CN115028574A - Ionic liquid and preparation method and application thereof - Google Patents
Ionic liquid and preparation method and application thereof Download PDFInfo
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- CN115028574A CN115028574A CN202210657307.3A CN202210657307A CN115028574A CN 115028574 A CN115028574 A CN 115028574A CN 202210657307 A CN202210657307 A CN 202210657307A CN 115028574 A CN115028574 A CN 115028574A
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- CN
- China
- Prior art keywords
- ionic liquid
- chinensis bunge
- pistacia chinensis
- biodiesel
- chloride
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 106
- 235000014123 Pistacia chinensis Nutrition 0.000 claims abstract description 87
- 240000000432 Pistacia chinensis Species 0.000 claims abstract description 87
- 239000003225 biodiesel Substances 0.000 claims abstract description 62
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 32
- 239000003208 petroleum Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 19
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 8
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 75
- 238000002390 rotary evaporation Methods 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000012295 chemical reaction liquid Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 235000019198 oils Nutrition 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- QVRCRKLLQYOIKY-UHFFFAOYSA-M 1-methyl-3-prop-2-enylimidazol-1-ium;chloride Chemical compound [Cl-].C[N+]=1C=CN(CC=C)C=1 QVRCRKLLQYOIKY-UHFFFAOYSA-M 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 2
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 239000003921 oil Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000012216 screening Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- -1 fatty acid ester Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/10—Production of fats or fatty oils from raw materials by extracting
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of biodiesel preparation, and particularly discloses an ionic liquid and a preparation method and application thereof. The ionic liquid is prepared from 1-allyl-3-methylimidazole chloride and metal chloride. The preparation method of the biodiesel comprises the following steps: taking the pistacia chinensis bunge seeds as raw materials, and taking the ionic liquid and the petroleum ether as extraction solvents to obtain pistacia chinensis bunge seed oil through extraction; the extracted pistacia chinensis bunge seed oil and short-chain alcohol are used as raw materials, the ionic liquid is used as a catalyst, and the biodiesel is prepared through esterification reaction. The ionic liquid provided by the invention can be used as an extractant for extracting the pistacia chinensis bunge seed oil to enable the yield of the pistacia chinensis bunge seed oil to reach 40-50%, and can also be used as a catalyst for the reaction of the pistacia chinensis bunge seed oil and short-chain alcohol to realize the preparation of the biodiesel by a one-pot method, so that the preparation process is greatly simplified, the yield of the biodiesel can reach 93-98.4%, and the ionic liquid has extremely high popularization and application values.
Description
Technical Field
The invention relates to the technical field of biodiesel preparation, in particular to an ionic liquid and a preparation method and application thereof.
Background
With the gradual exhaustion of fossil energy and the emergence of energy crisis, the development of new green and environment-friendly energy has become a necessary trend. The biodiesel is fatty acid ester prepared by ester exchange or esterification of animal and vegetable oil, waste gas oil or microbial oil and short-chain alcohol, has the characteristics of carbon reduction, environmental protection, high fuel property, wide raw material source and the like, and has great potential to be a substitute of fossil diesel. The pistacia chinensis bunge is taken as a representative of energy forest substances, has the characteristics of wide distribution, high seed oil content and the like, and the palmitic acid, the sub-fatty acid, the fatty acid and the stearic acid which are rich in the pistacia chinensis bunge seed oil are ideal biodiesel raw materials, so that the planting of the pistacia chinensis bunge is vigorously developed, and the high-efficiency extraction of the pistacia chinensis bunge seed oil has very important significance for the application of the biodiesel.
At present, the biodiesel is mainly prepared by an acid-base catalysis method in industrialization, but the catalyst adopted by the acid-base catalysis is generally strong acid and strong base, so that the corrosion to equipment is large, a large amount of methanol is needed in the reaction process, and the reaction temperature is high, so that the preparation cost and the energy consumption of the biodiesel are high. Moreover, the adopted strong acid and strong base catalyst is difficult to remove in the product, so that the post-treatment step is complicated, and the adverse effect on the environment is easy to generate. The solid acid-base heterogeneous catalyst solves the problems that the traditional catalyst is difficult to separate and has great pollution to the environment, but the reaction is heterogeneous, the mass transfer rate is slow, the reaction activity is low, the reaction rate is slow, and the industrial production is difficult to realize. Therefore, the development of the method for preparing the biodiesel, which has mild reaction conditions, high reaction efficiency and low production cost, has very important significance for expanding the application of the biodiesel.
