CN115677497B - Production method of ethyl benzoate - Google Patents
Production method of ethyl benzoate Download PDFInfo
- Publication number
- CN115677497B CN115677497B CN202211352887.1A CN202211352887A CN115677497B CN 115677497 B CN115677497 B CN 115677497B CN 202211352887 A CN202211352887 A CN 202211352887A CN 115677497 B CN115677497 B CN 115677497B
- Authority
- CN
- China
- Prior art keywords
- reaction kettle
- ethanol
- benzoyl chloride
- reaction
- ethyl benzoate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 114
- 238000006243 chemical reaction Methods 0.000 claims abstract description 104
- 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 42
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000007921 spray Substances 0.000 claims description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 11
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 description 23
- 230000008016 vaporization Effects 0.000 description 14
- 238000009834 vaporization Methods 0.000 description 13
- 239000000047 product Substances 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 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
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000012295 chemical reaction liquid Substances 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
- 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
- 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
- 239000005711 Benzoic acid Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- 238000001228 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
- 238000005481 NMR spectroscopy Methods 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
- 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
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 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
- 230000007774 longterm Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 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
- 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
- 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
Landscapes
- 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; introducing gaseous ethanol from the bottom of the reaction kettle, spraying benzoyl chloride from the top of the reaction kettle, and enabling the gaseous ethanol and the benzoyl chloride to contact in a countercurrent way in the reaction kettle and react to form ethyl benzoate. The invention takes the ethanol and the benzoyl chloride as raw materials, the raw materials can be directly reacted without participation of solvents and catalysts, the cost is saved, the operation is simplified, and the invention is 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 simple process, simple raw materials and no need of catalyst and solvent.
Background
Ethyl benzoate is an organic compound with a molecular formula of C 9H10O2, is colorless transparent liquid, has slightly fruit smell, is insoluble in water, is slightly soluble in hot water, is miscible with ethanol, diethyl ether, petroleum ether, propylene glycol, chloroform, mineral oil, most of non-volatile oil and the like, is insoluble in glycerin, and naturally exists in peaches, pineapples, currants and black tea. The ethyl benzoate has very wide application, is commonly used for preparing perfume essence and artificial essential oil, is also widely used in foods, and is also used as a solvent for cellulose esters, cellulose ethers, resins and the like. In addition, ethyl benzoate is a commonly used organic synthetic intermediate.
At present, the common preparation method of the industrial ethyl benzoate comprises the following steps: the benzoic acid and the ethanol are esterified under the catalysis of sulfuric acid to form the reaction formula. However, the method has larger waste water amount and serious pollution, and in addition, the method often uses strong acid such as sulfuric acid and the like, so that equipment corrosion is particularly serious. In addition, the method is a liquid-liquid reaction, raw materials are required to be fully contacted by continuous stirring, the reaction time is required to be eight hours to finish the reaction, the production efficiency is seriously affected, impurities are increased, and the reaction conversion rate is reduced.
Another common preparation method is: the method is prepared by esterifying benzoic acid and ethanol under the catalysis of cation exchange resin, and has high yield and about 92% of conversion rate by using the cation exchange resin, but the cation exchange resin has high cost and complex operation mode.
The preparation method comprises the following steps: benzoyl chloride reacts with ethanol, but triethylamine or pyridine is required to be used as an acid-binding agent in the reaction, which causes an increase in production cost.
The patent of publication No. CN109160880 mentions that sodium benzoate and chloroethane are used as raw materials, and phase transfer pressurizing catalysis is adopted to obtain ethyl benzoate, so that the selectivity and the conversion rate of the reaction are improved. The method uses a large amount of toluene as a solvent, and in practical application, the solvent cannot be recovered hundred percent, and part of toluene is inevitably volatilized, so that the toluene mainly affects the central nervous system of a human body and stimulates the respiratory tract and the skin.
Disclosure of Invention
According to the prior art, most of the existing preparation methods of ethyl benzoate adopt solvents and catalysts, and the invention provides a production method of ethyl benzoate, which does not need the solvents and the catalysts to participate in the reaction, and raw materials are fed and contacted in a special mode, so that the reaction is faster, the operation is simple and convenient, the cost is saved, and the conversion rate and the 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) Introducing gaseous ethanol from the bottom of the reaction kettle, spraying benzoyl chloride from the top of the reaction kettle, and enabling the gaseous ethanol and the benzoyl chloride to contact in a countercurrent way in the reaction kettle and react to form ethyl benzoate.
