CN110483276A - A kind of D-ALPHA-Hydroxypropionic acid extracting method - Google Patents
A kind of D-ALPHA-Hydroxypropionic acid extracting method Download PDFInfo
- Publication number
- CN110483276A CN110483276A CN201910684425.1A CN201910684425A CN110483276A CN 110483276 A CN110483276 A CN 110483276A CN 201910684425 A CN201910684425 A CN 201910684425A CN 110483276 A CN110483276 A CN 110483276A
- Authority
- CN
- China
- Prior art keywords
- resin
- fermentation liquid
- alpha
- hydroxypropionic acid
- bed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
-
- 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
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Abstract
The present invention is suitable for technical field of bioengineering, provides a kind of D-ALPHA-Hydroxypropionic acid extracting method, comprising: be separated by solid-liquid separation D-ALPHA-Hydroxypropionic acid calcium fermentation liquid, remove removing protein and pigment, obtain the first fermentation liquid；First fermentation liquid is subjected to continuous ionic exchange processing by cation bed resin and obtains the second fermentation liquid to adsorb calcium ion；Second fermentation liquid is subjected to continuous ionic exchange processing by anion bed resin and obtains third fermentation liquid to adsorb sulfate radical, chloride ion；The cation bed resin and anion bed resin are subjected to pneumatic jack washing process, obtain water lotion；The water lotion and third fermentation liquid are subjected to concentration to get D-ALPHA-Hydroxypropionic acid.On the one hand, the problem big the present invention overcomes water consumption, resin mode of washing have been higher by the utilization rate of water much by the way of mixing wastewater with air, and water consumption is the 1/3 of fixed bed；On the other hand, amount of resin of the present invention is few, only the 30% of the amount of resin of fixed bed.
Description
Technical field
The invention belongs to technical field of bioengineering more particularly to a kind of D-ALPHA-Hydroxypropionic acid extracting methods.
Background technique
Currently, the market of D-ALPHA-Hydroxypropionic acid is mainly in North America and Europe, either production or application has all accounted for the big of market
The producer of half of the country, the country, China large-scale production D-ALPHA-Hydroxypropionic acid is formed not yet, and most of Dependent Demand is in import, due to price
The reason of monopolization and polylactic acid market etc. are not formed, domestic enterprise never flourish in the market in D-ALPHA-Hydroxypropionic acid.But
It is undeniably, D-ALPHA-Hydroxypropionic acid market tomorrow requirement is very big, and growth momentum should not be underestimated.
D-ALPHA-Hydroxypropionic acid fermentation method produces at present, is the trend of clean manufacturing, most common production technology is calcium salt method, but calcium
Salt method can introduce a large amount of inorganic salts, and dominant cation has calcium, magnesium, potassium etc., anion have chloride ion, sulfate radical, phosphate radical from
Son etc..Cationic total amount is 600-800ppm, and anion total amount is 1000-1200ppm, and national standard sun anion must not all be examined
Out.Very high to D-ALPHA-Hydroxypropionic acid purity requirement especially when doing PLA (polylactic acid), salinity directly affects esterification when being esterified
Yield.Traditional desalination de-ash process is resin ion exchange process, extraction, electrodialysis embrane method etc., and wherein resin ion is inhaled
Attached method is widely used, good operability, stable product quality, and far better than extraction and embrane method, but refining effect is still poor, and
Ash content index is not able to satisfy polymer grade ash requirements.
It can be seen that there are the introducings of a large amount of anions and canons for existing D-ALPHA-Hydroxypropionic acid extracting method, to gained D-ALPHA-Hydroxypropionic acid performance
There is certain influence, is unable to satisfy national standard, and refining effect is poor and ash content index is not able to satisfy polymer grade ash requirements
Technical problem.
Summary of the invention
The embodiment of the present invention provides a kind of D-ALPHA-Hydroxypropionic acid extracting method, it is intended to solve existing D-ALPHA-Hydroxypropionic acid extracting method and exist greatly
The introducing for measuring anions and canons, has certain influence to gained D-ALPHA-Hydroxypropionic acid performance, is unable to satisfy national standard, and refining effect is poor, with
And ash content index is not able to satisfy the problem of polymer grade ash requirements.
