CN113233978A - Synthetic method of organic carboxylic ester - Google Patents
Synthetic method of organic carboxylic ester Download PDFInfo
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- 150000001733 carboxylic acid esters Chemical class 0.000 title claims abstract description 29
- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 85
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 64
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000000243 solution Substances 0.000 claims abstract description 33
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 32
- 238000010992 reflux Methods 0.000 claims abstract description 29
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000001308 synthesis method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000012043 crude product Substances 0.000 claims abstract description 4
- 238000007670 refining Methods 0.000 claims abstract description 3
- 238000004821 distillation Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- FSWCCQWDVGZMRD-UHFFFAOYSA-N 4-methylcyclohexene Chemical compound CC1CCC=CC1 FSWCCQWDVGZMRD-UHFFFAOYSA-N 0.000 claims description 4
- UZPWKTCMUADILM-UHFFFAOYSA-N 3-methylcyclohexene Chemical compound CC1CCCC=C1 UZPWKTCMUADILM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000036632 reaction speed Effects 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- PMGCQNGBLMMXEW-UHFFFAOYSA-N Isoamyl salicylate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1O PMGCQNGBLMMXEW-UHFFFAOYSA-N 0.000 description 11
- 230000002194 synthesizing effect Effects 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthetic method of organic carboxylic ester, belonging to the technical field of chemical synthesis. The synthesis method of the organic carboxylic ester mainly comprises the following steps: adding organic carboxylic acid and alcohol into a reaction container with water diversion and reflux, and adding a certain amount of cyclohexene and concentrated phosphoric acid catalyst; heating for esterification reaction, separating a byproduct, namely water and an azeotropic dehydrating agent to form an azeotrope out of the reaction container through a flow dividing device, and obtaining a reaction mixed solution after the reaction is finished; separating phosphoric acid solution in the reaction mixed solution to obtain crude organic carboxylic ester; separating the azeotropic dehydrating agent and the residual raw material in the crude product of the organic carboxylic ester; refining to obtain the organic carboxylic ester. The synthesis method of the organic carboxylic ester has the advantages of low cost, high reaction speed, high selectivity, environmental friendliness, and excellent application value and application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for catalytic synthesis of organic carboxylic ester by using concentrated phosphoric acid and cyclohexene.
Background
The present method for industrially producing organic carboxylic ester is mainly direct esterification of carboxylic acid and alcohol, and adopts concentrated sulfuric acid as catalyst, and the concentrated sulfuric acid possesses strong acidity and dewatering property, so that its catalytic activity is high and reaction speed is high, but the concentrated sulfuric acid possesses strong corrosivity and strong oxidizing property, and has high requirements for equipment material, and is easy to produce side reaction, its reaction selectivity is poor, and its product is easy to be coloured, and its after-treatment also has the procedures of neutralization and water-washing, etc., so that it can result in long technological route, large loss of product, and can produce lots of waste liquor, and can produce environmental pollution.
The use of concentrated sulfuric acid as a catalyst has another disadvantage that as the reaction proceeds, the water produced by the reaction reduces the concentration of sulfuric acid, weakens the dehydration capacity of the catalyst, and in order to increase the reaction rate and the product yield, more concentrated sulfuric acid needs to be supplemented as the reaction proceeds, thereby increasing side reactions and also producing a large amount of waste liquid. If an organic acid anhydride is used instead of the organic carboxylic acid, although the amount of sulfuric acid used is reduced, the acid anhydride is expensive, which also increases the production cost and decreases the competitiveness.
Toluene is usually added during the production of the esterification reaction. Toluene is used as an azeotropic water-carrying agent and forms an azeotrope with low boiling point with water, so that the water generated in the reaction is removed from the reaction system, the reaction is promoted to be continuously carried out in a forward direction, and the purposes of reducing the using amount of sulfuric acid and improving the yield of the product are achieved. However, the boiling point of toluene is relatively high, which results in high energy consumption for carrying out water-dividing reflux during the esterification reaction; and after the esterification reaction is finished, toluene with a higher boiling point is difficult to separate from the crude product of the organic carboxylic ester.
