CN105777643A - Method using immobilized ionic liquid as catalyst to synthesize lubricant base oil - Google Patents
Method using immobilized ionic liquid as catalyst to synthesize lubricant base oil Download PDFInfo
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Abstract
The invention discloses a method using immobilized ionic liquid as a catalyst to synthesize lubricant base oil. The method is characterized in that oleic acid and pentaerythritol are taken as the raw materials, and immobilized imidazole ionic liquid is taken as the catalyst and solubilizer. An impregnation method or a sol-gel method is adopted to prepare the immobilized ionic liquid; the added catalyst accounts for 0.5 to 3% of the total mole number of alcohols and acids, the reaction temperature is 130 to 160 DEG C, the reaction pressure is a normal pressure, and the reaction time is 0.5 to 3 hours. The method is characterized in that concentrated sulfuric acid and hydrofluoric acid, which are pollutant to the environment, are not used; compared with the inorganic acid catalyst for alcohol-acid esterification, the immobilized ionic liquid has the advantages that the reaction conditions are mild, the catalytic activity is high, the reaction time is short, the esterification rate is high, the production technology is simplified, the operation of catalyst recovery is simple, and the catalyst can be repeatedly used.
Description
Technical field
The present invention relates to organic chemical reactions method, the method particularly relating to the ionic liquid-catalyzed synthetic lubricant base oil of a kind of solid-carrying type.
Technical background
Along with the development of modern chemical industry and car industry, being in great demand of lubricating oil, therefore, people increasingly pay close attention to oil quality and prepare the pollution that environment is likely to result in.Synthetic base oil refers to the lube base oil by being chemically synthesized.Comparing mineral oil, synthetic lubricant fluid has Heat stability is good, and heat decomposition temperature is high, and the advantages such as resistance to low temperature is good, are current very important chemical industry basic products.Synthetic base oil has many types, is most commonly that synthesizing ester.Traditional alcoholic acid esterification technology generally uses the inorganic acid as catalyst of the severe corrosives such as concentrated sulphuric acid, there is esterification yield low, etching apparatus contaminated environment, product and the problem such as catalyst difficulty separates, therefore industrial to developing existing economic benefit, to have again the demand of eco-friendly novel alcoholic acid esterification system concurrently extremely urgent.Ionic liquid is the new material received much concern in recent years, has good stability, non-volatile, nonflammable, dissolubility and the advantage such as acidity is adjustable, show the characteristic of excellence in a lot of acid catalytic systems, also have application in the esterification reaction as novel green catalysts and solvents.Song Hang etc. are a kind of " preparation of temperature sensitive acidic ionic liquid and the method for catalytic hydroxy acid esterifying thereof " disclosed in 201010211280.2 at application number, during benzothiazole salt temperature sensitive acidic ionic liquid prepared by the method reacts for catalytic hydroxy acid esterifying, ionic liquid has highly acid, and the feature such as have good stability.Zhang Suojiang etc. are " a kind of catalytic hydroxy acid esterifying process " disclosed in Chinese invention patent CN1554638A, and the method is using ionic liquid as catalyst, the form of ionic liquid is: A+B-, wherein A is the nitrogen-containing compound such as alkyl pyridine, imidazoles, and B is simple halogen fluorine, chlorine, bromine or TA, TfO-、NO3 -Deng, the esterification of catalysis has higher selectivity, and technique is simple, and catalyst stability is good.But the ionic liquid synthesis complexity that the method for above-mentioned synthetic ester uses, and there is the substantial amounts of organic solvent of reaction needed, the problems such as esterification yield is not high, and catalyst difficulty separates, post processing more complicated.
