oil base oil refining.

[0046] S1, 2-amino terephthalic acid, cerium chloride and DMF are uniformly mixed with water, wherein the molar volume ratio of the 2-amino terephthalic acid, cerium chloride and DMF is 1 mmol:0.8 mmol:5 ml, the volume ratio of the DMF and water is 1:4.3, the mixture is placed in a hydrothermal reaction kettle, hydrothermal reaction is carried out at 125 DEG C for 72 h, filtration, washing and drying are carried out after the reaction to obtain material A; montmorillonite is added into dilute sulfuric acid with a mass concentration of 18%, wherein the mass-volume ratio of the montmorillonite and dilute sulfuric acid is 1 g:4 ml, the mixture is activated in a boiling water bath for 3.8 h, suction filtration, water washing and drying are carried out, and then the mixture is calcined at 175 DEG C for 130 min to obtain material B;

[0047] S2, acyl chlorination of graphene oxide is obtained; material A is added into dichloroethane, acyl chlorinated graphene oxide and DMF are added, wherein the weight ratio of the material A, acyl chlorinated graphene oxide is 1:1.7, reaction is carried out at 105 DEG C for 38 h, and material C is obtained after separation;

[0048] S3, mixing material B with water, wherein the weight of material B is 2.5% of the weight of water, stirring at 55℃ for 38min, then adding cetyl trimethyl ammonium bromide, wherein the weight of cetyl trimethyl ammonium bromide is 0.6 times of the weight of material B, stirring at 55℃ for 180min, washing with water, filtering, and drying to obtain material D;

[0049] S4, adding material C into ethanol, uniformly dispersing by ultrasonic, then adding material D, wherein the weight ratio of material C and material D is 1:5.2, stirring at 45℃ for 9h, suction filtering, drying, uniformly mixing the obtained solid product with activated carbon to obtain the adsorbent for refining lubricating base oil; the weight ratio of the solid product and activated carbon is 7:2.5.

[0050] Comparative Example 1

[0051] The difference from Example 5 is only that the graphene oxide is not modified, and the graphene oxide is used instead of material C in Example 5; specifically comprising the following steps:

[0052] S1, adding montmorillonite into dilute sulfuric acid with a mass concentration of 18%, wherein the mass-volume ratio of montmorillonite and dilute sulfuric acid is 1g:4ml, activating in a boiling water bath for 3.8h, suction filtering, washing with water, drying, and then calcining at 175℃ for 130min to obtain material B;

[0053] S2, mixing material B with water, wherein the weight of material B is 2.5% of the weight of water, stirring at 55℃ for 38min, then adding cetyl trimethyl ammonium bromide, wherein the weight of cetyl trimethyl ammonium bromide is 0.6 times of the weight of material B, stirring at 55℃ for 180min, washing with water, filtering, and drying to obtain material D;

[0054] S3, adding graphene oxide into ethanol, uniformly dispersing by ultrasonic, then adding material D, wherein the weight ratio of graphene oxide and material D is 1:5.2, stirring at 45℃ for 9h, suction filtering, drying, uniformly mixing the obtained solid product with activated carbon to obtain the adsorbent for refining lubricating base oil; the weight ratio of the solid product and activated carbon is 7:2.5.

[0055] Comparative Example 2

[0056] The difference from Example 5 is only that it does not include the modification step S3, but directly uses material B obtained in S2 to replace material D in Example 5 to react with material C.

[0057] Comparative Example 3

[0058] The preparation comprises the following steps: adding graphene oxide into ethanol, uniformly dispersing by ultrasonic, then adding sulfuric acid activated montmorillonite, wherein the weight ratio of the graphene oxide and the sulfuric acid activated montmorillonite is 1:5.2, stirring at 45 DEG C for 9h, suction filtration, drying, mixing the obtained solid product with activated carbon to obtain the adsorbent for refining the lubricating oil base oil; the weight ratio of the solid product and the activated carbon is 7:2.5; wherein the sulfuric acid activated montmorillonite is prepared according to the following process: adding montmorillonite into dilute sulfuric acid with a mass concentration of 18%, wherein the mass-volume ratio of the montmorillonite and the dilute sulfuric acid is 1g:4ml, activating in a boiling water bath for 3.8h, suction filtration, water washing, drying, and then calcining at 175 DEG C for 130min.

