CN109053627B - Comprehensive recovery method of 2-mercaptobenzothiazole, triethylamine and dichloromethane in ceftriaxone sodium dichloromethane mother liquor - Google Patents
Comprehensive recovery method of 2-mercaptobenzothiazole, triethylamine and dichloromethane in ceftriaxone sodium dichloromethane mother liquor Download PDFInfo
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Abstract
The invention discloses a comprehensive recovery method of 2-mercaptobenzothiazole, triethylamine and dichloromethane in ceftriaxone sodium dichloromethane mother liquor. The method comprises the following steps: (1) recovering 2-mercaptobenzothiazole, (2) recovering triethylamine, and (3) recovering dichloromethane. The comprehensive recovery scheme of the ceftriaxone sodium dichloromethane mother liquor has the advantages of simplicity in operation, high yield, low cost, small pollution and the like, can realize comprehensive recovery of 2-mercaptobenzothiazole, triethylamine and dichloromethane, maximally recycles organic matters, and reduces the pollution to the environment by the organic matters; the wastewater generated in the recovery process is used mechanically, so that the use amount of acid and alkali in the extraction process is reduced, the discharge amount of sewage is controlled, and the method has good practical prospect.
Description
Technical Field
The invention belongs to the technical field of medicines and chemical industry, and relates to a comprehensive recovery method of 2-mercaptobenzothiazole (M for short), triethylamine and dichloromethane in ceftriaxone sodium dichloromethane mother liquor.
Background
Ceftriaxone sodium is the third generation of broad-spectrum, high-efficiency, long-acting, low-toxicity cephalosporin, and has very wide clinical application. The main method for producing ceftriaxone sodium at present is as follows: 7-ACA is used as a main raw material and condensed with triazine ring to generate a 7-ACT intermediate, the 7-ACT and AE active ester are subjected to triethylamine catalytic reaction in a methanol-dichloromethane system to generate ceftriaxone sodium, and meanwhile, a byproduct M is generated; adding water and sodium acetate into the reaction solution for reaction, standing for layering, and carrying out crystallization of ceftriaxone sodium on an aqueous layer, wherein an organic layer is dichloromethane mother solution, and the main components comprise M3-5 wt%, triethylamine 3-4 wt%, dichloromethane 91-94 wt% and impurities. Therefore, the dichloromethane, triethylamine and the byproduct M are comprehensively recovered from the ceftriaxone sodium dichloromethane mother liquor, so that the production cost can be reduced, and the environmental pollution can be reduced.
2-mercaptobenzothiazole (also known as 2-mercaptobenzothiazole, and is also known as accelerator M) is an important vulcanization accelerator in the rubber industry and is widely applied to various rubbers. In the pharmaceutical industry, dibenzothiazyl disulfide produced therefrom is an important starting material for the production of cephalosporin intermediates. A large amount of byproducts M can be generated in the production process of ceftriaxone sodium, ceftizoxime sodium and cefotaxime sodium, the post-treatment is troublesome, the recovery cost is high, and a lot of enterprises transfer wastes to other places or directly discharge the wastes, so that serious environmental pollution is caused. Therefore, the research and development of resource utilization technology can recycle the by-products, greatly reduce the discharge amount of waste, meet the requirement of circular economy, and have important social and economic significance.
Triethylamine (systematic name N, N-diethylethylamine) is used as a solvent, a catalyst and a raw material in the organic synthesis industry. In the antibiotic production industry, triethylamine is mainly used as an organic base to play a role in catalyzing in the reaction process, so that the reaction rate is improved. Because the article has large using amount, high price and great pollution to the environment, the triethylamine in the recovered waste liquid plays an important role in reducing cost and improving efficiency of manufacturers and reducing pollution discharge pressure.
Chinese patent ZL03132624.2 reports a method for recovering M from cefotaxime sodium production waste residue, and the recovery method comprises the following steps: a. leaching: leaching the waste residue generated in the production of cefotaxime sodium in an alkaline solution; b. and (3) filtering: filtering the leaching solution; c. and (3) precipitation: adding 1-2% sulfuric acid solution into the leaching solution to separate out M; d. and (3) filtering: filtering to obtain a crude product M; and then recrystallized. Because the process is extracted from waste residues, the subsequent process needs to be refined to obtain M with better quality. The process is complex to operate, has high energy consumption, needs to add new solvent for extraction, generates a large amount of high-salt water and causes certain harm to the environment.
