CN102234228A - Method for synthesizing trimethylolpropane fatty acid ester under catalysis of ionic liquid - Google Patents
Method for synthesizing trimethylolpropane fatty acid ester under catalysis of ionic liquid Download PDFInfo
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- CN102234228A CN102234228A CN2010101666115A CN201010166611A CN102234228A CN 102234228 A CN102234228 A CN 102234228A CN 2010101666115 A CN2010101666115 A CN 2010101666115A CN 201010166611 A CN201010166611 A CN 201010166611A CN 102234228 A CN102234228 A CN 102234228A
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Abstract
The invention relates to a method for synthesizing trimethylolpropane fatty acid ester under the catalysis of ionic liquid, which comprises the following steps of: adding trimethylolpropane and fatty acid serving as raw materials into a reaction kettle, performing dehydration and esterification reaction at the temperature of between 120 and 180 DEG C for 4 to 10 hours under the action of an acidic ionic liquid catalyst and a water carrying agent until no water is distilled off, reducing the temperature, and standing to separate the ionic liquid catalyst so as to obtain the trimethylolpropane fatty acid ester. The method has the advantages of simplicity, high catalytic activity, reaction selectivity, hydrolytic stability and biodegradability, no byproduct, higher ester conversion rate, stable product quality, and low volatility and acid value.
Description
Technical field
The present invention relates to a kind of method of ionic liquid-catalyzed synthesizing trimethylol propane olein, particularly use the method for presence of acidic ionic liquid catalyst synthesizing trimethylol propane fatty acid ester, belong to chemical material field.
Background technology
The kind of trimethylolpropane fatty acid ester is more, Application Areas is more extensive, and it has excellent lubricating property, good annealing cleanness, good stability to hydrolysis and low volatility are applicable to metal processing and rolling with fields such as oil, aircraft engine lubricating oil, preparation mediums.
The synthetic method of existing trimethylolpropane fatty acid ester mainly contains acid alcohol esterification process and ester-interchange method, the acid alcohol esterification process is a raw material with TriMethylolPropane(TMP) and lipid acid, is that catalyzer or solid catalyst reaction form with tosic acid, sulfuric acid, metatitanic acid four fourth vinegar etc.Use such an acidic catalyst, need processes such as washing, or need filtration procedure, the technology more complicated, and also the part catalyzer still remains in the product, causes product quality in storage process easily to change, and influences product stability.Ester-interchange method is a raw material with TriMethylolPropane(TMP) and fatty acid methyl ester or ethyl ester, based on basic catalyst, and its complex process, speed of response is slow, and esterification yield is not high, introduces basic catalyst and makes the aftertreatment complexity.Disclosing a kind of among the Chinese patent CN1379014A is catalyzer with the soild oxide, adopt TriMethylolPropane(TMP) and oleic acid elder generation dehydrating condensation to add the method that the water hydrolysis prepares tricarboxymethyl propane oleate again, the technical process complexity, but also need the filtering separation catalyzer, environment is polluted.
Summary of the invention
Purpose of the present invention is catalyzer with the acidic ion liquid for the shortcoming that overcomes above-mentioned prior art provides a kind of with deficiency just, the method of direct synthesizing trimethylol propane fatty acid ester, thereby processing method is simpler, speed of response is fast, the esterification yield height, the constant product quality that obtains, good stability to hydrolysis, biological degradability and low volatility.
