CN115677497A - Production method of ethyl benzoate - Google Patents
Production method of ethyl benzoate Download PDFInfo
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- CN115677497A CN115677497A CN202211352887.1A CN202211352887A CN115677497A CN 115677497 A CN115677497 A CN 115677497A CN 202211352887 A CN202211352887 A CN 202211352887A CN 115677497 A CN115677497 A CN 115677497A
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- reaction kettle
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- benzoyl chloride
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- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 118
- 238000006243 chemical reaction Methods 0.000 claims abstract description 100
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 86
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims 8
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 13
- 230000008016 vaporization Effects 0.000 description 13
- 238000009834 vaporization Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001802 infusion Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005086 pumping Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 244000144730 Amygdalus persica Species 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 235000001537 Ribes X gardonianum Nutrition 0.000 description 1
- 235000001535 Ribes X utile Nutrition 0.000 description 1
- 235000016919 Ribes petraeum Nutrition 0.000 description 1
- 244000281247 Ribes rubrum Species 0.000 description 1
- 235000002355 Ribes spicatum Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 235000006468 Thea sinensis Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000020279 black tea Nutrition 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000000346 nonvolatile oil Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a production method of ethyl benzoate, which comprises the following steps: vacuumizing the reaction kettle, and continuously introducing nitrogen into the reaction kettle; gaseous ethanol is introduced from the bottom of the reaction kettle, benzoyl chloride is sprayed from the top of the reaction kettle, and the gaseous ethanol and the benzoyl chloride are in countercurrent contact in the reaction kettle and react to form ethyl benzoate. The invention takes ethanol and benzoyl chloride as raw materials, the raw materials can directly react without the participation of solvent and catalyst, thereby saving cost, simplifying operation and being suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a production method of ethyl benzoate, in particular to a method for producing ethyl benzoate, which has the advantages of simple process, simple raw materials and no need of catalysts and solvents.
Background
The ethyl benzoate is an organic compound with a molecular formula of C 9 H 10 O 2 It is colorless transparent liquid, slightly fruity, insoluble in water, slightly soluble in hot water, miscible with ethanol, diethyl ether, petroleum ether, propylene glycol, chloroform, mineral oil and most nonvolatile oils, insoluble in glycerol, and naturally present in peach, pineapple, currant, black tea. Ethyl benzoate is used in a wide variety of applications, is commonly used in the formulation of perfume essences and artificial essential oils, is also used in large quantities in food, and is also used as a solvent for cellulose esters, cellulose ethers, resins, and the like. In addition, ethyl benzoate is a common organic synthetic intermediate.
At present, the common preparation method of ethyl benzoate in industry is as follows: the benzoic acid and the ethanol are esterified under the catalysis of sulfuric acid to generate the compound with the following reaction formula. However, the method has a large amount of waste water and serious pollution, and the corrosion of equipment is particularly serious because strong acid such as sulfuric acid is often used. In addition, the method is a liquid-liquid reaction, continuous stirring is needed to ensure that the raw materials are fully contacted, the reaction time needs eight hours to finish the reaction, the production efficiency is seriously influenced, impurities are increased, and the reaction conversion rate is reduced.
Another common preparation method is: under the catalysis of cation exchange resin, the catalyst is prepared by esterifying benzoic acid and ethanol, the method using the cation exchange resin has high yield and about 92 percent of conversion rate, but the cation exchange resin has high cost and complicated operation mode.
The preparation method is also as follows: benzoyl chloride reacts with ethanol, but triethylamine or pyridine is required to be used as an acid-binding agent in the reaction, which causes increase of production cost.
In patent publication No. CN109160880, sodium benzoate and ethyl chloride are used as raw materials, and ethyl benzoate is obtained by phase transfer and pressure catalysis, so that the selectivity and the conversion rate of the reaction are improved. The method uses a large amount of toluene as a solvent, the solvent cannot be recovered completely in practical application, the toluene inevitably volatilizes a part, and the toluene mainly affects the central nervous system of a human body and causes irritation to respiratory tracts and skin.
