阅读说明：本技术 利用废菜籽油和三嗪修饰的氧化镧制备钙基润滑脂的方法 (Method for preparing calcium-based lubricating grease by using waste rapeseed oil and triazine-modified lanthanum oxide ) 是由 祖庆年 于 2020-06-10 设计创作，主要内容包括：本发明公开了一种利用废菜籽油和三嗪修饰的氧化镧制备钙基润滑脂的方法,包括以下步骤,经过酸洗、水洗、碱洗和脱色后制备成精制废弃菜籽油,添加三嗪衍生物修饰的氧化镧,再皂化成钙基润滑脂,整个制备条件简单,条件易于控制,产率高；本发明制备的钙基润滑脂可以单独使用,也可以添加其它的添加剂使用,具有良好的摩擦学性能；本发明制备的钙基润滑脂适用于在工业加工,轴承润滑,齿轮润滑,钢丝绳和连轴接润滑等场合,具有良好的极压、抗磨性能和减摩性能。(The invention discloses a method for preparing calcium-based lubricating grease by using waste rapeseed oil and triazine-modified lanthanum oxide, which comprises the following steps of preparing refined waste rapeseed oil after acid washing, water washing, alkali washing and decoloring, adding triazine derivative-modified lanthanum oxide, and saponifying into calcium-based lubricating grease, wherein the whole preparation condition is simple, the condition is easy to control, and the yield is high; the calcium-based lubricating grease prepared by the invention can be used independently, and can also be added with other additives for use, so that the lubricating grease has good tribological performance; the calcium-based lubricating grease prepared by the invention is suitable for occasions such as industrial processing, bearing lubrication, gear lubrication, steel wire rope and connecting shaft connection lubrication and the like, and has good extreme pressure, wear resistance and antifriction performance.)

1. A method for preparing calcium-based lubricating grease by utilizing waste rapeseed oil and triazine-modified lanthanum oxide is characterized by comprising the following steps:

step one, refining waste rapeseed oil: taking waste rapeseed oil, carrying out suction filtration to remove solid impurities, adding phosphoric acid into the suction-filtered waste rapeseed oil for degumming, standing, adding water under stirring, carrying out centrifugal separation, then adding a NaOH solution into an upper oil sample, adding a NaCl solution, standing, adding distilled water under stirring, carrying out centrifugal dehydration, taking a supernatant, heating the supernatant for dehydration, adding activated carbon for decolorization, and carrying out suction filtration while hot to obtain refined waste oil;

step two, triazine modified lanthanum oxide: placing nanometer lanthanum oxide (20-50nm) in a reaction bottle, adding mixed liquid of triazine, tween 60, span 20, span 80 and OP-10, stirring at constant temperature, adding into refined waste rapeseed oil, stirring and performing ultrasonic treatment to obtain mixed liquid of triazine modified nanometer lanthanum oxide;

step three, saponification and fat forming: placing refined waste rapeseed oil and 12-hydroxystearic acid into a reaction bottle, introducing N₂And (2) anti-oxidation, heating to be completely molten, dropwise adding CaO emulsion while stirring, adding a mixed solution containing triazine modified nano lanthanum oxide, heating and saponifying, supplementing refined waste rapeseed oil during saponification so as to reduce the viscosity of the system, heating to dewater after saponification is finished, continuously adding refined waste rapeseed oil after moisture is removed, heating to carry out high-temperature refining, and stopping heating when the system is in a molten gel state to obtain the lubricating grease.

2. The method for preparing the calcium-based lubricating grease by using the waste rapeseed oil and the triazine-modified lanthanum oxide according to claim 1, wherein in the step one, the acid-washing amount of phosphoric acid is 0.8-1.0% of the weight of the waste rapeseed oil, the water-washing amount is 8-12% of the weight of the waste rapeseed oil, the alkali-washing amount is the amount of the phosphoric acid which is not reacted in the neutralization process, the decolorizing time of the activated carbon is 0.5-1 h, and the decolorizing temperature is 100-110 ℃.

3. The method for preparing calcium-based lubricating grease by using waste rapeseed oil and triazine-modified lanthanum oxide according to claim 1, wherein the ratio of triazine, tween 60, span 20, span 80 and OP-10 in the second step is 10: 3: 2: 1: 2, the ratio of nano lanthanum oxide (20-50nm) to the mixed solution is 1:10-30, and the mixture is stirred in a water bath kettle at a constant temperature of 70-95 ℃ for 0.5-1.5 h; the ratio of the mixed liquid containing the triazine modified nano lanthanum oxide particles to the refined waste rapeseed oil is 1:8-13, stirring is carried out for 2 hours, then ultrasonic treatment is carried out for 0.5 hour, and the stirring and the ultrasonic treatment are repeated for 3-4 times, so that the mixed liquid of the triazine modified nano lanthanum oxide is obtained.

