CN106083571B - A method of secondary recovery and purifying phenylacetic acid from 6-APA lysate - Google Patents
A method of secondary recovery and purifying phenylacetic acid from 6-APA lysate Download PDFInfo
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- CN106083571B CN106083571B CN201610428591.1A CN201610428591A CN106083571B CN 106083571 B CN106083571 B CN 106083571B CN 201610428591 A CN201610428591 A CN 201610428591A CN 106083571 B CN106083571 B CN 106083571B
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Abstract
A method of secondary recovery and purifying phenylacetic acid from 6-APA lysate, belong to the technical field of phenylacetic acid purification and recovery, after the acidification of 6-APA lysate, extractant is added and is extracted, organic phase passes through alkalization, separation water intaking phase, then through decoloration, two degree of acidifications, it obtains once recycling phenylacetic acid and primary crystalline mother solution after the recovery, once will adjust pH2.0-3.0 crystallization after macroporous resin adsorption, alkali desorption by crystalline mother solution after the recovery, it filters, is dry, obtaining secondary recovery phenylacetic acid.The present invention realizes the high efficiente callback to phenylacetic acid in 6-APA cracking waste liquid, and phenylacetic acid remains < 1mg/ml in mother liquor, effectively reduces pollution of the phenylacetic acid to environment.
Description
Technical field
The invention belongs to the technical field of phenylacetic acid purification and recovery, it is related to the purification and recovery benzene second from from 6-APA lysate
The method of acid, and in particular to a method of secondary recovery and purifying phenylacetic acid from 6-APA lysate utilize present invention side
Method also achieves the purifying to phenylacetic acid while realizing recycling, that is, recycles carry out synchronous with purifying.
Background technique
6-APA, that is, 6-amino-penicillanic acid, at present domestic production substantially use potassium salt of penicillin enzymatic cleavage to produce, remove
There are also a large amount of phenylacetic acid sylvite outside product penicillanic acid.Phenylacetic acid sylvite is dissolved in cracking waste liquid.Phenylacetic acid is medicine, agriculture
The intermediate of the organic syntheses such as medicine, fragrance, the production in medical industry for drugs such as penicillin, dibazol.To phenylacetic acid
It is subject to recycling and reusing, can economize on resources reduces the production cost of penicillanic acid, while can reduce phenylacetic acid again to environment
Pollution forms the sustainable Recycling Economy System of green.
The technique that phenylacetic acid is recycled in 6-APA lysate such as, first adjusts pH value to 6-APA lysate and is alkalinity, is added
Hydrogen peroxide recycle hexone, remainder take after settlement supernatant again alkali tune be added hydrogen peroxide after heat after use
Active carbon decoloring, filtering, filtrate adjust acidity, and crystallization is centrifuged, is dried to obtain phenylacetic acid.A kind of for another example recycling work of phenylacetic acid
Skill, waste liquid adjust extract split-phase with MIBK after pH is 2.0-3.0 first, and organic phase adjusts pH9.0-9.5 split-phase with alkali, phase of fetching water
After being heated to 50-60 DEG C plus carbon decoloring, filtering, filtrate adjust pH2.0-3.0 crystallization, the method for recycling phenylacetic acid.In practical behaviour
During work we have found that through crystallization recycle phenylacetic acid after filtrated stock in still remain higher concentration phenylacetic acid residual,
At concentrations up to 15-16mg/ml.This part phenylacetic acid still causes the waste and environmental pollution of resource.To this part residual benzene second
The secondary recovery of acid, which recycles, has huge economic and social benefit.
Summary of the invention
The present invention is the still benzene second containing high concentration in filtrated stock after solving once to be recycled in the prior art
Acid results in waste of resources and the problem of environmental pollution, provides one kind secondary recovery and purifying phenylacetic acid from 6-APA lysate
Method.
The present invention be realize its purpose the technical solution adopted is that:
A method of secondary recovery and purifying phenylacetic acid add after the acidification of 6-APA lysate from 6-APA lysate
Enter extractant to be extracted, organic phase obtains once recycling benzene by alkalization, separation water intaking phase then through decoloration, two degree of acidifications
Acetic acid and primary crystalline mother solution after the recovery will be adjusted once crystalline mother solution after the recovery after macroporous resin adsorption, alkali desorption
PH2.0-3.0 crystallization is saved, filters, is dry, obtaining secondary recovery phenylacetic acid.