The embodiments of the present invention are implemented as follows, a kind of D-ALPHA-Hydroxypropionic acid extracting method, comprising:
D-ALPHA-Hydroxypropionic acid calcium fermentation liquid is separated by solid-liquid separation, removes removing protein and pigment, obtains the first fermentation liquid；
First fermentation liquid is subjected to continuous ionic exchange processing by cation bed resin and obtains second to adsorb calcium ion
Fermentation liquid；
Second fermentation liquid is subjected to continuous ionic exchange processing by anion bed resin, to adsorb sulfate radical, chloride ion,
Obtain third fermentation liquid；
The cation bed resin and anion bed resin are subjected to pneumatic jack washing process, obtain water lotion；
The water lotion and third fermentation liquid are subjected to concentration to get D-ALPHA-Hydroxypropionic acid.
D-ALPHA-Hydroxypropionic acid extracting method provided in an embodiment of the present invention uses new type of continuous ion-exchange process, this artistic tree
Rouge dosage is few, and resin utilization rate is high, and it is even more Advantage height compared to fixed-bed process that effect, which is far superior to the effect of pillar in laboratory,
It is many out, on the one hand, the present invention overcomes the big problem of water consumption, resin mode of washing makes by the way of mixing wastewater with air
The utilization rate of water has been higher by very much, and water consumption is the 1/3 of fixed bed；On the other hand, amount of resin of the present invention is few, only fixed bed
Amount of resin 30%, resin service life was up to 3 years, and according to 10,000 tons/year, cation bed amount of resin is 5 tons, fixed bed dosage
It is 16 tons.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
D-ALPHA-Hydroxypropionic acid has been realized in industrialization, but fermentation and extraction process can introduce a large amount of inorganic salts, wherein purifying
Desalination workshop section has been applied primarily to ion-exchange process, and general desalination deliming mainly uses fixed-bed process, fixed-bed process
The problems such as water consumption is big, amount of resin is big, blowdown flow rate is big, yield is low, product purity is low is always to limit being produced into for D-ALPHA-Hydroxypropionic acid
This, the present invention mainly improves technique using continuous ion-exchange, carries out desalination deliming, this technique water consume is low, high income, product purity
It is high.
Currently, in the fixed-bed process of desalination deliming, cation bed removing cation, anion bed removes anion, according to strong acid sun
Resin adsorption amount 1.8mol, the 15-18 times of resin adsorption that feed volume reaches bed volume is saturated, but ADSORPTION IN A FIXED BED volume
13 times have cationic leakage substantially, because fixed-bed resin loadings are big, material flow is fast, and resin use for a long time will appear object
The case where expecting bias current, leads to have gap with theoretical adsorption capacity；The big resin of the big pressure drop of resin loadings is broken very serious, and resin needs
Often supplement；Wash water water consumption is big, and backwash effect directly affects the desalting effect of resin, needs lower resin of the big pressure of big flow
Thoroughly cleaning；Resin anion (R.A.) is weak base resin, adsorbance 2.9mol, and feed volume reach bed volume 20-22 times is set
Rouge adsorption saturation, but ADSORPTION IN A FIXED BED volume, which reaches 15-18 times, just has anion leakage, especially CL- ion, according to tree
Rouge absorption sequence is the high last absorption of price, and price is low to be revealed at first, therefore CL- ion is more difficult to control in anion bed；Yin tree
Rouge adsorbs D-ALPHA-Hydroxypropionic acid, and the swelling volume of resin is larger, and fixed-bed resin loadings are big, and resin expansion can increase the broken of resin；
Same resin expansion is two-way expansion, and it is serious to will lead to material bias current, resin the case where it is easy to appear multiple regeneration, and charging is just
Anion is revealed after the meeting；Also, D-ALPHA-Hydroxypropionic acid ash requirements are stringent, especially polymer grade ash requirements 15ppm, otherwise directly affect
Polymerization effect, fixed bed discharges, and ash content is unstable, and control is bad.
The D-ALPHA-Hydroxypropionic acid extracting method that embodiment provided by the invention provides, by the way that D-ALPHA-Hydroxypropionic acid calcium fermentation liquid is carried out solid-liquid point
From, remove removing protein and pigment, obtain the first fermentation liquid；First fermentation liquid is subjected to continuous ionic exchange by cation bed resin
Processing, to adsorb calcium ion, obtains the second fermentation liquid；Second fermentation liquid is carried out at continuous ionic exchange by anion bed resin
Reason, to adsorb sulfate radical, chloride ion, obtains third fermentation liquid；The cation bed resin and anion bed resin are carried out at pneumatic jack washing
Reason obtains water lotion；The water lotion and third fermentation liquid are subjected to concentration to get D-ALPHA-Hydroxypropionic acid；Using Novel connection
Continuous ion-exchange process, this process resin dosage is few, and resin utilization rate is high, and effect is far superior to the effect of pillar in laboratory,
It is even more that advantage is higher by much compared to fixed-bed process, on the one hand, the present invention overcomes the big problem of water consumption, resin mode of washing
By the way of mixing wastewater with air, it has been higher by the utilization rate of water very much, water consumption is the 1/3 of fixed bed；On the other hand, this hair
Bright amount of resin is few, only the 30% of the amount of resin of fixed bed, and resin service life was up to 3 years, according to 10,000 tons/year, cation bed tree
Rouge dosage is 5 tons, and fixed bed dosage is 16 tons.
