CN101811953A - Method for extracting succinic acid from fermentation broth - Google Patents
Method for extracting succinic acid from fermentation broth Download PDFInfo
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- CN101811953A CN101811953A CN200910046480A CN200910046480A CN101811953A CN 101811953 A CN101811953 A CN 101811953A CN 200910046480 A CN200910046480 A CN 200910046480A CN 200910046480 A CN200910046480 A CN 200910046480A CN 101811953 A CN101811953 A CN 101811953A
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Abstract
The invention relates to a method for extracting succinic acid from fermentation broth. The method includes the following steps that: (1) fermentation broth from which succinic acid can be obtained by way of microbial fermentation is ultrafiltered to remove mycelium cells and macromolecular impurities, so that clear filtrate is obtained; (2) H- storng-acid cation exchange resin is chosen, the filtrate obtained in the step 1 is exchanged by the ions of the H- storng-acid cation exchange resin, so that impurity cation is exchanged by H plus, and thereby succinic acid solution is obtained; (3) the succinic acid solution obtained in the step 2 is nanofiltered and decolored, so that decolored succinic acid solution is obtained; (4) the decolored succinic acid solution obtained in the step 3 is concentrated, crystallized, centrifuged and washed, so that succinic acid is obtained. Compared with the prior art, the invention has the advantages of reasonable process route, less steps, low energy consumption and cost, high product crystallization rate, high product purity, byproduct recyclability, energy saving and the like.
Description
Technical field
The present invention relates to the extraction separation of Succinic Acid, relate in particular to a kind of from fermented liquid the method for extraction separation Succinic Acid.
Background technology
Succinic Acid (Succinic Acid, Butanedioic Acid) claims succsinic acid again, is a kind of binary organic acid, and it is widely used as the raw material of special chemical products as 4 intermediate carbons, as is widely used in the industries such as pharmacy, food-processing, dyestuff, coating.
In recent years, succsinic acid attracts much attention as the raw material of biodegradable polymers.Use the raw material of succsinic acid as biodegradable polymer and speciality chemical, need it to have high purity, characteristics cheaply, is the reaction of raw material production the finished product or the quality that reduces the finished product to avoid the impurity inhibition in the succsinic acid by succsinic acid, and has the competitive power with other source succsinic acid.
In view of the minimizing day by day of petrochemical industry resource, and microbial fermentation is produced sustainability of natural resources, production efficiency height that succsinic acid has, is polluted less, low cost and other advantages, and the advantage that adopts this method to produce succsinic acid becomes increasingly conspicuous.
At present, succsinic acid commonly used produces bacterium to be had and separates from cud, as Ruminocoddus flavefaciens and Fibrobacter succinogenes, Actinobacillus succinogenes, the common trait that these microbial fermentations prepare succsinic acid is an anaerobically fermenting, produces succsinic acid with the glucide metabolism; Another kind of production method is converted into succsinic acid for adopting brevibacterium flavum (Brevibacterium flavum) with fumaric acid or its salt; Also have other can produce the microorganism of succsinic acid, example has mycocandida (genes Candida), Anaerobiospirillum succinoproducens (Anaerobiospirillum succiniciproducens) etc., but be not limited to above-mentioned described microorganism, also comprise the bacterial classification that adopts genetic engineering technique to obtain.
Adopt microbial fermentation or transform and produce succsinic acid, common characteristic is to add in the substratum nutritive substance for microbial growth, comprise that carbon is former (as available carbohydrate, as glucose, sucrose, starch etc.), available nitrogen former (as organonitrogens such as the albumen in various sources, polypeptide, amino acid, as inorganic nitrogens such as sulfate of ammoniac, urea, ammoniacal liquor), and various trace element, inorganic salt, VITAMIN etc.
Produce with microbial fermentation in the fermented liquid of succsinic acid, main component comprises thalline, insoluble nutritive ingredient, soluble nutritious components, small organic molecule and organic acid (formic acid, acetate, Succinic Acid etc.).Adopt the microbial transformation mode directly to join reaction substrate in the fermented liquid at the suitable stage of microorganism growth, or with the suitably processing of cell process, with other component separating in somatic cells and the fermented liquid, resuspending is used with reaction substrate in water and is reacted as centrifugal, membrane sepn, filtration etc.
In the process of enrichment succsinic acid, the control of pH value is very important.For preventing that the pH value that the succsinic acid accumulation brings from descending, in this process, add alkaline matter usually and neutralized, as sodium hydroxide, potassium hydroxide, liquefied ammonia (or ammoniacal liquor), magnesium hydroxide, calcium hydroxide, carbonate etc.
