CN103275812B - Method for preparing base oil of lubricating oil from waste animal and vegetable oil - Google Patents
Method for preparing base oil of lubricating oil from waste animal and vegetable oil Download PDFInfo
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Abstract
The invention relates to a method for preparing base oil of lubricating oil from waste animal and vegetable oil. The method comprises the following step that waste animal and vegetable oil is subjected to deacidification and methyl esterification treatment to form fatty acid methyl ester; and the fatty acid methyl ester and polyhydric alcohol undergo a transesterification reaction in the presence of one or more organic tin catalysts to produce polyol ester, wherein the one or more organic tin catalysts are selected from monobutyltin, stannous octoate, dimethyltin, dioctyltin and tetraphenyltin. The method adopts easily available raw materials, has allows mild technical conditions. The base oil of lubricating oil has good lubricity and biodegradability. The method can realize comprehensive utilization of waste animal and vegetable oil, can change waste animal and vegetable oil into values, and can improve safety of catering and food industries.
Description
Technical field
The present invention relates to a kind of preparation method of the polyol ester as lubricant base, belong to the synthetic field of polyol ester, particularly a kind ofly take waste oils and fats and prepare the method for environment-friendly type polyol Ester Lubricating Oil base oil as substrate.
technical background
Polyol ester is the compound that the class of carrying out esterification generation by organic acid and polyvalent alcohol can be used as lubricant, it has tribological property and the distinctive biological degradability of good high temperature performance, low volatility, excellence, be to have one of synthetic lubricant of application potential most, its market requirement has entered the rapid growth phase at present.Yet due to the impact of domestic high-quality organic acid scarcity of raw material, domestic market is mainly external product monopolization.The growing interest to environmental protection along with the lasting surging of world market crude oil price and people, the preparation of industrialization technology of development waste oils and fats polylol ester is extremely important.The annual waste oils and fats producing of China is about 3,000,000 tons, at present owing to there is no the processing technology of other high added value, often by illegal retailer, after simple process, is flowed into once again dining table, has had a strong impact on people's health.Patent CN101113362A provides a kind of method of biofuel of preparing by alcoholysis and esterification low cost with waste oils and fats; A kind of method of preparing biodiesel by ester interchange is provided in patent CN101586042A.Although the utilization that preparation biofuel can solve part waste oils and fats, catalyzer used is mainly bronsted lowry acids and bases bronsted lowry, and an acidic catalyst reaction times is longer, easily etching apparatus; Basic catalyst catalytic efficiency is high, but require very strict to waste oils and fats moisture and acid number, so remove the free acid of waste oils and fats, it is the prerequisite of using basic catalyst, the method of waste oils and fats deacidification has alkaline process and acid catalyzed esterification method, easily there is saponification phenomenon in alkaline process, acid system is repeatedly esterification of intermittent type, complex operation.
The pure vegetable and animals oils of take is prepared polyol ester as starting ester exchange process and is had been reported both at home and abroad, generally be divided into two steps, first by vegetables oil esterification, after gained fatty acid methyl ester is refined, under the effect of organic solvent system catalyst neutralisation, carry out transesterify with polyvalent alcohol and obtain polyol ester.(the Gryglewicz S such as Gryglewicz, Piechocki W.Grvglewicz G.Preparation of polyol esters based vegetable and animal fats.Bioresource Technology, 2003, 87, 35) studied respectively rapeseed oil, the natural animal-plant such as sweet oil and lard grease reacts the process that generates polyol ester with neopentyl glycol and TriMethylolPropane(TMP), (the Ghazi M such as Ghazi M, Resin G, Azni L.Bioenergy II:Production of biodegradable lubricant from Jatropha curcas and trimethylolpropane .International Journal of Chemical Reactor Engineering, 2009, 7, 68) with jatropha curcas oil, by the method for transesterify, prepared TriMethylolPropane(TMP) polyol ester.Transesterification catalyst is mainly methylate and lipase, and methylate catalyzer is very strict to ingredient requirement, and the reaction times is longer; Lipase-catalyzed dose of expensive and low conversion rate.And take the waste oils and fats of complicated component, as substrate ester-interchange method, prepare polyol ester and yet there are no relevant report.