Disclosure of Invention
Aiming at the problems of harsh reaction conditions, low reaction efficiency and high reaction cost of the method for preparing the biodiesel in the prior art, the invention provides the ionic liquid and the preparation method and the application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
an ionic liquid is prepared from 1-allyl-3-methylimidazole chloride and metal chloride.
Preferably, the transition metal chloride is zinc chloride, copper chloride or aluminum chloride.
Preferably, the ionic liquid is prepared from 1-allyl-3-methylimidazole chloride and aluminum chloride.
The method takes the 1-allyl-3-methylimidazole chloride and the metal chloride as raw materials to form the ionic liquid with good chemical stability, the raw materials are wide in source, green and environment-friendly, and the application range of the prepared ionic liquid is expanded.
Preferably, the molar ratio of the 1-allyl-3-methylimidazolium chloride to the metal chloride is 1: 1.0-1.1.
Preferably, the preparation method of the 1-allyl-3-methylimidazole chloride comprises the following steps: reacting 1-methylimidazole with chloropropene at 50-60 ℃ for 6-8 h under inert atmosphere, performing vacuum rotary evaporation, washing, and drying to obtain 1-allyl-3-methylimidazole chloride.
Further preferably, the molar ratio of the 1-methylimidazole to the chloropropene is 1: 1.1-1.3.
Illustratively, the vacuum degree of the vacuum rotary evaporation is 0.08MPa to 0.12MPa, the temperature of the vacuum rotary evaporation is 40 ℃ to 46 ℃, and the rotary evaporation is stopped when no liquid flows out.
It should be noted that the inert atmosphere in the present invention is provided by inert gas commonly used in the art, such as nitrogen, argon, etc.
Illustratively, after the reaction of 1-methylimidazole and chloropropene is finished, washing with diethyl ether for 2-3 times, and then drying in a vacuum drying oven for 48-60 h.
The invention also provides a preparation method of the ionic liquid, which comprises the following steps: adding 1-allyl-3-methylimidazole chloride and metal chloride into a solvent, uniformly mixing, heating to 50-60 ℃, reacting for 2-3 h, washing, rotary-steaming and drying to obtain the ionic liquid.
Preferably, the solvent is a dilute hydrochloric acid solution, absolute methanol or absolute ethanol.
Further, 1mL to 3mL of a solvent is added per mole of 1-allyl-3-methylchloroimidazole.
Further, the dilute hydrochloric acid solution is preferably a dilute hydrochloric acid solution with the mass concentration of 30-40%.
Illustratively, the prepared product is washed 2-3 times with a solution of diethyl ether.
Illustratively, the product prepared is dried by means of vacuum drying.
The preparation method of the ionic liquid provided by the invention is simple to operate, mild in reaction conditions, free of special equipment and suitable for industrial large-scale production.
The invention also provides application of the ionic liquid in preparation of biodiesel.
The invention also provides a method for preparing biodiesel by using the ionic liquid, which comprises the following steps: taking the pistacia chinensis bunge seeds as raw materials, and taking the ionic liquid and the petroleum ether as extraction solvents to obtain pistacia chinensis bunge seed oil through extraction;
the extracted pistacia chinensis bunge seed oil and short-chain alcohol are used as raw materials, the ionic liquid is used as a catalyst, and the biodiesel is prepared through esterification reaction.
Compared with the prior art, the ionic liquid provided by the invention can destroy hydrogen bonds among cellulose macromolecules through the interaction of double bonds, chloride ions and other groups contained in the ionic liquid and oxygen atoms and hydrogen atoms in cellulose-OH, so that the cell walls of the pistacia chinensis bunge seeds can be dissolved and destroyed in a short time, the extraction rate of the pistacia chinensis bunge seed oil is improved, and the yield of the pistacia chinensis bunge seed oil can reach 40-50%; and because the Pistacia chinensis Bunge seed oil has excellent extraction effect, the usage amount of petroleum ether can be effectively reduced; in addition, the ionic liquid provided by the invention has a good catalytic effect on esterification reaction or ester exchange reaction, so that the esterification reaction or ester exchange reaction of the pistacia chinensis bunge seed oil and the short-chain alcohol can be effectively promoted, and the yield of the biodiesel is improved.
The ionic liquid provided by the invention can be used as an extracting agent for extracting the pistacia chinensis bunge seed oil and a catalyst for the reaction of the pistacia chinensis bunge seed oil and the short-chain alcohol, so that the preparation of the biodiesel by using the pistacia chinensis bunge seed oil as a raw material through a one-pot method can be realized, the preparation process of the biodiesel is greatly simplified, the production efficiency of the biodiesel is improved, the yield of the biodiesel can reach 93-98.4%, and the ionic liquid has a very high popularization and application value.
Preferably, the method for preparing biodiesel specifically comprises the following steps:
crushing pistacia chinensis bunge seeds to obtain pistacia chinensis bunge seed powder; adding the ionic liquid and petroleum ether into the pistacia chinensis bunge seed powder, heating to 55-65 ℃, stirring and extracting for 55-65 min, removing the petroleum ether in the extract by rotary evaporation, adding short-chain alcohol, mixing uniformly, separating pistacia chinensis bunge seed residues, reacting the obtained filtrate at 65-75 ℃ for 130-160 min, adding ethyl acetate into the reaction liquid, standing for liquid separation, and removing the ethyl acetate from the obtained oil phase by rotary evaporation to obtain the biodiesel.
Preferably, the pistacia chinensis bunge seeds are crushed to be less than 30 meshes.
Preferably, the mass ratio of the ionic liquid to the pistacia chinensis bunge seed powder is 1: 3-5.
Preferably, the volume-mass ratio of the petroleum ether to the pistacia chinensis bunge seed powder is 1-2:1, wherein the volume unit is milliliter, and the mass unit is gram.
The preferable addition amount of the ionic liquid and the petroleum ether can ensure that the pistacia chinensis bunge seed oil is fully extracted on the premise of reducing the use amount of the petroleum ether as much as possible, so that the yield of the pistacia chinensis bunge seed oil is as high as 40-50%.
Preferably, the mass ratio of the short-chain alcohol to the pistacia chinensis bunge seed powder is 2-3: 1.
Illustratively, the short-chain fatty alcohol is methanol or ethanol.
Preferably, the volume ratio of the ethyl acetate to the reaction liquid is 4-6: 1.
The preparation method of the biodiesel provided by the invention realizes the purpose of preparing the biodiesel by a one-pot method, is simple and feasible, effectively reduces the preparation temperature of the biodiesel, has milder reaction conditions, greatly improves the reaction efficiency, effectively reduces the usage amount of petroleum ether in the process of extracting the pistacia chinensis bunge seed oil, is more environment-friendly, and in addition, the ionic liquid provided by the invention is water-soluble ionic liquid, is separated after the reaction is finished to obtain a mixed solution of the ionic liquid and water, can obtain the recycled ionic liquid after the water is removed, recycles the recycled ionic liquid for 4-5 times, still can ensure that the yield of the biodiesel reaches over 90 percent, solves the problem that the catalyst is difficult to separate and recycle after the esterification reaction is finished, and has higher popularization and application value.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
The embodiment of the invention provides an ionic liquid which is prepared from 1-allyl-3-methylimidazole chloride and zinc chloride in a molar ratio of 1:1, and the preparation method specifically comprises the following steps:
preparation of 1-allyl-3-methylchloridazole:
adding 0.2mol (16.42g) of 1-methylimidazole and 0.22mol (16.83g) of chloropropene into a three-neck flask, introducing nitrogen for protection, heating to 50 ℃, stirring for reaction for 8 hours, performing rotary evaporation at the vacuum degree of 0.08MPa and the temperature of 46 ℃ to remove excessive chloropropene until no liquid is evaporated, adding ether for washing for 2-3 times, removing the ethyl ether by rotary evaporation, and drying in a vacuum drying oven at the temperature of 60 ℃ for 48 hours to obtain 1-allyl-3-methylimidazole ([ Amim ] Cl);
preparation of [ Amim]Cl-ZnCl 2 Ionic liquid:
adding 0.1mol (15.86g) of 1-allyl-3-methylimidazolium chloride and 0.1mol (13.63g) of zinc chloride into a round-bottom flask, adding 0.3mL of 37 mass percent dilute hydrochloric acid solution, heating to 50 ℃, reacting for 3h, washing the product with water and diethyl ether for 1-2 times, removing residual diethyl ether, water and hydrochloric acid by rotary evaporation, and drying in vacuum at 60 ℃ for 24h to obtain [ Amim ]]Cl-ZnCl 2 The ionic liquid has the following structural formula.
The method for preparing the biodiesel by using the ionic liquid comprises the following steps:
crushing the pistacia chinensis bunge seeds to be below 30 meshes by using a grinder, and screening to obtain pistacia chinensis bunge seed powder; adding 5g of Pistacia chinensis seed powder into a flask, and adding 1g of Amim]Cl-ZnCl 2 Heating ionic liquid and 5mL of petroleum ether to 55 ℃, stirring and extracting for 65min, removing the petroleum ether in the extract by rotary evaporation, adding 10g of methanol, stirring and mixing for 30min at room temperature, separating out pistacia chinensis bunge seed residues, reacting the obtained filtrate at 65 ℃ for 160min, adding ethyl acetate with the volume of 4 times of the volume of the reaction liquid into the obtained reaction liquid, standing and separating the liquid, and removing the ethyl acetate from the obtained oil phase by rotary evaporation to obtain the biodiesel. Wherein, the yield of the pistacia chinensis bunge seed oil is 40.6 percent, and the yield of the biodiesel is 93.8 percent.
Example 2
The embodiment of the invention provides an ionic liquid, which is prepared from 1-allyl-3-methylimidazole chloride and copper chloride in a molar ratio of 1:1.1, and the preparation method specifically comprises the following steps:
preparation of 1-allyl-3-methylchloridazole:
adding 0.2mol (16.42g) of 1-methylimidazole and 0.26mol (19.90g) of chloropropene into a three-neck flask, filling nitrogen for protection, heating to 60 ℃, stirring for reaction for 6h, performing rotary evaporation at the vacuum degree of 0.12MPa and the temperature of 40 ℃ to remove excessive chloropropene until no liquid is evaporated, adding ether for washing for 2-3 times, performing rotary evaporation to remove the ethyl ether, and drying in a vacuum drying oven at the temperature of 60 ℃ for 48h to obtain 1-allyl-3-methylimidazole chloride ([ Amim ] Cl);
preparation of [ Amim]Cl-CuCl 2 Ionic liquid:
adding 0.1mol (15.86g) of 1-allyl-3-methylimidazole chloride and 0.11mol (14.79g) of copper chloride into a round-bottom flask, adding 0.3mL of a dilute hydrochloric acid solution with the mass fraction of 37%, heating to 60 ℃, reacting for 2h, washing the product with water and diethyl ether for 1-2 times respectively, removing residual diethyl ether, water and hydrochloric acid by rotary evaporation, and drying in vacuum at 60 ℃ for 24h to obtain [ Amim ℃]Cl-CuCl 2 The ionic liquid has the following structural formula.
The method for preparing the biodiesel by using the ionic liquid comprises the following steps:
crushing the pistacia chinensis bunge seeds to be below 30 meshes by using a grinder, and screening to obtain pistacia chinensis bunge seed powder; adding 3g of Pistacia chinensis seed powder into a flask, and adding 1g of Amim]Cl-CuCl 2 Heating the ionic liquid and 6mL of petroleum ether to 65 ℃, stirring and extracting for 55min, removing the petroleum ether in the extract by rotary evaporation, adding 9g of methanol, stirring and mixing for 30min at room temperature, separating out pistacia chinensis bunge seed residues, reacting the obtained filtrate at 75 ℃ for 130min, adding ethyl acetate with volume of 6 times of the volume of the reaction liquid into the obtained reaction liquid, standing and separating, and removing the ethyl acetate by rotary evaporation of the obtained oil phase to obtain the biodiesel. Wherein, the yield of the pistacia chinensis bunge seed oil is 41.5 percent, and the yield of the biodiesel is 95.8 percent.
Example 3
The embodiment of the invention provides an ionic liquid, which is prepared from 1-allyl-3-methylimidazole chloride and aluminum chloride in a molar ratio of 1:1, and the preparation method specifically comprises the following steps:
preparation of 1-allyl-3-methylchloridazole:
adding 0.2mol (16.42g) of 1-methylimidazole and 0.24mol (18.36g) of chloropropene into a three-neck flask, introducing nitrogen for protection, heating to 55 ℃, stirring for reaction for 7 hours, carrying out rotary evaporation at the vacuum degree of 0.1MPa and the temperature of 43 ℃ to remove excessive chloropropene until no liquid is evaporated, adding diethyl ether for washing for 2-3 times, carrying out rotary evaporation to remove the diethyl ether, and drying in a vacuum drying oven at the temperature of 60 ℃ for 48 hours to obtain 1-allyl-3-methylimidazole chloride ([ Amim ] Cl);
preparation of [ Amim]Cl-AlCl 3 Ionic liquid:
adding 0.1mol (15.86g) of 1-allyl-3-methylimidazole chloride and 0.1mol (13.33g) of aluminum chloride into a round-bottom flask, adding 0.3mL of a dilute hydrochloric acid solution with the mass fraction of 37%, heating to 55 ℃, reacting for 2h, washing the product with water and diethyl ether for 1-2 times respectively, removing residual diethyl ether, water and hydrochloric acid by rotary evaporation, and drying in vacuum at 60 ℃ for 24h to obtain [ Amim ℃]Cl-AlCl 3 The ionic liquid has the following structural formula.
The method for preparing the biodiesel by using the ionic liquid comprises the following steps:
crushing the pistacia chinensis bunge seeds to be below 30 meshes by using a grinder, and screening to obtain pistacia chinensis bunge seed powder; adding 4g of Pistacia chinensis seed powder into a flask, and adding 1g of Amim]Cl-AlCl 3 Heating the ionic liquid and 6mL of petroleum ether to 60 ℃, stirring and extracting for 60min, removing the petroleum ether in the extract by rotary evaporation, adding 10g of methanol, stirring and mixing for 30min at room temperature, separating out the pistacia chinensis bunge seed residue, reacting the obtained filtrate at 70 ℃ for 140min, adding ethyl acetate with volume 5 times of the volume of the reaction liquid into the reaction liquid, standing and separating, and removing the ethyl acetate by rotary evaporation of the obtained oil phase to obtain the biodiesel. Wherein, the yield of the pistacia chinensis bunge seed oil is 42.9 percent, and the yield of the biodiesel is 98.4 percent.
The aqueous phase obtained by standing and separating in the examples 1 to 3 is rotated to remove the aqueous phase to obtain the recycled ionic liquid, and the recycled ionic liquid is recycled for 4 to 5 times, so that the yield of the biodiesel can reach more than 90 percent.
Comparative example 1
The embodiment of the invention provides an ionic liquid, and a preparation method of the ionic liquid comprises the following steps:
preparation of [ Bmim ] Cl:
adding 0.2mol (16.42g) of 1-methylimidazole and 0.24mol (22.22g) of n-butyl chloride into a three-mouth flask, charging nitrogen for protection, heating to 60 ℃, stirring for reaction for 2 hours, performing rotary evaporation to remove excessive n-butyl chloride after the reaction is finished until no liquid is evaporated, adding ethyl acetate for washing for 2-3 times, performing rotary evaporation to remove ethyl acetate, and drying in a vacuum drying oven at 60 ℃ for 48 hours to obtain [ Bmim ] Cl;
preparation of [ Bmim ]]Cl-AlCl 3 Ionic liquid:
0.1mol (17.4g) [ Bmim ] was taken]Adding Cl and 0.1mol (13.33g) of aluminum chloride into a round-bottom flask, adding 0.3mL of dilute hydrochloric acid solution with the mass fraction of 37%, heating to 55 ℃ for reaction for 2h, washing the product with water and diethyl ether for 1-2 times respectively, removing residual diethyl ether, water and hydrochloric acid by rotary evaporation, and drying in vacuum at 60 ℃ for 24h to obtain [ Bmim ]]Cl-AlCl 3 An ionic liquid.
The method for preparing the biodiesel by using the ionic liquid comprises the following steps:
crushing the pistacia chinensis bunge seeds to be below 30 meshes by using a grinder, and screening to obtain pistacia chinensis bunge seed powder; adding 4g of Pistacia chinensis seed powder into a flask, and adding 1g of [ Bmim ]]Cl-AlCl 3 Heating the ionic liquid and 6mL of petroleum ether to 60 ℃, stirring and extracting for 60min, removing the petroleum ether in the extract by rotary evaporation, adding 10g of methanol, stirring and mixing for 30min at room temperature, separating out the pistacia chinensis bunge seed residue, reacting the obtained filtrate at 70 ℃ for 140min, adding ethyl acetate with volume 5 times of the volume of the reaction liquid into the obtained reaction liquid, standing and separating, and removing the ethyl acetate by rotary evaporation of the obtained oil phase to obtain the biodiesel. Wherein, the yield of the pistacia chinensis bunge seed oil is 35.7 percent, and the yield of the biodiesel is 56.2 percent.
Comparative example 2
The invention provides a preparation method of biodiesel, which comprises the following steps:
crushing the pistacia chinensis bunge seeds to be below 30 meshes by using a grinder, and screening to obtain pistacia chinensis bunge seed powder; adding 4g of Pistacia chinensis Bunge seed powder into a flask, adding 1g of AlCl 3 And 6mL of petroleum ether, heating to 60 ℃, stirring and extracting for 60min, removing the petroleum ether in the extract by rotary evaporation, adding 10g of methanol, stirring and mixing for 30min at room temperature, separating out the pistacia chinensis bunge seed residue, reacting the obtained filtrate at 70 ℃ for 140min, adding ethyl acetate with volume 5 times of the volume of the reaction solution into the reaction solution, standing and separating, and removing the ethyl acetate from the obtained oil phase by rotary evaporation to obtain the biodiesel. Wherein, the yield of the pistacia chinensis bunge seed oil is 24.6 percent, and the yield of the biodiesel is 45.6 percent.
Comparative example 3
The invention provides a preparation method of biodiesel, which comprises the following steps:
crushing the pistacia chinensis bunge seeds to be below 30 meshes by using a grinder, and screening to obtain pistacia chinensis bunge seed powder; adding 4g of pistacia chinensis bunge seed powder into a flask, and adding 1g of ZnCl 2 And 6mL of petroleum ether, heating to 60 ℃, stirring and extracting for 60min, removing the petroleum ether in the extract by rotary evaporation, adding 10g of methanol, stirring and mixing for 30min at room temperature, separating out the pistacia chinensis bunge seed residue, reacting the obtained filtrate for 140min at 70 ℃, adding ethyl acetate with volume 5 times of the volume of the reaction liquid into the reaction liquid, standing and separating, and removing the ethyl acetate from the obtained oil phase by rotary evaporation to obtain the biodiesel. Wherein, the yield of the pistacia chinensis bunge seed oil is 25.9 percent, and the yield of the biodiesel is 26.6 percent.
Comparative example 4
The invention provides a preparation method of biodiesel, which comprises the following steps:
crushing the pistacia chinensis bunge seeds to be below 30 meshes by using a grinder, and screening to obtain pistacia chinensis bunge seed powder; adding 4g of Pistacia chinensis seed powder into a flask, and adding 1g of CuCl 2 Mixing with 6mL petroleum ether, heating to 60 deg.C, stirring for 60min, removing petroleum ether, adding 10g methanol, stirring at room temperature for 30min, separating Pistacia chinensis seed residue, reacting the filtrate at 70 deg.C for 140min, and adding reaction solutionAnd 5 times of volume of ethyl acetate, standing, separating, and performing rotary evaporation on the obtained oil phase to remove the ethyl acetate to obtain the biodiesel. Wherein, the yield of the pistacia chinensis bunge seed oil is 25.8 percent, and the yield of the biodiesel is 43.3 percent.
Comparative example 5
The invention provides a preparation method of biodiesel, which comprises the following steps:
crushing the pistacia chinensis bunge seeds to be below 30 meshes by using a grinder, and screening to obtain pistacia chinensis bunge seed powder; adding 4g of pistacia chinensis bunge seed powder into a flask, adding 1g of [ Amim ] Cl and 6mL of petroleum ether, heating to 60 ℃, stirring and extracting for 60min, removing the petroleum ether in the extract by rotary evaporation, adding 10g of methanol, stirring and mixing for 30min at room temperature, separating pistacia chinensis bunge seed residues, reacting the obtained filtrate for 140min at 70 ℃, adding ethyl acetate with volume 5 times of the volume of the reaction liquid into the reaction liquid, standing for liquid separation, and removing the ethyl acetate from the obtained oil phase by rotary evaporation to obtain the biodiesel. Wherein, the yield of the pistacia chinensis bunge seed oil is 38.6 percent, and the yield of the biodiesel is 43.4 percent.
Comparative example 6
The invention provides a preparation method of biodiesel, which comprises the following steps:
crushing the pistacia chinensis bunge seeds by a grinder to be below 30 meshes, and screening to obtain pistacia chinensis bunge seed powder; adding 4g of Pistacia chinensis Bunge seed powder into a flask, and adding 1g of Amim]Cl and AlCl 3 Heating the mixture (the molar ratio is 1:1.1) and 6mL of petroleum ether to 60 ℃, stirring and extracting for 60min, removing the petroleum ether in the extract by rotary evaporation, adding 10g of methanol, stirring and mixing for 30min at room temperature, separating out the pistacia chinensis bunge seed residue, reacting the obtained filtrate at 70 ℃ for 140min, adding 5 times of volume of ethyl acetate into the reaction solution, standing and separating, and removing the ethyl acetate from the obtained oil phase by rotary evaporation to obtain the biodiesel. Wherein, the yield of the pistacia chinensis bunge seed oil is 36.4 percent, and the yield of the biodiesel is 73.6 percent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The ionic liquid is characterized by being prepared from 1-allyl-3-methylimidazole chloride and metal chloride.
2. The ionic liquid of claim 1, wherein the transition metal chloride is zinc chloride, copper chloride, or aluminum chloride.
3. The ionic liquid of claim 1 or claim 2, wherein the molar ratio of 1-allyl-3-methylchloridazole to metal chloride is from 1:1.0 to 1.1.
4. The ionic liquid of claim 1, wherein the 1-allyl-3-methylimidazolium chloride is prepared by a process comprising the steps of: reacting 1-methylimidazole with chloropropene at 50-60 ℃ for 6-8 h under inert atmosphere, performing vacuum rotary evaporation, washing, and drying to obtain 1-allyl-3-methylimidazole chloride.
5. The ionic liquid of claim 4, wherein the molar ratio of 1-methylimidazole to chloropropene is from 1:1.1 to 1.3.
6. A process for the preparation of an ionic liquid according to any one of claims 1 to 5, comprising the steps of: adding 1-allyl-3-methylimidazolium chloride and metal chloride into a solvent, uniformly mixing, heating to 50-60 ℃, reacting for 2-3 h, washing, rotary steaming and drying to obtain the ionic liquid.
7. Use of an ionic liquid according to any one of claims 1 to 5 in the preparation of biodiesel.
8. A method for preparing biodiesel by using the ionic liquid as claimed in any one of claims 1 to 5, wherein Pistacia chinensis Bunge seed oil is obtained by extracting Pistacia chinensis Bunge seed as raw material with the ionic liquid and petroleum ether as extraction solvent;
the extracted pistacia chinensis bunge seed oil and short-chain alcohol are used as raw materials, the ionic liquid is used as a catalyst, and the biodiesel is prepared through esterification reaction.
9. The method for preparing biodiesel according to claim 8, which comprises the following steps:
crushing pistacia chinensis bunge seeds to obtain pistacia chinensis bunge seed powder; adding the ionic liquid and petroleum ether into the pistacia chinensis bunge seed powder, heating to 55-65 ℃, stirring and extracting for 55-65 min, removing the petroleum ether in the extract by rotary evaporation, adding short-chain alcohol, mixing uniformly, separating pistacia chinensis bunge seed residues, reacting the obtained filtrate at 65-75 ℃ for 130-160 min, adding ethyl acetate into the reaction liquid, standing for liquid separation, and removing the ethyl acetate by rotary evaporation of the obtained oil phase to obtain the biodiesel.
10. The method for preparing biodiesel according to claim 9, wherein the mass ratio of the ionic liquid to the pistacia chinensis bunge seed powder is 1: 3-5; and/or
The volume-mass ratio of the petroleum ether to the pistacia chinensis bunge seed powder is 1-2:1, wherein the volume unit is milliliter, and the mass unit is gram; and/or
The mass ratio of the short-chain alcohol to the pistacia chinensis bunge seed powder is 2-3: 1.
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| Title |
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| J.APPL POLYM.SCI: ""1-Allyl-3-methylimidazolium Halometallate lonic liquids as Efficient Catalysts for the Glycolysis of Poly(ethylene terephthalate"", 《J.APPL POLYM.SCI》, vol. 129, no. 6, pages 3575 * |
| 何乐芹等: ""离子液体催化黄连木籽油酯交换制备生物柴油"", 《工程科技 I辑》, pages 1 - 4 * |
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