Therefore, obtaining highly purified succsinic acid from fermented liquid need adopt a series of separation means to remove the various impurity in the fermented liquid.
In the existing extraction process of succsinic acid, as document 1 (the Chinese patent method of separating and extracting succinic acid " a kind of from anaerobic fermented liquid ", contriver: Yao Zhong, Wu Hao, Liu Hui etc., number of patent application: describe 200610086003.7), adopt thalline and macromole soluble impurity in the two-stage membrane sepn step removal fermented liquid, through activated carbon decolorizing, concentrated, crystallization, obtain the succsinic acid crystallization then.In the fermenting process of succsinic acid, accumulation along with succsinic acid, the pH value of fermented liquid constantly reduces, low pH value will influence the growth and the metabolism of thalline, to influence the further accumulation of succsinic acid conversely, therefore in the process of fermentation, must add a certain amount of neutralizing agent such as liquefied ammonia (or ammoniacal liquor), sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, carbonate etc., with neutralization because the pH value decline that the product accumulation of succsinic acid brings.Therefore there is a large amount of impurity cationics in the fermented liquid.The membrane sepn process only can be held back macromolecular impurity in the document 1 described method, gac mainly plays decolorization, because the existence of a large amount of impurity cationics, in evaporating concentration process, can't obtain the high density succsinic acid, thereby crystallization yield is reduced, and succsinic acid crystalline quality does not reach the finished product requirement simultaneously, need be further purified to satisfy the harsh requirement of post-order process to the succsinic acid quality.
And document 2 (Chinese patent " method of purifying succinic acid from fermented liquid ", number of patent application: 200480028494.9) reported the method that adopts H-type strong acidic ion resin to remove impurity cationic in the fermented liquid, this method can effectively be removed the impurity cationic in the fermented liquid.In this technology, earlier fermented liquid is carried out simple pre-treatment, adopted conventional means (as centrifugal) to remove thalline in the fermented liquid.In the fermented liquid usually except that containing thalline, also contain a large amount of albumen, polysaccharide, colloid etc., these impurity can reduce the exchange capacity of ion exchange resin, reduce the work-ing life of ion exchange resin, part macromole impurity can flow out along with succsinic acid simultaneously, take in the subsequent technique, influence crystalline purity and yield.In addition, adopt in the succsinic acid crystallization that this technology obtains because the existence of albumen, polysaccharide makes succsinic acid crystal and mother liquor separation difficulty in commercial process.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the defective that above-mentioned prior art exists that a kind of technology is simple, Impurity removal is thorough, production cost is low, the method for product yield and purity are high from fermented liquid extraction separation Succinic Acid.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that this method may further comprise the steps:
(1) fermented liquid that microbial fermentation is obtained Succinic Acid carries out ultra-filtration and separation, removes somatic cells and macromole impurity, obtains the filtrate of clear;
(2) select H-type storng-acid cation exchange resin for use, the filtrate that step (1) obtains exchanges through H-type storng-acid cation exchange resin ion, and impurity cationic is exchanged into H
+, obtain Succinic Acid solution;
(3) the Succinic Acid solution that obtains of step (2) is through nanofiltration decolouring, the Succinic Acid solution that obtains decolouring;
(4) the Succinic Acid solution of the decolouring that obtains of step (3) through concentrating, crystallization, centrifugal, washing, obtain Succinic Acid.
Ultra-filtration and separation in the described step (1) adopts ultrafiltration membrane system or microfiltration membrane system, and the molecular weight cut-off 〉=10000MW of described ultrafiltration membrane system or membrane filtration aperture are 10-200nm, and the membrane filtration aperture of described microfiltration membrane system is 10-200nm.
The working pressure of described ultra-filtration and separation is 0.1-1Mpa, and service temperature is 20-90 ℃, and cycles of concentration is 5-50 times, and the dialysis water consumption is fermentating liquid volume 3%-20%.
The kit form of described ultrafiltration membrane system comprises tubular type, rolling, tubular fibre or board-like, and the kit form of described microfiltration membrane system comprises tubular type, rolling, tubular fibre or board-like.
The membrane element of described ultrafiltration membrane system comprises mineral membrane or organic high molecular layer, and the membrane element of described microfiltration membrane system comprises mineral membrane or organic high molecular layer.
Described mineral membrane comprise stainless steel as supporting layer, metal oxide as the stainless steel membrane of membrane filtration layer or with the ceramic membrane of metal oxide as supporting layer and membrane filtration layer, described organic high molecular layer comprises polysulfone membrane, poly (ether sulfone) film, polyamide membrane, polyolefin film.
