CN115385787B - Preparation method of 2-carboxyl benzaldehyde - Google Patents
Preparation method of 2-carboxyl benzaldehyde Download PDFInfo
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- CN115385787B CN115385787B CN202211330562.3A CN202211330562A CN115385787B CN 115385787 B CN115385787 B CN 115385787B CN 202211330562 A CN202211330562 A CN 202211330562A CN 115385787 B CN115385787 B CN 115385787B
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Abstract
The invention provides a preparation method of 2-carboxybenzaldehyde, and belongs to the field of preparation of 2-carboxybenzaldehyde. The preparation method of the 2-carboxyl benzaldehyde comprises the following steps: hydrolyzing, cooling, crystallizing, and refining. The hydrolysis method comprises the steps of mixing deionized water, 3-bromophenylphthalein and tetramethylammonium hydroxide aqueous solution, and carrying out heat preservation hydrolysis at the temperature of 96-98 ℃. According to the preparation method of the 2-carboxyl benzaldehyde, 3-bromophenylphthalide is completely hydrolyzed, and the reaction conversion rate of the 3-bromophenylphthalide is 99.30-99.39%; the yield of the prepared 2-carboxybenzaldehyde is 99.04-99.15%, and the purity is 99.56-99.76%.
Description
Technical Field
The invention relates to the field of preparation of 2-carboxybenzaldehyde, and in particular relates to a preparation method of 2-carboxybenzaldehyde.
Background
2-carboxybenzaldehyde, also called salicylaldehyde, is a colorless transparent oily liquid, has special smell and bitter almond taste, is active in chemical property, is slightly soluble in water, can perform substitution, condensation, oxidation, wittig (Wittig) and other reactions, and has wide application in chemical industry. 2-carboxybenzaldehyde is used as a raw material for producing coumarin and edible flavor due to its unique fragrance and characteristics; meanwhile, the 2-carboxybenzaldehyde is also widely applied to the fields of pesticides, medicines, electroplating, petrochemical industry, polymer additives, chemical analysis reagents and the like.
For example, in the pharmaceutical industry, 2-carboxybenzaldehyde is not only an important intermediate for the synthesis of anticancer drugs, but also useful for the preparation of antibacterial agents, antiasthmatic agents, and the like. The halogenated salicylaldehyde synthesized by taking the 2-carboxybenzaldehyde as the raw material has good bacteriostatic action, and has good bacteriostatic action on escherichia coli, bacillus subtilis, staphylococcus aureus and the like. In the petroleum industry, the adducts of 2-carboxybenzaldehyde are useful as lubricants, settling agents for gasoline, polyester lubricants, petroleum antioxidants, etc. In electroplating industry, 2-carboxybenzaldehyde is also widely used as brightening agent and homogenizing agent for nickel plating. In addition, 2-carboxybenzaldehyde is also a good UV absorber.
In recent years, the demand for 2-carboxybenzaldehyde has increased considerably. In addition, due to the wide application of 2-carboxybenzaldehyde, higher requirements are also put on the quality of 2-carboxybenzaldehyde; in particular, in the fields of perfumes and medicines, the requirement on indexes such as purity of chlorine-free 2-carboxybenzaldehyde is higher and higher, so that the research and development of a green process for preparing 2-carboxybenzaldehyde have important industrial value.
In the prior art, the preparation method of the 2-carboxyl benzaldehyde mainly comprises the following steps: hydrolyzing 3-bromophenylphthalide or 3-chlorophthalide in water under the heating condition of water bath, crystallizing, centrifuging, and drying to obtain 2-carboxybenzaldehyde. However, in the preparation method, the hydrolysis reaction is incomplete, the yield of the 2-carboxybenzaldehyde is only 70-80%, and the purity is only 99.5%, so that the effective improvement cannot be obtained; meanwhile, a large amount of hydrolysis mother liquor can be produced in the hydrolysis process, the hydrolysis mother liquor cannot be effectively utilized and is often treated as production wastewater, the wastewater treatment pressure is high, the environment-friendly operation cost is high for realizing the standard discharge of wastewater, and the production energy consumption and the cost are high.
