Method for coupling conversion and extraction of lactic acid from aqueous lactate raw material
Technical Field
The invention relates to the production and conversion of lactic acid, in particular to a method for coupling conversion and extraction of lactic acid from lactate aqueous solution.
Background
Lactic acid is one of three generally recognized organic acids and is widely applied to the fields of food, medicine, chemical industry, new materials and the like. Can be used for preparing chemical products or biological materials such as lactate, propylene glycol, propylene oxide, acrylic acid, polylactic acid and the like. At present, the biological fermentation method is mostly adopted for producing lactic acid in industry. The components in the lactic acid fermentation liquor are very complex, besides lactic acid or lactate, a large amount of thalli, pigments, unconverted substrates, proteins, inorganic salts, byproduct organic acids and the like exist, the impurities are various, great difficulty is brought to subsequent separation and refining of lactic acid, and the product is obtained through a long process.
In the process of producing lactic acid by fermentation, an increase in the production of lactic acid inhibits the fermentation activity of the microorganism. The method commonly used is to add alkali, salt or metal oxide and the like to neutralize lactic acid. Most of the lactic acid in the fermentation broth obtained by the method is lactate, and the lactate needs to be converted into lactic acid through acidification in the subsequent process.
Taking a common calcium salt acidification method as an example, calcium carbonate or calcium hydroxide is added in the fermentation process to neutralize the generated lactic acid to form a fermentation liquor containing calcium lactate, sulfuric acid is added in the fermentation liquor for acidification, and calcium sulfate solids are separated and removed after acidification to obtain a crude lactic acid solution. The process is a main method for producing the lactic acid at present, has the advantages of mature process, easy control and the like, but concentrated sulfuric acid used for acidification can cause pollution, and the generated calcium sulfate also needs to be treated as solid waste.
CN103153935A discloses a method for preparing a lactic acid-amine complex and barium carbonate by reacting a sugar with barium hydroxide to prepare barium lactate and contacting with ammonia or an amine and with carbon dioxide, or with a carbonate and/or bicarbonate of ammonia or an amine. The method takes sugar as raw material, generates lactic acid by a chemical reaction method, and provides an extraction scheme of the lactic acid. The method chemically generates lactic acid, and provides a method for extracting lactic acid. However, lactic acid produced by the method is racemic, heavy metal is used in the method, and the product is a lactic acid-amine complex which still needs to be further separated.
Wanjunfen et al (the tenth national academy of supercritical fluid technology and research and application, and the third proceedings of the research and discussion of supercritical fluid technology on both sides of the strait 2015: 386-. Wherein the carbon dioxide can be derived from the fermentation process and the calcium carbonate produced can also be recycled as a neutralising agent for the fermentation process. Meanwhile, the method does not use sulfuric acid, does not generate solid waste such as calcium sulfate and is a green pollution-free separation method. However, studies have also found that the process conditions to achieve high conversion are: the temperature is 31-32 ℃, the pressure is 13-14MPa, the calcium lactate accounts for 2.3 percent of the mass fraction of the fermentation broth, the reaction balance can be achieved within 1.5h, and the conversion rate can reach more than 80 percent. There is a problem one: the operating pressure is too high; the second problem is that: the content of calcium lactate in the fermentation broth is much lower than that of lactate in the fermentation broth produced in the fermentation process on an industrial operation scale (lactate accounts for >10% of the mass fraction of the fermentation broth). When the mass fraction of calcium lactate is 10%, the conversion rate is less than 25%. The third problem is that: the method can only be applied to calcium lactate aqueous solution, and the raw materials are sodium lactate, ammonium lactate and the like, and the cation of the raw material is lactate raw material of which the carbonate is soluble salt, so the method cannot be used for conversion.
Further refining of lactic acid is usually carried out by adsorption methods during the production of lactic acid. The conventional adsorption method is a process in which lactic acid is extracted from a fermentation broth by adding an adsorbent to the fermentation broth or passing the fermentation broth through an anion or cation exchange resin, followed by desorption. Crosslinked polyvinylpyridine resin (PVP), microporous ultrahigh crosslinked resin, tertiary amine resin, ion exchange resin, etc. are commonly used. However, when the resin is eluted after adsorption, chemical reagents such as acid and alkali are required to remove introduced impurities from the eluted materials, and the generated waste liquid is required to be treated and discharged. And hot water is used as an eluent, so that the method is a green and environment-friendly scheme without introducing impurities. Hodgkin et al (CN 201110457464), Huangchaoxia et al (ion exchange and adsorption, 1994, 10(1): 18-25.), Huyou Hui et al (the chemical world, 1998, 7: 357- & 360.), Wu et al (Colloids and Surfaces A: Physicochem. Eng. Aspects, 2012, 407: 29-37.), Schopper chevalia chevalis et al (proceedings of the Anhui institute of engineering and technology (Nature science edition), 2003(01): 4-7.), etc. have been studied for the elution of hot water for adsorption of lactic acid, respectively, and have a considerable effect when the adsorbent is a resin such as PVP, D-301, AX-1, DR1, DR2, etc.