H-type storng-acid cation exchange resin in the described step (2) comprises new H-type storng-acid cation exchange resin or regeneration of process mineral acid and the reusable H-type storng-acid cation exchange resin that uses first.
Described mineral acid comprises hydrochloric acid, sulfuric acid.
The nanofiltration membrane system is adopted in nanofiltration decolouring in the described step (3), and the working pressure of nanofiltration decolouring is 1.0-3.5Mpa, and service temperature is 10-70 ℃, and the dialysis water inventory is the 10%-100% of feeding liquid volume.
The nanofiltration membrane element of described nanofiltration membrane system to the rejection of sal epsom greater than 10%.
The nanofiltration membrane element of described nanofiltration membrane system is preferably greater than 96% to the rejection of sal epsom.
Described nanofiltration membrane element is preferably greater than 98% to the rejection of sal epsom.
Compared with prior art, the present invention has the following advantages:
1. micro-filtration and one step of ultrafiltration are finished, a step is removed insoluble impurities and macromole soluble impurities such as thalline, comprises albumen, polysaccharide and colloidal solid etc., and operational path shortens;
2. the feed liquid of fermentation ends need not dilution and can directly enter the film system and separate, and the concentration of the feed liquid succsinic acid of acquisition is higher, reduces the burden of thickening before the crystallization, reduces the energy consumption in the whole production technology, reduces production costs;
3. increase ion exchange process can high-level efficiency, remove positively charged ion and amino acid impurity in the fermented liquid at low cost, improves the crystallization yield and the purity of product;
4. adopt nanofiltration technique further to remove impurity, and after removing a large amount of pigments, replace or the minimizing activated carbon dosage, final product quality is more guaranteed, and the primary crystallization yield is more up to more than 90%, handle the crystallization that the back obtains through nanofiltration, be difficult for the centrifugal problem when thoroughly having solved in the traditional technology Crystallization Separation;
5. byproduct can obtain efficient recovery and utilize save energy again.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
It is 10000MW or above tubular type, board-like, tubular fibre or rolling ultrafiltration membrane system that molecular weight cut-off is adopted in ultrafiltration of the present invention, and perhaps the membrane filtration aperture is the tubular type of 10-200nm, board-like, tubular fibre or rolling ultrafiltration or microfiltration membrane.This system comprises membrane element, pump, transport pipe, controlling elements is formed, membrane element can be stainless steel membrane, the film that inorganics such as ceramic membrane are made, it also can be polymeric membrane, include but not limited to polysulfones, polyethersulfone, polymeric amide, poly-tetrafluoro, polyolefine etc., described stainless steel membrane with stainless steel as supporting layer, metal oxide is as the membrane filtration layer, described stainless steel membrane is a tubular membrane, described ceramic membrane is for to make supporting layer and filtering layer with metal oxide, described ceramic membrane is a tubular membrane, and described metal oxide includes but not limited to aluminum oxide, zirconium white, titanium oxide.
The fermented liquid that contains succsinic acid and salt thereof to be separated directly obtains clarifying filtrate through the separation of film system, thalline in the fermented liquid, albumen, polysaccharide and other macromolecular substance and insoluble substance tunicle are held back and are obtained concentrated solution, and succsinic acid and salt and other small-molecule substance that is dissolved in the fermented liquid see through film.
The operational conditions of ultrafiltration system is that working pressure is 0.1-1Mpa, and service temperature 20-90 ℃, cycles of concentration 10-50 times, the dialysis water yield accounts for fermentating liquid volume 3%-20%.
Still contain a large amount of solvability impurity in the clear filtrate that processing obtains through step (1), particularly a large amount of alkaline matters that do not descend and add for maintenance pH value during the fermentation.The existence of these impurity causes when evaporation concentration can't obtain higher cycles of concentration, thereby can't obtain higher crystallization yield, and there is the quality that will influence the succsinic acid finished product in this part impurity simultaneously.H will be removed so adopt ion exchange method in the filtrate
+Impurity cationic in addition and the H on the ion exchange resin
+Exchange, thus succinic acid solution obtained.