Chinese patent CN101735041A discloses a preparation method of o-carboxybenzaldehyde, and discloses that 3-bromophenylphthalide and water are hydrolyzed for 2 hours under a boiling condition, and then crystallization and refining are carried out to prepare the o-carboxybenzaldehyde. However, the process has the defects that the hydrolysis of the 3-bromophenylphthalide is incomplete, the yield of the o-carboxybenzaldehyde is 80.4%, the purity is 99.5%, and the effective improvement cannot be obtained; meanwhile, in the preparation process of o-carboxybenzaldehyde, a large amount of wastewater (hydrolysis mother liquor) is generated in the hydrolysis process, and the wastewater treatment pressure is high.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of 2-carboxyl benzaldehyde, which adopts 3-bromophenylphthalide as a raw material, has complete hydrolysis reaction, and prepares the 2-carboxyl benzaldehyde with high yield and purity; the hydrolysis mother liquor generated in the hydrolysis process can be effectively utilized, the wastewater output of each ton of products is effectively reduced, the wastewater treatment pressure of enterprises is reduced, the related cost of the environmental protection operation of the enterprises is reduced, and the production energy consumption and the production cost are reduced.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of 2-carboxyl benzaldehyde comprises the following steps: hydrolyzing, cooling, crystallizing, and refining.
The hydrolysis method comprises the steps of putting deionized water into a hydrolysis kettle, heating to 70-75 ℃, and preserving heat; then adding a predetermined amount of 3-bromophenylphthalide, heating to 96-98 ℃, and preserving heat; adding a predetermined amount of tetramethylammonium hydroxide aqueous solution at a feeding speed of 20-30mL/min under the condition of stirring, and after the addition is finished, continuously preserving the heat for 25-35min at the temperature of 96-98 ℃ to finish the hydrolysis step to obtain hydrolysate;
in the hydrolysis, the molar ratio of 3-bromophenylphthalein, tetramethylammonium hydroxide and deionized water is 1.2-1.3;
in the hydrolysis, the concentration of the tetramethyl ammonium hydroxide in the aqueous solution of the tetramethyl ammonium hydroxide is 22 to 25 weight percent;
meanwhile, hydrolysis waste gas G1 generated in the hydrolysis process is condensed by a condenser, is treated by a primary alkali liquor absorption tower and is discharged by an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 8-10 wt%.
The cooling crystallization method comprises the steps of cooling the hydrolysate to 5-8 ℃ under the stirring condition, and carrying out heat preservation crystallization until no solid is separated out; then centrifuging at 8000-10000rpm to obtain crude 2-carboxybenzaldehyde product and the first centrifuged mother liquor. Wherein, the subsequent refining treatment of the 2-carboxybenzaldehyde crude product is carried out; concentrating and refining the first centrifugal mother liquor to prepare a byproduct, namely tetramethyl ammonium bromide;
meanwhile, waste gas G2 generated in the processes of cooling crystallization and centrifugation is treated by a primary alkali liquor absorption tower and then is discharged through an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 8-10 wt%.
The refining comprises the following steps: dissolving, removing impurities, crystallizing, centrifuging and drying.
The dissolving method comprises the steps of putting a preset amount of 2-carboxybenzaldehyde crude product into a 2-carboxybenzaldehyde refining kettle filled with a solvent, heating to 80-85 ℃ under the stirring condition, preserving heat and stirring until the 2-carboxybenzaldehyde crude product is completely dissolved to obtain a dissolved substance;
in the dissolving, the volume ratio of the 2-carboxybenzaldehyde crude product to the solvent is 1-15;
in the dissolving, the solvent is deionized water or second centrifugal mother liquor prepared in the crystallization and centrifugation step. In the process, the first dissolution is carried out by using deionized water; in the subsequent refining process, after a second centrifugal mother liquor is obtained through crystallization and centrifugation, the second centrifugal mother liquor is preferentially selected and recycled to the dissolving step to be used as a solvent for reuse.
The impurity removing method comprises the steps of putting a predetermined amount of modified activated carbon into a dissolved substance at the temperature of 70-80 ℃, and stirring and adsorbing for 20-40min; then, filtering to obtain filtrate;
in the impurity removal, the ratio of the modified activated carbon to the solute by weight is 0.09-0.13.