For solving an above-mentioned difficult problem, functionalized ion liquid is immobilized on inorganic porous material or high-molecular organic material, prepares solid-carrying type ionic-liquid catalyst, thus overcoming immobilized thing to separate difficult, post processing more complicated, the problems such as catalyst amount is big.Zhao Yajuan etc. are " a kind of load-type ion liquid catalyst and its preparation method and application " disclosed in Chinese invention patent CN101664700A, and the catalyst described in the method is that supported on carriers has pyridines acidic ion liquid [XPy] HS04, carrier is Y-Al203、Si02, mesopore molecular sieve, SBA-15 etc., apply it and catalyze and synthesize diethylene glycol, there is catalyst activity height, life-span long, reaction condition is gentle, the features such as production technology is simple.Xu Hang etc. are " a kind of load-type ion liquid catalyst, its preparation method and application thereof " disclosed in 201010101778.3 at application number, this method provide a kind of load-type ion liquid catalyst for producing vinyl acetate by acetylene method, it is with mesopore molecular sieve for carrier, with zinc acetate for active component, it is connected with imidazoles acetate ionic liquid between carrier with active component.Ionic liquid is formed at catalyst surface and intends liquid phase microenvironment, increases course of reaction mass transfer and conductivity of heat, and good stability, life-span length, activity are high, selectivity is good.Functionalization solid-carrying type ionic liquid successful Application in these organic synthesis, is increasingly subject to the attention of chemical circles.
Therefore, exploitation activity height, stable in catalytic performance, product and the segregative functionalized ion liquid of catalyst catalyze and synthesize lube base oil technique oneself cause great concern, the patent of invention of current application associated therewith mainly has following items.
Zhou Feng etc. are a kind of " containing BTA group ionic liquid and its preparation method and application " disclosed in 201110098075.4 at application number, ionic liquid prepared by the method is with imidazoles for cation, hexafluoro-phosphate radical, tetrafluoroborate or two (trimethyl fluoride sulfonyl) amine anion are anion, and the cyclosubstituted end group of its imidazoles is containing BTA group.Ionic liquid uses as lube oil additive or grease additive.
S Ai Lemali etc. are a kind of " preparation method with the high viscosity base oil improving viscosity index (VI) " disclosed in 201180052106.0 at application number, and the method includes making boiling point one or more olefin oligomerizations less than 82 DEG C to produce to have 36mm at 100 DEG C in the reactor under ionic-liquid catalyst and one or more C5+ alhpa olefins exist2The base oil of the kinematic viscosity of/s or higher and the VI more than 55.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 formula can be characterized as Q+A-, wherein Q+For ammonium cation, cation, boron ion, iodine cation or sulfur cation, A-For electronegative ion such as Cl-、Br-、Cl04 -、N03 -、BF4 -、BC14 -、PF6 -、SbF6 -、AlC14 -、TaF6 -、CuC12 -、FeC13 -Deng.
Tight Zong Cheng etc. are a kind of " Ionic liquid/vegetable oil microemulsion type biological lubricant base oil and preparation method thereof " disclosed in 201310113686.0 at application number, the method is in mass fraction, it consists of ionic liquid 1 part, vegetable oil 1-30 part, surfactant 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 tetrafluoroborate and 1-ethoxy-3-methyl imidazolium tetrafluoroborate ionic liquid;Described vegetable oil is one or more in soybean oil, Oleum Ricini, jatropha curcas oil, Oleum Helianthi, Testa oryzae oil and Petiolus Trachycarpi oil.Obtaining the reversed phase ion liquid micro liquid system of clear homogeneous after preparation, stability is high, raw material sources environmental protection, and gained lube base oil has the viscosity-temperature characteristics of excellence, heat stability and the nanometer additive compatibility.
Zhou Feng etc. are " a kind of antioxidant ionic liquid containing sterically hindered phenol and its preparation method and application " disclosed in 200910117591.X at application number, the cation of ionic liquid prepared by the method is the glyoxaline cation that sterically hindered phenol replaces, and anion is hexafluoro-phosphate radical, tetrafluoroborate or two trifluoromethane sulfonic acid roots.Ionic liquid can use as lube oil additive, and it is possible not only to improve oil ageing stability, and can be obviously improved the tribological property of lubricating oil.
