CN116283498B - Method for recovering organic solvent from waste liquid of potassium clavulanate production - Google Patents
Method for recovering organic solvent from waste liquid of potassium clavulanate production Download PDFInfo
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- 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
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- 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
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- 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
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- 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
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D503/00—Heterocyclic compounds containing 4-oxa-1-azabicyclo [3.2.0] heptane ring systems, i.e. compounds containing a ring system of the formula:, e.g. oxapenicillins, clavulanic acid derivatives; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring
- C07D503/02—Preparation
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D503/00—Heterocyclic compounds containing 4-oxa-1-azabicyclo [3.2.0] heptane ring systems, i.e. compounds containing a ring system of the formula:, e.g. oxapenicillins, clavulanic acid derivatives; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring
- C07D503/10—Heterocyclic compounds containing 4-oxa-1-azabicyclo [3.2.0] heptane ring systems, i.e. compounds containing a ring system of the formula:, e.g. oxapenicillins, clavulanic acid derivatives; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring with a carbon atom having three bonds to hetero atoms with at the most one bond to halogen, e.g. an ester or nitrile radical, directly attached in position 2
- C07D503/12—Heterocyclic compounds containing 4-oxa-1-azabicyclo [3.2.0] heptane ring systems, i.e. compounds containing a ring system of the formula:, e.g. oxapenicillins, clavulanic acid derivatives; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring with a carbon atom having three bonds to hetero atoms with at the most one bond to halogen, e.g. an ester or nitrile radical, directly attached in position 2 unsubstituted in position 6
- C07D503/14—Heterocyclic compounds containing 4-oxa-1-azabicyclo [3.2.0] heptane ring systems, i.e. compounds containing a ring system of the formula:, e.g. oxapenicillins, clavulanic acid derivatives; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring with a carbon atom having three bonds to hetero atoms with at the most one bond to halogen, e.g. an ester or nitrile radical, directly attached in position 2 unsubstituted in position 6 with hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, other than a carbon atom having three bonds to hetero atoms with at the most one bond to halogen, attached in position 3
- C07D503/16—Radicals substituted by hetero atoms or by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. an ester or nitrile radical
- C07D503/18—Radicals substituted by hetero atoms or by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. an ester or nitrile radical by oxygen atoms
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Abstract
本发明涉及一种从克拉维酸钾生产废液中回收有机溶剂的方法。该方法包括除盐工序、粗蒸工序、碱提工序和脱水工序。本发明采用精馏与渗透汽化膜脱水技术相结合的方案，结合碱提工序，有效地去除了回收溶剂中的盐和水分，显著地降低了工艺能耗，并且回收的溶剂可再利用于克拉维酸钾的制备。
The present invention relates to a method for recovering an organic solvent from potassium clavulanate production wastewater. The method comprises a desalting process, a rough distillation process, an alkali extraction process and a dehydration process. The present invention adopts a scheme combining distillation with pervaporation membrane dehydration technology, and combines the alkali extraction process to effectively remove salt and water in the recovered solvent, significantly reducing process energy consumption, and the recovered solvent can be reused in the preparation of potassium clavulanate.
Description
Technical Field
The invention belongs to the technical field of pharmacy, and relates to a method for recycling an organic solvent from waste liquid in potassium clavulanate production.
Background
Potassium clavulanate is a beta-lactamase inhibitor, is not effective when being singly used, and is often used in combination with penicillin medicines to overcome the drug resistance caused by beta-lactamase produced by microorganisms and improve the curative effect. The production of the clavulanate potassium takes clavulanate tertiary butylamine salt as a raw material, and the clavulanate tertiary butylamine salt and a salifying agent potassium isooctanoate are subjected to reaction crystallization to obtain the clavulanate potassium salt, wherein the reaction equation is as follows:
Liu Baoshu et al, entitled "research on potassium clavulanate reaction crystallization", report on the technological scheme of potassium clavulanate reaction and crystallization, and currently, the crystallization solvent of potassium clavulanate mainly comprises ethanol, isopropanol or a mixture of the two. According to analysis of the potassium clavulanate production process, the production waste liquid mainly comprises organic solvent ethanol, isopropanol or a mixture of the organic solvent ethanol and the isopropanol, uncrystallized potassium clavulanate, potassium isooctanoate and tert-butylamine isooctanoate salt generated by reaction. As an example, the pH of the production waste liquid is generally 8-10, wherein the organic solvent is ethanol, isopropanol or a mixture of ethanol and isopropanol, the ratio of ethanol to isopropanol in the mixture system of ethanol and isopropanol is the mixture of any ratio of ethanol and isopropanol, the concentration of uncrystallized potassium clavulanate is 0.1-1 wt%, the concentration of unreacted potassium iso-octoate is 0.5-2.5 wt%, the concentration of tert-butylamine iso-octoate salt generated by the reaction is 2-5 wt% and the concentration of water is 1-5 wt%.
Since potassium clavulanate is very soluble in water, the recycling standard for the recovered solvent has strict requirements for the water content of the recovered solvent in addition to strict requirements for impurity control. According to the traditional distillation recovery theory of a tower kettle, the recovery of the component waste liquid needs to be subjected to strict dehydration treatment besides desalting, isooctanoic acid removal and impurity removal. In order to achieve the above purpose, the reuse standard can be achieved through multiple rectification and extraction rectification modes. In the operation process, the problems of complex process, extraction solvent introduction and huge energy consumption exist.
With the development of inorganic pervaporation membrane technology in recent years, the inorganic pervaporation membrane technology has made great progress in the dehydration of organic solvents, and industrial production has been realized. However, in this technology, if the waste liquid is not sufficiently pretreated in the recovery of the organic solvent from the waste liquid of potassium clavulanate production, the membrane pores are seriously clogged, which affects the application of the technology.
Disclosure of Invention
The present invention has been accomplished in view of the above-mentioned problems occurring in the prior art. The invention aims to provide a method for effectively recovering an organic solvent from potassium clavulanate production waste liquid, which is simple and convenient to operate, effectively removes salt and moisture in the recovered solvent, can be reused for preparing potassium clavulanate, and simultaneously remarkably reduces the process energy consumption.
According to the invention, the method for recycling the organic solvent from the potassium clavulanate production waste liquid provided by the invention comprises the following steps:
(1) Desalting step
Adding concentrated sulfuric acid into the potassium clavulanate production waste liquid to convert the tert-butylamine iso-octoate into tert-butylamine sulfate, separating out the tert-butylamine sulfate, and filtering to obtain a feed liquid for removing the tert-butylamine sulfate;
(2) Rough steaming process
Transferring the feed liquid with the tertiary butylamine sulfate removed into a distillation tower for distillation, and collecting an organic solvent fraction with improved purity at the top of the distillation tower;
(3) Alkali extraction process
Adding an alkali salt water extractant into the organic solvent fraction collected from the tower top, stirring at 50-80 ℃, standing for layering, and obtaining an organic solvent layer with improved purity;
(4) Dehydration step
And heating and vaporizing the obtained organic solvent layer with improved purity, and separating the organic solvent from water by vaporized steam through a pervaporation membrane separation unit to obtain the purified organic solvent.
FIG. 1 is a process flow diagram of a method of the present invention for recovering an organic solvent from a waste solution of potassium clavulanate production. The method for recovering an organic solvent from a waste liquid from potassium clavulanate production according to the present invention will be described in more detail with reference to fig. 1.
As described above, the pH of the waste liquid of potassium clavulanate production is generally 8-10, wherein the organic solvent is ethanol, isopropanol or a mixture of the ethanol and the isopropanol, the concentration of uncrystallized potassium clavulanate is 0.1-1 wt%, the concentration of unreacted potassium isooctanoate is 0.5-2.5 wt%, the concentration of tert-butylamine isooctanoate salt generated by the reaction is 2-5 wt% and the concentration of water is 1-5 wt%.
In the desalting step (1), concentrated sulfuric acid is added into the waste liquid from the production of potassium clavulanate to convert the tert-butylamine iso-octoate into tert-butylamine sulfate, and the tert-butylamine sulfate is separated out, and the solution is filtered to obtain the solution for removing the tert-butylamine sulfate.
Specifically, concentrated sulfuric acid (for example, about 98% concentrated sulfuric acid by mass) is added to the potassium clavulanate production waste liquid to make the pH value of the waste liquid be 1-5.5, and preferably 2-4.5, at this time, tert-butylamine iso-octoate in the waste liquid is converted into iso-octoate and tert-butylamine sulfate, the iso-octoate is dissolved in the waste liquid, and the tert-butylamine sulfate is precipitated in a solid form. The tert-butylamine salt is filtered off by filtration, so that by this step the majority of the tert-butylamine ions can be removed as "tert-butylamine salt".
In the step (2) of the rough distillation step, the feed solution from which the tertiary butylamine salt is removed is transferred to a distillation column, distillation is carried out, and an organic solvent fraction with improved purity is collected at the top of the column.
Specifically, the feed liquid from which the tertiary butylamine salt is removed is transferred to a distillation column for distillation, wherein the distillation column is a continuous distillation column or a batch distillation column, and is preferably a continuous distillation column. Distillation is not limited and may be performed according to a conventional process in the art.
The above-mentioned feed solution from which t-butylamine sulfate has been removed is transferred to a distillation column for distillation, and an organic solvent fraction of increased purity, i.e., ethanol, isopropanol or a mixture of both of them, is collected at the top of the column, while the waste liquid remaining at the bottom of the column contains high boiling point substances such as residual t-butylamine sulfate and isooctanoic acid, and can be further processed as required. The step is carried out under the acidic condition, acidic compounds brought in by the clavulanic acid tert-butylamine in the system, such as formic acid, acetic acid, propionic acid and the like, can generate ester compounds with ethanol and isopropanol under the action of sulfuric acid, and a small amount of clavulanic acid and degradation products thereof are distilled out along with the tower kettle.
In the alkaline extraction step (3), an alkaline salt water extractant is added into the organic solvent fraction collected at the top of the tower, and the mixture is stirred for 2 to 3 hours at 50 to 80 ℃ and is stood for layering, so that an organic solvent layer with improved purity is obtained.
The method comprises the steps of adding an alkali brine extractant into an organic solvent fraction collected at the top of the tower, wherein the alkali brine extractant is an aqueous solution of potassium hydroxide and inorganic potassium salt, the inorganic potassium salt is potassium carbonate, potassium chloride or potassium nitrate, preferably potassium carbonate, the alkali brine extractant is prepared according to the following weight ratio, water is potassium hydroxide, the weight ratio of the inorganic potassium salt is 1:0.1-0.6:0.2-0.6, and the addition amount of the alkali brine extractant is 10-20% of the volume of the organic solvent fraction collected at the top of the tower.
The alkaline extraction procedure can hydrolyze ester compounds in the organic solvent fraction to form salts, the clavulanic acid and degradation products thereof are destroyed to form salts, related impurities are extracted into a water phase through liquid separation operation at 50-80 ℃, and a small amount of water in the water phase enters the organic solvent layer. Therefore, the obtained organic solvent layer with improved purity has a moisture content of 5-20wt% and a pH of 8-10.
In the step (4) of dehydration, the organic solvent layer with improved purity obtained above is heated and vaporized, and vaporized steam is separated from the organic solvent and water by a pervaporation membrane separation unit, so as to obtain dehydrated and purified organic solvent.
The heating and vaporization of the organic solvent layer with the improved purity can be performed by adopting a vaporization tower, wherein the vaporization tower can be an intermittent pressurized rectifying tower and is used for preheating the organic solvent of the organic solvent layer to 90-150 ℃ and then entering the pervaporation membrane separation unit in a steam form, and the steam pressure is 0.1-0.3 MPa.
The pervaporation membrane separation unit is formed by combining 10-50 membrane separators in parallel and series to achieve different treatment requirements and production capacities. The membrane adopted by the membrane separator is a water permeable membrane, preferably a chitosan membrane, a PVA membrane, a PVDF membrane, a sodium alginate membrane or a molecular sieve membrane.
In the dehydration process, the pervaporation membrane separation unit takes a pervaporation membrane as a boundary, and can be briefly called a high-pressure side and a low-pressure side, wherein the high-pressure side is high-pressure solvent steam input through a vaporization tower, the low-pressure side is connected with a vacuum system, the pressure is maintained at 200Pa-5000Pa through suction of a vacuum pump, water molecules permeate the pervaporation membrane under the pressure difference between the high-pressure side and the low-pressure side, the high-pressure side enters the low-pressure side, and therefore separation of the water molecules and an organic solvent is achieved, and separated two phases are respectively condensed to obtain recovered solvent and water.
The resulting dehydrated and purified organic solvent has a moisture content of 0.1wt% to 0.3wt%.
Advantageous effects
Compared with the existing distillation technology, the invention adopts a scheme of combining rectification and pervaporation membrane dehydration technology. The invention has the advantage of no introduction of organic extraction solvent, thereby avoiding the operation of extraction and rectification, reducing the influence of the organic extraction solvent on the product quality, saving a large amount of organic solvent and energy consumption and saving the recovery cost.
The alkaline extraction process of the alkaline brine extractant provided by the invention is different from the traditional alkaline dehydration operation, and through the alkaline extraction process, the water content of the feed liquid is increased, but the quality of the liquid to be recovered is obviously improved, the ester impurities and macromolecular organic compounds in the recovered solvent are thoroughly degraded, and the degradation products are extracted into an alkaline brine phase, so that the quality of the recovered solvent is improved, and the problem of pervaporation blockage is solved.
The dehydration process provided by the invention adopts an intermittent pressurized rectifying tower to replace the traditional heat exchanger vaporization mode, thereby achieving the purposes of vaporization feeding and separation of salt compounds in organic solvents, reducing the pressure of salt discharge and blockage during the operation of a pervaporation membrane separation unit and improving the working efficiency.
The purity of the organic solvent product recovered by the method can be controlled to be more than 99%, the water content can be controlled to be less than 0.3%, and the method has the condition of recycling in the production of potassium clavulanate.
Drawings
FIG. 1 is a process flow diagram of a method of the present invention for recovering an organic solvent from a waste solution of potassium clavulanate production.
Detailed Description
The method of the present invention for recovering an organic solvent from a waste liquid from potassium clavulanate production will be described in further detail by way of examples, and the scope of the present invention is not limited to the following examples, which are given for illustrative purposes only and are not intended to limit the present invention in any way.
Example 1
9500L (waste liquid components: ethanol, water content 5%, pH 8.3, potassium clavulanate concentration 0.5%, potassium iso-octoate concentration 0.8%, tert-butylamine iso-octoate salt concentration 3%, calculated in weight percentage) of waste liquid of potassium clavulanate production ethanol is taken, stirring is started, concentrated sulfuric acid is added to adjust pH=4, and solid of tert-butylamine sulfate is separated out in the process. Filtering the feed liquid by a centrifugal machine, wherein filter residues can be used for recycling tert-butylamine, and collecting filtrate to obtain feed liquid with tert-butylamine sulfate removed.
The continuous rectifying column is opened, the above-mentioned feed liquid is fed into the continuous rectifying column to make rectification, the ethyl alcohol fraction whose purity is raised at 73 deg.C-80 deg.C (based on local air pressure) is collected at about 8600L at top of column, and the waste liquor containing isooctanoic acid etc. is collected at bottom of column (if necessary, further treated).
360Kg of potassium hydroxide and 180kg of potassium chloride are added into 700kg of water to be mixed and dissolved, so as to prepare the alkaline brine extractant of the aqueous solution of potassium chloride and potassium hydroxide. The extractant was mixed with the above fraction and stirred to a temperature of 70℃and stirred for 2 hours with heat preservation, followed by 1 hour of standing and then delamination while hot to give an extract of about 8900L, which had a moisture content of 7.8wt% and a pH of 8.9.
Transferring the extract into a pressurized rectifying tower, starting heating distillation, and enabling high-temperature gas at the top of the tower to enter a pervaporation membrane separation unit when the steam pressure in the kettle reaches 0.15 MPa. Wherein, alcohol-water separation is carried out by adopting a pervaporation membrane separation unit consisting of a membrane separator consisting of PVDF membranes, the high pressure is measured at 0.15MPa, the low pressure side pressure is controlled at 3000Pa, and the recovered ethanol after water removal is about 8000L, the water content is 0.15wt% and the purity is 99.3%.
Example 2
11000L of waste liquid from the production of isopropanol by using potassium clavulanate (the waste liquid comprises isopropanol as a solvent, water content of 2%, pH of 9.1, concentration of potassium clavulanate of 0.3%, concentration of potassium isooctanoate of 0.9% and concentration of tert-butylamine isooctanoate salt of 2.6% in percentage by weight) is taken, stirring is started, concentrated sulfuric acid is added to adjust pH to be 3, and in the process, the solid of tert-butylamine sulfate is separated out. Filtering the feed liquid by a centrifugal machine, wherein filter residues can be used for recycling tert-butylamine, and collecting filtrate to obtain feed liquid with tert-butylamine sulfate removed.
The continuous rectifying tower is opened, the feed liquid is fed into the continuous rectifying tower for rectification, about 10000L of propanol fraction with the purity improved at 75-85 ℃ is collected at the top of the tower, and waste liquid containing isooctanoic acid and the like (further treatment can be carried out according to the requirement) is collected at the bottom of the tower.
Adding 500kg of potassium hydroxide and 300kg of potassium carbonate into 1000kg of water, mixing and dissolving to prepare the alkaline brine extractant of the aqueous solution of potassium carbonate and potassium hydroxide. The extractant was mixed with the above fraction and stirred to a temperature of 65℃and stirred for 3 hours with heat preservation, followed by 1 hour of standing and then delamination while hot to give about 10500L of an extract having a moisture content of 8.2wt% and a pH of 9.6.
Transferring the extract into a pressurized rectifying tower, starting heating distillation, and enabling high-temperature gas at the top of the tower to enter a pervaporation membrane separation unit when the steam pressure in the kettle reaches 0.2 MPa. Wherein, alcohol-water separation is carried out by adopting a pervaporation membrane separation unit consisting of a membrane separator consisting of NaA membranes, the high pressure is measured at 0.2MPa, the low pressure side pressure is controlled at 1000Pa, and the recovered isopropanol after water removal is 9500L, the water content is 0.11wt% and the purity is 99.5%.
Example 3
12500L of mixed waste liquid of ethanol and isopropanol produced by potassium clavulanate (the waste liquid component is ethanol: isopropanol=1:1V/V, the water content is 4.3%, the pH is 8.5, the potassium clavulanate concentration is 0.5%, the potassium isooctanoate concentration is 1.1%, the tert-butylamine isooctanoate salt concentration is 2.2% by weight percent) is taken, stirring is started, concentrated sulfuric acid is added to adjust the pH to=3.5, and the tert-butylamine sulfate solid is separated out in the process. Filtering the feed liquid by a centrifugal machine, wherein filter residues can be used for recycling tert-butylamine, and collecting filtrate to obtain feed liquid with tert-butylamine sulfate removed.
The continuous rectifying column is opened, the above-mentioned feed liquid is fed into the continuous rectifying column to make rectification, about 11000L of ethyl alcohol isopropyl alcohol fraction with high purity at 70-85 deg.C is collected at top of column, and waste liquor containing isooctanoic acid and the like is collected at bottom of column (if necessary, further treatment can be made).
300Kg of potassium hydroxide and 300kg of potassium nitrate are added into 1500kg of water to be mixed and dissolved, and then the alkaline brine extractant of the aqueous solution of potassium nitrate and potassium hydroxide is prepared. The extractant was mixed with the above fractions and then stirred to 80℃and stirred for 2 hours with heat preservation, followed by 1 hour of standing and then hot stratification to give an extract of about 11900L, which had a moisture content of 14% by weight and a pH of 9.9.
Transferring the extract into a pressurized rectifying tower, starting heating distillation, and enabling high-temperature gas at the top of the tower to enter a pervaporation membrane separation unit when the steam pressure in the kettle reaches 0.23 MPa. Wherein, alcohol-water separation is carried out by adopting a pervaporation membrane separation unit consisting of a membrane separator consisting of NaA membranes, the high pressure measurement pressure is 0.23MPa, the low pressure side pressure is controlled at 5000Pa, and the recovered ethanol isopropanol mixed solution after water removal is about 10000L, the water content is 0.25wt% and the purity is 99.2%.
Claims (9)
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| CN108558909A (en) * | 2018-05-17 | 2018-09-21 | 国药集团威奇达药业有限公司 | The method of active ingredient in synthetical recovery clavulanic acid tert-butylamine salt crystalline mother solution |
| CN108773924A (en) * | 2018-05-03 | 2018-11-09 | 国药集团威奇达药业有限公司 | The comprehensive recovering process of active ingredient in clavulanic acid extraction raffinate |
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| CN113979856B (en) * | 2021-11-09 | 2024-04-19 | 国药集团威奇达药业有限公司 | Method for recovering tert-butylamine and isooctanoate from potassium clavulanate kettle residual liquid |
| CN113979872B (en) * | 2021-11-09 | 2024-07-26 | 国药集团威奇达药业有限公司 | Comprehensive recovery method of active ingredients in potassium clavulanate kettle residual liquid |
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| CN108773924A (en) * | 2018-05-03 | 2018-11-09 | 国药集团威奇达药业有限公司 | The comprehensive recovering process of active ingredient in clavulanic acid extraction raffinate |
| CN108558909A (en) * | 2018-05-17 | 2018-09-21 | 国药集团威奇达药业有限公司 | The method of active ingredient in synthetical recovery clavulanic acid tert-butylamine salt crystalline mother solution |
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