In embodiments of the present invention, the separation of solid and liquid of D-ALPHA-Hydroxypropionic acid calcium fermentation liquid is by the way of conventional centrifugal, and D-ALPHA-Hydroxypropionic acid
Go removing protein and pigment by the way of conventional ultrafiltration in fermentation liquid.
In embodiments of the present invention, cation bed resin is 001*7 resin, Jining Hua Kai resin Co., Ltd is derived from, by it
It is loaded according to the ratio of velocity ratio 1:8, it is excessively high that each column resin loadings not will cause feed pressure, and resin have to break substantially
It is broken, overcome the case where cation bed resin is easily broken.
In embodiments of the present invention, anion bed resin is D-319 resin, derives from Jining Hua Kai resin Co., Ltd.
It is above-mentioned to carry out first fermentation liquid continuously by cation bed resin as another preferred embodiment of the invention
Ion-exchange treatment the step of to adsorb calcium ion, obtain the second fermentation liquid, specifically includes:
By first fermentation liquid according to the feed flow rate of 4 times of bed volumes, it is added in cation bed resin, passes through continuous ionic
Exchange process based on two-by-two and three string modes handle, carry out the absorption of calcium ion, obtain the second fermentation liquid.
It is above-mentioned to carry out second fermentation liquid continuously by anion bed resin as another preferred embodiment of the invention
Ion-exchange treatment the step of to adsorb sulfate radical, chloride ion, obtain third fermentation liquid, specifically includes:
By second fermentation liquid according to the feed flow rate of 3 times of bed volumes, it is added in anion bed resin, passes through continuous ionic
Exchange process based on two-by-two and three string modes handle, carry out sulfate radical, chloride ion absorption, obtain third fermentation liquid.
It is above-mentioned to carry out second fermentation liquid continuously by anion bed resin as another preferred embodiment of the invention
Ion-exchange treatment the step of to adsorb sulfate radical, chloride ion, obtain third fermentation liquid, specifically includes:
By second fermentation liquid according to the feed flow rate of 3 times of bed volumes, it is added in anion bed resin, passes through continuous ionic
Exchange process based on two-by-two and three string modes handle, carry out sulfate radical, chloride ion absorption, obtain third fermentation liquid.
It is above-mentioned that the cation bed resin and anion bed resin are subjected to pneumatic jack water as another preferred embodiment of the invention
The step of washing processing, obtaining water lotion, specifically includes:
The cation bed resin and anion bed resin are subjected to pneumatic jack washing process in a manner of plural serial stage, washed
Liquid, wherein wash water flow control is 3 times of bed volumes, and leaching requirement is 1.5 times of resin volumes.
It is above-mentioned to carry out the water lotion and third fermentation liquid at concentration as another preferred embodiment of the invention
The step of reason is to get D-ALPHA-Hydroxypropionic acid, specifically includes:
The water lotion and third fermentation liquid are subjected to reduction vaporization concentration, temperature is 80~100 DEG C, vacuum degree
It is 210~250bar up to D-ALPHA-Hydroxypropionic acid.
As another preferred embodiment of the invention, the D-ALPHA-Hydroxypropionic acid extracting method further include:
Hydrochloric acid solution is added in the cation bed resin, and sodium hydroxide solution is added in the anion bed resin, it will
Calcium ion, sulfate radical and chloride ion are eluted out from cation bed resin, anion bed resin respectively.
The specific implementation of the embodiment of the present invention can be with are as follows: resin subregion is loaded, resin on a turntable alternately
It uses, is divided into four areas, area is freed in respectively transition, it is therefore an objective to which cation bed resin is switched to H+Type, anion bed resin switch to OH-；Gas
Push up water wash zone, it is therefore an objective to the regenerative agent after transition be flushed in such a way that pneumatic jack is washed and free tank and apply；Feed zone, and go here and there
The mode of connection makes every center pillar reach maximum adsorbance, index controllability；Pneumatic jack water wash zone, it is therefore an objective to by feed zone column not
The material top of purifying is back into batch can.
