CN106083571A - A kind of secondary recovery and method of purification phenylacetic acid from 6 APA lysates - Google Patents
A kind of secondary recovery and method of purification phenylacetic acid from 6 APA lysates Download PDFInfo
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- CN106083571A CN106083571A CN201610428591.1A CN201610428591A CN106083571A CN 106083571 A CN106083571 A CN 106083571A CN 201610428591 A CN201610428591 A CN 201610428591A CN 106083571 A CN106083571 A CN 106083571A
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- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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Abstract
A kind of secondary recovery and method of purification phenylacetic acid from 6 APA lysates, belong to the technical field that phenylacetic acid purification reclaims, after 6 APA lysate acidifyings, adding extractant and extract, organic facies is by alkalization, separation water intaking phase, then through decolouring, two degree of acidifyings, crystalline mother solution after once being reclaimed phenylacetic acid and once reclaiming, the crystalline mother solution after once reclaiming, after macroporous resin adsorption, alkali desorption, regulates pH2.0 3.0 crystallize, sucking filtration, be dried, obtain secondary recovery phenylacetic acid.Present invention achieves the high efficiente callback of phenylacetic acid in 6 APA cracking waste liquids, in mother solution, phenylacetic acid residual ＜ 1mg/ml, effectively reduces the phenylacetic acid pollution to environment.
Description
Technical field
The invention belongs to the technical field that phenylacetic acid purification reclaims, relate to reclaiming benzene second from purification from 6-APA lysate
The method of acid, is specifically related to a kind of secondary recovery and method of purification phenylacetic acid from 6-APA lysate, utilizes side of the present invention
Method, while realizing reclaiming, also achieves the purification to phenylacetic acid, i.e. reclaims and Tong Bu carries out with purification.
Background technology
6-APA i.e. 6-amino-penicillanic acid, current domestic production substantially uses potassium salt of penicillin enzymatic cleavage to produce, removes
Substantial amounts of phenylacetic acid potassium salt is also had outside product penicillanic acid.Phenylacetic acid potassium salt is dissolved in cracking waste liquid.Phenylacetic acid is medicine, agriculture
The intermediate of the organic synthesis such as medicine, spice, for the production of the medicine such as penicillin, bendazol in medical industry.To phenylacetic acid
In addition recycling, can economize on resources and reduce the production cost of penicillanic acid, can reduce again phenylacetic acid to environment simultaneously
Pollute, form green continuable Recycling Economy System.
In 6-APA lysate, reclaim the technique of phenylacetic acid such as, first 6-APA lysate regulation pH value is alkalescence, adds
Hydrogen peroxide reclaims hexone, and remainder takes after settlement after supernatant alkali tune again adds hydrogen peroxide post-heating and uses
Activated carbon decolorizing, filtration, filtrate regulation acidity, crystallize, it is centrifuged, is dried to obtain phenylacetic acid.A kind of recovery work of phenylacetic acid
Skill, first waste liquid regulates pH is to extract split-phase with MIBK after 2.0-3.0, and organic facies alkali regulates pH9.0-9.5 split-phase, phase of fetching water
Carbon decoloring, filtration, filtrate regulation pH2.0-3.0 crystallize, the method reclaiming phenylacetic acid is added after being heated to 50-60 DEG C.Grasp in reality
The phenylacetic acid residual that still there is higher concentration in the filtrated stock after crystallize reclaims phenylacetic acid is we have found that during work, its
At concentrations up to 15-16mg/ml.This part phenylacetic acid still causes waste and the environmental pollution of resource.To this part residual benzene second
The secondary recovery recycling of acid has huge economic and social benefit.
Summary of the invention
The present invention solves after prior art once reclaims, filtrated stock still contains the benzene second of high concentration
Acid, the problem causing the wasting of resources and environmental pollution, it is provided that a kind of secondary recovery and purification phenylacetic acid from 6-APA lysate
Method.
The present invention the technical scheme is that for realizing its purpose
A kind of secondary recovery and method of purification phenylacetic acid from 6-APA lysate, after being acidified by 6-APA lysate, adds
Entering extractant to extract, organic facies, by alkalization, separation water intaking phase, then through decolouring, two degree of acidifyings, is once reclaimed benzene
Crystalline mother solution after acetic acid and once recovery, the crystalline mother solution after once reclaiming, after macroporous resin adsorption, alkali desorption, is adjusted
Joint pH2.0-3.0 crystallize, sucking filtration, be dried, obtain secondary recovery phenylacetic acid.
