CN101234961A - Method for preparing lactic acid by applying double pole film electrodialysis technique - Google Patents
Method for preparing lactic acid by applying double pole film electrodialysis technique Download PDFInfo
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- CN101234961A CN101234961A CNA2008100203960A CN200810020396A CN101234961A CN 101234961 A CN101234961 A CN 101234961A CN A2008100203960 A CNA2008100203960 A CN A2008100203960A CN 200810020396 A CN200810020396 A CN 200810020396A CN 101234961 A CN101234961 A CN 101234961A
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Abstract
The invention discloses a method for preparing lactic acid with bipolar membrane electrodialysis technology. Lactic acid fermentation liquid passes through an electrodialyzer, which transforms contained lactates into lactic acid. The membrane tank configuration of the adopted electrodialyzer can be of two-cell type including an acid cell and a salt cell divided by an anion membrane or of three-chamber type including an acid cell, a salt cell and a base cell divided by a cation membrane and an anion membrane. For preparation, lactic acid fermentation liquid is transmitted into the salt cell and water is transmitted into the acid cell or the base cell. Under the effect of a circulating pump, the materials flow circularly with a current density of 80-160mA/cm2 at an operation temperature of 25-60 DEG C. The invention can completely supersede the prior calcium lactate acidifying technology without addition of acids for H+ supply and without production of waste acid, salt or base liquid. The transformation efficiency of lactic acid is higher than 98 percent, the recovery of lactic acid is higher than 90 percent and the current efficiency is higher than 70 percent, so the method can reduce environment pollution and lower consumption of chemical raw materials and energy and has remarkable industrial application value and environmental benefit.
Description
Technical field
The invention belongs to the membrane technique field, particularly the method for bipolar membrane electrodialysis device separating lactic acid radical ion from Lactated fermented liquid.
Background technology
Lactic acid is a kind of important organic acid, at aspects such as food, medicine, chemical industry a lot of purposes is arranged, particularly can be as the monomer of synthesized degradable material poly(lactic acid) and be subjected to extensive concern.The tradition lactic acid-producing adopts calcium salt method to extract lactic acid, generally generate the fermented liquid that contains calcium lactate by adding the calcium neutralizing agent during the fermentation, through periodic crystallisation, wash brilliant back and add sulfuric acid solution and extract lactic acid, and by the refining product that obtains of steps such as adsorption bleaching repeatedly.Traditional fermentation calcium salt method can consume a large amount of alkali and sulfuric acid in N-process and acidolysis process, and a large amount of calcium sulfate of meeting by-product, and it extracts, and treating process step is various, and labour intensity and production cost are all very big, and quality product is also unstable.
The objective of the invention is the bipolar membrane electrodialysis technology and replace present calcium salt method.The domestic existing relevant report (ZL 8710485.8) that utilizes electrodialytic technique to prepare lactic acid, the common electrical dialysis is handled the organic acid salt fermented liquid, obtains organic acid, and process is simple relatively, consumes industrial chemicals and reduces relatively, pollutes also few.But it can not produce H voluntarily
+So, still to add a large amount of acid, so still can produce a large amount of corresponding bisulfate waste liquors, pollute.Jiang Weijun etc. (ZL92105427.0) have utilized Bipolar Membrane and cavity block to form the film group unit of salt/alkali two cell-type configurations and the in parallel or placed in-line mode component film electrodialyzer that is connected to each other to prepare gluconic acid, adopting the Sunmorl N 60S liquid of 1.2mol/L is raw material, current density 100mA/cm
2, transformation efficiency reaches 98% behind the circulation 6h.But Luo Tiehong (membrane science and technology [J], 2007,27 (4): find when 66-69) waiting the membrane permeation device separating lactic acid of studying similar structures that water moves to the salt chamber, make the lactic acid concn that finally obtains be lower than initial Sodium.alpha.-hydroxypropionate concentration, this industrial be disadvantageous because increased the energy of concentrated needs, and utilize in the lactic acid of this method preparation and also contain the part lactic acid salt, these lactic acid salts will run off in downstream processes such as molecular distillation, cause the loss of product and the rising of cost.Therefore, the industrial bipolar membrane electrodialysis technology that still needs a kind of better separation and Extraction lactic acid.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing lactic acid by applying double pole film electrodialysis technique,, improve the lactic acid yield simultaneously to avoid adding a large amount of acid.
