CN103805308A - Preparation method for alcohol ether type environment-friendly lubricant base oil - Google Patents
Preparation method for alcohol ether type environment-friendly lubricant base oil Download PDFInfo
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- CN103805308A CN103805308A CN201410053819.4A CN201410053819A CN103805308A CN 103805308 A CN103805308 A CN 103805308A CN 201410053819 A CN201410053819 A CN 201410053819A CN 103805308 A CN103805308 A CN 103805308A
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 68
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000000314 lubricant Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002199 base oil Substances 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000004593 Epoxy Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 38
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 23
- 238000004821 distillation Methods 0.000 claims abstract description 15
- 238000000967 suction filtration Methods 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 39
- 239000002551 biofuel Substances 0.000 claims description 28
- 239000003921 oil Substances 0.000 claims description 24
- 235000019198 oils Nutrition 0.000 claims description 24
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 13
- 239000004359 castor oil Substances 0.000 claims description 6
- 235000019438 castor oil Nutrition 0.000 claims description 6
- 230000007613 environmental effect Effects 0.000 claims description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 235000012424 soybean oil Nutrition 0.000 claims description 6
- 239000003549 soybean oil Substances 0.000 claims description 6
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims description 6
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- -1 nonanol- Chemical compound 0.000 claims description 5
- 239000011973 solid acid Substances 0.000 claims description 4
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 3
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 3
- 229940057402 undecyl alcohol Drugs 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 abstract description 13
- 230000004048 modification Effects 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 239000004519 grease Substances 0.000 abstract description 2
- 239000003225 biodiesel Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 230000006837 decompression Effects 0.000 abstract 1
- 239000010687 lubricating oil Substances 0.000 description 14
- 239000003513 alkali Substances 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 11
- 238000006317 isomerization reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
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- 239000002253 acid Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
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- 235000010446 mineral oil Nutrition 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 231100000241 scar Toxicity 0.000 description 4
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- 230000018109 developmental process Effects 0.000 description 3
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- 241000196324 Embryophyta Species 0.000 description 2
- 241001168730 Simo Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
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- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of lubricant modification technique, and particularly relates to a preparation method for alcohol ether type environment-friendly lubricant base oil. The preparation method comprises the steps: putting fatty alcohol and supported heteropoly acid catalyst into a four-neck flask with a condensed pipe and a thermometer, stirring and backflowing under the heating condition, then adding epoxy biodiesel, carrying out ring-opening reaction under the heating condition, determining the epoxy value of a reaction system in the reaction process, stopping reaction when the epoxy value is less than 0.08, cooling the reaction system to room temperature, performing suction filtration to recover the supported heteropoly acid catalyst, putting the filtrate into a separating funnel, washing to be neutral, and then performing decompression distillation, finally to obtain isomerized grease alcohol ether.
Description
Technical field
The invention belongs to modifying lubricating oil Technology field, particularly a kind of preparation method of alcohol ether type environmental friendly lubricant base oil.
Background technology
Modern machinery and equipment to the requirement of lubricating oil is: (1) is environmentally friendly, nontoxic, biodegradable; (2) there is higher oxidation-resistance, have longer work-ing life; (3) require that pour point is low, viscosity index is high, can adapt to the special occasions of severe cold and high temperature operating mode; (4) be convenient to the oil product of synthetic different viscosity grade.
Visible lubricating oil plays an important role to the lubricated of equipment, is generally mineral oil, synthetic oil, animals and plants wet goods.The consumption maximum of its mineral oil in fluid, cheap due to it, performance meets the lubricating requirement of most of equipment, in occupation of the dominant position in market, but mineral oil complicated component, biological degradability is poor, severe contamination and harm environment.Therefore the environmental problem that, mineral oil brings has obtained increasing attention.Biofuel has that lubricity is good, environment friendly, the good advantage such as substituting, is a kind of liquid fuel with development potentiality.In twice oil crisis of 20 century 70s and the appearance nineties, people recognize that biofuel can be used as fuel and replaces oil shortage gradually, solve the problem of shortage of resources.But it is poor that biofuel has oxidative stability, stability to hydrolysis and low-temperature performance be the shortcoming such as bad also, need carry out modification to it and synthesize high-quality lubricating oil.Adopt the method for epoxy-open loop to carry out chemical modification to it.