Adsorption temp is 20-60 DEG C, and crystalline mother solution is 0.5-5.0BV/h through the flow velocity of macroporous resin.
Alkali desorption temperature is 30-80 DEG C, and alkali concn used is 0.5%-10%, and the volume of alkali used is 0.5-5BV.This
Bright alkali used is selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution, sodium bicarbonate aqueous solution, aqueous sodium carbonate or ammonia
One or more mixed solution is when selecting the aqueous sodium carbonate mixed solution with ammonia as alkali desorbing agent, logical
Cross the mass ratio 5:1 controlling 0.5%-10% aqueous sodium carbonate with 0.5%-10% ammonia so that desorption effect is substantially better than
Single alkali liquor desorption, compared to only improving more than 1.3% with the desorption rate of sodium hydrate aqueous solution or sodium bicarbonate aqueous solution,
And then further increase the response rate and the purity of final phenylacetic acid.Optimum is chosen as sodium hydrate aqueous solution and potassium hydroxide
The mixing of aqueous solution is as alkali desorbing agent, and wherein 0.5%-10% sodium hydrate aqueous solution is water-soluble with 0.5%-10% potassium hydroxide
The mass ratio of liquid is 2.3:1.2, uses the desorption effect of this alkali desorbing agent compared to only with sodium hydrate aqueous solution or bicarbonate
The desorption rate of sodium water solution improves more than 2%.
Acidifying, the pH value of two degree of acidifyings control as 2.0-3.0, it is ensured that the abundant crystallize of phenylacetic acid, improve phenylacetic acid
The response rate.
With dichloromethane, methyl iso-butyl ketone (MIBK), hexamethylene, tetrachloromethane or chloroform as extractant, stirring extraction during extraction
Take, stand split-phase, take organic facies.When further extracting, it is composite extractant by solvent selection, with volume ratio 1:0.8:
The ratio of 1.2 selects methyl iso-butyl ketone (MIBK), hexamethylene and chloroform to be that composite extractant extracts, compared to single extraction
Agent, effect of extracting significantly improves, and the purity once reclaiming phenylacetic acid being obtained by extraction reaches more than 99%, compared to single extractant
And existing extraction and recovery phenylacetic acid purity is increased.
Temperature during extraction is 10-50 DEG C, and extraction time is 10-30min.
The pH value of alkalization controls as 8.0-11.0.
During decolouring, bleaching temperature is 30-70 DEG C, and decolour 10-60min, can obtain optimal decolorizing effect, otherwise decolour not
Thoroughly.
Big pore resin is LXT series plastics, LX series plastics or XDA series plastics, such as LXT-267 resin,
LXT-233 resin, LX-1 resin, LX-032 resin, LX-1180 resin, LX-1600 resin, LXT-053 resin, LXT-1180
One or more mixing in resin, LXT-081 resin, XDA-1 resin, XDA-9 resin.Preferably, mixing is used
Resin adsorbs, it has been investigated that use hybrid resin to carry out adsorbing compared to single resin absorption effect more preferably, and absorption
After, in mother solution, the phenylacetic acid content of residual is lower than single content, by controlling the ratio of hybrid resin, can further carry
The purity of high product, is that the hybrid resin of the LX-1180 resin of 5:4 and LX-1600 resin is the most prominent with volume ratio especially, then with
Operation during desorption combines, and further improves the response rate and the purity of phenylacetic acid.
The present invention the technical scheme is that for realizing its purpose
1, present invention achieves the high efficiente callback of phenylacetic acid in 6-APA cracking waste liquid, after absorption, in mother solution, phenylacetic acid is residual
Stay ＜ 1mg/ml, effectively reduce the phenylacetic acid pollution to environment；
2, during the present invention solves 6-APA cracking waste liquid, present in phenylacetic acid recovery, phenylacetic acid product purity is low, it is impossible to
The problem of direct reuse；
3, the phenylacetic acid purity reclaimed in the present invention is high, phenylacetic acid purity > 99.0%, penicillin fermentation can be directly applied to
Produce, it is achieved that the Recycling Economy System of penicillin production；
4, present invention achieves the high efficiente callback to phenylacetic acid, the response rate of phenylacetic acid is more than 95%；
5, present invention process is simple, the highest to equipment requirements, it is easy to industrial applications.