The objective of the invention is to realize by following technical proposal:
A kind of method of synthesizing trimethylolpropane fatty acid ester under catalysis of ionic liquid; It is take trimethylolpropane and aliphatic acid as raw material; Be that 1～1.2: 3 ratios add in the reactor in molar ratio with trimethylolpropane and Fatty acids composition; Under acidic ionic liquid catalysts and the effect of band aqua; The esterification of dewatering; The dehydration esterification reaction temperature is that 120～180 ℃, reaction time are 4～10 hours; Until anhydrous distillating; After the cooling; The standing separation ionic-liquid catalyst; Obtain trimethylolpropane fatty acid ester
Described lipid acid is animal oil fatty acid, vegetable fatty acids or two kinds of arbitrary proportion blended commercial fatty acids,
Described acidic ionic liquid catalysts is to be dissolved with ionic liquid [Hmim]+BF4-or [Heim]+BF4-and [the Hbim]+BF4-that Lewis tart inorganic salt are selected from FeCl3, SnCl4, AlCl3, ZnCl2, Zn (NO3) 2, the add-on of acidic ionic liquid catalysts is the 5-20% of TriMethylolPropane(TMP) and lipid acid gross weight
The mixture of one or both that described band aqua is hexanaphthene, toluene or dimethylbenzene or three kinds of arbitrary proportions, the mass ratio 0.1～1: 1 of band aqua consumption and lipid acid;
Described method, undertaken by following step:
(a) be that 1～1.2: 3 mixed adds in the reactor in molar ratio with TriMethylolPropane(TMP) and lipid acid, add the band aqua again, the mass ratio of band aqua and lipid acid is 0.1～1: 1,
(b) ionic liquid being selected from the proportioning of FeCl3, SnCl4, ZnCl2, Zn (NO3) 2 with being dissolved with the acid inorganic salt of Lewis, is 1 by mass ratio: the 0.01-1 mixed, and the preparation acidic ionic liquid catalysts,
(c) again in acidic ionic liquid catalysts 5～20% ratios addings (a) the item material with (b) by TriMethylolPropane(TMP) and lipid acid gross weight, under agitation be warming up to 120～180 ℃, the esterification of dewatering, distillate the water that reaction generates, behind reaction 4～10h, anhydrous distillating is cooled to 70 ℃, and standing separation gets the trimethylolpropane fatty acid ester product.
The synthetic method of trimethylolpropane fatty acid ester of the present invention, with TriMethylolPropane(TMP) and lipid acid is raw material, TriMethylolPropane(TMP), the another name trihydroxymethyl propane, molecular formula is CH3CH2 (CH2OH) 3, lipid acid is animal oil fatty acid, vegetable fatty acids or the acid of two kinds of arbitrary proportion blended industry oil fat, general acid number 209～235mgKOH/g, TriMethylolPropane(TMP) and lipid acid are 1～1.2: 3 mixed in molar ratio, to be that 0.1～1: 1 mixed adds in the reactor again with the mass ratio of aqua and lipid acid, excessive TriMethylolPropane(TMP) can be complete with fatty acid response, the generating portion diester, the viscosity-temperature characteristics of product both can have been improved, reaction is carried out fully, thereby obtained low acid number target product, simplify technical process.
With ionic liquid with have that the acid inorganic salt of Lewis are selected from FeCl3, SnCl4, ZnCl2, Zn (NO3) 2 with the ionic liquid proportioning, by mass ratio is 1: the 0.01-1 mixed, the preparation acidic ionic liquid catalysts, the ionic liquid of preparing is acid by force, strength of acid is even, and non-corrosiveness.
Again 5～20% ratios of prepared acidic ionic liquid catalysts in TriMethylolPropane(TMP) and lipid acid gross weight are added in the reaction mass of configuration, under agitation be warming up to 120～180 ℃, the esterification of dewatering, distillate the water that reaction generates, behind reaction 4～10h, anhydrous distillating is cooled to 70 ℃, and standing separation gets the trimethylolpropane fatty acid ester product.Because ionic liquid is acid strong, strength of acid is even, do not dissolve each other with raw material and reaction product, can high ester conversion rate, highly selective generates target product, and through standing separation catalyst ion liquid and product.
Owing to take technique scheme to make the technology of the present invention compared with prior art, have following advantage and effect:
(a) because the employing acidic ionic liquid catalysts is synthetic simple, the catalytic activity height, reaction preference height, no coupling product generate, and improve ester conversion rate, highly selective generation trimethylolpropane fatty acid ester product summary product.
(b) ionic-liquid catalyst and reaction product separate easily, product need not refining step, and technical process is simple, energy consumption is low, the reaction process non-pollutant discharge, the process cleaning, ionic-liquid catalyst can be recycled, and corrodibility is low.
(c) by synthetic tricarboxymethyl propane oleate of the present invention, constant product quality has good stability to hydrolysis, favorable biological degradability and low volatility, and acid number is low.
Embodiment
Following example will be further specified method provided by the invention, but therefore not limit the present invention.
