CN105541612A - Method for catalyzed synthesis of lubricating base oil from supported ionic liquid - Google Patents
Method for catalyzed synthesis of lubricating base oil from supported ionic liquid Download PDFInfo
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- CN105541612A CN105541612A CN201510948326.1A CN201510948326A CN105541612A CN 105541612 A CN105541612 A CN 105541612A CN 201510948326 A CN201510948326 A CN 201510948326A CN 105541612 A CN105541612 A CN 105541612A
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- C07—ORGANIC CHEMISTRY
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- 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
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
The present invention discloses a method for preparing lubricating base oil from supported ionic liquid. The method is characterized by using oleic acid and pentaerythritol as raw materials, and using a supported imidazole ionic liquid as a catalyst and a solvent. The present invention employs a dipping method or a sol-gel method for preparing the supported ionic liquid catalyst: addition amount of catalyst of 0.5%-3% of the total mole number of alcohol and acid, the reaction temperature of 130-160 DEG C, atmospheric pressure, and reaction time of 0.5-3 h. The method is characterized by no usage of concentrated sulfuric acid and hydrofluoric acid, which are pollute the environment. Compared to the traditional inorganic acid as an alcohol acid esterification catalyst, the supported ionic liquid has the advantages of mild reaction conditions, high catalytic activity, short reaction time, high esterification rate, simplified production process, simple catalyst recycling operation and reusability.
Description
Technical field
The present invention relates to organic chemical reactions method, particularly relate to a kind of method that load-type ion liquid catalyzes and synthesizes lubricant base.
Background technology
Along with the development of modern chemical industry and car industry, being in great demand of lubricating oil, therefore, people more and more pay close attention to oil quality and prepare the pollution that may cause environment.Synthetic base oil refers to the lubricant base synthesized by chemical process.The advantages such as compare mineral oil, ucon oil has Heat stability is good, and heat decomposition temperature is high, and resistance to low temperature is good are current very important chemical industry basic products.Synthetic base oil has many types, and modal is synthesizing ester.Traditional alcoholic acid esterification technology uses the inorganic acid as catalyst of the severe corrosives such as the vitriol oil usually, there is esterification yield low, etching apparatus contaminate environment, product and the problem such as catalyzer difficulty is separated, therefore industrial to have again the demand of eco-friendly novel alcoholic acid esterification system concurrently to the existing economic benefit of exploitation very urgent.Ionic liquid is the novel material received much concern in recent years, has good stability, non-volatile, nonflammable, solvability and the advantage such as acidity is adjustable, show excellent characteristic as novel green catalysts and solvents, also have application in the esterification reaction in a lot of acid catalytic systems.Song Hang etc. are disclose one " preparation of temperature sensitive acidic ionic liquid and the method for catalytic hydroxy acid esterifying thereof " in 201010211280.2 at application number, benzothiazole salt temperature sensitive acidic ionic liquid prepared by the method is in catalytic hydroxy acid esterifying reaction, ionic liquid has strongly-acid, and the feature such as have good stability.Zhang Suojiang etc. disclose " a kind of catalytic hydroxy acid esterifying process " in Chinese invention patent CN1554638A, and the method is using ionic liquid as catalyzer, and the form of ionic liquid is: A
+b
-, wherein A is the nitrogenous compound such as alkyl pyridine, imidazoles, and B is simple haloid element fluorine, chlorine, bromine or TA, TfO
-, NO
3 -deng, the esterification of catalysis has higher selectivity, and technique is simple, and catalyst stability is good.But the ionic liquid that the method for above-mentioned synthetic ester uses synthesis is complicated, and there is a large amount of organic solvent of reaction needed, and esterification yield is not high, catalyzer difficulty is separated, the problems such as aftertreatment more complicated.
