CN103880658A - Direct esterification synthesis method of pentaerythritol oleate - Google Patents
Direct esterification synthesis method of pentaerythritol oleate Download PDFInfo
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- CN103880658A CN103880658A CN201410090863.2A CN201410090863A CN103880658A CN 103880658 A CN103880658 A CN 103880658A CN 201410090863 A CN201410090863 A CN 201410090863A CN 103880658 A CN103880658 A CN 103880658A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention discloses a direct esterification synthesis method of pentaerythritol oleate. The method comprises the following steps: (1) quantitatively weighing oleic acid, pentaerythritol and a catalyst according to a ratio, adding in a reactor, and introducing nitrogen into the reactor, wherein the pressure of the nitrogen is 0.5-3kg/cm<2> per hour; (2) heating the reactor, setting the initial heating temperature to be 180 DEG C, preserving the heat at 180-220 DEG C and reacting for 7-18 hours; and (3) sampling and measuring an acid value of a sample, stopping reacting when the acid value of the sample is less than 1mgKOH/g, and filtering to obtain the product. The method has high feasibility; compared with a conventional similar esterification reaction, the method has the advantages that a universal methylbenzene toxic organic substance dehydrating agent is not used, solvent wash deacidification or alkaline wash deacidification is also avoided, the environmental pollution and the high energy consumption problem brought by solvent recovery is greatly reduced, and the method has an obvious improvement in terms of environment protection and energy conservation.
Description
Technical field
The present invention relates to a kind of novel process of direct esterification synthesis of pentaerythritol oleic acid ester.
Background technology
At present, Global Oil resource is reducing day by day.In China, along with rapid development of economy, the import volume of oil, also soaring year by year, is become to global second petroleum import big country now, be only second to the U.S.; CNPC's strategic reserves wretched insufficiency, the external interdependency of crude oil in China is to increase year by year, has reached 57%, exceedes the U.S..Based on this, adopt grease derivative product to replace part petroleum products and be applied to different industries, there is larger realistic meaning.
The annual demand for lubricating oil amount of China is about 9,500,000 t, accounts for 9.8% of world's lubricating oil consumption.Most traditional mineral substance lubricating oil for refining of petroleum production.Because conventional lubrication oil is mixture, molecular size differs, and material composition is different, and lubricant effect is poor.Ucon oil is as novel high-end product, and core technology is monopolized by English, Mei Deng developed country always.At present, American-European ucon oil accounts for market usage ratio and exceedes 50%, and China is only 15%, and base oil is serious dependence on import still, localization rate of parts and components less than 3%.
Lubricating oil more than 95% derives from oil, lubricating oil is in use nearly 50% by mode entered environments such as volatilizations, leakage, wherein hydraulic efficiency oil loss is in use up to 70%～80%, and the biological degradability of petroleum base lubricating oil is poor, and degradation rate only has 10%～30%.On the other hand, if the energy of having verified by the present horizon mining world, oil only can maintain 30～40 years, and Global Oil resource day by day deficient caused the nervous situation of petroleum base lubricating oil resource shortage.Thereby, as raw material synthetic environment can be subject to extensive concern by acceptance type lubricant base, there is very large market potential take the renewable resources widely of originating.
Fatty acid pentaerythritol ester is one of ester class oil of excellent performance, in its molecule due to the special construction of quaternary carbon atom, making does not have hydrogen atom can form with hydroxyl oxygen the resonance structure ring of six atoms on β position, and its ester structure only could be destroyed under high-energy condition.Therefore, pentaerythritol fatty ester has shown good thermostability, oxidative stability, stability to hydrolysis, low-temperature fluidity, viscosity temperature characteristic, lubricity, and biological degradability is good, nontoxic, aspect a lot of, can substitute crude oil, be widely used in the fields such as aviation, metal processing, weaving, process hides.