In the impurity removal, the preparation method of the modified activated carbon comprises the steps of putting activated carbon and deionized water in a volume ratio of 1:2-3 into a high-pressure reactor, preserving heat for 2-3 hours at 150-180 ℃, placing the activated carbon in a vacuum environment, and drying at 70-80 ℃ until the weight is unchanged; then putting into 1.5-2.5 times volume of polyethyleneimine water solution, stirring at 50-80rpm for 1-2h, filtering, and drying at 150-170 ℃ until the weight is unchanged to obtain modified activated carbon;
the specification of the active carbon is that the specific surface area is 800-1000m 2 Per g, the average pore diameter is 1-3nm, the particle size is 200-300 mu m, and the graphitization degree of the active carbon is 75-80% by XRD detection;
the polyethyleneimine aqueous solution is prepared by the following method: mixing 3-5 parts by weight of polyethyleneimine with deionized water, and stirring uniformly at the temperature of 40-50 ℃.
The crystallization centrifugation method comprises the steps of transferring filtrate obtained in the impurity removal step into a cooling crystallization kettle, cooling to 2-5 ℃, and carrying out heat preservation crystallization until no solid is separated out; then centrifuging at 10000-12000rpm to obtain wet 2-carboxybenzaldehyde product and the second centrifuged mother liquid. Wherein, the subsequent drying treatment of the wet product of the 2-carboxybenzaldehyde is carried out; recycling the second centrifugal mother liquor to the dissolving step, transferring the second centrifugal mother liquor into a 2-carboxybenzaldehyde refining kettle, and dissolving the 2-carboxybenzaldehyde crude product as a solvent;
meanwhile, waste gas G3 generated in the crystallization and centrifugation process is treated by a primary alkali liquor absorption tower and then is discharged through an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 8-10 wt%.
The drying method comprises the steps of putting the wet 2-carboxybenzaldehyde product into a dryer, and drying at 60-70 ℃ in a vacuum environment until the weight of the wet 2-carboxybenzaldehyde product is unchanged to obtain a finished 2-carboxybenzaldehyde product;
wherein, the waste gas G4 generated in the drying process is dedusted by a cloth bag, treated by a primary alkali liquor absorption tower and discharged through an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 8-10 wt%.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the 2-carboxyl benzaldehyde, the specific organic alkali tetramethyl ammonium hydroxide is set to participate in the reaction in the hydrolysis process, so that the hydrolysis is promoted, the 3-bromophenylphthalide can be completely hydrolyzed, and the reaction conversion rate of the 3-bromophenylphthalide is 99.30-99.39%; meanwhile, a byproduct of tetramethylammonium bromide can be prepared, so that the hydrolysis mother liquor (first centrifugal mother liquor) can be effectively utilized; meanwhile, through modification treatment of the activated carbon with a specific specification, the modified activated carbon can effectively adsorb impurities in a 2-carboxybenzaldehyde crude product dissolved substance, the impurity content of the 2-carboxybenzaldehyde crude product dissolved substance can be controlled at an extremely low level, time and energy consumption required by refining are further reduced, and the purity of a prepared 2-carboxybenzaldehyde finished product is improved.
(2) The yield of the 2-carboxybenzaldehyde prepared by the preparation method of the 2-carboxybenzaldehyde is 99.04-99.15%, and the purity is 99.56-99.76%.
(3) The preparation method of the 2-carboxyl benzaldehyde can effectively utilize the hydrolysis mother liquor, and can prepare the byproduct tetramethylammonium bromide by concentrating and refining the hydrolysis mother liquor (the first centrifugal mother liquor); meanwhile, the second centrifugal mother liquor in the refining process can be effectively recycled to the dissolving step as a solvent; the whole process engineering almost has no wastewater, compared with the prior art, the production amount of wastewater of each ton of products is reduced by 1.26-1.30 tons, the wastewater treatment pressure of production enterprises is effectively reduced, the related environment-friendly operation cost of wastewater treatment is saved, the energy consumption of wastewater treatment is reduced, the production cost is effectively reduced, and the environment-friendly degree is high.
(4) The preparation method of the 2-carboxyl benzaldehyde can improve the yield of the 2-carboxyl benzaldehyde and simultaneously improve the purity of the 2-carboxyl benzaldehyde; can effectively utilize the waste water in the production process, has mild reaction conditions, low production energy consumption and low cost, and can be suitable for large-scale industrial production.
Drawings
FIG. 1 is a gas chromatogram of a 2-carboxybenzaldehyde product obtained in example 1.
FIG. 2 is a gas chromatogram of the 2-carboxybenzaldehyde product obtained in example 2.
FIG. 3 is a gas chromatogram of the 2-carboxybenzaldehyde product obtained in example 3.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A preparation method of 2-carboxyl benzaldehyde comprises the following steps:
1. hydrolysis
Adding deionized water (558.5 kg, 31 kmol) into a hydrolysis kettle, heating to 70 ℃, and preserving heat; then adding a predetermined amount of 3-bromophenylphthalide (213 kg, 1 kmol), heating to 96 ℃, and preserving heat; adding a predetermined amount of tetramethylammonium hydroxide aqueous solution at a feeding speed of 20mL/min under the condition of stirring, and after the addition is finished, continuously preserving the temperature for 25min at the temperature of 96 ℃ to finish the hydrolysis step to obtain the hydrolysate.
Wherein the aqueous tetramethylammonium hydroxide solution contained 109.4kg (1.2 kmol) of tetramethylammonium hydroxide, and the concentration of tetramethylammonium hydroxide in the solution was 22wt%.
Detection shows that the content of the 3-bromophenylphthalide in the hydrolysate is 1.49kg.
Meanwhile, hydrolysis waste gas G1 generated in the hydrolysis process is condensed by a condenser, is treated by a primary alkali liquor absorption tower and is discharged by an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 8 wt%.
2. Cooling crystallization
Under the condition of stirring, cooling the hydrolysate to 8 ℃, and carrying out heat preservation and crystallization until no solid is separated out; then, the crude 2-carboxybenzaldehyde (136.2 kg) and the first mother liquor were obtained by centrifugation at 8000 rpm. Wherein, the subsequent refining treatment of the 2-carboxybenzaldehyde crude product is carried out; the first centrifugal mother liquor is concentrated and refined to prepare a byproduct of tetramethyl ammonium bromide.
Meanwhile, waste gas G2 generated in the processes of cooling crystallization and centrifugation is treated by a primary alkali liquor absorption tower and then is discharged through an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 8 wt%.
3. Refining
1) Dissolution
Putting the crude product (136.2 kg) of 2-carboxybenzaldehyde into a 2-carboxybenzaldehyde refining kettle filled with a solvent, heating to 80 ℃ under the condition of stirring, and keeping the temperature and stirring until the crude product of 2-carboxybenzaldehyde is completely dissolved to obtain a dissolved substance.
Wherein the volume ratio of the 2-carboxybenzaldehyde crude product to the solvent is 1.
The solvent is deionized water or recycled second centrifugal mother liquor. In the process, the first dissolution is carried out by using deionized water; in the subsequent refining process, after a second centrifugal mother liquor is obtained through crystallization and centrifugation, the second centrifugal mother liquor is preferentially selected and recycled to the dissolving step to be used as a solvent for reuse.
2) Removing impurities
Adding a predetermined amount of modified activated carbon into the dissolved matter at the temperature of 70 ℃, and stirring and adsorbing for 20min; then, the filtrate was obtained by suction filtration.
Wherein the ratio of the modified activated carbon to the solute by weight is 0.09.
The preparation method of the modified activated carbon comprises the steps of putting activated carbon and deionized water in a volume ratio of 1:2 into a high-pressure reactor, preserving heat for 2 hours at 150 ℃, placing the activated carbon in a vacuum environment, and drying at 70 ℃ until the weight is unchanged; then putting the mixture into 1.5 times of volume of polyethyleneimine aqueous solution, stirring for 1h at 50rpm, filtering, and drying at 150 ℃ until the weight is unchanged to obtain the modified activated carbon.
Wherein the specification of the active carbon is that the specific surface area is 800m 2 The average pore diameter is 1nm, the particle size is 200 mu m, and the graphitization degree of the activated carbon is 75 percent by XRD detection.
The polyethyleneimine aqueous solution is prepared by the following method: mixing polyethyleneimine with deionized water in a weight ratio of 3.
3) Centrifugation of crystals
Transferring the filtrate obtained in the impurity removal step into a cooling crystallization kettle, cooling to 5 ℃, and carrying out heat preservation crystallization until no solid is separated out; then, 2-carboxybenzaldehyde wet product (130.1 kg) and a second centrifugal mother liquor were obtained by centrifugal separation at a centrifugal rotation speed of 10000 rpm. Wherein, the subsequent drying treatment of the wet product of the 2-carboxybenzaldehyde is carried out; and the second centrifugal mother liquor is recycled to the dissolving step and transferred into a 2-carboxybenzaldehyde refining kettle to be used as a solvent to dissolve the 2-carboxybenzaldehyde crude product.
Meanwhile, waste gas G3 generated in the crystallization and centrifugation process is treated by a primary alkali liquor absorption tower and then is discharged through an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 8 wt%.
4) Drying
Placing wet 2-carboxybenzaldehyde (130.1 kg) in a dryer, drying at 60 deg.C under vacuum to obtain 2-carboxybenzaldehyde product (120.95 kg), and analyzing by gas chromatography to obtain 2-carboxybenzaldehyde with purity of 99.56%.
Wherein, the waste gas G4 generated in the drying process is dedusted by a cloth bag, treated by a primary alkali liquor absorption tower and discharged through an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 8 wt%.
Example 2
A preparation method of 2-carboxyl benzaldehyde specifically comprises the following steps:
1. hydrolysis
Adding deionized water (576.5 kg, 32 kmol) into a hydrolysis kettle, heating to 72 ℃, and preserving heat; then adding a predetermined amount of 3-bromophenylphthalide (213 kg, 1 kmol), heating to 97 ℃, and preserving heat; adding a predetermined amount of tetramethylammonium hydroxide aqueous solution at a feeding speed of 25mL/min under the condition of stirring, and after the addition is finished, continuously preserving the temperature for 30min at the temperature of 97 ℃ to finish the hydrolysis step to obtain the hydrolysate.
Wherein the aqueous solution of tetramethylammonium hydroxide contains 114kg (1.25 kmol) of tetramethylammonium hydroxide, and the concentration of tetramethylammonium hydroxide in the solution is 24wt%.
Detection shows that the content of the 3-bromophenylphthalide in the hydrolysate is 1.34kg.
Meanwhile, hydrolysis waste gas G1 generated in the hydrolysis process is condensed by a condenser, is treated by a primary alkali liquor absorption tower and is discharged by an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 9 wt%.
2. Cooling crystallization
Under the condition of stirring, cooling the hydrolysate to 6 ℃, and carrying out heat preservation and crystallization until no solid is separated out; then, crude 2-carboxybenzaldehyde (137.0 kg) and the first mother liquor were obtained by centrifugation at 9000 rpm. Wherein, the subsequent refining treatment of the 2-carboxybenzaldehyde crude product is carried out; the first centrifugal mother liquor is concentrated and refined to prepare a byproduct of tetramethyl ammonium bromide.
Meanwhile, waste gas G2 generated in the processes of cooling crystallization and centrifugation is treated by a primary alkali liquor absorption tower and then is discharged through an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 9 wt%.
3. Refining
1) Dissolution
Putting a predetermined amount of 2-carboxybenzaldehyde crude product (137.0 kg) into a 2-carboxybenzaldehyde refined kettle filled with a solvent, heating to 82 ℃ under the condition of stirring, and keeping the temperature and stirring until the 2-carboxybenzaldehyde crude product is completely dissolved to obtain a dissolved substance.
Wherein the volume ratio of the 2-carboxybenzaldehyde crude product to the solvent is 1.
The solvent is deionized water or recycled second centrifugal mother liquor. In the process, the first dissolution is carried out by using deionized water; in the subsequent refining process, after a second centrifugal mother liquor is obtained through crystallization and centrifugation, the second centrifugal mother liquor is preferentially selected and recycled to the dissolving step to be used as a solvent for reuse.
2) Removing impurities
Adding a predetermined amount of modified activated carbon into the dissolved matter at 75 ℃, and stirring and adsorbing for 30min; then, the filtrate was obtained by suction filtration.
Wherein, the ratio of the modified activated carbon to the solute by weight is 0.1.
The preparation method of the modified activated carbon comprises the steps of putting activated carbon and deionized water in a volume ratio of 1; then putting the mixture into 2 times volume of polyethyleneimine aqueous solution, stirring for 1.5h at 60rpm, filtering, and drying at 160 ℃ until the weight is unchanged to obtain the modified activated carbon.
Wherein the specification of the active carbon is that the specific surface area is 900m 2 The grain diameter is 250 mu m, and the graphitization degree of the active carbon is 78 percent by XRD detection.
The polyethyleneimine aqueous solution is prepared by the following method: mixing polyethyleneimine with deionized water in a weight ratio of 4.