Wherein, the purpose in wash water area is to continue non-purified material ejection to feed removing impurities, and wash water is divided into two-by-two and gone here and there
Connection controls wash water speed in 3 times of bed layer flow speeds, and layer, which is washed, can guarantee washing effect, control leaching requirement, and leaching requirement can control
1.5 times of resin volumes, wash water rear pillar is interior to remain lactic acid concn < 0.1%, loss amount < 0.2%, traditional fixed bed water consumption
Reach 3-4 times of resin volume, remains lactic acid concn 0.3-0.4%, total losses amount > 1% in wash water rear pillar.
Wherein, the cation bed resin in feed zone is upper feeding, is transformed into H+Type, dilatancy is maximum, removes cationic process
Resin volume becomes smaller, and upper feeding can guarantee that the layer of resin inhales effect, and dominant cation is calcium ion in lactic acid solution, using even
For continuous ion-exchange technique using simultaneously the modes of three strings, Fractional Collections make resin reach maximum adsorption effect two-by-two, feed flow rate is 4 times of beds
Layer volume, general 001*7 resinite friendship amount are 1.8mol, can guarantee that the maximum of resin is inhaled using continuous ionic exchange processing
It is attached, and calcium ion removal efficiency reaches 100% in discharging, control is preferable, control can be carried out in third first column in parallel,
Treating capacity is 15-18 times of bed volume, and traditional handicraft control is poor, and impurity removal percentage is up to 99%, and resin is easy to out
Existing bias current, 10 times of bed volumes for the treatment of capacity highest；Negative resin into, resin uses D-319 under being, is transformed into OH-Type, D-ALPHA-Hydroxypropionic acid
Adsorptivity it is stronger, resin expansion is strong, under into can reduce damage of the resin expansion to resin, charging is using two-by-two and three strings
Mode, can guarantee there are enough swap times, feed flow rate is 3 times of bed volumes, major impurity ion in lactic acid solution
For sulfate radical, chloride ion, lactate ion is adsorbed first after the charging of lactic acid concn high resin, as adsorbance increases, chloride ion,
Sulfate radical successively participates in exchanging, and lactate is ejected, and resin at this time is lactate type, sulfate radical chloride ion and cream in material
Acid group exchange, D319 resinite friendship amount are 2.6mol, and removal efficiency reaches 100%, and treating capacity reaches 20-22 times of bed volume, Gu
Fixed bed removal efficiency only has 98%, and continuous ionic is exchanged in anion bed area lactic acid loss amount < 1%, and fixed bed has reached 3-4%, loss
Larger, the reason is that chloride ion is that monovalent ion is easy to reveal, lactic acid has part and cannot thoroughly be ejected.
Wherein, pneumatic jack water wash zone, same use and concatenated mode, have used the mode of pneumatic jack first, have kept release agent complete
Portion, which is pushed up back, frees tank, is then washed with the mode of plural serial stage, guarantees in resin without entrainment, 3 times of beds of wash water flow control
Layer volume, leaching requirement are 1.5 times of resin volumes, and fixed bed leaching requirement is larger can to reach 3-4 times of resin volume, and water consumption is big.
Wherein, it is to be eluted out the foreign ion of resin adsorption in the way of ion exchange that area is freed in transition, cation bed
Turn H using HCL+Type, anion bed turn OH using NaOH-The regeneration effect of type, resin directly affects the using effect of resin, is related to
The ways of relief of product quality, continuous ion-exchange technique can greatly save release agent, and reach optimal regeneration effect, use
The release agent of 5% concentration, regeneration volume uses 2 times of resin volumes, and concatenated mode can guarantee alternately regenerated effect, Gu
The mode that fixed bed is generally impregnated using a large amount of regenerative agent, regenerant consumption reach 4 times of resin volume or more, regenerant consumption
Greatly, inefficient.
It is described further below by way of technical effect of the specific embodiment to D-ALPHA-Hydroxypropionic acid extracting method of the invention.