The selected ion exchange resin of the present invention is storng-acid cation exchange resin, the storng-acid cation exchange resin that the present invention is selected for use is with hydrochloric acid, sulfuric acid or other mineral acid regenerations H-type resin, fermented liquid separates the filtrate that obtains clear through ultrafiltration or micro-filtration, removes H in the ultrafiltrate
+Other outer positively charged ions and the H on the resin
+Exchange obtains succinic acid solution, and simultaneously, H-type strong acidic ion resin is removed H
+Other outer positively charged ion institutes are saturated, and the present invention adopts hydrochloric acid, sulfuric acid or other mineral acids that resin is regenerated, and again resin regeneration is become H-type resin, and resin is used for following batch of production.Owing to remove H in the ultrafiltrated
+Outer positively charged ion mainly is to be brought by the neutralizing agent that adds in the fermenting process, after ultrafiltrated exchanges through H-type storng-acid cation exchange resin, owing to the positively charged ion difference in the neutralizing agent selected in the fermenting process, strong acidic ion resin mainly is saturated to ammonium type, sodium type or other cationic saturated resins.Adopt hydrochloric acid, sulfuric acid or other mineral acids resin to be carried out in the regenerated process H
+With the cationic exchange on the resin, owing to select different regenerators can obtain hydrochloride, vitriol or other inorganic acid salt solution.This part hydrochloride, vitriol or other inorganic acid salt solution are through concentrating, can obtaining the higher inorganic salt of purity after the crystallization, because the selection difference of neutralizing agent and regenerator, we can obtain different inorganic salt.This part inorganic salt can be used as chemical fertilizer or other purposes, thereby realizes huge economic benefit.The invention solves conventional resins technology and can produce the technology drawback of a large amount of brine wastes, realized the cleaner production of resin technology, and obtained huge economic benefit feedback.
Be used for regenerated hydrochloric acid, sulfuric acid or other mineral acids, in the resin regeneration process, can not be utilized fully, comprise a certain amount of mineral acid that is not utilized in hydrochloride, vitriol or other inorganic acid salt solution that the present invention obtains, before concentrating, we need add a certain amount of neutralizing agent this part mineral acid that neutralizes, in order to guarantee the purity of inorganic salt, can preferably use with fermenting process in identical neutralizing agent.
Still contain color and luster and other impurity and other quality index that a certain amount of pigment will influence finished product through in the feed liquid of ion exchange treatment.The present invention selects nanofiltration membrane to hold back pigment and other impurity, obtains purified succinic acid solution, and more than 10%, preferably sulfuric acid magnesium rejection is more than 96% to the magnesium sulfate rejection rate for selected nanofiltration membrane; Preferably sulfuric acid magnesium rejection is more than 98%.
Feed liquid through ion-exchange obtains directly obtains purified succinic acid solution through the nanofiltration membrane system handles.The nanofiltration membrane system comprises membrane element, pump, pipeline, valve, controlling elements etc.
Nanofiltration system is operated under the pressure of 1.0-3.SMpa, and service temperature 10-70 ℃, adopt dialysis while concentrating, the dialysis water inventory is the 10%-100% of charging.
Feed liquid through the nanofiltration decolorizing purification, adopt conventional concentrated means, concentrate as multiple-effect evaporation etc., feed liquid is concentrated into the slurries of succsinic acid concentration 15%-60% (weight percent), crystallization, centrifugal, washing acquisition Succinic Acid crystallization, described crystalline temperature is 0-30 ℃, and the time is 3-30 hour.
Embodiment 1
A kind of from fermented liquid the method for extraction separation Succinic Acid, this method may further comprise the steps:
(1) fermented liquid that microbial fermentation is obtained Succinic Acid carries out ultra-filtration and separation, removes somatic cells and macromole impurity, obtains the filtrate of clear;
It is the 10-200nm tubular ultra-filtration membrane system of (comprising 10nm, 50nm, 100nm, 150nm or 200nm etc.) that described ultra-filtration and separation adopts the membrane filtration aperture, the working pressure of ultra-filtration and separation is 0.4Mpa, service temperature is 80 ℃, cycles of concentration is 40 times, and dialysis water yield consumption is a fermentating liquid volume 4%; Described ultrafiltration membrane system mainly is made up of membrane element, pump, transport pipe, controlling elements, and described membrane element is the tubular type stainless steel membrane, this stainless steel membrane with stainless steel as supporting layer, titanium oxide as the membrane filtration layer;
(2) select the H-type storng-acid cation exchange resin of regeneration of sulfuric acid for use, the filtrate that step (1) obtains through ammonium type Zeo-karb, is passed through H-type storng-acid cation exchange resin ion exchange process earlier again, and impurity cationic is exchanged into H
+, obtain Succinic Acid solution;
(3) the Succinic Acid solution that obtains of step (2) is through nanofiltration decolouring, the Succinic Acid solution that obtains decolouring;
The nanofiltration membrane system is adopted in described nanofiltration decolouring, and the working pressure of nanofiltration decolouring is 1.5Mpa, and service temperature is 10 ℃, the dialysis while concentrating, and the dialysis water inventory is 10% of a feeding liquid volume; Described nanofiltration membrane film is to magnesium sulfate rejection rate 98%;
(4) to concentrate, feed liquid is concentrated into Succinic Acid concentration through multiple-effect evaporation be 15% (weight percent) to the Succinic Acid solution of the decolouring that obtains of step (3), and 5 ℃ of crystallizations 8 hours, centrifugal, washing obtain the Succinic Acid crystallization.