3) Centrifugation of crystals
Transferring the filtrate obtained in the impurity removal step into a cooling crystallization kettle, cooling to 3 ℃, and carrying out heat preservation crystallization until no solid is separated out; then, 2-carboxybenzaldehyde wet product (131.3 kg) and a second centrifugal mother liquor were obtained by centrifugal separation at a centrifugal rotation speed of 11000 rpm. Wherein, the subsequent drying treatment of the wet product of the 2-carboxybenzaldehyde is carried out; and the second centrifugal mother liquor is recycled to the dissolving step and transferred into a 2-carboxybenzaldehyde refining kettle to be used as a solvent to dissolve the 2-carboxybenzaldehyde crude product.
Meanwhile, waste gas G3 generated in the crystallization and centrifugation process is discharged through an exhaust funnel after being treated by a primary alkali liquor absorption tower. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 9 wt%.
4) Drying
Placing wet 2-carboxybenzaldehyde (131.3 kg) in a dryer, drying at 65 deg.C under vacuum to obtain 2-carboxybenzaldehyde product (121.05 kg), and analyzing by gas chromatography to obtain 2-carboxybenzaldehyde with purity of 99.76%.
Wherein, the waste gas G4 generated in the drying process is dedusted by a cloth bag, treated by a primary alkali liquor absorption tower and discharged through an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is tetramethyl ammonium hydroxide aqueous solution with the concentration of 9 wt%.
Example 3
A preparation method of 2-carboxyl benzaldehyde comprises the following steps:
1. hydrolysis
Adding deionized water (612.5 kg, 34 kmol) into a hydrolysis kettle, heating to 75 ℃, and preserving heat; then adding a predetermined amount of 3-bromophenhthalide (213 kg, 1 kmol), heating to 98 ℃, and preserving heat; adding a predetermined amount of tetramethylammonium hydroxide aqueous solution at a feeding speed of 30mL/min under the condition of stirring, and after the addition is finished, continuously preserving the heat for 35min at the temperature of 98 ℃ to finish the hydrolysis step to obtain the hydrolysate.
Wherein the aqueous tetramethylammonium hydroxide solution contains 118.5kg (1.3 kmol) of tetramethylammonium hydroxide, and the concentration of the tetramethylammonium hydroxide in the solution is 25wt%.
Detection proves that the content of the 3-bromophenyl phthalein in the hydrolysate is 1.30kg.
Meanwhile, the hydrolysis waste gas G1 generated in the hydrolysis process is condensed by a condenser, is treated by a primary alkali liquor absorption tower and is discharged by an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is a tetramethylammonium hydroxide aqueous solution with the concentration of 10 wt%.
2. Cooling crystallization
Under the condition of stirring, cooling the hydrolysate to 5 ℃, and carrying out heat preservation and crystallization until no solid is separated out; then, at a centrifugal rotational speed of 10000rpm, a crude product (137.1 kg) of 2-carboxybenzaldehyde and a first centrifugal mother liquor were obtained by centrifugal separation. Wherein, the subsequent refining treatment of the 2-carboxybenzaldehyde crude product is carried out; the first centrifugal mother liquor is concentrated and refined to prepare a byproduct of tetramethyl ammonium bromide.
Meanwhile, waste gas G2 generated in the processes of cooling crystallization and centrifugation is treated by a primary alkali liquor absorption tower and then is discharged through an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is a tetramethylammonium hydroxide aqueous solution with the concentration of 10 wt%.
3. Refining
1) Dissolution
Putting a predetermined amount of 2-carboxybenzaldehyde crude product (137.1 kg) into a 2-carboxybenzaldehyde refining kettle filled with a solvent, heating to 85 ℃ under the condition of stirring, and keeping the temperature and stirring until the 2-carboxybenzaldehyde crude product is completely dissolved to obtain a dissolved substance.
Wherein the volume ratio of the 2-carboxybenzaldehyde crude product to the solvent is 1.
The solvent is deionized water or recycled second centrifugal mother liquor. In the process, the first dissolution is carried out by using deionized water; in the subsequent refining process, after obtaining second centrifugal mother liquor through crystallization and centrifugation, the second centrifugal mother liquor is preferably selected and recycled to the dissolving step to be used as a solvent for reuse.
2) Removing impurities
Adding a predetermined amount of modified activated carbon into the dissolved matter at the temperature of 80 ℃, and stirring and adsorbing for 40min; then, the filtrate was obtained by suction filtration.