Chinese patent CN102351809B reports a method for recovering M from a mother liquor of a crystallization of ceftriaxone sodium, which comprises the following steps: adjusting the pH value of ceftriaxone sodium crystallization mother liquor to 2-5 by using a sulfuric acid solution, heating and distilling, evaporating a solvent of about 80% of the mother liquor, cooling the residual liquor, filtering, adding a certain amount of water into the filtrate, performing crystallization by using the characteristic of low solubility of 2-mercaptobenzothiazole in water, filtering, washing with water, and drying to obtain the 2-mercaptobenzothiazole. The method has the following defects: firstly, a certain amount of unknown impurities are generated after the ceftriaxone sodium mother liquor is distilled at high temperature, and are easily separated out along with M in the crystallization process, so that the purity of M is reduced; ② the method does not relate to a method for treating the residual liquid after M separation, and if the organic solvent which is not distilled cleanly is directly discharged, the environment can be polluted, and great harm can be caused.
As mentioned above, methylene dichloride, M and triethylamine are contained in methylene dichloride mother liquor generated in the production process of ceftriaxone sodium, but the methods do not involve the recovery of triethylamine. Therefore, there is a need for a process for the integrated recovery of 2-mercaptobenzothiazole, triethylamine and dichloromethane from the mother liquor of triamcinolone acetonide sodium dichloromethane.
Disclosure of Invention
Therefore, the invention aims to provide a comprehensive recovery method of 2-mercaptobenzothiazole, triethylamine and dichloromethane in ceftriaxone sodium dichloromethane mother liquor, which has the advantages of simple operation, high yield, low cost, small pollution and the like, can realize comprehensive recovery of 2-mercaptobenzothiazole, triethylamine and dichloromethane, maximally recycle organic matters and reduce organic matter pollution to the environment.
In order to solve the technical problems, the invention provides a comprehensive recovery method of 2-mercaptobenzothiazole, triethylamine and dichloromethane in ceftriaxone sodium dichloromethane mother liquor, which comprises the following steps:
(1) recovery of 2-mercaptobenzothiazole
Adding water into the ceftriaxone sodium dichloromethane mother liquor, adjusting the pH value of the ceftriaxone sodium dichloromethane mother liquor to be alkaline by using alkali, stirring, standing and phase splitting to obtain an organic phase 1 and a water phase 1; adding acid into the obtained water phase 1, adjusting the pH value of the water phase to separate out 2-mercaptobenzothiazole, filtering, washing with water, and drying to obtain 2-mercaptobenzothiazole;
(2) recovery of triethylamine
Adding water into the organic phase 1 obtained in the step (1), adjusting the pH value of the organic phase to be acidic by using acid, stirring, standing and phase splitting to obtain an organic phase 2 and a water phase 2; adding alkali into the obtained water phase 2, adjusting the pH value to be alkaline, stirring, standing, phase splitting, and taking the upper layer to obtain crude triethylamine; rectifying the crude triethylamine according to the requirement to obtain high-purity triethylamine;
(3) recovery of methylene chloride
And (3) rectifying the organic phase 2 obtained in the step (2) to obtain high-purity dichloromethane.
FIG. 1 is a process flow diagram of the comprehensive recovery method of 2-mercaptobenzothiazole, triethylamine and dichloromethane in ceftriaxone sodium dichloromethane mother liquor, and the comprehensive recovery method of 2-mercaptobenzothiazole, triethylamine and dichloromethane in ceftriaxone sodium dichloromethane mother liquor is described in more detail below with reference to FIG. 1.
In the step (1) of recovering 2-mercaptobenzothiazole, adding water into the ceftriaxone sodium dichloromethane mother liquor, adjusting the pH value to be alkaline by using alkali, stirring, standing and phase splitting to obtain an organic phase 1 and a water phase 1; adding acid into the obtained water phase 1, adjusting the pH value of the water phase to separate out the 2-mercaptobenzothiazole, filtering, washing and drying to obtain the 2-mercaptobenzothiazole.