Adsorption temp is 20-60 DEG C, and flow velocity of the crystalline mother solution through macroreticular resin is 0.5-5.0BV/h.
Alkali desorption temperature is 30-80 DEG C, and alkali concentration used is 0.5%-10%, and the volume of alkali used is 0.5-5BV.This hair
Bright alkali used is selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution, sodium bicarbonate aqueous solution, aqueous sodium carbonate or ammonium hydroxide
One or more kinds of mixed solutions leads to when selecting the mixed solution of aqueous sodium carbonate and ammonium hydroxide as alkali desorbing agent
The mass ratio 5:1 for crossing control 0.5%-10% aqueous sodium carbonate and 0.5%-10% ammonium hydroxide, so that desorption effect is substantially better than
Single lye desorption, compared to only using the desorption rate of sodium hydrate aqueous solution or sodium bicarbonate aqueous solution to improve 1.3% or more,
And then further improve the rate of recovery and purity of final phenylacetic acid.Optimal is selected 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 and 0.5%-10% potassium hydroxide are water-soluble
The mass ratio of liquid is 2.3:1.2, using the desorption effect of the alkali desorbing agent compared to only with sodium hydrate aqueous solution or bicarbonate
The desorption rate of sodium water solution improves 2% or more.
Acidification, two degree of pH value controls being acidified are 2.0-3.0, it is ensured that the abundant crystallization of phenylacetic acid improves phenylacetic acid
The rate of recovery.
Use methylene chloride, methyl iso-butyl ketone (MIBK), hexamethylene, tetrachloromethane or chloroform as extractant, stirring extraction when extraction
It takes, stands split-phase, take organic phase.It is composite extractant by solvent selection when further extraction, with volume ratio 1:0.8:
It is that composite extractant is extracted that 1.2 ratio, which selects methyl iso-butyl ketone (MIBK), hexamethylene and chloroform, compared to single extraction
Agent, effect of extracting significantly improve, and the purity for the primary recycling phenylacetic acid being obtained by extraction is up to 99% or more, compared to single extractant
And existing extraction and recovery phenylacetic acid purity is increased.
Temperature when extraction is 10-50 DEG C, extraction time 10-30min.
The pH value control of alkalization is 8.0-11.0.
When decoloration, bleaching temperature is 30-70 DEG C, and decolourize 10-60min, can get optimal decolorizing effect, otherwise decolourizes not
Thoroughly.
Big pore resin be 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
The mixing of one or more of resin, LXT-081 resin, XDA-1 resin, XDA-9 resin.Preferably, using mixing
Resin is adsorbed, it has been investigated that being adsorbed, absorption more preferable compared to single resin adsorption effect using hybrid resin
Afterwards, remaining phenylacetic acid content is lower than single content in mother liquor, by controlling the ratio of hybrid resin, can further mention
The purity of high product, especially with volume ratio be 5:4 LX-1180 resin and LX-1600 resin hybrid resin it is the most prominent, then with
Operation when desorption combines, and further improves the rate of recovery and purity of phenylacetic acid.
The present invention be realize its purpose the technical solution adopted is that:
1, the present invention realizes the high efficiente callback to phenylacetic acid in 6-APA cracking waste liquid, and it is residual to adsorb phenylacetic acid in post mother liquor
< 1mg/ml is stayed, pollution of the phenylacetic acid to environment is effectively reduced；
2, the present invention solve 6-APA cracking waste liquid in phenylacetic acid recycling present in phenylacetic acid product purity is low, cannot
The problem of direct reuse；
3, the phenylacetic acid purity is high recycled in the present invention, phenylacetic acid purity > 99.0% can directly apply to penicillin fermentation
Production, realizes the Recycling Economy System of penicillin production；
4, the present invention realizes the high efficiente callback to phenylacetic acid, and the rate of recovery of phenylacetic acid is more than 95%；
5, present invention process is simple, not high to equipment requirement, is easy to industrial applications.
The temperature and adsorption flow rate for needing strict control to adsorb when absorption, by the long-term creative research of inventor, always
Tie control adsorption flow rate be 0.5-5.0BV/h, adsorption temp be 20-60 DEG C, the adsorption effect that can have been obtained and
The high-recovery and purity of phenylacetic acid, not exclusively, the excessively slow treatment effect of flow velocity is bad for the too fast absorption of flow velocity.The excessively high influence of temperature produces
Product purity.Temperature is too low bad to adsorption effect.
The concentration that strict control desorption temperature and desorbing agent used are needed when desorption is ground by the long-term creativeness of inventor
Study carefully, summarizing to control desorption temperature is 30-80 DEG C, and the concentration of desorbing agent used is 0.5%-10%, the desorption effect not only obtained
Fruit is good, and can get the phenylacetic acid of high-purity, can further improve the rate of recovery of phenylacetic acid, and control alkali desorption concentration is
0.5-10% can obtain optimal desorption effect, the excessively high influence product purity of alkali concentration.
Specific embodiment
The present invention adjusts pH2.0-3.0 by cracking waste liquid to 6-APA, extractant is added, 10-50 DEG C of temperature control, stirring (extracts
Take) 10-30min, it stands, split-phase, takes organic phase.Organic phase sodium hydroxide adjusts pH8.0-11.0, and stirring is stood, split-phase.
Water intaking phase, is warming up to 30-70 DEG C, and active carbon decoloring 10-60min, filtering is added, and filtrate cools down, adjusting pH2.0-3.0 crystallization,
It filters, it is so dry that once to recycle phenylacetic acid.Through macroreticular resin, in flow velocity 0.5-5.0BV/h, (BV is macroreticular resin body to crystalline mother solution
Product), Adsorption Concentration, the rear alkali with 0.5%-10% are desorbed at 30-80 DEG C of temperature at 20-60 DEG C of temperature, adjust pH2.0-3.0 analysis
Crystalline substance filters, and is dried to obtain the phenylacetic acid crystal of white.It realizes to the secondary recovery of phenylacetic acid in 6-APA cracking waste liquid and pure
Change.Contained phenylacetic acid concentration is identical in the 6-APA cracking waste liquid, makees combined with specific embodiments below to the present invention further
Explanation.
Embodiment 1
By 40ml XDA-1 resin, (30 × 250mm of Ф) is fitted into the glass adsorption column of jacketed.
1) it takes 6-APA cracking waste liquid 400ml in 1L there-necked flask, adjusts pH2.0-3.0 with hydrochloric acid and carbon tetrachloride is added
200ml quickly stirs 15min, stands, layering.It takes organic layer that sodium hydroxide solution is added dropwise and adjusts pH10.0, stir 10min, it is quiet
It sets, split-phase.Water intaking phase, is heated to 50 DEG C, and active carbon 15g decoloration 30min, filtering is added, and filtrate is cooled to 18 DEG C of dropwise addition hydrochloric acid
PH2.0-3.0, crystallization are adjusted, growing the grain 30min is filtered, so dry that once to recycle phenylacetic acid with cold purified water filter wash cake.Mother liquor
Phenylacetic acid concentration 15.5mg/ml, cross XDA-1 resin column, with the flow velocity of 2.5BV/h 40 DEG C cross resin columns, treating capacity 400ml,
After absorption, phenylacetic acid concentration 0.57mg/ml in mother liquor.
2) it after adsorbing, is desorbed with 1% sodium hydrate aqueous solution in 55 DEG C, volume 120ml is desorbed, concentration is desorbed
48.75mg/ml, desorption liquid are cooled to 20 DEG C, adjust pH2.0-3.0 crystallization with hydrochloric acid, filter, dry secondary recovery white knot
Crystalline phenylacetic acid 5.8g, purity 99.75%.
Embodiment 2
By the hybrid resin of 80ml LX-1180 resin and LX-1600 resin, wherein LX-1180 resin and LX-1600 tree
The volume ratio of rouge is 5:4, is fitted into the glass adsorption column of jacketed (30 × 250mm of Ф).
