CN116332874B - Separation and recovery method of waste solvent in pharmaceutical industry - Google Patents
Separation and recovery method of waste solvent in pharmaceutical industry Download PDFInfo
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- CN116332874B CN116332874B CN202210914070.2A CN202210914070A CN116332874B CN 116332874 B CN116332874 B CN 116332874B CN 202210914070 A CN202210914070 A CN 202210914070A CN 116332874 B CN116332874 B CN 116332874B
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- 239000010887 waste solvent Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000011084 recovery Methods 0.000 title claims abstract description 32
- 238000000926 separation method Methods 0.000 title claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 254
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 106
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011259 mixed solution Substances 0.000 claims abstract description 42
- 238000004821 distillation Methods 0.000 claims abstract description 38
- 238000000622 liquid--liquid extraction Methods 0.000 claims abstract description 28
- 238000000638 solvent extraction Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000012043 crude product Substances 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 238000005373 pervaporation Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003463 adsorbent Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000000741 silica gel Substances 0.000 claims description 15
- 229910002027 silica gel Inorganic materials 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 69
- 230000000694 effects Effects 0.000 description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 9
- 239000002274 desiccant Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000002906 medical waste Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 208000010445 Chilblains Diseases 0.000 description 1
- 206010008528 Chillblains Diseases 0.000 description 1
- 206010011985 Decubitus ulcer Diseases 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 208000004210 Pressure Ulcer Diseases 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- -1 amine compound Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 229940058302 antinematodal agent piperazine and derivative Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000010826 pharmaceutical waste Substances 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
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- Chemical & Material Sciences (AREA)
- Organic 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 recovery, and discloses a separation and recovery method of waste solvents in the pharmaceutical industry, which comprises the following steps: taking a waste solvent containing piperazine, n-hexane, ethanol and water, introducing the waste solvent into a rectifying tower for rectification, extracting a mixed solution of the n-hexane, the ethanol and the water from the top of the rectifying tower, and extracting a piperazine crude product from the tower kettle; adsorbing and drying the piperazine crude product by an adsorbent to obtain anhydrous piperazine; introducing an extractant into the obtained mixed solution of n-hexane, ethanol and water, and performing liquid-liquid extraction to obtain industrial n-hexane at the upper layer and ethanol-water mixed solution at the lower layer; and (3) conveying the obtained ethanol and water mixed solution to a distillation tower for distillation, extracting a mixture of ethanol and water from the tower top, and dehydrating the mixture by entering a pervaporation membrane in a steam form to obtain the industrial grade absolute ethanol. The recovery method provided by the invention has the characteristics of high yield, low energy consumption, good quality, capability of recycling, simple and convenient production process and stable operation, and is suitable for industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of separation and recovery of medical waste solvents, in particular to a separation and recovery method of a mixed waste solvent containing piperazine, cyclohexane and ethanol.
Background
Piperazine is also called hexahydropiperazine and para-diazane, is an important hexacyclic amine compound with a molecular formula of C 4 H 10 N 2 The molecular weight is 86.14, which is colorless transparent needle-like or leaf-like crystal with mild ammonia taste. Piperazine and derivatives thereofThe piperazine is an important fine chemical and medical intermediate, has wide application fields, has twenty or more medicaments produced by taking piperazine as a raw material, is mainly used for preparing medicaments such as insect expelling, tuberculosis resisting, bacteria resisting and the like, and can be used as an anti-inflammatory agent, and can be used for preventing and treating diabetes, obesity and the like. Piperazine has wide application and high economic value.
Cyclohexane is an organic compound, and is referred to as hexahydrobenzene, and has the chemical formula C 6 H 12 Is colorless and has a pungent smell, is insoluble in water, is soluble in most organic solvents, is extremely easy to burn, is often used as a general solvent, a chromatographic standard substance and is used for organic synthesis, is mainly used for manufacturing cyclohexanol and cyclohexanone, and further produces adipic acid and caprolactam, and is a monomer for producing polyamide. Cyclohexane is also used in the pharmaceutical industry, mainly for the synthesis of pharmaceutical intermediates.