For solving an above-mentioned difficult problem, by functionalized ion liquid load on inorganic porous material or organic polymer material, obtained load-type ion liquid catalyst, thus overcome loaded article separation difficulty, aftertreatment more complicated, the problems such as catalyst levels is large.Zhao Yajuan etc. disclose in Chinese invention patent CN101664700A " a kind of load-type ion liquid catalyst and its preparation method and application ", and the catalyzer described in the method is that supported on carriers has pyridines acidic ion liquid [XPy] HS0
4, carrier is Y-Al
20
3, Si0
2, mesopore molecular sieve, SBA-15 etc., apply it and catalyze and synthesize glycol ether, have that catalyst activity is high, the life-span is long, reaction conditions is gentle, the features such as production technique is simple.Xu Hang etc. are disclose in 201010101778.3 " a kind of load-type ion liquid catalyst, its preparation method and application thereof " at application number, this method provide a kind of load-type ion liquid catalyst for producing vinyl acetate by acetylene method, it take mesopore molecular sieve as carrier, be active ingredient with zinc acetate, be connected with imidazoles acetate ionic liquid between carrier with active ingredient.Ionic liquid is formed at catalyst surface and intends liquid phase microenvironment, increases reaction process mass transfer and thermal conduction, and good stability, the life-span is long, activity is high, selectivity good.The successful Application of functionalization load-type ion liquid in these organic synthesis, is more and more subject to the attention of chemical circles.
Therefore, active high, the technique that the segregative functionalized ion liquid of stable in catalytic performance, product and catalyzer catalyzes and synthesizes lubricant base of exploitation oneself cause great concern, patent of invention that is current and its related application mainly contains following several.
Zhou Feng etc. are disclose one " containing benzotriazole group ionic liquid and its preparation method and application " in 201110098075.4 at application number, ionic liquid prepared by the method take imidazoles as positively charged ion, hexafluoro-phosphate radical, tetrafluoroborate or two (trimethyl fluoride sulfonyl) amine negative ion are negatively charged ion, and the cyclosubstituted end group of its imidazoles is containing benzotriazole group.Ionic liquid uses as lubricating oil additive or grease additive.
S Ai Lemali etc. are disclose one in 201180052106.0 " to have the preparation method of the high viscosity base oil improving viscosity index " at application number, and the method comprises one or more olefin oligomerizations making boiling point be less than 82 DEG C under ionic-liquid catalyst and one or more C5+ alhpa olefins exist in the reactor and has 36mm at 100 DEG C to produce
2the kinematic viscosity of/s or higher and be greater than 55 the base oil of VI.First component of ionic-liquid catalyst comprises Lewis acid: aluminum halide, aikyl aluminum halide, gallium halide and alkyl halide gallium.The second component of ionic-liquid catalyst is the mixture of organic salt or salt, and general formula can be characterized by Q
+a
-, wherein Q
+for ammonium cation, phosphonium cation, boron ion, iodine positively charged ion or sulphur positively charged ion, A
-for electronegative ion such as Cl
-, Br
-, Cl0
4 -, N0
3 -, BF
4 -, BC1
4 -, PF
6 -, SbF
6 -, AlC1
4 -, TaF
6 -, CuC1
2 -, FeC1
3 -deng.
Tight Zong Cheng etc. are disclose one " Ionic liquid/vegetable oil microemulsion type biological lubricant base oil and preparation method thereof " in 201310113686.0 at application number, the method is in mass fraction, it consists of ionic liquid 1 part, vegetables oil 1-30 part, tensio-active agent 1.5-68 part, cosurfactant consumption is 0-12 times of ionic liquid consumption.Described ionic liquid is one or more in 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hexafluorophosphate, 1-butyl-3-Methylimidazole bromine salt, 1-butyI-pyridinium a tetrafluoro borate and 1-hydroxyethyl-3-methyl imidazolium tetrafluoroborate ionic liquid; Described vegetables oil is one or more in soybean oil, Viscotrol C, jatropha curcas oil, sunflower seed oil, Rice pollard oil and plam oil.Obtain the reversed phase ion liquid micro liquid system of clear homogeneous after preparation, stability is high, raw material sources environmental protection, and gained lubricant base has excellent viscosity-temperature characteristics, thermostability and nanometer additive consistency.