Tight Zong Cheng etc. application number be disclosed in 201010286234.9 " a kind of with ionic liquid be catalyst preparing biological lubricant and preparation method ", Vegetable oil lipoprotein and trimethylolpropane are mixed by the method by weight 1-3:1, are subsequently adding above two raw material gross weight number B-acid ionic liquid O.5-1.5% and make catalyst;Again by above-mentioned heating material to 120-180 DEG C, stirring, react 4-8h;Then reacted material is rapidly cooled to 30-50 DEG C, rotational flow settlement, become solid after the cooling of B-acid ionic liquid, after rotational flow settlement, be deposited in eddy flow pot bottom, and product and unreacted material completely is still in liquid phase;Finally product and unreacted material completely being entered rectifying column distillation, rectification bottom product is biological lubricant.Wherein B-acid ionic liquid is pyridine-sulfonic acid functional group or imidazole sulfonic acid functional group proton is cation, and heteropoly acid is anion ion liquid.
But there are no the solid-carrying type ionic liquid prepared using infusion process or sol-gal process as catalyst and solubilizing agent, reported by the technological invention of esterification synthetic lubricant base oil or academic research.
Glyoxaline ion liquid is carried out immobilized by the present invention, realize supported ionic liquids, and it is applied to lube base oil synthetic reaction, catalyst easily reclaimed and can reuse, simplifying production technology, while improving esterification yield, reduce ionic liquid consumption, reduce equipment corrosion, reduce environmental pollution, be expected to develop the Green Chemistry catalyst substituting tradition severe corrosive acid catalyst.
Summary of the invention
The invention provides the preparation of a kind of solid-carrying type ionic liquid and the method utilizing it as catalyst synthetic lubricant base oil, this catalyst avoids conventional inorganic acid catalyst and there is the problems such as subsequent treatment complexity, equipment corrosion be serious, and this catalyst shows good heat stability and efficient catalysis activity in the esterification reaction, the separation of catalyst product and raw material simultaneously is easier to, simplify production technology, save production cost.
The technical solution used in the present invention is:
Described glyoxaline ion liquid consists of: [Hmim]+X-,
Cation A+For glyoxaline cation ([Hmim]+):
Anion X-For: phosphate radical, acetate, n-butyric acie root or p-methyl benzenesulfonic acid root；
Ionic liquid structural formula is:
1. adopt the immobilized above-mentioned ionic liquid of infusion process, i.e. solid-carrying type glyoxaline ion liquid catalyst.It specifically comprises the following steps that
(1) prepared by glyoxaline ion liquid: 1 mass parts N-Methylimidazole. and 0.5-3 mass parts acid being mixed, add 1-8ml solvent, Stirring, reaction temperature controls at 60-120 DEG C.With this understanding, reaction carries out 3-10h, obtains weak yellow liquid；The weak yellow liquid obtained carries out decompression distillation, and the vacuum controlling decompression 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) 1 mass parts ion liquid dissolving is prepared in 0.5-2 mass parts solvent ionic liquid solution, 1-5 mass parts carrier is joined in 0.5-3 mass parts ionic liquid solution, at 15-85 DEG C, stirring dipping 12h-24h, stops heating, centrifugation after cooling, remove supernatant liquid, adding distilled water wash, recentrifuge separates, and removes supernatant liquid, the solid of lower floor vacuum drying in the baking oven of 90-150 DEG C, prepare solid-carrying type glyoxaline ion liquid.
2. adopting the immobilized functionalization glyoxaline ion liquid of sol-gal process, it specifically comprises the following steps that
(1) prepared by glyoxaline ion liquid: 1 mass parts N-Methylimidazole. and 0.5-3 mass parts acid being mixed, add 1-8ml solvent, Stirring, reaction temperature controls at 60-120 DEG C.With this understanding, reaction carries out 3-10h, obtains weak yellow liquid；The weak yellow liquid obtained carries out decompression distillation, and the vacuum controlling decompression 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) after 1 parts by volume tetraethyl orthosilicate and 0.5-5 parts by volume dehydrated alcohol being mixed, heating is to 30-80 DEG C, it is slowly added into the ionic liquid prepared subsequently, stirring mixing, until forming uniform mixed phase, adds 0.5-5 volume hydrochloric acid, reactant mixture gradually forms gel, it is maintained at 60-100 DEG C and continues aging 6-24h, finally vacuum drying 2-6h at 100-150 DEG C, prepare solid-carrying type glyoxaline ion liquid.