In the invention, the ceftriaxone sodium dichloromethane mother liquor refers to: when the ceftriaxone sodium is produced, 7-ACT and AE active ester are subjected to triethylamine catalytic reaction in a methanol-dichloromethane system to generate the ceftriaxone sodium, and meanwhile, a byproduct M is generated; adding water and sodium acetate into the reaction solution for reaction, standing for layering, and carrying out crystallization of ceftriaxone sodium on an aqueous layer, wherein an organic layer is dichloromethane mother solution, and the main components comprise M3-5 wt%, triethylamine 3-4 wt%, dichloromethane 91-94 wt% and impurities.
Firstly, adding water into the ceftriaxone sodium dichloromethane mother liquor, preferably 1.0-1.5 times of the ceftriaxone sodium dichloromethane mother liquor in volume, and then adjusting the pH value of the mother liquor to be alkaline by using solid sodium hydroxide, potassium hydroxide or a mixture thereof or an aqueous solution of the sodium hydroxide, the potassium hydroxide or the mixture thereof. Specifically, an aqueous solution of sodium hydroxide, potassium hydroxide or a mixture thereof with the concentration of 10 wt% -32 wt%, preferably 25 wt% -32 wt% is adopted, the pH value of the mother solution is adjusted to 12-13.5, the temperature is controlled to be 0-25 ℃, preferably 10-20 ℃ in the adjusting process, meanwhile, the mother solution is fully stirred for 1-2 hours, so that 2-mercaptobenzothiazole is converted into a sodium salt or potassium salt form, the sodium salt or potassium salt form is transferred to a water phase, and then the organic phase 1 and the water phase 1 are obtained after standing and phase separation.
Then, an acid was added to the obtained aqueous phase 1, and the pH thereof was adjusted to precipitate 2-mercaptobenzothiazole. Specifically, the pH value of the water phase 1 is adjusted to 6-9 by using hydrochloric acid (with the concentration of 15-36 wt%, preferably 25-36 wt%), sulfuric acid (with the concentration of 15-98 wt%, preferably 50-98 wt%) or a mixed solution of the hydrochloric acid and the sulfuric acid in any proportion, the temperature is controlled to be 0-25 ℃, preferably 5-20 ℃ in the adjusting process, sodium salt or potassium salt of 2-mercaptobenzothiazole is precipitated from the water phase in a solid form of 2-mercaptobenzothiazole in the adjusting process, and the 2-mercaptobenzothiazole with the purity being equal to or larger than 98.0% is obtained through filtering, washing and drying, and meanwhile, the filtrate is collected to be used as the wastewater 1.
The two steps in the step (1) are used for achieving the purpose of separating and purifying the 2-mercaptobenzothiazole. 2-mercaptobenzothiazole is converted from a weak acid form to a weak acid salt form under the action of strong alkali, the weak acid is transferred from dichloromethane mother liquor to water, and then water phase containing M is regulated by acid, so that M weak acid salt is converted into M weak acid and then separated out from the water solution in a solid form, thereby realizing separation and purification. In addition, the filtrate collected by filtering M in the water phase 1, namely the wastewater 1, has the characteristics of high triethylamine content (0.010-0.015 g/ml) and high wastewater index (COD (chemical oxygen demand) (30000-40000 mg/L) and ammonia nitrogen (ammonia nitrogen) (800-1000 mg/L), as shown in figure 1, the filtrate, namely the wastewater 1, can be used for the step (2) instead of water, namely the filtrate is added into the organic phase 1 obtained in the step (1), then the pH value of the filtrate is adjusted by acid to be acidic, and the filtrate is stirred, stood and subjected to phase separation to obtain an organic phase 2 and a water phase 2. Therefore, the recovery rate of triethylamine can be improved, and the final sewage discharge amount is reduced.
In the step (2), triethylamine is recycled, water or the wastewater 1 is added into the organic phase 1 obtained in the step (1), then acid is used for adjusting the pH value of the organic phase 1 to be acidic, and the organic phase 2 and the water phase 2 are obtained after stirring, standing and phase separation; adding alkali into the obtained water phase 2, adjusting the pH value to be alkaline, stirring, standing, phase splitting, and taking the upper layer to obtain crude triethylamine; and rectifying the crude triethylamine according to the requirement to obtain the high-purity triethylamine.