Disclosure of Invention
In order to solve the problems of low conversion rate, generation of solid waste and other pollution, only application to calcium lactate feed liquid, harsh conversion conditions and the like existing in the conversion and extraction of lactic acid in the post-treatment process of aqueous lactate solution, particularly fermentation liquid after lactic acid fermentation in the prior art, the invention provides a method for coupling the conversion and extraction of lactic acid from aqueous lactate raw materials, which realizes the conversion and extraction of lactic acid simultaneously under relatively mild conditions and has higher conversion rate.
The technical purpose is realized by the following technical scheme:
a method for coupling conversion and extraction of lactic acid from a water-containing raw material of lactate comprises the steps of mixing the water-containing raw material of lactate with a solid adsorbent, continuously introducing carbon dioxide into the mixture, keeping the pressure at more than or equal to 5MPa and the temperature at 5-30 ℃ for reaction, separating the solid adsorbent from a feed liquid, and eluting the solid adsorbent with water to obtain the lactic acid; the solid adsorbent is resin which can selectively adsorb organic acid but not inorganic ions and can be desorbed after the temperature is raised.
Further, in the above method, the solid adsorbent is a thermally regenerated resin, more specifically, at least one selected from the group consisting of a polyvinylpyridine resin (PVP), a tertiary amine type macroporous styrene-divinylbenzene copolymer resin (D301), and a lysine-chloromethyl polystyrene resin (DR 2).
Further, in the above method, the solid adsorbent is added in an amount of not less than 3 times, preferably 3 to 4 times, the mass of lactate in the feed liquid on a dry basis.
Further, in the above method, the lactate salt in the aqueous lactate salt material is present in a mass fraction of 1% to 50%, preferably 4% to 20%, based on the weight of lactate.
Further, in the above method, it is preferable to maintain the pressure at 5 to 10MPa after the introduction of carbon dioxide.
Furthermore, in the method, after the carbon dioxide is introduced, the reaction time is more than or equal to 1 hour, and preferably 1 to 3 hours.
Further, in the above method, the separation of the solid adsorbent from the solution is carried out by discharging the solution from the reaction system after the reaction is completed, releasing carbon dioxide and recovering the carbon dioxide, and the solid adsorbent is obtained.
Further, in the method, the elution is to wash the solid adsorbent with water at the temperature of 1-10 ℃, discard the liquid, then elute with water at the temperature of 80-90 ℃, and collect the eluent to obtain the crude lactic acid solution.
Furthermore, when water with the temperature of 80-90 ℃ is used for elution, the elution water is more than or equal to 3 times of the mass of the feed liquid.
Further, in the above method, the aqueous material of lactate is previously subjected to sterilization treatment.
Further, the salt ions in the aqueous starting material of the lactate salt should be ions which are highly soluble in the carbonate salt, such as sodium ions, ammonium ions.
In the above process, it will be understood by those skilled in the art that lactic acid in the aqueous feed of the lactate salt may be used in the process of the present invention either in the free lactate ion or in undissociated form.
Compared with the prior art, the method has the following advantages:
(1) the method selects a mode of combining the solid adsorbent capable of adsorbing lactic acid with high-pressure treatment of carbon dioxide, can simultaneously convert and extract the lactic acid from the water-containing raw material, and compared with the traditional calcium salt sulfuric acid acidification method, the method uses the carbon dioxide to replace sulfuric acid as an acidifier, does not generate solid waste of calcium sulfate, and is a green pollution-free separation method.
(2) After the conversion and extraction of lactic acid are carried out by adopting the method of the invention, carbonate solution is generated and can be reused for pH adjustment in the fermentation process, thereby realizing the full utilization of byproducts.
(3) Compared with the method only using carbon dioxide as an acidulant, the method has lower operation pressure and higher conversion rate, and the absorption and extraction of lactic acid are synchronously carried out, thereby simplifying the post-treatment process and having mild reaction conditions.
(4) The adsorbent which can be desorbed by hot water is selected, acid and alkali are avoided, extra impurities cannot be introduced in the desorption and regeneration processes of the adsorbent, and pollution is avoided.
(5) Since the adsorbent selected hardly adsorbs inorganic salt ions, the dilute lactic acid solution eluted from the adsorbent hardly contains inorganic salt ions, and removal of inorganic salts is achieved while extracting lactic acid.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
And (2) performing sterilization, decoloration and ultrafiltration treatment on sodium lactate fermentation liquor, wherein the mass fraction of lactate in the aqueous feed liquid is 12%. The impurity content of the treated sodium lactate fermentation broth is shown in table 1.
Table 1.