The preparation technology of epoxy biofuel is ripe, epoxy biofuel is the good substitute of traditional fine chemicals, it has reduced iodine number, has improved oxidation stability, has improved lubricity, but its low-temperature performance does not improve, this has limited its practical application to a great extent.Oxyethane activity in epoxy biofuel is high, is easy to be functionalized, and is conducive to carry out further modification.By epoxy bond is carried out to ring-opening reaction, prepare high performance environmentally friendly lubricant base.
Along with the enhancing of expanding economy and people's value of survival idea, people are more and more higher to the specification of quality of environment.Adopting solid acid is that catalyzer carries out ring-opening reaction, has simplified post-processing step, has avoided the discharge of a large amount of waste liquids, has effectively prevented environmental pollution, and the easily-activated regeneration of solid acid catalyst.Therefore, development and developing green lubricating oil, not only have the meaning of environmental protection Sustainable development, and have great society and economic implications.
Summary of the invention
Technical problem to be solved by this invention is: a kind of efficient, eco-friendly method of preparing alcohol ether type lubricant base is provided.
The technical solution adopted in the present invention is: under the environment at solid-carrying heteropolyacid as catalyzer, fatty alcohol mixed with epoxy biofuel, carries out isomery etherificate ring-opening reaction, obtain isomerized oil lipidol ether,
Concrete steps are: fatty alcohol and solid-carrying heteropolyacid catalyst are put in the four-hole boiling flask with prolong and thermometer, under the condition of heating, stir, reflux, then add epoxy biofuel, and under heating condition, carry out ring-opening reaction, the oxirane value of assaying reaction system in reaction process, in the time that oxirane value is less than 0.08, stopped reaction, reaction system is cooled to room temperature, reclaim solid-carrying heteropolyacid catalyst through suction filtration, filtrate is placed in to separating funnel, washing is to neutral, underpressure distillation again, finally obtains isomerized oil lipidol ether.
Above-mentioned solid-carrying heteropolyacid catalyst is selected from, SW
12/ C, PW
12/ C, PMo
12/ C, SMo
12/ C, PW
12/ SiO
2, one or more mixtures in TPA/C, TPA/SBA-15 solid acid catalyst; Preferably PW
12/ SiO
2, TPA/SBA-15 or their mixture (in mixture, PW
12/ SiO
2, TPA/SBA-15 mass ratio is 55:45-65:35).
Above-mentioned ring-opening reaction can be carried out under microwave-assisted condition, and for example, ring-opening reaction can be carried out in microwave-assisted equipment, so just without having introduced heating unit in addition,
In the present invention, the specification of selected microwave-assisted equipment is: XH-MC-1 microwave building-up reactions instrument, and power: 100～900W, 9 grades of power are manually adjustable; Thermometric and temperature control scope: 0～300 ℃, temperature measurement accuracy: 2 ‰; Temperature-controlled precision ± 1 ℃; Reaction volume: 10～1000mL; Charactron shows to give puts temperature, Current Temperatures, reaction times.
In above-mentioned preparation method, fatty alcohol is the organic alcohols of a chain length 2-13 carbon atom, is selected from one or more Organic Alcohols in ethanol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, isooctyl alcohol, nonanol-, nonylcarbinol, undecyl alcohol, lauryl alcohol and tridecanol;
Epoxy biofuel is epoxidized vegetable oil fatty acid ester, is selected from epoxy soybean oil fatty acid methyl ester, epoxy rapeseed oil fatty acid methyl ester or epoxy castor oil fatty acid methyl ester;
The mass ratio 1:(0.2-4 of epoxy biofuel and fatty alcohol), for example, 1:0.2,1:0.5,1:1,1:2; The preferably mass ratio 1:(0.3-3 of epoxy biofuel and fatty alcohol);
The mass ratio of epoxy biofuel and catalyzer is 100:(2-7), for example, 100:3,100:5,100:6,100:7; Preferably the mass ratio of epoxy biofuel and catalyzer is 100:(3-5).
