CN116217388A - Synthesis method of methyl benzoate - Google Patents
Synthesis method of methyl benzoate Download PDFInfo
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- CN116217388A CN116217388A CN202310146192.6A CN202310146192A CN116217388A CN 116217388 A CN116217388 A CN 116217388A CN 202310146192 A CN202310146192 A CN 202310146192A CN 116217388 A CN116217388 A CN 116217388A
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- China
- Prior art keywords
- methyl benzoate
- reaction
- acid
- volume ratio
- catalyst
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- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229940095102 methyl benzoate Drugs 0.000 title claims abstract description 33
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 16
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 14
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 14
- 150000007524 organic acids Chemical class 0.000 claims abstract description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- -1 at the temperature Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
-
- 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
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- B01J35/19—
-
- 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
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a synthesis method of methyl benzoate, which comprises the following steps: s1: putting benzoic acid, a catalyst, a catalytic auxiliary agent and a methanol solvent A into a reaction container; s2: dropwise adding the heated methanol solvent B into a reaction container for reaction; s3: after the reaction is finished, distilling the reaction liquid to obtain methyl benzoate; the mass volume ratio of the benzoic acid to the catalyst promoter to the methanol solvent A is 100g:5-10g:0.5-1.5g:20-30mL; the mass volume ratio of the benzoic acid to the methanol solvent B is 100g:100-200mL; the catalyst is compounded by organic acid and inorganic acid according to the volume ratio of 3-5:1; the organic acid is p-toluenesulfonic acid; the inorganic acid is H 2 SO 4 、H 2 Sn(HSO 4 ) 6 And H 4 Fe(CN) 6 The mixture is compounded according to the volume ratio of 6:1-3:1-3. The synthesis method of the invention improves the synthesis yield of methyl benzoate.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a synthesis method of methyl benzoate.
Background
At present, sulfuric acid is mainly used as a catalyst for synthesizing methyl benzoate, and the methyl benzoate is prepared by reacting a large amount of methanol with benzoic acid, wherein the molar ratio of the benzoic acid to the methanol is 1:3-10, and the method has the problem that the synthesis yield of the methyl benzoate is low although a large amount of methanol is used because the methanol is used in an excessive amount and is easy to cause environmental pollution.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a synthesis method of methyl benzoate, and the synthesis yield of the methyl benzoate is improved.
The invention provides a synthesis method of methyl benzoate, which comprises the following steps:
s1: putting benzoic acid, a catalyst, a catalytic auxiliary agent and a methanol solvent A into a reaction container;
s2: dropwise adding the heated methanol solvent B into a reaction container for reaction;
s3: and (3) distilling the reaction liquid after the reaction is finished to obtain the methyl benzoate.
Preferably, the mass volume ratio of the benzoic acid, the catalyst auxiliary agent and the methanol solvent A is 100g:5-10g:0.5-1.5g:20-30mL.
Preferably, the mass volume ratio of benzoic acid to methanol solvent B is 100g:100-200mL.
Preferably, the catalyst is compounded by organic acid and inorganic acid according to the volume ratio of 3-5:1.
Preferably, the organic acid is p-toluene sulfonic acid.
Preferably, the mineral acid is H 2 SO 4 、H 2 Sn(HSO 4 ) 6 And H 4 Fe(CN) 6 The mixture is compounded according to the volume ratio of 6:1-3:1-3.
Preferably, the catalyst promoter is one or more of titanium dioxide, vanadium pentoxide, tungsten trioxide, cerium dioxide, zirconium oxide and ruthenium dioxide.
Preferably, the temperature of the heated methanol solvent B in the S2 is 105-115 ℃, the reaction temperature is 105-115 ℃, and the reaction time is 3-5h.