Embodiment 1:
Get TriMethylolPropane(TMP) 134.17g, industry animal oil fatty acid (acid number 209mgKOH/g) 847.41g mixes and adds in the reactor, add hexanaphthene 84.74g again, getting FeCl3 0.491g mixes with 1-Methylimidazole fluoroborate [Hmim]+BF4-, preparation acidic ionic liquid catalysts 49.08g adds in the reactor, under agitation be warming up to 120 ℃, the esterification of dewatering distillates the water that reaction generates, behind the reaction 10h, anhydrous distillating is cooled to 70 ℃, and standing separation gets trimethylolpropane fatty acid ester product 922.51g, ionic liquid 48.98g, conversion rate of fatty acid 95%, product acid number 10.7mgKOH/g does not have other by product.
Embodiment 2:
Get TriMethylolPropane(TMP) 161.00g, industrial plant fatty acid oil (acid number 243mgKOH/g) 847.41g mixes and adds in the reactor, add hexanaphthene 423.71g again, getting SnCl4 8.07g mixes with 1-butyl imidazole fluoroborate [Hbim]+BF4-, preparation acidic ionic liquid catalysts 80.67g adds in the reactor, under agitation be warming up to 140 ℃, the esterification of dewatering distillates the water that reaction generates, behind the reaction 6h, anhydrous distillating is cooled to 70 ℃, and standing separation gets trimethylolpropane fatty acid ester product 947.89g, ionic liquid 80.52g, conversion rate of fatty acid 97%, product acid number 4.25mgKOH/g does not have other by product.
Embodiment 3:
Get TriMethylolPropane(TMP) 147.58g, industrial plant fatty acid oil (acid number 243mgKOH/g) 847.41g mixes and adds in the reactor, add toluene 677.93g again, getting ZnCl2 49.97g mixes with 1-Methylimidazole fluoroborate [Hmim]+BF4-, preparation acidic ionic liquid catalysts 99.50g adds in the reactor, under agitation be warming up to 150 ℃, the esterification of dewatering distillates the water that reaction generates, behind the reaction 10h, anhydrous distillating is cooled to 70 ℃, and standing separation gets trimethylolpropane fatty acid ester product 935.18g, ionic liquid 99.35g, conversion rate of fatty acid 99.1%, product acid number 1.45mgKOH/g does not have other by product.
Embodiment 4:
Get TriMethylolPropane(TMP) 134.17g, industrial plant fatty acid oil and industrial plant fatty acid oil were by combination in 1: 1, (acid number 224mgKOH/g) 847.41g mixes and adds in the reactor, add dimethylbenzene and hexanaphthene again by 1: 1 combination 847.41g, getting En (CO3) 2 147.24g mixes with 1-Methylimidazole fluoroborate [Hmim]+BF4-, preparation acidic ionic liquid catalysts 147.24g adds in the reactor, under agitation be warming up to 140 ℃, the esterification of dewatering, distillate the water that reaction generates, behind the reaction 8h, anhydrous distillating, be cooled to 70 ℃, standing separation gets trimethylolpropane fatty acid ester product 922.65g, ionic liquid 147.21g, lipid acid acid transformation efficiency 99.4%, product acid number 0.71mgKOH/g does not have other by product.
Embodiment 5:
Get TriMethylolPropane(TMP) 134.17g, industrial plant fatty acid oil and industrial plant fatty acid oil were by combination in 1: 2, (acid number 235mgKOH/g) 847.41g mixes and adds in the reactor, add toluene and hexanaphthene again by combination in 1: 0.5) 423.71g, getting Zn (CO3) 2 157.05g mixes with 1-butyl imidazole fluoroborate [Hbim]+BF4-, preparation acidic ionic liquid catalysts 196.32g adds in the reactor, under agitation be warming up to 180 ℃, the esterification of dewatering, distillate the water that reaction generates, behind the reaction 4h, anhydrous distillating, be cooled to 70 ℃, standing separation gets trimethylolpropane fatty acid ester product 922.63g, ionic liquid 196.29g, conversion rate of fatty acid 99.6%, product acid number 0.65mgKOH/g does not have other by product.
Claims (3)
1. the method for a synthesizing trimethylolpropane fatty acid ester under catalysis of ionic liquid; It is characterized in that: it is take trimethylolpropane and aliphatic acid as raw material; Be that 1～1.2: 3 ratios add in the reactor in molar ratio with trimethylolpropane and Fatty acids composition; Under acidic ionic liquid catalysts and the effect of band aqua; The esterification of dewatering; The dehydration esterification reaction temperature is that 120～180 ℃, reaction time are 4～10 hours; Until anhydrous distillating; After the cooling; The standing separation ionic-liquid catalyst; Obtain trimethylolpropane fatty acid ester
Described lipid acid is animal oil fatty acid, vegetable fatty acids or two kinds of arbitrary proportion blended commercial fatty acids,
Described acidic ionic liquid catalysts is to be dissolved with ionic liquid [Hmim]+BF4-or [Heim]+BF4-and [the Hbim]+BF4-that Lewis tart inorganic salt are selected from FeCl3, SnCl4, AlCl3, ZnCl2, Zn (NO3) 2, the add-on of acidic ionic liquid catalysts is the 5-20% of TriMethylolPropane(TMP) and lipid acid gross weight
The mixture of one or both that described band aqua is hexanaphthene, toluene or dimethylbenzene or three kinds of arbitrary proportions, the mass ratio 0.1～1: 1 of band aqua consumption and lipid acid.
2. the method for ionic liquid-catalyzed synthesizing trimethylol propane fatty acid ester according to claim 1, it is characterized in that: the ionic liquid of described acidic ion liquid is selected from 1-Methylimidazole fluoroborate [Hmim]+BF4-, 1-ethyl imidazol(e) fluoroborate [Heim]+BF4-or 1-butyl imidazole fluoroborate [Hbim]+BF4-, ionic liquid is selected from the proportioning of FeCl3, SnCl4, ZnCl2, Zn (NO3) 2 with being dissolved with the acid inorganic salt of Lewis, is 1: 0.01～1 by mass ratio.
3. method according to claim 1 is characterized in that described method undertaken by following step:
(a) be that 1～1.2: 3 mixed adds in the reactor in molar ratio with TriMethylolPropane(TMP) and lipid acid, add the band aqua again,
(b) ionic liquid being selected from the proportioning of FeCl3, SnCl4, ZnCl2, Zn (NO3) 2 with being dissolved with the acid inorganic salt of Lewis, is 1: 0.01～1 mixed by mass ratio, the preparation acidic ionic liquid catalysts,
(c) again in acidic ionic liquid catalysts 5～20% ratios addings (a) the item material with (b) by TriMethylolPropane(TMP) and lipid acid gross weight, under agitation be warming up to 120～180 ℃, the esterification of dewatering, distillate the water that reaction generates, behind reaction 4～10h, anhydrous distillating is cooled to 70 ℃, and standing separation gets the trimethylolpropane fatty acid ester product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592089A (en) * | 2015-01-05 | 2015-05-06 | 内蒙古工业大学 | Catalytic synthesis of 3-amino-alkylindole by using [HMim] BF4 ionic liquid in water |
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| CN1379014A (en) * | 2002-04-29 | 2002-11-13 | 王伟松 | Method for synthesizing trimethylolpropane oleate |
| CN1405140A (en) * | 2002-11-07 | 2003-03-26 | 华东师范大学 | Method of esterifying in ion liquid [Hmim]+ BF4- |
| EP1426368A1 (en) * | 2000-06-28 | 2004-06-09 | Vitae - Caps, S.A. | Method for extracting and purifying natural tocopherols and sterols by esterification with trimethyl propane |
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| US5716554A (en) * | 1995-02-21 | 1998-02-10 | Shiseido Co., Ltd. | Ultraviolet light absorbent |
| EP1426368A1 (en) * | 2000-06-28 | 2004-06-09 | Vitae - Caps, S.A. | Method for extracting and purifying natural tocopherols and sterols by esterification with trimethyl propane |
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| CN101172253A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Esterification catalysts and esterification process of organic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592089A (en) * | 2015-01-05 | 2015-05-06 | 内蒙古工业大学 | Catalytic synthesis of 3-amino-alkylindole by using [HMim] BF4 ionic liquid in water |
| CN104592089B (en) * | 2015-01-05 | 2019-04-16 | 内蒙古工业大学 | [HMim] BF in water4Ionic liquid-catalyzed synthesis 3- amine alkyl-indol |
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Application publication date: 20111109 |