CN101955849B - Biological lubricant prepared with ionic liquid as catalyst and preparation method - Google Patents
Biological lubricant prepared with ionic liquid as catalyst and preparation method Download PDFInfo
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- CN101955849B CN101955849B CN2010102862349A CN201010286234A CN101955849B CN 101955849 B CN101955849 B CN 101955849B CN 2010102862349 A CN2010102862349 A CN 2010102862349A CN 201010286234 A CN201010286234 A CN 201010286234A CN 101955849 B CN101955849 B CN 101955849B
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Abstract
The invention discloses a biological lubricant prepared with ionic liquid as a catalyst and a preparation method. The preparation method specifically comprises the following steps: (1) mixing vegetable oil and trimethylolpropane in a weight ratio of 1-3:1 and then adding the B acid ionic liquid accounting for 0.5-1.5% of the above two raw materials by weight as the catalyst; (2) heating the above materials to 120-180 DEG C and stirring the materials to react for 4-8h; (3) rapidly cooling the materials after reaction to 30-50 DEG C, carrying out hydrocyclone settlement, cooling the B acid ionic liquid to solid, the solid settling at the bottom of a hydrocyclone tank after hydrocyclone settlement and the product and the materials which do not fully react being still liquid; and (4) distilling the product and the materials which do not fully react in a rectifying column, thus obtaining the biological lubricant at the bottom of the rectifying column. The biological lubricant has good biodegradability, good quality, low toxicity, good oxidation resistance and heat stability and lower cost as the intermediate products can be recycled.
Description
Technical field
Patent of the present invention relates to a kind of biological lubricating oil and preparation method thereof, and particularly relating to a kind of is biological lubricating oil of catalyzer and preparation method thereof with
acid ion liquid.
Background of invention
The biodegradable ability of traditional mineral based lubricating oil in physical environment can be trapped in the water and soil earth for a long time, and environment is caused serious pollution.EPA points out that oil has acute lethal toxicity to aquatic organism, and long-term subacute lethal toxicity (promptly can not cause biological death, but destroy its normal ecology) is also arranged.It is very urgent with low-temperature performance, readily biodegradable property and hypotoxic lubricating oil that exploitation has superior thermostability.Renewable resources is a raw material to originate widely, pays close attention to but the base oil of synthetic environment acceptance type lubricating oil receives widely, has very big market potential.And wherein be that the over-all properties of neopentyl polyol ester of representative is outstanding with the tricarboxymethyl propane oleate.
As one type of emerging environmental friendliness green solvent; Ionic liquid is acid with its high-density, be easy to separate and advantage such as reusable edible has received concern more and more widely, and
acidic ion liquid application aspect esterification has in recent years received people's attention.Esterification is a reaction type common in the organic chemical reactions, can synthesize a series of ester compounds and environment friendly biological fuel through this type reaction, is widely used in aspects such as fine chemistry industry and fossil energy.There is more drawback in traditional an acidic catalyst (like the vitriol oil, phosphoric acid, superpower solid acid etc.), and is serious like equipment corrosion, in the reaction process side reaction more, cause reaction preference on the low side, later separation difficulty; Though solid super-strong acid can overcome the part shortcoming of liquid acid, still there are technical problems such as easy inactivation, work-ing life be short, do not meet the requirement of Green Chemical Technology.
acidic ion liquid; Compare with the water-fast system ionic liquid of the s-generation with first-generation aluminum chloride system ionic liquid, have high-density acidity, empty G&W stablized, be easy to advantages such as separation, low-steam pressure, reusable edible; It is not halogen-containing simultaneously, has solvent, catalyzer dual function concurrently, does not have corrosion, and solubility property is good in water, is the green catalyst of a new generation, has the potentiality that replace traditional an acidic catalyst.