Disclosure of Invention
It can be seen from the above prior art that solvents and catalysts are mostly used in the current preparation methods of ethyl benzoate, and the invention provides a production method of ethyl benzoate, which does not need the solvents and catalysts to participate in the reaction, and the raw materials are fed and contacted in a special way, so that the reaction is faster, and the method has the advantages of simple operation and cost saving, and the conversion rate and yield of the product are higher.
The specific technical scheme of the invention is as follows:
a process for the production of ethyl benzoate, the process comprising the steps of:
(1) Vacuumizing the reaction kettle, and continuously introducing nitrogen into the reaction kettle;
(2) Gaseous ethanol is introduced from the bottom of the reaction kettle, benzoyl chloride is sprayed from the top of the reaction kettle, and the gaseous ethanol and the benzoyl chloride are in countercurrent contact in the reaction kettle and react to form ethyl benzoate.
Further, in the step (1), vacuumizing is carried out to keep the vacuum degree in the reaction kettle between 0.01MPa and 0.1MPa,
continuously introducing nitrogen into the reaction kettle to keep the nitrogen introduction speed at 0.1m 3 /h～0.4m 3 /h。
Further, in the step (2), ethanol is stored in an ethanol storage tank, benzoyl chloride is stored in a benzoyl chloride storage tank, and the two storage tanks are subjected to nitrogen evacuation. Wherein the water content of the ethanol is not more than 0.01wt%. Before entering the reaction kettle, the ethanol can be vaporized into a gaseous state through the vaporization tank.
Furthermore, in the step (2), the flow rate of the gaseous ethanol is controlled to be 90-100kg/h, and the conveying speed of the benzoyl chloride is controlled to be 270-290 kg/h. Ethanol and benzoyl chloride were added at controlled rates by a metering pump.
Further, in the step (2), the molar ratio of ethanol to benzoyl chloride is 1:0.9 to 1.1, preferably with a slight excess of ethanol, maintained at a molar ratio of ethanol to benzoyl chloride of 1.01 to 1.05:1.
further, in the step (2), benzoyl chloride is sprayed into the reaction kettle through the spray heads, and the number of the spray heads can be one or two or more.
Further, in the step (2), the temperature of the reaction kettle is kept at 30-70 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃, and after the raw materials are added, the reaction is continued for 3-6 hours under heat preservation.
Further, nitrogen is introduced into the reaction kettle when the ethanol is added, HCl gas generated in the reaction is taken away by the nitrogen, the nitrogen is introduced from the bottom of the reaction kettle, the nitrogen bubbles in the reaction kettle along with the addition of the raw materials, hydrogen chloride formed in the reaction is fully taken away, and the nitrogen introduction is stopped until the alcoholysis dechlorination dehydrogenation reaction is finished. And absorbing gas exhausted from the reaction kettle by water, thereby converting hydrogen chloride gas into hydrochloric acid and realizing the recovery of the hydrogen chloride.
The invention has the following advantages:
1. the invention takes ethanol and benzoyl chloride as raw materials, the raw materials can directly react without the participation of solvent and catalyst, thereby saving cost, simplifying operation and being suitable for large-scale industrial production.
2. The method omits the use of a conventional acid binding agent, the hydrogen chloride gas in the reaction product is carried out of the reaction kettle along with the nitrogen, the forward reaction is promoted, the complete reaction is ensured, and the product conversion rate and the yield are high.
3. The raw materials of the invention are all organic matters, and are dried without water intervention, thereby reducing the possibility of product hydrolysis, having better product quality and being convenient for long-term storage and transportation.
4. The hydrogen chloride gas generated in the production process can be uniformly recycled and sold, so that the HCl is prevented from being discharged to pollute the environment, and the method is more environment-friendly.
5. The raw materials used in the invention, such as benzoyl chloride and ethanol, are all the raw materials which are used and stored in chemical plants daily, no extra purchase is needed, the price is low, and the production cost of the product is low.
Drawings
FIG. 1 is a schematic diagram of a system for producing ethyl benzoate.
FIG. 2 is the nuclear magnetic spectrum of the product ethyl benzoate.
FIG. 3 is a mass spectrum of the product ethyl benzoate.