In view of the above problems, research and development of a low-cost and efficient method for catalytically synthesizing organic carboxylic acid esters is an important issue to be researched.
Disclosure of Invention
In view of the above, the present invention provides a low-cost and high-efficiency method for catalytically synthesizing organic carboxylic ester.
The purpose of the invention is realized by the following modes:
the invention provides a low-cost and high-efficiency method for catalytically synthesizing organic carboxylic ester, which uses concentrated phosphoric acid and cyclohexene as catalysts, uses the phosphoric acid to provide an acid center, and ensures that the cyclohexene is responsible for dehydration, thereby promoting the forward movement of reaction balance and accelerating the reaction speed.
A synthetic method of organic carboxylic ester mainly comprises the following steps: (1) adding organic carboxylic acid and alcohol into a reaction container with water diversion and reflux, adding a certain amount of azeotropic dehydrating agent, adding a certain amount of concentrated phosphoric acid catalyst, and uniformly mixing;
(2) heating for esterification reaction, separating a byproduct, namely water and an azeotropic dehydrating agent to form an azeotrope out of the reaction container through a flow dividing device, and obtaining a reaction mixed solution after the reaction is finished;
(3) separating the phosphoric acid solution in the reaction mixed solution obtained in the step (2) to obtain an organic carboxylic ester crude product;
(4) separating the azeotropic dehydrating agent and the residual raw materials in the crude organic carboxylic ester obtained in the step (3);
(5) refining to obtain the organic carboxylic ester.
Further, the molar weight ratio of the organic carboxylic acid to the alcohol in the step (1) is 1: 0.8-5.
Further, in the step (1), the azeotropic dehydrating agent is cyclohexene, and the molar weight ratio of the azeotropic dehydrating agent to the organic carboxylic acid is 0.1-5: 1.
Further, the molar weight ratio of the concentrated phosphoric acid catalyst to the organic carboxylic acid in the step (1) is 0.1-5: 1.
Further, the reaction vessel with the divided water reflux in the step (1) comprises a reactor, a divided water reflux device and a condenser.
Further, the reaction vessel with the water diversion reflux in the step (1) is respectively a reactor, a fractionator, a water diversion reflux vessel and a condenser from bottom to top.
Further, the reactor is a microreactor, a flask, a kettle-type reactor, a tower-type reactor or a tubular reactor; the fractionator is a tubular fractionator, a tower fractionator or a glass fractionating tube; in order to raise the azeotropic dehydrating solvent and water from the reactor to the top of the fractionator, it is necessary to provide a higher temperature, and therefore the height and fractionation efficiency of the fractionator are adjusted, and the temperature of the reactor can be raised accordingly; the water diversion reflux device is used for separating the water obtained by azeotropic distillation and the azeotropic dehydrating agent, the condenser is used for reducing the concentration of organic matters in the gas, and the condenser can also be replaced by a heat exchanger and is cooled by using media such as air, water and the like.
Further, the temperature of the esterification reaction in the step (2) is not lower than 80 ℃.
Further, the synthesis method also comprises transferring the azeotropic dehydrating agent separated from the azeotrope back to the bottom of the reaction vessel. The azeotropic dehydrating agent not only continuously takes away the water formed by the esterification reaction in an azeotropic form, thereby enabling the reaction to be continuously carried out in a forward direction, but also can provide a vaporization center and generate bubbles to play a role in stirring.
Furthermore, the azeotropic dehydrating agent separated from the azeotrope flows back to the bottom of the reaction container through a pipeline or is conveyed back to the bottom of the reaction container through a pump.
Further, in the step (3), the phosphoric acid solution and the crude organic carboxylic ester in the reaction mixed solution are separated by a liquid separation method.
Further, for the solid organic carboxylic ester with a high melting point, the phosphoric acid solution in the reaction mixed solution and the crude organic carboxylic ester are separated in the step (3) by a filtration method.