Zhou Feng etc. are disclose in 200910117591.X " a kind of antioxidant ionic liquid containing sterically hindered phenol and its preparation method and application " at application number, the positively charged ion of ionic liquid prepared by the method is the glyoxaline cation that sterically hindered phenol replaces, and negatively charged ion is hexafluoro-phosphate radical, tetrafluoroborate or two trifluoromethane sulfonic acid roots.Ionic liquid can be used as lubricating oil additive and uses, and it not only can improve oxidation of lubricating oil stability, and obviously can improve the tribological property of lubricating oil.
Tight Zong Cheng etc. are disclose biological lubricant and the preparation method of catalyst preparing " a kind of be " in 201010286234.9 with ionic liquid at application number; Vegetable oil lipoprotein and TriMethylolPropane(TMP) mix by weight 1-3:1 by the method, then add above-mentioned two kinds of raw material gross weight numbers B acid ion liquid O.5-1.5% and make catalyzer; Again by above-mentioned heating material to 120-180 DEG C, stir, reaction 4-8h; Then reacted material is cooled to 30-50 DEG C rapidly, rotational flow settlement, becomes solid after B acid ion liquid cooling, after rotational flow settlement, be deposited in eddy flow pot bottom, and product and unreacted completely material still in liquid phase; Finally by product and unreacted completely material enter rectifying tower distillation, rectifying bottom product is biological lubricant.Wherein B acidic ion liquid is pyridine-sulfonic acid functional group or imidazole sulfonic acid functional group proton is positively charged ion, and heteropolyacid is anion ion liquid.
But there are no the load-type ion liquid prepared using pickling process or sol-gel method as catalyzer and solubilizing agent, by technological invention or the academic research report of esterification synthetic lubricant base oil.
Glyoxaline ion liquid is carried out load by the present invention, realize ionic liquid loadedization, and be applied to lubricant base building-up reactions, catalyzer easily reclaimed and can reuse, simplifying production technique, while improving esterification yield, reduce ionic liquid consumption, reduce equipment corrosion, reduce environmental pollution, be expected to the Green Chemistry catalyzer developing alternative traditional severe corrosive acid catalyst.
Summary of the invention
The invention provides the preparation of a kind of load-type ion liquid and utilize it as the method for catalyzer synthetic lubricant base oil, this catalyzer avoids conventional inorganic acid catalyst and there is the problems such as subsequent disposal complexity, equipment corrosion be serious, and this catalyzer shows good thermostability and efficient catalytic activity in the esterification reaction, catalyst product is easier to being separated of raw material simultaneously, simplify production technique, save production cost.
The technical solution used in the present invention is: load-type ion liquid catalyzes and synthesizes the method for lubricant base, it is characterized in that: with oleic acid and tetramethylolmethane for raw material, using load-type ion liquid as catalyzer and solubilizing agent, by esterification synthetic lubricant base oil.
Usually, ionic liquid of the present invention is glyoxaline ion liquid, and it consists of: [Hmim]
+x
-, cation A
+for glyoxaline cation ([Hmim]
+):
Negatively charged ion X
-for: phosphate radical, acetate, butanic acid root or tosic acid root;
Ionic liquid structural formula is:
。
Described ionic liquid is imidazoles acetate, imidazoles butanic acid salt, imidazole phosphate or imidazoles tosic acid ionic liquid.
Described loading type glyoxaline ion liquid catalyzer adopts pickling process preparation, and its concrete steps are as follows:
(1) glyoxaline ion liquid preparation: by 1 mass parts N-Methylimidazole and 0.5-3 mass parts acid mixing, add 1-8ml solvent, Stirring, temperature of reaction controls at 60-120 DEG C.With this understanding, 3-10h is carried out in reaction, obtains weak yellow liquid; The weak yellow liquid obtained is carried out underpressure distillation, and the vacuum tightness controlling underpressure distillation is 0.05-0.2MPa, and head temperature is 70-110 DEG C, and distillation time is 1-5h, namely obtains functionalization glyoxaline ion liquid [Hmim]
+x
-.