3. the enforcement of esterification, it specifically comprises the following steps that
The mol ratio of described oleic acid and tetramethylolmethane is 3-6:1, and the addition of solid-carrying type glyoxaline ion liquid is the 0.5%-3% of alkyd integral molar quantity.
Described esterification reaction temperature is 130-160 DEG C, and the response time is 0.5-3h.
After reaction terminates, through simple filtration, solid-carrying type glyoxaline ion liquid catalyst can separate, it is possible to reuses.
Beneficial effect:
1. reaction time of esterification is short, good catalyst activity, and in lube base oil esterification experiment, the esterification yield of PETO reaches 92.1%-99.3%.
2. ionic liquid has steam and forces down, cleans the features such as nontoxic, and as catalyst, reaction condition is gentle, and use procedure is non-volatile, pollution-free, overcomes the acid catalyst pollution to environment and the corrosion to equipment.
3. ionic liquid is after immobilized, and catalyst reclaimer operation is simple, and the life-span is long, while Simplified flowsheet, reduces production cost.
Detailed description of the invention
Embodiment is given below so that the invention will be further described.Be necessary it is pointed out here that, following example, it is not intended that limiting the scope of the invention, if the present invention is made some nonessential improvement and adjustment according to the invention described above content by person skilled in art, still fall within protection scope of the present invention.
The synthesis of embodiment 1(ionic liquid) preparation method of imidazole acetate ionic liquid
Weigh N-Methylimidazole. 8.0g and acetic acid 4.0g in 250ml there-necked flask, add 1ml water as solvent, Stirring, temperature is controlled at 60 DEG C.With this understanding, reaction carries out 3h, obtains weak yellow liquid.
The weak yellow liquid obtained carries out decompression distillation, and the vacuum controlling decompression distillation is 0.05MPa, and head temperature is 70 DEG C, and distillation time is 1h, namely obtains imidazole acetate ionic liquid [Hmim] CH3COO。
The synthesis of embodiment 2(ionic liquid) preparation method of imidazoles n-butyric acie ionic liquid
Weigh N-Methylimidazole. 8.02g and n-butyric acie 24.06g in 250ml there-necked flask, add 8ml water as solvent, magnetic stirrer, electric heating cover heats, and condensate return reacts at a reflux temperature, reaction temperature controls at 120 DEG C, reacts 10h, obtains yellow liquid.
The liquid obtained carries out decompression distillation, and control vacuum is 0.2MPa, and head temperature is about 110 DEG C, and distillation time is 5h.Namely imidazoles n-butyric acie ionic liquid [Hmim] C is obtained4H7O2。
The synthesis of embodiment 3(ionic liquid) preparation method of imidazole phosphate ionic liquid
Weighing N-Methylimidazole. 16.4g 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, and reaction temperature controls at 80 DEG C, reacts 7h, obtains yellow liquid.
The liquid obtained carries out decompression distillation, and control vacuum is 0.05MPa, and head temperature is about 75 DEG C, and distillation time is 3h, namely obtains imidazole phosphate ionic liquid [Hmim] H2PO4。
The synthesis of embodiment 4(ionic liquid) preparation method of imidazoles p-methyl benzenesulfonic acid ionic liquid
Weigh N-Methylimidazole. 16.4g and p-methyl benzenesulfonic acid 34.4g in 250ml there-necked flask, add 5ml water as solvent, magnetic stirrer, electric heating cover heats, and condensate return reacts at a reflux temperature, reaction temperature controls at 80 DEG C, reacts 16h, obtains brown color liquid.
The liquid obtained carries out decompression distillation, and control vacuum is 0.05MPa, and head temperature is about 70 DEG C, and distillation time is 4h, namely obtains imidazoles p-methyl benzenesulfonic acid ionic liquid [Hmim] TsO.
The synthesis of embodiment 5(solid-carrying type ionic liquid) be carrier with NaY molecular sieve preparation method
With NaY molecular sieve for carrier impregnation, with 2.5ml water, 5.0g imidazoles p-methyl benzenesulfonic acid ionic liquid [Hmim] TsO is dissolved, 15gNaY molecular sieve is soaked in the solution, at 15 DEG C after continuously stirred 12h, by drying 4h at the head product 90 DEG C obtained, obtain final catalyst [Hmim] TsO/NaY.
The synthesis of embodiment 6(solid-carrying type ionic liquid) with γ-Al2O3Molecular sieve is the preparation method of carrier
With γ-Al2O3Molecular sieve is carrier impregnation, weighs 5.0g imidazoles p-methyl benzenesulfonic acid ionic liquid [Hmim] TsO, adds 10ml distilled water and dissolves, 25g γ-Al2O3It is immersed in the aqueous solution of ionic liquid, stirring dipping 24h at 85 DEG C, by drying 4h at the head product 150 DEG C obtained, obtain 10g final catalyst [Hmim] TsO/ γ-Al2O3。
The synthesis of embodiment 7(solid-carrying type ionic liquid) be carrier with SBA-15 molecular sieve preparation method
With SBA-15 for carrier impregnation, weigh 5.08g imidazoles p-methyl benzenesulfonic acid ionic liquid [Hmim] TsO, add 5ml distilled water to dissolve, 5gSBA-15 is immersed in the aqueous solution of ionic liquid, stand 24h, by drying 4h at the head product 120 DEG C obtained, obtain 10g final catalyst [Hmim] TsO/SBA-15.
The synthesis of embodiment 8(solid-carrying type ionic liquid) be carrier with ZSM-5 molecular sieve preparation method
With ZSM-5 for carrier impregnation, weigh 5.08g imidazoles p-methyl benzenesulfonic acid ionic liquid [Hmim] TsO, add 5ml distilled water to dissolve, 5gZSM-5 is immersed in the aqueous solution of ionic liquid, stand 24h, by drying 4h at the head product 120 DEG C obtained, obtain 10g final catalyst [Hmim] TsO/ZSM-5.
The synthesis of embodiment 9(solid-carrying type ionic liquid) with the Graphene Gr preparation method being carrier
With Graphene for carrier impregnation, weigh 5.08g imidazoles p-methyl benzenesulfonic acid ionic liquid [Hmim] TsO, add 5ml distilled water to dissolve, 5g Graphene is immersed in the aqueous solution of ionic liquid, stand 24h, by drying 4h at the head product 120 DEG C obtained, obtain 10g final catalyst [Hmim] TsO/Gr.
The synthesis of embodiment 10(solid-carrying type ionic liquid) prepare with sol-gal process
20ml tetraethyl orthosilicate (TESO) and 10ml ethanol are mixed in reactor, heating is to 30 DEG C, add imidazoles p-methyl benzenesulfonic acid ionic liquid ([Hmim] TsO) 8.16g immediately, stirring mixing, until forming uniform mixed phase, adding 10ml5mol/L hydrochloric acid, reactant mixture gradually forms gel, is maintained at 60 DEG C of reaction 6h.After reaction, gained head product vacuum drying 2h at 100 DEG C, obtains pale yellow crystals, i.e. 16g final catalyst [Hmim] TsO/silicagel.
The synthesis of embodiment 11(solid-carrying type ionic liquid) prepare with sol-gal process
20ml tetraethyl orthosilicate (TESO) and 100ml ethanol are mixed in reactor, heating is to 80 DEG C, add imidazoles p-methyl benzenesulfonic acid ionic liquid ([Hmim] TsO) 8.16g immediately, stirring mixing, until forming uniform mixed phase, adding 100ml5mol/L hydrochloric acid, reactant mixture gradually forms gel, is maintained at 100 DEG C of reaction 24h.After reaction, gained head product vacuum drying 6h at 150 DEG C, obtains pale yellow crystals, i.e. 16g final catalyst [Hmim] TsO/silicagel.
Embodiment 12(esterification)
By O.0002mo1 γ-Al2O3Immobilized imidazole acetate ionic liquid [Hmim] CH3COO/γ-Al2O3, O.03mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 7.5ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 130 DEG C, it is sufficiently stirred for down a point water reaction 0.5h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 92.1% through decompression distillation.