1) it takes 6-APA cracking waste liquid 900ml in 1L there-necked flask, adjusts pH2.0-3.0 with hydrochloric acid and 400ml volume ratio is added
It is that composite extractant is extracted that the ratio of 1:0.8:1.2, which selects methyl iso-butyl ketone (MIBK), hexamethylene and chloroform, is quickly stirred
15min is stood, layering.It takes organic layer that sodium hydroxide solution is added dropwise and adjusts pH10.0, stir 20min, stand, split-phase.Water intaking
Phase is heated to 55 DEG C, and active carbon 36g decoloration 20min, filtering is added, and filtrate is cooled to 12 DEG C of dropwise addition hydrochloric acid and adjusts pH2.0-
3.0, crystallization, growing the grain 30min is filtered, so dry that once to recycle phenylacetic acid with cold purified water filter wash cake.Mother liquor phenylacetic acid concentration
14.8mg/ml, cross hybrid resin column, with the flow velocity of 1.5BV/h 30 DEG C cross resin columns, treating capacity 900ml, after absorption, mother liquor
Middle phenylacetic acid concentration 0.23mg/ml.
2) it after adsorbing, is desorbed with the mixed solution of 3% aqueous sodium carbonate and ammonium hydroxide in 65 DEG C, volume is desorbed
Concentration 52.16mg/ml is desorbed in 250ml, and desorption liquid is cooled to 20 DEG C, adjusts pH2.0-3.0 crystallization with hydrochloric acid, filters, dry
White crystalline phenylacetic acid 13g, purity 99.9%.
Embodiment 3
By 300ml LXT-1180 resin, (40 × 500mm of Ф) is fitted into the glass adsorption column of jacketed.
1) it takes 6-APA cracking waste liquid 2800ml in 5L there-necked flask, adjusts pH2.0-3.0 with hydrochloric acid and 1500ml volume is added
Than the methylene chloride and hexamethylene composite extractant for 1:1.5,15min is quickly stirred, is stood, layering.Take organic layer that hydrogen is added dropwise
Sodium hydroxide solution adjusts pH10.0, stirs 20min, stands, split-phase.Water intaking phase, is heated to 65 DEG C, and active carbon 60g decoloration is added
20min, filtering, filtrate are cooled to 16 DEG C of dropwise addition hydrochloric acid and adjust pH2.0-3.0, crystallization, and growing the grain 30min is filtered, with cold purified water
Filter wash cake, it is so dry that once to recycle phenylacetic acid.Mother liquor 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 liquor.
2) it after adsorbing, is desorbed with 7% sodium hydrate aqueous solution in 70 DEG C, volume 850ml is desorbed, concentration is desorbed
47.49mg/ml, desorption liquid are cooled to 15 DEG C, adjust pH2.0-3.0 crystallization with hydrochloric acid, filter, dry white crystalline benzene second
Sour 40.3g, purity 99.75%.
Embodiment 4
By 40ml XDA-9 resin, (30 × 250mm of Ф) is fitted into the glass adsorption column of jacketed.
1) it takes 6-APA cracking waste liquid 400ml in 1L there-necked flask, adjusts pH2.0-3.0 with hydrochloric acid and methyl-isobutyl is added
Ketone 210ml quickly stirs 10min, stands, layering.It takes organic layer that sodium hydroxide solution is added dropwise and adjusts pH8.0, stir 15min,
It stands, split-phase.Water intaking phase, is heated to 30 DEG C, and active carbon 15g decoloration 50min, filtering is added, and filtrate is cooled to 18 DEG C of dropwise addition salt
Acid for adjusting pH 2.0-3.0, crystallization, growing the grain 30min are filtered, so dry that once to recycle phenylacetic acid with cold purified water filter wash cake.It is female
Liquid phenylacetic acid concentration 15.5mg/ml crosses XDA-9 resin column, crosses resin column, treating capacity at 20 DEG C with the flow velocity of 2.5BV/h
400ml, after absorption, phenylacetic acid concentration 0.58mg/ml in mother liquor.
2) it after adsorbing, is desorbed with 0.5% sodium hydrate aqueous solution in 35 DEG C, volume 120ml is desorbed, concentration is desorbed
48.5mg/ml, desorption liquid are cooled to 20 DEG C, adjust pH2.0-3.0 crystallization with hydrochloric acid, filter, dry white crystalline benzene second
Sour 5.75g, purity 99.65%.
Embodiment 5
By 40ml XDA-1 resin, (30 × 250mm of Ф) is fitted into the glass adsorption column of jacketed.
1) it takes 6-APA cracking waste liquid 400ml in 1L there-necked flask, adjusts pH2.0-3.0 with hydrochloric acid and hexamethylene is added
250ml quickly stirs 30min, stands, layering.It takes organic layer that sodium hydroxide solution is added dropwise and adjusts pH11.0, stir 10min, it is quiet
It sets, split-phase.Water intaking phase, is heated to 40 DEG C, and active carbon 15g decoloration 20min, filtering is added, and filtrate is cooled to 18 DEG C of dropwise addition hydrochloric acid
PH2.0-3.0, crystallization are adjusted, growing the grain 30min is filtered, so dry that once to recycle phenylacetic acid with cold purified water filter wash cake.Mother liquor
Phenylacetic acid concentration 15.5mg/ml, cross XDA-1 resin column, with the flow velocity of 2.5BV/h 60 DEG C cross resin columns, treating capacity 400ml,
After absorption, phenylacetic acid concentration 0.57mg/ml in mother liquor.
2) it after adsorbing, is desorbed with 5% sodium hydrate aqueous solution in 75 DEG C, volume 120ml is desorbed, concentration is desorbed
48.78mg/ml, desorption liquid are cooled to 20 DEG C, adjust pH2.0-3.0 crystallization with hydrochloric acid, filter, dry white crystalline benzene second
Sour 5.81g, purity 99.6%.
Embodiment 6
By 40ml LX-1 resin, (40 × 500mm of Ф) is fitted into the glass adsorption column of jacketed.
1) it takes 6-APA cracking waste liquid 400ml in 1L there-necked flask, adjusts pH2.0-3.0 with hydrochloric acid and carbon tetrachloride is added
200ml quickly stirs 18min, stands, layering.It takes organic layer that sodium hydroxide solution is added dropwise and adjusts pH9.0, stir 13min, it is quiet
It sets, split-phase.Water intaking phase, is heated to 60 DEG C, and active carbon 15g decoloration 50min, filtering is added, and filtrate is cooled to 18 DEG C of dropwise addition hydrochloric acid
PH2.0-3.0, crystallization are adjusted, growing the grain 30min is filtered, so dry that once to recycle phenylacetic acid with cold purified water filter wash cake.Mother liquor
Phenylacetic acid concentration 15.5mg/ml crosses LX-1 resin column, resin column is crossed at 50 DEG C with the flow velocity of 2.5BV/h, treating capacity 400ml inhales
It is attached, phenylacetic acid concentration 0.57mg/ml in mother liquor.
2) it after adsorbing, is desorbed with 7% sodium hydrate aqueous solution in 80 DEG C, volume 120ml is desorbed, concentration is desorbed
49mg/ml, desorption liquid are cooled to 20 DEG C, adjust pH2.0-3.0 crystallization with hydrochloric acid, filter, dry white crystalline phenylacetic acid
5.83g, purity 99.65%.
Embodiment 7
By the hybrid resin of 40ml XDA-1 resin and XDA-9 resin, the wherein volume of XDA-1 resin and XDA-9 resin
Than being fitted into the glass adsorption column of jacketed (40 × 500mm of Ф) for 6.4:3.6.
1) take 6-APA cracking waste liquid 400ml in 1L there-necked flask, adjusting pH2.0-3.0 volume ratio is added with hydrochloric acid is 1:1
Carbon tetrachloride and methyl iso-butyl ketone (MIBK) 200ml, quickly stir 13min, stand, layering.Take organic layer that sodium hydroxide solution is added dropwise
PH8.5 is adjusted, 18min is stirred, is stood, split-phase.Water intaking phase, is heated to 45 DEG C, and active carbon 15g decoloration 20min is added, filters,
Filtrate is cooled to 12 DEG C of dropwise addition hydrochloric acid and adjusts pH2.0-3.0, crystallization, and growing the grain 30min is filtered, dry with cold purified water filter wash cake
It obtains and once recycles phenylacetic acid.Mother liquor phenylacetic acid concentration 14.5mg/ml crosses hybrid resin column, with the flow velocity of 2.5BV/h in 38 DEG C of mistakes
Resin column, treating capacity 400ml, after absorption, phenylacetic acid concentration 0.285mg/ml in mother liquor.
