CN116283498A - Method for recovering organic solvent from potassium clavulanate production waste liquid - Google Patents
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- CN116283498A CN116283498A CN202310215536.4A CN202310215536A CN116283498A CN 116283498 A CN116283498 A CN 116283498A CN 202310215536 A CN202310215536 A CN 202310215536A CN 116283498 A CN116283498 A CN 116283498A
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- 239000003960 organic solvent Substances 0.000 title claims abstract description 65
- 239000007788 liquid Substances 0.000 title claims abstract description 59
- ABVRVIZBZKUTMK-JSYANWSFSA-M potassium clavulanate Chemical compound [K+].[O-]C(=O)[C@H]1C(=C/CO)/O[C@@H]2CC(=O)N21 ABVRVIZBZKUTMK-JSYANWSFSA-M 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 239000012528 membrane Substances 0.000 claims abstract description 43
- 238000005373 pervaporation Methods 0.000 claims abstract description 23
- 238000000605 extraction Methods 0.000 claims abstract description 15
- 230000018044 dehydration Effects 0.000 claims abstract description 13
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 13
- 238000011033 desalting Methods 0.000 claims abstract description 6
- 238000010025 steaming Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 238000004821 distillation Methods 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 21
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 19
- BGMXQLNMDVZYRF-UHFFFAOYSA-N tert-butylazanium;hydrogen sulfate Chemical compound CC(C)(C)[NH3+].OS([O-])(=O)=O BGMXQLNMDVZYRF-UHFFFAOYSA-N 0.000 claims description 18
- 239000012267 brine Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 230000008016 vaporization Effects 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 238000009834 vaporization Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 238000001944 continuous distillation Methods 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 238000000998 batch distillation Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 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 2
- 239000002904 solvent Substances 0.000 abstract description 14
- 238000004064 recycling Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 229940038649 clavulanate potassium Drugs 0.000 abstract description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 9
- -1 clavulanate tertiary butylamine salt Chemical class 0.000 description 9
- 208000005156 Dehydration Diseases 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- HZZVJAQRINQKSD-UHFFFAOYSA-N Clavulanic acid Natural products OC(=O)C1C(=CCO)OC2CC(=O)N21 HZZVJAQRINQKSD-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HZZVJAQRINQKSD-PBFISZAISA-N clavulanic acid Chemical compound OC(=O)[C@H]1C(=C/CO)/O[C@@H]2CC(=O)N21 HZZVJAQRINQKSD-PBFISZAISA-N 0.000 description 4
- 229960003324 clavulanic acid Drugs 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- SXWZSWLBMCNOPC-UHFFFAOYSA-M potassium;6-methylheptanoate Chemical compound [K+].CC(C)CCCCC([O-])=O SXWZSWLBMCNOPC-UHFFFAOYSA-M 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007857 degradation product Substances 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229940090805 clavulanate Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AINBZKYUNWUTRE-UHFFFAOYSA-N ethanol;propan-2-ol Chemical compound CCO.CC(C)O AINBZKYUNWUTRE-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 108090000204 Dipeptidase 1 Proteins 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003781 beta lactamase inhibitor Substances 0.000 description 1
- 102000006635 beta-lactamase Human genes 0.000 description 1
- 229940126813 beta-lactamase inhibitor Drugs 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002031 ethanolic fraction Substances 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940126085 β‑Lactamase Inhibitor Drugs 0.000 description 1
Images
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- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C07D503/02—Preparation
-
- C—CHEMISTRY; METALLURGY
- 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
The invention relates to a method for recycling an organic solvent from potassium clavulanate production waste liquid. The method comprises a desalting process, a rough steaming process, an alkaline extraction process and a dehydration process. The invention adopts the scheme of combining rectification and pervaporation membrane dehydration technology, combines an alkaline extraction procedure, effectively removes salt and moisture in the recovered solvent, obviously reduces the process energy consumption, and the recovered solvent can be reused for preparing the clavulanate potassium.