Firstly, water is added into the organic phase 1 obtained in the step (1), and preferably water in an amount which is 1.0 to 1.5 times the volume of the organic phase 1 is added. As described above, the filtrate from the above step (1) in which M is filtered, i.e., the waste water 1, can be used as water therein and added to the organic phase 1. Then, the pH value of the organic phase 1 after adding water is adjusted to 2-4 by using hydrochloric acid (the concentration is 15-36 wt%, preferably 25-36 wt%), sulfuric acid (the concentration is 15-98 wt%, preferably 50-98 wt%) or a mixed solution of the hydrochloric acid and the sulfuric acid in any proportion, the temperature is controlled to be 0-25 ℃, preferably 10-20 ℃, and the organic phase is fully stirred for 0.5-2 hours, so that triethylamine is converted into a triethylamine salt form, the triethylamine salt is transferred from the dichloromethane organic phase to the water phase, and then the triethylamine salt is allowed to stand for phase separation to obtain an organic phase 2 (namely crude dichloromethane) and a water phase 2.
Then, a base was added to the aqueous phase 2 to adjust the pH thereof to be alkaline. Specifically, solid sodium hydroxide, potassium hydroxide or a mixture thereof, or an aqueous solution (preferably with a concentration of 20 wt% -32 wt%) of sodium hydroxide, potassium hydroxide or a mixture thereof is used for adjusting the pH value of the water phase 2 to 12-13.5, the temperature is raised to 30-60 ℃, preferably 45-55 ℃, standing is carried out for phase separation, crude triethylamine is obtained from the upper layer, and the water phase, namely the wastewater 2, is obtained from the lower layer.
And (2) neutralizing triethylamine in the organic phase 1 with acid to form triethylamine salt, transferring the triethylamine salt into a water phase 2 through extraction separation, dissociating the triethylamine after the pH value of the water phase 2 is adjusted to 12-13.5, and then carrying out phase separation at 30-60 ℃ (the solubility of the triethylamine in water is low at 30-60 ℃) to obtain crude triethylamine at the upper layer and wastewater 2 at the lower layer. The lower-layer wastewater 2 has the characteristics of high alkalinity (pH of 12-13.5), high triethylamine content (0.015-0.020 g/ml) and high wastewater index (COD: 40000-50000 mg/L and ammonia nitrogen: 1300-1500 mg/L), and can be used for replacing water to be circularly applied to the M extraction process in the step (1) as shown in figure 1, namely, the water is replaced and added into the ceftriaxone sodium dichloromethane mother liquor, so that the recovery rate of triethylamine can be improved, the alkali dosage in the step (1) is reduced, and the final wastewater discharge amount is reduced.
According to the requirement, the crude triethylamine is rectified to obtain the triethylamine with the purity being equal to or larger than 99 percent (measured by gas chromatography and area normalization method). Specifically, the rectification process of the crude triethylamine is atmospheric distillation (under the atmospheric pressure), and the theoretical number of pedals of the adopted rectification tower is 20-28, preferably 23-25. Transferring the crude triethylamine into a rectifying tower kettle, slowly heating, starting total reflux for 0.5-3 hours, preferably 1-2 hours when the kettle temperature reaches more than or equal to 80 ℃ and the top temperature is more than or equal to 70 ℃, then controlling the reflux extraction ratio to be 2: 1-5: 1, preferably 3:1, starting to collect qualified triethylamine, and collecting 70-73 ℃ fraction, namely the qualified triethylamine. The residue is used for the next distillation because only the fraction of 70-73 ℃ is collected in the rectification process, the residue contains a certain amount of triethylamine, and the residue is used for the next rectification process in order to improve the recovery rate.
