CN114181070A - Method for extracting high-purity L-lactic acid by using molecular distillation heavy phase and nanofiltration membrane concentrated solution - Google Patents

Method for extracting high-purity L-lactic acid by using molecular distillation heavy phase and nanofiltration membrane concentrated solution Download PDF

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CN114181070A
CN114181070A CN202111629696.0A CN202111629696A CN114181070A CN 114181070 A CN114181070 A CN 114181070A CN 202111629696 A CN202111629696 A CN 202111629696A CN 114181070 A CN114181070 A CN 114181070A
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lactic acid
nanofiltration membrane
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molecular distillation
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谷晨曦
刘喆
余莉花
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Pulis Biotechnology Co ltd
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Abstract

本发明公开一种以分子蒸馏重相和纳滤膜浓液提取高纯L‑乳酸的方法,包括以下步骤:(1)重相乳酸通和纳滤膜浓液混合稀释保温后通过顺序式模拟移动床色谱柱分离得到提取液和含有杂质的残液;(2)提取液脱色后进行离子交换;(3)离交液经纳滤膜过滤,膜浓液加入预处理罐中与步骤(1)中的重相乳酸按一定比例混合后循环步骤(1)和步骤(2),纳滤膜清液进入MVR浓缩得到L‑乳酸的浓缩液;(4)浓缩液经过分子蒸馏得到轻相成品乳酸和重相乳酸,重相乳酸返回步骤(1)的连续模拟移动床预处理。本发明利用顺序式模拟移动床色谱提纯,将纳滤膜浓液和重相乳酸中含有的乳酸提取出来,使得成品L‑乳酸纯度达到96‑98%,降低了生产成本,同时提升工艺生产中L‑乳酸的收率。

Figure 202111629696

The invention discloses a method for extracting high-purity L-lactic acid by using molecular distillation heavy phase and nanofiltration membrane dope, comprising the following steps: (1) the heavy-phase lactic acid and the nanofiltration membrane dope are mixed, diluted and kept warm, and then simulated in a sequential manner. The moving bed chromatographic column is separated to obtain the extract and the residual liquid containing impurities; (2) the extract is decolorized and then ion-exchanged; (3) the ionized liquid is filtered through a nanofiltration membrane, and the membrane dope is added to the pretreatment tank to be combined with step (1). The heavy-phase lactic acid in ) is mixed in a certain proportion and circulates step (1) and step (2), and the nanofiltration membrane clear liquid enters the MVR and is concentrated to obtain the concentrated solution of L-lactic acid; (4) the concentrated solution obtains the light-phase finished product through molecular distillation Lactic acid and heavy-phase lactic acid, heavy-phase lactic acid is returned to the continuous simulated moving bed pretreatment of step (1). The present invention utilizes sequential simulated moving bed chromatographic purification to extract the lactic acid contained in the nanofiltration membrane dope and the heavy-phase lactic acid, so that the purity of the L-lactic acid of the finished product reaches 96-98%, the production cost is reduced, and the process efficiency is improved at the same time. Yield of L-lactic acid.

Figure 202111629696

Description

Method for extracting high-purity L-lactic acid by using molecular distillation heavy phase and nanofiltration membrane concentrated solution
Technical Field
The invention relates to the technical field of lactic acid purification, in particular to a method for extracting high-purity L-lactic acid by using a molecular distillation heavy phase and a nanofiltration membrane concentrated solution.
Background
Lactic acid is an important organic acid, and is widely present in humans, animals and plants. Lactic acid, lactate and derivatives thereof have wide application in the fields of food, feed, chemical industry, medicine and the like. Poly L-lactic acid generated by recent L-lactic acid polymerization is used as a new material, and a biodegradable material, a green packaging material, a household film and the like manufactured by the poly L-lactic acid are used for solving the increasingly serious problem of white pollution of the environment, are considered as the new material with the most development prospect in the new century, and have very wide application prospects.
In the process of producing refined lactic acid, 10-15% of heavy phase lactic acid can be produced by molecular distillation, the heavy phase lactic acid is enriched in impurities such as sugar, pigment, protein and the like in the original lactic acid, and the content of the lactic acid is generally 65-80. The heavy phase lactic acid contains a plurality of impurities, so the use is narrow, and the heavy phase lactic acid is difficult to sell in the market. Therefore, it is an urgent problem to provide a method for producing high-purity lactic acid and increasing the yield of polymer-grade lactic acid by refining the heavy-phase lactic acid as a raw material. Meanwhile, in the refining and purifying stage of the lactic acid, part of the lactic acid enters a nanofiltration membrane concentrated solution and a molecular distillation heavy phase in the processes of an organic nanofiltration membrane and molecular distillation impurity removal, so that the yield is reduced.
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.
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The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a process flow diagram of the present invention.
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.