The strict temperature controlling absorption and adsorption flow rate is needed, through the creative research that inventor is long-term, always during absorption
Tying control adsorption flow rate is 0.5-5.0BV/h, and adsorption temp is 20-60 DEG C, and the adsorption effect that can obtain can guarantee that again
The high-recovery of phenylacetic acid and purity, the too fast absorption of flow velocity is incomplete, and it is the best that flow velocity crosses slow treatment effect.The too high impact of temperature is produced
Product purity.Temperature is too low the best to adsorption effect.
Needing strict control desorption temperature and the concentration of desorbing agent used during desorption, the creativeness long-term through inventor is ground
Studying carefully, sum up control desorption temperature and be 30-80 DEG C, the concentration of desorbing agent used is 0.5%-10%, the desorption effect not only obtained
The best, and highly purified phenylacetic acid can be obtained, can further improve the response rate of phenylacetic acid, controlling alkali desorption concentration is
0.5-10% can obtain optimal desorption effect, and alkali concn is too high affects product purity.
Detailed description of the invention
The present invention is by 6-APA cracking waste liquid regulation pH2.0-3.0, adding extractant, temperature control 10-50 DEG C, stirring (extraction
Take) 10-30min, standing, split-phase, take organic facies.Organic facies sodium hydroxide regulates pH8.0-11.0, stirs, stands, split-phase.
Water intaking phase, is warming up to 30-70 DEG C, adds activated carbon decolorizing 10-60min, filters, and filtrate is lowered the temperature, and regulates pH2.0-3.0 crystallize,
Sucking filtration, is dried once to reclaim phenylacetic acid.Through macroporous resin, at flow velocity 0.5-5.0BV/h, (BV is macroporous resin body to crystalline mother solution
Long-pending), Adsorption Concentration, the alkali of rear 0.5%-10% are desorbed in temperature 30-80 DEG C at temperature 20-60 DEG C, regulate pH2.0-3.0 and analyse
Crystalline substance, sucking filtration, it is dried to obtain the phenylacetic acid crystal of white.Achieve the secondary recovery of phenylacetic acid in 6-APA cracking waste liquid and pure
Change.In described 6-APA cracking waste liquid, contained phenylacetic acid concentration is identical, makees the present invention further below in conjunction with specific embodiment
Explanation.
Embodiment 1
By 40ml XDA-1 resin, load in the glass adsorption column of jacketed (Ф 30 × 250mm).
1) take 6-APA cracking waste liquid 400ml in 1L there-necked flask, with hydrochloric acid regulation pH2.0-3.0 add carbon tetrachloride
200ml, quickly stirs 15min, stands, layering.Take organic layer dropping sodium hydroxide solution regulation pH10.0, stir 10min, quiet
Put, split-phase.Water intaking phase, is heated to 50 DEG C, adds activated carbon 15g decolouring 30min, filters, and filtrate is cooled to 18 DEG C of dropping hydrochloric acid
Regulation pH2.0-3.0, crystallize, growing the grain 30min, sucking filtration, with cold purified water filter wash cake, it is dried once to reclaim phenylacetic acid.Mother solution
Phenylacetic acid concentration 15.5mg/ml, crosses XDA-1 resin column, crosses resin columns with the flow velocity of 2.5BV/h at 40 DEG C, treating capacity 400ml,
After absorption, phenylacetic acid concentration 0.57mg/ml in mother solution.
2), after absorption terminates, with 1% sodium hydrate aqueous solution in 55 DEG C of desorptions, it is desorbed volume 120ml, is desorbed concentration
48.75mg/ml, desorption liquid is cooled to 20 DEG C, regulates pH2.0-3.0 crystallize, sucking filtration with hydrochloric acid, is dried to obtain secondary recovery white knot
Crystalline phenylacetic acid 5.8g, purity 99.75%.
Embodiment 2
By 80ml LX-1180 resin and the hybrid resin of LX-1600 resin, wherein LX-1180 resin and LX-1600 tree
The volume ratio of fat is 5:4, loads in the glass adsorption column of jacketed (Ф 30 × 250mm).