And (3) rectifying the organic phase 2 obtained in the step (2) in the dichloromethane recovered in the step (3) to obtain high-purity dichloromethane. Specifically, the dichloromethane rectification process is atmospheric distillation (under the atmospheric pressure), and the theoretical number of pedals of the rectifying tower is 20-30, preferably 20-25. Transferring the crude dichloromethane into a rectifying tower kettle, slowly heating, starting total reflux for 1-3 hours, preferably for 1-2 hours when the kettle temperature reaches more than or equal to 38 ℃ and the top temperature is more than or equal to 35 ℃, then controlling the reflux extraction ratio to be 1: 1-4: 1, preferably 2:1 or 3:1, starting collecting fractions at 35-39 ℃, standing, and then removing water to obtain qualified dichloromethane with the purity of more than or equal to 99% (gas chromatography determination, area normalization method).
The comprehensive recovery method of 2-mercaptobenzothiazole, triethylamine and dichloromethane in ceftriaxone sodium dichloromethane mother liquor has the beneficial effects that:
the invention is a whole set of comprehensive recovery scheme of ceftriaxone sodium dichloromethane mother liquor, the main recovered substance M can reach the national industrial standard, and the recovery rate is more than 90%; the recovery rate of the main recovered substance triethylamine is more than 80%, the purity can reach more than 99%, and the requirement of production, recovery and reuse is met; the recovery rate of the main recovered substance dichloromethane is more than 90%, the purity can reach more than 99%, and the recycling requirement of production is met.
The method recycles the useful substances in the ceftriaxone sodium dichloromethane mother liquor to the maximum extent, and the wastewater generated in the recycling process is reused, so that the consumption of alkali in the extraction process is reduced, and the discharge amount of the wastewater is controlled. The method has good indexes in all aspects and has good practical prospect.
Drawings
FIG. 1 is a process flow diagram of the comprehensive recovery method of 2-mercaptobenzothiazole, triethylamine and dichloromethane in ceftriaxone sodium dichloromethane mother liquor.
Detailed Description
The present invention is described in more detail below by way of examples, but the scope of the present invention is not limited to these examples.
Example 1
(1) Recovery of 2-mercaptobenzothiazole
Taking 3L of ceftriaxone sodium dichloromethane mother liquor (M content: 4wt%, triethylamine content: 3wt%, dichloromethane content: 91.5 wt%, impurity 1.5 wt%), adding 3L of water, adjusting pH to 12 with 30 wt% sodium hydroxide solution, controlling temperature at 10-15 ℃ in the adjusting process, violently stirring for 1 hour, standing for phase separation to obtain an organic phase 1 and a water phase 1; the pH value of the water phase 1 is adjusted to 6 by using 92.5 wt% sulfuric acid, the temperature is controlled to be 15-20 ℃ in the process, a large amount of earthy yellow solid is separated out, and then the obtained product is filtered, washed and dried to obtain 146.1g of 2-mercaptobenzothiazole with the content of 98.56% (liquid chromatography determination and quantitative analysis), and the recovery rate is 92.3%. While collecting the filtered filtrate (i.e., wastewater 1).
(2) Recovery of triethylamine
Adding 3L of the filtrate (namely the wastewater 1) obtained in the step (1) into the organic phase 1, adjusting the pH value to 2.0 by using 92.5 wt% sulfuric acid, controlling the temperature to be 15-20 ℃ in the process, violently stirring for 1 hour, standing and phase splitting to obtain a water phase 2 and an organic phase 2; and (3) adjusting the pH value of the water phase 2 to 12 by using 30 wt% of sodium hydroxide solution, heating to 40 ℃, standing for phase separation, taking the upper layer to obtain crude triethylamine, and taking the lower layer as wastewater 2 (which can be used in the next batch).
The obtained crude triethylamine is transferred into a rectifying tower kettle to be rectified under normal pressure (the theoretical pedal number of the rectifying tower is 25), the temperature is slowly increased, when the kettle temperature reaches more than or equal to 80 ℃, the top temperature is more than or equal to 70 ℃, total reflux is started for 1 hour, then the reflux extraction ratio is controlled to be 3:1, qualified triethylamine is started to be collected, fractions at 70-73 ℃ are collected, 64.2g of triethylamine, 5 percent of water (Karschner titration), 99.53 percent of purity (gas chromatography determination, area normalization method) are obtained, the recovery rate is 52.1 percent, and the kettle residue is sleeved into the next batch for distillation.