Summary of the invention
In order to solve the defective that above-mentioned technology exists, it is the biological lubricating oil and the preparation method of Preparation of Catalyst with the ionic liquid that the present invention provides a kind of, and this technological process is simple and direct, and it is low effectively to reduce production costs.The present invention is a raw material with natural fats and oils (staple is a triglyceride level) and TriMethylolPropane(TMP); With B acid ion liquid is catalyzer; Through transesterification,, obtain biological lubricating oil trimethyl propane three esters and sub product glycerine with the glycerine in TriMethylolPropane(TMP) substituted glycerol three esters; Product becomes solid-liquid two phases with catalyzer respectively after cooling, have from separating function.
The present invention specifically realizes through following technical proposals:
A kind of is the preparation method of the biological lubricating oil of catalyzer with the ionic liquid, comprises the steps:
(1) with Vegetable oil lipoprotein and TriMethylolPropane(TMP) by weight 1～3: 1 is mixed, and the B acid ion liquid that adds above-mentioned different raw material gross weight several 0.5～1.5% is then made catalyzer;
(2) above-mentioned material is heated to 120～180 ℃, stirs, reacted 4～8 hours; Wherein, trihydroxy-propane and triglyceride level transesterification reaction formula as shown in the formula:
(3) reacted material is cooled to 30～50 ℃ rapidly, the eddy flow sedimentation becomes solid after the B acid ion liquid cooling, after the eddy flow sedimentation, is deposited in the eddy flow pot bottom, and product and unreacted completely material still be liquid phase;
(4) with product and unreacted completely material get into the rectifying tower distillation, the rectifying tower top product is a glycerine, the rectifying intermediate material is a TriMethylolPropane(TMP) and unreacted glyceride stock completely, the rectifying bottom product is biological lubricating oil.
Preferably, B acidic ion liquid described in the step (1) is that pyridine-sulfonic acid functional group or imidazoles sulfonic acid functional group proton are positively charged ion, and heteropolyacid is an anion ion liquid.
Preferably, said heteropolyacid is phospho-wolframic acid, phospho-molybdic acid or silicotungstic acid root.
Preferably, add again after in the step (3) said B acid ion liquid (catalyzer) being separated in the reaction of step (1) and carry out recycle.
Preferably, rectifying intermediate material described in the step (4) is returned in the reaction that joins step (1) repetition (1)～(4) step 2～3 times.
Preferably, distillation described in the step (4) is rectification under vacuum.
Preferably, Vegetable oil lipoprotein is plam oil, Oleum Verniciae fordii, rapeseed oil or VT 18 described in the step (1).
The lubricating oil that aforesaid method makes can be done gear grease, hydraulicefficiency oil and chain greasisng oil.
The present invention compared with prior art has following advantage:
(1) the raw oil wide material sources used of the present invention are raw material with frequently seen plants grease such as plam oil, Oleum Verniciae fordii, rapeseed oil, Trisun Oil R 80 or VT 18, and raw material supply is stable, and with respect to fossil feedstock, cost is cheaper.
(2) method technology of the present invention is simple, and not high to equipment requirements, production cost is low, is fit to the different scales enterprise production.
(3) the B acid ion liquid that uses of the present invention is meant that pyridine-sulfonic acid functional group or imidazoles sulfonic acid functional group proton are positively charged ion, and heteropolyacid (phospho-wolframic acid, phospho-molybdic acid or silicotungstic acid root) is an anion ion liquid; Phospho-wolframic acid root, phospho-molybdic acid root or silicotungstic acid root, its zero pour is high, and ionic liquid at high temperature is in a liquid state, and is prone to be solid under the normal temperature; Because system temperature is higher, and catalyzer and reactant all are in a liquid state, catalyzer can fully contact with reaction substrate during catalyzed reaction; Catalytic efficiency (is high, and reaction finishes the back through reducing system temperature, and catalyzer is solid; Form phase difference with product, realize that product separates purpose certainly with catalyzer, biological lubricating oil synthesis process is greatly simplified; And pyridine-sulfonic acid group or imidazoles sulfonic acid group sun catalytic activity are strong, but with respect to conventional strong acid and strong base catalyzer, little to equipment corrosion, the work material of equipment requires low, can effectively reduce fixed investment.