1) take 6-APA cracking waste liquid 900ml in 1L there-necked flask, with hydrochloric acid regulation pH2.0-3.0 add 400ml volume ratio
The ratio of 1:0.8:1.2 selects methyl iso-butyl ketone (MIBK), hexamethylene and chloroform to be that composite extractant extracts, and quickly stirs
15min, stands, layering.Take organic layer dropping sodium hydroxide solution regulation pH10.0, stir 20min, stand, split-phase.Water intaking
Phase, is heated to 55 DEG C, adds activated carbon 36g decolouring 20min, filters, and filtrate is cooled to 12 DEG C of dropping hydrochloric acid regulation pH2.0-
3.0, crystallize, growing the grain 30min, sucking filtration, with cold purified water filter wash cake, it is dried once to reclaim phenylacetic acid.Mother solution phenylacetic acid concentration
14.8mg/ml, crosses hybrid resin post, crosses resin columns with the flow velocity of 1.5BV/h at 30 DEG C, treating capacity 900ml, after absorption, and mother solution
Middle phenylacetic acid concentration 0.23mg/ml.
2), after absorption terminates, with the mixed solution of 3% aqueous sodium carbonate and ammonia in 65 DEG C of desorptions, it is desorbed volume
250ml, is desorbed concentration 52.16mg/ml, and desorption liquid is cooled to 20 DEG C, regulates pH2.0-3.0 crystallize, sucking filtration with hydrochloric acid, is dried
White crystalline phenylacetic acid 13g, purity 99.9%.
Embodiment 3
By 300ml LXT-1180 resin, load in the glass adsorption column of jacketed (Ф 40 × 500mm).
1) take 6-APA cracking waste liquid 2800ml in 5L there-necked flask, with hydrochloric acid regulation pH2.0-3.0 add 1500ml volume
Ratio is dichloromethane and the hexamethylene composite extractant of 1:1.5, quickly stirs 15min, stands, and is layered.Take organic layer dropping hydrogen
Sodium hydroxide solution regulation pH10.0, stirs 20min, stands, split-phase.Water intaking phase, is heated to 65 DEG C, adds activated carbon 60g decolouring
20min, filters, and filtrate is cooled to 16 DEG C of dropping hydrochloric acid regulation pH2.0-3.0, crystallize, growing the grain 30min, sucking filtration, uses cold purified water
Filter wash cake, is dried once to reclaim phenylacetic acid.Mother solution phenylacetic acid concentration 15.2mg/ml, crosses LXT-1180 resin column, with 3BV/h
Flow velocity 20 DEG C cross resin columns, treating capacity 2800ml, absorption absorption after, phenylacetic acid concentration 0.56mg/ml in mother solution.
2), after absorption terminates, with 7% sodium hydrate aqueous solution in 70 DEG C of desorptions, it is desorbed volume 850ml, is desorbed concentration
47.49mg/ml, desorption liquid is cooled to 15 DEG C, regulates pH2.0-3.0 crystallize, sucking filtration with hydrochloric acid, is dried to obtain white crystalline benzene second
Acid 40.3g, purity 99.75%.
Embodiment 4
By 40ml XDA-9 resin, load in the glass adsorption column of jacketed (Ф 30 × 250mm).
1) take 6-APA cracking waste liquid 400ml in 1L there-necked flask, with hydrochloric acid regulation pH2.0-3.0 add methyl-isobutyl
Ketone 210ml, quickly stirs 10min, stands, layering.Take organic layer dropping sodium hydroxide solution regulation pH8.0, stir 15min,
Stand, split-phase.Water intaking phase, is heated to 30 DEG C, adds activated carbon 15g decolouring 50min, filters, and filtrate is cooled to 18 DEG C of dropping salt
Acid for adjusting pH 2.0-3.0, crystallize, growing the grain 30min, sucking filtration, with cold purified water filter wash cake, it is dried once to reclaim phenylacetic acid.Female
Liquid phenylacetic acid concentration 15.5mg/ml, crosses XDA-9 resin column, crosses resin column, treating capacity with the flow velocity of 2.5BV/h at 20 DEG C
400ml, after absorption, phenylacetic acid concentration 0.58mg/ml in mother solution.
2), after absorption terminates, with 0.5% sodium hydrate aqueous solution in 35 DEG C of desorptions, it is desorbed volume 120ml, is desorbed concentration
48.5mg/ml, desorption liquid is cooled to 20 DEG C, regulates pH2.0-3.0 crystallize, sucking filtration with hydrochloric acid, is dried to obtain white crystalline benzene second
Acid 5.75g, purity 99.65%.
Embodiment 5
By 40ml XDA-1 resin, load in the glass adsorption column of jacketed (Ф 30 × 250mm).
1) take 6-APA cracking waste liquid 400ml in 1L there-necked flask, with hydrochloric acid regulation pH2.0-3.0 add hexamethylene
250ml, quickly stirs 30min, stands, layering.Take organic layer dropping sodium hydroxide solution regulation pH11.0, stir 10min, quiet
Put, split-phase.Water intaking phase, is heated to 40 DEG C, adds activated carbon 15g decolouring 20min, filters, and filtrate is cooled to 18 DEG C of dropping hydrochloric acid
Regulation pH2.0-3.0, crystallize, growing the grain 30min, sucking filtration, with cold purified water filter wash cake, it is dried once to reclaim phenylacetic acid.Mother solution
Phenylacetic acid concentration 15.5mg/ml, crosses XDA-1 resin column, crosses resin columns with the flow velocity of 2.5BV/h at 60 DEG C, treating capacity 400ml,
After absorption, phenylacetic acid concentration 0.57mg/ml in mother solution.
2), after absorption terminates, with 5% sodium hydrate aqueous solution in 75 DEG C of desorptions, it is desorbed volume 120ml, is desorbed concentration
48.78mg/ml, desorption liquid is cooled to 20 DEG C, regulates pH2.0-3.0 crystallize, sucking filtration with hydrochloric acid, is dried to obtain white crystalline benzene second
Acid 5.81g, purity 99.6%.
Embodiment 6
By 40ml LX-1 resin, load in the glass adsorption column of jacketed (Ф 40 × 500mm).
1) take 6-APA cracking waste liquid 400ml in 1L there-necked flask, with hydrochloric acid regulation pH2.0-3.0 add carbon tetrachloride
200ml, quickly stirs 18min, stands, layering.Take organic layer dropping sodium hydroxide solution regulation pH9.0, stir 13min, quiet
Put, split-phase.Water intaking phase, is heated to 60 DEG C, adds activated carbon 15g decolouring 50min, filters, and filtrate is cooled to 18 DEG C of dropping hydrochloric acid
Regulation pH2.0-3.0, crystallize, growing the grain 30min, sucking filtration, with cold purified water filter wash cake, it is dried once to reclaim phenylacetic acid.Mother solution
Phenylacetic acid concentration 15.5mg/ml, crosses LX-1 resin column, crosses resin column, treating capacity 400ml with the flow velocity of 2.5BV/h at 50 DEG C, inhales
Attached, phenylacetic acid concentration 0.57mg/ml in mother solution.
2), after absorption terminates, with 7% sodium hydrate aqueous solution in 80 DEG C of desorptions, it is desorbed volume 120ml, is desorbed concentration
49mg/ml, desorption liquid is cooled to 20 DEG C, regulates pH2.0-3.0 crystallize, sucking filtration with hydrochloric acid, is dried to obtain white crystalline phenylacetic acid
5.83g, purity 99.65%.
Embodiment 7
By the hybrid resin of 40ml XDA-1 resin Yu XDA-9 resin, wherein XDA-1 resin and the volume of XDA-9 resin
Ratio is 6.4:3.6, loads in the glass adsorption column of jacketed (Ф 40 × 500mm).
1) take 6-APA cracking waste liquid 400ml in 1L there-necked flask, with hydrochloric acid regulation pH2.0-3.0 add volume ratio be 1:1
Carbon tetrachloride and methyl iso-butyl ketone (MIBK) 200ml, quickly stir 13min, stands, layering.Take organic layer dropping sodium hydroxide solution
Regulation pH8.5, stirs 18min, stands, split-phase.Water intaking phase, is heated to 45 DEG C, adds activated carbon 15g decolouring 20min, filters,
Filtrate is cooled to 12 DEG C of dropping hydrochloric acid regulation pH2.0-3.0, crystallize, growing the grain 30min, sucking filtration, with cold purified water filter wash cake, is dried
Obtain and once reclaim phenylacetic acid.Mother solution phenylacetic acid concentration 14.5mg/ml, crosses hybrid resin post, with the flow velocity of 2.5BV/h 38 DEG C of mistakes
Resin column, treating capacity 400ml, after absorption, phenylacetic acid concentration 0.285mg/ml in mother solution.
2), after absorption terminates, take off in 63 DEG C with the mixed aqueous solution of 6% sodium hydrate aqueous solution with potassium hydroxide aqueous solution
Attached, wherein sodium hydroxide is 2.3:1.2 with the mass ratio of potassium hydroxide, is desorbed volume 120ml, is desorbed concentration 47.33mg/ml,
Desorption liquid is cooled to 20 DEG C, regulates pH2.0-3.0 crystallize, sucking filtration with hydrochloric acid, is dried to obtain white crystalline phenylacetic acid 5.67g, pure
Degree 99.93%.