(3) Recovery of methylene chloride
And (2) transferring the organic phase 2 into a dichloromethane rectifying tower kettle to carry out normal pressure rectification (the theoretical pedal number of the rectifying tower is 23), slowly raising the temperature, starting total reflux for 1 hour when the kettle temperature reaches not less than 38 ℃ and the top temperature is not less than 35 ℃, then controlling the reflux extraction ratio to be 2:1, collecting fractions at 35-39 ℃, standing, and then dehydrating to obtain qualified dichloromethane 2.44L with the purity of not less than 99.38% (gas chromatography determination, area normalization method), wherein the recovery rate is 90.8%.
Example 2
(1) Recovery of 2-mercaptobenzothiazole
Taking 3L of ceftriaxone sodium dichloromethane mother liquor (M content: 4wt%, triethylamine content: 3wt%, dichloromethane content: 91.5 wt%, impurity 1.5 wt%), adding 3L of wastewater 2 generated by triethylamine recovery in the step (2) of the embodiment 1, adjusting the pH value to 13 by using 30 wt% of sodium hydroxide solution, controlling the temperature to be 15-20 ℃ in the adjusting process, stirring vigorously for 2 hours, standing for phase separation to obtain an organic phase 1 and a water phase 1; the pH value of the water phase 1 is adjusted to 9 by using 92.5 wt% sulfuric acid, the temperature is controlled to be 5-10 ℃ in the process, a large amount of earthy yellow solid is separated out, and then the obtained product is filtered, washed and dried to obtain 143.7g of 2-mercaptobenzothiazole with the content of 98.21% (liquid chromatography determination and quantitative analysis), and the recovery rate is 90.5%. While collecting the filtered filtrate (i.e., wastewater 1).
(2) Recovery of triethylamine
Adding 3L of the filtrate (namely the wastewater 1) obtained in the step (1) into the organic phase 1, adjusting the pH value to 3.0 by using 92.5 wt% sulfuric acid, controlling the temperature to be 15-20 ℃ in the process, violently stirring for 2 hours, standing and phase splitting to obtain a water phase 2 and an organic phase 2; and (3) adjusting the pH value of the water phase 2 to 13 by using 30 wt% of sodium hydroxide solution, heating to 55 ℃, standing for phase separation, taking the upper layer to obtain crude triethylamine, and taking the lower layer to be wastewater 2.
The obtained crude triethylamine is transferred into a rectifying tower kettle to be rectified under normal pressure (the theoretical pedal number of the rectifying tower is 25), the temperature is slowly increased, when the kettle temperature reaches more than or equal to 80 ℃, the top temperature is more than or equal to 70 ℃, total reflux is started for 2 hours, then the reflux extraction ratio is controlled to be 3:1, qualified triethylamine is started to be collected, fractions at 70-73 ℃ are collected, 112.4g of triethylamine, 5.8% of water are obtained (Karschner titration), the purity is 99.31% (gas chromatography determination, area normalization method), the recovery rate is 90.5%, and the kettle residue is sleeved in the next batch of distillation.
(3) Recovery of methylene chloride
And (3) transferring the organic phase 2 into a dichloromethane rectifying tower kettle to carry out normal pressure rectification (the theoretical pedal number of the rectifying tower is 23), slowly raising the temperature, starting total reflux for 1 hour when the kettle temperature reaches more than or equal to 38 ℃ and the top temperature is more than or equal to 35 ℃, then controlling the reflux extraction ratio to be 2:1, collecting fractions at 35-39 ℃, standing, and then dehydrating to obtain qualified dichloromethane 2.48L with the purity of more than or equal to 99.42% (gas chromatography determination, area normalization method), wherein the recovery rate is 92.3%.
Example 3
(1) Recovery of 2-mercaptobenzothiazole
Taking 3L of ceftriaxone sodium dichloromethane mother liquor (M content: 4wt%, triethylamine content: 3wt%, dichloromethane content: 91.5 wt%, impurity 1.5 wt%), adding 3L of wastewater 2 generated by triethylamine recovery in the step (2) in the embodiment 2, adjusting the pH value to 13 by using 30 wt% of sodium hydroxide solution, controlling the temperature to be 15-20 ℃ in the adjusting process, stirring vigorously for 1 hour, standing for phase separation to obtain an organic phase 1 and a water phase 1; the pH value of the water phase 1 is adjusted to 7 by 50 wt% of sulfuric acid, the temperature is controlled to be 5-10 ℃ in the process, a large amount of earthy yellow solid is separated out, and then the obtained product is filtered, washed and dried to obtain 144.8g of 2-mercaptobenzothiazole with the content of 98.28% (liquid chromatography determination and quantitative analysis) and the recovery rate of 91.2%. While collecting the filtered filtrate.