In the figure, 1, an ethanol storage tank; 2. a benzoyl chloride storage tank; 3. a reaction kettle; 4. a first infusion metering pump; 5. a second infusion metering pump; 6. a reaction liquid storage tank; 7. a vaporization tank; 8. a distillation tank; 9. an ethanol recovery tank; 10. a product storage tank; 11. a third infusion metering pump; 12. a spray head; 13. a gas absorption tank; 14. a nitrogen compressor; 15. and (4) a nitrogen buffer tank.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to be exemplary only and not limiting as to the scope of the invention.
Example 1
Fig. 1 is a schematic structural diagram of a production system of ethyl benzoate, the production system includes a reaction kettle, a cavity is arranged inside the reaction kettle, at least one spray head is arranged at the top of the cavity inside the reaction kettle, the spray head is connected with a benzoyl chloride storage tank through a pipeline, an exhaust port is further arranged at the top of the reaction kettle, a nitrogen inlet is further arranged at the lower part or the bottom of the reaction kettle, the exhaust port is connected with a gas absorption tank, the gas absorption tank is connected with a nitrogen buffer tank through a nitrogen compressor, and an air outlet of the nitrogen buffer tank is connected with the nitrogen inlet of the reaction kettle. An ethanol inlet is formed in the lower portion or the bottom of the reaction kettle and is connected with a vaporization tank, and the vaporization tank is connected with an ethanol storage tank. The bottom of reation kettle is equipped with the discharge gate, the discharge gate links to each other with the feed inlet of reaction liquid storage tank, and the discharge gate of reaction liquid storage tank links to each other with the retort, and the upper portion of retort is equipped with the ethanol export, the ethanol export links to each other with the ethanol recovery jar, and the bottom of retort is equipped with the product export, the product export links to each other with the product storage tank.
Furthermore, a first infusion metering pump is arranged on a pipeline connecting the ethanol storage tank and the vaporization tank and used for accurately pumping ethanol into the vaporization tank according to a specified amount, and a second infusion metering pump is arranged on a pipeline connecting the benzoyl chloride storage tank and the spray head and used for pumping the benzoyl chloride into the reaction kettle according to a specified flow rate. And a third infusion metering pump is arranged on a pipeline connecting the reaction liquid storage tank and the distillation retort and is used for pumping the reaction liquid into the distillation retort for processing.
Further, a condenser is arranged at the top of the reaction kettle, and the reaction kettle is connected with a vacuum pump.
Further, the gas absorption tank is filled with water for absorbing hydrogen chloride in the gas and converting the hydrogen chloride into hydrochloric acid. The gas after passing through the gas absorption tank is nitrogen, and enters the nitrogen buffer tank after being compressed by the nitrogen compressor, the nitrogen buffer tank is provided with a pressure gauge and a flowmeter, the outflow of the nitrogen is controlled by the flowmeter, and the nitrogen is then introduced into the reaction kettle. The gas absorption tank, nitrogen compressor, and nitrogen buffer tank may be collectively referred to as a nitrogen recycle system.
The working process of the production system is as follows: pumping ethanol into a vaporization tank by a first infusion metering pump, closing a valve after pumping a certain amount of ethanol, simultaneously starting a vacuum pump of a reaction kettle to keep the vacuum degree in the reaction kettle at 0.01-0.1 MPa, and starting a nitrogen circulating system to ensure that the nitrogen introduction speed is 0.1m 3 /h～0.4m 3 And h, opening a condenser at the top of the reaction kettle, feeding gaseous ethanol into the reaction kettle from the lower part or the bottom of the vaporization tank, opening a second infusion metering pump, pumping benzoyl chloride into a spray head, spraying the benzoyl chloride into the reaction kettle in a spray manner through the spray head, starting reaction after reactants are mixed, bubbling nitrogen in the reaction kettle, fully taking away hydrogen chloride formed by the reaction, and stopping introducing nitrogen until the alcoholysis dechlorination dehydrogenation reaction is finished. The gas discharged from the reaction vessel was absorbed with water in a gas absorption tank, thereby converting the hydrogen chloride gas into hydrochloric acid. After the reaction is finished, the obtained reaction liquid enters a reaction liquid storage tank, is pumped into a distillation kettle by a third infusion metering pump, excessive ethanol is evaporated in the distillation kettle, the condensed ethanol enters an ethanol recovery tank, and the residual liquid is a product and enters a product storage tank.
