CN116332713B - Method for recycling organic solvent in waste liquid in drug synthesis process - Google Patents
Method for recycling organic solvent in waste liquid in drug synthesis process Download PDFInfo
- Publication number
- CN116332713B CN116332713B CN202210914097.1A CN202210914097A CN116332713B CN 116332713 B CN116332713 B CN 116332713B CN 202210914097 A CN202210914097 A CN 202210914097A CN 116332713 B CN116332713 B CN 116332713B
- Authority
- CN
- China
- Prior art keywords
- tertiary butyl
- rectifying tower
- tower
- waste liquid
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000007788 liquid Substances 0.000 title claims abstract description 47
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 239000003814 drug Substances 0.000 title claims abstract description 32
- 239000003960 organic solvent Substances 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 28
- 229940079593 drug Drugs 0.000 title claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 88
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 44
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 44
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims abstract description 43
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 230000018044 dehydration Effects 0.000 claims abstract description 37
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 37
- 238000001179 sorption measurement Methods 0.000 claims abstract description 37
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000000622 liquid--liquid extraction Methods 0.000 claims abstract description 11
- 238000000638 solvent extraction Methods 0.000 claims abstract description 11
- 239000002274 desiccant Substances 0.000 claims description 45
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 22
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 22
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 22
- 239000012312 sodium hydride Substances 0.000 claims description 22
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 22
- 238000010992 reflux Methods 0.000 claims description 21
- 239000002808 molecular sieve Substances 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010887 waste solvent Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 description 14
- 239000012043 crude product Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000007781 pre-processing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 239000010812 mixed waste Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/36—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
-
- 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
-
- 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
-
- 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
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- 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
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of solvent recycling and discloses a recycling method of an organic solvent in waste liquid in a drug synthesis process, which comprises the following steps of S1, adding the waste liquid generated in the drug synthesis process into a rectifying tower for rectification to obtain industrial-grade ethylbenzene; s2, adding pure water into the light components extracted from the top of the rectifying tower to perform liquid-liquid extraction separation to obtain a mixture of methyl tertiary butyl ether and tertiary butyl acetate and a mixture of tetrahydrofuran, tertiary butyl alcohol and ethanol; s3, carrying out reduced pressure rectification and adsorption dehydration on the mixture of the methyl tertiary butyl ether and the tertiary butyl acetate to obtain industrial grade methyl tertiary butyl ether and industrial grade tertiary butyl acetate; and S4, rectifying, drying and dehydrating the tetrahydrofuran, tertiary butanol and ethanol mixture to obtain the industrial grade tetrahydrofuran. The method can realize the recycling of the organic solvent, save energy and reduce consumption, reduce the pollution degree of the waste solvent to the environment in the medicine industry, save the production cost and is suitable for industrialized mass production.
Description
Technical Field
The invention relates to the technical field of solvent recycling, in particular to a recycling method of an organic solvent in waste liquid in a drug synthesis process.
Background
In the preparation process of the medicine, a large amount of solvents such as methyl tertiary butyl ether, ethylbenzene, tetrahydrofuran, tertiary butyl acetate, tertiary butyl alcohol and the like are needed, and due to the long synthetic process route and the involved reaction steps, a large amount of mixed waste liquid containing the solvents can be generated, and if the mixed waste liquid is directly discharged, not only can the environment be polluted greatly, but also a large amount of solvents are wasted, and the economic cost is increased.
Because the organic solvents involved in preparing different medicines are different, the components are complex, the concentrations of COD, BOD, suspended matters and the like are high, the fluctuation of water quality and quantity is large, the method belongs to high-concentration organic wastewater, and the prior art generally adopts a physical method, a chemical method, a biological method or a combination of any two methods for treatment so as to achieve the purpose of discharging the wastewater, but the recovery of the organic solvents in the waste liquid is not considered, so that a large amount of organic solvents are wasted, and the wastewater treatment cost is increased.
Therefore, how to provide a method for recycling waste liquid containing methyl tertiary butyl ether generated by a drug intermediate is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a method for recycling organic solvent in waste liquid in the drug synthesis process, so as to solve the technical problems that the waste solvent discharged in the existing drug synthesis process is serious in environmental pollution and cannot be effectively recycled.