(2) Recovery of triethylamine
Adding the filtrate (namely the wastewater 1) obtained in the step (1) into the organic phase 1, adjusting the pH value to 4.0 by using 92.5 wt% sulfuric acid, controlling the temperature to be 15-20 ℃, violently stirring for 1 hour, standing and phase-separating to obtain a water phase 2 and an organic phase 2; and (3) adjusting the pH value of the water phase 2 to 13 by using 30 wt% of sodium hydroxide solution, heating to 60 ℃, standing for phase separation, taking the upper layer to obtain crude triethylamine, and taking the lower layer to be wastewater 2.
The obtained crude triethylamine is transferred into a rectifying tower kettle to be rectified under normal pressure (the theoretical pedal number of the rectifying tower is 25), the temperature is slowly increased, when the kettle temperature reaches more than or equal to 80 ℃, the top temperature is more than or equal to 70 ℃, total reflux is started for 2 hours, then the reflux extraction ratio is controlled to be 3:1, qualified triethylamine is started to be collected, fractions at 70-73 ℃ are collected, 107.4g of triethylamine, 6.2% of water are obtained (Karschner titration), the purity is 99.25% (gas chromatography determination, area normalization method), the recovery rate is 86.1%, and the kettle residue is sleeved in the next batch of distillation.
(3) Recovery of methylene chloride
And (3) transferring the organic phase 2 into a dichloromethane rectifying tower kettle to carry out normal pressure rectification (the theoretical pedal number of the rectifying tower is 23), slowly raising the temperature, starting total reflux for 1 hour when the kettle temperature reaches more than or equal to 38 ℃ and the top temperature is more than or equal to 35 ℃, then controlling the reflux extraction ratio to be 2:1, collecting fractions at 35-39 ℃, standing, and then dehydrating to obtain qualified dichloromethane 2.50L with the purity of more than or equal to 99.45% (gas chromatography determination, area normalization method), wherein the recovery rate is 93.0%.
Claims (10)
1. A comprehensive recovery method of 2-mercaptobenzothiazole, triethylamine and dichloromethane in ceftriaxone sodium dichloromethane mother liquor comprises the following steps:
(1) recovery of 2-mercaptobenzothiazole
Adding water into the ceftriaxone sodium dichloromethane mother liquor, adjusting the pH value of the ceftriaxone sodium dichloromethane mother liquor to be alkaline by using alkali, wherein the pH value is 12-13.5, stirring, standing and phase splitting to obtain an organic phase 1 and a water phase 1; adding acid into the obtained water phase 1, adjusting the pH value of the water phase to 6-9 to separate out 2-mercaptobenzothiazole, and filtering, washing and drying the mixture to obtain 2-mercaptobenzothiazole;
(2) recovery of triethylamine
Adding water into the organic phase 1 obtained in the step (1), adjusting the pH value of the organic phase to be acidic by using acid, stirring, standing and phase splitting to obtain an organic phase 2 and a water phase 2; adding alkali into the obtained water phase 2, adjusting the pH value to be alkaline, heating to 30-60 ℃, stirring, standing for phase splitting, and taking the upper layer to obtain crude triethylamine; rectifying the crude triethylamine according to the requirement to obtain triethylamine;
(3) recovery of methylene chloride
Rectifying the organic phase 2 obtained in the step (2) to obtain dichloromethane,
wherein, the ceftriaxone sodium dichloromethane mother liquor refers to: when the ceftriaxone sodium is produced, 7-ACT and AE active ester are subjected to triethylamine catalytic reaction in a methanol-dichloromethane system to generate the ceftriaxone sodium, and meanwhile, a byproduct is 2-mercaptobenzothiazole; adding water and sodium acetate into the reaction solution for reaction, standing for layering, carrying out a crystallization process of ceftriaxone sodium on an aqueous layer, and obtaining an organic layer which is the ceftriaxone sodium dichloromethane mother liquor.