Summary of the invention
The object of the present invention is to provide and a kind ofly take waste oils and fats and prepare the method for polyol Ester Lubricating Oil base oil as substrate.
The method of utilizing waste oils and fats base to prepare lubricant base of the present invention, comprise to waste oils and fats deacidify, esterification processes and to obtain fatty acid methyl ester, then under condition fatty acid methyl ester and polyvalent alcohol being existed at organotin catalysts, carry out transesterification reaction and obtain polyol ester, wherein organotin catalysts is one or more mixtures in Monobutyltin, stannous octoate, tin methide, dioctyl tin, tin tetraphenyl.
The polyvalent alcohol using is neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP), ditrimethylolpropane, tetramethylolmethane, dipentaerythritol.
The polyol ester that the present invention obtains is DOPCP
, trimethylolethane ester
, trihydroxymethylpropanyl ester
, ditrimethylolpropane ester
, pentaerythritol ester
, bis(pentaerythritolester)
, wherein, the saturated fatty chain hydrocarbon that R is C12-C20 or unsaturated fatty acids chain hydrocarbon, and in R, the ratio of each fatty chain hydrocarbon is: C16 is that 20%-35%, C18 are 50%-75%, all the other are other fatty chain hydrocarbons in C12-C20.
The concrete steps of the method that waste oils and fats base prepares lubricant base of utilizing of the present invention are:
(1) waste oils and fats is removed to acid-respons
In the reactor of reflux exchanger is housed, add waste oils and fats, methyl alcohol and an acidic catalyst after purification, at the temperature of 65-80 ℃, react 1-4h.
Wherein the mass ratio of waste oils and fats and methyl alcohol is 4-7:1, and the consumption of an acidic catalyst is 0.5～2.0% of waste oils and fats quality.
Preferably, an acidic catalyst is the vitriol oil and strong phosphoric acid, and its volume ratio is 1:1-3.
(2) esterification reaction of organic acid
In waste oils and fats after deacidification, add basic catalyst and methyl alcohol, at the temperature of 65-80 ℃, react 1-4h, by the mixture stratification after esterification, upper strata is methyl alcohol and fatty acid methyl ester, lower floor is glycerin layer, adopt distillation under vacuum to remove residue methyl alcohol on upper strata, obtain fatty acid methyl ester, methyl alcohol can be collected reuse.
Wherein the consumption of methyl alcohol is the 5%-15% of waste oils and fats quality, and the consumption of basic catalyst is the 0.5%-2.0% of waste oils and fats quality.
Preferably, basic catalyst is one or more mixtures in potassium hydroxide, sodium hydroxide, salt of wormwood, sodium soap.
(3) ester-interchange method is prepared polyol ester
In being housed, the reactor of vacuum condensing unit add fatty acid methyl ester, polyvalent alcohol, organotin catalysts to carry out transesterification reaction, temperature of reaction is 120-220 ℃, reaction times is 6-14h, whole process adopts reliever to remove by-product carbinol, after completion of the reaction, gained crude product is filtered and obtains polyol ester product.
Wherein the mass ratio of fatty acid methyl ester and polyvalent alcohol is 5.5-10:1, and the consumption of organotin catalysts is the 0.5%-3.0% of waste oils and fats quality.
The beneficial effect that the present invention produces is that compared with prior art, tool of the present invention has the following advantages:
Adopted the method for efficient acid catalyst waste oils and fats deacidification, not only ensured the effect (acid number <1.0mgKOH/g) of waste oils and fats deacidification, and simplified the operation steps deacidifying, also realized the operate continuously of waste oils and fats deacidification and basic catalyst catalysis esterification.Several organotin effective catalyst catalyzed transesterifications that adopt the present invention to select are prepared polyol ester, and adopt reliever solvent-free process, have significantly improved the technique feature of environmental protection.The present invention be take waste oils and fats as substrate, raw material is easy to get, product cost is low, technique produces without waste water, not only can effectively solve the comprehensive utilization of waste oils and fats, improve China's healthy diet, also can make full use of resource, the dependence of the lubricating oil industry of reduction China fast development to petroleum resources, creates considerable economic benefit.