(2) by 1 mass parts ion liquid dissolving obtained ionic liquid solution in 0.5-2 mass parts solvent, 1-5 mass parts carrier is joined in 0.5-3 mass parts ionic liquid solution, at 15-85 DEG C, stir dipping 12h-24h, stop heating, centrifugation after cooling, remove supernatant liquid, add distilled water wash again, recentrifuge is separated, and removes supernatant liquid, the vacuum-drying in the baking oven of 90-150 DEG C of the solid of lower floor, obtained loading type glyoxaline ion liquid.
Loading type glyoxaline ion liquid of the present invention also can adopt sol-gel method to prepare, and its concrete steps are as follows:
(1) glyoxaline ion liquid preparation: by 1 mass parts N-Methylimidazole and 0.5-3 mass parts acid mixing, add 1-8ml solvent, Stirring, temperature of reaction controls at 60-120 DEG C.With this understanding, 3-10h is carried out in reaction, obtains weak yellow liquid; The weak yellow liquid obtained is carried out underpressure distillation, and the vacuum tightness controlling underpressure distillation is 0.05-0.2MPa, and head temperature is 70-110 DEG C, and distillation time is 1-5h, namely obtains functionalization glyoxaline ion liquid [Hmim]
+x
-.
(2) by after 1 parts by volume tetraethyl orthosilicate and the mixing of 0.5-5 parts by volume dehydrated alcohol, be heated to 30-80 DEG C, slowly add the ionic liquid prepared subsequently, be uniformly mixed, until form uniform mixed phase, add 0.5-5 volume hydrochloric acid, reaction mixture forms gel gradually, remain on 60-100 DEG C and continue aging 6-24h, finally vacuum-drying 2-6h at 100-150 DEG C, obtained loading type glyoxaline ion liquid.
Acetify reaction of the present invention is using load-type ion liquid as catalyst for esterification reaction and solubilizing agent, and the add-on of load-type ion liquid is the 0.5%-3% of alkyd integral molar quantity, and the mol ratio of oleic acid and tetramethylolmethane is 3-6:1.
Described esterification reaction temperature is 130-160 DEG C, and the reaction times is 0.5-3h.
After reaction terminates, through simple filtration, loading type glyoxaline ion liquid catalyzer can separate, and can reuse.
Beneficial effect:
1. reaction time of esterification is short, good catalyst activity, and in lubricant base esterification experiment, the esterification yield of PETO reaches 92%-99%.
2. ionic liquid has that steam forces down, the clean feature such as nontoxic, and as catalyzer, reaction conditions is gentle, and use procedure is non-volatile, pollution-free, overcomes the pollution of acid catalyst to environment and the corrosion to equipment.
3. ionic liquid is after overload, and catalyst recovery is simple to operate, and the life-span is long, while Simplified flowsheet, reduces production cost.
Embodiment
Provide embodiment below so that the invention will be further described.Be necessary to herein means out, following examples can not be interpreted as limiting the scope of the invention, if person skilled in art makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to protection scope of the present invention.
The synthesis of embodiment 1(ionic liquid) preparation method of imidazole acetate ionic liquid
Weigh mol ratio be the N-Methylimidazole 8.21g of 1:1 and acetic acid 6.01g in 250ml there-necked flask, add 2ml water as solvent, Stirring, temperature controlled at 80 DEG C.With this understanding, 6h is carried out in reaction, obtains weak yellow liquid.
The weak yellow liquid obtained is carried out underpressure distillation, and the vacuum tightness controlling underpressure distillation is 0.07MPa, and head temperature is 92 DEG C, and distillation time is 3h, namely obtains imidazole acetate ionic liquid [Hmim] CH
3cOO.
The synthesis of embodiment 2(ionic liquid) preparation method of imidazoles butanic acid ionic liquid
Weigh mol ratio be the N-Methylimidazole 8.21g of 1:1 and butanic acid 8.82g in 250ml there-necked flask, add 2ml water as solvent, magnetic stirrer, electric heating cover heats, and condensate return, reacts at a reflux temperature, temperature of reaction controls at 80 DEG C, and reaction 7h, obtains yellow liquid.
The liquid obtained is carried out underpressure distillation, and control vacuum tightness is 0.05MPa, and head temperature is about 75 DEG C, and distillation time is 4h.Namely imidazoles butanic acid ionic liquid [Hmim] C is obtained
4h
7o
2.