Wherein, the ratio of the modified activated carbon to the solute by weight is 0.13.
The preparation method of the modified activated carbon comprises the steps of putting activated carbon and deionized water in a volume ratio of 1:3 into a high-pressure reactor, preserving heat at 180 ℃ for 3 hours, placing the activated carbon in a vacuum environment, and drying at 80 ℃ until the weight is unchanged; then putting the mixture into 2.5 times of volume of polyethyleneimine aqueous solution, stirring for 2 hours at 80rpm, filtering, and drying at 170 ℃ until the weight is unchanged to obtain the modified activated carbon.
Wherein the specification of the active carbon is as follows,specific surface area of 1000m 2 The graphite/g has the average pore diameter of 3nm and the particle size of 300 mu m, and the graphitization degree of the active carbon is 80 percent by XRD detection.
The polyethyleneimine aqueous solution is prepared by the following method: mixing polyethyleneimine with the weight ratio of 5.
3) Centrifugation of crystals
Transferring the filtrate obtained in the impurity removal step into a cooling crystallization kettle, cooling to 2 ℃, and carrying out heat preservation crystallization until no solid is separated out; then, 2-carboxybenzaldehyde wet product (131.5 kg) and a second mother liquor were obtained by centrifugation at 12000 rpm. Wherein, the subsequent drying treatment of the wet product of the 2-carboxybenzaldehyde is carried out; and the second centrifugal mother liquor is recycled to the dissolving step and transferred into a 2-carboxybenzaldehyde refining kettle to be used as a solvent to dissolve the 2-carboxybenzaldehyde crude product.
Meanwhile, waste gas G3 generated in the crystallization and centrifugation process is treated by a primary alkali liquor absorption tower and then is discharged through an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is a tetramethylammonium hydroxide aqueous solution with the concentration of 10 wt%.
4) Drying the mixture
Placing wet 2-carboxybenzaldehyde (131.5 kg) in a dryer, drying at 70 deg.C under vacuum to obtain 2-carboxybenzaldehyde product (121.08 kg), and analyzing with gas chromatography to obtain 2-carboxybenzaldehyde with purity of 99.65%.
Wherein, the waste gas G4 generated in the drying process is dedusted by a cloth bag, treated by a primary alkali liquor absorption tower and discharged through an exhaust funnel. The alkali liquor adopted in the primary alkali liquor absorption tower is a tetramethylammonium hydroxide aqueous solution with the concentration of 10 wt%.
Comparative example 1
The technical scheme of the embodiment 3 is adopted, and the difference is that 1) in the hydrolysis step, a tetramethyl ammonium hydroxide aqueous solution is omitted; 2) In the refining impurity removal step, the same specification of active carbon is adopted to replace modified active carbon.
The reaction conversion (in terms of 3-bromophenphthalide), yield, purity index of the finished 2-carboxybenzaldehyde obtained in examples 1 to 3 and comparative example 1 are shown in the following table:
further, examples 1 to 3 show the amount of waste water produced per ton of 2-carboxybenzaldehyde compared to the amount of waste water produced per ton of 2-carboxybenzaldehyde produced according to the technical scheme disclosed in chinese patent CN101735041a, as shown in the following table:
all percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The preparation method of the 2-carboxyl benzaldehyde is characterized by comprising the following steps: hydrolyzing, cooling, crystallizing and refining;
the hydrolysis method comprises the steps of putting deionized water into a hydrolysis kettle, heating to 70-75 ℃, and preserving heat; then adding 3-bromophenylphthalide, heating to 96-98 ℃, and keeping the temperature; adding aqueous solution of tetramethyl ammonium hydroxide under stirring, and continuing thermal insulation hydrolysis at 96-98 ℃ to obtain hydrolysate;
in the hydrolysis, the molar ratio of 3-bromophenylphthalein, tetramethylammonium hydroxide and deionized water is 1.2-1.3;
in the hydrolysis, the concentration of the tetramethyl ammonium hydroxide in the tetramethyl ammonium hydroxide aqueous solution is 22-25wt%;
the cooling crystallization method comprises the steps of cooling the hydrolysate to 5-8 ℃ for crystallization, and then carrying out centrifugal separation to obtain a 2-carboxybenzaldehyde crude product and a first centrifugal mother liquor;