Further, in the step (4), the azeotropic dehydrating agent and the residual raw material are separated from the crude organic carboxylic ester by distillation or distillation under reduced pressure.
Further, the aqueous solution containing phosphoric acid is recovered, cyclohexene is used as a water-carrying agent, and the water-carrying agent is concentrated and then continuously recycled.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention uses concentrated phosphoric acid and cyclohexene as catalysts, the phosphoric acid has stronger acidity and weaker oxidizability, the conversion rate of the phosphoric acid catalytic reaction is high, side reaction is not easy to occur, and the reaction speed can be accelerated by increasing the concentration of the phosphoric acid. The boiling point of the phosphoric acid is high, and the reaction product can be separated from the phosphoric acid by a distillation method, so that the phosphoric acid can be recycled; the cyclohexene and water can form an azeotrope, the dehydration capability is strong, the azeotropic temperature is only 70 ℃, trace water generated in the esterification reaction and the cyclohexene with low boiling point are removed from a reaction system in the form of the azeotrope, the water content in the azeotropic solution can reach up to 10 percent, so that the high-efficiency dehydration effect is achieved, the solubility of the cyclohexene (with the density of 0.8g/mL) in water is low, the cyclohexene floats on the water and is naturally separated from the water, the content of organic matters in the separated water is extremely low, no organic wastewater is generated, and the environmental pollution is small. The cyclohexene has a low boiling point and can be separated from the high boiling reaction products by distillation, so that the cyclohexene can be recycled.
2. The cyclohexene separated in the azeotropic form is transferred back to the bottom of the reaction vessel, so that water formed by the esterification reaction is continuously taken away in the azeotropic form, the reaction is continuously carried out in a forward direction, and the conversion rate of the reaction is improved. And the low boiling point cyclohexene is heated and converted into gas in the process of transferring to the reaction vessel, so that the gas-liquid contact area is increased, the gaseous cyclohexene is fully contacted with the solution, a vaporization center can be provided for the mixed solution, bubbles are generated, and the stirring effect is achieved. Therefore, the reaction vessel is simplified, the stirring devices are reduced, the manufacturing cost and the operating cost of the equipment are reduced, and the effects of energy conservation and emission reduction are achieved.
3. The synthetic method of the organic carboxylic ester is obviously superior to the synthetic method using concentrated sulfuric acid as a catalyst, has low cost, high reaction speed, high selectivity and environmental friendliness, and has excellent application value and application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described below.
Fig. 1 is a schematic structural view of a water diversion and reflux device in embodiment 1.
FIG. 2 is a schematic structural view of a divided water reflux apparatus in comparative example 1.
Fig. 3 is a schematic structural view of the water-dividing fractionation reflux apparatus in embodiments 2 and 3.
FIG. 4 is a schematic view showing the structure of the fractional distillation reflux apparatus for comparative examples 2 and 3
Detailed Description
The present invention is described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto, and it is obvious that the examples in the following description are only some examples of the present invention, and it is obvious for those skilled in the art to obtain other similar examples without inventive exercise and falling into the scope of the present invention.
Example 1
Butyl acetate is a chemical product with wide application, and is mainly used in the fields of medicines, daily chemicals, food additives and the like. The invention provides a method for synthesizing butyl acetate by catalyzing concentrated phosphoric acid and cyclohexene through a water diversion reflux device by taking concentrated phosphoric acid and cyclohexene as catalysts.
The main steps for preparing butyl acetate are as follows: a50 mL round-bottom flask was charged with 9.1mL butanol (0.1mol) and 6.6mL acetic acid (0.11mol), and 3-4 drops of concentrated phosphoric acid and 4mL cyclohexene were added and mixed well. As shown in FIG. 1, a water separator and a spherical condenser tube were installed, and water was previously added to the water separator to 0.5cm below the branched tube opening. And adjusting the temperature of the heater to 100 ℃, heating and refluxing to separate out generated water, and stopping heating when the oil-water interface does not rise any more, which indicates that no water is generated any more. After the reaction is finished, pouring the mixed substances in the flask and the organic layer in the water separator into a separating funnel, washing with 10mL of water, then washing with 10mL of sodium carbonate solution (the mass percentage omega is 0.10), finally washing with 10mL of saturated sodium chloride aqueous solution, transferring the obtained organic layer solution into a conical flask, drying with anhydrous magnesium sulfate, filtering, transferring into a round-bottom flask, recovering cyclohexene from the obtained solution by a reduced pressure distillation method, heating and distilling, collecting fractions at 138-143 ℃, obtaining 9.5g of butyl acetate, and obtaining the product yield of 82%.