Above-mentioned ring-opening reaction, temperature of reaction is 30-60 ℃, for example, and 30 ℃, 50 ℃, 60 ℃, preferably 30-50 ℃; Reaction times is 1-3h, for example, and 1h, 2h, 3h, preferably 1-2h.
In above-mentioned preparation method, the object of underpressure distillation is: steam water and remaining small molecules organic solvent, make product concentrated, obtain novel synthetic lubricant base oil.
Beneficial effect of the present invention is: the alcohol ether type lubricant base that adopts aforesaid method to prepare is carried out to physicochemical property test, as acid number, density, viscosity, oxidative stability, frictional behaviour, low-temperature performance etc., find that this alcohol ether type lubricant base physicochemical property is very good, be well suited for the application of lubricating oil;
In preparation method of the present invention, the solid-carrying heteropolyacid catalyst adopting is a kind of very strong protonic acid, catalysis intensity is much higher than conventional mineral acid, as sulfuric acid etc., solid-carrying heteropolyacid not only has higher catalytic activity and selectivity, and be heterogeneous catalyst, be easy to Separation and Recovery, simplify production technique.Compared with the conventional vitriol oil, tosic acid etching apparatus, aftertreatment complexity, contaminate environment, the solid-carrying heteropolyacid adopting in the present invention has kept the high temperature active of classical acid catalyzer, the advantage of highly selective, corrosion and the pollution problem of acid catalyzed reaction are overcome again, and reuse utilization ratio and reach 96%, the scope of application is more extensive, is existing huge potential improving aspect technical process, energy-conservation consumption, environment protection;
Microwave-assisted means are for organic synthesis, and speed of response will be accelerated tens of even thousands of times than ordinary method, thereby Reaction time shorten improves transformation efficiency.Microwave reactor is simple to operate, reproducible, selects identical power and working hour can obtain identical reaction conditions in reaction process.Natural microwave disperses not concentrate, can not serve as a kind of energy, and the microwave that utilizes magnetron that electric energy is changed, oscillation frequency with 2450MHz per second penetrates medium, output microwave power is adjustable arbitrarily, in reaction process, ensure continuously microwave radiation according to the suitable output rating of need to selecting of chemical reaction, thereby accelerated speed of reaction.Microwave to the effect of catalyzed reaction is: the type of heating of microwave uniqueness can be accelerated protonated formation greatly, is conducive to the carrying out of reaction.
Compared with the method for conventional catalyst catalysis, use the collaborative catalysis of solid supported heteropoly acid catalyst reaction of microwave-assisted, not only significantly shorten the reaction times, improve the productive rate of product, reduce pour point, improved the oxidative stability of product, and environmental sound;
Because the epoxy bond of epoxy biofuel is more active, low-temperature fluidity and oxidative stability are poor, by the fatty alcohol by different chain length, unsettled epoxy bond is opened, generated grease alcohol ether type compound, thereby improved low temperature rheologic behavio(u)r and oxidative stability.After etherification modified through open loop isomery, the alcohol ether type lubricating oil obtaining has possessed following advantage: (1) is biodegradable, environmentally friendly.(2) pour point is low, and viscosity index is high.(3) long service life and good in oxidation resistance.(4) can synthesize low, in or the oil product of high different grades.Processing unit of the present invention is less demanding, simple to operate, reaction conditions is gentle, and product separates with catalyzer is easy, has avoided the discharge of a large amount of waste liquids, has effectively prevented from environmental pollution being suitable for large-scale industrial production.
Accompanying drawing explanation
Fig. 1: in the present invention, utilize epoxy biofuel to prepare the process flow sheet of lubricant base.
Embodiment
Embodiment 1:
Take 68g ethanol and 6g solid-carrying heteropolyacid catalyst PW
12/ SiO
2be put in the four-hole boiling flask with prolong and thermometer, be heated to 30 ℃ under whipped state, then add 200g epoxy soybean oil fatty acid methyl ester, recording the initial oxirane value of reaction system is 5.46, and at this temperature, carries out ring-opening reaction.In reaction process, in 30min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08 (t=4.5h), stopped reaction.Above-mentioned solution is cooled to room temperature, reclaims solid-carrying heteropolyacid catalyst PW through suction filtration
12/ SiO
2, filtrate is placed in to separating funnel, alkali cleaning, be washed to pH=7, then underpressure distillation, finally obtain the isomerized oil lipidol ether of clear.
Embodiment 2:
Take 84.4g Virahol and 6g solid-carrying heteropolyacid catalyst TPA/SBA-15 is put in the four-hole boiling flask with prolong and thermometer, under whipped state, be heated to 30 ℃, then add 200g epoxy rapeseed oil fatty acid methyl ester, recording the initial oxirane value of reaction system is 5.46, and at this temperature, carries out ring-opening reaction.In reaction process, in 30min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08 (t=5h), stopped reaction.Above-mentioned solution is cooled to room temperature, reclaims solid-carrying heteropolyacid catalyst TPA/SBA-15 through suction filtration, and filtrate is placed in to separating funnel, alkali cleaning, is washed to pH=7, then underpressure distillation, finally obtains the isomerized oil lipidol ether of clear.
Embodiment 3:
Take 114.4g propyl carbinol and 7g solid-carrying heteropolyacid catalyst SiMo
12/ C is put in the four-hole boiling flask with prolong and thermometer, is heated to 35 ℃ under whipped state, then adds 200g epoxy castor oil fatty acid methyl ester, and recording the initial oxirane value of reaction system is 5.46, and at this temperature, carries out ring-opening reaction.In reaction process, in 30min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08 (t=4h), stopped reaction.Above-mentioned solution is cooled to room temperature, reclaims solid-carrying heteropolyacid catalyst SiMo through suction filtration
12/ C, is placed in separating funnel by filtrate, alkali cleaning, is washed to pH=7, then underpressure distillation, finally obtains the isomerized oil lipidol ether of clear.
Embodiment 4:
All the other steps, parameter are identical with embodiment 2, just the catalyzer in embodiment 2 are changed into solid-carrying heteropolyacid mixed catalyst " PW
12/ SiO
2, TPA/SBA-15(mass ratio is 60:40) ",
In reaction process, in 30min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08, t=2h.
Embodiment 5:
In microwave reactor, take 154.6g Pentyl alcohol and 7.2g solid-carrying heteropolyacid catalyst PMo
12/ C is put in the four-hole boiling flask with prolong and thermometer, Microwave-assisted firing to 40 ℃ under whipped state, then adds 200g epoxy soybean oil fatty acid methyl ester, and recording the initial oxirane value of reaction system is 5.46, and at this temperature, carrying out ring-opening reaction, microwave power is 650W.In reaction process, in 10min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08 (t=1.4h), stopped reaction.Above-mentioned solution is cooled to room temperature, reclaims solid-carrying heteropolyacid catalyst PMo through suction filtration
12/ C, is placed in separating funnel by filtrate, alkali cleaning, is washed to pH=7, then underpressure distillation, finally obtains the isomerized oil lipidol ether of clear.
Embodiment 6:
In microwave reactor, take 160.8g primary isoamyl alcohol and 7.2g solid-carrying heteropolyacid catalyst " SiW
12/ C, TPA/SBA-15(mass ratio are 65:35) " be put in the four-hole boiling flask with prolong and thermometer; Microwave-assisted firing to 40 ℃ under whipped state; then add 200g epoxy castor oil fatty acid methyl ester; recording the initial oxirane value of reaction system is 5.46; and at this temperature, carry out ring-opening reaction, microwave power is 650W.In reaction process, in 10min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08 (t=1.4h), stopped reaction.Above-mentioned solution is cooled to room temperature, reclaims solid-carrying heteropolyacid catalyst " SiW through suction filtration
12/ C, TPA/SBA-15 ", filtrate is placed in to separating funnel, alkali cleaning, be washed to pH=7, then underpressure distillation, finally obtain the isomerized oil lipidol ether of clear.
Embodiment 7:
In microwave reactor, take 274.2g isooctyl alcohol and 8g solid-carrying heteropolyacid catalyst TPA/C is put in the four-hole boiling flask with prolong and thermometer, Microwave-assisted firing to 42 ℃ under whipped state, then add 200g epoxy rapeseed oil fatty acid methyl ester, recording the initial oxirane value of reaction system is 5.46, and at this temperature, carrying out ring-opening reaction, microwave power is 700W.In reaction process, in 10min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08 (t=1.6h), stopped reaction.Above-mentioned solution is cooled to room temperature, reclaims solid-carrying heteropolyacid catalyst TPA/C through suction filtration, and filtrate is placed in to separating funnel, alkali cleaning, is washed to pH=7, then underpressure distillation, finally obtains the isomerized oil lipidol ether of clear.
Embodiment 8:
In microwave reactor, take 354.3g nonanol-, suction filtration, recovery, the dry solid-carrying heteropolyacid catalyst TPA/C obtaining in 8g embodiment 7, be put in the four-hole boiling flask with prolong and thermometer, Microwave-assisted firing to 44 ℃ under whipped state, then adds 200g epoxy soybean oil fatty acid methyl ester, and recording the initial oxirane value of reaction system is 5.46, and at this temperature, carrying out ring-opening reaction, microwave power is 750W.In reaction process, in 10min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08 (t=1.6h), stopped reaction.Above-mentioned solution is cooled to room temperature, reclaims solid-carrying heteropolyacid catalyst through suction filtration, and filtrate is placed in to separating funnel, alkali cleaning, is washed to pH=7, then underpressure distillation, finally obtains the isomerized oil lipidol ether of clear.
Embodiment 9:
Take 388.8g nonylcarbinol and 8.32g solid-carrying heteropolyacid catalyst PW
12/ C is put in the four-hole boiling flask with prolong and thermometer, is heated to 45 ℃ under whipped state, then adds 200g epoxy rapeseed oil fatty acid methyl ester, and recording the initial oxirane value of reaction system is 5.46, and at this temperature, carries out ring-opening reaction.In reaction process, in 30min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08 (t=4h), stopped reaction.Above-mentioned solution is cooled to room temperature, reclaims solid-carrying heteropolyacid catalyst PW through suction filtration
12/ C, is placed in separating funnel by filtrate, alkali cleaning, is washed to pH=7, then underpressure distillation, finally obtains the isomerized oil lipidol ether of clear.
Embodiment 10:
Take 483.7g undecyl alcohol and 8.5g solid-carrying heteropolyacid catalyst TPA/SBA-15 is put in the four-hole boiling flask with prolong and thermometer, under whipped state, be heated to 46 ℃, then add 200g epoxy castor oil fatty acid methyl ester, recording the initial oxirane value of reaction system is 5.46, and at this temperature, carries out ring-opening reaction.In reaction process, in 30min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08 (t=4.5h), stopped reaction.Above-mentioned solution is cooled to room temperature, reclaims solid-carrying heteropolyacid catalyst TPA/SBA-15 through suction filtration, and filtrate is placed in to separating funnel, alkali cleaning, is washed to pH=7, then underpressure distillation, finally obtains the isomerized oil lipidol ether of clear.