Ester class base oil is that over-all properties is better, an Application and Development class ucon oil the earliest, and current aero gas turbine engine in the world almost all uses ester class oil.Ester class oil can be divided into dibasic acid esters, polyol ester and multiple ester.The research of esters syntholube starts from the World War II eve, at that time mainly as aircraft engine lubricating oil.Ester class oil is the base oil of the ucon oil of a class widespread use, there is prescribed molecular structure, not containing contained unstable impurity in plain mineral oil, multiple ester bond in its ester molecule has been given ester molecule with polarity, thereby give the many unrivaled performances of ester class oil and application characteristic, the performance requriements that meets modern industry and automobile-used lubricant harshness, has very large development space.
For adapting to the develop rapidly of aero engine technology, need to improve the thermal load ability to bear of lubricating oil in esters.Around this key, carry out fruitful fundamental research abroad.Occur that in early days high temperature performance is better than the dibasic acid esters oil of mineral oil, synthesized again afterwards the better neopentyl polyol ester of high-temperature behavior.Meanwhile, the application of novel antioxidant, has improved the thermal safety of ester class oil effectively.The external existing ester class oil that additive Concord Action is good, compatibleness is higher of carrying out.
Aspect ester class oil production technology, abroad carry out the work around stabilised quality, cost, the aspect such as enhance the competitiveness, develop the patented technology of oneself, as harmless catalyzing esterification exploitation, efficient fractionation apparatus and advanced aftertreatment technology, simplified production technique, reduced material consumption and energy consumption.
China's lubricating oil in esters synthetic technology exploitation starts from the beginning of the sixties, has developed high, medium and low viscosity ester class aircraft oil and instrument oil to the seventies.With foreign technology comparison, aspect ester lubricant synthetic technology, China also has many gaps, as high-efficiency environment friendly catalyzer, specialist additive, middle low carbon chain polyol ester synthetic technology, effective compounded technology etc.
Along with the development of modern industry and the raising day by day of environmental requirement, lubricating oil in esters base oil has obtained more and more widely application because of its unique high temperature performance, viscosity temperature characteristic, lubricity, biodegradable performance.At present abroad not only for military field, and the industrial circles such as automobile, petrochemical complex, metallurgy, machinery are widely used in.In developed country's demand steady-state growths such as America and Europes, particularly, due to the requirement to aspects such as motor vehicle emission and prolongation oil draining periods, the demand of ester class oil is increasing, and annual growth reaches 15% left and right.
Estimate 2013, the demand of global pentaerythritol stearate will reach 4.19 ten thousand tons, within 2014, will reach 4.75 ten thousand tons, within 2015, will reach 5.38 ten thousand tons, within 2016, will reach 6.11 ten thousand tons, within 2017, will reach more than 6.93 ten thousand tons.2013, the demand of global PETO will reach 4.10 ten thousand tons, within 2014, will reach 4.36 ten thousand tons, within 2015, will reach 4.64 ten thousand tons, within 2016, will reach 4.94 ten thousand tons, within 2017, will reach more than 5.27 ten thousand tons.
China originates in the initial stage sixties for the research of esters syntholube, and at present, having worked out polyol ester class lubricating oil has 4050,4051,4106 etc.It is the focus of research now take vegetables oil and derivative thereof as raw material ucon oil.What the people such as Fu Tingjin, official's bodyguard dragon utilized is mixed fatty acid and the tetramethylolmethane esterification including oleic acid, and catalyzer comprises sulfuric acid, solid acid catalyst and metal catalyst etc.The people such as Zhou Cun utilize oleic acid to react with tetramethylolmethane, have carried out the selection of experiment of single factor and catalyzer, and experiment is found to make catalyzer with tin protoxide, and catalyst quality mark is 0.8%, and temperature of reaction is at 200 ℃, and product is better.The old little firm people of grade finds to make catalyzer with metal-powder, and catalyzer has been used as 0.5% of oleic acid, 210-220 ℃ of temperature of reaction, and reaction 4h, esterification yield is more than 95%.In addition, the people such as Xu Min have studied the structure activity relationship of polyol ester, find that the low-temperature performance of tetramethylolmethane base oil is subject to former molecular impact of fatty acid carbons, and odd number is better than even number, and collateralization degree more high product low-temperature performance is better.In a word, the domestic research work for polyol ester, also in the initial stage, has wide prospect.