Comparative example 1
A method for synthesizing butyl acetate by using concentrated sulfuric acid catalysis through a water diversion reflux device. The main steps for preparing butyl acetate are as follows: a50 mL round-bottom flask was charged with 9.1mL of butanol (0.1mol) and 6.6mL of acetic acid (0.11mol), and then 3-4 drops of concentrated sulfuric acid were added and mixed well. As shown in FIG. 2, a water separator and a spherical condenser tube were installed, and water was previously added to the water separator to 0.5cm below the branched tube opening. Adjusting the temperature of the heater to 100 ℃, heating, refluxing and stirring to separate out generated water, and stopping stirring and heating when the interface of oil and water does not rise any more, which indicates that no water is generated any more. After the reaction is finished, the mixture in the flask is poured into a separating funnel, washed with 10mL of water, then washed with 10mL of sodium carbonate solution (the mass percentage omega is 0.10), finally washed with 10mL of saturated sodium chloride aqueous solution, the obtained organic layer solution is transferred to an erlenmeyer flask, dried with anhydrous magnesium sulfate, filtered, transferred to a round bottom flask, the obtained solution is heated and distilled, fractions at 138-143 ℃ are collected, 7.5g of butyl acetate is obtained, and the yield of the product is 65%.
The other reason that the yield of the method for synthesizing butyl acetate by catalyzing concentrated phosphoric acid and cyclohexene is high is that the solubility of butanol in water is high, a part of butanol can be dissolved in water and lost, and the solubility of cyclohexene in water is low, so that the butanol in water can be extracted. By using the technical scheme of the invention, the butanol is brought back to the flask through liquid-liquid extraction after the cyclohexene and the water are subjected to azeotropic distillation, so that the butanol is reacted again, and the yield of the product is improved. Therefore, the method for synthesizing butyl acetate by using the concentrated phosphoric acid and the cyclohexene for catalysis can obtain higher product yield.
Example 2
The isoamyl salicylate is also called isoamyl salicylate, is a chemical product with high application value, and has wide application in the fields of essence, medicine and the like. The invention provides a method for synthesizing isoamyl salicylate by using concentrated phosphoric acid and cyclohexene as catalysts through a water diversion reflux device.
The main steps for preparing the isoamyl salicylate are as follows: 27.6g (0.2mol) of salicylic acid, 27.0mL (0.25mol) of isoamyl alcohol, 8mL of cyclohexene and 2mL of concentrated phosphoric acid are added in turn to a 100mL round-bottom flask and mixed uniformly. As shown in FIG. 3, the reaction apparatus was installed, water was added into the water separator in advance, 5mm below the branch pipe mouth, the heater temperature was adjusted to 130 deg.C, heating was carried out under reflux, the generated water was separated, and heating was stopped when the water-oil interface did not rise any more, indicating that no water was generated. Pouring the mixed substance in the flask and the organic layer in the water separator into a separating funnel, washing with 10mL of water, washing with 10mL of sodium carbonate solution (the mass percentage omega is 0.10) and washing with 10mL of saturated sodium chloride aqueous solution to neutrality in sequence, transferring the obtained organic layer solution into a conical flask, drying with anhydrous magnesium sulfate, filtering, transferring into a round-bottom flask, recovering cyclohexene from the obtained solution by a reduced pressure distillation method, then carrying out reduced pressure distillation to collect a fraction at 142-144 ℃ (-740mmHg), namely an isoamyl salicylate product, and collecting 35.8g of isoamyl salicylate, wherein the yield of the product is 85.9%. Organic solvents with similar low boiling point and high water carrying capacity can also be used as water carrying agents, such as 4-methyl-1-cyclohexene and 3-methyl-1-cyclohexene.