In order to solve the technical scheme, the invention provides a method for recycling an organic solvent in waste liquid in a drug synthesis process, which comprises the following steps:
s1, adding waste liquid generated in the drug synthesis process into a first rectifying tower for rectification, wherein the heavy component extracted from the bottom of the first rectifying tower is industrial grade ethylbenzene;
s2, adding pure water into the light components extracted from the top of the first rectifying tower to perform liquid-liquid extraction separation to obtain a mixture of methyl tertiary butyl ether and tertiary butyl acetate and a mixture of tetrahydrofuran, tertiary butanol and ethanol;
s3, conveying the mixture of methyl tertiary butyl ether and tertiary butyl acetate obtained by separation to a vacuum tower for vacuum rectification, and carrying out adsorption dehydration on heavy components and light components respectively extracted from the top and the bottom of the vacuum tower to obtain industrial-grade methyl tertiary butyl ether and industrial-grade tertiary butyl acetate;
and S4, conveying the mixture of tetrahydrofuran, tertiary butanol and ethanol obtained by separation to a second rectifying tower for rectification, and drying and dehydrating light components extracted from the top of the second rectifying tower to obtain the industrial-grade tetrahydrofuran.
Preferably, in the method for recycling the organic solvent in the waste liquid in the drug synthesis process, the operating pressure of the first rectifying tower in the step S1 is normal pressure, the bottom temperature of the first rectifying tower is 137-150 ℃, the top temperature of the first rectifying tower is 98-130 ℃, and the reflux ratio is 1-10.
Preferably, in the method for recycling the organic solvent in the waste liquid in the drug synthesis process, the rate of adding the waste liquid into the first rectifying tower in the step S1 is 0.3-0.5L/h.
Preferably, in the method for recycling the organic solvent in the waste liquid in the drug synthesis process, the temperature of the liquid-liquid extraction separation in the step S2 is 25-35 ℃ and the time is 10-40min.
Preferably, in the method for recycling the organic solvent in the waste liquid in the drug synthesis process, the volume ratio of the light component extracted from the top of the first rectifying tower in the step S2 to the pure water is 1: (0.3-2).
Preferably, in the method for recycling the organic solvent in the waste liquid in the drug synthesis process, the operating pressure of the pressure reduction tower in the step S3 is 10-60kPa, the bottom temperature of the pressure reduction tower is 45-100 ℃, the top temperature of the pressure reduction tower is 40-93 ℃, and the reflux ratio is 2-8.
Preferably, in the method for recycling the organic solvent in the waste liquid in the drug synthesis process, in the step S3, the heavy component is a crude product of tert-butyl acetate, and the drying agent used for adsorption and dehydration of the heavy component is activated alumina or molecular sieve.
Preferably, in the method for recycling the organic solvent in the waste liquid in the drug synthesis process, in the step S3, the light component is methyl tert-butyl ether, and the drying agent used for adsorption and dehydration of the light component comprises lithium aluminum hydride, sodium hydride, calcium chloride and molecular sieve.
Preferably, in the method for recycling the organic solvent in the waste liquid in the drug synthesis process, the step S4 further includes: drying and pre-treating the mixture of tetrahydrofuran, tertiary butanol and ethanol obtained by separation;
the drying agent used in the drying pretreatment process comprises lithium aluminum hydride and/or sodium hydride, and when the drying agent is a mixture of the lithium aluminum hydride and the sodium hydride, the mass ratio of the lithium aluminum hydride to the sodium hydride is 1: (0.5-3), further preferably 1: (1-2).
Preferably, in the method for recycling the organic solvent in the waste liquid in the drug synthesis process, the operating pressure of the second rectifying tower in the step S4 is normal pressure, the bottom temperature of the second rectifying tower is 60-85 ℃, the top temperature of the second rectifying tower is 55-68 ℃, and the reflux ratio is 3-5.
