Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for extracting high-purity L-lactic acid by using a molecular distillation heavy phase and a nanofiltration membrane concentrated solution, wherein the high-content impurities generated by nanofiltration membrane and molecular distillation are mixed and then purified and refined by a sequential simulated moving bed system, so that the loss rate of lactic acid is reduced, and the quality and the yield of the L-lactic acid product are improved.
The purpose of the invention can be realized by the following technical scheme:
a method for extracting high-purity L-lactic acid by using a molecular distillation heavy phase and nanofiltration membrane concentrated solution comprises the following steps:
(1) adding water to dilute heavy-phase lactic acid obtained by molecular distillation in the traditional lactic acid production process and concentrated solution obtained by filtering with a nanofiltration membrane, adding the diluted solution into a pretreatment tank, preserving the solution for a period of time at constant temperature, feeding the solution into a sequential simulated moving bed, and separating the solution by a sequential simulated moving bed chromatographic column to obtain an extracting solution of a target product and residual liquid containing impurities;
(2) decoloring the extracting solution obtained in the step (1) by using granular activated carbon, continuously feeding the decoloring solution into an ion exchange column in a continuous ion exchange system for ion exchange, wherein the ion exchange column is formed by connecting a cation column and an anion column in series, and the decoloring solution is subjected to cation exchange and anion exchange in sequence to obtain an ion exchange solution;
(3) filtering the ion exchange liquid by a nanofiltration membrane to obtain a nanofiltration membrane clear liquid and a nanofiltration membrane concentrated liquid, adding the nanofiltration membrane concentrated liquid into a pretreatment tank, mixing the nanofiltration membrane concentrated liquid and the heavy-phase lactic acid in the step (1) according to a certain proportion, and then circulating the step (1) and the step (2), wherein the nanofiltration membrane clear liquid enters MVR to be concentrated to obtain a concentrated liquid of L-lactic acid;
(4) and (3) subjecting the L-lactic acid concentrated solution to molecular distillation to obtain a light-phase finished product lactic acid and a high-impurity heavy-phase lactic acid part, and returning the heavy-phase lactic acid to the continuous simulated moving bed treatment in the step (1).
Further preferably, the heavy phase lactic acid obtained by molecular distillation in the step (1) is diluted by adding water to a solid content of 40-45 wt%
Further preferably, the nanofiltration membrane concentrated solution and the heavy phase lactic acid are mixed according to the mass ratio of 1:1-3 in the step (3).
Further preferably, the eluent of the sequential simulated moving bed is deionized water, the operating temperature of the sequential simulated moving bed is 60 ℃, the number of chromatographic columns of the sequential simulated moving bed is at least 6, the sequential simulated moving bed is switched in different regions of the column through a double-channel automatic valve, and the fixed phase adsorbent filled in the chromatographic columns is weak positive exchange resin.
Further preferably, the feeding speed of the sequential simulated moving bed is set to be 45.5-47.5ml/min, and the dry-based purity of lactic acid of the feeding component of the sequential simulated moving bed2More than 80 percent, less than 4 percent of anion, less than 12 percent of impurity organic acid and cation and less than 8 percent of total sugar.
The invention has the beneficial effects that:
the method comprehensively utilizes the mixed waste liquid of the molecular distillation heavy phase and the nanofiltration membrane concentrated liquid, can extract lactic acid contained in the nanofiltration membrane concentrated liquid and the heavy phase lactic acid which are difficult to treat, improves the purity of the finished product L-lactic acid, reduces the production cost, achieves the quality of the L-lactic acid which is used as the polylactic acid raw material, and simultaneously improves the yield of the L-lactic acid in the process production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in figure 1, the method for extracting the high-purity L-lactic acid by using the molecular distillation heavy phase and the nanofiltration membrane concentrated solution is a method for extracting the high-purity L-lactic acid by using mixed waste liquid of the molecular distillation heavy phase and the nanofiltration membrane concentrated solution in the traditional calcium salt method lactic acid production process as raw materials.
The method comprises the following steps:
s1 separation and purification of L-lactic acid
The nanofiltration membrane concentrated solution and the molecular distillation heavy-phase lactic acid are injected into a continuous simulated moving bed pretreatment tank according to the mass ratio of 1:1-3, are mixed, are diluted by adding water until the dry basis percentage is 40% -45%, are stored at the constant temperature of 60 ℃ for 48 hours, are fed into a sequential simulated moving bed chromatographic column through a filter with the size of 5 mu m, and are stored at the constant temperature so as to depolymerize lactic acid dimers and polymers in the mixed solution into lactic acid, and the mixed feeding component of the heavy-phase lactic acid and the nanofiltration membrane concentrated solution has the following requirements:
1. the purity of the lactic acid dry basis is more than 80 percent;
2. anion < 4%; impurity organic acids and cations: < 12%;
3. total sugar: < 8%;
the pretreated feed continuously enters separation equipment, the packing of a separation column is exchange resin and is set into 6 units, the separation equipment has stronger binding capacity to the target product lactic acid, the flow of the raw material flowing through a chromatographic column is accurately controlled, the product is divided into an extracting solution part with high recovery rate and a residual liquid part with high impurity content, and the feeding speed is set to be 45.5ml/min-47.5 ml/min.
The concentration of partial milk L-lactic acid of the final extracting solution reaches 190g/L-220g/L, and the purity of the lactic acid reaches 90-92 percent; the yield of lactic acid reaches 94% -98%; the removal rate of other organic heteropolyacids is 45-50 percent; the total sugar removal rate is 85-90%.