[0059] The adsorbents of example 5 and comparative examples 1-3 are respectively used for adsorbing base oil raw material oil with total oxygen content of 1.8%, color >8.0, basic nitrogen content of 81ppm, and rotary oxygen bomb of 142min, the mixed adsorption temperature is 200 DEG C, the mixed adsorption time is 20min, and the mass ratio of adsorbent to oil is 0.04:1; it is tested that the total oxygen content of the oil treated by the adsorbent of example 5 is 0.2%, the color is <0.5, the basic nitrogen content is 9ppm, and the rotary oxygen bomb is 243min, while the total oxygen content of the oil treated by the adsorbents of comparative examples 1-3 is 0.5-0.8%, the color is 3.5-5.5, the basic nitrogen content is >21ppm, and the rotary oxygen bomb is <208min; wherein the color is measured by petroleum product color determination method GB / T6540, the oxygen content is measured by standard test method for determining total oxygen content in gasoline and methanol fuels by reduction pyrolysis ASTM D5622, and the basic nitrogen content is measured according to national standard SH / T0413-1992.

[0060] The above merely describes the preferred embodiments of the present application, but the protection scope of the present application is not limited to this, any person skilled in the art can make equivalent substitution or change according to the technical scheme and the inventive concept of the present application within the technical range disclosed by the present application, which should be covered in the protection scope of the present application.

Claims

1. A method for preparing an adsorbent for refining lubricating oil base oil, characterized in that, Includes the following steps: S1. Mix 2-aminoterephthalic acid, cerium chloride, DMF and water evenly, place in a hydrothermal reactor, and carry out hydrothermal reaction at 110-135℃ for 50-80h. After the reaction is completed, filter, wash and dry to obtain material A; add montmorillonite to dilute sulfuric acid with a mass concentration of 15-20%, activate in boiling water bath for 3-5h, filter, wash with water, dry and calcine to obtain material B; S2. Acyl chloride of graphene oxide to obtain acyl chloride graphene oxide; add material A to dichloroethane, add acyl chloride graphene oxide and DMF, react at 80-110℃ for 30-45h, and separate material C after the reaction is completed. S3. Mix material B with water and stir at 45-55℃ for 30-50 minutes. Then add hexadecyltrimethylammonium bromide and stir at 45-55℃ for 100-200 minutes. Wash with water, filter and dry to obtain material D. S4. Add material C to ethanol, disperse it evenly by ultrasonication, then add material D, stir at 35-55℃ for 5-12 hours, filter and dry, and mix the obtained solid product evenly with activated carbon to obtain the adsorbent for refining lubricating oil base oil.

2. The method for preparing the adsorbent for refining lubricating oil base oil according to claim 1, characterized in that, In S1, the molar volume ratio of 2-aminoterephthalic acid, cerium chloride, and DMF is 1 mmol: 0.3-1 mmol: 3-5 ml.

3. The method for preparing the adsorbent for refining lubricating oil base oil according to claim 1, characterized in that, In S1, the volume ratio of DMF to water is 1:2-5.

4. The method for preparing the adsorbent for refining lubricating oil base oil according to claim 1, characterized in that, In S1, the mass concentration of the dilute sulfuric acid is 18%; the mass-volume ratio of the montmorillonite to the dilute sulfuric acid is 1g:3-5ml.

5. The method for preparing the adsorbent for refining lubricating oil base oil according to claim 1, characterized in that, In S1, the calcination temperature is 150-180℃ and the time is 80-200 min.

6. The method for preparing the adsorbent for refining lubricating oil base oil according to claim 1, characterized in that, In S2, the weight ratio of material A to acyl-chlorinated graphene oxide is 1:1-2.

5.

7. The method for preparing the adsorbent for refining lubricating oil base oil according to claim 1, characterized in that, In S3, the weight of material B is 2-3% of the weight of water; the weight of hexadecyltrimethylammonium bromide is 0.3-0.8 times the weight of material B.

8. The method for preparing the adsorbent for refining lubricating oil base oil according to claim 1, characterized in that, In S4, the weight ratio of material C to material D is 1:3-6.

9. The method for preparing the adsorbent for refining lubricating oil base oil according to any one of claims 1-8, characterized in that, In S4, the weight ratio of the solid product to activated carbon is 5-10:1-3.

10. An adsorbent for refining lubricating oil base oil, characterized in that, It is prepared by the method for preparing adsorbent for refining lubricating oil base oil as described in any one of claims 1-9.