4. The method for preparing calcium-based lubricating grease by using waste rapeseed oil and triazine-modified lanthanum oxide according to claim 1, wherein 12-hydroxystearic acid and refined waste rapeseed oil in the third step are prepared into 5% emulsion with the ratio of 1:15-25 and the ratio of 12-hydroxystearic acid to CaO being 5-10: 1; the saponification temperature is 110-120 ℃, the saponification time is 0.5-1 h, and the refining temperature is 230-240 ℃.

Technical Field

The invention relates to a method for preparing lubricating grease, in particular to a method for preparing calcium-based lubricating grease by using waste rapeseed oil and triazine-modified lanthanum oxide.

Background

Rapeseed oil consumed in China in years is 430-480 ten thousand tons, about 20% of rapeseed oil becomes waste in the using process, and the waste contains a large amount of organic matters, so that the direct discharge is easy to pollute the environment. At present, the waste rapeseed oil in China is not well utilized, and on the contrary, a part of the waste rapeseed oil is changed into illegal cooking oil to be returned to a dining table, so that the food safety is harmed.

In the aspect of conversion and utilization of waste rapeseed oil, soap powder or feed oil is mainly manufactured before. In some researches, rapeseed oil and various short-chain alcohols are subjected to alcoholysis reaction to generate corresponding fatty acid methyl ester or ethyl ester, the performance of the fatty acid methyl ester or ethyl ester reaches the standard of fossil raw material diesel oil, meanwhile, the rapeseed oil is catalyzed into biodiesel in some researches, China builds a production device which takes waste cooking oil and waste oil residue as raw materials and produces one million tons of diesel oil every year in China in Hebei in 2001, and the product meets the quality standard of national light diesel oil. One part is to use the waste rapeseed oil as a chemical basic raw material, such as a nonanoic acid plasticizer and the like.

In recent years, the grease industry in China is rapidly developed, and has become an important support for the chemical industry in China. In 2018, 72 Chinese grease manufacturers before the Chinese ranking produce about 38.3 million tons of grease in total, and the grease has complete varieties including lithium grease, calcium grease, aluminum grease, bentonite grease and the like, and can basically meet the requirements of various industries in China. Grease yields in china in 2018 still account for nearly 1/3% of the global total yield, chinese market lime soap thickeners account for nearly 15% of all thickeners, and less than 10% in 2015. The market share of the lithium soap thickener in the Chinese market is reduced from over 80 percent to below 74 percent.

Although the grease in China has large yield and complete varieties, the high-end grease needs to be imported, has high performance and low yield of the grease (such as complex lithium-based, aluminum-based and calcium-based greases, complex sulfonate grease, polyurea-based grease and the like) with high dropping point and long service life.

The base oil in the grease is generally mineral oil in the past, and is partially synthetic oil at present, so that the preparation of the grease is limited due to the limitation of petroleum resources.

Triazine derivatives are well applied as lubricating oil additives, and the main reason for generating good lubricating performance is that triazine rings can form a good adsorption film on the metal contact surface, and the boundary film has good tribological performance.

Rare earth compounds are limited as lubricating oil additives due to poor oil solubility, and the rare earth compounds are dissolved into base oil by adding a large amount of surfactant, but the stability of the rare earth compounds still has certain problems.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a method for preparing calcium-based lubricating grease by using waste rapeseed oil and triazine-modified lanthanum oxide, the waste rapeseed oil is used as a raw material to prepare the calcium-based lubricating grease, and the finished product has good extreme pressure, wear resistance and antifriction performance.

In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing calcium-based lubricating grease by utilizing waste rapeseed oil and triazine-modified lanthanum oxide comprises the following steps:

step one, refining waste rapeseed oil: taking waste rapeseed oil, carrying out suction filtration to remove solid impurities, adding phosphoric acid into the suction-filtered waste rapeseed oil at 50-70 ℃ for degumming, standing, adding water under stirring, carrying out centrifugal separation, then taking an upper oil sample, adding a NaOH solution, adding a NaCl solution, standing, adding distilled water under stirring, carrying out centrifugal dehydration, taking a supernatant, heating the supernatant for dewatering, adding activated carbon for decolorization, and carrying out suction filtration while hot to obtain refined waste oil;

step two, triazine modified lanthanum oxide: placing nanometer lanthanum oxide (20-50nm) in a reaction bottle, adding mixed liquid of triazine, tween 60, span 20, span 80 and OP-10, stirring at constant temperature, adding into refined waste rapeseed oil, stirring and performing ultrasonic treatment to obtain mixed liquid of triazine modified nanometer lanthanum oxide;

step three, saponification and fat forming: placing refined waste rapeseed oil and 12-hydroxystearic acid into a reaction bottleGeneral formula N₂Anti-oxidation, heating to complete melting, dropwise adding CaO emulsion while stirring, a mixed solution containing triazine modified nano lanthanum oxide, heating for saponification, and supplementing refined waste rapeseed oil in the process to reduce the viscosity of the system so that the reaction can be normally carried out; and (3) heating for dehydration after saponification is finished, continuously adding refined waste rapeseed oil after moisture is completely removed, heating for high-temperature refining, and stopping heating when the system is in a molten gel state to obtain the lubricating grease.