In synthesis of pentaerythritol oleic acid ester technique, also there is following problem at present:
(1) there is band aqua: mostly adopt toluene, dimethylbenzene, benzene etc. as band aqua, the water that building-up reactions is generated is sloughed.Need to carry out solvent recuperation or remove, operation sequence be more, and cost is higher, and has problem of environmental pollution.
(2) aftertreatment technology complexity: mostly adopt that underpressure distillation, molecular distillation, organic solvent repeatedly wash, band aqua in reaction product is removed in washing, alkali cleaning, filter media etc., catalyzer, residual acid etc., operation is more, and running cost is higher.
(3) product acid number is high: the acid number of the crude product without aftertreatment that PETO synthetic technology obtains is at present all far above 1, to pass through molecular distillation, or adopt certain filter media or adopt certain filtration process to filter or adopt organic solvent repetitive scrubbing, the acid number of the aftertreatment products obtaining just can reach below 1, operation sequence is more, and cost is higher.
Summary of the invention
In view of above-mentioned weak point; the object of the present invention is to provide a kind of nothing with aqua, direct esterification building-up reactions is prepared the novel process of PETO under nitrogen protection; to avoid the weak point of above-mentioned technology, more environmental protection is safer more efficient to make its building-up process.
In order to achieve the above object, the technical solution used in the present invention is:
A kind of method of direct esterification synthesis of pentaerythritol oleic acid ester comprises the following steps:
(1) take in proportion quantitative oleic acid; tetramethylolmethane; catalyzer is in reactor; and pass into nitrogen to reactor; nitrogen pressure is that 0.5-3 kg/cm is per hour; pass into main its provide protection of nitrogen, avoid or the unsaturated double-bond generation thermooxidizing that reduces in reactant causes product color burn.
(2) heat this reactor, setting initial heating temperature is 180 ℃, insulation reaction 7 hours to 18 hours at 180 ℃～220 ℃;
(3) acid number of sampling and measuring sample, according to its acid number of GB/T9104-2008 standard test (mgKOH/g); For PETO product, in the time that the acid number of sample is below 1mgKOH/g, i.e. stopped reaction, filters and obtains product;
Get product sample analysis: scales/electronic balance weighing, according to its acid number of GB/T9104-2008 standard test (mgKOH/g), is calculated as follows its transformation efficiency (Q) and is:
Wherein, AV
0for the acid number of starting material oleic acid, AV
1for the acid number of sample.
Described oleic acid comprises technical grade oleic acid or AG oleic acid.
Described tetramethylolmethane comprises technical grade pentaerythritol or AG tetramethylolmethane.
Described catalyzer is that described catalyzer is esterifying catalyst, and this esterifying catalyst can be selected from one or more in tin protochloride, aluminium sesquioxide, silicon oxide etc.
Described catalyst levels accounts for 1.0～4.0% of oleic acid and tetramethylolmethane weight sum.
The described oleic acid of step (1) and tetramethylolmethane add according to mole 4:1.0～1.2.
The acid number of described PETO is less than 1, and its sour transformation efficiency reaches more than 99%.
Heating temperature of the present invention is: reacting by heating material actual temperature, within the scope of 180～220 ℃, is advisable to be no more than 220 ℃, otherwise easily causes material product color burn.
Be heat-up time of the present invention: the reaction times needing under nitrogen protection condition is longer, at 7 hours within the scope of 18 hours, otherwise the time not reaction not exclusively, product acid number is higher;
The acid number of PETO of the present invention is less than 1, and its sour transformation efficiency reaches more than 99%.
The present invention adopts nitrogen protection reaction conditions: pass into nitrogen replacement air prevent from forming oxide compound cause product color and luster deepen.
The present invention suitably reduces temperature of reaction: be controlled within the scope of 180～220 ℃ by temperature of reaction, prevent or reduce high temperature generation oxidation stain and react.
The present invention, by increasing the reaction times (7-18 hour), makes fully to be reacted between reactant, finally obtains high-quality product, and reaction product quality is better, its acid number≤1.