Do not achieve the above object, the technical solution used in the present invention is as follows:
A kind of method of preparing lactic acid by applying double pole film electrodialysis technique, lactic acid fermentation liquid changes into lactic acid through electrodialyzer with contained lactic acid salt, and the membrane cisterna of employed electrodialyzer is configured as salt/sour two cell-types that are separated into cavity block or the acid/salt/alkali three-chamber type that is separated into by the positive and negative film; During preparation, lactic acid fermentation liquid is sent into the salt chamber, water is sent into sour chamber or alkali chamber, and material circulates under the recycle pump effect, and current density is 80～160mA/cm
2, 25 ℃～60 ℃ of service temperatures were reacted 4～6 hours.
Wherein, described lactic acid is L-lactic acid or D, L-lactic acid.
Wherein, described lactic acid salt is sodium ion, potassium ion, ammonium ion or calcium ion etc. and the formed salt compounds of lactate, or the mixture of above several salt.
Wherein, used electrodialyzer is formed a film group unit by dividing plate, Bipolar Membrane, cationic exchange membrane and anion-exchange membrane by the membrane cisterna configuration of setting, and one or several film group units are assembled between the pair of electrodes formation bipolar membrane electrodialysis device.The membrane cisterna configuration comprises salt/sour two cell-types and acid/salt/the alkali three-chamber type as shown in Figure 1, 2.
Be separated into sour chamber and salt chamber with cavity block between salt/two Bipolar Membrane of sour two cell-types.Lactic acid salt enters salt chamber, the right, and under the DC electric field effect, the negatively charged ion lactate enters acid chamber, the left side by cavity block, forms lactic acid; And the positively charged ion (Na in the salt chamber
+, K
+, NH
4 +, Ca
2+Deng) OH that produces with Bipolar Membrane
-Form alkali.This electroosmose process can make the mixture of pure lactic acid and salt and alkali.
Acid/salt/alkali three-chamber type is separated by Bipolar Membrane cavity block and anode membrane and is formed sour chamber, salt chamber and alkali chamber.After lactic acid salt enters intermediary salt chamber, under electric field action, its positively charged ion (Na
+, K
+, NH
4 +, Ca
2+Deng) enter the alkali chamber by anode membrane, the OH that separates with Bipolar Membrane
-Form alkali; The negatively charged ion lactate then enters sour chamber by cavity block, the H that separates with Bipolar Membrane
+Form lactic acid.
More than several film group units can take in parallel or placed in-line mode connects.
Beneficial effect: the method for preparing lactic acid by applying double pole film electrodialysis technique of the present invention can be converted into lactic acid with lactic acid salt, can replace present calcium lactate acidification technique fully, and need not add acid for H
+, react required H
+And OH
-By water electrolysis, do not produce any soda acid bisulfate waste liquor fully.Two Room method transformation efficiencys can reach more than 95%, energy consumption is at 2.6kWh/kg, current efficiency is about 80%, the rate of recovery of lactic acid can reach more than 90%, three Room method transformation efficiencys can reach more than 97%, energy consumption is at 5.5kWh/kg, and current efficiency is about 90%, and the rate of recovery of lactic acid can reach more than 90%.The lactic acid salt that remains in the two Room methods in the salt chamber can return in the fermentation system with the alkali that generates; Residual lactic acid salt can continue to be retained in the salt chamber of electrodialyzer and reacts in the three Room methods, changes into lactic acid, and the soda ash of generation can be used for regulating the pH of fermentation system.Entire separation system adopts closed circulation, and non-pollutant discharge is the green technology of a green engineering, has significant industrial application value and environmental benefit.The present invention both can be used as an independent lock out operation step and had existed, and also can use with fermentation step to combine, and formed reaction-separation Fourier Series expansion technique.
Description of drawings
Fig. 1 is that the electrodialysis unit of salt/sour two cell-types prepares the fundamental diagram of lactic acid.
Fig. 2 is that the electrodialysis unit of acid/salt/alkali three-chamber type prepares the fundamental diagram of lactic acid.
Embodiment:
Embodiment 1:
To pump into the salt chamber (Fig. 1) of salt/sour two cell-type electrodialyzers through pretreated lactic acid fermentation liquid 2L (lactate content is 1.5mol/L) with the speed of 70L/h.The lactic acid solution that with the 0.6L initial concentration is 0.2mol/L again pumps into sour chamber with the speed of 60L/h, to increase the electroconductibility of sour chamber solution.Control voltage makes current density maintain 160mA/cm
2, 60 ℃ of service temperatures, reaction 4h, the transformation efficiency of lactate reaches 95%, energy consumption 2.6kWh/kg, current efficiency is about 80%, and the rate of recovery of lactic acid can reach 90%.
Embodiment 2:
To pump into the salt chamber (Fig. 2) of acid/salt/alkali three-chamber type electrodialyzer through pretreated lactic acid fermentation liquid 2L (lactate content is 1.5mol/L) with the speed of 100L/h.The lactic acid solution that with the 1L initial concentration is 0.2mol/L again pumps into sour chamber with the speed of 60L/h, and the 1L initial concentration is that the NaOH solution of 0.1mol/L pumps into the alkali chamber with the speed of 70L/h, to increase the electroconductibility of each chamber solution of soda acid.Control voltage makes current density maintain 80mA/cm
2, 40 ℃ of service temperatures, reaction 6h, the transformation efficiency of lactate reaches 97%, energy consumption 5.5kWh/kg, current efficiency 90%, the rate of recovery of lactic acid can reach 90%.
Embodiment 3:
Identical with the method for embodiment 1, different is that electrodialyzer is to be assembled in three film repeating units shown in Figure 1 between the pair of electrodes, forms a plurality of lattice chamber, and its lattice chamber is combined as anolyte compartment-sour chamber-salt chamber-sour chamber-salt chamber-sour chamber-salt chamber-cathode compartment.The lactic acid solution that initial concentration is 0.2mol/L is all poured in the acid chamber, and flow velocity 80L/h is to increase the electroconductibility of sour chamber solution.The fermented liquid that lactate content is 1.5mol/L, flow velocity 100L/h are all poured in the salt chamber.Control voltage makes current density maintain 160mA/cm
2, 25 ℃ of service temperatures, reaction 6h, the transformation efficiency of lactate reaches 94%, energy consumption 3.2kWh/kg, current efficiency is about 80%, and the rate of recovery of lactic acid can reach 90%.
Claims (3)
1, a kind of method of preparing lactic acid by applying double pole film electrodialysis technique, lactic acid fermentation liquid changes into lactic acid through electrodialyzer with contained lactic acid salt, it is characterized in that the module unit of employed electrodialyzer is salt/sour two cell-types that are separated into cavity block or the acid/salt/alkali three-chamber type that is separated into by the positive and negative film; During preparation, lactic acid fermentation liquid is sent into the salt chamber, water is sent into sour chamber or alkali chamber, and material circulates under the recycle pump effect, and current density is 80～160mA/cm
2, 25 ℃～60 ℃ of service temperatures were reacted 4～6 hours.
2, the method for preparing lactic acid by applying double pole film electrodialysis technique according to claim 1 is characterized in that described lactic acid is L-lactic acid or D, L-lactic acid.
3, the method for preparing lactic acid by applying double pole film electrodialysis technique according to claim 1, it is characterized in that described lactic acid salt is sodium ion, potassium ion, ammonium ion or calcium ion and the formed salt compounds of lactate, or the mixture of above several salt.
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|---|---|---|---|
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ301168B6 (en) * | 2008-10-09 | 2009-11-25 | Ústav chemických procesu Akademie ved Ceské republiky | Method of and apparatus for terephthalic acid isolation |
| CN102070402A (en) * | 2010-12-14 | 2011-05-25 | 清华大学 | Method for desalting 1,3-propanediol fermentation liquor |
| CN102250973A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院过程工程研究所 | Calcium salt method-electrodialysis coupling technology-based lactic acid cleaner production method |
| CN101525285B (en) * | 2009-04-22 | 2011-11-23 | 哈尔滨工业大学 | Method for separating acetic acid in fermentation liquid for biohydrogen production by bipolar membrane electrodialysis technique |
| CN102796775A (en) * | 2011-05-26 | 2012-11-28 | 中国科学院城市环境研究所 | Method for extracting lactic acid fermentation product of kitchen waste |
| CN105063108A (en) * | 2015-07-24 | 2015-11-18 | 中山大学 | Enhancing method for producing malic acid through biological electrodialysis |
| CN105688676A (en) * | 2016-04-08 | 2016-06-22 | 中国科学院过程工程研究所 | Technique for preparing hypophosphorous acid through bipolar membrane electroosmosis method |
| CN106187731A (en) * | 2016-07-05 | 2016-12-07 | 南京林业大学 | A kind of electrodialysis desalination and acid convert the method that one-step method produces xylonic |
| CN110508140A (en) * | 2019-08-29 | 2019-11-29 | 自然资源部天津海水淡化与综合利用研究所 | A kind of purification process of caprolactam hydrolyzate |
| CN112469494A (en) * | 2018-06-06 | 2021-03-09 | 孟山都技术公司 | Three compartment bipolar membrane electrodialysis of amino acid salts |
| CN114685249A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Preparation method of o-phenylphenol |
-
2008
- 2008-03-04 CN CNA2008100203960A patent/CN101234961A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ301168B6 (en) * | 2008-10-09 | 2009-11-25 | Ústav chemických procesu Akademie ved Ceské republiky | Method of and apparatus for terephthalic acid isolation |
| CN101525285B (en) * | 2009-04-22 | 2011-11-23 | 哈尔滨工业大学 | Method for separating acetic acid in fermentation liquid for biohydrogen production by bipolar membrane electrodialysis technique |
| CN102250973A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院过程工程研究所 | Calcium salt method-electrodialysis coupling technology-based lactic acid cleaner production method |
| CN102070402A (en) * | 2010-12-14 | 2011-05-25 | 清华大学 | Method for desalting 1,3-propanediol fermentation liquor |
| CN102796775A (en) * | 2011-05-26 | 2012-11-28 | 中国科学院城市环境研究所 | Method for extracting lactic acid fermentation product of kitchen waste |
| CN105063108B (en) * | 2015-07-24 | 2019-02-19 | 中山大学 | A kind of intensifying method of biology electrodialysis production malic acid |
| CN105063108A (en) * | 2015-07-24 | 2015-11-18 | 中山大学 | Enhancing method for producing malic acid through biological electrodialysis |
| CN105688676A (en) * | 2016-04-08 | 2016-06-22 | 中国科学院过程工程研究所 | Technique for preparing hypophosphorous acid through bipolar membrane electroosmosis method |
| CN105688676B (en) * | 2016-04-08 | 2018-04-03 | 中国科学院过程工程研究所 | The technique that a kind of bipolar membrane electrodialysis method prepares hypophosphorous acid |
| CN106187731A (en) * | 2016-07-05 | 2016-12-07 | 南京林业大学 | A kind of electrodialysis desalination and acid convert the method that one-step method produces xylonic |
| CN112469494A (en) * | 2018-06-06 | 2021-03-09 | 孟山都技术公司 | Three compartment bipolar membrane electrodialysis of amino acid salts |
| CN110508140A (en) * | 2019-08-29 | 2019-11-29 | 自然资源部天津海水淡化与综合利用研究所 | A kind of purification process of caprolactam hydrolyzate |
| CN114685249A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Preparation method of o-phenylphenol |
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