The beneficial technical effects of the invention are as follows:
the invention adopts a dripping mode to add the methanol heated to 105-115 ℃ into the materials, at the temperature, water generated by the reaction can be discharged in time, and the reaction is promoted to be continuously carried out in the forward and backward directions, so that the reaction is more thorough; compared with the existing method which takes sulfuric acid as a catalyst, the catalyst provided by the invention has higher synthesis yield; furthermore, the inorganic acid of the present invention is formed from H 2 SO 4 、H 2 Sn(HSO 4 ) 6 And H 4 Fe(CN) 6 The three components are compounded according to the volume ratio of 6:1-3:1-3, and have a certain synergistic promotion effect on improving the synthesis yield of methyl benzoate, so that the synthesis yield of the application is greatly improved; the invention also adds catalytic auxiliary agent in the synthesis process, in particular to one or more of titanium dioxide, vanadium pentoxide, tungsten trioxide, cerium dioxide, zirconium oxide and ruthenium dioxide, which can also further improve the synthesis yield of methyl benzoate.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
The instrument according to the embodiment of the invention comprises: JJ-1 precision booster electric stirrer (Shanghai river star instruments Co., ltd.); 2XZ-2 rotary vane vacuum pump (Shi vacuum equipment Co., ltd., in the ocean); heating jacket (Beijing Zhongxing Wei industry Co., ltd.); agilent 7890B gas chromatograph (Agilent, usa).
The reagents according to the embodiment of the invention are all of industrial grade.
Example 1
The invention provides a synthesis method of methyl benzoate, which comprises the following steps:
s1: 100g of benzoic acid, 8g of catalyst, 1g of catalyst auxiliary agent and 25mL of methanol solvent A are added into a three-neck flask provided with a constant pressure funnel, a thermometer, a condenser pipe and a stirrer to be placed into a reaction vessel;
s2: dropwise adding 150mL of methanol solvent B heated to 110 ℃ into a reaction container, reacting for 4 hours at 110 ℃, and keeping the methanol balance in and out during the reaction;
s3: and after the reaction is finished, heating the reaction liquid to 130 ℃ under normal pressure to evaporate the methanol, then evaporating the methyl benzoate under negative pressure until no reflux exists, and collecting the evaporated methyl benzoate.
The catalyst is compounded by organic acid and inorganic acid according to the volume ratio of 4:1; the organic acid is p-toluenesulfonic acid; the inorganic acid is H 2 SO 4 、H 2 Sn(HSO 4 ) 6 And H 4 Fe(CN) 6 Compounding according to the volume ratio of 3:1:1.
The catalyst promoter is titanium dioxide.
Example 2
The invention provides a synthesis method of methyl benzoate, which comprises the following steps:
s1: 100g of benzoic acid, 5g of catalyst, 0.5g of catalyst auxiliary agent and 20mL of methanol solvent A are added into a three-neck flask provided with a constant pressure funnel, a thermometer, a condenser and a stirrer to be placed into a reaction vessel;
s2: dropwise adding 100mL of methanol solvent B heated to 105 ℃ into a reaction container, reacting for 3 hours at 105 ℃, and keeping the methanol balance in and out during the reaction;
s3: and after the reaction is finished, heating the reaction liquid to 130 ℃ under normal pressure to evaporate the methanol, then evaporating the methyl benzoate under negative pressure until no reflux exists, and collecting the evaporated methyl benzoate.
The catalyst is compounded by organic acid and inorganic acid according to the volume ratio of 3:1; the organic acid is p-toluenesulfonic acid; the inorganic acid is H 2 SO 4 、H 2 Sn(HSO 4 ) 6 And H 4 Fe(CN) 6 Compounding according to the volume ratio of 6:1:1.
The catalyst auxiliary agent is compounded by vanadium pentoxide and tungsten trioxide according to the mass ratio of 1:1.
Example 3
The invention provides a synthesis method of methyl benzoate, which comprises the following steps:
s1: 100g of benzoic acid, 10g of catalyst, 1.5g of catalyst auxiliary agent and 30mL of methanol solvent A are added into a three-neck flask provided with a constant pressure funnel, a thermometer, a condenser and a stirrer to be placed into a reaction vessel;
s2: 200mL of methanol solvent B heated to 115 ℃ is dropwise added into the reaction vessel to react for 5 hours at 115 ℃, and the equilibrium of methanol in and out is maintained in the reaction process;
s3: and after the reaction is finished, heating the reaction liquid to 130 ℃ under normal pressure to evaporate the methanol, then evaporating the methyl benzoate under negative pressure until no reflux exists, and collecting the evaporated methyl benzoate.