Embodiment 2
A kind of from fermented liquid the method for extraction separation Succinic Acid, this method may further comprise the steps:
(1) fermented liquid that microbial fermentation is obtained Succinic Acid carries out ultra-filtration and separation, removes somatic cells and macromole impurity, obtains the filtrate of clear;
It is the 10-200nm tubular ultra-filtration membrane system of (comprising 10nm, 50nm, 100nm, 150nm or 200nm etc.) that described ultra-filtration and separation adopts the membrane filtration aperture, the working pressure of ultra-filtration and separation is 0.3Mpa, service temperature is 70 ℃, cycles of concentration is 30 times, and dialysis water yield consumption is a fermentating liquid volume 10%; Described ultrafiltration membrane system mainly is made up of membrane element, pump, transport pipe, controlling elements, and described membrane element is a tubular ceramic membrane, this ceramic membrane with aluminum oxide as supporting layer and membrane filtration layer;
(2) select the H-type storng-acid cation exchange resin of regeneration of hydrochloric acid for use, the filtrate that step (1) obtains is through H-type storng-acid cation exchange resin ion exchange process, and impurity cationic is exchanged into H
+, obtain Succinic Acid solution;
(3) the Succinic Acid solution that obtains of step (2) is through nanofiltration decolouring, the Succinic Acid solution that obtains decolouring;
The nanofiltration membrane system is adopted in described nanofiltration decolouring, and the working pressure of nanofiltration decolouring is 2Mpa, and service temperature is 25 ℃, the dialysis while concentrating, and the dialysis water inventory is 20% of a feeding liquid volume; Described nanofiltration membrane is to magnesium sulfate rejection rate 20%;
(4) to concentrate, feed liquid is concentrated into Succinic Acid concentration through multiple-effect evaporation be 20% (weight percent) to the Succinic Acid solution of the decolouring that obtains of step (3), and 8 ℃ of crystallizations 10 hours, centrifugal, washing obtain the Succinic Acid crystallization.
Embodiment 3
A kind of from fermented liquid the method for extraction separation Succinic Acid, this method may further comprise the steps:
(1) fermented liquid that microbial fermentation is obtained Succinic Acid carries out ultra-filtration and separation, removes somatic cells and macromole impurity, obtains the filtrate of clear;
Described ultra-filtration and separation adopts the plate-type hyperfiltration membrane system of molecular weight cut-off 〉=10000MW (comprising 10000MW, 30000MW, 50000MW, 80000MW or 100000MW etc.), the working pressure of ultra-filtration and separation is 0.3Mpa, service temperature is 40 ℃, cycles of concentration is 10 times, dialysis water yield consumption is a fermentating liquid volume 15%, described ultrafiltration membrane system mainly is made up of membrane element, pump, transport pipe, controlling elements, and described membrane element is the polysulfones organic high molecular layer;
(2) select H-type storng-acid cation exchange resin for use, the filtrate that step (1) obtains is through H-type storng-acid cation exchange resin ion exchange process, and impurity cationic is exchanged into H
+, obtain Succinic Acid solution;
(3) the Succinic Acid solution that obtains of step (2) is through nanofiltration decolouring, the Succinic Acid solution that obtains decolouring;
The nanofiltration membrane system is adopted in described nanofiltration decolouring, and the working pressure of nanofiltration decolouring is 2.5Mpa, and service temperature is 30 ℃, the dialysis while concentrating, and the dialysis water inventory is 30% of a feeding liquid volume; Described nanofiltration membrane system mainly is made up of membrane element, pump, pipeline, valve, controlling elements, and the material of described membrane element is a polymeric amide;
(4) to concentrate, feed liquid is concentrated into Succinic Acid concentration through multiple-effect evaporation be 30% (weight percent) to the Succinic Acid solution of the decolouring that obtains of step (3), and 10 ℃ of crystallizations of spending the night, centrifugal, washing obtain the Succinic Acid crystallization.