The invention provides a recycling method of organic solvent in waste liquid in the drug synthesis process, which has the beneficial effects that compared with the prior art:
the invention removes impurities in the waste solvent of the intermediate of the synthetic medicine by a series of methods such as normal pressure rectification, liquid-liquid extraction, adsorption drying and the like, and simultaneously recovers and obtains the industrial-grade organic solvent, thereby realizing the recycling of the organic solvent, saving energy, reducing consumption, reducing the pollution degree of the waste solvent to the environment in the medicine industry, saving the production cost and being suitable for industrialized mass production.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
S1, taking waste liquid containing 47% of methyl tertiary butyl ether, 16% of ethylbenzene, 12% of tetrahydrofuran, 20% of tertiary butyl acetate, 2% of tertiary butyl alcohol, 2% of water, 0.5% of ethanol and the balance of other impurities, adding the waste liquid into a first rectifying tower at the rate of 0.4L/h for rectification, wherein the operating pressure of the first rectifying tower is normal pressure, the temperature of the tower bottom is 138 ℃, the temperature of the tower top is 105 ℃, the reflux ratio is 5, and the heavy component extracted from the tower bottom of the first rectifying tower is industrial grade ethylbenzene;
s2, adding pure water into the light component extracted from the top of the first rectifying tower, and performing liquid-liquid extraction separation for 15min at the temperature of 25 ℃, wherein the volume ratio of the light component extracted from the top of the first rectifying tower to the pure water is 1:0.5, obtaining a mixture of methyl tertiary butyl ether and tertiary butyl acetate and a mixture of tetrahydrofuran, tertiary butyl alcohol and ethanol;
s3, conveying the mixture of methyl tertiary butyl ether and tertiary butyl acetate obtained through separation to a vacuum tower for vacuum rectification, wherein the operating pressure of the vacuum tower is 10-60kPa, the tower bottom temperature of the vacuum tower is 80 ℃, the tower top temperature is 75 ℃, the reflux ratio is 3, the light component methyl tertiary butyl ether crude product is extracted from the tower top of the vacuum tower, the industrial grade methyl tertiary butyl ether is obtained after adsorption and dehydration, the heavy component tertiary butyl acetate crude product is extracted from the tower bottom of the vacuum tower, and the industrial grade tertiary butyl acetate is obtained after adsorption and dehydration;
s4, drying and preprocessing the mixture of tetrahydrofuran, tertiary butanol and ethanol obtained by separation, and then conveying the mixture to a second rectifying tower for rectification, wherein the operating pressure of the second rectifying tower is normal pressure, the bottom temperature of the second rectifying tower is 66 ℃, the top temperature of the second rectifying tower is 62 ℃, the reflux ratio is 3, and the light component extracted from the top of the second rectifying tower is dried and dehydrated, thus obtaining the industrial tetrahydrofuran.
The drying agent used for heavy component adsorption and dehydration in the step S3 is activated alumina, the drying agent used for light component adsorption and dehydration is a molecular sieve, and the drying agent used in the drying pretreatment process in the step S4 is a mixture of lithium aluminum hydride and sodium hydride which are mixed in equal mass.
Example 2
S1, taking waste liquid containing 52% of methyl tertiary butyl ether, 11% of ethylbenzene, 20% of tetrahydrofuran, 15% of tertiary butyl acetate, 0.5% of tertiary butyl alcohol, 0.5% of water, 0.8% of ethanol and the balance of other impurities, adding the waste liquid into a first rectifying tower at the rate of 0.3L/h for rectifying, wherein the operating pressure of the first rectifying tower is normal pressure, the tower bottom temperature is 138 ℃, the tower top temperature is 110 ℃, the reflux ratio is 3, and the heavy component extracted from the tower bottom of the first rectifying tower is industrial grade ethylbenzene;
s2, adding pure water into the light components extracted from the top of the first rectifying tower, and performing liquid-liquid extraction separation for 10min at the temperature of 30 ℃, wherein the volume ratio of the light components extracted from the top of the first rectifying tower to the pure water is 1:0.3, obtaining a mixture of methyl tertiary butyl ether and tertiary butyl acetate, and a mixture of tetrahydrofuran, tertiary butyl alcohol and ethanol;
s3, conveying the mixture of methyl tertiary butyl ether and tertiary butyl acetate obtained through separation to a vacuum tower for vacuum rectification, wherein the operating pressure of the vacuum tower is 10-60kPa, the tower bottom temperature of the vacuum tower is 100 ℃, the tower top temperature is 93 ℃, the reflux ratio is 2, the light component methyl tertiary butyl ether crude product is extracted from the tower top of the vacuum tower, the industrial grade methyl tertiary butyl ether is obtained after adsorption and dehydration, the heavy component tertiary butyl acetate crude product is extracted from the tower bottom of the vacuum tower, and the industrial grade tertiary butyl acetate is obtained after adsorption and dehydration;
s4, drying and preprocessing the mixture of tetrahydrofuran, tertiary butanol and ethanol obtained by separation, and then conveying the mixture to a second rectifying tower for rectification, wherein the operating pressure of the second rectifying tower is normal pressure, the bottom temperature of the second rectifying tower is 85 ℃, the top temperature of the second rectifying tower is 66 ℃, the reflux ratio is 4, and the light component extracted from the top of the second rectifying tower is dried and dehydrated, thus obtaining the industrial tetrahydrofuran.
