CN102452933A - Preparation method of carboxylic ester - Google Patents
Preparation method of carboxylic ester Download PDFInfo
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- CN102452933A CN102452933A CN2010105197592A CN201010519759A CN102452933A CN 102452933 A CN102452933 A CN 102452933A CN 2010105197592 A CN2010105197592 A CN 2010105197592A CN 201010519759 A CN201010519759 A CN 201010519759A CN 102452933 A CN102452933 A CN 102452933A
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Abstract
The invention provides a preparation method of carboxylic ester. The preparation method comprises that carboxylic acid is contacted with alcohol under esterification condition in the presence of a catalyst, wherein the catalyst is a supported catalyst, the supported catalyst comprises a carrier and a sulfonic acid group supported on the carrier, and the carrier is FDU-14. According to the preparation method of carboxylic ester provided by the invention, on one hand, the supported catalyst can not corrode equipment, on the other hand, high reaction conversion rate can be obtained when the supported catalyst is used for preparing the carboxylic ester, side reaction is less, and product selectivity is good. Concretely, when the preparation method of carboxylic ester provided by the invention is used for preparing ethyl acetate, based on the reactant which is not superfluous stoichiometrically, reaction conversion rate can reach more than 99wt%, and yield of ethyl acetate can reach more than 90wt%.
Description
Technical field
The present invention relates to a kind of preparation method of carboxylicesters.
Background technology
Usually use the catalyzer of the vitriol oil as esterification in the industry, but adopt the vitriol oil to be as the shortcoming of catalyzer: facility investment is big, side reaction is many, product separate complex, liquid waste disposal difficulty and corrosion on Equipment are serious.Therefore, to replace the vitriol oil be the key that addresses the above problem to the catalyzer of development of new.
(Synthesis of ordered microporous silicates with organosulfur surface groups and their applications as solid acid catalysts [J] .Chem.Mater such as Lim M H; 1998; 10:467-470) and (Synthesis of oleic acid esters catalyzed by immobilized lipase [J] .Agric.Food Chem. such as Maja H; 1996,44:338-342) disclose and can use the catalyzer as esterification such as solid super-strong acid and Zeo-karb.But adopt above-mentioned solid super-strong acid and Zeo-karb to have as the esterification of catalyzer that the product productive rate is low, by product is more and the problem of product separation difficulty.
Therefore, provide reaction conversion ratio height, good product selectivity and the few method for preparing carboxylicesters of side reaction to remain a technical problem that needs to be resolved hurrily.
Summary of the invention
The by-product of esterification that the objective of the invention is to overcome prior art is many, the product productive rate is low, and then makes and the problem of product separation difficulty a kind of method for preparing carboxylicesters efficiently is provided.
Contriver of the present invention is surprised to find that: through sulfonic group being loaded on the loaded catalyst that obtains on the FDU-14 carrier when being used for the esterification by acetate and ethanol preparation ETHYLE ACETATE; The transformation efficiency of acetate and the productive rate of ETHYLE ACETATE are obviously higher when all using solid super-strong acid and Zeo-karb as catalyzer, and the amount of by product is obviously lower.
Thus, the invention provides a kind of preparation method of carboxylicesters, this method is included in catalyzer and exists down; Under enzymatic synthesis condition; Carboxylic acid is contacted with alcohol, and said catalyzer is a loaded catalyst, and this loaded catalyst comprises carrier and loads on the sulfonic group on the said carrier; Wherein, said carrier is FDU-14.
Preparing method according to carboxylicesters of the present invention adopts loaded catalyst as catalyzer; Said loaded catalyst comprises carrier and loads on the sulfonic group on the said carrier; And said carrier is FDU-14; This loaded catalyst can not produce corrosion to equipment on the one hand, and reaction conversion ratio is high on the other hand, side reaction is few and the product productive rate is high.
Particularly, in the time of will being used to prepare ETHYLE ACETATE according to the preparation method of carboxylicesters of the present invention, in stoichiometry excessive reactant not, the transformation efficiency of reaction can reach more than the 99 weight %, and the productive rate of ETHYLE ACETATE can reach more than the 90 weight %.
Description of drawings
Fig. 1 is isothermal nitrogen adsorption-desorption curve of FDU-14.
Fig. 2 is FDU-14-SO
3The isothermal nitrogen adsorption of H-desorption curve.
Fig. 3 is the pore size distribution curve figure of the FDU-14 of isothermal nitrogen adsorption-desorption method mensuration.
Fig. 4 is the FDU-14-SO that isothermal nitrogen adsorption-desorption method is measured
3The pore size distribution curve figure of H.
Fig. 5 is X-ray diffraction (XRD) figure of FDU-14.
Fig. 6 is FDU-14-SO
3The X-ray diffractogram of H.
Embodiment
The invention provides a kind of preparation method of carboxylicesters; This method is included in catalyzer and exists down, under enzymatic synthesis condition, carboxylic acid is contacted with alcohol; Said catalyzer is a loaded catalyst; This loaded catalyst comprises carrier and loads on the sulfonic group on the said carrier that wherein, said carrier is FDU-14.
According to loaded catalyst of the present invention, said carrier is order mesoporous resin material FDU-14.The skeleton of FDU-14 is made up of resol, contains a large amount of aromatic nucleus in the skeleton structure, so hydrophobicity is stronger, has excellent hydrothermal stability.And FDU-14 has cube and the symbiotic pore passage structure of six sides, has bigger duct size.
According to the present invention, the most probable aperture of said carrier is preferably 1-3nm, and more preferably 2-3nm further is preferably 2.5-3nm, most preferably is 2.8nm.According to the present invention, the specific surface area of said carrier is preferably 200-400m
2/ g, more preferably 300-400m
2/ g further is preferably 350-400m
2/ g most preferably is 375m
2/ g.According to the present invention, the pore volume of said carrier is preferably 0.1-0.2mL/g, 0.15-0.2mL/g more preferably, and more preferably 0.18-0.2mL/g most preferably is 0.2mL/g.
According to the present invention, the carrier that satisfies above-mentioned requirements can be synthetic according to existing method.For example, can be with reference to J.Am.Chem.Soc., 2005,127 (39): disclosed method is synthetic among the 13508-13509.
Concrete, said FDU-14 can prepare according to the method that comprises the steps:
(1) be the formaldehyde solution of 20-50 weight % and the NaOH aqueous solution that concentration is 0.05-0.2mol/L according to phenol with phenol, concentration: the mass ratio of formaldehyde: NaOH is 1: 0.5-2: 0.05-0.2 stirred 1-3 hour down at 50-100 ℃; After reducing to 10-45 ℃ (like room temperature); Adding by ethylene oxide-propylene oxide-ethylene oxide triblock copolymer template (like P123; Number-average molecular weight Mn=5800) in the mixing solutions that (registration number at U.S. chemical abstract is 9003-11-6) and deionized water are formed; The mass ratio of template and deionized water is 1: 5-20; Reheat is warming up to 66-100 ℃ after 50-65 ℃ and heated and stirred 100-150 hour, stir and reduce to 10-50 ℃ (like room temperature) after 24-100 hour, obtains solid sample after the spinning; Again solid sample is put into 25-100 ℃ baking oven and dry, obtain former powder mesoporous material polymkeric substance;
(2) be incubated 3-20 hour more former powder mesoporous material polymkeric substance is risen to 25-500 ℃ with PM 0.5-5 ℃ condition by 10-50 ℃ (like room temperature) in muffle furnace after, obtain mesoporous material polymkeric substance FDU-14 behind the removed template method.
According to the present invention, load has sulfonic group on the said carrier.According to the method for the invention, said sulfonic group can contain sulfonic monomer and loaded on the said carrier through in the process of preparation carrier, using, can also be through being loaded on the said carrier with the method for the stifling carrier of oleum.Adopt the method for the stifling carrier of oleum to come the load sulfonic group simple and easy to do, and have good Modulatory character.That is, the duration of contact through control FDU-14 and oleum and control the consumption of oleum just can be easily to loading on the HSO on the carrier
3 -Amount regulate.
Particularly, the sulfonic method of load for example can be according to Adv.Funct.Mater. on said carrier, and 2007,17, disclosed method among the 2455-2461.Preferably, comprise in the sulfonic method of load on the said carrier: is 1 with oleum with weight ratio with FDU-14: 5-20 contacts 1-10 hour under 25-100 ℃, and the concentration of sulphur trioxide is 20-80 weight % in the said oleum.Preferably, the weight ratio of FDU-14 and oleum is 1: 10-20; More preferably, the weight ratio of FDU-14 and oleum is 1: 14-18.Said FDU-14 is preferably 50-70 ℃, more preferably 60 ℃ with the temperature that contacts of oleum.Be preferably 1-5 hour the duration of contact of said FDU-14 and oleum, more preferably 2 hours.
The content of sulfonic group and carrier can change within a large range in the said loaded catalyst.Total amount with said loaded catalyst is a benchmark, and in element sulphur, said sulfonic content can be 1-10 weight %, is preferably 2-8 weight %, and more preferably 5-8 weight % most preferably is 7 weight %; The content of said carrier can be 90-99 weight %, is preferably 92-98 weight %, and more preferably 92-95 weight % most preferably is 93 weight %.
According to invention, in the element sulphur in the said loaded catalyst, the mol ratio of said carboxylic acid and said loaded catalyst can be 100-400: 1, be preferably 200-300: and 1,250-300 more preferably: 1, most preferably be 220-230: 1.
According to the present invention, said alcohol can be this area various monohydroxy-alcohols and/or divalent alcohol commonly used.Preferably, said alcohol is the monohydroxy-alcohol of 1-10 for carbonatoms.More preferably, said alcohol is one or more in methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 2-methyl-2-propyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 2-methyl-2-butanols, 2-methyl-3-butanols, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentene alcohol, 1-enanthol, 1 nonyl alcohol, 1-decanol and the phenylcarbinol.Most preferably, said alcohol is ethanol.
According to the present invention, said carboxylic acid can be this area various monocarboxylic acids and/or di-carboxylic acid commonly used.Preferably, said carboxylic acid is that carbonatoms is the monocarboxylic acid of 1-10.More preferably, said carboxylic acid is one or more in formic acid, acetate, propionic acid, butyric acid, valeric acid, n-nonanoic acid, enanthic acid, capric acid and the phenylformic acid.Most preferably, said carboxylic acid is an acetate.
Contriver of the present invention finds in research process, is specially adapted to by acetate and ethanol preparation ETHYLE ACETATE according to the preparation method of carboxylicesters of the present invention.
According to the present invention, said enzymatic synthesis condition can be for well known to a person skilled in the art enzymatic synthesis condition.Preferably, said enzymatic synthesis condition comprises: the mol ratio of said carboxylic acid and said alcohol can be 1: 0.5-10 is preferably 1: 1-2, and more preferably 1: 1-1.5 further is preferably 1: 1-1.2 most preferably is 1: 1; Temperature can be 90-150 ℃, is preferably 90-120 ℃; Time can be 1-72 hour, is preferably 1-6 hour.
Below in conjunction with embodiment the present invention is described in more detail.
In following examples, X-ray diffraction analysis is to carry out on the X-ray diffractometer of D8 Advance in the model available from German Bruker AXS company; TEM analysis is to carry out on the transmission electron microscope of Tecnai 20 in the model available from Dutch FEI Co.; Scanning electron microscope analysis is to carry out on the sem of XL-30 in the model available from U.S. FEI Co.; Gas chromatographic analysis is to carry out on the gas chromatograph of 7890A in the model available from U.S. An Jielun company; X-ray fluorescence analysis is carried out being purchased on the XRF energy spectrometer that model from Spectro Analypical Instruments GmbH is SPECTRO MIDEX; The experiment of nitrogen adsorption-desorption is carried out being purchased on the nitrogen adsorption desorption appearance that model from U.S. Kang Ta company is Autosorb-1.
Preparation example 1
With reference to Adv.Funct.Mater., 2007,17, disclosed method among the 2455-2461 prepares FDU-14 according to following steps:
The formaldehyde solution of 38 weight % of 2.8 gram phenol, 7.1 grams and the NaOH aqueous solution of 69 gram 0.1mol/L are joined in the single port bottle of 250mL successively, stirred 1.5 hours at 72 ℃, reduce to room temperature after; The mixing solutions that adding is made up of 6.72 gram polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymers (P123, available from BASF AG, molecular-weight average is 5800) and 70 gram deionized waters; Again with the mixture heating up to 64 that obtains ℃; 64 ℃ of following heated and stirred 120 hours, be warming up to 72 ℃ again, stir and reduce to room temperature after 48 hours; Obtain solid product after the spinning, again solid product is put into 80 ℃ baking oven and dry;
The solid product that obtains is risen to 350 ℃ with the speed of 1 ℃ of PM by 25 ℃, and, after removing the polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer, obtain FDU-14 350 ℃ of insulations 6 hours;
(density is 1.99g/cm with the oleum of 0.3 gram FDU-14 and 5mL 50 weight %
3) add in the reaction kettle of 20mL; And under 60 ℃ of conditions, left standstill 2 hours, after the filtration, that solid product is extremely neutral with 90 ℃ hot water injection; And, obtain according to loaded catalyst of the present invention (called after FDU-SO after being cooled to room temperature 150 ℃ of following vacuum-dryings 6 hours
3H).
Adopt nitrogen adsorption-desorption to test to FDU-SO
3H characterizes.
Fig. 1 is isothermal nitrogen adsorption-desorption curve of FDU-14, and Fig. 2 is FDU-14-SO
3The isothermal nitrogen adsorption of H-desorption curve.Adsorption-desorption curve among Fig. 1 and 2 is typical IV type curve, proves FDU-14-SO
3H has the characteristic of typical mesoporous material.
Fig. 3 is the pore size distribution curve figure of the FDU-14 of isothermal nitrogen adsorption-desorption method mensuration, and Fig. 4 is the FDU-14-SO that isothermal nitrogen adsorption-desorption method is measured
3The pore size distribution curve figure of H.Find out FDU-14-SO by Fig. 4
3The aperture curve of H all is evenly distributed, and the peak shape symmetry is (concrete data provide in table 1) better.
Table 1
| Sample | Specific surface area (m 2/g) | Pore volume (mL/g) | Most probable aperture (nm) |
| FDU-14 | 375 | 0.2 | 2.8 |
| FDU-14-SO 3H | 250 | 0.14 | 2.2 |
Table 2 is the x-ray fluorescence analysis result, and the result in the table 2 shows FDU-14-SO
3H contains element sulphur really.
Table 2
| Sample | The content of S (weight %) |
| FDU-14 | 0 |
| FDU-14-SO 3H | 7 |
Present embodiment is used to explain the preparation method according to carboxylicesters of the present invention.
Restrain the FDU-14-SO that is equipped with example 1 preparation with 0.5
3H adds in the there-necked flask of 100mL; And then add successively 11.5 the gram ethanol and 15 the gram acetate; With said mixture stirring reaction 3 hours under the reflux condition, be cooled to 25 ℃ after, reaction product is carried out the FDU-14-SO that spinning obtains product liquid and is recovered as solid phase
3H.With the composition of gas chromatographic analysis product liquid liquid, wherein, with acetometer, the transformation efficiency of reaction is 99 weight %, and the productive rate of ETHYLE ACETATE is 92 weight %.
FDU-14-SO with embodiment 1 recovery
3H is 150 ℃ of following vacuum-dryings 6 hours, be cooled to room temperature after, take by weighing 0.5g; Take by weighing 11.5 gram ethanol again and 15 gram acetate are put into the 100mL there-necked flask successively, under the reflux condition, stirred 3 hours, be cooled to 25 ℃ after; Spinning utilizes gas chromatographic analysis reaction product liquid composition, wherein; With acetometer, the transformation efficiency of reaction is 88 weight %, and the productive rate of ETHYLE ACETATE is 55 weight %.
Comparative Examples 1
23 gram ethanol and 30 gram acetate are put into the 100mL there-necked flask successively, do not add catalyzer, under the reflux condition, stirred 3 hours; After being cooled to room temperature, spinning obtains product liquid, with the composition of gas chromatographic analysis product liquid liquid; Wherein, With acetometer, the transformation efficiency of reaction is 76 weight %, and the productive rate of ETHYLE ACETATE is 36 weight %.
The result of embodiment 1 shows, adopts loaded catalyst according to the preparation method of carboxylicesters of the present invention, not only can obtain high transformation efficiency and product productive rate, and said loaded catalyst is easy to separate with reaction product.And the result of embodiment 2 shows that the loaded catalyst of recovery still has very high catalytic activity.
Claims (10)
1. the preparation method of a carboxylicesters, this method are included in catalyzer and exist down, under enzymatic synthesis condition; Carboxylic acid is contacted with alcohol, and said catalyzer is a loaded catalyst, and this loaded catalyst comprises carrier and loads on the sulfonic group on the said carrier; It is characterized in that said carrier is FDU-14.
2. method according to claim 1, wherein, in the element sulphur in the said loaded catalyst, the mol ratio of said carboxylic acid and said loaded catalyst is 100-400: 1.
3. method according to claim 1 and 2 wherein, is a benchmark with the total amount of said loaded catalyst, and in element sulphur, said sulfonic content is 1-10 weight %, and the content of said carrier is 90-99 weight %.
4. method according to claim 1, wherein, the most probable aperture of said carrier is 1-3nm, the specific surface area of said carrier is 200-400m
2/ g, the pore volume of said carrier are 0.1-0.2mL/g.
5. method according to claim 1, wherein, said enzymatic synthesis condition comprises: the mol ratio of said carboxylic acid and said alcohol is 1: 0.5-10, temperature is 90-150 ℃, the time is 1-72 hour.
6. according to claim 1 or 5 described methods, wherein, said alcohol is the monohydroxy-alcohol of 1-10 for carbonatoms.
7. method according to claim 6; Wherein, said alcohol is one or more in methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 2-methyl-2-propyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 2-methyl-2-butanols, 2-methyl-3-butanols, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentene alcohol, 1-enanthol, 1 nonyl alcohol, 1-decanol and the phenylcarbinol.
8. according to claim 1 or 5 described methods, wherein, said carboxylic acid is that carbonatoms is the monocarboxylic acid of 1-10.
9. method according to claim 8, wherein, said carboxylic acid is one or more in formic acid, acetate, propionic acid, butyric acid, valeric acid, n-nonanoic acid, enanthic acid, capric acid and the phenylformic acid.
10. according to claim 1 or 5 described methods, wherein, said carboxylic acid is an acetate, and said alcohol is ethanol.
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Cited By (3)
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| CN103145551A (en) * | 2013-03-11 | 2013-06-12 | 北京理工大学 | Application of phosphotungstic acid serving as catalyst in mixed alcohol esterification |
| CN110614094A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with carrier of cubic and hexagonal symbiotic pore channel structure with cubic core structure, preparation method and application |
| CN115487861A (en) * | 2021-06-18 | 2022-12-20 | 中国石油化工股份有限公司 | Shaped esterification catalyst, preparation method thereof and application thereof in isoamyl acetate synthesis |
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Application publication date: 20120516 |