Embodiment 4
A kind of from fermented liquid the method for extraction separation Succinic Acid, this method may further comprise the steps:
(1) fermented liquid that microbial fermentation is obtained Succinic Acid carries out ultra-filtration and separation, removes somatic cells and macromole impurity, obtains the filtrate of clear;
The tubular ultra-filtration membrane system of employing molecular weight cut-off 〉=10000MW (comprising 10000MW, 30000MW, 50000MW, 80000MW or 100000MW etc.) that described ultra-filtration and separation adopts, the working pressure of ultra-filtration and separation is 1Mpa, service temperature is 45 ℃, cycles of concentration is 10 times, and dialysis water yield consumption is a fermentating liquid volume 20%; Described ultrafiltration membrane system mainly is made up of membrane element, pump, transport pipe, controlling elements, and described membrane element is the tetrafluoroethylene organic high molecular layer;
(2) with selected storng-acid cation exchange resin regeneration H-type, the filtrate that step (1) obtains is through H-type storng-acid cation exchange resin ion exchange process, and impurity cationic is exchanged into H
+, obtain Succinic Acid solution;
(3) the Succinic Acid solution that obtains of step (2) is through nanofiltration decolouring, the Succinic Acid solution that obtains decolouring;
The nanofiltration membrane system is adopted in described nanofiltration decolouring, and the working pressure of nanofiltration decolouring is 3.0Mpa, and service temperature is 45 ℃, the dialysis while concentrating, and the dialysis water inventory is 50% of a feeding liquid volume;
(4) to concentrate, feed liquid is concentrated into Succinic Acid concentration through multiple-effect evaporation be 40% (weight percent) to the Succinic Acid solution of the decolouring that obtains of step (3), and 10 ℃ of crystallizations 24 hours, centrifugal, washing obtain the Succinic Acid crystallization.
Embodiment 5
A kind of from fermented liquid the method for extraction separation Succinic Acid, this method may further comprise the steps:
(1) fermented liquid that microbial fermentation is obtained Succinic Acid carries out ultra-filtration and separation, removes somatic cells and macromole impurity, obtains the filtrate of clear;
It is the 10-200nm tubular ultra-filtration membrane system of (comprising 10nm, 50nm, 100nm, 150nm or 200nm etc.) that described ultra-filtration and separation adopts the membrane filtration aperture, the working pressure of ultra-filtration and separation is 0.1Mpa, service temperature is 90 ℃, cycles of concentration is 50 times, and dialysis water yield consumption is a fermentating liquid volume 3%; Described ultrafiltration membrane system mainly is made up of membrane element, pump, transport pipe, controlling elements, and described membrane element is the tubular type stainless steel membrane, this stainless steel membrane with stainless steel as supporting layer, titanium oxide as the membrane filtration layer;
(2) select the H-type storng-acid cation exchange resin of regeneration of sulfuric acid for use, the filtrate that step (1) obtains through ammonium type Zeo-karb, is passed through H-type storng-acid cation exchange resin ion exchange process earlier again, and impurity cationic is exchanged into H
+, obtain Succinic Acid solution;
(3) the Succinic Acid solution that obtains of step (2) is through nanofiltration decolouring, the Succinic Acid solution that obtains decolouring;
The nanofiltration membrane system is adopted in described nanofiltration decolouring, and the working pressure of nanofiltration decolouring is 2.6Mpa, and service temperature is 70 ℃, the dialysis while concentrating, and the dialysis water inventory is 100% of a feeding liquid volume; Described nanofiltration membrane film is to magnesium sulfate rejection rate 98%;
(4) to concentrate, feed liquid is concentrated into Succinic Acid concentration through multiple-effect evaporation be 45% (weight percent) to the Succinic Acid solution of the decolouring that obtains of step (3), and 5 ℃ of crystallizations 8 hours, centrifugal, washing obtain the Succinic Acid crystallization.
Claims (12)
1. the method for an extraction separation Succinic Acid from fermented liquid is characterized in that, this method may further comprise the steps:
(1) fermented liquid that microbial fermentation is obtained Succinic Acid carries out ultra-filtration and separation, removes somatic cells and macromole impurity, obtains the filtrate of clear;
(2) select H-type storng-acid cation exchange resin for use, the filtrate that step (1) obtains exchanges through H-type storng-acid cation exchange resin ion, and impurity cationic is exchanged into H
+, obtain Succinic Acid solution;
(3) the Succinic Acid solution that obtains of step (2) is through nanofiltration decolouring, the Succinic Acid solution that obtains decolouring;
(4) the Succinic Acid solution of the decolouring that obtains of step (3) through concentrating, crystallization, centrifugal, washing, obtain Succinic Acid.