(4) the renewable resources Vegetable oil lipoprotein is the biological lubricating oil of raw material production to originate widely in the present invention, and biological degradability is good, and quality is good; Toxicity is low; Intermediate product can recycling, therefore, but the environment acceptance type lubricating oil that this biology lubricating oil is a kind of green.Triglyceride level accounts for more than 85% of total amount in the natural fats and oils; Monoglyceride content has only about 5%; By the strong catalytic performance of B acid ion liquid; Triglyceride level is converted into trihydroxy-propane three esters, eliminates the thermolability of bringing by the β-H on the carboxyl adjacent carbons, thereby can improve the antioxidant property and the Heat stability is good of biological lubricating oil.
Description of drawings
Fig. 1 is the biological lubricating oil preparing method's of the present invention schema.
Embodiment
Below in conjunction with specific embodiment the present invention is done further concrete detailed description the in detail, but embodiment of the present invention is not limited thereto, the processing parameter for not indicating especially can carry out with reference to routine techniques.
Embodiment 1
By flow process process step shown in Figure 1, carry out B acid ion liquid catalyst triglyceride level synthesising biological lubricating oil.
1, with adding plam oil, TriMethylolPropane(TMP) in the reactor drum, both are mixed by weight 1: 1, and 0.5% the phospho-wolframic acid sulfonyl pyrrole acid ion liquid that adds above-mentioned different raw material gross weight is made catalyzer.
2, above-mentioned material is heated to 160 ℃, stirs, reacted 6 hours;
3, with being cooled to 40 ℃ in the reacted material immigration water cooler; The eddy flow sedimentation; Phospho-wolframic acid sulfonyl pyrrole acid ion liquid (catalyzer) cooling back becomes solid; After the eddy flow sedimentation, be deposited in the eddy flow pot bottom, and the complete raw material of product and unreacted still is liquid phase, adds again after phospho-wolframic acid sulfonyl pyrrole acid ion liquid catalyst is separated and carry out recycle in the reactor drum.
4, product and unreacted material entering completely rectifying tower underpressure distillation; The cat head working pressure is 20kPa, and the rectifying tower top product is a glycerine, and the glycerine yield is 43.1%; Bottom product is biological lubricating oil; The TriMethylolPropane(TMP) transformation efficiency is 46.4%, and intermediate material is TriMethylolPropane(TMP) and the glyceride stock for reacting completely, and this intermediate material is returned join the reactor cycles utilization again.
5, the rectifying tower intermediate material is after 3 circulations, and the glycerine yield is 83.1%, and biological yield of lubricating oil is 86.4%, and the TriMethylolPropane(TMP) transformation efficiency is 91.7%.
The biological lubricants performance of plam oil so that above-mentioned B acid ion liquid is Preparation of Catalyst sees table 1 for details.
Table 1
| Character | Plam oil | The biological lubricating oil of plam oil |
| Kinematic viscosity (40 ℃, cSt) | 40 | 91 |
| Kinematic viscosity (100 ℃, cSt) | 8.3 | 12.9 |
| Viscosity index | 190 | 290 |
| Pour point (℃) | -13 | -24 |
| Flash-point (℃) | 230 | 245 |
| Oxidizing temperature (℃) | 174 | 214 |
Embodiment 2
By flow process process step shown in Figure 1, carry out B acid ion liquid catalyst triglyceride level synthesising biological lubricating oil.
1, with adding Oleum Verniciae fordii, TriMethylolPropane(TMP) in the reactor drum, both are mixed by weight 3: 1, and 1.5% the phospho-molybdic acid pyridine-sulfonic acid salt ion liquid that adds above-mentioned different raw material gross weight is made catalyzer.
2, above-mentioned material is heated to 180 ℃, stirs, reacted 8 hours;
3, with being cooled to 50 ℃ in the reacted material immigration water cooler; The eddy flow sedimentation; Phospho-wolframic acid sulfonyl pyrrole acid ion liquid (catalyzer) cooling back becomes solid; After the eddy flow sedimentation, be deposited in the eddy flow pot bottom, and the complete raw material of product and unreacted still is liquid phase, adds again after phospho-wolframic acid sulfonyl pyrrole acid ion liquid catalyst is separated and carry out recycle in the reactor drum.