The present invention compared with prior art, has the following advantages and effect:
1. without adding band aqua, avoid the problems such as toxicity that organic solvent brings, environmental pollution, cost recovery, simplify technological process, make more convenient operation feasible;
2. adopt esterifying catalyst, under nitrogen protection, through long period reaction, can synthesize and obtain the high esterification yield high-quality of low acid number PETO;
3. without vacuumizing, there is no sulphur and heavy metal contamination, running cost is low, nothing refining consumption, safety environment protecting energy saving;
4. crude product direct filtration just can obtain the high esterification yield product of low acid number, does not need solvent wash depickling or alkali cleaning depickling, energy-conserving and environment-protective;
5. synthesis technique of the present invention is simple, and starting material are the common stable chemical materials on market, without starting material problem in short supply;
6. technology provided by the present invention is not only applicable to PETO, also be applicable to other tetramethylolmethane senior middle school low carbon chain ester, as serial pentaerythritol fatty esters such as tetramethylolmethane carbon 18-carbon 22 esters, tetramethylolmethane cetylate, tetramethylolmethane laurate, tetramethylolmethane carbon 6-carbon 12 esters, have broad application prospects.
Embodiment
By following examples, PETO direct esterification new synthetic process is described in further details, following examples are explanation of the invention and the present invention is not limited to following examples.
Embodiment 1:(PETO-23)
Oleic acid 170 g
Tetramethylolmethane 23.0 g
Tin protochloride 5.0 g
200～210 ℃ of temperature of reaction
Reaction times 11 h
Average acid number 0.43 mgKOH/g of product
Product acid transformation efficiency 99.78 %
Concrete operations are as follows:
A takes quantitative oleic acid in proportion, tetramethylolmethane, and catalyzer equals in 500ml four-hole boiling flask reactor, and this flask is placed in heating jacket;
B connects respectively reflux condensing tube, glass-stem thermometer sleeve pipe, water trap, airway etc. in four outlets of this flask;
C passes into nitrogen to reactor, and nitrogen pressure is that 0.5-3 kg/cm is per hour, heats this reactor, insulation reaction 11 hours at 200～210 ℃;
The acid number of f sampling and measuring sample, according to its acid number of GB/T9104-2008 standard test (mgKOH/g);
G, in the time that the acid number of sample is below 1mgKOH/g, gets final product stopped reaction, filters and obtains product;
H gets product sample analysis: scales/electronic balance weighing, according to its acid number of GB/T9104-2008 standard test (mgKOH/g), is calculated as follows it and turns
Rate (Q) is:
Wherein, AV
0for the acid number of starting material oleic acid, AV
1for the acid number of sample.
Embodiment 2:(PETO-24)
Oleic acid 170 g
Tetramethylolmethane 21.6 g
Tin protochloride 5.0 g
200～210 ℃ of temperature of reaction
Reaction times 17 h
Product acid number 0.65 mgKOH/g
Product acid transformation efficiency 99.67 %
Concrete operation method is with embodiment 1.
Example 3:(PETO-25)
Oleic acid 170 g
Tetramethylolmethane 22.4 g
Aluminium sesquioxide 5.0 g
200～210 ℃ of temperature of reaction
Reaction times 12 h
Product acid number 0.75 mgKOH/g
Product acid transformation efficiency 99.62 %
Concrete operation method is with embodiment 1.
Example 4:(PETO-27)
Oleic acid 170 g
Tetramethylolmethane 23.1 g
Silicon oxide 5.0 g
200～210 ℃ of temperature of reaction
Reaction times 13 h
Product acid number 0.88 mgKOH/g
Product acid transformation efficiency 99.56 %
Concrete operation method is with embodiment 1.
The present invention is mainly adopting new techniques and catalyst for making direct esterification synthesis of pentaerythritol oleic acid ester, do not need the band aqua of toluene and so on, carry out solvent-free direct esterification building-up reactions, the PETO product acid number obtaining is less than 1, just can obtain the PETO product of the high esterification yield of low acid number (acid number is less than 1) through direct filtration, without solvent wash or alkali cleaning depickling.Experimental result shows, this novel building-up reactions has higher feasibility, similar esterification comparison with routine, do not use general toluene toxic organic compound dewatering agent, do not use solvent wash depickling or alkali cleaning depickling yet, greatly reduce environmental pollution and reclaimed the high energy consumption problem that solvent brings, aspect environmental protection and energy saving, having had comparatively significantly and improve.
Claims (9)
1. a method for direct esterification synthesis of pentaerythritol oleic acid ester, is characterized in that, the method comprises the following steps:
(1) take in proportion quantitative oleic acid, tetramethylolmethane, catalyzer, in reactor, and passes into nitrogen to reactor, and nitrogen pressure is that 0.5-3 kg/cm is per hour;
(2) heat this reactor, setting initial heating temperature is 180 ℃, insulation reaction 7 hours to 18 hours at 180 ℃～220 ℃;
(3) acid number of sampling and measuring sample, in the time that the acid number of sample is below 1mgKOH/g, i.e. stopped reaction, filters and obtains product.
2. according to the method described in claims 1, it is characterized in that: described oleic acid comprises technical grade oleic acid or AG oleic acid.
3. according to the method described in claims 1, it is characterized in that: described tetramethylolmethane comprises technical grade pentaerythritol or AG tetramethylolmethane.
4. according to the method described in claims 1, it is characterized in that: described catalyzer is esterifying catalyst.
5. according to the method described in claims 4, it is characterized in that: described esterifying catalyst is selected from one or more in tin protochloride, aluminium sesquioxide, silicon oxide.
6. according to the method described in claims 1, it is characterized in that: in oleic acid and tetramethylolmethane weight sum, described catalyst levels is 1.0～4.0%.
7. according to the method described in claims 1, it is characterized in that: the described oleic acid of step (1) and tetramethylolmethane add according to mole 4:1.0～1.2.
8. the PETO being made by method described in claim 1.
9. the acid number of PETO according to claim 7 is less than 1, and its sour transformation efficiency reaches more than 99%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230706A (en) * | 2014-09-01 | 2014-12-24 | 安庆市中创生物工程有限公司 | Preparation method of pentaerythritol oleate |
| CN104402720A (en) * | 2014-11-19 | 2015-03-11 | 浙江合诚化学有限公司 | Preparation method of castor oil polyoxyethylene ether oleate |
| CN104945247A (en) * | 2015-06-30 | 2015-09-30 | 百川化工(如皋)有限公司 | Preparation process of neopentyl polyol oleate |
| CN105294432A (en) * | 2015-09-18 | 2016-02-03 | 四川泸天化股份有限公司 | Method for synthesizing ethylene glycol distearate in absence of solvent at ordinary pressure |
| CN115353919A (en) * | 2022-09-07 | 2022-11-18 | 新乡市瑞丰新材料股份有限公司 | Preparation method of flame-retardant base oil polyol oleate for hydraulic oil |
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| JPH041156A (en) * | 1990-04-18 | 1992-01-06 | Lion Corp | Production of ester |
| CN101173103A (en) * | 2007-10-22 | 2008-05-07 | 李熊伟 | Method of producing polyvinyl ester chloride inside and outside lubricant agent |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230706A (en) * | 2014-09-01 | 2014-12-24 | 安庆市中创生物工程有限公司 | Preparation method of pentaerythritol oleate |
| CN104402720A (en) * | 2014-11-19 | 2015-03-11 | 浙江合诚化学有限公司 | Preparation method of castor oil polyoxyethylene ether oleate |
| CN104402720B (en) * | 2014-11-19 | 2016-03-02 | 浙江皇马科技股份有限公司 | A kind of preparation method of castor oil polyoxyethylene ether oleic acid ester |
| CN104945247A (en) * | 2015-06-30 | 2015-09-30 | 百川化工(如皋)有限公司 | Preparation process of neopentyl polyol oleate |
| CN105294432A (en) * | 2015-09-18 | 2016-02-03 | 四川泸天化股份有限公司 | Method for synthesizing ethylene glycol distearate in absence of solvent at ordinary pressure |
| CN115353919A (en) * | 2022-09-07 | 2022-11-18 | 新乡市瑞丰新材料股份有限公司 | Preparation method of flame-retardant base oil polyol oleate for hydraulic oil |
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Application publication date: 20140625 |