2. according to claim 1 from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that, ultra-filtration and separation in the described step (1) adopts ultrafiltration membrane system or microfiltration membrane system, molecular weight cut-off 〉=the 10000MW of described ultrafiltration membrane system or membrane filtration aperture are 10-200nm, and the membrane filtration aperture of described microfiltration membrane system is 10-200nm.
3. according to claim 1 from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that the working pressure of described ultra-filtration and separation is 0.1-1Mpa, service temperature is 20-90 ℃, cycles of concentration is 5-50 times, and the dialysis water consumption is fermentating liquid volume 3%-20%.
4. according to claim 2 from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that, the kit form of described ultrafiltration membrane system comprises tubular type, rolling, tubular fibre or board-like, and the kit form of described microfiltration membrane system comprises tubular type, rolling, tubular fibre or board-like.
According to claim 2 or 4 described from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that, the membrane element of described ultrafiltration membrane system comprises mineral membrane or organic high molecular layer, and the membrane element of described microfiltration membrane system comprises mineral membrane or organic high molecular layer.
6. according to claim 5 from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that, described mineral membrane comprise stainless steel as supporting layer, metal oxide as the stainless steel membrane of membrane filtration layer or with the ceramic membrane of metal oxide as supporting layer and membrane filtration layer, described organic high molecular layer comprises polysulfone membrane, poly (ether sulfone) film, polyamide membrane, polyolefin film.
7. according to claim 1 from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that the H-type storng-acid cation exchange resin in the described step (2) comprises new H-type storng-acid cation exchange resin or regeneration of process mineral acid and the reusable H-type storng-acid cation exchange resin that uses first.
8. according to claim 7 from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that described mineral acid comprises hydrochloric acid, sulfuric acid.
9. according to claim 1 from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that, the nanofiltration membrane system is adopted in nanofiltration decolouring in the described step (3), the working pressure of nanofiltration decolouring is 1.0-3.5Mpa, service temperature is 10-70 ℃, and the dialysis water inventory is the 10%-100% of feeding liquid volume.
10. according to claim 9 from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that, the nanofiltration membrane element of described nanofiltration membrane system to the rejection of sal epsom greater than 10%.
11. according to claim 10 from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that the nanofiltration membrane element of described nanofiltration membrane system is preferably greater than 96% to the rejection of sal epsom.
12. according to claim 11 from fermented liquid the method for extraction separation Succinic Acid, it is characterized in that described nanofiltration membrane element is preferably greater than 98% to the rejection of sal epsom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100464804A CN101811953B (en) | 2009-02-23 | 2009-02-23 | Method for extracting succinic acid from fermentation broth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100464804A CN101811953B (en) | 2009-02-23 | 2009-02-23 | Method for extracting succinic acid from fermentation broth |
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| Publication Number | Publication Date |
|---|---|
| CN101811953A true CN101811953A (en) | 2010-08-25 |
| CN101811953B CN101811953B (en) | 2013-03-06 |
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Cited By (13)
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| CN102323263A (en) * | 2011-08-19 | 2012-01-18 | 南宁奕德环境科技有限公司 | Method for rapidly detecting succinic acid content in fermentation broth |
| CN102363594A (en) * | 2011-11-09 | 2012-02-29 | 中国科学院过程工程研究所 | Method for separating and purifying succinic acid from fermentation broth |
| CN102476989A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院过程工程研究所 | Succinic acid separating apparatus and method based on full membrane separation system |
| CN102617325A (en) * | 2011-01-27 | 2012-08-01 | 中国科学院过程工程研究所 | Method for decoloration of succinic acid fermentation broth by ion exchange resin |