The synthesis of embodiment 3(ionic liquid) preparation method of imidazole phosphate ionic liquid
Weigh mol ratio be the N-Methylimidazole 16.4g of 1:1 and phosphatase 11 9.6g in 250ml there-necked flask, add 3ml water as solvent, magnetic stirrer, electric heating cover heats, and condensate return, reacts at a reflux temperature, temperature of reaction controls at 80 DEG C, and reaction 7h, obtains yellow liquid.
The liquid obtained is carried out underpressure distillation, and control vacuum tightness is 0.05MPa, and head temperature is about 75 DEG C, and distillation time is 3h, namely obtains imidazole phosphate ionic liquid [Hmim] H
2pO
4.
The synthesis of embodiment 4(ionic liquid) preparation method of imidazoles tosic acid ionic liquid
Weighing mol ratio is that the N-Methylimidazole 16.4g of 1:1 and tosic acid 34.4g is in 250ml there-necked flask, add 5ml water as solvent, magnetic stirrer, electric heating cover heats, condensate return, reacts at a reflux temperature, and temperature of reaction controls at 80 DEG C, reaction 16h, obtains brown color liquid.
The liquid obtained is carried out underpressure distillation, and control vacuum tightness is 0.05MPa, and head temperature is about 70 DEG C, and distillation time is 4h, namely obtains imidazoles tosic acid ionic liquid [Hmim] TsO.
The synthesis of embodiment 5(load-type ion liquid) take NaY molecular sieve as the preparation method of carrier
Take NaY molecular sieve as carrier impregnation, with 5ml water, 5.08g imidazoles tosic acid ionic liquid [Hmim] TsO is dissolved, 5gNaY molecular sieve is soaked in the solution, after Keep agitation 24h, dry 4h by the head product 120 DEG C obtained, obtain 10g final catalyst [Hmim] TsO/NaY.
The synthesis of embodiment 6(load-type ion liquid) with γ-Al
2o
3molecular sieve is the preparation method of carrier
With γ-Al
2o
3molecular sieve is carrier impregnation, takes 5.08g imidazoles tosic acid ionic liquid [Hmim] TsO, adds 5ml distilled water and dissolves, 5g γ-Al
2o
3be immersed in the aqueous solution of ionic liquid, leave standstill 24h, dry 4h by the head product 120 DEG C obtained, obtain 10g final catalyst [Hmim] TsO/ γ-Al
2o
3.
The synthesis of embodiment 7(load-type ion liquid) preparation method that is carrier with SBA-15 molecular sieve
Take SBA-15 as carrier impregnation, take 5.08g imidazoles tosic acid ionic liquid [Hmim] TsO, add 5ml distilled water to dissolve, 5gSBA-15 is immersed in the aqueous solution of ionic liquid, leave standstill 24h, dry 4h by the head product 120 DEG C obtained, obtain 10g final catalyst [Hmim] TsO/SBA-15.
The synthesis of embodiment 8(load-type ion liquid) take ZSM-5 molecular sieve as the preparation method of carrier
Take ZSM-5 as carrier impregnation, take 5.08g imidazoles tosic acid ionic liquid [Hmim] TsO, add 5ml distilled water to dissolve, 5gZSM-5 is immersed in the aqueous solution of ionic liquid, leave standstill 24h, dry 4h by the head product 120 DEG C obtained, obtain 10g final catalyst [Hmim] TsO/ZSM-5.
The synthesis of embodiment 9(load-type ion liquid) preparation method that is carrier with Graphene Gr
Take Graphene as carrier impregnation, take 5.08g imidazoles tosic acid ionic liquid [Hmim] TsO, add 5ml distilled water to dissolve, 5g Graphene is immersed in the aqueous solution of ionic liquid, leave standstill 24h, dry 4h by the head product 120 DEG C obtained, obtain 10g final catalyst [Hmim] TsO/Gr.