Embodiment 1
D-ALPHA-Hydroxypropionic acid calcium fermentation liquid (D-ALPHA-Hydroxypropionic acid calcium concentration 110g/L, no residual sugar, fermentation liquid pH 6.5) is subjected to conventional solid-liquid
It separates, remove removing protein and pigment, obtain the first fermentation liquid；By first fermentation liquid according to the feed flow rate of 4 times of bed volumes,
It is added in 001*7 resin, continuous ionic exchange process based on handling two-by-two and by way of three strings, carries out the suction of calcium ion
It is attached, obtain the second fermentation liquid；It by second fermentation liquid according to the feed flow rate of 3 times of bed volumes, is added in D-319 resin, leads to
Cross continuous ionic exchange process based on two-by-two and three string modes handle, carry out sulfate radical, chloride ion absorption, obtain third fermentation
Liquid；The 001*7 resin and D-319 resin are subjected to pneumatic jack washing process in a manner of plural serial stage, obtain water lotion,
In, wash water flow control is 3 times of bed volumes, and leaching requirement is 1.5 times of resin volumes；By the water lotion and third fermentation liquid
It carries out using concentration is evaporated under reduced pressure, temperature is 80 DEG C, and vacuum degree is 210bar to get D-ALPHA-Hydroxypropionic acid.
Embodiment 2
D-ALPHA-Hydroxypropionic acid calcium fermentation liquid (D-ALPHA-Hydroxypropionic acid calcium concentration 100g/L, no residual sugar, fermentation liquid pH 6.0) is subjected to conventional solid-liquid
It separates, remove removing protein and pigment, obtain the first fermentation liquid；By first fermentation liquid according to the feed flow rate of 4 times of bed volumes,
It is added in 001*7 resin, continuous ionic exchange process based on handling two-by-two and by way of three strings, carries out the suction of calcium ion
It is attached, obtain the second fermentation liquid；It by second fermentation liquid according to the feed flow rate of 3 times of bed volumes, is added in D-319 resin, leads to
Cross continuous ionic exchange process based on two-by-two and three string modes handle, carry out sulfate radical, chloride ion absorption, obtain third fermentation
Liquid；The 001*7 resin and D-319 resin are subjected to pneumatic jack washing process in a manner of plural serial stage, obtain water lotion,
In, wash water flow control is 3 times of bed volumes, and leaching requirement is 1.5 times of resin volumes；By the water lotion and third fermentation liquid
It carries out using concentration is evaporated under reduced pressure, temperature is 90 DEG C, and vacuum degree is 220bar to get D-ALPHA-Hydroxypropionic acid.
Embodiment 3
D-ALPHA-Hydroxypropionic acid calcium fermentation liquid (D-ALPHA-Hydroxypropionic acid calcium concentration 110g/L, no residual sugar, fermentation liquid pH 6.0) is subjected to conventional solid-liquid
It separates, remove removing protein and pigment, obtain the first fermentation liquid；By first fermentation liquid according to the feed flow rate of 4 times of bed volumes,
It is added in 001*7 resin, continuous ionic exchange process based on handling two-by-two and by way of three strings, carries out the suction of calcium ion
It is attached, obtain the second fermentation liquid；It by second fermentation liquid according to the feed flow rate of 3 times of bed volumes, is added in D-319 resin, leads to
Cross continuous ionic exchange process based on two-by-two and three string modes handle, carry out sulfate radical, chloride ion absorption, obtain third fermentation
Liquid；The 001*7 resin and D-319 resin are subjected to pneumatic jack washing process in a manner of plural serial stage, obtain water lotion,
In, wash water flow control is 3 times of bed volumes, and leaching requirement is 1.5 times of resin volumes；By the water lotion and third fermentation liquid
It carries out using concentration is evaporated under reduced pressure, temperature is 110 DEG C, and vacuum degree is 230bar to get D-ALPHA-Hydroxypropionic acid.
Embodiment 4
D-ALPHA-Hydroxypropionic acid calcium fermentation liquid (D-ALPHA-Hydroxypropionic acid calcium concentration 120g/L, no residual sugar, fermentation liquid pH 7.0) is subjected to conventional solid-liquid
It separates, remove removing protein and pigment, obtain the first fermentation liquid；By first fermentation liquid according to the feed flow rate of 4 times of bed volumes,
It is added in 001*7 resin, continuous ionic exchange process based on handling two-by-two and by way of three strings, carries out the suction of calcium ion
It is attached, obtain the second fermentation liquid；It by second fermentation liquid according to the feed flow rate of 3 times of bed volumes, is added in D-319 resin, leads to
Cross continuous ionic exchange process based on two-by-two and three string modes handle, carry out sulfate radical, chloride ion absorption, obtain third fermentation
Liquid；The 001*7 resin and D-319 resin are subjected to pneumatic jack washing process in a manner of plural serial stage, obtain water lotion,
In, wash water flow control is 3 times of bed volumes, and leaching requirement is 1.5 times of resin volumes；By the water lotion and third fermentation liquid
It carries out using concentration is evaporated under reduced pressure, temperature is 110 DEG C, and vacuum degree is 250bar to get D-ALPHA-Hydroxypropionic acid.