Comparative example 2
A method for synthesizing isoamyl salicylate by using concentrated sulfuric acid catalysis through a water diversion reflux device. The main steps for preparing the isoamyl salicylate are as follows: 27.6g (0.2mol) of salicylic acid, 27.0mL (0.25mol) of isoamyl alcohol, 8mL of toluene and 2mL of concentrated sulfuric acid are sequentially added to a 100mL round-bottom flask and uniformly mixed with stirring. The reaction apparatus was installed as shown in FIG. 4. Water is added into the water separator in advance, and the water is 5mm lower than the branch pipe opening. And adjusting the temperature of the heater to 130 ℃, heating and refluxing to separate out generated water, stopping heating and stirring when the interface of oil and water does not rise any more, which indicates that no water is generated any more. Pouring the mixture in the flask into a separating funnel, washing with 10mL of water, washing with 10mL of sodium carbonate solution (the mass percent omega is 0.10) and washing with 10mL of saturated sodium chloride aqueous solution to be neutral in sequence, transferring the obtained organic layer solution into a conical flask, drying with anhydrous magnesium sulfate, filtering, transferring into a round-bottom flask, carrying out reduced pressure distillation on the obtained solution, collecting the fraction at 142-144 ℃ (-740mmHg), namely the isoamyl salicylate product, and collecting 16.6g of isoamyl salicylate, wherein the yield of the product is 39.9%.
Example 3
Dibutyl phthalate is a common plasticizer, which can ensure that products have good flexibility, phthalic anhydride and butanol which are commonly used in industrial production are subjected to esterification reaction under the action of sulfuric acid, but the price of phthalic anhydride is higher, and if dibutyl phthalate can be synthesized by using phthalic acid with lower price, the production cost can be obviously reduced. The invention provides a method for catalytically synthesizing isoamyl salicylate by concentrated phosphoric acid and cyclohexene through a water-splitting fractionation reflux device by taking concentrated phosphoric acid and cyclohexene as catalysts.
The main steps for preparing dibutyl phthalate are as follows: 16.6g (0.1mol) of phthalic acid, 27.5mL (0.3mol) of butanol, 8mL of cyclohexene and 4mL of concentrated phosphoric acid were added in this order to a 100mL round-bottomed flask and mixed well with stirring. As shown in FIG. 3, the reaction apparatus was installed, and water was previously added to the water separator at a position 1cm below the branched pipe. Adjusting the temperature of the heater to 130 ℃, stirring, heating and refluxing to separate out generated water, and stopping heating and stirring when the interface of oil and water does not rise any more, which indicates that no water is generated any more. After cooling, the liquid in the flask and the organic layer in the water separator were transferred to a separatory funnel, washed with 10mL of water, 10mL of a sodium carbonate solution (mass percent ω is 0.10), and washed with 10mL of a saturated aqueous sodium chloride solution in this order until the solution was neutral, the resulting organic layer solution was transferred to a conical flask, dried over anhydrous magnesium sulfate, filtered, and transferred to a round-bottomed flask, the resulting solution was subjected to reduced pressure distillation to recover cyclohexene and excess butanol, the remaining substance was dibutyl phthalate, 25.2g of dibutyl phthalate was collected, and the product yield was 90.6%.