in the cooling crystallization, the prepared 2-carboxybenzaldehyde crude product is refined; concentrating and refining the prepared first centrifugal mother liquor to prepare tetramethyl ammonium bromide;
the refining of the crude 2-carboxybenzaldehyde comprises the following steps: dissolving, removing impurities, crystallizing, centrifuging and drying;
the dissolving method comprises the steps of putting the 2-carboxybenzaldehyde crude product into a solvent, heating, stirring and dissolving to obtain a dissolved substance;
in the dissolving, the solvent is deionized water or second centrifugal mother liquor prepared in the crystallization and centrifugation step;
in the dissolving, the volume ratio of the crude 2-carboxybenzaldehyde product to the solvent is 1;
the impurity removal method comprises the steps of putting modified activated carbon into a dissolved substance at the temperature of 70-80 ℃, stirring and adsorbing, and carrying out suction filtration to obtain a filtrate;
in the impurity removal, the ratio of the modified activated carbon to the dissolved matters in parts by weight is 0.09-0.13;
in the impurity removal, the preparation method of the modified activated carbon comprises the steps of putting activated carbon and deionized water in a volume ratio of 1:2-3 into a closed environment, preserving heat for 2-3h at 150-180 ℃, drying the activated carbon in vacuum, putting the dried activated carbon into 1.5-2.5 times of polyethyleneimine water solution, stirring for 1-2h, filtering, and drying at 150-170 ℃ until the weight is unchanged to prepare the modified activated carbon;
the specification of the active carbon is that the specific surface area is 800-1000m 2 Per gram, the average pore diameter is 1-3nm, the particle size is 200-300 mu m, and the graphitization degree of the activated carbon is 75-80% through XRD detection;
the crystallization centrifugation method comprises the steps of cooling the filtrate to 2-5 ℃ for crystallization, and performing centrifugal separation to obtain a 2-carboxybenzaldehyde wet product and a second centrifugal mother liquor;
in the crystallization and centrifugation, the prepared 2-carboxybenzaldehyde wet product is dried to prepare a finished product of 2-carboxybenzaldehyde; and the second centrifugal mother liquor is used as a solvent and recycled to the dissolving step.
2. The process for producing 2-carboxybenzaldehyde according to claim 1, wherein the feed rate of the aqueous tetramethylammonium hydroxide solution in the hydrolysis is 20 to 30mL/min;
after the tetramethyl ammonium hydroxide aqueous solution is put into the reactor, the thermal insulation hydrolysis time is 25-35min under the temperature condition of 96-98 ℃.
3. The method for preparing 2-carboxybenzaldehyde according to claim 1, wherein in the step of removing impurities and in the step of preparing modified activated carbon, the polyethyleneimine aqueous solution is prepared by the following steps: mixing 3-5 parts by weight of polyethyleneimine with deionized water, and stirring uniformly at the temperature of 40-50 ℃.
4. The method for preparing 2-carboxybenzaldehyde according to claim 1, wherein the waste gas generated during hydrolysis, cooling crystallization, crystallization centrifugation and drying is treated by primary alkali solution absorption;
in the first-stage alkali liquor absorption, the alkali liquor is a tetramethylammonium hydroxide aqueous solution with the concentration of 8-10 wt%.
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| US2870194A (en) * | 1956-05-14 | 1959-01-20 | Exxon Research Engineering Co | Process for preparing 2, 2'-biaryldicarboxylic acids |
| EP1591435A3 (en) * | 2004-03-26 | 2007-11-28 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Method for preparing 2,6-Naphtalene dicarboxyclic acid |
| CN101735041B (en) * | 2009-12-17 | 2013-06-12 | 太仓市运通化工厂 | Preparation method of 2-carboxybenzaldehyde |
| CN104447304A (en) * | 2014-11-26 | 2015-03-25 | 太仓运通生物化工有限公司 | Preparation method of carboxybenzaldehyde |
| CN104447303A (en) * | 2014-11-26 | 2015-03-25 | 太仓运通生物化工有限公司 | Preparation technology of carboxybenzaldehyde |
| CN110615734B (en) * | 2018-06-20 | 2022-03-04 | 福建博诺安科医药科技有限公司 | Industrialized synthesis method of o-aldehyde phenyl fatty acid |
| CN112358391B (en) * | 2020-11-17 | 2023-04-11 | 舞阳威森生物医药有限公司 | Preparation method of o-carboxyl benzaldehyde |
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