2) de- in 63 DEG C with the mixed aqueous solution of 6% sodium hydrate aqueous solution and potassium hydroxide aqueous solution after adsorbing
Attached, wherein the mass ratio of sodium hydroxide and potassium hydroxide is 2.3:1.2, and volume 120ml is desorbed, and concentration 47.33mg/ml is desorbed,
Desorption liquid is cooled to 20 DEG C, adjusts pH2.0-3.0 crystallization with hydrochloric acid, filters, and dry white crystalline phenylacetic acid 5.67g is pure
Degree 99.93%.
Embodiment 8
By 40ml LXT-053 resin, (30 × 250mm of Ф) is fitted into the glass adsorption column of jacketed.
1) it takes 6-APA cracking waste liquid 400ml in 1L there-necked flask, adjusts pH2.0-3.0 with hydrochloric acid and carbon tetrachloride is added
200ml quickly stirs 25min, stands, layering.It takes organic layer that sodium hydroxide solution is added dropwise and adjusts pH10.5, stir 10min, it is quiet
It sets, split-phase.Water intaking phase, is heated to 55 DEG C, and active carbon 15g decoloration 30min, filtering is added, and filtrate is cooled to 18 DEG C of dropwise addition hydrochloric acid
PH2.0-3.0, crystallization are adjusted, growing the grain 30min is filtered, so dry that once to recycle phenylacetic acid with cold purified water filter wash cake.Mother liquor
Phenylacetic acid concentration 15.5mg/ml crosses LXT-053 resin column, crosses resin column, treating capacity at 40 DEG C with the flow velocity of 2.5BV/h
400ml, after absorption, phenylacetic acid concentration 0.58mg/ml in mother liquor.
2) it after adsorbing, is desorbed with 8% sodium hydrate aqueous solution in 70 DEG C, volume 120ml is desorbed, concentration is desorbed
48.75mg/ml, desorption liquid are cooled to 20 DEG C, adjust pH2.0-3.0 crystallization with hydrochloric acid, filter, dry white crystalline benzene second
Sour 5.83g, purity 99.6%.
Comparative example 1
A kind of recovery process of phenylacetic acid, the process step of the invention are as follows: take 1000mL waste liquid to be fitted into three-necked flask, use
20% hydrochloric acid tune pH value 2.0-3.0, is added extractant, and temperature controls at 5-80 DEG C, stops after stirring 20-30min, will mix
Liquid moves into separatory funnel, stratification；Organic phase is taken, with sodium hydroxide tune pH value to 9.0-9.5, is moved into quiet in separatory funnel
Layering is set, divides and goes organic phase；By heated aqueous to 50-60 DEG C, add 5-25g activity carbon decoloring, filters；Filtrate is cooled down, simultaneously
20% hydrochloric acid is added dropwise while stirring to pH 2.0-3.0, growing the grain；White plates crystal is obtained through filtering, is weighed after dry, is counted
Yield is calculated, detects phenylacetic acid content, rate of recovery 90-92%, purity 97-98%, phenylacetic acid remains > 16.5mg/ in mother liquor
ml。
Comparative example 2
The technique that phenylacetic acid is extracted from the waste liquid of 6-APA cracking production needs to steam hexone by reconciling
And settle, decolorization filtering, acidizing crystal, centrifugal dehydration and drying technical process, reconcile steam methyl tert-butyl benzylacetone simultaneously settle
It is in the process exactly the cracking waste liquid containing sodium phenylacetate to be squeezed into reconciliation distillation still, tune pH value is 10-14, adds dioxygen under room temperature
Water, the capacity of hydrogen peroxide be every 1000kg weight waste liquid in 3-10L is added, then heat kettle liquid to 100-106 DEG C, Zhi Daota
Top stops heating after distillating without hexone, when cooling kettle liquid is to 30-50 DEG C, put kettle liquid to subsider, settle 10h with
On, subsequently into decolorization filtering process；Decolorization filtering process is exactly to take the supernatant in subsider into decoloration kettle, and tune pH value is
10-14, under room temperature plus hydrogen peroxide, the capacity of hydrogen peroxide is relative to 1- is added in the initial cracking waste liquid of every 1000kg weight
5L is heated to 40-50 DEG C of kettle liquid to decoloration kettle, and into decoloration kettle plus active carbon, the weight of active carbon are relative to every 1000kg
2-6kg is added in the initial cracking waste liquid of weight, stirs, is heated to 100-110 DEG C, and maintain the temperature 15min or more, it is cooling
To 40-60 DEG C, plate-frame filtering is used；The finally acidified crystallization of filtrate, centrifugal dehydration and drying process, obtain phenylacetic acid white crystals
Object, rate of recovery 92-94%, purity 98.5-99%, phenylacetic acid remains > 15.7mg/ml in mother liquor.