2. The integrated recovery process of claim 1, wherein the ceftriaxone sodium dichloromethane mother liquor comprises: 3 to 5 weight percent of 2-mercaptobenzothiazole, 3 to 4 weight percent of triethylamine and 91 to 94 weight percent of dichloromethane.
3. The comprehensive recovery method according to claim 1 or 2, wherein in the step (1) of recovering 2-mercaptobenzothiazole, solid sodium hydroxide, potassium hydroxide or a mixture thereof, or an aqueous solution of sodium hydroxide, potassium hydroxide or a mixture thereof is used to adjust the pH value of the mother liquor to 12-13.5, the temperature is controlled to be 0-25 ℃ in the adjustment process, simultaneously, the mother liquor is fully stirred for 1-2 hours, so that the 2-mercaptobenzothiazole is converted into a sodium salt or potassium salt form, the sodium salt or potassium salt form is transferred to an aqueous phase, and then the organic phase 1 and the aqueous phase 1 are obtained after standing and phase separation.
4. The integrated recovery method according to claim 1 or 2, wherein in the step (1) of recovering 2-mercaptobenzothiazole, hydrochloric acid, sulfuric acid or a mixed solution thereof in any proportion is added to the obtained water phase 1 to adjust the pH value of the water phase 1 to 6-9, and the temperature is controlled to 0-25 ℃ during the adjustment.
5. The integrated recovery method according to claim 1 or 2, wherein in the step (1) of recovering 2-mercaptobenzothiazole, the filtrate collected by filtering 2-mercaptobenzothiazole as the aqueous phase 1 is used as the water added to the organic phase 1 obtained in the step (1) in the step (2), i.e., the waste water 1.
6. The comprehensive recovery method according to claim 1 or 2, wherein in the triethylamine recovered in the step (2), 1.0 to 1.5 times of the volume of the organic phase 1 is added to the organic phase 1 obtained in the step (1), and then the pH value of the organic phase 1 after adding water is adjusted to 2 to 4 by using hydrochloric acid, sulfuric acid or a mixed solution thereof in any proportion, while the temperature is controlled to 0 to 25 ℃, and the mixture is fully stirred for 0.5 to 2 hours.
7. The comprehensive recovery method of claim 1 or 2, wherein in the triethylamine recovered in the step (2), the pH value of the water phase 2 is adjusted to 12-13.5 by using solid sodium hydroxide, potassium hydroxide or a mixture thereof, or an aqueous solution of sodium hydroxide, potassium hydroxide or a mixture thereof, the temperature is raised to 45-55 ℃, the mixture is stirred and kept stand to perform phase separation, crude triethylamine is obtained from the upper layer, and the water phase is obtained from the lower layer, namely the wastewater 2.
8. The integrated recovery process of claim 7, wherein the waste water 2 is recycled to step (1) as water to be added to the mother liquor of ceftriaxone sodium dichloromethane.
9. The comprehensive recovery method as claimed in claim 1 or 2, characterized in that in the triethylamine recovered in the step (2), the rectification process of the crude triethylamine is atmospheric distillation, the theoretical plate number of the adopted rectification tower is 20-28, when the kettle temperature reaches more than or equal to 80 ℃, the top temperature is more than or equal to 70 ℃, the total reflux is started for 0.5-3 hours, then the reflux extraction ratio is controlled to be 2: 1-5: 1, and the fraction at 70-73 ℃ is collected to be the triethylamine.
10. The comprehensive recovery method of claim 1 or 2, wherein in the step (3), the dichloromethane is recovered, the rectification process of the dichloromethane is atmospheric distillation, the theoretical plate number of the rectifying tower is 20-30, when the kettle temperature reaches not less than 38 ℃ and the top temperature is not less than 35 ℃, the total reflux is started for 1-3 hours, then the reflux extraction ratio is controlled to be 1: 1-4: 1, the fraction at 35-39 ℃ is collected, and the dichloromethane is obtained by separating water after standing.
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