4, product and unreacted material entering completely rectifying tower underpressure distillation; The cat head working pressure is 20kPa, and the rectifying tower top product is a glycerine, and the glycerine yield is 56.6%; Bottom product is biological lubricating oil; The TriMethylolPropane(TMP) transformation efficiency is 60.3%, and intermediate material is TriMethylolPropane(TMP) and the glyceride stock for reacting completely, and this intermediate material is returned join the reactor cycles utilization again.
5, the rectifying tower intermediate material is after 2 circulations, and the glycerine yield is 85.2%, and biological yield of lubricating oil is 86.3%, and the TriMethylolPropane(TMP) transformation efficiency is 92.8%.
The biological lubricants performance of Oleum Verniciae fordii so that above-mentioned B acid ion liquid is Preparation of Catalyst sees table 2 for details.
Table 2
| Character | Oleum Verniciae fordii | The biological lubricating oil of Oleum Verniciae fordii |
| Kinematic viscosity (40 ℃, cSt) | 43 | 92 |
| Kinematic viscosity (100 ℃, cSt) | 8.3 | 13.3 |
| Viscosity index | 172 | 270 |
| Pour point (℃) | -9 | -19 |
Embodiment 3
By flow process process step shown in Figure 1, carry out B acid ion liquid catalyst triglyceride level synthesising biological lubricating oil.
1, with adding rapeseed oil, TriMethylolPropane(TMP) in the reactor drum, both are mixed by weight 2: 1, and 1.0% the silicotungstic acid imidazoles sulfonate ion liquid that adds above-mentioned different raw material gross weight is made catalyzer.
2, above-mentioned material is heated to 120 ℃, stirs, reacted 4 hours;
3, with being cooled to 30 ℃ in the reacted material immigration water cooler; The eddy flow sedimentation; Phospho-wolframic acid sulfonyl pyrrole acid ion liquid (catalyzer) cooling back becomes solid; After the eddy flow sedimentation, be deposited in the eddy flow pot bottom, and the complete raw material of product and unreacted still is liquid phase, adds again after silicotungstic acid imidazoles azochlorosulfonate acid ion liquid catalyst is separated and carry out recycle in the reactor drum.
4, product and unreacted material entering completely rectifying tower underpressure distillation; The cat head working pressure is 20kPa, and the rectifying tower top product is a glycerine, and the glycerine yield is 51.6%; Bottom product is biological lubricating oil; The TriMethylolPropane(TMP) transformation efficiency is 54.4%, and intermediate material is TriMethylolPropane(TMP) and the glyceride stock for reacting completely, and this intermediate material is returned join the reactor cycles utilization again.
5, the rectifying tower intermediate material is after 2 circulations, and the glycerine yield is 76.3%, and biological yield of lubricating oil is 77.9%, and the TriMethylolPropane(TMP) transformation efficiency is 80.5%.
The biological lubricants performance of rapeseed oil so that above-mentioned B acid ion liquid is Preparation of Catalyst sees table 3 for details.