Embodiment
Embodiment 1:
In the 500ml there-necked flask of spherical condensation tube is housed, add the waste oils and fats 270g after purification, methyl alcohol 40g, each 0.5ml of the vitriol oil and strong phosphoric acid, mixes and is placed in 70 ℃ of waters bath with thermostatic control, under continuous stirring condition, reacts 2h; After completion of the reaction, then add basic catalyst KOH 1.35g, and add methyl alcohol 15.0g, continue stirring reaction 2h, stratification then, gets the mixed solution of upper strata methyl alcohol and fatty acid methyl ester, and lower floor is glycerin layer; Then methyl alcohol and the underpressure distillation of fatty acid methyl ester mixolimnion are removed to methyl alcohol, obtain fatty acid methyl ester; Again by fatty acid methyl ester 180g, TriMethylolPropane(TMP) (TMP) 26.8g and tin methide 1.5g join in the there-necked flask that reliever is housed, under agitation condition, be warmed up to 140 ℃ of insulation reaction 8h, reaction after finishing to drop to room temperature is filtered crude product, obtains TriMethylolPropane(TMP) polyol esters of fatty acids product.
Embodiment 2:
In the 500ml there-necked flask of spherical condensation tube is housed, add the waste oils and fats 270g after purification, methyl alcohol 40g, each 0.5ml of the vitriol oil and strong phosphoric acid, mixes and is placed in 70 ℃ of waters bath with thermostatic control, under continuous stirring condition, reacts 2h; After completion of the reaction, then add basic catalyst KOH 1.35g, and add methyl alcohol 20g, continue stirring reaction 2h, stratification then, gets the mixed solution of upper strata methyl alcohol and fatty acid methyl ester, and lower floor is glycerin layer; Then methyl alcohol and the underpressure distillation of fatty acid methyl ester mixolimnion are removed to methyl alcohol, obtain fatty acid methyl ester; Again by fatty acid methyl ester 180g, neopentyl glycol (NPG) 31.2g and dioctyl tin 1.5g join in the there-necked flask that reliever is housed, under agitation condition, be warmed up to 120 ℃ of insulation reaction 6h, reaction after finishing to drop to room temperature is filtered crude product, obtains neopentyl glycol polyol esters of fatty acids product.
Table 1 is the test of embodiment 1 and 2 products obtained therefrom correlated performances.
| Project | Acid number (mgKOH/g) | 40 ℃ of viscosity (mm 2/s） | 100 ℃ of viscosity (mm 2/s） | Viscosity index | Pour point (℃) |
| Testing method | GB/T 264 | GB/T 265 | GB/T 265 | GB/T 2541 | GB/T 3535 |
| Example 1 | 0.08 | 33.24 | 7.60 | 208 | -5 |
| Example 2 | 0.06 | 15.62 | 4.57 | 226 | -6 |
Claims (7)
1. a method of utilizing waste oils and fats to prepare lubricant base, comprise to waste oils and fats deacidify, esterification processes and to obtain fatty acid methyl ester, then under condition fatty acid methyl ester and polyvalent alcohol being existed at organotin catalysts, carry out transesterification reaction and obtain polyol ester, it is characterized in that, concrete steps are:
(1) waste oils and fats is removed to acid-respons: in the waste oils and fats after purification, add methyl alcohol and an acidic catalyst, at the temperature of 65-80 ℃, react 1-4h; Described an acidic catalyst is the mixture of the vitriol oil and strong phosphoric acid, and its volume ratio is 1:1-3;
(2) esterification reaction of organic acid: add basic catalyst and methyl alcohol in the waste oils and fats after deacidification, at the temperature of 65-80 ℃, react 1-4h, by mixture stratification after completion of the reaction, upper strata is methyl alcohol and fatty acid methyl ester, lower floor is glycerin layer, adopt distillation under vacuum to remove residue methyl alcohol on upper strata, obtain fatty acid methyl ester; Described basic catalyst is one or more the mixture in potassium hydroxide, sodium hydroxide, salt of wormwood, sodium soap;
(3) transesterification reaction: add organotin catalysts in fatty acid methyl ester and polyvalent alcohol, temperature of reaction is 120-220 ℃, and the reaction times is 6-14h, and whole process adopts reliever to remove by-product carbinol, after completion of the reaction, gained crude product is filtered and obtains polyol ester product; Described organotin catalysts is one or more mixtures in Monobutyltin, stannous octoate, tin methide, dioctyl tin, tin tetraphenyl.