Embodiment 8
By 40ml LXT-053 resin, load in the glass adsorption column of jacketed (Ф 30 × 250mm).
1) take 6-APA cracking waste liquid 400ml in 1L there-necked flask, with hydrochloric acid regulation pH2.0-3.0 add carbon tetrachloride
200ml, quickly stirs 25min, stands, layering.Take organic layer dropping sodium hydroxide solution regulation pH10.5, stir 10min, quiet
Put, split-phase.Water intaking phase, is heated to 55 DEG C, adds activated carbon 15g decolouring 30min, filters, and filtrate is cooled to 18 DEG C of dropping hydrochloric acid
Regulation pH2.0-3.0, crystallize, growing the grain 30min, sucking filtration, with cold purified water filter wash cake, it is dried once to reclaim phenylacetic acid.Mother solution
Phenylacetic acid concentration 15.5mg/ml, crosses LXT-053 resin column, crosses resin column, treating capacity with the flow velocity of 2.5BV/h at 40 DEG C
400ml, after absorption, phenylacetic acid concentration 0.58mg/ml in mother solution.
2), after absorption terminates, with 8% sodium hydrate aqueous solution in 70 DEG C of desorptions, it is desorbed volume 120ml, is desorbed concentration
48.75mg/ml, desorption liquid is cooled to 20 DEG C, regulates pH2.0-3.0 crystallize, sucking filtration with hydrochloric acid, is dried to obtain white crystalline benzene second
Acid 5.83g, purity 99.6%.
Comparative example 1
The recovery process of a kind of phenylacetic acid, the process step of the invention is: takes 1000mL waste liquid and loads in there-necked flask, uses
The hydrochloric acid of 20% adjusts pH value 2.0-3.0, adds extractant, and temperature controls at 5-80 DEG C, stops after stirring 20-30min, will mixing
Liquid moves in separatory funnel, stratification；Take organic facies, adjust pH value to 9.0-9.5 with sodium hydroxide, move in separatory funnel quiet
Put layering, divide and go organic facies；By heated aqueous to 50-60 DEG C, add 5-25g activated carbon decolorizing, filter；Filtrate is lowered the temperature, simultaneously
The hydrochloric acid of dropping 20% is to pH 2.0-3.0, growing the grain while stirring；Obtain white plates crystal through sucking filtration, weigh after drying, meter
Calculating yield, detect phenylacetic acid content, the response rate is 90-92%, and purity is 97-98%, phenylacetic acid residual ＞ 16.5mg/ in mother solution
ml。
Comparative example 2
The technique extracting phenylacetic acid from the waste liquid that 6-APA cracking produces, needs to steam hexone through mediation
And settle, decolorization filtering, acidizing crystal, centrifuge dehydration and dry technical process, be in harmonious proportion and steam methyl tert-butyl benzylacetone and also settle
During exactly the cracking waste liquid containing sodium phenylacetate is squeezed into mediation distillating still, tune pH value is to add dioxygen under 10-14, room temperature
Water, the capacity of hydrogen peroxide be every 1000kg weight waste liquid in add 3-10L, then heating kettle liquid is to 100-106 DEG C, until tower
Top stops heating after distillating without hexone, when cooling reactor liquid is to 30-50 DEG C, puts still liquid to subsider, settle 10h with
On, subsequently into decolorization filtering process；Decolorization filtering process is exactly to take in the extremely decolouring still of the supernatant in subsider, and tune pH value is
10-14, adds hydrogen peroxide under room temperature, the capacity of hydrogen peroxide is to add 1-relative in the initially cracking waste liquid of every 1000kg weight
5L, is heated to still liquid 40-50 DEG C to decolouring still, adds activated carbon in decolouring still, and the weight of activated carbon is relative to every 1000kg
The initially cracking waste liquid of weight adds 2-6kg, stirring, is heated to 100-110 DEG C, and maintains more than this temperature 15min, cooling
To 40-60 DEG C, use plate-and-frame filtration；The last acidified crystallization of filtrate, centrifuge dehydration and dry run, obtain phenylacetic acid white crystals
Thing, the response rate is 92-94%, and purity is 98.5-99%, phenylacetic acid residual ＞ 15.7mg/ml in mother solution.
Comparative example 3
The recovery purification process of a kind of phenylacetic acid, comprises the following steps:
1) take PAA--butyl acetate mother solution 600mL in 1000mL three-necked bottle, add 300mL purified water, stir 10min soon, layering
20min；
2) taking the PAA--butyl acetate liquid 600mL after washing and add 200mL purified water, stirring, dropping 30mL30%NaOH adjusts pH
12, add 3mL H2O2, heat 80 DEG C, after stirring 30min, split-phase 20min；
3) water intaking phase 230mL, adds activated carbon 1.15g, 30 DEG C, stirs 20min, G4 funnel sucking filtration, can obtain 230mL PAA--Na
Liquid；
4) take PAA--Na liquid 230mL in 500mL three-necked bottle, 25 DEG C, drip 30%HCI, make into pH2.0,5 DEG C, stir slowly
2h, sucking filtration, to dry, obtains wet product PAA；
5) above-mentioned wet product is taken in 100 DEG C, 0.98MP, 5h, vacuum drying, obtain purification PAA finished product 25.5g, measure the response rate
Being 85%, purity is 99.5%, phenylacetic acid residual ＞ 15.8mg/ml in mother solution.
Comparative example 4
The method reclaiming phenylacetic acid, comprises the following steps:
1) first measure phenylacetic acid content in waste water, as a example by the waste water of concentration 0.3g/mL, measure waste water 1000mL, add
Salt acid for adjusting pH value is 1, and owing to phenylacetic acid is water insoluble, so phenylacetic acid can become solid to suspend in water, sucking filtration obtains benzene second
Acid coarse fodder 354g, coarse fodder color is yellow or brown；
2) take above-mentioned crude product 100g, measure toluene 120mL and pour in beaker, then in dissolving crude product to toluene, glass
Rod stirring, treats that crude product all dissolves, is then introduced in the pears type separatory funnel of 250mL；
3) measure the concentrated sulphuric acid of 2mL95% with pipet and instill separatory funnel, then shake separatory funnel, static split-phase,
So 2-3 time repeatedly, until solution is light yellow；
4) regulating solution ph in separatory funnel with the sodium hydroxide solution that concentration is 20% is 14, shakes 30min, static
30min, split-phase, aqueous phase is sodium phenylacetate solution, and organic facies recycles；
5) sodium phenylacetate solution obtained above is put in beaker, add 2-3g activated carbon, beaker is put into constant temperature magnetic
Stirring decolouring, temperature 70 C, bleaching time 30min on power agitator；
6) in sodium phenylacetate solution obtained above add concentration be 20% hydrochloric acid solution regulation pH value to 1, obtain
Pure phenylacetic acid, sucking filtration, obtain solid phenylacetic acid 92g；
7) solid phenylacetic acid is put in the beaker equipped with 100mL salt-free water, temperature is risen to 70 DEG C, then beaker is put
In constant temperature blender with magnetic force, stirring, then it is cooled to room temperature with the speed of 1 DEG C/h, obtains flakey solid phenylacetic acid, vacuum
Sucking filtration；
8) solid phenylacetic acid obtained above is put into vacuum drying oven to dry, obtain phenylacetic acid fine work, survey fusing point
For 76-78 DEG C, the response rate is 85%, and purity is 99.5%, phenylacetic acid residual ＞ 17mg/ml in mother solution.
Comparative example 5
From the production waste liquid of 6-APA, reclaim phenylacetic acid, comprise the following steps:
1) take 500mL waste liquid and add 1L equipped with in the there-necked flask of electric stirring, start stirring, drip mass fraction 20%
Hydrochloric acid be 2.0-2.5 to pH, add a certain amount of extractant, control certain temperature, stir the regular hour, stop, will
Mixed liquor moves in 1L separatory funnel, after stratification, and split-phase；
2) sodium hydroxide of organic facies mass fraction 20% being neutralized to pH is 9.0-9.5, stands, and divides and goes organic facies,
By heated aqueous to uniform temperature, it is slowly dropped into the hydrochloric acid of mass fraction 10% while stirring to pH2.0-2.5, rises to a constant temperature
Degree, stirs, adds appropriate activated carbon decolorizing, insulated and stirred 15min, filtered while hot；
3) filtrate is cooled under predetermined circumstances 10 DEG C of crystallization below, makes product all separate out, obtain white after sucking filtration
Color flat crystal, is vacuum dried rear load-bearing, surveys PAA content, and yield is 89-92%, and purity is 99-99.5%, benzene second in mother solution
Acid residual ＞ 16mg/ml.