Adding 100g of the treated sodium lactate fermentation broth into a reactor, adding 48g of solid adsorbent PVP resin (based on the dry weight of the resin), namely 4 times of the weight of lactate in the feed liquid, introducing carbon dioxide into the reactor, pressurizing to 8.0MPa, controlling the temperature to be 10 ℃, keeping the constant temperature and the constant pressure, and fully stirring for reaction for 2 hours. And then discharging the feed liquid to a buffer tank, reducing the pressure, recovering carbon dioxide, washing the solid adsorbent by using pure water with the temperature of 5 ℃ in a sufficient amount, retaining the washing liquid, measuring the content of the residual lactic acid or lactate in the feed liquid and the washing liquid by using liquid chromatography, and calculating the extraction rate.
Example 2
The conditions were the same as in example 1 except that the solid adsorbent was replaced with an equal weight of D301 resin.
Example 3
The conditions were the same as in example 1 except that the solid adsorbent was replaced with an equal weight of DR2 resin.
Example 4
The reaction conditions were the same as in example 1 except that the reaction temperature after carbon dioxide charging was adjusted to 5 ℃.
Example 5
The reaction conditions were the same as in example 1 except that the reaction temperature after carbon dioxide charging was adjusted to 20 ℃.
Example 6
The reaction conditions were the same as in example 1 except that the reaction temperature after carbon dioxide charging was adjusted to 30 ℃.
Comparative example 1
The reaction conditions were the same as in example 1 except that the reaction temperature after carbon dioxide charging was adjusted to 40 ℃.
Example 7
The reaction conditions were the same as in example 1 except that the reaction pressure after carbon dioxide charging was adjusted to 5.0 MPa.
Example 8
The reaction conditions were the same as in example 1 except that the reaction pressure after carbon dioxide charging was adjusted to 7.0 MPa.
Example 9
The reaction conditions were the same as in example 1 except that the reaction pressure after carbon dioxide charging was adjusted to 10.0 MPa.
Example 10
The reaction conditions were the same as in example 1 except that the reaction pressure after carbon dioxide charging was adjusted to 15.0 MPa.
Comparative example 2
The reaction conditions were the same as in example 1 except that the reaction pressure after carbon dioxide charging was adjusted to 4.0 MPa.
Example 11
The conditions were the same as in example 1 except that the amount of the PVP resin added was adjusted to 36g (3 times the lactate content in the feed solution).
Example 12
The conditions were the same as in example 1 except that the amount of the PVP resin added was adjusted to 96g (8 times the lactate content in the feed solution).
Comparative example 3
The conditions were the same as in example 1 except that the amount of the PVP resin added was adjusted to 24g (2 times the lactate content in the feed solution).
Example 13
The procedure was carried out under the same conditions as in example 1 except that 4% by mass of lactate was used in an aqueous feed solution of sodium lactate and 16g of solid adsorbent was added (4 times the lactate content in the feed solution).
Example 14
The procedure was carried out under the same conditions as in example 1 except that 20% by mass of lactate was used in the aqueous feed solution of sodium lactate and 80g of solid adsorbent was added (4 times the lactate content in the feed solution).
Example 15
The reaction conditions were the same as in example 1 except that the reaction time after carbon dioxide charging was 1 hour.
Example 16
The reaction conditions were the same as in example 1 except that the reaction time after carbon dioxide charging was 3 hours.
Example 17
The reaction conditions were the same as in example 1 except that the reaction time after carbon dioxide charging was 6 hours.
Comparative example 4
The reaction conditions were the same as in example 1 except that the reaction time after carbon dioxide charging was 0.5 h.
Example 17
The conditions were the same as in example 1 except that the lactate salt in the feed solution was ammonium lactate.
The results of the extraction rate of lactic acid in the above examples and comparative examples are shown in Table 2.
Table 2.
Recovery of lactic acid by desorption of adsorbent
Example 19
The solid adsorbent of example 1 was eluted with 300g of water at 90 ℃ and the impurity content of the eluate is shown in Table 3. And measuring the content of lactic acid in the eluent by liquid chromatography, and calculating the elution rate.
Table 3.
Example 20
The solid adsorbent in example 2 was eluted in the same manner as in example 19.
Example 21
The solid adsorbent in example 3 was eluted in the same manner as in example 19.
Example 22
The solid adsorbent in example 1 was eluted with 300g of water at 80 ℃ and the content of lactic acid in the eluate was measured by liquid chromatography to calculate the elution rate.
Comparative example 5
The conditions were the same as in example 19 except that water at 70 ℃ was used instead of water at 80 ℃.
Comparative example 6
The conditions were the same as in example 19 except that the amount of water used was 200 g.
The results of the elution rate of lactic acid in the above examples and comparative examples are shown in Table 4.
TABLE 4
The above non-limiting examples are intended to provide those of ordinary skill in the art with a more complete understanding of the present invention, and are not intended to limit the invention in any way.