The drying agent used for heavy component adsorption and dehydration in the step S3 is a molecular sieve, the drying agent used for light component adsorption and dehydration is calcium chloride, and the drying agent used in the drying pretreatment process in the step S4 is lithium aluminum hydride.
Example 3
S1, taking waste liquid containing 40% of methyl tertiary butyl ether, 20% of ethylbenzene, 20% of tetrahydrofuran, 17% of tertiary butyl acetate, 1% of tertiary butyl alcohol, 1% of water, 0.6% of ethanol and the balance of other impurities, adding the waste liquid into a first rectifying tower at the rate of 0.5L/h for rectification, wherein the operating pressure of the first rectifying tower is normal pressure, the temperature of the tower bottom is 138 ℃, the temperature of the tower top is 120 ℃, the reflux ratio is 1, and the heavy component extracted from the tower bottom of the first rectifying tower is industrial grade ethylbenzene;
s2, adding pure water into the light components extracted from the top of the first rectifying tower, and carrying out liquid-liquid extraction separation for 20min at the temperature of 35 ℃, wherein the volume ratio of the light components extracted from the top of the first rectifying tower to the pure water is 1:1, obtaining a mixture of methyl tertiary butyl ether and tertiary butyl acetate and a mixture of tetrahydrofuran, tertiary butyl alcohol and ethanol;
s3, conveying the mixture of methyl tertiary butyl ether and tertiary butyl acetate obtained through separation to a vacuum tower for vacuum rectification, wherein the operating pressure of the vacuum tower is 10-60kPa, the tower bottom temperature of the vacuum tower is 65 ℃, the tower top temperature is 58 ℃, the reflux ratio is 5, the light component methyl tertiary butyl ether crude product is extracted from the tower top of the vacuum tower, the industrial grade methyl tertiary butyl ether is obtained after adsorption and dehydration, the heavy component tertiary butyl acetate crude product is extracted from the tower bottom of the vacuum tower, and the industrial grade tertiary butyl acetate is obtained after adsorption and dehydration;
s4, drying and preprocessing the mixture of tetrahydrofuran, tertiary butanol and ethanol obtained by separation, and then conveying the mixture to a second rectifying tower for rectification, wherein the operating pressure of the second rectifying tower is normal pressure, the bottom temperature of the second rectifying tower is 78 ℃, the top temperature of the second rectifying tower is 68 ℃, the reflux ratio is 5, and the light component extracted from the top of the second rectifying tower is dried and dehydrated, thus obtaining the industrial tetrahydrofuran.
In the step S3, the drying agent used for heavy component adsorption and dehydration is a molecular sieve, the drying agent used for light component adsorption and dehydration is sodium hydride, and the drying agent used in the drying pretreatment process in the step S4 is sodium hydride.
Example 4
S1, taking waste liquid containing 58% of methyl tertiary butyl ether, 10% of ethylbenzene, 18% of tetrahydrofuran, 10% of tertiary butyl acetate, 2% of tertiary butyl alcohol, 1% of water, 0.5% of ethanol and the balance of other impurities, adding the waste liquid into a first rectifying tower at the rate of 0.4L/h for rectification, wherein the operating pressure of the first rectifying tower is normal pressure, the temperature of the tower bottom is 145 ℃, the temperature of the tower top is 130 ℃, the reflux ratio is 10, and the heavy component extracted from the tower bottom of the first rectifying tower is industrial grade ethylbenzene;
s2, adding pure water into the light components extracted from the top of the first rectifying tower, and carrying out liquid-liquid extraction separation for 40min at the temperature of 25 ℃, wherein the volume ratio of the light components extracted from the top of the first rectifying tower to the pure water is 1:1.5, obtaining a mixture of methyl tertiary butyl ether and tertiary butyl acetate and a mixture of tetrahydrofuran, tertiary butyl alcohol and ethanol;
s3, conveying the mixture of methyl tertiary butyl ether and tertiary butyl acetate obtained through separation to a vacuum tower for vacuum rectification, wherein the operating pressure of the vacuum tower is 10-60kPa, the tower bottom temperature of the vacuum tower is 45 ℃, the tower top temperature is 40 ℃, the reflux ratio is 8, the light component methyl tertiary butyl ether crude product is extracted from the tower top of the vacuum tower, the industrial grade methyl tertiary butyl ether is obtained after adsorption and dehydration, the heavy component tertiary butyl acetate crude product is extracted from the tower bottom of the vacuum tower, and the industrial grade tertiary butyl acetate is obtained after adsorption and dehydration;
s4, drying and preprocessing the mixture of tetrahydrofuran, tertiary butanol and ethanol obtained by separation, and then conveying the mixture to a second rectifying tower for rectification, wherein the operating pressure of the second rectifying tower is normal pressure, the bottom temperature of the second rectifying tower is 65 ℃, the top temperature of the second rectifying tower is 60 ℃, the reflux ratio is 3, and the light component extracted from the top of the second rectifying tower is dried and dehydrated, thus obtaining the industrial tetrahydrofuran.