The synthesis of embodiment 10(load-type ion liquid) prepare with sol-gel method
20ml tetraethyl orthosilicate (TESO) and 15ml ethanol are mixed in reactor, be heated to 60 DEG C, add imidazoles tosic acid ionic liquid ([Hmim] TsO) 8.16g immediately, be uniformly mixed, until form uniform mixed phase, add 10ml5mol/L hydrochloric acid, reaction mixture forms gel gradually, remains on 60 DEG C of reaction 12h.Gained head product vacuum-drying 3h at 150 DEG C after reaction, obtains pale yellow crystals, i.e. 16g final catalyst [Hmim] TsO/silicagel.
Embodiment 11(esterification)
By O.0014mo1NaY molecular sieve carried imidazole acetate ionic liquid [Hmim] CH
3cOO/NaY, O.06mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 7.5ml cyclohexane give is water entrainer, intensification makes system temperature remain on 160 DEG C, abundant stirring lower point of water reaction 2.5h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 93.2%.
Embodiment 12(esterification)
To O.0014mo1 γ-Al
2o
3imidazole acetate ionic liquid [Hmim] CH of load
3cOO/ γ-Al
2o
3, O.06mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 7.5ml cyclohexane give is water entrainer, intensification makes system temperature remain on 155 DEG C, abundant stirring lower point of water reaction 2h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 94.1%.
Embodiment 13(esterification)
By imidazole acetate ionic liquid [Hmim] CH of O.0014mo1SBA-15 load
3cOO/SBA-15, O.06mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 7.5ml cyclohexane give is water entrainer, intensification makes system temperature remain on 155 DEG C, abundant stirring lower point of water reaction 2h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 94.6%.
Embodiment 14(esterification)
By O.0012mo1NaY molecular sieve carried imidazoles butanic acid ionic liquid [Hmim] C
4h
7o
2/ NaY, O.05mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 7ml cyclohexane give is water entrainer, intensification makes system temperature remain on 150 DEG C, abundant stirring lower point of water reaction 2h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 94.0%.
Embodiment 15(esterification)
To O.0012mo1 γ-Al
2o
3imidazoles butanic acid ionic liquid [Hmim] C of load
4h
7o
2/ γ-Al
2o
3, O.05mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 7ml cyclohexane give is water entrainer, intensification makes system temperature remain on 145 DEG C, abundant stirring lower point of water reaction 2h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 95.3%.
Embodiment 16(esterification)
By imidazoles butanic acid ionic liquid [Hmim] C of O.0012mo1SBA-15 load
4h
7o
2/ SBA-15, O.05mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 7ml cyclohexane give is water entrainer, intensification makes system temperature remain on 145 DEG C, abundant stirring lower point of water reaction 2h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 95.7%.
Embodiment 17(esterification)
By O.0011mo1NaY molecular sieve carried imidazole phosphate ionic liquid [Hmim] H
2pO
4/ NaY, O.045mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 6ml cyclohexane give is water entrainer, intensification makes system temperature remain on 145 DEG C, abundant stirring lower point of water reaction 1.5h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 95.1%.
Embodiment 18(esterification)
To O.0011mo1 γ-Al
2o
3imidazole phosphate ionic liquid [Hmim] H of load
2pO
4/ γ-Al
2o
3, O.045mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 6ml cyclohexane give is water entrainer, intensification makes system temperature remain on 145 DEG C, abundant stirring lower point of water reaction 1.5h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 96.5%.
Embodiment 19(esterification)
By imidazole phosphate ionic liquid [Hmim] H of O.0011mo1SBA-15 load
2pO
4/ SBA-15, O.045mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 6ml cyclohexane give is water entrainer, intensification makes system temperature remain on 140 DEG C, abundant stirring lower point of water reaction 1.5h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 97.3%.
Embodiment 20(esterification)
By imidazole phosphate ionic liquid [Hmim] H of O.0011mo1ZSM-5 load
2pO
4/ ZSM-5, O.045mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 6ml cyclohexane give is water entrainer, intensification makes system temperature remain on 140 DEG C, abundant stirring lower point of water reaction 1.5h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 97.9%.
Embodiment 21(esterification)
By imidazole phosphate ionic liquid [Hmim] H of O.0011mo1Gr load
2pO
4/ Gr, O.045mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 6ml cyclohexane give is water entrainer, intensification makes system temperature remain on 140 DEG C, abundant stirring lower point of water reaction 1.5h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 98.5%.