S2 refining and purifying L-lactic acid
(1) Pigment in the extract is removed by granular activated carbon, granular activated carbon is filled in an activated carbon decoloring column, the decoloring column adopts a parallel connection mode, a feeding mode adopts a low-inlet-high-outlet mode, the chroma of a decolored solution after decoloring is less than 30hazen, and the retention time of the extract in the activated carbon decoloring column is controlled to be 45 min. The regeneration mode of the granular activated carbon adopts a multi-section regeneration furnace for thermal regeneration, acid and alkali consumption is not generated, and the environmental pollution is reduced.
(2) The decolorized solution enters a continuous ion exchange system, an ion exchange column is formed by connecting a cation column and an anion column in series, wherein the cation column and the anion column can be arranged in parallel, the cation column adopts strong-acid cation exchange resin as a filler, the anion column adopts weak-base anion exchange resin as a filler, the decolorized solution sequentially passes through the cation exchange column and the anion exchange column to obtain an ion exchange solution, the ion exchange aims at removing anions and cations in the primary decolorized solution and a small amount of pigment, the product purity is improved, the pollution to a nanofiltration membrane in a later process can be reduced, the service cycle of the nanofiltration membrane is prolonged, and therefore the production cost is reduced. Calcium ion in the feed liquid after ion exchange is less than or equal to 2ppm, magnesium ion is less than or equal to 1ppm,4Sodium ion is less than or equal to 1ppm, sulfate ion is less than or equal to 2ppm, chloride ion is less than or equal to 2ppm, and chroma is less than 20 hazen.
(3) And filtering the ion exchange liquid by using a nanofiltration membrane, wherein the purity of the L-lactic acid in the clear liquid of the nanofiltration membrane reaches 93-95%, the filtering purpose of the nanofiltration membrane is to remove residual sugar, macromolecular protein, inorganic salt, pigment and the like in the clear liquid of the nanofiltration membrane, further improve the purity of the L-lactic acid, ensure the quality of the final L-lactic acid product, and then carrying out MVR (mechanical vapor recompression) concentration treatment to obtain a lactic acid concentrated solution with the L-lactic acid content of 85%.
(4) Short-range distillation, namely continuously concentrating the concentrated L-lactic acid by adopting scraper plate evaporation until the content of the L-lactic acid is 98-100%, and then refining by molecular distillation to obtain an L-lactic acid product which meets the production raw material of polylactic acid; and (3) allowing the heavy-phase lactic acid to flow into a continuous simulated moving bed chromatographic device to be mixed with a nanofiltration membrane concentrated solution for heat preservation treatment, and continuously separating and purifying the membrane concentrated solution and the molecular distillation heavy phase.
The following examples are given for more details:
example 1
Mixing the nanofiltration membrane concentrated solution and the molecular distillation heavy phase lactic acid according to the mass ratio of 1:1, adding water to dilute until the dry basis percentage is 40%, preserving at the constant temperature of 60 ℃ for 48h, setting the flow rate at 45.5ml/min, feeding the mixture to a sequential simulated moving bed chromatographic column through a 5-micron filter to prepare an extracting solution, wherein the concentration of partial milk L-lactic acid in the extracting solution reaches 190g/L, and the purity of the lactic acid reaches 90%; the yield of lactic acid reaches 94 percent; the removal rate of other organic heteropolyacids is 45 percent; the total sugar removal rate is 85%, the retention time of the extracting solution in an active carbon decoloring column is controlled to be 2h, the extracting solution sequentially passes through an ion exchange system and a nanofiltration system, after being concentrated to 85% by MVR, the purity of the light phase finished product lactic acid obtained by molecular distillation is 96%.
Example 2
Mixing the nanofiltration membrane concentrated solution and the molecular distillation heavy phase lactic acid according to the mass ratio of 1:2, adding water to dilute until the dry basis percentage is 43%, preserving at the constant temperature of 60 ℃ for 48h, setting the flow rate at 46.5ml/min, feeding the mixture to a sequential simulated moving bed chromatographic column through a 5-micron filter to prepare an extracting solution, wherein the concentration of partial milk L-lactic acid in the extracting solution reaches 220g/L, and the purity of the lactic acid reaches 92%; the yield of the lactic acid reaches 98 percent; the removal rate of other organic heteropolyacids is 50 percent; the total sugar removal rate is 90%, the retention time of the extracting solution in an active carbon decoloring column is controlled to be 2h, the extracting solution sequentially passes through an ion exchange system and a nanofiltration system, after being concentrated to 85% by MVR, the purity of the light phase finished product lactic acid obtained by molecular distillation is 99%.
Example 3
Mixing the nanofiltration membrane concentrated solution and the molecular distillation heavy phase lactic acid according to the mass ratio of 1:3, adding water to dilute until the dry basis percentage is 45%, preserving at the constant temperature of 60 ℃ for 48h, setting the flow rate at 47.5ml/min, feeding the mixture to a sequential simulated moving bed chromatographic column through a 5-micron filter to prepare an extracting solution, wherein the concentration of partial milk L-lactic acid in the extracting solution reaches 210g/L, and the purity of the lactic acid reaches 91%; the yield of the lactic acid reaches 96 percent; the removal rate of other organic heteropolyacids is 48 percent; the total sugar removal rate is 88 percent, the retention time of the extracting solution in an active carbon decoloring column is controlled to be 2 hours, the extracting solution sequentially passes through an ion exchange system and a nanofiltration system, after being concentrated to 85 percent by MVR, the purity of the light phase finished product lactic acid obtained by molecular distillation is 98 percent.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.