Comparative example 3
A method for synthesizing dibutyl phthalate by using concentrated sulfuric acid catalysis through a water-diversion fractionation reflux device. The main steps for preparing dibutyl phthalate are as follows: 14.8g (0.1mol) of phthalic anhydride, 27.5mL (0.3mol) of butanol and 4mL of concentrated sulfuric acid were sequentially added to a 100mL round-bottomed flask, and mixed well with stirring. As shown in FIG. 4, the reaction apparatus was installed, and water was previously added to the water separator at a position 1cm below the branched pipe. And adjusting the temperature of the heater to 130 ℃, heating and refluxing to separate out generated water, and stopping heating when the oil-water interface does not rise any more, which indicates that no water is generated any more. After cooling, the liquid in the flask was transferred to a separatory funnel, washed with 10mL of water, 10mL of a sodium carbonate solution (mass percentage ω is 0.10), and washed with 10mL of a saturated aqueous sodium chloride solution in this order to be neutral, the resulting organic layer solution was transferred to a conical flask, dried over anhydrous magnesium sulfate, filtered, and transferred to a round bottom flask, and the resulting solution was subjected to reduced pressure distillation to recover excess butanol, and the remaining substance was dibutyl phthalate, and 20.6g of dibutyl phthalate was collected, and the product yield was 74.1%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A synthetic method of organic carboxylic ester is characterized by mainly comprising the following steps:
(1) adding organic carboxylic acid and alcohol into a reaction container with water diversion and reflux, adding a certain amount of azeotropic dehydrating agent, and adding a certain amount of concentrated phosphoric acid catalyst;
(2) heating for esterification reaction, separating an azeotrope formed by water generated by the esterification reaction and the azeotropic dehydrating agent out of the reaction container through a flow dividing device, and obtaining a reaction mixed solution after the reaction is finished;
(3) separating the phosphoric acid solution in the reaction mixed solution obtained in the step (2) to obtain an organic carboxylic ester crude product;
(4) separating the azeotropic dehydrating agent and the residual raw materials in the crude organic carboxylic ester obtained in the step (3);
(5) refining to obtain the organic carboxylic ester.
2. The synthesis method according to claim 1, wherein the molar weight ratio of the organic carboxylic acid to the alcohol in the step (1) is 1: 0.8-5.
3. The synthesis method according to claim 1, wherein the azeotropic dehydrating agent in the step (1) comprises cyclohexene, 4-methyl-1-cyclohexene or 3-methyl-1-cyclohexene, and the molar weight ratio of the azeotropic dehydrating agent to the organic carboxylic acid is 0.1-5: 1.
4. The synthesis method according to claim 1, wherein the molar weight ratio of the concentrated phosphoric acid catalyst to the organic carboxylic acid in the step (1) is 0.1-5: 1.
5. The synthesis method according to any one of claims 1 to 4, wherein the reaction vessel with divided water reflux in step (1) comprises a reactor, a divided water reflux device and a condenser.
6. The synthesis method according to claim 5, wherein the reaction vessel with the divided water reflux in the step (1) is a reactor, a fractionator, a divided water reflux device and a condenser respectively from bottom to top.
7. The synthesis method of claim 5, further comprising transferring the azeotropic dehydrating solvent separated from the azeotrope back to the reaction vessel and continuing to separate water formed by the esterification reaction, thereby allowing the reaction to proceed in a forward direction. The dehydrating agent needs to be introduced into the bottom of the reaction vessel, and is heated at the bottom of the reaction vessel to be converted into gas, and the generated bubbles play a role in stirring the mixed solution.
8. The synthesis method according to claim 5, wherein in the step (3), the phosphoric acid solution and the crude organic carboxylic ester in the reaction mixed solution are separated by liquid separation or filtration.
9. The synthesis method according to claim 8, wherein the azeotropic dehydrating agent and the residual unreacted raw materials are separated from the crude organic carboxylic ester in the step (4) by distillation or distillation under reduced pressure.
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| US20020028963A1 (en) * | 2000-09-05 | 2002-03-07 | Oxeno Olefinchemie Gmbh | Process for preparing carboxylic esters |
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| CN102701970A (en) * | 2012-06-26 | 2012-10-03 | 太仓市周氏化学品有限公司 | Method for catalyzing synthesis of ethyl acetate by using phosphoric acid |
| CN108083966A (en) * | 2017-12-27 | 2018-05-29 | 中国天辰工程有限公司 | A kind of method of azeotropic distillation separating cyclohexene and 1,3- cyclohexadiene |
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