Embodiment 22(esterification)
Imidazoles tosic acid ionic liquid Hmim by O.001mo1NaY molecular sieve carried] TsO/NaY, O.04mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 5ml cyclohexane give is water entrainer, intensification makes system temperature remain on 145 DEG C, abundant stirring lower point of water reaction 1h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 96.1%.
Embodiment 23(esterification)
To O.001mo1 γ-Al
2o
3the imidazoles tosic acid ionic liquid Hmim of load] TsO/ γ-Al
2o
3, O.04mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 5ml cyclohexane give is water entrainer, intensification makes system temperature remain on 140 DEG C, abundant stirring lower point of water reaction 1h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 97.6%.
Embodiment 24(esterification)
Imidazoles tosic acid ionic liquid Hmim by O.001mo1SBA-15 load] TsO/SBA-15, O.04mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 5ml cyclohexane give is water entrainer, intensification makes system temperature remain on 140 DEG C, abundant stirring lower point of water reaction 1h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 99.1%.
Embodiment 25(esterification)
Imidazoles tosic acid ionic liquid Hmim by O.001mo1ZSM-5 load] TsO/ZSM-5, O.04mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 5ml cyclohexane give is water entrainer, intensification makes system temperature remain on 140 DEG C, abundant stirring lower point of water reaction 1h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 99.3%.
Embodiment 26(esterification)
Imidazoles tosic acid ionic liquid Hmim by O.001mo1Gr load] TsO/Gr, O.04mo1 oleic acid and O.01mo1 tetramethylolmethane, add in the round-bottomed flask that reflux condensation mode division box is housed, separately adding 5ml cyclohexane give is water entrainer, intensification makes system temperature remain on 140 DEG C, abundant stirring lower point of water reaction 1h, stopped reaction, cooling, leave standstill, filtering separation liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO through underpressure distillation, esterification yield 99.5%.
Claims (10)
1. load-type ion liquid catalyzes and synthesizes a method for lubricant base, it is characterized in that: with oleic acid and tetramethylolmethane for raw material, using load-type ion liquid as catalyzer and solubilizing agent, by esterification synthetic lubricant base oil.
2. load-type ion liquid as claimed in claim 1 catalyzes and synthesizes the method for lubricant base, it is characterized in that: described ionic liquid is glyoxaline ion liquid, and it consists of: [Hmim]
+x
-, cation A
+for glyoxaline cation ([Hmim]
+):
Negatively charged ion X
-for: phosphate radical, acetate, butanic acid root or tosic acid root;
Ionic liquid structural formula is:
。
3. load-type ion liquid as claimed in claim 2 catalyzes and synthesizes the method for lubricant base, it is characterized in that: described ionic liquid is imidazoles acetate, imidazoles butanic acid salt, imidazole phosphate or imidazoles tosic acid ionic liquid.
4. load-type ion liquid as claimed in claim 1 catalyzes and synthesizes the method for lubricant base, it is characterized in that: described load-type ion liquid adopts pickling process to be prepared, the steps include: 1 mass parts ion liquid dissolving obtained ionic liquid solution in 0.5-2 mass parts solvent, 1-5 mass parts carrier is joined in 0.5-3 mass parts ionic liquid solution, dipping 12h-24h is stirred at 15-85 DEG C, stop heating, centrifugation after cooling, remove supernatant liquid, add distilled water wash again, recentrifuge is separated, remove supernatant liquid, the vacuum-drying in the baking oven of 90-150 DEG C of the solid of lower floor, obtained load-type ion liquid.
5. load-type ion liquid as claimed in claim 4 catalyzes and synthesizes the method for lubricant base, it is characterized in that: described solvent is methyl alcohol, water, ethanol, isopropylcarbinol, primary isoamyl alcohol, n-hexyl alcohol or acetic acid.
6. load-type ion liquid as claimed in claim 4 catalyzes and synthesizes the method for lubricant base, it is characterized in that: described carrier is NaY, γ-Al
2o
3, SBA-15, ZSM-5 or Gr.