Further, in the first step, the acid-washing phosphoric acid amount is 0.8-1.0% of the weight of the waste rapeseed oil, the water-washing water amount is 8-12% of the weight of the waste rapeseed oil, the alkali-washing amount is the amount of the phosphoric acid which is not reacted in the neutralization process, the decolorizing time of the activated carbon is 0.5-1 h, and the decolorizing temperature is 100-110 ℃.

Further, in the second step, the ratio of the triazine, the Tween 60, the span 20, the span 80 and the OP-10 is 10: 3: 2: 1: 2, the ratio of the nano lanthanum oxide (20-50nm) to the mixed solution is 1:10-30, and the mixture is stirred in a water bath kettle at a constant temperature of 70-95 ℃ for 0.5-1.5 h; the ratio of the mixed liquid containing the triazine modified nano lanthanum oxide particles to the refined waste rapeseed oil is 1:8-13, stirring is carried out for 2 hours, then ultrasonic treatment is carried out for 0.5 hour, and the stirring and the ultrasonic treatment are repeated for 3-4 times, so that the mixed liquid of the triazine modified nano lanthanum oxide is obtained.

Further, in the third step, 12-hydroxystearic acid and refined waste rapeseed oil are mixed in a ratio of 1:15-25, and 12-hydroxystearic acid and CaO are mixed in a ratio of 5-10:1 to prepare 5% emulsion; the saponification temperature is 110-120 ℃, the saponification time is 0.5-1 h, and the refining temperature is 230-240 ℃.

Compared with the prior art, the method has the advantages that the waste rapeseed oil is used as a raw material, the refined waste rapeseed oil is prepared after acid washing, water washing, alkali washing and decoloring, the triazine derivative modified lanthanum oxide is added, and the calcium-based lubricating grease is prepared by saponification, so that the whole preparation condition is simple, the condition is easy to control, and the yield is high; the calcium-based lubricating grease prepared by the invention can be used independently, and can also be added with other additives for use, so that the lubricating grease has good tribological performance; the calcium-based lubricating grease prepared by the invention is suitable for occasions such as industrial processing, bearing lubrication, gear lubrication, steel wire rope and connecting shaft connection lubrication and the like, and has good extreme pressure, wear resistance and antifriction performance.

Detailed Description

The present invention will be further described with reference to the following examples.

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

A method for preparing calcium-based lubricating grease by utilizing waste rapeseed oil and triazine-modified lanthanum oxide comprises the following steps:

step one, refining waste rapeseed oil: taking a certain amount of waste rapeseed oil, carrying out suction filtration to remove solid impurities, adding phosphoric acid which is 0.8-1.0% of the weight of the waste rapeseed oil into the waste rapeseed oil at 50-70 ℃ for degumming, standing, adding water which is 8-12% of the weight of the waste rapeseed oil under stirring, carrying out centrifugal separation, taking an upper oil sample, adding NaOH solution, adding NaCl solution, adding distilled water under stirring, standing, carrying out centrifugal dehydration, taking a supernatant, heating the supernatant for removing water, adding activated carbon for decolorization for 0.5-1 h, carrying out hot suction filtration at the decolorization temperature of 100-110 ℃ to obtain refined waste oil;

step two, triazine modified lanthanum oxide: placing nanometer lanthanum oxide (20-50nm) in a reaction bottle, adding mixed liquor of triazine, tween 60, span 20, span 80 and OP-10 in a ratio of 10: 3: 2: 1: 2, stirring at a constant temperature of 70-95 ℃ for 0.5-1.5h in a water bath kettle at a constant temperature of 1-30 ℃ to obtain mixed liquor containing triazine modified nanometer lanthanum oxide particles, adding the mixed liquor into refined waste rapeseed oil, wherein the ratio of the mixed liquor to the refined waste rapeseed oil is 1:8-13, stirring for 2h and then carrying out ultrasonic treatment for 0.5h, and repeatedly stirring and carrying out ultrasonic treatment for 3-4 times to obtain mixed liquor of triazine modified nanometer lanthanum oxide;

step three, saponification and fat forming: placing refined waste rapeseed oil and 12-hydroxystearic acid into a reaction bottle, and placing 12-hydroxystearic acid and refined waste vegetablesThe proportion of the seed oil is 1:15-25, and N is introduced₂And (2) anti-oxidation, heating to complete melting, dropwise adding a mixed solution of CaO emulsion and triazine-modified nano lanthanum oxide while stirring, preparing 5% of emulsion from 12-hydroxystearic acid and CaO emulsion at a ratio of 5-10:1, heating for saponification, wherein the saponification temperature is 110-120 ℃, supplementing refined waste rapeseed oil for continuous saponification, the saponification temperature is 180-190 ℃, so that the viscosity of the system is reduced, so that the reaction can be normally carried out, heating for dehydration after saponification is finished, continuously adding refined waste rapeseed oil after moisture is removed, heating for high-temperature refining, wherein the high-temperature refining temperature is 230-240 ℃, and stopping heating when the system is in a molten gel state, thus obtaining the lubricating grease.