In the step S3, the drying agent used for heavy component adsorption and dehydration is activated alumina, the drying agent used for light component adsorption and dehydration is lithium aluminum hydride, and the drying agent used in the drying pretreatment process in the step S4 is lithium aluminum hydride.
Example 5
S1, taking waste liquid containing 60% of methyl tertiary butyl ether, 15% of ethylbenzene, 10% of tetrahydrofuran, 13% of tertiary butyl acetate, 0.8% of tertiary butyl alcohol, 0.5% of water, 0.3% of ethanol and the balance of other impurities, adding the waste liquid into a first rectifying tower at the rate of 0.3L/h for rectifying, wherein the operating pressure of the first rectifying tower is normal pressure, the tower bottom temperature is 150 ℃, the tower top temperature is 98 ℃, the reflux ratio is 7, and the heavy component extracted from the tower bottom of the first rectifying tower is industrial grade ethylbenzene;
s2, adding pure water into the light components extracted from the top of the first rectifying tower, and carrying out liquid-liquid extraction separation for 20min at the temperature of 30 ℃, wherein the volume ratio of the light components extracted from the top of the first rectifying tower to the pure water is 1:2, obtaining a mixture of methyl tertiary butyl ether and tertiary butyl acetate and a mixture of tetrahydrofuran, tertiary butyl alcohol and ethanol;
s3, conveying the mixture of methyl tertiary butyl ether and tertiary butyl acetate obtained through separation to a vacuum tower for vacuum rectification, wherein the operating pressure of the vacuum tower is 10-60kPa, the tower bottom temperature of the vacuum tower is 56 ℃, the tower top temperature is 50 ℃, the reflux ratio is 3, the light component methyl tertiary butyl ether crude product is extracted from the tower top of the vacuum tower, the industrial grade methyl tertiary butyl ether is obtained after adsorption and dehydration, the heavy component tertiary butyl acetate crude product is extracted from the tower bottom of the vacuum tower, and the industrial grade tertiary butyl acetate is obtained after adsorption and dehydration;
s4, drying and preprocessing the mixture of tetrahydrofuran, tertiary butanol and ethanol obtained by separation, and then conveying the mixture to a second rectifying tower for rectification, wherein the operating pressure of the second rectifying tower is normal pressure, the bottom temperature of the second rectifying tower is 60 ℃, the top temperature of the second rectifying tower is 55 ℃, the reflux ratio is 4, and the light component extracted from the top of the second rectifying tower is dried and dehydrated, thus obtaining the industrial tetrahydrofuran.
The drying agent used for heavy component adsorption and dehydration in the step S3 is a molecular sieve, the drying agent used for light component adsorption and dehydration is a molecular sieve, and the drying agent used in the drying pretreatment process in the step S4 is a mixture of lithium aluminum hydride and sodium hydride which are mixed in equal mass.
The quality of ethylbenzene, methyl tert-butyl ether, tert-butyl acetate and tetrahydrofuran obtained by the treatment in examples 1 to 5 was examined, and the results are shown in tables 1 to 4.