Example 2
The ethyl benzoate is produced by adopting the production system, and the steps are as follows:
940.2kg of benzoyl chloride and 318.2kg of ethanol are respectively pumped into a benzoyl chloride storage tank and an ethanol storage tank, and N is used after feeding is finished 2 The two reservoirs were evacuated.
The nitrogen circulation system of the reaction kettle is started to carry out nitrogen circulation, and the introduction speed of the nitrogen is 0.2m 3 And h, simultaneously starting a vacuum pump, vacuumizing the reaction kettle, and keeping the vacuum degree between 0.08 and 0.1MPa. Opening a condenser at the top of the reaction kettle, introducing ethanol into a vaporization tank, introducing the ethanol into the bottom of the reaction kettle after the ethanol is vaporized by the vaporization tank, controlling the flow rate of gaseous ethanol to be 95kg/h, then opening a discharge valve of a benzoyl chloride storage tank, spraying benzoyl chloride into the reaction kettle from a spray head at the top of the reaction kettle by using a metering pump, controlling the conveying speed of the benzoyl chloride to be 280kg/h, reacting the benzoyl chloride with the gaseous ethanol through countercurrent contact, keeping the temperature of the reaction kettle at 60 ℃, continuously reacting in the reaction kettle for 4h after the feeding of the benzoyl chloride and the ethanol is finished, continuously introducing nitrogen for 0.5h, stopping introducing nitrogen, obtaining 956.8kg of ethyl benzoate, wherein the conversion rate of raw materials is 95%. The NMR and mass spectra of the obtained ethyl benzoate are shown in FIGS. 2 and 3.
Example 2
The ethyl benzoate is produced by adopting the production system, and the steps are as follows:
140kg of benzoyl chloride and 47kg of ethanol are respectively pumped into a benzoyl chloride storage tank and an ethanol storage tank, and N is used after feeding is finished 2 The two reservoirs were evacuated.
The nitrogen circulation system of the reaction kettle is started to carry out nitrogen circulation, and the introduction speed of the nitrogen is 0.4m 3 And h, simultaneously starting a vacuum pump, vacuumizing the reaction kettle, keeping the vacuum degree at 0.01-0.05MPa, opening a condenser at the top of the reaction kettle, introducing ethanol into a vaporization tank, vaporizing the ethanol by the vaporization tank, then introducing the ethanol into the bottom of the reaction kettle, controlling the flow rate of gaseous ethanol at 90-100kg/h, then starting a discharge valve of a benzoyl chloride storage tank, spraying benzoyl chloride into the reaction kettle from a spray head at the top of the reaction kettle by using a metering pump, controlling the conveying speed of the benzoyl chloride at 270-290kg/h, and keeping the gaseous ethanol and the benzoyl chlorideThe mole ratio of benzoyl chloride is 1.01-1.05: the method comprises the following steps of 1, enabling benzoyl chloride and gaseous ethanol to react through countercurrent contact, keeping the temperature of a reaction kettle at 30 +/-1 ℃, continuing to react in a tower type reaction kettle for 6 hours after feeding of the benzoyl chloride and the ethanol is finished, continuing to introduce nitrogen for 0.5 hour, stopping introducing nitrogen after the reaction is finished, obtaining 142.5kg of ethyl benzoate after the reaction, and enabling the conversion rate of raw materials to be 95%.
Comparative example 1
940.2kg of benzoyl chloride and 308.8kg of ethanol are added into the reaction kettle at one time, a vacuum pump of the reaction kettle is started, and the vacuum degree of the reaction kettle is kept between 0.08 MPa and 0.1MPa. The temperature of the reaction kettle is kept at 60 ℃, the reaction is carried out for 4 hours at the temperature, the reaction device is opened, obvious acidic gas overflows at the moment, 755.3g of ethyl benzoate is obtained, and the conversion rate of the raw materials is 75%.
Comparative example 2
Ethyl benzoate was produced according to the method of example 1, except that: only the vacuum pump is started, and nitrogen is not continuously introduced into the reaction kettle. 805.7kg of ethyl benzoate was obtained, with a raw material conversion of 80%.
Comparative example 3
Ethyl benzoate was produced according to the method of example 1, except that: the flow rate of gaseous ethanol was controlled at 120kg/h, and the delivery rate of benzoyl chloride was controlled at 353kg/h. The amount of the obtained ethyl benzoate 856.1g, the conversion of the starting material, was 85%.
Claims (9)
1. The production method of the ethyl benzoate is characterized by comprising the following steps:
(1) Vacuumizing the reaction kettle, and continuously introducing nitrogen into the reaction kettle;
(2) Gaseous ethanol is introduced from the bottom of the reaction kettle, benzoyl chloride is sprayed from the top of the reaction kettle, and the gaseous ethanol and the benzoyl chloride are in countercurrent contact in the reaction kettle and react to form ethyl benzoate.
2. The continuous production method according to claim 1, wherein: in the step (1), vacuumizing to keep the vacuum degree in the reaction kettle between 0.01MPa and 0.1MPa.
3. The continuous production method according to claim 1, wherein: in the step (1), the nitrogen gas was introduced at a rate of 0.1m 3 /h～0.4m 3 /h。
4. The continuous production method according to claim 1, wherein: in the step (2), the flow rate of the gaseous ethanol is controlled to be 90-100kg/h, and the conveying speed of the benzoyl chloride is controlled to be 270-290 kg/h.
5. The continuous production method according to claim 1 or 4, wherein: the molar ratio of ethanol to benzoyl chloride is 1:0.9 to 1.1, preferably 1.01 to 1.05:1.
6. the continuous production method according to claim 1, wherein: in the step (2), benzoyl chloride is sprayed into the reaction kettle through a spray head.
7. The continuous production method according to claim 1, wherein: in the step (2), the temperature of the reaction kettle is kept at 30-70 ℃, and after the raw materials are added, the reaction is continued for 3-6 hours under heat preservation.
8. The continuous production method according to claim 1, wherein: in the step (2), the hydrogen chloride gas generated by the reaction is continuously discharged out of the reaction kettle.
9. The continuous production method according to claim 1, wherein: the whole reaction process does not need solvent and catalyst.
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|---|---|---|---|
| CN202211352887.1A CN115677497B (en) | 2022-11-01 | Production method of ethyl benzoate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211352887.1A CN115677497B (en) | 2022-11-01 | Production method of ethyl benzoate |
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| CN115677497A true CN115677497A (en) | 2023-02-03 |
| CN115677497B CN115677497B (en) | 2024-05-14 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101631762A (en) * | 2007-03-13 | 2010-01-20 | 埃克森美孚化学专利公司 | Process for producing esters |
| CN103864615A (en) * | 2012-12-07 | 2014-06-18 | 中化蓝天集团有限公司 | Method for preparing ethyl trifluoroacetate through continuous non-catalytic method |
| CN103936587A (en) * | 2014-03-11 | 2014-07-23 | 山东省泰和水处理有限公司 | Triacetin preparation method |
| CN108017538A (en) * | 2017-12-25 | 2018-05-11 | 荆州市江汉精细化工有限公司 | A kind of preparation method of n-butyl acetate |
| CN110003002A (en) * | 2019-04-26 | 2019-07-12 | 济南万兴达化工有限公司 | A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101631762A (en) * | 2007-03-13 | 2010-01-20 | 埃克森美孚化学专利公司 | Process for producing esters |
| CN103864615A (en) * | 2012-12-07 | 2014-06-18 | 中化蓝天集团有限公司 | Method for preparing ethyl trifluoroacetate through continuous non-catalytic method |
| CN103936587A (en) * | 2014-03-11 | 2014-07-23 | 山东省泰和水处理有限公司 | Triacetin preparation method |
| CN108017538A (en) * | 2017-12-25 | 2018-05-11 | 荆州市江汉精细化工有限公司 | A kind of preparation method of n-butyl acetate |
| CN110003002A (en) * | 2019-04-26 | 2019-07-12 | 济南万兴达化工有限公司 | A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester |
Non-Patent Citations (1)
| Title |
|---|
| 李公春 等: "苯甲酸乙酯的合成", 河北化工, vol. 33, no. 1, pages 46 - 47 * |
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