Ethanol is also called alcohol, has fat-solubility, is colorless, inflammable and volatile liquid, has pungent mellow smell, can be mixed with most organic solvents, is more soluble in water, is widely used in wine industry, organic synthesis, industrial solvents, antifreezing agents and dyes, is mainly used in industries such as chemical industry, pharmacy, synthetic fibers, synthetic resins, synthetic rubber, plastics and the like, and is mainly used in clinic for cleaning medical instruments, sterilizing and disinfecting, preventing pressure sores and chilblains, treating abstinence syndrome, pathological tissue fixing liquid and the like.
Along with the continuous development of the pharmaceutical industry, related medical raw materials and intermediates are more and more widely applied, and due to the wide application of piperazine, cyclohexane, ethanol and the like in the pharmaceutical industry, a large amount of medical waste solvents consisting of the piperazine, cyclohexane, ethanol and the like can be generated, if the medical waste solvents are improperly treated, not only can environmental pollution be caused, but also a large amount of resources can be wasted, and the technology for recycling the medical waste is available in the prior art, but the recycled products are mostly high in purity or water content, cannot be effectively utilized, and have a limited application range.
Disclosure of Invention
In view of the above, the invention provides a method for separating and recovering waste solvents in the pharmaceutical industry, which aims to solve the problems that the existing pharmaceutical waste solvents are difficult to separate and recover or the separation effect is poor, so that the application range of recovered products is limited.
In order to solve the technical problems, the invention adopts the following technical scheme:
a separation and recovery method of waste solvent in the pharmaceutical industry comprises the following steps:
s1, taking a waste solvent containing piperazine, n-hexane, ethanol and water, introducing the waste solvent into a rectifying tower for rectification, extracting a mixed solution of the n-hexane, the ethanol and the water from the tower top, and extracting a piperazine crude product from the tower bottom;
s2, adsorbing and drying the piperazine crude product by an adsorbent to obtain anhydrous piperazine;
s3, introducing an extractant into the mixed solution of normal hexane, ethanol and water obtained in the step S1, and performing liquid-liquid extraction to obtain industrial-grade normal hexane on the upper layer and ethanol-water mixed solution on the lower layer;
and S4, conveying the ethanol and water mixed solution obtained in the step S3 to a distillation tower for distillation, extracting a mixture of ethanol and water from the tower top, and dehydrating the mixture in a steam form in a pervaporation membrane to obtain industrial grade absolute ethanol.
Preferably, in the above separation and recovery method of the waste solvent in the pharmaceutical industry, the adsorbent in step S2 is sodium hydroxide and/or color-changing silica gel.
Preferably, in the above separation and recovery method of the waste solvent in the pharmaceutical industry, the step S3 further includes the following steps:
A. detecting the content of ethanol water solution and ethanol in the mixed solution of n-hexane, ethanol and water;
B. and determining the adding amount of the extractant according to the ratio of the ethanol content to the ethanol water solution content.
Preferably, in the separation and recovery method of the waste solvent in the pharmaceutical industry, when the ratio of the ethanol content to the ethanol aqueous solution content is lower than 35%, no extractant is required to be added.
Preferably, in the separation and recovery method of the waste solvent in the pharmaceutical industry, when the ratio of the ethanol content to the ethanol aqueous solution content is greater than or equal to 35%, an extractant is introduced into the n-hexane, ethanol and water mixed solution until the ratio of the ethanol content to the ethanol aqueous solution content is lower than 35%.
Experimental research shows that if the ratio of the ethanol content to the ethanol aqueous solution content is lower than 35%, n-hexane can be well layered with ethanol and water, and an extraction agent is not required to be added, but a good extraction effect can be achieved only by using the aqueous solution in the mixed solution of n-hexane, ethanol and water; if the ratio of the ethanol content to the ethanol aqueous solution content is higher than 35%, the ethanol aqueous solution is partially miscible with n-hexane, and if no additional extractant is added, the n-hexane cannot be extracted effectively.
Preferably, in the separation and recovery method of the waste solvent in the pharmaceutical industry, the liquid-liquid extraction temperature in the step S3 is 10-38 ℃;
further preferably, the liquid-liquid extraction temperature in step S3 is 20 ℃.
Preferably, in the above separation and recovery method of the waste solvent in pharmaceutical industry, the mixture of ethanol and water in step S4 is 0.1-3m 3 The rate of/h enters the pervaporation membrane;
it is further preferred that the mixture of ethanol and water in step S4 is 1-2m 3 The rate of/h enters the pervaporation membrane.
Preferably, in the above separation and recovery method of the waste solvent in pharmaceutical industry, in the step S4, the temperature of the top of the distillation column is 60-90 ℃, the temperature of the bottom of the distillation column is 90-120 ℃, and the reflux ratio is 0.1-2.
Preferably, in the method for separating and recovering the waste solvent in the pharmaceutical industry, the aqueous solution extracted from the tower bottom of the distillation tower in the step S4 is used as the extractant for recycling, so that recycling of water resources can be realized, and energy consumption is reduced.
The invention provides a separation and recovery method of waste solvent in the pharmaceutical industry, which has the beneficial effects that compared with the prior art:
the invention separates piperazine, normal hexane, ethanol and water through a series of low-energy-consumption separation procedures such as rectification, adsorption drying, liquid-liquid extraction, distillation, pervaporation membrane dehydration and the like, and respectively reaches the industrial level standard, thereby realizing the recycling of waste solvents in the pharmaceutical industry; in addition, the adsorption drying procedure and the drying agent are selected so that the piperazine performance obtained by separation is more excellent; according to the invention, the solvent utilization is maximized and the energy consumption is reduced by controlling the addition amount of the extractant and the extraction temperature in the liquid-liquid extraction process;
the recovery method provided by the invention has the characteristics of high yield, low energy consumption, good quality, capability of recycling, simple and convenient production process and stable operation, and is suitable for industrial large-scale 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
The embodiment provides a separation and recovery method of waste solvent in the pharmaceutical industry, which comprises the following steps:
s1, taking a waste solvent containing 4.5% of piperazine, 39% of normal hexane, 55.7% of ethanol and 0.8% of water, introducing the waste solvent into a rectifying tower for rectification, extracting a mixed solution of normal hexane, ethanol and water from the top of the rectifying tower, and extracting a piperazine crude product from the bottom of the rectifying tower;
s2, adsorbing and drying the piperazine crude product by sodium hydroxide and color-changing silica gel in sequence to obtain anhydrous piperazine;
s3, introducing an aqueous solution with the volume 1.2 times of the volume of the waste solvent into the mixed solution of normal hexane, ethanol and water for liquid-liquid extraction, wherein the liquid-liquid extraction temperature is 20 ℃, the upper layer is obtained as industrial-grade normal hexane, and the lower layer is obtained as ethanol and water mixed solution;
s4, conveying the ethanol and water mixed solution obtained in the step S3 to a distillation tower for distillation, wherein the temperature of the top of the distillation tower is 80 ℃, the temperature of a tower kettle is 110 ℃, the reflux ratio is 0.8, and extracting the gas phase of the ethanol and water mixture from the top of the distillation tower at 2m 3 Rate of/hAnd (3) dehydrating by penetrating into a vaporization membrane to obtain industrial grade absolute ethyl alcohol.
Example 2
The embodiment provides a separation and recovery method of waste solvent in the pharmaceutical industry, which comprises the following steps:
s1, taking a waste solvent containing 4.5% of piperazine, 64.5% of n-hexane, 30% of ethanol and 1% of water, introducing the waste solvent into a rectifying tower for rectification, extracting a mixed solution of n-hexane, ethanol and water from the top of the rectifying tower, and extracting a piperazine crude product from the bottom of the rectifying tower;
s2, adsorbing and drying the piperazine crude product by sodium hydroxide to obtain anhydrous piperazine;
s3, introducing an aqueous solution with the volume of 0.8 times of the volume of the waste solvent into the mixed solution of normal hexane, ethanol and water for liquid-liquid extraction, wherein the liquid-liquid extraction temperature is 28 ℃, the upper layer is obtained as industrial-grade normal hexane, and the lower layer is obtained as ethanol and water mixed solution;
s4, conveying the ethanol and water mixed solution obtained in the step S3 to a distillation tower for distillation, wherein the temperature of the top of the distillation tower is 90 ℃, the temperature of a tower kettle is 120 ℃, the reflux ratio is 1.5, and extracting the gas phase of the ethanol and water mixture from the top of the distillation tower at 1m 3 And (3) dehydrating the mixture at the rate of/h in a pervaporation membrane to obtain industrial grade absolute ethyl alcohol.
Example 3
The embodiment provides a separation and recovery method of waste solvent in the pharmaceutical industry, which comprises the following steps:
s1, taking a waste solvent containing 4% of piperazine, 30% of normal hexane, 60.8% of ethanol and 5.2% of water, introducing the waste solvent into a rectifying tower for rectification, extracting a mixed solution of normal hexane, ethanol and water from the top of the rectifying tower, and extracting a piperazine crude product from the bottom of the rectifying tower;
s2, adsorbing and drying the piperazine crude product through color-changing silica gel to obtain anhydrous piperazine;
s3, introducing an aqueous solution with the volume 1.5 times of the volume of the waste solvent into the mixed solution of normal hexane, ethanol and water for liquid-liquid extraction, wherein the liquid-liquid extraction temperature is 10 ℃, the upper layer is obtained as industrial-grade normal hexane, and the lower layer is obtained as ethanol and water mixed solution;
s4, conveying the ethanol and water mixed solution obtained in the step S3 to a distillation tower for distillation,the temperature of the top of the distillation column is 60 ℃, the temperature of the bottom of the distillation column is 90 ℃, the reflux ratio is 2, and the gas phase of the mixture of ethanol and water is extracted from the top of the distillation column at 3m 3 And (3) dehydrating the mixture at the rate of/h in a pervaporation membrane to obtain industrial grade absolute ethyl alcohol.
Example 4
The embodiment provides a separation and recovery method of waste solvent in the pharmaceutical industry, which comprises the following steps:
s1, taking a waste solvent containing 10% of piperazine, 75% of normal hexane, 13% of ethanol and 2% of water, introducing the waste solvent into a rectifying tower for rectification, extracting a mixed solution of normal hexane, ethanol and water from the top of the rectifying tower, and extracting a piperazine crude product from the bottom of the rectifying tower;
s2, adsorbing and drying the piperazine crude product by sodium hydroxide and color-changing silica gel in sequence to obtain anhydrous piperazine;
s3, introducing aqueous solution with the volume of 0.3 times of the volume of the waste solvent into the mixed solution of normal hexane, ethanol and water for liquid-liquid extraction, wherein the liquid-liquid extraction temperature is 38 ℃, the upper layer is obtained as industrial-grade normal hexane, and the lower layer is obtained as ethanol and water mixed solution;
s4, conveying the ethanol and water mixed solution obtained in the step S3 to a distillation tower for distillation, wherein the temperature of the top of the distillation tower is 70 ℃, the temperature of a tower kettle is 100 ℃, the reflux ratio is 0.1, and extracting the gas phase of the ethanol and water mixture from the top of the distillation tower to be 0.8m 3 And (3) dehydrating the mixture at the rate of/h in a pervaporation membrane to obtain industrial grade absolute ethyl alcohol.
Example 5
The embodiment provides a separation and recovery method of waste solvent in the pharmaceutical industry, which comprises the following steps:
s1, taking a waste solvent containing 3% of piperazine, 43% of normal hexane, 48.3% of ethanol and 5.7% of water, introducing the waste solvent into a rectifying tower for rectification, extracting a mixed solution of normal hexane, ethanol and water from the top of the rectifying tower, and extracting a piperazine crude product from the bottom of the rectifying tower;
s2, adsorbing and drying the piperazine crude product through color-changing silica gel to obtain anhydrous piperazine;
s3, introducing aqueous solution with the same volume as the waste solvent into the mixed solution of normal hexane, ethanol and water for liquid-liquid extraction, wherein the liquid-liquid extraction temperature is 10 ℃, the upper layer is obtained as industrial-grade normal hexane, and the lower layer is obtained as ethanol and water mixed solution;
s4, conveying the ethanol and water mixed solution obtained in the step S3 to a distillation tower for distillation, wherein the temperature of the top of the distillation tower is 85 ℃, the temperature of a tower kettle is 115 ℃, the reflux ratio is 1.2, and extracting the gas phase of the ethanol and water mixture from the top of the distillation tower to be 0.1m 3 And (3) dehydrating the mixture at the rate of/h in a pervaporation membrane to obtain industrial grade absolute ethyl alcohol.
Example 6
The embodiment provides a separation and recovery method of waste solvent in the pharmaceutical industry, which comprises the following steps:
s1, taking a waste solvent containing 5.5% of piperazine, 61.3% of n-hexane, 10% of ethanol and 23.2% of water, introducing the waste solvent into a rectifying tower for rectification, extracting a mixed solution of n-hexane, ethanol and water from the top of the rectifying tower, and extracting a piperazine crude product from the bottom of the rectifying tower;
s2, adsorbing and drying the piperazine crude product by sodium hydroxide to obtain anhydrous piperazine;
s3, performing liquid-liquid extraction on the mixed solution of n-hexane, ethanol and water at the temperature of 15 ℃, taking water in the mixed solution as an extractant, obtaining industrial n-hexane at the upper layer, and obtaining the mixed solution of ethanol and water at the lower layer;
s4, conveying the ethanol and water mixed solution obtained in the step S3 to a distillation tower for distillation, wherein the temperature of the top of the distillation tower is 75 ℃, the temperature of a tower kettle is 110 ℃, the reflux ratio is 0.8, and extracting the gas phase of the ethanol and water mixture from the top of the distillation tower at 1.5m 3 And (3) dehydrating the mixture at the rate of/h in a pervaporation membrane to obtain industrial grade absolute ethyl alcohol.
The invention detects the performance indexes of piperazine, normal hexane and ethanol recovered in examples 1-6 respectively, and the detection results are shown in tables 1-3.
TABLE 1 piperazine quality test results
TABLE 2 n-hexane quality detection results
TABLE 3 ethanol quality detection results
Comparative example 1
The comparative example provides a method for separating and recovering waste solvent in the pharmaceutical industry, which is basically the same as that of example 1, and only differs in the type and order of addition of the drying agent in step S2.
The comparative example uses desiccant as a variable to study the effect of desiccant on piperazine recovery, and specifically uses sodium hydroxide, allochroic silica gel, sodium hydroxide and allochroic silica gel, allochroic silica gel and sodium hydroxide, calcium chloride, activated alumina and allochroic silica gel, sodium hydroxide and activated alumina as desiccant, and the effect on piperazine recovery is shown in table 4.
TABLE 4 influence of drying agent on piperazine recovery effect
| Type of desiccant | Purity (wt%) | Moisture (wt%) |
| Sodium hydroxide | 99.76 | 0.008 |
| Color-changing silica gel | 99.70 | 0.007 |
| Sodium hydroxide and color-changing silica gel | 99.90 | 0.003 |
| Color-changing silica gel and sodium hydroxide | 99.83 | 0.006 |
| Calcium chloride | 99.69 | 0.012 |
| Activated alumina | 99.75 | 0.011 |
| Activated alumina and allochroic silica gel | 99.83 | 0.009 |
| Sodium hydroxide and activated alumina | 99.81 | 0.008 |
It can be seen from table 4 that the determination of the type of drying agent has a very important influence on the piperazine recovery effect, and that the purity and water content of piperazine can be optimized when the piperazine crude product is dried sequentially with sodium hydroxide and allochroic silica gel.
Comparative example 2
The comparative example provides a method for separating and recovering waste solvent in the pharmaceutical industry, which is basically the same as that of example 1, and only differs in the liquid-liquid extraction temperature in step S3.
In this comparative example, the effect of the liquid-liquid extraction temperature on the recovery effect of n-hexane was investigated by using the liquid-liquid extraction temperature as a variable, and specifically, the effect of liquid-liquid extraction was performed at temperatures of 0℃C, 5℃C, 10℃C, 20℃C, 30℃C, 38℃C and 40℃C, respectively, and the effect thereof on the recovery effect of n-hexane was shown in Table 5.
TABLE 5 influence of liquid-liquid extraction temperature on n-hexane recovery effect
| Liquid-liquid extraction temperature | Purity (wt/%) | Density (20 ℃ C.) (g/mL) | Evaporation residue (wt/%) | Moisture (wt/%) |
| 0℃ | 82.6 | 0.658 | 0.001 | 0.035 |
| 5℃ | 93.4 | 0.659 | 0.0009 | 0.021 |
| 10℃ | 97.5 | 0.661 | 0.0007 | 0.007 |
| 20℃ | 98.2 | 0.660 | 0.0007 | 0.005 |
| 30℃ | 98.1 | 0.660 | 0.0006 | 0.005 |
| 38℃ | 97.8 | 0.661 | 0.0006 | 0.004 |
| 40℃ | 95.1 | 0.661 | 0.0005 | 0.029 |
As is clear from Table 5, when the liquid-liquid extraction temperature is too high or too low, cyclohexane meeting the industrial-grade standard cannot be obtained, the temperature has a great influence on the purity, moisture and the like of the recovered cyclohexane, and when the temperature is too high, cyclohexane, ethanol and water are mutually soluble and difficult to separate, so that the liquid-liquid extraction temperature is selected to be 10-38 ℃, and the energy consumption and the recovery effect are comprehensively considered, and the liquid-liquid extraction temperature is optimal to be 20 ℃.
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 (5)
1. The separation and recovery method of the waste solvent in the pharmaceutical industry is characterized by comprising the following steps of:
s1, taking a waste solvent containing piperazine, n-hexane, ethanol and water, introducing the waste solvent into a rectifying tower for rectification, extracting a mixed solution of the n-hexane, the ethanol and the water from the tower top, and extracting a piperazine crude product from the tower bottom;
s2, adsorbing and drying the piperazine crude product by an adsorbent to obtain anhydrous piperazine;
s3, introducing an extractant into the mixed solution of normal hexane, ethanol and water obtained in the step S1, and performing liquid-liquid extraction to obtain industrial-grade normal hexane on the upper layer and ethanol-water mixed solution on the lower layer;
s4, conveying the ethanol and water mixed solution obtained in the step S3 to a distillation tower for distillation, extracting a mixture of ethanol and water from the tower top, and dehydrating the mixture in a steam form in a pervaporation membrane to obtain industrial grade absolute ethanol;
step S3 further comprises the steps of:
A. detecting the content of ethanol water solution and ethanol in the mixed solution of n-hexane, ethanol and water;
B. determining the addition amount of the extractant according to the ratio of the ethanol content to the ethanol water solution content;
when the ratio of the ethanol content to the ethanol aqueous solution content is lower than 35%, an extractant is not required to be added;
when the ratio of the ethanol content to the ethanol water solution content is more than or equal to 35%, introducing an extractant into the n-hexane, ethanol and water mixed solution until the ratio of the ethanol content to the ethanol water solution content is lower than 35%;
the liquid-liquid extraction temperature in the step S3 is 10-38 ℃.
2. The method for separating and recovering waste solvent in pharmaceutical industry according to claim 1, wherein the adsorbent in step S2 is sodium hydroxide and/or allochroic silica gel.
3. The method for separating and recovering waste solvent from pharmaceutical industry according to claim 1, wherein the mixture of ethanol and water in step S4 is 0.1-3m 3 The rate of/h enters the pervaporation membrane.
4. The method for separating and recovering waste solvent in pharmaceutical industry according to claim 1, wherein in step S4, the temperature of the top of the distillation column is 60-90 ℃, the temperature of the bottom of the distillation column is 90-120 ℃, and the reflux ratio is 0.1-2.
5. The method for separating and recovering waste solvent in pharmaceutical industry according to claim 1, wherein the aqueous solution extracted from the distillation column bottom in step S4 is recycled as extractant.
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| CN113527057A (en) * | 2021-06-15 | 2021-10-22 | 四川熔增环保科技有限公司 | Method for recovering and purifying ethanol-ethyl acetate-piperazine waste solvent |
| CN113549029A (en) * | 2021-06-15 | 2021-10-26 | 四川熔增环保科技有限公司 | Method for recovering and purifying mixed waste solvent of ethanol, normal hexane, piperazine and water |
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| CN113527057A (en) * | 2021-06-15 | 2021-10-22 | 四川熔增环保科技有限公司 | Method for recovering and purifying ethanol-ethyl acetate-piperazine waste solvent |
| CN113549029A (en) * | 2021-06-15 | 2021-10-26 | 四川熔增环保科技有限公司 | Method for recovering and purifying mixed waste solvent of ethanol, normal hexane, piperazine and water |
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