Comparative example 3
A kind of recovery purifying method of phenylacetic acid, comprising the following steps:
1) it takes PAA-- butyl acetate mother liquor 600mL in 1000mL three-necked bottle, adds 300mL purified water, stir 10min fastly, be layered
20min；
2) it takes the PAA-- butyl acetate liquid 600mL after washing to add 200mL purified water, stirs, 30mL30%NaOH tune pH is added dropwise
12,3mL H is added2O2, 80 DEG C, after stirring 30min are heated, split-phase 20min；
3) fetch water phase 230mL, adds active carbon 1.15g, 30 DEG C, stirs 20min, G4 funnel filters, and can obtain 230mL PAA--Na
Liquid；
4) it takes PAA--Na liquid 230mL in 500mL three-necked bottle, 25 DEG C, 30%HCI is added dropwise, makes into pH2.0,5 DEG C, stirs slowly
2h filters to doing, obtains wet product PAA；
5) it takes above-mentioned wet product in 100 DEG C, 0.98MP, 5h, is dried in vacuo, PAA finished product 25.5g must be purified, measure the rate of recovery
It is 85%, purity 99.5%, phenylacetic acid remains > 15.8mg/ml in mother liquor.
Comparative example 4
The method for recycling phenylacetic acid, comprising the following steps:
1) phenylacetic acid content in waste water is first measured, by taking the waste water of concentration 0.3g/mL as an example, waste water 1000mL is measured, is added
Salt acid for adjusting pH value is 1, and since phenylacetic acid is not soluble in water, so phenylacetic acid can suspend in water at solid, suction filtration obtains benzene second
Sour coarse fodder 354g, coarse fodder color are yellow or brown；
2) above-mentioned crude product 100g is taken, toluene 120mL is measured and pours into beaker, then crude product is dissolved into toluene, glass
Stick stirring is all dissolved to crude product, is then introduced into the pears type separatory funnel of 250mL；
3) separatory funnel is instilled with the concentrated sulfuric acid that pipette measures 2mL95%, then shakes separatory funnel, static split-phase,
2-3 times repeatedly, until solution is in light yellow；
4) it is 14 that the sodium hydroxide solution for being 20% with concentration, which adjusts solution ph in separatory funnel, shakes 30min, static
30min, split-phase, water phase are sodium phenylacetate solution, and organic phase recycles；
5) sodium phenylacetate solution obtained above is put into beaker, 2-3g active carbon is added, beaker is put into constant temperature magnetic
Decoloration, temperature 70 C, bleaching time 30min are stirred on power blender；
6) hydrochloric acid solution that concentration is 20% is added in sodium phenylacetate solution obtained above and adjusts pH value to 1, obtains
Pure phenylacetic acid filters, obtains solid phenylacetic acid 92g；
7) solid phenylacetic acid is put into the beaker equipped with 100mL salt-free water, temperature is risen to 70 DEG C, then beaker is put
Onto constant temperature blender with magnetic force, then stirring is cooled to room temperature with the speed of 1 DEG C/h, obtains flakey solid phenylacetic acid, vacuum
It filters；
8) solid phenylacetic acid obtained above is put into vacuum oven to dry, obtains phenylacetic acid fine work, survey fusing point
It is 76-78 DEG C, the rate of recovery 85%, purity 99.5%, phenylacetic acid remains > 17mg/ml in mother liquor.