Claims (9)
1. secondary recovery and a method for purification phenylacetic acid from 6-APA lysate, after being acidified by 6-APA lysate, adds extraction
Taking agent to extract, organic facies, by alkalization, separation water intaking phase, then through decolouring, two degree of acidifyings, is once reclaimed phenylacetic acid
Crystalline mother solution after once reclaiming, it is characterised in that: the crystalline mother solution after once reclaiming takes off through macroporous resin adsorption, alkali
Attached, regulate pH2.0-3.0 crystallize, sucking filtration, be dried, obtain secondary recovery phenylacetic acid.
A kind of secondary recovery and the method for purification phenylacetic acid, its feature from 6-APA lysate the most according to claim 1
Being: adsorption temp is 20-60 DEG C, crystalline mother solution is 0.5-5.0BV/h through the adsorption flow rate of macroporous resin.
A kind of secondary recovery and the method for purification phenylacetic acid, its feature from 6-APA lysate the most according to claim 1
Being: alkali desorption temperature is 30-80 DEG C, alkali concn used is 0.5%-10%, and the volume of alkali used is 0.5-5BV.
A kind of secondary recovery and the method for purification phenylacetic acid, its feature from 6-APA lysate the most according to claim 1
It is: acidifying, the pH value of two degree of acidifyings control as 2.0-3.0.
A kind of secondary recovery and the method for purification phenylacetic acid, its feature from 6-APA lysate the most according to claim 1
It is: extract as extractant, stirring with dichloromethane, methyl iso-butyl ketone (MIBK), hexamethylene, tetrachloromethane or chloroform during extraction,
Stand split-phase, take organic facies.
A kind of secondary recovery and the method for purification phenylacetic acid, its feature from 6-APA lysate the most according to claim 1
Being: temperature during extraction is 10-50 DEG C, extraction time is 10-30min.
A kind of secondary recovery and the method for purification phenylacetic acid, its feature from 6-APA lysate the most according to claim 1
It is: the pH value of alkalization controls as 8.0-11.0.
A kind of secondary recovery and the method for purification phenylacetic acid, its feature from 6-APA lysate the most according to claim 1
Being: during decolouring, bleaching temperature is 30-70 DEG C, and decolour 10-60min.
A kind of secondary recovery and the method for purification phenylacetic acid, its feature from 6-APA lysate the most according to claim 1
Being, big pore resin is LXT series plastics, LX series plastics or XDA series plastics.
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| CN109534983A (en) * | 2017-09-22 | 2019-03-29 | 联邦制药(内蒙古)有限公司 | Phenylacetic acid method for recovering waste liquid in a kind of improved 6-APA production |
| CN111302932A (en) * | 2020-03-31 | 2020-06-19 | 联邦制药(内蒙古)有限公司 | Method for recycling sodium phenylacetate |
| CN113861019A (en) * | 2021-11-04 | 2021-12-31 | 山东普洛得邦医药有限公司 | Continuous production method for recovering phenylacetic acid from 7-amino-3-vinyl cephalosporanic acid production wastewater |
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| CN1075801C (en) * | 1999-01-18 | 2001-12-05 | 郝常明 | Process for extracting phenylacetic acid from waste liquid of cracking production of 6-amino-penicillanic acid |
| CN102911037A (en) * | 2011-08-02 | 2013-02-06 | 张晋铭 | Recovery technology of phenylacetic acid |
| CN104003867B (en) * | 2014-05-22 | 2015-08-05 | 江苏宝众宝达药业有限公司 | Method for recovering p-hydroxyphenylacetic acid from waste liquid |
| CN105132513B (en) * | 2015-09-30 | 2019-01-15 | 湖南福来格生物技术有限公司 | Whole water phase straight forward system for Amoxicillin or ampicillin method |
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| CN109534983A (en) * | 2017-09-22 | 2019-03-29 | 联邦制药(内蒙古)有限公司 | Phenylacetic acid method for recovering waste liquid in a kind of improved 6-APA production |
| CN109534983B (en) * | 2017-09-22 | 2021-06-15 | 联邦制药(内蒙古)有限公司 | Improved method for recovering phenylacetic acid waste liquid in 6-APA production |
| CN111302932A (en) * | 2020-03-31 | 2020-06-19 | 联邦制药(内蒙古)有限公司 | Method for recycling sodium phenylacetate |
| CN113861019A (en) * | 2021-11-04 | 2021-12-31 | 山东普洛得邦医药有限公司 | Continuous production method for recovering phenylacetic acid from 7-amino-3-vinyl cephalosporanic acid production wastewater |
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