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, published paper "potassium clavulanate reaction crystallization study", report on the process schemes of potassium clavulanate reaction and crystallization, and at present, 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 the following components: organic solvent is used as main component, namely organic solvent ethanol, isopropanol or the mixture of the two; uncrystallized potassium clavulanate; potassium isooctanoate and t-butylamine salt of isooctanoate produced by the 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 the ethanol and the isopropanol, and the ratio of the ethanol to the isopropanol in the mixture system of the ethanol and the isopropanol is any ratio of the ethanol and the isopropanol; the concentration range of the uncrystallized potassium clavulanate is 0.1 to 1 weight percent; the concentration range of unreacted potassium iso-octoate is 0.5wt percent to 2.5wt percent; the concentration range of the tert-butylamine iso-octoate salt generated by the reaction is 2-5 wt%; the water content 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 solution of potassium clavulanate production is generally 8-10, wherein the organic solvent is ethanol, isopropanol or a mixture of the two; the concentration range of the uncrystallized potassium clavulanate is 0.1 to 1 weight percent; the concentration range of unreacted potassium iso-octoate is 0.5wt percent to 2.5wt percent; the concentration range of the tert-butylamine iso-octoate salt generated by the reaction is 2-5 wt%; the water content 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 (mass percent)) is added to the potassium clavulanate production waste liquid so that the pH thereof is 1 to 5.5, and preferably 2 to 4.5; at this time, the tert-butylamine salt of isooctanoic acid in the waste liquid is converted into isooctanoic acid and tert-butylamine sulfate, the isooctanoic acid is dissolved in the waste liquid, and the tert-butylamine sulfate is precipitated in the form of solid. 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.
Transferring the feed liquid with the tertiary butylamine salt removed into a distillation tower for distillation, and collecting organic solvent fractions with improved purity, namely ethanol, isopropanol or a mixture of the ethanol and the isopropanol with improved purity at the top of the distillation tower; 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 needed. 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 the temperature of between 50 and 80 ℃ and is stood for layering, so that an organic solvent layer with improved purity is obtained.
Specifically, adding an alkali brine extractant into the organic solvent fraction collected from the top of the tower, wherein the alkali brine extractant is an aqueous solution of potassium hydroxide and inorganic potassium salt, and the inorganic potassium salt is potassium carbonate, potassium chloride or potassium nitrate, preferably potassium carbonate; the alkaline brine extractant is prepared from the following components in parts by weight: potassium hydroxide: the weight ratio of the inorganic potassium salt is 1:0.1 to 0.6:0.2 to 0.6; the addition amount of the alkaline brine extractant is 10-20% of the volume of the organic solvent fraction collected at the top of the tower.
The alkali 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 to the water phase through liquid separation operation at 50-80 ℃, and a small amount of water in the water phase can enter the organic solvent layer. Thus, the resulting organic solvent layer having an improved purity, wherein the moisture content is 5wt% to 20wt% and the pH is 8 to 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 a 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 described as a high-pressure side and a low-pressure side, wherein the high-pressure side is high-pressure solvent vapor input through a vaporization tower, the low-pressure side is connected with a vacuum system, and the pressure is maintained at 200Pa-5000Pa through suction of a vacuum pump; the water molecules permeate through the pervaporation membrane under the pressure difference between the high pressure side and the low pressure side, and the high pressure side enters the low pressure side, so that the separation of the water molecules and the organic solvent is realized, and the separated two phases are respectively condensed to obtain the 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 feed liquid is fed into the continuous rectifying column to carry out rectification, the ethanol fraction with improved purity of 73 ℃ -80 ℃ (based on local pressure) is collected at the top of the column and the waste liquid containing isooctanoic acid and the like (which can be further processed as required) is collected at the bottom of the column.
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 7.8% by weight 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.
Starting a continuous rectifying tower, inputting the feed liquid into the continuous rectifying tower for rectification, collecting about 10000L of propanol fraction with improved purity at 75-85 ℃ at the top of the tower, and collecting waste liquid containing isooctanoic acid and the like at the bottom of the tower (further processing can be performed according to the requirement).
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 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 8.2% by weight 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 feed liquid is fed into the continuous rectifying column for rectification, about 11000L of ethanol isopropanol fraction with improved purity at 70-85 ℃ is collected at the top of the column, and waste liquid containing isooctanoic acid and the like (further treatment can be carried out according to the need) is collected at the bottom of the column.
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 incubated for 2 hours, followed by 1 hour of standing and then delamination while hot 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 (10)
1. A method for recovering an organic solvent from a waste liquid of potassium clavulanate production, comprising:
(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.
2. The method for recovering an organic solvent from a potassium clavulanate production waste liquid according to claim 1, characterized in that the pH of the potassium clavulanate production waste liquid is 8 to 10, wherein the organic solvent is ethanol, isopropanol or a mixture of both; the concentration range of the potassium clavulanate is 0.1 to 1 weight percent; the concentration range of the potassium iso-octoate is 0.5 to 2.5 weight percent; the concentration range of the tert-butylamine iso-octoate salt is 2-5 wt%; the water content is 1-5 wt%.
3. The method for recovering an organic solvent from a waste liquid of potassium clavulanate production according to claim 1 or 2, wherein 98 mass% of concentrated sulfuric acid is added to the waste liquid of potassium clavulanate production in the step (1) of desalting to have a pH of 1 to 5.5.
4. The method for recovering an organic solvent from a waste liquid from potassium clavulanate production according to claim 1 or 2, characterized in that in the step (2) of the crude distillation process, the distillation column is a continuous distillation column or a batch distillation column.
5. The method for recovering an organic solvent from a waste liquid from potassium clavulanate production according to claim 1 or 2, wherein in the step (3) of alkali extraction, an alkali salt aqueous extractant is added to the organic solvent fraction collected at the top of the column, and the mixture is stirred at 50 to 80 ℃ for 2 to 3 hours, and the mixture is allowed to stand and delaminate to obtain an organic solvent layer having an improved purity.
6. The method for recovering an organic solvent from a waste liquid of potassium clavulanate production according to claim 1 or 2, characterized in that in the step (3) of alkaline extraction, the alkaline brine extractant is an aqueous solution of potassium hydroxide and an inorganic potassium salt, and the inorganic potassium salt is potassium carbonate, potassium chloride or potassium nitrate, preferably potassium carbonate; the alkaline brine extractant is prepared from the following components in parts by weight: potassium hydroxide: the weight ratio of the inorganic potassium salt is 1:0.1 to 0.6:0.2 to 0.6; the addition amount of the alkaline brine extractant is 10-20% of the volume of the organic solvent fraction.
7. The method for recovering an organic solvent from a waste liquid from potassium clavulanate production according to claim 1 or 2, wherein in the step (4) dehydration step, a vaporization column is used to heat and vaporize the organic solvent layer having the improved purity.
8. The method for recovering an organic solvent from a waste liquid of potassium clavulanate production according to claim 7, wherein the vaporization tower is a batch type pressurized rectifying tower, and the organic solvent enters a pervaporation membrane separation unit in a vapor form at the top of the tower, and the vapor pressure is 0.1MPa to 0.3MPa.
9. The method for recovering an organic solvent from a waste liquid from potassium clavulanate production according to claim 1 or 2, wherein in the step (4) of dehydration, the pervaporation membrane of the pervaporation membrane separation unit is a chitosan membrane, a PVA membrane, a PVDF membrane, a sodium alginate membrane or a molecular sieve membrane.
10. The method for recovering an organic solvent from a waste liquid of potassium clavulanate production according to claim 1 or 2, characterized in that the recovered purified organic solvent has a moisture content of 0.1 to 0.3wt%.
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| WO1993025557A1 (en) * | 1992-06-11 | 1993-12-23 | Smithkline Beecham Plc | Process for the preparation of clavulanic acid |
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| CN113979872A (en) * | 2021-11-09 | 2022-01-28 | 国药集团威奇达药业有限公司 | Comprehensive recovery method of effective components in potassium clavulanate kettle residual liquid |
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