2. a kind of method of utilizing waste oils and fats to prepare lubricant base as claimed in claim 1, is characterized in that: described polyvalent alcohol is neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP), ditrimethylolpropane, tetramethylolmethane, dipentaerythritol.
3. a kind of method of utilizing waste oils and fats to prepare lubricant base as claimed in claim 2, is characterized in that: described polyol ester is DOPCP
, trimethylolethane ester
, trihydroxymethylpropanyl ester
, ditrimethylolpropane ester
, pentaerythritol ester
, bis(pentaerythritolester)
, wherein, the saturated fatty chain hydrocarbon that R is C12-C20 or unsaturated fatty acids chain hydrocarbon, and in R, the ratio of each fatty chain hydrocarbon is: C16 is that 20%-35%, C18 are 50%-75%, all the other are other fatty chain hydrocarbons in C12-C20.
4. a kind of method of utilizing waste oils and fats to prepare lubricant base as claimed in claim 1, it is characterized in that: the mass ratio of the waste oils and fats described in step (1) and methyl alcohol is 4-7:1, the consumption of an acidic catalyst is the 0.5%-2.0% of waste oils and fats quality.
5. a kind of method of utilizing waste oils and fats to prepare lubricant base as claimed in claim 1, it is characterized in that: the basic catalyst consumption described in step (2) is the 0.5%-2.0% of waste oils and fats quality, the consumption of methyl alcohol is the 5%-15% of waste oils and fats quality.
6. a kind of method of utilizing waste oils and fats to prepare lubricant base as claimed in claim 1, is characterized in that: the mass ratio of the fatty acid methyl ester described in step (3) and polyvalent alcohol is 5.5-10:1.
7. a kind of method of utilizing waste oils and fats to prepare lubricant base as claimed in claim 1, is characterized in that: the consumption of described organotin catalysts is the 0.5%-3.0% of waste oils and fats quality.
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| CN103468412B (en) * | 2013-09-11 | 2015-08-12 | 上海金兆节能科技有限公司 | Utilize the method that waste grease prepares lubricant compositions and the degradable micro lubricating oil using said composition to prepare |
| CN104726184A (en) * | 2015-02-09 | 2015-06-24 | 新疆福克油品股份有限公司 | Environment-friendly bio-based gear oil composition |
| CN104726183B (en) * | 2015-02-09 | 2017-07-04 | 新疆福克油品股份有限公司 | A kind of bio-based rolling mill compound composition |
| CN104711126A (en) * | 2015-02-13 | 2015-06-17 | 新疆福克油品股份有限公司 | High-quality utilization method for waste oil |
| CN105037146A (en) * | 2015-06-30 | 2015-11-11 | 百川化工(如皋)有限公司 | Di-trimethylolpropane laurate and preparation method thereof |
| CN107254363A (en) * | 2017-08-07 | 2017-10-17 | 蓝德环保科技集团股份有限公司 | A kind of waste oil prepares the method and environmental type base oil of environmental type base oil |
| CN112939770B (en) * | 2021-02-04 | 2022-02-25 | 丰益表面活性材料（连云港）有限公司 | Method for preparing fatty acid polyol ester |
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