Embodiment 5
D-ALPHA-Hydroxypropionic acid calcium fermentation liquid (D-ALPHA-Hydroxypropionic acid calcium concentration 120g/L, no residual sugar, fermentation liquid pH 6.0) is subjected to conventional solid-liquid
It separates, remove removing protein and pigment, obtain the first fermentation liquid；By first fermentation liquid according to the feed flow rate of 4 times of bed volumes,
It is added in 001*7 resin, continuous ionic exchange process based on handling two-by-two and by way of three strings, carries out the suction of calcium ion
It is attached, obtain the second fermentation liquid；It by second fermentation liquid according to the feed flow rate of 3 times of bed volumes, is added in D-319 resin, leads to
Cross continuous ionic exchange process based on two-by-two and three string modes handle, carry out sulfate radical, chloride ion absorption, obtain third fermentation
Liquid；The 001*7 resin and D-319 resin are subjected to pneumatic jack washing process in a manner of plural serial stage, obtain water lotion,
In, wash water flow control is 3 times of bed volumes, and leaching requirement is 1.5 times of resin volumes；By the water lotion and third fermentation liquid
It carries out using concentration is evaporated under reduced pressure, temperature is 100 DEG C, and vacuum degree is 220bar to get D-ALPHA-Hydroxypropionic acid.
Calcium ion content in second fermentation liquid obtained by embodiments of the present invention 1-5 is detected, and to third
Sulfate radical, chloride ion content are detected in fermentation liquid, while being measured conventional fixed-type bed and being extracted calcium ion, sulphur in D-ALPHA-Hydroxypropionic acid method
Acid group, chloride ion content, and further compare the two ion removal efficiency, lactic acid loss amount and ash content, the results are shown in Table 1:
Table 1
To sum up, cation bed resin is upper feeding in 1-5 of the embodiment of the present invention, is transformed into H+Type, dilatancy are maximum, removing sun from
Subprocess resin volume becomes smaller, and upper feeding can guarantee that the layer of resin inhales effect, and dominant cation is calcium ion in lactic acid solution,
By continuous ion-exchange technique using two-by-two and three string in the way of, Fractional Collections make resin reach maximum adsorption effect, feed flow rate
For 4 times of bed volumes, and 001*7 resinite friendship amount is 1.8mol, can guarantee the maximum adsorption of resin using continuous ion-exchange, and
Calcium ion removal efficiency reaches 100% in discharging, and control is preferable, can carry out control, processing in third first column in parallel
Amount is 15-18 times of bed volume；Traditional fixed-bed type technique control is poor, and calcium ion removal efficiency is up to 99%, and resin is very
It is easy to appear bias current, 10 times of bed volumes for the treatment of capacity highest.
In addition, into resin uses D-319, is transformed into OH under anion bed resin is in 1-5 of the embodiment of the present invention-Type, D- cream
The adsorptivity of acid is stronger, and resin expansion is strong, under into can reduce damage of the resin expansion to resin, charging is using two-by-two and three
The mode of string can guarantee there are enough swap times, and feed flow rate is 3 times of bed volumes, in lactic acid solution major impurity from
Son be sulfate radical, chloride ion, lactic acid concn high resin charging after adsorb lactate ion first, as adsorbance increases, chlorine from
Son, sulfate radical successively participate in exchanging, and lactate is ejected, and resin at this time is lactate type, the sulfate radical chloride ion in material
It is exchanged with lactate, D319 resinite friendship amount is 2.6mol, and removal efficiency reaches 100%, and treating capacity reaches 20-22 times of bed body
Product, traditional fixed-bed type removal efficiency only have 98%, and for the continuous ion-exchange of the present invention in anion bed area lactic acid loss amount < 1%, tradition is fixed
Bed has reached 3-4%, and loss is larger, the reason is that chloride ion is that monovalent ion is easy to reveal, lactic acid has part not
It can thoroughly be ejected.
In addition, D-ALPHA-Hydroxypropionic acid ash content is stably controlled as 15ppm in 1-5 of the embodiment of the present invention, and traditional fixed-bed type discharging
Ash content is unstable, and control is bad, and ash content control range is 15-80ppm.