Embodiment 11:
Take 588.4g lauryl alcohol and 9g solid-carrying heteropolyacid catalyst PW
12/ SiO
2be put in the four-hole boiling flask with prolong and thermometer, be heated to 48 ℃ under whipped state, then add 200g epoxy soybean oil fatty acid methyl ester, recording the initial oxirane value of reaction system is 5.46, and at this temperature, carries out ring-opening reaction.In reaction process, in 30min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08 (t=5h), stopped reaction.Above-mentioned solution is cooled to room temperature, reclaims solid-carrying heteropolyacid catalyst PW through suction filtration
12/ SiO
2, filtrate is placed in to separating funnel, alkali cleaning, be washed to pH=7, then underpressure distillation, finally obtain the isomerized oil lipidol ether of clear.
Embodiment 12:
Take 665g tridecanol and 10.0g solid-carrying heteropolyacid catalyst PW
12/ SiO
2be put in the four-hole boiling flask with prolong and thermometer, be heated to 50 ℃ under whipped state, then add 200g epoxy castor oil fatty acid methyl ester, recording the initial oxirane value of reaction system is 5.46, and at this temperature, carries out ring-opening reaction.In reaction process, in 30min, sample, measure its oxirane value, in the time that oxirane value is less than 0.08 (t=5.5h), stopped reaction.Above-mentioned solution is cooled to room temperature, reclaims solid-carrying heteropolyacid catalyst PW through suction filtration
12/ SiO
2, filtrate is placed in to separating funnel, alkali cleaning, be washed to pH=7, then underpressure distillation, finally obtain the isomerized oil lipidol ether of clear.
In each embodiment, the physicochemical property of final product base oil as shown in Table 1: while measuring kinematic viscosity, sample 15g, sample 20g while measuring pour point, measure flash-point sampling 25g, measure WSD sampling 20g, measure the every sub-sampling 20g of PB, measure RBOT sampling 50g.
The alcohol ether type lubricant base physicochemical property of table one isomerization modification of the present invention
In upper table, kinematic viscosity adopts special capillary viscosimeter (Φ=1.5 and 3.0 according to standard GB/T/T265-88, viscous modulus is respectively 0.289 and 7.448) measure, viscosity index is tabled look-up according to formula VI=[(L-U by standard GB/T/T1995-1998 according to the viscosity that records)/(L-H)] × 100 calculate, in formula: L-identical with 100 ℃ of kinematic viscosity of sample, viscosity index is 0 the oil product kinematic viscosity in the time of 40 ℃, mm
2/ s; Kinematic viscosity when H-with 100 ℃, sample is identical, the kinematic viscosity of the oil product that viscosity index is 100 in the time of 40 ℃, mm
2/ s; Kinematic viscosity when 40 ℃, U-sample, mm
2/ s.The pour point of chemical modification biofuel is measured according to standard GB/T/T3535-2006 with the SYD-510F multifunctional low-temperature tester that Shanghai Peng Pu refrigerator factory produces.Flash-point is measured according to GB/T3635-2008 " the mensuration Cleveland opening agar diffusion method of Flash Point for Petroleum Products and burning-point ".Adopt four ball formula friction wear testing machines to measure last non seizure load (PB) and the wear scar diameter (WSD) of modification biological diesel oil according to the standard of GB/T3142-1982, the test condition of wear scar diameter is: load 392N, rotating speed 1455r/min, under room temperature condition, long time consuming 30min, steel ball used is that diameter is the GCr15 standard rolling bearing steel ball of 12.7mm, and hardness is 60～63HRC.Oxidation induction period (RBOT) adopts rotary oxygen bomb method to measure according to national petroleum chemical industry standard SH/T0193-2008.
In upper table, data show, the alcohol ether type lubricant base of isomerization modification of the present invention, compared with biofuel, has the following advantages:
(1) frictional behaviour excellence: four-ball tester frictional experiment, using wear scar diameter as index, long mill 30min under 392N pressure, the alcohol ether type lubricating oil wear scar diameter of isomerization modification is 0.52mm to the maximum, general biofuel is 0.63mm, and the alcohol ether type lubricating oil frictional behaviour of isomerization modification is better than biofuel.The alcohol ether type lubricating oil P that contains alkoxyl group of isomerization modification
bvalue is all greater than the 509.6N of biofuel.
(2) low temperature rheology better performances: the pour point of the alcohol ether type lubricating oil of isomerization modification declines to a great extent than the pour point of biofuel, biofuel is approximately-3 ℃, and the pour point of the alcohol ether type lubricating oil of isomerization modification is all lower than-11 ℃; Viscosity is all higher than biofuel, take the alcohol ether type lubricating oil of isomerization modification as base oil, carries out compositely with low viscosity oil plant, can modulate the lube stock of a series of viscosity grades.
(3) oxidative stability significantly improves: through rotary oxygen bomb method (140 ℃) test, the alcohol ether type oxidation of lubricating oil of isomerization modification is all greater than 24min inductive phase.
Claims (10)
1. the preparation method of an alcohol ether type environmental friendly lubricant base oil, it is characterized in that: described preparation method is, under the environment at solid-carrying heteropolyacid as catalyzer, fatty alcohol to be mixed with epoxy biofuel, carry out isomery etherificate ring-opening reaction, obtain isomerized oil lipidol ether.
2. the preparation method of lubricant base as claimed in claim 1, it is characterized in that: concrete preparation process is, fatty alcohol and solid-carrying heteropolyacid catalyst are put in the four-hole boiling flask with prolong and thermometer, under heating condition, stir, reflux, then add epoxy biofuel, and under heating condition, carry out ring-opening reaction, the oxirane value of assaying reaction system in reaction process, in the time that oxirane value is less than 0.08, stopped reaction, reaction system is cooled to room temperature, reclaim solid-carrying heteropolyacid catalyst through suction filtration, filtrate is placed in to separating funnel, washing is to neutral, underpressure distillation again, finally obtain isomerized oil lipidol ether.
3. the preparation method of lubricant base as claimed in claim 1 or 2, is characterized in that: described solid-carrying heteropolyacid catalyst is SW
12/ C, PW
12/ C, PMo
12/ C, SMo
12/ C, PW
12/ SiO
2, one or more mixtures in TPA/C, TPA/SBA-15 solid acid catalyst.
4. the preparation method of lubricant base as claimed in claim 3, is characterized in that: described solid-carrying heteropolyacid catalyst is PW
12/ SiO
2, TPA/SBA-15 or their mixture, wherein in mixture, PW
12/ SiO
2with TPA/SBA-15 mass ratio be 55:45-65:35.
5. the preparation method of lubricant base as claimed in claim 1 or 2, is characterized in that: described ring-opening reaction, under microwave-assisted condition, carry out.
6. the preparation method of lubricant base as claimed in claim 1 or 2, it is characterized in that: described fatty alcohol is the organic alcohols of 2-13 carbon atoms of chain length, i.e. one or more Organic Alcohols in ethanol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, isooctyl alcohol, nonanol-, nonylcarbinol, undecyl alcohol, lauryl alcohol and tridecanol.
7. the preparation method of lubricant base as claimed in claim 1 or 2, it is characterized in that: described epoxy biofuel is epoxidized vegetable oil fatty acid ester, i.e. epoxy soybean oil fatty acid methyl ester, epoxy rapeseed oil fatty acid methyl ester or epoxy castor oil fatty acid methyl ester.
8. the preparation method of lubricant base as claimed in claim 1 or 2, is characterized in that: described epoxy biofuel and mass ratio 1:0.2-4 of fatty alcohol.
9. the preparation method of lubricant base as claimed in claim 1 or 2, is characterized in that: described epoxy biofuel and the mass ratio of catalyzer are 100:2-7.
10. the preparation method of lubricant base as claimed in claim 2, is characterized in that: the temperature of described ring-opening reaction is 30-60 ℃.
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