Table 3
| Character | Rapeseed oil | The biological lubricating oil of rapeseed oil |
| Kinematic viscosity (40 ℃, cSt) | 45.6 | 94.2 |
| Kinematic viscosity (100 ℃, cSt) | 10.07 | 15.5 |
| Viscosity index | 216 | 320 |
| Total acid value (mgKOHg-1) | 1.4 | 0.17 |
| Pour point (℃) | -12 | -21 |
| Flash-point (℃) | 240 | 255 |
| Oxidizing temperature (℃) | 164 | 206 |
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. one kind is the preparation method of the biological lubricating oil of catalyzer with the ionic liquid, it is characterized in that, comprises the steps:
(1) with Vegetable oil lipoprotein and TriMethylolPropane(TMP) by weight 1～3: 1 is mixed, and the B acid ion liquid that adds above-mentioned two kinds of raw material gross weights several 0.5～1.5% is then made catalyzer;
(2) above-mentioned material is heated to 120～180 ℃, stirs, reacted 4～8 hours;
(3) reacted material is cooled to 30～50 ℃ rapidly, the eddy flow sedimentation becomes solid after the B acid ion liquid cooling, after the eddy flow sedimentation, is deposited in the eddy flow pot bottom, and product and unreacted completely material still be liquid phase;
(4) product and unreacted completely material get into the rectifying tower distillation, the rectifying tower top product is a glycerine, the rectifying intermediate material is a TriMethylolPropane(TMP) and unreacted glyceride stock completely, the rectifying bottom product is biological lubricating oil;
B acid ion liquid described in the step (1) is that pyridine-sulfonic acid functional group or imidazoles sulfonic acid functional group proton are positively charged ion, and heteropolyacid is an anion ion liquid; Said heteropolyacid is phospho-wolframic acid, phospho-molybdic acid or silicotungstic acid root.
2. preparation method according to claim 1 is characterized in that, B acid ion liquid described in the step (3) adds again after separating in the reaction of step (1) and carries out recycle.
3. preparation method according to claim 1 is characterized in that, rectifying intermediate material described in the step (4) is returned in the reaction that joins step (1) repetition (1)～(4) step 2～3 times.
4. preparation method according to claim 1 is characterized in that, distillation described in the step (4) is rectification under vacuum.
5. preparation method according to claim 1 is characterized in that, Vegetable oil lipoprotein is plam oil, Oleum Verniciae fordii, rapeseed oil or VT 18 described in the step (1).
6. one kind is the biological lubricating oil of Preparation of Catalyst with the ionic liquid, it is characterized in that, it is made by any described preparation method of claim of claim 1～5.
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| CN102492560B (en) * | 2011-11-28 | 2013-04-17 | 华南理工大学 | Production device and production method for distribution type plant oil transesterification |
| CN104368386B (en) * | 2014-11-12 | 2016-05-11 | 聊城大学 | A kind of heteropoly acid modified catalyst and preparation and application thereof |
| CN104694259B (en) * | 2015-02-13 | 2017-08-22 | 中国科学院广州能源研究所 | A kind of method that solubilized easily separated ionic liquid homogeneous catalysis prepares biodiesel |
| CN109810744B (en) * | 2019-03-28 | 2022-07-05 | 常州大学 | Method for preparing biological lubricating oil by catalysis of acidic polymeric ionic liquid |
| CN112625803B (en) * | 2020-12-16 | 2022-06-03 | 正大国际科技(常德)集团有限公司 | Preparation method of environment-friendly bio-based lubricating grease |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594280A (en) * | 2004-06-25 | 2005-03-16 | 清华大学 | Pyridine sulfonic acid salt ion liquid and its preparing process and application |
| CN101219995A (en) * | 2008-01-14 | 2008-07-16 | 华东理工大学 | Ion liquid based on heteropoly acid and synthesis thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594280A (en) * | 2004-06-25 | 2005-03-16 | 清华大学 | Pyridine sulfonic acid salt ion liquid and its preparing process and application |
| CN101219995A (en) * | 2008-01-14 | 2008-07-16 | 华东理工大学 | Ion liquid based on heteropoly acid and synthesis thereof |
Non-Patent Citations (4)
| Title |
|---|
| Uosukainen E等.Transesterification of Trimethylolpropane and Rapeseed Oil Methyl Ester to Environmentally Acceptable Lubricants.《J. Amer. Oil Chem. Soc.》.1998,第75卷(第11期),1557-1563. * |
| 刘范嘉等.三羟甲基丙烷油酸酯的合成研究.《齐齐哈尔大学学报》.2003, * |
| 李凯欣等.B酸离子液体[HSO_(3-)bpy]HSO_4在麻疯树油酯交换反应中的应用研究.《粮油加工》.2010,(第4期),35-38. * |
| 邢凤兰等.酯交换法合成三羟基丙烷油酸酯的研究.《精细与专用化学品》.2007,(第18期), * |
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