Claims (5)

1.一种以分子蒸馏重相和纳滤膜浓液提取高纯L-乳酸的方法,其特征在于,包括以下步骤:1. a method for extracting high-purity L-lactic acid with molecular distillation heavy phase and nanofiltration membrane dope, is characterized in that, comprises the following steps: (1)将分子蒸馏得到的重相乳酸和纳滤膜过滤后得到的浓液加去离子水稀释后加入预处理罐恒温保存一段时间,然后向顺序式模拟移动床进料,通过顺序式模拟移动床色谱柱分离得到目标产品的提取液和含有杂质的残液;(1) Dilute the heavy-phase lactic acid obtained by molecular distillation and the concentrated solution obtained by nanofiltration membrane filtration, add deionized water to dilute it, add it to the pretreatment tank and keep it at a constant temperature for a period of time, and then feed it to the sequential simulated moving bed, through sequential simulation The moving bed chromatographic column is used to separate the extract of the target product and the residual liquid containing impurities; (2)将步骤(1)得到的提取液用颗粒活性炭进行脱色,脱色液继续进入连续离子交换系统中的离子交换柱进行离子交换,离子交换柱由阳离子柱和阴离子柱串联组成,脱色液依次经过阳离子交换和阴离子换后得到离交液;(2) decolorizing the extract obtained in step (1) with granular activated carbon, the decolorizing solution continues to enter the ion exchange column in the continuous ion exchange system for ion exchange, and the ion exchange column is composed of a cation column and an anion column in series, and the decolorizing solution is sequentially After cation exchange and anion exchange, the ionized liquid is obtained; (3)离交液经纳滤膜过滤后得到纳滤膜清液和纳滤膜浓液,纳滤膜浓液加入预处理罐中与步骤(1)中的重相乳酸按一定比例混合后循环步骤(1)和步骤(2),纳滤膜清液进入MVR浓缩得到L-乳酸的浓缩液;(3) After the ionized liquid is filtered by the nanofiltration membrane, the nanofiltration membrane clear liquid and the nanofiltration membrane dope are obtained, and the nanofiltration membrane dope is added to the pretreatment tank and mixed with the heavy phase lactic acid in step (1) in a certain proportion. Circulating step (1) and step (2), the nanofiltration membrane clear liquid enters MVR and is concentrated to obtain the concentrated solution of L-lactic acid; (4)L-乳酸浓缩液经过分子蒸馏得到轻相成品乳酸和高杂质重相乳酸部分,重相乳酸再返回步骤(1)的连续模拟移动床预处理罐处理。(4) The L-lactic acid concentrate is subjected to molecular distillation to obtain the light-phase finished lactic acid and the high-impurity heavy-phase lactic acid part, and the heavy-phase lactic acid is returned to the continuous simulated moving bed pretreatment tank of step (1) for processing. 2.根据权利要求1所述的以分子蒸馏重相和纳滤膜浓液提取高纯L-乳酸的方法,其特征在于,所述步骤(1)中分子蒸馏得到的重相乳酸加水稀释至固含量40-45wt%。2. the method for extracting high-purity L-lactic acid with molecular distillation heavy phase and nanofiltration membrane dope according to claim 1, is characterized in that, in described step (1), the heavy phase lactic acid that molecular distillation obtains is diluted with water to Solid content 40-45wt%. 3.根据权利要求1所述的以分子蒸馏重相和纳滤膜浓液提取高纯L-乳酸的方法,其特征在于,所述步骤(3)中纳滤膜浓液和重相乳酸按质量比1:1-3混合。3. the method for extracting high-purity L-lactic acid with molecular distillation heavy phase and nanofiltration membrane dope according to claim 1, is characterized in that, in described step (3), nanofiltration membrane dope and heavy phase lactic acid press Mass ratio 1:1-3 mix. 4.根据权利要求1所述的以分子蒸馏重相和纳滤膜浓液提取高纯L-乳酸的方法,其特征在于,所述顺序式模拟移动床的洗脱剂为去离子水,操作温度为60℃,色谱柱至少为6个,顺序式模拟移动床通过双通道自动阀门在柱子的不同区切换,色谱柱内所装填固定相吸附剂为弱阳性交换树脂。4. the method for extracting high-purity L-lactic acid with molecular distillation heavy phase and nanofiltration membrane dope according to claim 1, is characterized in that, the eluent of described sequential simulation moving bed is deionized water, and operation The temperature is 60°C, the number of chromatographic columns is at least 6, the sequential simulated moving bed is switched in different areas of the column through a dual-channel automatic valve, and the stationary phase adsorbent filled in the chromatographic column is a weakly positive exchange resin. 5.根据权利要求1所述的以分子蒸馏重相和纳滤膜浓液提取高纯L-乳酸的方法,其特征在于,所述顺序式模拟移动床进料速度设定为45.5-47.5ml/min,顺序式模拟移动床进料组分的乳酸干基纯度大于80%、阴离子含量小于4wt%、杂质有机酸和阳离子含量小于12wt%、总糖小于8wt%。5. the method for extracting high-purity L-lactic acid with molecular distillation heavy phase and nanofiltration membrane dope according to claim 1, is characterized in that, described sequential simulation moving bed feed rate is set to 45.5-47.5ml /min, the lactic acid dry basis purity of the sequential simulated moving bed feed component is greater than 80%, the anion content is less than 4wt%, the impurity organic acid and cation content is less than 12wt%, and the total sugar is less than 8wt%.
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