It is worth noting that, D-ALPHA-Hydroxypropionic acid extracting method provided in an embodiment of the present invention, uses new type of continuous ion exchange
Technique, this process resin dosage is few, and resin utilization rate is high, and effect is far superior to the effect of pillar in laboratory, compares fixed bed
Technique is even more that advantage is higher by very much, on the one hand, the case where being easily broken the present invention overcomes cation bed resin, resin is according to velocity ratio
The ratio of 1:8 is loaded, and each column resin loadings cannot cause feed pressure excessively high, and resin does not have broken substantially；It also overcomes
The big problem of water consumption, resin mode of washing have been higher by the utilization rate of water very much, water consumption by the way of mixing wastewater with air
It is the 1/3 of traditional fixed-bed type；On the other hand, amount of resin of the present invention is few, and the 30% of the amount of resin of only traditional fixed-bed type,
Resin service life was up to 3 years, and according to 10,000 tons/year, cation bed amount of resin is 5 tons, and fixed bed dosage is 16 tons, and tradition is fixed
Bed service life highest is also 3 years, and negative resin is identical as positive resin.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of D-ALPHA-Hydroxypropionic acid extracting method characterized by comprising
D-ALPHA-Hydroxypropionic acid calcium fermentation liquid is separated by solid-liquid separation, removes removing protein and pigment, obtains the first fermentation liquid；
First fermentation liquid is subjected to continuous ionic exchange processing by cation bed resin and obtains the second fermentation to adsorb calcium ion
Liquid；
Second fermentation liquid is subjected to continuous ionic exchange processing by anion bed resin, to adsorb sulfate radical, chloride ion, obtains the
Three fermentation liquids；
The cation bed resin and anion bed resin are subjected to pneumatic jack washing process, obtain water lotion；
The water lotion and third fermentation liquid are subjected to concentration to get D-ALPHA-Hydroxypropionic acid.
2. D-ALPHA-Hydroxypropionic acid extracting method as described in claim 1, which is characterized in that the cation bed resin is 001*7 resin, according to
The ratio of velocity ratio 1:8 is loaded.
3. D-ALPHA-Hydroxypropionic acid extracting method as described in claim 1, which is characterized in that described that first fermentation liquid is passed through cation bed
Resin carries out continuous ionic exchange processing, the step of to adsorb calcium ion, obtain the second fermentation liquid, specifically includes:
By first fermentation liquid according to the feed flow rate of 4 times of bed volumes, it is added in cation bed resin, is exchanged by continuous ionic
Technique based on two-by-two and three string modes handle, carry out the absorption of calcium ion, obtain the second fermentation liquid.
4. D-ALPHA-Hydroxypropionic acid extracting method as described in claim 1, which is characterized in that described to go the method for removing protein and pigment to adopt
With the mode of ultrafiltration.
5. D-ALPHA-Hydroxypropionic acid extracting method as described in claim 1, which is characterized in that the anion bed resin is D-319 resin.
6. D-ALPHA-Hydroxypropionic acid extracting method as described in claim 1, which is characterized in that described that second fermentation liquid is passed through anion bed
Resin carries out continuous ionic exchange processing, the step of to adsorb sulfate radical, chloride ion, obtain third fermentation liquid, specifically includes:
By second fermentation liquid according to the feed flow rate of 3 times of bed volumes, it is added in anion bed resin, is exchanged by continuous ionic
Technique based on two-by-two and three string modes handle, carry out sulfate radical, chloride ion absorption, obtain third fermentation liquid.
7. D-ALPHA-Hydroxypropionic acid extracting method as described in claim 1, which is characterized in that described by the cation bed resin and anion bed tree
The step of rouge carries out pneumatic jack washing process, obtains water lotion, specifically includes:
The cation bed resin and anion bed resin are subjected to pneumatic jack washing process in a manner of plural serial stage, obtain water lotion,
In, wash water flow control is 3 times of bed volumes, and leaching requirement is 1.5 times of resin volumes.
8. D-ALPHA-Hydroxypropionic acid extracting method as described in claim 1, which is characterized in that described that the water lotion and third ferment
Liquid carries out the step of concentration is to get D-ALPHA-Hydroxypropionic acid, specifically includes:
The water lotion and third fermentation liquid are subjected to reduction vaporization concentration, temperature is 80~100 DEG C, and vacuum degree is
210~250bar is up to D-ALPHA-Hydroxypropionic acid.
9. D-ALPHA-Hydroxypropionic acid extracting method as described in claim 1, which is characterized in that further include:
Hydrochloric acid solution is added in the cation bed resin, and sodium hydroxide solution is added in the anion bed resin, by calcium from
Son, sulfate radical and chloride ion are eluted out from cation bed resin, anion bed resin respectively.