| CN102731288A (en) * | 2011-03-31 | 2012-10-17 | 中国石油化工股份有限公司 | Method for separating high-purity succinic acid from fermentation broth |
| CN103012106A (en) * | 2012-11-27 | 2013-04-03 | 青岛琅琊台集团股份有限公司 | Method for extracting succinic acid by applying membrane technology |
| CN105732457A (en) * | 2016-04-01 | 2016-07-06 | 江西科技师范大学 | Method for preparing succinimide with succinic acid fermentation liquor |
| CN108047022A (en) * | 2017-12-12 | 2018-05-18 | 河北科莱维生物科技有限公司 | A kind of method for preparing succinic acid |
| CN109265337A (en) * | 2018-10-30 | 2019-01-25 | 徐州绿油油生物肥料有限公司 | A kind of embrane method extraction process for extracting succinic acid from bio-fermented liquid |
| CN110141969A (en) * | 2019-05-27 | 2019-08-20 | 常茂生物化学工程股份有限公司 | A kind of two compartment method electrolytic separation of Bipolar Membrane anode membrane continuously prepares L-TARTARIC ACID method |
| CN111943836A (en) * | 2019-05-16 | 2020-11-17 | 帝斯曼知识产权资产管理有限公司 | Improved process for recovery of 2-keto-L-gulonic acid |
| CN112778358A (en) * | 2019-11-08 | 2021-05-11 | 中国科学院天津工业生物技术研究所 | Separation and extraction method of small molecular compound prepared by in vitro multienzyme system |
| CN113773189A (en) * | 2021-08-02 | 2021-12-10 | 合肥信达膜科技有限公司 | Application of membrane process in lactic acid production |
Family Cites Families (4)
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| US5132456A (en) * | 1991-05-07 | 1992-07-21 | The Regents Of The University Of California | Sorption of carboxylic acid from carboxylic salt solutions at PHS close to or above the pKa of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine |
| EP1669459B1 (en) * | 2003-09-30 | 2014-10-22 | Ajinomoto Co., Inc. | Method of purifying succinic acid from fermentation liquid |
| CN101215583B (en) * | 2008-01-18 | 2010-11-10 | 南京工业大学 | Method for preparing succinic acid by coupling fermentation and membrane separation unit |
| CN101348429B (en) * | 2008-09-05 | 2011-03-16 | 江南大学 | Method for extracting amber acid in fermentation liquor by cationic resin exchange |
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| CN102476989B (en) * | 2010-11-30 | 2014-04-30 | 中国科学院过程工程研究所 | Succinic acid separating apparatus and method based on full membrane separation system |
| CN102476989A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院过程工程研究所 | Succinic acid separating apparatus and method based on full membrane separation system |
| CN102617325B (en) * | 2011-01-27 | 2014-12-24 | 中国科学院过程工程研究所 | Method for decoloration of succinic acid fermentation broth by ion exchange resin |
| CN102617325A (en) * | 2011-01-27 | 2012-08-01 | 中国科学院过程工程研究所 | Method for decoloration of succinic acid fermentation broth by ion exchange resin |
| CN102731288A (en) * | 2011-03-31 | 2012-10-17 | 中国石油化工股份有限公司 | Method for separating high-purity succinic acid from fermentation broth |
| CN102731288B (en) * | 2011-03-31 | 2014-04-02 | 中国石油化工股份有限公司 | Method for separating high-purity succinic acid from fermentation broth |
| CN102323263A (en) * | 2011-08-19 | 2012-01-18 | 南宁奕德环境科技有限公司 | Method for rapidly detecting succinic acid content in fermentation broth |
| CN102363594A (en) * | 2011-11-09 | 2012-02-29 | 中国科学院过程工程研究所 | Method for separating and purifying succinic acid from fermentation broth |
| CN103012106A (en) * | 2012-11-27 | 2013-04-03 | 青岛琅琊台集团股份有限公司 | Method for extracting succinic acid by applying membrane technology |
| CN105732457A (en) * | 2016-04-01 | 2016-07-06 | 江西科技师范大学 | Method for preparing succinimide with succinic acid fermentation liquor |
| CN105732457B (en) * | 2016-04-01 | 2018-09-11 | 江西科技师范大学 | A method of preparing succimide using succinic acid fermentation liquor |
| CN108047022A (en) * | 2017-12-12 | 2018-05-18 | 河北科莱维生物科技有限公司 | A kind of method for preparing succinic acid |
| CN109265337A (en) * | 2018-10-30 | 2019-01-25 | 徐州绿油油生物肥料有限公司 | A kind of embrane method extraction process for extracting succinic acid from bio-fermented liquid |
| CN111943836A (en) * | 2019-05-16 | 2020-11-17 | 帝斯曼知识产权资产管理有限公司 | Improved process for recovery of 2-keto-L-gulonic acid |
| CN110141969A (en) * | 2019-05-27 | 2019-08-20 | 常茂生物化学工程股份有限公司 | A kind of two compartment method electrolytic separation of Bipolar Membrane anode membrane continuously prepares L-TARTARIC ACID method |
| CN112778358A (en) * | 2019-11-08 | 2021-05-11 | 中国科学院天津工业生物技术研究所 | Separation and extraction method of small molecular compound prepared by in vitro multienzyme system |
| CN113773189A (en) * | 2021-08-02 | 2021-12-10 | 合肥信达膜科技有限公司 | Application of membrane process in lactic acid production |
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