Comparative example 5
Phenylacetic acid is recycled from the production waste liquid of 6-APA, comprising the following steps:
1) it takes 500mL waste liquid that 1L is added equipped in the three-necked flask of electric stirring, starts stirring, mass fraction 20% is added dropwise
Hydrochloric acid to pH be 2.0-2.5, a certain amount of extractant is added, controls certain temperature, stirs the regular hour, stops, will
Mixed liquor moves into 1L separatory funnel, after stratification, split-phase；
2) organic phase is neutralized to pH with the sodium hydroxide of mass fraction 20% is 9.0-9.5, is stood, and divides and goes organic phase,
By heated aqueous to certain temperature, it is slowly dropped into the hydrochloric acid of mass fraction 10% while stirring to pH2.0-2.5, rises to certain temperature
Degree, stirs evenly, and suitable active carbon decoloring is added, and insulated and stirred 15min is filtered while hot；
3) filtrate is cooled to 10 DEG C of following crystallization under predetermined circumstances, product is precipitated all, is obtained after suction filtration white
Color flat crystal is dried in vacuo rear load-bearing, surveys PAA content, yield 89-92%, purity 99-99.5%, benzene second in mother liquor
Acid residual > 16mg/ml.
Claims (7)
1. a kind of secondary recovery from 6-APA lysate and the method for purifying phenylacetic acid add extraction after the acidification of 6-APA lysate
Agent is taken to be extracted, organic phase obtains once recycling phenylacetic acid by alkalization, separation water intaking phase then through decoloration, two degree of acidifications
With primary crystalline mother solution after the recovery, it is characterised in that: take off primary crystalline mother solution after the recovery by macroporous resin adsorption, alkali
It is attached, pH2.0-3.0 crystallization is adjusted, filters, is dry, obtains secondary recovery phenylacetic acid, adsorption temp is 20-60 DEG C, and crystallization is female
Adsorption flow rate of the liquid through macroreticular resin is 0.5-5.0BV/h, and alkali desorption temperature is 30-80 DEG C, and alkali concentration used is 0.5%-
10%, the volume of alkali used is 0.5-5BV.
2. a kind of secondary recovery from 6-APA lysate according to claim 1 and the method for purifying phenylacetic acid, feature
Be: acidification, two degree of pH value controls being acidified are 2.0-3.0.
3. a kind of secondary recovery from 6-APA lysate according to claim 1 and the method for purifying phenylacetic acid, feature
It is: uses methylene chloride, methyl iso-butyl ketone (MIBK), hexamethylene, tetrachloromethane or chloroform as extractant when extraction, stirring extracts,
Split-phase is stood, organic phase is taken.
4. a kind of secondary recovery from 6-APA lysate according to claim 1 and the method for purifying phenylacetic acid, feature
Be: temperature when extraction is 10-50 DEG C, extraction time 10-30min.
5. a kind of secondary recovery from 6-APA lysate according to claim 1 and the method for purifying phenylacetic acid, feature
Be: the pH value control of alkalization is 8.0-11.0.
6. a kind of secondary recovery from 6-APA lysate according to claim 1 and the method for purifying phenylacetic acid, feature
Be: when decoloration, bleaching temperature is 30-70 DEG C, and decolourize 10-60min.
7. a kind of secondary recovery from 6-APA lysate according to claim 1 and the method for purifying phenylacetic acid, feature
It is, big pore resin is LXT series plastics, LX series plastics or XDA series plastics.
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| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1227216A (en) * | 1999-01-18 | 1999-09-01 | 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 |
| CN104003867A (en) * | 2014-05-22 | 2014-08-27 | 江苏宝众宝达药业有限公司 | Method for recovering p-hydroxyphenylacetic acid from waste liquid |
| CN105132513A (en) * | 2015-09-30 | 2015-12-09 | 湖南福来格生物技术有限公司 | Method for preparing amoxicillin or ampicillin in full-water-phase through mode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1227216A (en) * | 1999-01-18 | 1999-09-01 | 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 |
| CN104003867A (en) * | 2014-05-22 | 2014-08-27 | 江苏宝众宝达药业有限公司 | Method for recovering p-hydroxyphenylacetic acid from waste liquid |
| CN105132513A (en) * | 2015-09-30 | 2015-12-09 | 湖南福来格生物技术有限公司 | Method for preparing amoxicillin or ampicillin in full-water-phase through mode |
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