10. D-ALPHA-Hydroxypropionic acid extracting method as claimed in claim 9, which is characterized in that the concentration of hydrochloric acid solution and hydroxide
Sodium solution concentration is 5%, and dosage is 2 times of resin volumes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910684425.1A CN110483276A (en) | 2019-07-26 | 2019-07-26 | A kind of D-ALPHA-Hydroxypropionic acid extracting method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910684425.1A CN110483276A (en) | 2019-07-26 | 2019-07-26 | A kind of D-ALPHA-Hydroxypropionic acid extracting method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110483276A true CN110483276A (en) | 2019-11-22 |
Family
ID=68548575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910684425.1A Withdrawn CN110483276A (en) | 2019-07-26 | 2019-07-26 | A kind of D-ALPHA-Hydroxypropionic acid extracting method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110483276A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880710A (en) * | 2021-10-22 | 2022-01-04 | 万华化学集团股份有限公司 | Lactic acid purification method |
| WO2023155797A1 (en) * | 2022-02-16 | 2023-08-24 | 欧尚元智能装备有限公司 | Method for purifying l-lactic acid |
-
2019
- 2019-07-26 CN CN201910684425.1A patent/CN110483276A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880710A (en) * | 2021-10-22 | 2022-01-04 | 万华化学集团股份有限公司 | Lactic acid purification method |
| CN113880710B (en) * | 2021-10-22 | 2023-10-20 | 万华化学集团股份有限公司 | Purification method of lactic acid |
| WO2023155797A1 (en) * | 2022-02-16 | 2023-08-24 | 欧尚元智能装备有限公司 | Method for purifying l-lactic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shen et al. | A combined process of activated carbon adsorption, ion exchange resin treatment and membrane concentration for recovery of dissolved organics in pre-hydrolysis liquor of the kraft-based dissolving pulp production process | |
| Boonmee et al. | Improved lactic acid production by in situ removal of lactic acid during fermentation and a proposed scheme for its recovery | |
| CN106818752B (en) | A kind of preparation method of high-content kasugarnycin aqua | |
| WO2011082378A2 (en) | Purification of succinic acid from the fermentation broth containing ammonium succinate | |
| CN110483276A (en) | A kind of D-ALPHA-Hydroxypropionic acid extracting method | |
| CN107382713A (en) | A kind of technique of purification of lactic acid | |
| CN103388198A (en) | Method for preparing acid base from waste liquid of viscose sodium sulphate by bipolar membrane electrodialysis method | |
| CN103341320A (en) | Novel process for recycling acid and base from viscose sodium sulfate waste liquid by using a bipolar membrane electrodialysis method | |
| CN108793203A (en) | A kind of technique for extracting lithium from seawater | |
| CN102432479B (en) | Method for extracting L-valine from L-valine fermentation liquid | |
| CN103071389A (en) | Method for recovering threonine from threonine crystallization mother liquor | |
| CN103341321A (en) | Viscose sodium sulfate waste liquor acid and alkali recycling technology by virtue of bipolar membrane electrodialysis method | |
| CN100339351C (en) | Method for separating remaining sugar and extracting organic acid from organic acid fermentation liquor and corresponding organic acid mother liquor | |
| CN102557970B (en) | Preparation method of anhydrous betaine | |
| CN106755613B (en) | Purification method of starch sugar | |
| CN102698602B (en) | The method reclaiming threonine from threonine crystallization mother liquid | |
| CN113083253B (en) | Weak acid cation resin for extracting vitamin B12 and synthetic method thereof | |
| CN112174856B (en) | Purification production process of organic sulfonic acid | |
| CN111392712B (en) | Nitrogen modified mesoporous carbon material, preparation method thereof and application of nitrogen modified mesoporous carbon material as electro-adsorption desalination electrode material | |
| CN104673872A (en) | Method for recycling DCPC (deacetyl cephalosporin C) from cephalosporin C resin adsorption waste liquor | |
| CN111359594A (en) | Boric acid adsorption material and preparation method thereof | |
| CN104496756B (en) | The electrodialysis process of xylitol is prepared with viscose rayon press lye for raw material | |
| CN110294726A (en) | The preparation method of ISOASCORBIC ACID potassium | |
| CN105238841A (en) | Recycling and conversion method of DCPC in cephalosporin C adsorption waste liquid | |
| CN108975358A (en) | The method of ion-exchange membrane electrolysis production lithium hydroxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20191122 |
|
| WW01 | Invention patent application withdrawn after publication |