Embodiment 13(esterification)
By O.0021mo1SBA-15 immobilized imidazole acetate ionic liquid [Hmim] CH3COO/SBA-15, O.06mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 7.5ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 160 DEG C, it is sufficiently stirred for down a point water reaction 3h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 99.3% through decompression distillation.
Embodiment 14(esterification)
By imidazoles n-butyric acie ionic liquid [Hmim] C of O.0012mo1NaY Supported on Zeolite4H7O2/ NaY, O.05mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 7ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 150 DEG C, it is sufficiently stirred for down a point water reaction 2h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 94.0% through decompression distillation.
Embodiment 15(esterification)
By O.0012mo1 γ-Al2O3Immobilized imidazoles n-butyric acie ionic liquid [Hmim] C4H7O2/γ-Al2O3, O.05mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 7ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 145 DEG C, it is sufficiently stirred for down a point water reaction 2h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 95.3% through decompression distillation.
Embodiment 16(esterification)
By O.0012mo1SBA-15 immobilized imidazoles n-butyric acie ionic liquid [Hmim] C4H7O2/ SBA-15, O.05mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 7ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 145 DEG C, it is sufficiently stirred for down a point water reaction 2h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 95.7% through decompression distillation.
Embodiment 17(esterification)
By imidazole phosphate ionic liquid [Hmim] H of O.0011mo1NaY Supported on Zeolite2PO4/ NaY, O.045mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 6ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 145 DEG C, it is sufficiently stirred for down a point water reaction 1.5h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 95.1% through decompression distillation.
Embodiment 18(esterification)
By O.0011mo1 γ-Al2O3Immobilized imidazole phosphate ionic liquid [Hmim] H2PO4/γ-Al2O3, O.045mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 6ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 145 DEG C, it is sufficiently stirred for down a point water reaction 1.5h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 96.5% through decompression distillation.
Embodiment 19(esterification)
By O.0011mo1SBA-15 immobilized imidazole phosphate ionic liquid [Hmim] H2PO4/ SBA-15, O.045mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 6ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 140 DEG C, it is sufficiently stirred for down a point water reaction 1.5h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 97.3% through decompression distillation.
Embodiment 20(esterification)
By O.0011mo1ZSM-5 immobilized imidazole phosphate ionic liquid [Hmim] H2PO4/ ZSM-5, O.045mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 6ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 140 DEG C, it is sufficiently stirred for down a point water reaction 1.5h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 97.9% through decompression distillation.
Embodiment 21(esterification)
By O.0011mo1Gr immobilized imidazole phosphate ionic liquid [Hmim] H2PO4/ Gr, O.045mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 6ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 140 DEG C, it is sufficiently stirred for down a point water reaction 1.5h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 98.5% through decompression distillation.
Embodiment 22(esterification)
By the imidazoles p-methyl benzenesulfonic acid ionic liquid Hmim of O.001mo1NaY Supported on Zeolite] TsO/NaY, O.04mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 5ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 145 DEG C, it is sufficiently stirred for down a point water reaction 1h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 96.1% through decompression distillation.
Embodiment 23(esterification)
By O.001mo1 γ-Al2O3Immobilized imidazoles p-methyl benzenesulfonic acid ionic liquid Hmim] TsO/ γ-Al2O3, O.04mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 5ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 140 DEG C, it is sufficiently stirred for down a point water reaction 1h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 97.6% through decompression distillation.
Embodiment 24(esterification)
Imidazoles p-methyl benzenesulfonic acid ionic liquid Hmim by O.001mo1SBA-15 immobilized] TsO/SBA-15, O.04mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 5ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 140 DEG C, it is sufficiently stirred for down a point water reaction 1h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 99.1% through decompression distillation.
Embodiment 25(esterification)
Imidazoles p-methyl benzenesulfonic acid ionic liquid Hmim by O.001mo1ZSM-5 immobilized] TsO/ZSM-5, O.04mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 5ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 140 DEG C, it is sufficiently stirred for down a point water reaction 1h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 98.3% through decompression distillation.
Embodiment 26(esterification)
Imidazoles p-methyl benzenesulfonic acid ionic liquid Hmim by O.001mo1Gr immobilized] TsO/Gr, O.04mo1 oleic acid and O.01mo1 tetramethylolmethane, it is equipped with in the round-bottomed flask of reflux condensation mode division box, the another 5ml cyclohexane give that adds is water entrainer, intensification makes system temperature be maintained at 140 DEG C, it is sufficiently stirred for down a point water reaction 1h, stopped reaction, cooling, standing, isolated by filtration liquid phase also reclaims ionic-liquid catalyst.Ester collects PETO, esterification yield 98.5% through decompression distillation.
Claims (10)
1. the method for the ionic liquid-catalyzed synthetic lubricant base oil of solid-carrying type, it is characterised in that: with oleic acid and tetramethylolmethane for raw material, using solid-carrying type ionic liquid as catalyst and solubilizing agent, by esterification synthetic lubricant base oil.
2. the method for the ionic liquid-catalyzed synthetic lubricant base oil of a kind of solid-carrying type as claimed in claim 1, it is characterized in that: above-mentioned solid-carrying type ionic liquid adopts infusion process to be prepared, the steps include: in 0.5-2 mass parts solvent, prepare 1 mass parts ion liquid dissolving ionic liquid solution, 1-5 mass parts carrier is joined in 0.5-3 mass parts ionic liquid solution, stirring dipping 12h-24h at 15-85 DEG C, stop heating, centrifugation after cooling, remove supernatant liquid, add distilled water wash, recentrifuge separates, remove supernatant liquid, the solid of lower floor vacuum drying 4h in the baking oven of 90-150 DEG C, prepare solid-carrying type ionic liquid.
3. the preparation of solid-carrying type ionic liquid as claimed in claim 2, it is characterised in that: the ionic liquid of above-mentioned addition is imidazoles acetate, imidazoles n-butyric acie salt, imidazole phosphate or imidazoles p-methyl benzenesulfonic acid ionic liquid.
4. the preparation of solid-carrying type ionic liquid as claimed in claim 2, it is characterised in that: above-mentioned solvent is methanol, water, ethanol, isobutanol, isoamyl alcohol, hexanol or acetic acid.
5. the preparation of solid-carrying type ionic liquid as claimed in claim 2, it is characterised in that: above-mentioned carrier is NaY, γ-Al2O3, SBA-15, ZSM-5 or Gr.
6. the method for the ionic liquid-catalyzed synthetic lubricant base oil of a kind of solid-carrying type as claimed in claim 1, it is characterized in that: above-mentioned solid-carrying type ionic liquid adopts sol-gal process 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, heating is to 30-80 DEG C, it is slowly added into the ionic liquid prepared subsequently, stirring mixing, until forming uniform mixed phase, add 0.5-5 volume hydrochloric acid, reactant mixture gradually forms gel, it is maintained at 60-100 DEG C and continues aging 6-24h, last vacuum drying 2-6h at 100-150 DEG C, prepare solid-carrying type ionic liquid.
7. the preparation of solid-carrying type ionic liquid as claimed in claim 6, it is characterised in that: the ionic liquid of above-mentioned addition is imidazoles acetate, imidazoles n-butyric acie salt, imidazole phosphate or imidazoles p-methyl benzenesulfonic acid ionic liquid.
8. the method for the ionic liquid-catalyzed synthetic lubricant base oil of a kind of solid-carrying type as claimed in claim 1, it is characterized in that: solid-carrying type ionic liquid is as catalyst for esterification reaction, solubilizing agent, the addition of above-mentioned ionic 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. the method for the ionic liquid-catalyzed synthetic lubricant base oil of a kind of solid-carrying type as claimed in claim 1, it is characterised in that: described esterification reaction temperature is 130-160 DEG C, normal pressure, and the response time is 0.5-3 hour.
10. the method for the ionic liquid-catalyzed synthetic lubricant base oil of a kind of solid-carrying type as claimed in claim 1, it is characterised in that: after reaction terminates, through simple filtration, solid-carrying type ionic-liquid catalyst can separate, it is possible to reuses.
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