7. load-type ion liquid as claimed in claim 1 catalyzes and synthesizes the method for lubricant base, it is characterized in that: described load-type ion liquid adopts sol-gel method to be prepared, the steps include: after 1 parts by volume tetraethyl orthosilicate and the mixing of 0.5-5 parts by volume dehydrated alcohol, be heated to 30-80 DEG C, slowly add the ionic liquid prepared subsequently, be uniformly mixed, until form uniform mixed phase, add 0.5-5 volume hydrochloric acid, reaction mixture forms gel gradually, remain on 60-100 DEG C and continue aging 6-24h, finally vacuum-drying 2-6h at 100-150 DEG C, obtained load-type ion liquid.
8. load-type ion liquid as claimed in claim 1 catalyzes and synthesizes the method for lubricant base, it is characterized in that: load-type ion liquid is as catalyst for esterification reaction and solubilizing agent, the add-on of described load-type ion liquid is the 0.5%-3% of alkyd integral molar quantity, and the mol ratio of oleic acid and tetramethylolmethane is 3-6:1.
9. load-type ion liquid as claimed in claim 1 catalyzes and synthesizes the method for lubricant base, and it is characterized in that: described esterification reaction temperature is 130-160 DEG C, normal pressure, the reaction times is 0.5-3 hour.
10. load-type ion liquid as claimed in claim 1 catalyzes and synthesizes the method for lubricant base, it is characterized in that: after reaction terminates, through simple filtration, load-type ion liquid catalyst can separate, and reusable.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658990A (en) * | 2017-03-31 | 2018-10-16 | 南京科技职业学院 | A kind of novel imidazole simultaneously [1,5-a] Pyrazine Bu Ludun kinase inhibitors |
| CN112174876A (en) * | 2020-10-14 | 2021-01-05 | 江苏高科石化股份有限公司 | Preparation method and application of pyridine ionic liquid acidic catalyst |
| CN112439453A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Preparation method of catalyst for vinyl acetate by acetylene method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381437A (en) * | 2002-04-29 | 2002-11-27 | 王伟松 | Method for synthesizing pentaerythritol oleate |
| CN101245006A (en) * | 2008-03-14 | 2008-08-20 | 江南大学 | Process for producing pentaerythritol oleate |
| CN102887825A (en) * | 2012-09-04 | 2013-01-23 | 陕西省石油化工研究设计院 | Method for preparing polyol ester lubricating oil by using composite solid acid catalyst |
| CN105777643A (en) * | 2014-12-22 | 2016-07-20 | 南京化工职业技术学院 | Method using immobilized ionic liquid as catalyst to synthesize lubricant base oil |
-
2015
- 2015-12-17 CN CN201510948326.1A patent/CN105541612A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381437A (en) * | 2002-04-29 | 2002-11-27 | 王伟松 | Method for synthesizing pentaerythritol oleate |
| CN101245006A (en) * | 2008-03-14 | 2008-08-20 | 江南大学 | Process for producing pentaerythritol oleate |
| CN102887825A (en) * | 2012-09-04 | 2013-01-23 | 陕西省石油化工研究设计院 | Method for preparing polyol ester lubricating oil by using composite solid acid catalyst |
| CN105777643A (en) * | 2014-12-22 | 2016-07-20 | 南京化工职业技术学院 | Method using immobilized ionic liquid as catalyst to synthesize lubricant base oil |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658990A (en) * | 2017-03-31 | 2018-10-16 | 南京科技职业学院 | A kind of novel imidazole simultaneously [1,5-a] Pyrazine Bu Ludun kinase inhibitors |
| CN108658990B (en) * | 2017-03-31 | 2021-03-23 | 南京科技职业学院 | Novel imidazo [1,5-a ] pyrazine Bruton kinase inhibitors |
| CN112439453A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Preparation method of catalyst for vinyl acetate by acetylene method |
| CN112174876A (en) * | 2020-10-14 | 2021-01-05 | 江苏高科石化股份有限公司 | Preparation method and application of pyridine ionic liquid acidic catalyst |
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