The catalyst is compounded by organic acid and inorganic acid according to the volume ratio of 5:1; the organic acid is p-toluenesulfonic acid; the inorganic acid is H 2 SO 4 、H 2 Sn(HSO 4 ) 6 And H 4 Fe(CN) 6 Compounding according to the volume ratio of 2:1:1.
The catalyst auxiliary agent is composed of cerium dioxide, zirconium oxide and ruthenium dioxide according to the mass ratio of 1:1:1.
Comparative example 1
Inorganic acid H of the scheme 2 SO 4 The other conditions were the same as in example 1.
Comparative example 2
The inorganic acid in the scheme is H 2 SO 4 And H 4 Fe(CN) 6 The preparation is carried out according to the volume ratio of 2:1, and the other conditions are the same as those of the example 1.
Comparative example 3
The inorganic acid in the scheme is H 2 SO 4 And H 2 Sn(HSO 4 ) 6 The preparation is carried out according to the volume ratio of 2:1, and the other conditions are the same as those of the example 1.
Since the more thorough the esterification reaction proceeds, the lower the acid value of the product, the acid value of the product was used as an index for examining the degree of the esterification reaction. The acid values of the products prepared in examples 1 to 3 and comparative examples 1 to 3 were measured, and the results are shown in Table 1.
TABLE 1 acid value of reaction products detection results
As can be seen from example 1 of Table 1, the acid values of the prepared reaction products were all lower than 0.5mgKOH/g, demonstrating that the synthesis method of the present application has a very high product synthesis rate, and as can be seen from the results of example 1 and comparative examples 1 to 3, when the inorganic acid in the catalyst was H 2 SO 4 、H 2 Sn(HSO 4 ) 6 And H 4 Fe(CN) 6 Can obviously improve the synthesis rate of the product during the compounding and can be used for preparing H 2 SO 4 In the presence of H 2 Sn(HSO 4 ) 6 And H 4 Fe(CN) 6 The method also has a certain synergistic effect on improving the synthesis rate of the product.
Claims (8)
1. The synthesis method of methyl benzoate is characterized by comprising the following steps:
s1: putting benzoic acid, a catalyst, a catalytic auxiliary agent and a methanol solvent A into a reaction container;
s2: dropwise adding the heated methanol solvent B into a reaction container for reaction;
s3: and (3) distilling the reaction liquid after the reaction is finished to obtain the methyl benzoate.
2. The method for synthesizing methyl benzoate according to claim 1, wherein the mass-volume ratio of benzoic acid, catalyst auxiliary agent and methanol solvent A is 100g:5-10g:0.5-1.5g:20-30mL.
3. The method for synthesizing methyl benzoate according to claim 1, wherein the mass-volume ratio of benzoic acid to methanol solvent B is 100g:100-200mL.
4. The method for synthesizing methyl benzoate according to claim 1, wherein the catalyst is compounded by organic acid and inorganic acid according to a volume ratio of 3-5:1.
5. The method for synthesizing methyl benzoate according to claim 4, wherein the organic acid is p-toluene sulfonic acid.
6. The method for synthesizing methyl benzoate according to claim 4, wherein the inorganic acid is H 2 SO 4 、H 2 Sn(HSO 4 ) 6 And H 4 Fe(CN) 6 The mixture is compounded according to the volume ratio of 6:1-3:1-3.
7. The method for synthesizing methyl benzoate according to claim 1, wherein the catalyst promoter is one or more of titanium dioxide, vanadium pentoxide, tungsten trioxide, cerium dioxide, zirconium oxide and ruthenium dioxide.
8. The method for synthesizing methyl benzoate according to claim 1, wherein the temperature of the heated methanol solvent B in S2 is 105-115 ℃, the reaction temperature is 105-115 ℃ and the reaction time is 3-5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310146192.6A CN116217388A (en) | 2023-02-22 | 2023-02-22 | Synthesis method of methyl benzoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310146192.6A CN116217388A (en) | 2023-02-22 | 2023-02-22 | Synthesis method of methyl benzoate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116217388A true CN116217388A (en) | 2023-06-06 |
Family
ID=86576404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310146192.6A Pending CN116217388A (en) | 2023-02-22 | 2023-02-22 | Synthesis method of methyl benzoate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116217388A (en) |
-
2023
- 2023-02-22 CN CN202310146192.6A patent/CN116217388A/en active Pending
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