Further, in the step (1), the vacuum is pumped to keep the vacuum degree in the reaction kettle to be 0.01 MPa-0.1 MPa,
Continuously introducing nitrogen into the reaction kettle, wherein the introducing speed of the nitrogen is kept to be 0.1m 3/h～0.4m3/h.
Further, in the step (2), ethanol is stored in an ethanol tank, benzoyl chloride is stored in a benzoyl chloride tank, and both tanks are subjected to nitrogen evacuation. Wherein the water content of the ethanol is not more than 0.01wt%. Ethanol can be vaporized into a gaseous state by a vaporization tank before entering the reaction kettle.
Further, in the step (2), the flow rate of the gaseous ethanol is controlled to be 90-100 kg/h, and the conveying speed of the benzoyl chloride is controlled to be 270-290 kg/h. The rate of addition of ethanol and benzoyl chloride was controlled 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 a slight excess of ethanol, maintained at a molar ratio of ethanol to benzoyl chloride of 1.01 to 1.05:1.
In the step (2), benzoyl chloride is sprayed into the reaction kettle through 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 ℃, such as 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃, and the heat preservation reaction is continued for 3-6 hours after the raw material addition is completed.
Further, nitrogen is introduced into the reaction kettle when the ethanol is added, HCl gas generated by 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 by the reaction is fully taken away, and the nitrogen introduction is stopped until the alcoholysis dechlorination dehydrogenation reaction is finished. The gas discharged from the reaction kettle is absorbed by water, so that the hydrogen chloride gas is converted into hydrochloric acid, and the recovery of the hydrogen chloride is realized.
The invention has the following advantages:
1. The invention takes the ethanol and the benzoyl chloride as raw materials, the raw materials can be directly reacted without participation of solvents and catalysts, the cost is saved, the operation is simplified, and the invention is suitable for large-scale industrial production.
2. The method omits the use of a conventional acid binding agent, and hydrogen chloride gas in the reaction product is carried out of the reaction kettle along with nitrogen, so that the forward reaction is promoted, the thorough reaction is ensured, and the product conversion rate and the yield are high.
3. The raw materials of the invention are organic matters, and the drying treatment is carried out, so that no water intervention is carried out, the possibility of product hydrolysis is reduced, the product quality is better, and the long-term storage and transportation are convenient.
4. The hydrogen chloride gas generated in the production process can be uniformly recycled and sold, so that the environment pollution caused by HCl external pollution is avoided, and the method is more environment-friendly.
5. The raw materials used in the invention, such as benzoyl chloride and ethanol, are daily used and reserved in chemical plants, and have the advantages of no need of additional purchase, low price and low production cost.
Drawings
FIG. 1 is a schematic diagram of a system for producing ethyl benzoate.
FIG. 2 is a nuclear magnetic spectrum of ethyl benzoate as a product.
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 pot; 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. nitrogen buffer tank.
Detailed Description
The invention is further illustrated by the following specific examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
Example 1
Fig. 1 is a schematic structural diagram of a production system of ethyl benzoate according to the present invention, where the production system includes a reaction kettle, a cavity is formed inside the reaction kettle, at least one spray head is disposed 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 disposed at the top of the reaction kettle, a nitrogen inlet is further disposed at the lower part or bottom of the reaction kettle, the exhaust port is connected with a gas absorbing tank, the gas absorbing tank is connected with a nitrogen buffer tank through a nitrogen compressor, and an air outlet of the nitrogen buffer tank is connected with a nitrogen inlet of the reaction kettle. The lower part or the bottom of the reaction kettle is provided with an ethanol inlet which 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 solution storage tank, and the discharge gate of reaction solution 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.
Further, a first transfusion metering pump is arranged on a pipeline connected with the ethanol storage tank and the vaporization tank and used for accurately pumping ethanol into the vaporization tank according to a specified quantity, and a second transfusion metering pump is arranged on a pipeline connected with the benzoyl chloride storage tank and the spray head and used for pumping benzoyl chloride into the reaction kettle according to a specified flow rate. And a third infusion metering pump is arranged on a pipeline connected with the reaction liquid storage tank and the distillation tank and used for pumping the reaction liquid into the distillation tank for treatment.
Further, the top of the reaction kettle is also provided with a condenser, and the reaction kettle is also connected with a vacuum pump.
Further, the gas absorption tank is filled with water for absorbing hydrogen chloride in the gas and converting it into hydrochloric acid. The gas passing through the gas absorption tank is nitrogen, the nitrogen enters the nitrogen cache tank after being compressed by the nitrogen compressor, a pressure gauge and a flowmeter are arranged on the nitrogen cache tank, the outflow of the nitrogen is controlled through the flowmeter, and the nitrogen is introduced into the reaction kettle again. 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 through a first infusion metering pump, pumping a certain amount of ethanol into the vaporization tank, closing a valve, simultaneously opening a vacuum pump of the reaction kettle, keeping the vacuum degree in the reaction kettle at 0.01-0.1 MPa, starting a nitrogen circulation system, ensuring that the nitrogen gas is introduced at a speed of 0.1m 3/h～0.4m3/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 benzoyl chloride into the reaction kettle in a spray manner through the spray head, starting reaction after the reactants are mixed, bubbling nitrogen gas 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 is 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, and is distilled out of redundant ethanol in the distillation kettle, enters an ethanol recovery tank after being condensed, 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 were pumped into the benzoyl chloride storage tank and the ethanol storage tank, respectively, and after the completion of the feed, the two storage tanks were evacuated with N 2.
And (3) starting a nitrogen circulation system of the reaction kettle to circulate nitrogen, wherein the nitrogen introducing speed is 0.2m 3/h, and simultaneously starting a vacuum pump to vacuumize the reaction kettle, and keeping the vacuum degree at 0.08-MPa-0.1 MPa. 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 of gaseous ethanol at 95kg/h, 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 a metering pump, controlling the conveying speed of the benzoyl chloride at 280kg/h, enabling the benzoyl chloride and the gaseous ethanol to react by countercurrent contact, keeping the temperature of the reaction kettle at 60 ℃, continuing to react in the reaction kettle for 4h after the benzoyl chloride and the ethanol are fed, continuing to introduce nitrogen for 0.5h, ending the reaction, stopping introducing nitrogen, and obtaining 956.8kg of ethyl benzoate, wherein the raw material conversion rate is 95%. The nuclear magnetic resonance detection spectrum and mass spectrum of the obtained ethyl benzoate are shown in fig. 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 were pumped into the benzoyl chloride storage tank and the ethanol storage tank, respectively, and after the completion of the feed, the two storage tanks were evacuated with N 2.
The nitrogen circulation system of the reaction kettle is started to circulate nitrogen, the nitrogen introducing speed is 0.4m 3/h, a vacuum pump is started at the same time, the reaction kettle is vacuumized, the vacuum degree is kept at 0.01-0.05MPa, a condenser at the top of the reaction kettle is opened, ethanol is introduced into a vaporization tank, the ethanol enters the bottom of the reaction kettle after being vaporized by the vaporization tank, the flow rate of gaseous ethanol is controlled at 90-100kg/h, a discharge valve of a benzoyl chloride storage tank is started at the moment, benzoyl chloride is sprayed into the reaction kettle from a spray head at the top of the reaction kettle by a metering pump, the conveying speed of the benzoyl chloride is controlled at 270-290kg/h, and the molar ratio of the gaseous ethanol to the benzoyl chloride is kept at 1.01-1.05:1, benzoyl chloride reacts with gaseous ethanol through countercurrent contact, the temperature of a reaction kettle is kept at 30+/-1 ℃, after benzoyl chloride and ethanol are fed, no obvious acid gas escapes after the reaction is continued in a tower reaction kettle for 6 hours, nitrogen is continuously introduced for 0.5 hour, the reaction is ended, nitrogen introduction is stopped, 142.5kg of ethyl benzoate is obtained after the reaction, and the raw material conversion rate is 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 to be 0.08-MPa-0.1 MPa. 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, at the moment, obvious acid gas overflows, 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 procedure 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, and the conversion of the raw material was 80%.
Comparative example 3
Ethyl benzoate was produced according to the procedure of example 1, except that: the flow rate of the gaseous ethanol is controlled to be 120kg/h, and the conveying speed of the benzoyl chloride is controlled to be 353kg/h. 856.1g of ethyl benzoate were obtained, and the conversion of the starting material was 85%.
Claims (3)
1. The production method of the ethyl benzoate is characterized by comprising the following steps of:
(1) Vacuumizing the reaction kettle, and continuously introducing nitrogen into the reaction kettle;
(2) Introducing gaseous ethanol from the bottom of a reaction kettle, spraying benzoyl chloride from the top of the reaction kettle, and enabling the gaseous ethanol and the benzoyl chloride to contact in a countercurrent way in the reaction kettle and react to form ethyl benzoate;
the whole reaction process does not need solvent and catalyst;
In the step (1), the nitrogen gas is introduced at a speed of 0.1m 3/h～0.4m3/h;
In the step (2), the flow rate of the gaseous ethanol is controlled to be 90-100 kg/h, and the conveying speed of benzoyl chloride is controlled to be 270-290 kg/h;
the molar ratio of the ethanol to the benzoyl chloride is 1.01-1.05:1, a step of;
in the step (2), the temperature of the reaction kettle is kept at 30-70 ℃;
in the step (2), benzoyl chloride is sprayed into the reaction kettle through a spray head;
in the step (2), after the raw materials are added, the heat preservation reaction is continued for 3 to 6 hours.
2. The continuous production method according to claim 1, characterized in that: in the step (1), the vacuum is pumped to keep the vacuum degree in the reaction kettle to be 0.01 MPa-0.1 MPa.
3. The continuous production method according to claim 1, characterized in that: in the step (2), the hydrogen chloride gas generated by the reaction is continuously discharged out of the reaction kettle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211352887.1A CN115677497B (en) | 2022-11-01 | 2022-11-01 | Production method of ethyl benzoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211352887.1A CN115677497B (en) | 2022-11-01 | 2022-11-01 | Production method of ethyl benzoate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115677497A CN115677497A (en) | 2023-02-03 |
| CN115677497B true CN115677497B (en) | 2024-05-14 |
Family
ID=85048216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211352887.1A Active CN115677497B (en) | 2022-11-01 | 2022-11-01 | Production method of ethyl benzoate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115677497B (en) |
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 |
-
2022
- 2022-11-01 CN CN202211352887.1A patent/CN115677497B/en active Active
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 |
|---|
| 苯甲酸乙酯的合成;李公春 等;河北化工;第33卷(第1期);46-47转70 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115677497A (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101747298B (en) | Process for preparing high-purity diketene | |
| WO2021078239A1 (en) | Gas-liquid bubbling bed reactor, reaction system and method for synthesizing carbonate | |
| US11299450B2 (en) | System and process for co-producing dimethyl carbonate and ethylene glycol | |
| CN101928389A (en) | Method for preparing glycidol ether terminated propenol polyoxyethylene ether | |
| CN111848557A (en) | Preparation process of furfural | |
| CN105111079A (en) | Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol | |
| CN110218151A (en) | A kind of device and method that tower reactor Flash Type heat pump reactive distillation prepares propyl propionate | |
| CN110304997A (en) | A kind of production method of 2,2- dimethoxy propane | |
| CN114163333B (en) | Method for synthesizing methyl ethyl carbonate in one step | |
| CN115677497B (en) | Production method of ethyl benzoate | |
| CN101648881B (en) | New synthesis process of aminoglycerol | |
| CN213222199U (en) | Reaction device of vinyl ether compound | |
| CN108947758A (en) | A method of catalysis dibenzofurans open loop prepares biphenyl | |
| CN109160880B (en) | Preparation method of ethyl benzoate | |
| CN101410166A (en) | Mixture for carbon dioxide recovery/utilization and transportation | |
| CN111701618A (en) | Ionic liquid catalyst and preparation method and application thereof | |
| CN111807956A (en) | Production process of isooctyl acrylate of ultralow-concentration oligomer | |
| CN218422814U (en) | Production system of ethyl benzoate | |
| CN103483577A (en) | Preparation method of glycidyl terminated allyl alcohol polyoxyethylene ether | |
| CN114230445B (en) | Preparation method and production system of ethylene glycol monovinyl ether | |
| CN107973728A (en) | System and technique a kind of while that prepare methyl carbamate, dimethyl carbonate | |
| CN209338426U (en) | A kind of equipment of coproduction ethylene glycol and dimethyl carbonate | |
| CN109836312B (en) | Method for synthesizing isoeugenol methyl ether | |
| CN115466255B (en) | Tropine and synthetic method thereof | |
| CN109646977A (en) | A kind of reactive distillation coupled and its preparing the application in formic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240416 Address after: 252300, No. 399 Qinghe West Road, Shizilou Office, Yanggu County, Liaocheng City, Shandong Province Applicant after: Shandong Huatai New Material Technology Research and Development Co.,Ltd. Country or region after: China Address before: Room 301, building 9, 1288 Zhongchun Road, Minhang District, Shanghai 201100 Applicant before: Shanghai acorn Chemical Co.,Ltd. Country or region before: China |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |