CN101817740B - Emulsion for extracting citric acid from fermentation liquor and using method thereof - Google Patents
Emulsion for extracting citric acid from fermentation liquor and using method thereof Download PDFInfo
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- CN101817740B CN101817740B CN 201010160668 CN201010160668A CN101817740B CN 101817740 B CN101817740 B CN 101817740B CN 201010160668 CN201010160668 CN 201010160668 CN 201010160668 A CN201010160668 A CN 201010160668A CN 101817740 B CN101817740 B CN 101817740B
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- citric acid
- milk sap
- interior water
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Abstract
The invention discloses emulsion for extracting citric acid from fermentation liquor and a using method thereof. The emulsion is prepared by mixing an oil phase and an internal water phase, wherein the oil phase consists of a surfactant, a carrier and an oil solvent in a certain volume ratio; and the internal water phase is alkaline solution. The emulsion for extracting the citric acid from the fermentation liquor of the invention has the advantages of high mass transfer speed, high separation efficiency, high yield, simple and convenient process, recyclable oil phase, low energy consumption and the like. The method is low in operation cost and particularly suitable for the extraction of the citric acid from the fermentation liquor and overcomes the shortcomings of high investment, low efficiency, high energy consumption, large population and the like.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering.The isolation technique that relates to citric acid in a kind of fermented liquid.
Background technology
The method of producing at present citric acid mainly contains calcium salt extraction method, ion exchange adsorption, solvent extration etc.Calcium salt method has the advantages such as technical maturity, easy to operate, constant product quality.But shortcoming is also very obvious, and is many such as the leaching process unit operation, and total recovery is difficult to be higher than 80%; Citric acid consume a large amount of industrial chemicals, and the energy consumption of solid-liquid separation is large through repeatedly phase transformation; Produce a large amount of waste water, waste residue.Ion exchange adsorption technique is simple, and energy consumption reduces greatly, and yield is brought up to more than 85%, but this technique also exists exchange resin to need frequent regeneration, and has certain life-span, can produce a large amount of deficiencies such as solid waste.
Compare with calcium salt method, solvent extration has saved neutralization and acidolysis two procedures, has saved industrial chemicals, has reduced energy consumption, can not produce a large amount of waste residues in leaching process, is beneficial to environmental protection.Compare with ion exchange method, but solvent extration has advantages such as processing power is large, good separating effect, the high operate continuously of the rate of recovery.But because the composition of citric acid fermentation broth is complicated, contain the impurity such as sugar, protein, pigment, mycelia, require extraction agent to have efficient selectivity, and nontoxic, without inexpensive, the easy recovery of burn into.Though organic amine, esters extractant commonly used has comparatively ideal effect of extracting at present, and certain toxicity is all arranged, and generally can only obtain industrial goods, and can not satisfy the requirement of medicine, food.
What the most of production firms of China adopted is traditional calcium salt extraction method, and Miles company of the U.S. second largest citric acid production factory just adopted solvent extration to extract citric acid from fermented liquid as far back as 1981, and the Pfilzer company in U.S. Haaman and Reimer company and Europe also all adopts solvent extration.Recent two decades comes, and the investigator is also attempting the new method of research both at home and abroad, and such as membrane separation process, electroosmose process, membrane technique etc., but these methods all do not break through progress, mostly rest on laboratory stage.
The emulsion liquid film separation method is proposed by it (N.N.Li) of Li Nian the earliest, and patented (US3410794).This method is that milk sap is dispersed in the aqueous solution that certain solute need to separate, form a kind of film layer structure of multiple emulsion, separated solute successively with film mutually in the release agent of flowing carrier and interior aqueous phase react, thereby the oil film that passes between two waters carries out selective migration.When milk sap contacted with feed liquid, the foreign minister that the solute penetration that need to separate is crossed milk sap entered interior phase, changed into and can not stay interior phase through the material of film phase with the reagent effect.Then will not contain the separation of emulsion of water and the solute of this solute, the milk sap of solute reclaims solute behind breakdown of emulsion, and milk sap recycles.The advantages such as that this method has is efficient, energy-conservation, selectivity is good, applied widely can be removed organic and mineral compound, ionic and the impurity such as nonionic compound, acidity and basic cpd.But most of emulsion liquid films of developing so far are difficult to possess simultaneously the fundamental propertys such as hypertonicity, highly selective and high stability that the membrane sepn process should need.The technical barriers such as poor stability, easy swelling and breakdown of emulsion difficulty of emulsion liquid film in sepn process solves not yet fully at present, thereby hindered the process of industrialization of Emulsion Liquid Membrane Separation Technique.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, a kind of prescription and preparation method of milk sap are provided, have effectively solved the problems such as the liquid film that exists in the existing emulsion liquid film sepn process is unstable, breakdown of emulsion is difficult, significantly increase the percentage extraction of citric acid, reduce cost, and environmentally friendly.
One, milk sap of the present invention adopts the newborn technique of system made after being mixed by interior water and oil phase:
1, oil phase mixes institute by tensio-active agent, carrier, Oil solvent by following volume ratio and consists of:
Tensio-active agent/carrier/Oil solvent=1/ (0.2 ~ 1.5)/(5 ~ 10);
2, the volume ratio of oil phase and interior water is:
Oil phase/interior water=1/ (0.8 ~ 2).
3, described tensio-active agent is to include Tween 40, Tween 60, Tween 80 compositions single or mutually combination, or the organic surface active agent of the combined composition of itself and Span 80;
4, described carrier is for including Alamine 336, Trioctylamine, tributyl phosphate, TRPO, N, and the single component of N '-dialkyl amide, N-alkylamide, petrolenum sulfoxide or the citric acid of combined composition are in conjunction with carrier;
5, described Oil solvent is to include n-tetradecane, hexanaphthene composition single or mutually combination, or the non-polar solvent of the combined composition of itself and kerosene;
6, described interior water is to include NaOH, KOH, Na single or mutually combination
2CO
3, K
2CO
3The basic solution of composition.
7, the mass concentration of interior water is chosen in 5% ~ 20% and is advisable.
When two, using in the milk sap extractive fermentation liquid of the present invention citric acid:
One) should carry out successively in the steps below:
1, extract behind mixed fermentation liquid and the milk sap;
2, extract is carried out standing demix, isolate the fermented liquid of extract lower floor;
3, the milk sap on extract upper strata after the layering is further carried out the layering of oil phase and interior water;
4. extract after the interior water after the layering being collected;
5, internally the extract of water carries out the neutral adjusting of pH;
6, the interior water extract after the neutral adjusting of pH is carried out condensing crystal, make the Citrate trianion product.
When two) extracting, the volume ratio that milk sap and fermented liquid mix is preferably:
Milk sap/fermented liquid=1/ (1 ~ 10).
Three) the neutral scope of regulating of pH is preferably 6 ~ 8.
Three, the various raw materials such as the tensio-active agent that milk sap of the present invention adopts, Oil solvent, interior water are its wide material sources, with low cost not only.And tensio-active agent and carrier all have preferably compatibility, under the effect of tensio-active agent, easily forms water-in-oil w/o type milk sap.Select suitable proportioning, can not only make stable milk sap, and Extraction of Citric Acid efficient also obviously improves.The preparation method of milk sap of the present invention is simple, and the milk sap that makes is easy to breakdown of emulsion.
Four, adopt the citric acid in the milk sap extractive fermentation liquid of the present invention, break intrinsic equilibrium-limited in the traditional extraction technology, the extraction in the liquid-liquid extraction has been merged into a step with two processes of stripping finish, can effectively particularly reclaim the enrichment citric acid the dilute solution from fermented liquid solution.Have that rate of mass transfer is fast, the separation efficiency high, and overcome that the traditional way operation steps is various, separation cycle is long, energy consumption is large, cost is high, yield is low and the shortcoming such as solid waste disposal.Therefore, compare with traditional citric acid extracting process, have equipment simple, less investment, the advantage such as working cost is low, and is easy and simple to handle, applied widely.
Description of drawings
Accompanying drawing 1 ~ accompanying drawing 4 is working process letter schematic diagrams of citric acid in the milk sap extractive fermentation liquid of the present invention.Among the figure:
I-outer water, II-film phase, III-interior water, A-citric acid, B-carrier, C-yellow soda ash, AB-citrate-carrier complex compound, AC-Trisodium Citrate, CB-carbonate-carrier complex compound, D-water and carbonic acid gas.
Embodiment
Below in conjunction with accompanying drawing working process of the present invention is further detailed:
Among Fig. 1, emulsion liquid film is again Bao Shui (W/O/W) type of oil-in-water, and interior water III is for the basic solution (take yellow soda ash C as example) that chemical reaction generates Citrate trianion occuring with citric acid A, and outer water I is the fermented liquid after fermented liquid or the dilution.Water I and film phase II are at the interface outside, the citric acid A of outer water I can the carrier B in film phase II be combined and be generated citrate-carrier complex compound AB, thereby the citric acid in the outer water I has just moved in the film phase II with the form of citrate-carrier complex compound AB.
Among Fig. 2, in interior water III and film phase II at the interface, yellow soda ash C reacts in the citrate in the film phase II-carrier complex compound AB and the interior water III, and Formed acid group in film phase II-carrier complex compound CB generates Trisodium Citrate AC in interior water III.
Among Fig. 3, the carbonate in the film phase II-carrier complex compound CB moves to outer water I and film phase II at the interface, then reacts with citric acid A, generates citrate-carrier complex compound AB in film phase II, and aqueous phase has generated water and carbonic acid gas D outside.
Among Fig. 4, in the emulsion liquid film in the present invention, the yellow soda ash C that citric acid A can optionally see through in film phase II and the interior water III under the effect of carrier B reacts, in interior water III, generate Trisodium Citrate AC, generate outside water and carbonic acid gas D in the water I, thereby the citric acid A in the fermented liquid just is extracted in the interior water III with the form of Trisodium Citrate AC.Process through breakdown of emulsion, the Trisodium Citrate AC in the interior water III is collected crystallization, the organism in the film phase II is reclaimed again system breast.In the process of citric acid, because carrier has high selectivity, citric acid can be extracted to interior aqueous phase in the fermented liquid so only have in the emulsion liquid film extractive fermentation liquid, and other impurity can not enter interior water, thereby have optionally extracted citric acid.
Below the detailed concrete case of several examples of the present invention:
Embodiment 1: with Tween 60, tributyl phosphate, n-tetradecane by volume 1:0.5:7 mix, add isopyknic mass concentration and be 10% Na
2CO
3The aqueous solution.Mixing solutions is with the speed system breast 140s of 10000r/m, and system becomes the milky milk sap of homogeneous by muddiness.With filtering fermentation liquor, separate suspended substance wherein, place extraction container to stir.Be that the ratio of 1:7 joins milk sap in the fermented liquid that is stirring in the volume ratio of milk sap and fermented liquid, the control mixing speed is 200r/min, extraction time 120min.Extraction is left standstill 10min after finishing, and separates the fermented liquid that removes out lower floor.The milk sap on upper strata places 100 ℃ the hot breakdown of emulsion of environment, after oil phase and interior water layering, water in the lower floor is collected.Interior aqueous phase solution pH value is adjusted to 6.8, then through concentrated, crystallization, drying and other steps, make the Trisodium Citrate product.
After testing: in this example citric acid percentage extraction be 91.8%, the purity 99.0% of Trisodium Citrate product.
Embodiment 2: with Tween 60, TOA, hexanaphthene by volume 1:0.667:6.667 mix, add isopyknic mass concentration and be 12.5% Na
2CO
3The aqueous solution.Mixing solutions when system becomes the homogeneous oyster white by muddiness, namely obtains milk sap at the newborn 30min of ultrasonic mechanism.The extraction of citric acid is with embodiment 1 in the fermented liquid.
After testing, the citric acid in this example percentage extraction be 90.2%, the purity 97.0% of Trisodium Citrate product.
Embodiment 3: with Tween 60+Span 80 (volume ratio 1:1), tributyl phosphate, n-tetradecane by volume 1:0.2:5 mix, be that to add mass concentration be 5% Na for the volume ratio of 1:0.8 by oil phase and interior water
2CO
3The aqueous solution.Mixing solutions is with the speed system breast 180s of 10000r/m, and system becomes the milky milk sap of homogeneous by muddiness.
The extraction of citric acid is with embodiment 1 in the fermented liquid.Experimental result is as follows: when the volume ratio of milk sap and fermented liquid was 1:1, the control mixing speed was 200r/min, stopped extraction behind the 120min.Water in reclaiming adjusts to 6 with the pH value, then through concentrated, crystallization, drying and other steps, makes the Trisodium Citrate product.
After testing: in this example citric acid percentage extraction be 90.1%, the purity 98.5% of Trisodium Citrate product.
Embodiment 4: with Tween 80, tributyl phosphate+Alamine 336 (volume ratio 1:1), kerosene by volume 1:1.5:10 mix, be that to add mass concentration be 20% Na for the volume ratio of 1:2 by oil phase and interior water
2CO
3The aqueous solution.Mixing solutions is with the speed system breast 180s of 10000r/m, and system becomes the milky milk sap of homogeneous by muddiness.
The extraction of citric acid is with embodiment 1 in the fermented liquid.Experimental result is as follows: when the volume ratio of milk sap and fermented liquid was 1:10, the control mixing speed was 200r/min, stopped behind the extraction 120min.Water in reclaiming, decolouring are processed a step, with aqueous citric acid solution pH value of solution are adjusted to 8.0, then through concentrated, crystallization, drying and other steps, make the Trisodium Citrate product.
After testing: in this example citric acid percentage extraction be 85.9%, the purity 97.6% of Trisodium Citrate product.
Embodiment 5: with Tween 60, tributyl phosphate, kerosene+hexanaphthene (volume ratio 1: 1) by volume 1:0.5:7 mix, add isopyknic mass concentration and be 20% the NaOH aqueous solution.Mixing solutions is with the speed system breast 140s of 10000r/m, and system becomes the milky milk sap of homogeneous by muddiness.The extraction of citric acid is with embodiment 1 in the fermented liquid.
After testing: in this example citric acid percentage extraction be 88.1%, the purity 98.5% of Trisodium Citrate product.
Claims (5)
1. a milk sap that is used for extractive fermentation liquid citric acid is made by the newborn technique of employing system after interior water and the oil phase mixing, it is characterized in that:
1) described oil phase mixes institute by tensio-active agent, carrier, Oil solvent by following volume ratio and consists of:
Tensio-active agent/carrier/Oil solvent=1/ (0.2 ~ 1.5)/(5 ~ 10);
2) volume ratio of described oil phase and interior water is:
Oil phase/interior water=1/ (0.8 ~ 2);
3) described tensio-active agent is Tween 40, Tween 60, Tween80 composition single or mutually combination, or the organic surface active agent of the combined composition of itself and Span 80;
4) described carrier is Alamine 336, Trioctylamine, tributyl phosphate, TRPO, N, and the single component of N '-dialkyl amide, N-alkylamide, petrolenum sulfoxide or the citric acid of combined composition are in conjunction with carrier;
5) described Oil solvent is n-tetradecane, hexanaphthene composition single or mutually combination, or the non-polar solvent of the combined composition of itself and kerosene;
6) described interior water is NaOH, KOH, Na single or mutually combination
2CO
3, K
2CO
3The basic solution of composition.
2. a kind of milk sap for extractive fermentation liquid citric acid according to claim 1 is characterized in that:
The mass concentration of described interior water is 5% ~ 20%.
3. method of utilizing citric acid in the milk sap extractive fermentation liquid claimed in claim 1 and obtaining Citrate trianion is characterized in that being made of successively following step:
1) will extract after fermented liquid and the milk sap mixing;
2) extract is carried out standing demix, isolate the fermented liquid of extract lower floor;
3) milk sap on extract upper strata after the layering is further carried out the layering of oil phase and interior water;
4) will extract after the interior water collection after the layering;
5) internally the extract of water carries out the neutral adjusting of pH;
6) the interior water extract after the neutral adjusting of pH is carried out condensing crystal, make the Citrate trianion product.
4. citric acid and obtain the method for Citrate trianion in the milk sap extractive fermentation liquid according to claim 3 is characterized in that:
The volume ratio of described milk sap and fermented liquid is:
Milk sap/fermented liquid=1/ (1 ~ 10).
5. citric acid and obtain the method for Citrate trianion according to claim 3 or in the 4 described milk sap extractive fermentation liquid is characterized in that:
The neutral scope of regulating of described pH is 6 ~ 8.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144794A (en) * | 1994-05-27 | 1997-03-12 | 刘世斋 | Method for extracting citric acid |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144794A (en) * | 1994-05-27 | 1997-03-12 | 刘世斋 | Method for extracting citric acid |
Non-Patent Citations (4)
| Title |
|---|
| 发酵柠檬酸提取方法的研究进展;朱亦仁等;《精细与专用化学品》;20031231(第14期);第18-20,24页 * |
| 朱亦仁等.发酵柠檬酸提取方法的研究进展.《精细与专用化学品》.2003,(第14期),第18-20,24页. |
| 朱亦仁等.液膜法提取发酵液中的柠檬酸——分离原理及膜配方.《水处理技术》.2000,第26卷(第5期),第277-280页. |
| 液膜法提取发酵液中的柠檬酸——分离原理及膜配方;朱亦仁等;《水处理技术》;20001031;第26卷(第5期);第277-280页 * |
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