TABLE 1 ethylbenzene quality test results
| Name of the name | Industry standard | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Purity (wt%) | ≥99.8 | 99.97 | 99.95 | 99.96 | 99.97 | 99.94 |
TABLE 2 methyl tert-butyl ether quality test results
| Name of the name | Industry standard | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Purity (wt%) | ≥99.0 | 99.96 | 99.92 | 99.93 | 99.92 | 99.94 |
| Moisture (wt%) | ≤0.05 | 0.008 | 0.010 | 0.012 | 0.008 | 0.011 |
| Chromaticity (Hazen) | ≤10 | 2 | 2 | 3 | 3 | 2 |
TABLE 3 quality detection results of tert-butyl acetate
TABLE 4 tetrahydrofuran quality test results
| Name of the name | Industry standard | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Purity (wt%) | ≥99.8 | 99.97 | 99.96 | 99.96 | 99.95 | 99.96 |
| Chromaticity (Hazen) | ≤5 | 2 | 2 | 2 | 2 | 2 |
| Moisture (wt%) | ≤0.05 | 0.009 | 0.008 | 0.01 | 0.009 | 0.009 |
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that the rate of feeding the waste liquid into the first rectifying column in step S1 is different.
The influence of the waste liquid adding rate on the ethylbenzene recovery effect was investigated by using the waste liquid adding rate in the step S1 as a variable, and specifically, the purity of the recovered ethylbenzene was shown in Table 5 when the waste liquid adding rate was 0.1L/h, 0.2L/h, 0.3L/h, 0.5L/h, 0.6L/h, and 0.7L/h, respectively.
TABLE 5 Effect of velocity on ethylbenzene recovery
As shown in the table above, when the rate of adding the waste liquid into the first rectifying tower is 0.1L/h and 0.2L/h, the purity of the recovered ethylbenzene also meets the industrial grade standard, but the ethylbenzene purity and the treatment time are comprehensively considered, and 0.3-0.5L/h is selected as the optimal condition.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that the dehydration desiccant is adsorbed in step S3.
And (3) performing a test by taking a drying agent used in the adsorption and dehydration process in the step (S3) as a variable, and researching the influence of the selection of the drying agent on the recovery effect of methyl tertiary butyl ether and tertiary butyl acetate.
Specifically, when adsorption dehydration is performed on a crude product of tert-butyl acetate, the influence of adsorption dehydration and the selection of the drying agent on the recovery effect of tert-butyl acetate is studied by taking the time when adsorption dehydration is not performed and the adsorption dehydration drying agent is respectively activated alumina, a molecular sieve, calcium chloride, sodium hydride and lithium aluminum hydride as variables, and the influence results are shown in Table 6.
TABLE 6 influence of desiccant species on recovery of tert-butyl acetate
Further, when adsorption dehydration is performed on the crude methyl tert-butyl ether product, the influence of adsorption dehydration and the selection of the drying agent on the recovery effect of methyl tert-butyl ether is studied by taking the time when adsorption dehydration is not performed and the adsorption dehydration drying agent is respectively active alumina, a molecular sieve, calcium chloride, sodium hydride, lithium aluminum hydride and sodium hydroxide as variables, and the influence results are shown in table 7.
TABLE 7 influence of desiccant species on methyl tert-butyl ether recovery
It can be seen from tables 6 to 7 that the addition or non-addition of the drying agent and the selection of the type of the drying agent have an important influence on the effect after the recovery of the organic solvent, particularly the change of the water content, and the purpose of reducing the water content can not be achieved by any type of drying agent, and the corresponding drying agent should be selected for different organic solvents.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that the drying pretreatment step in step S4 is different.
And (3) testing by taking a drying agent used in the drying pretreatment process in the step S4 as a variable, and researching the influence of the selection of the drying agent on the tetrahydrofuran recovery effect.
Specifically, the influence of the drying pretreatment process and the selection of the drying agent on the tetrahydrofuran recovery effect was studied with the drying agent of the tetrahydrofuran, t-butanol and ethanol mixture not subjected to the drying pretreatment being activated alumina, molecular sieve, calcium chloride, sodium hydride and lithium aluminum hydride as variables, and the influence results are shown in table 8.
TABLE 8 influence of desiccant species on tetrahydrofuran recovery effect
Based on the results of table 8, the drying agents sodium hydride and lithium aluminum hydride with more excellent comprehensive effects were selected as drying agents, and further the influence of the drying agents sodium hydride and lithium aluminum hydride on the tetrahydrofuran recovery effect was studied by taking the mass ratio of sodium hydride to lithium aluminum hydride as a variable, and the influence results are shown in table 9.
TABLE 9 influence of desiccant proportion on tetrahydrofuran recovery effect
As can be seen from table 9, when the mass ratio of lithium aluminum hydride to sodium hydride is 1: (0.5-4), industrial grade tetrahydrofuran can be obtained, but when the addition amount of sodium hydride is excessive, the chromaticity, the moisture and the like of the tetrahydrofuran are not changed any more to a smooth trend, and the purity of the tetrahydrofuran is gradually reduced, so that the mass ratio of lithium aluminum hydride to sodium hydride is determined to be 1: (0.5-3), and when the mass ratio of the lithium aluminum hydride to the sodium hydride is 1 (1-2), the index of each detection item of the tetrahydrofuran is optimal.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the solution disclosed in the embodiments, since it corresponds to the method disclosed in the embodiments, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The method for recycling the organic solvent in the waste liquid in the drug synthesis process is characterized by comprising the following steps of:
s1, adding waste liquid generated in the drug synthesis process into a first rectifying tower for rectification, wherein the heavy component extracted from the bottom of the first rectifying tower is industrial grade ethylbenzene;
s2, adding pure water into the light components extracted from the top of the first rectifying tower to perform liquid-liquid extraction separation to obtain a mixture of methyl tertiary butyl ether and tertiary butyl acetate and a mixture of tetrahydrofuran, tertiary butanol and ethanol;
s3, conveying the mixture of methyl tertiary butyl ether and tertiary butyl acetate obtained by separation to a vacuum tower for vacuum rectification, and carrying out adsorption dehydration on heavy components and light components respectively extracted from the top and the bottom of the vacuum tower to obtain industrial-grade methyl tertiary butyl ether and industrial-grade tertiary butyl acetate;
s4, conveying the mixture of tetrahydrofuran, tertiary butanol and ethanol obtained by separation to a second rectifying tower for rectification, and drying and dehydrating light components extracted from the top of the second rectifying tower to obtain industrial tetrahydrofuran;
the operation pressure of the first rectifying tower in the step S1 is normal pressure, the bottom temperature of the first rectifying tower is 137-150 ℃, the top temperature of the first rectifying tower is 98-130 ℃, and the reflux ratio is 1-10;
the rate of adding the waste liquid into the first rectifying tower in the step S1 is 0.3-0.5L/h;
in the step S3, the light component is methyl tertiary butyl ether, and the drying agent used for adsorption and dehydration of the light component comprises lithium aluminum hydride, sodium hydride, calcium chloride and molecular sieve.
2. The method for recycling organic solvent in waste liquid in drug synthesis process according to claim 1, wherein the temperature of the liquid-liquid extraction separation in step S2 is 25-35 ℃ for 10-40min.
3. The method for recycling organic solvent in waste liquid in drug synthesis process according to claim 1, wherein the volume ratio of light component to pure water extracted from the top of the first rectifying tower in step S2 is 1: (0.3-2).
4. The method for recycling organic solvent in waste liquid in synthetic process of medicine according to claim 1, wherein the operation pressure of the vacuum tower in step S3 is 10-60kPa, the bottom temperature of the vacuum tower is 45-100 ℃, the top temperature of the vacuum tower is 40-93 ℃, and the reflux ratio is 2-8.
5. The method for recycling organic solvent in waste liquid in drug synthesis process according to claim 1, wherein in step S3, the heavy component is crude tert-butyl acetate, and the drying agent used for adsorption and dehydration of the heavy component is activated alumina and molecular sieve.
6. The method for recycling organic solvent in waste liquid of pharmaceutical synthesis process according to claim 1, wherein step S4 is preceded by: drying and pre-treating the mixture of tetrahydrofuran, tertiary butanol and ethanol obtained by separation;
the drying agent used in the drying pretreatment process comprises lithium aluminum hydride and/or sodium hydride, and when the drying agent is a mixture of the lithium aluminum hydride and the sodium hydride, the mass ratio of the lithium aluminum hydride to the sodium hydride is 1: (0.5-3).
7. The method for recycling organic solvent in waste liquid in synthetic process of medicine according to claim 1, wherein in step S4, the operating pressure of the second rectifying tower is normal pressure, the bottom temperature of the second rectifying tower is 60-85 ℃, the top temperature of the second rectifying tower is 55-68 ℃, and the reflux ratio is 3-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210914097.1A CN116332713B (en) | 2022-07-28 | 2022-07-28 | Method for recycling organic solvent in waste liquid in drug synthesis process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210914097.1A CN116332713B (en) | 2022-07-28 | 2022-07-28 | Method for recycling organic solvent in waste liquid in drug synthesis process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116332713A CN116332713A (en) | 2023-06-27 |
| CN116332713B true CN116332713B (en) | 2024-03-12 |
Family
ID=86891773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210914097.1A Active CN116332713B (en) | 2022-07-28 | 2022-07-28 | Method for recycling organic solvent in waste liquid in drug synthesis process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116332713B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180442A (en) * | 2018-10-29 | 2019-01-11 | 福建师范大学福清分校 | A kind of method that the adsorbing coupled technique of extracting rectifying-recycles methyl tertiary butyl ether(MTBE) in pharmacy procedure waste liquid |
| CN112920049A (en) * | 2019-12-05 | 2021-06-08 | 湖南中创化工股份有限公司 | Method and device for preparing tert-butyl acetate |
| CN113527071A (en) * | 2021-06-17 | 2021-10-22 | 四川熔增环保科技有限公司 | Method and equipment for recovering and purifying MTBE waste solvent generated in synthesis of drug intermediate |
-
2022
- 2022-07-28 CN CN202210914097.1A patent/CN116332713B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180442A (en) * | 2018-10-29 | 2019-01-11 | 福建师范大学福清分校 | A kind of method that the adsorbing coupled technique of extracting rectifying-recycles methyl tertiary butyl ether(MTBE) in pharmacy procedure waste liquid |
| CN112920049A (en) * | 2019-12-05 | 2021-06-08 | 湖南中创化工股份有限公司 | Method and device for preparing tert-butyl acetate |
| CN113527071A (en) * | 2021-06-17 | 2021-10-22 | 四川熔增环保科技有限公司 | Method and equipment for recovering and purifying MTBE waste solvent generated in synthesis of drug intermediate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116332713A (en) | 2023-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109081767B (en) | Synthetic rectification process method and equipment for methane chloride | |
| CN107382915B (en) | Energy-saving process for separating tetrahydrofuran-methanol by heat integration extraction rectification | |
| CN105254532B (en) | A kind of method of three tower variable-pressure rectification separating acetonitrile methyl alcohol-benzene ternary azeotrope | |
| CN104230657A (en) | Novel energy-saving three-tower continuous extractive distillation technology and extractive distillation system thereof | |
| CN103664446A (en) | Technology for separating n-hexane-methylcyclopentane through extractive distillation | |
| CN116332713B (en) | Method for recycling organic solvent in waste liquid in drug synthesis process | |
| CN109678820A (en) | A kind of method of complete thermal coupling abstraction distillation separation of tetrahydrofuran-ethyl alcohol-aqueous mixtures | |
| CN100453587C (en) | Recovery and using method of solution and unreaction monomer in process of producting polymer by solution polymerization process | |
| CN113233960B (en) | Multi-effect methanol rectification process method and device for avoiding ethanol accumulation | |
| CN112920048A (en) | Preparation method of high-purity 1, 3-butanediol dimethacrylate | |
| CN116332737B (en) | Recycling method of methyl tertiary butyl ether waste solvent | |
| CN106966881B (en) | Energy-saving method for separating trichloromethane-acetone-toluene mixture by extractive distillation | |
| CN115028523A (en) | Pressure-variable-heterogeneous azeotropic rectification separation method for butanone dehydration | |
| CN215906119U (en) | Multi-effect methanol rectification process method device for avoiding ethanol accumulation | |
| CN106431880B (en) | Novel variable-pressure rectification acetone, isopropyl ether object system method | |
| CN106966867B (en) | Energy-saving process for separating methanol, ethanol and benzene by three-tower heat integration pressure swing distillation | |
| CN116332874B (en) | Separation and recovery method of waste solvent in pharmaceutical industry | |
| CN114405059B (en) | Extraction solvent organic phase for purifying citric acid and method for extracting and separating citric acid | |
| CN116332719A (en) | Method for recycling dichloromethane waste solvent | |
| CN110180327A (en) | A kind of method and system of the tail gas resource utilization containing organic amine | |
| CN215427380U (en) | Butyl acetate recovery unit | |
| CN216934753U (en) | Rectifying device for recovering toluene and dimethyl tetrahydrofuran | |
| CN111675602B (en) | System and method for rectifying and purifying ethanol and butyraldehyde from butyraldehyde mother liquor | |
| CN217661572U (en) | Energy-saving device for preparing anhydrous alcohol by using molecular sieve | |
| CN113307980B (en) | Carbazolyl porous organic polymer material containing hierarchical pores and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |