CN111909001B - Deep purification method of high-purity glycerol - Google Patents
Deep purification method of high-purity glycerol Download PDFInfo
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Abstract
The invention discloses a deep purification method of high-purity glycerol, which comprises the following steps: performing high-speed countercurrent chromatographic separation on a glycerol raw material, collecting elution parts in different time periods, and collecting the glycerol elution parts; and (3) distilling the collected glycerol eluate at low temperature under reduced pressure to recover the solvent, thereby obtaining the high-purity glycerol. The invention provides a deep purification method of high-purity glycerol, which ensures effective separation of glycerol, reductive substances such as glyceraldehyde, formaldehyde and the like, fatty acid and diglycerol in a crude glycerol product, thereby obtaining the high-purity glycerol, and ensures that the total amount of miscellaneous peaks in a final glycerol product is less than or equal to 0.01%, the aldehyde and the reductive substances are less than or equal to 0.5ppm, and the fatty acid and ester are less than or equal to 0.1mL. Because the stationary phase and the fluidity of the high-speed countercurrent chromatography are both liquid, the liquid can be recycled, and compared with the traditional chromatographic separation, the process has no solid carrier adsorption loss and high sample recovery rate; no consumption of stationary phase material, and low separation cost. Compared with the traditional process, the process has the advantages of convenient operation, short production period and high yield.
Description
Technical Field
The invention relates to the technical field of separation and purification, in particular to a deep purification method of high-purity glycerol.
Background
Glycerol, also known as glycerol, is derived from a byproduct of oil hydrolysis, is non-toxic, colorless, non-irritating, and chemically stable, and can be used as a synthetic raw material or directly in industry, medicine and daily life due to its special physical properties and chemical structure (see fig. 5), thus having wide application. Glycerol has about 2000 applications, and is mainly applied to medicines, foods, cosmetics, alkyd resins, ester products, tobacco, explosives, cellophane, textile printing and dyeing industry, paper industry, rubber industry and the like.
In the prior art, the purification of crude glycerol is mostly carried out by adopting modes such as reduced pressure distillation, activated carbon adsorption, ion exchange and the like. Although the glycerin purified by adopting the prior art can meet the glycerin quality specified by the state, due to the limitations of the process (the long-time temperature is overhigh, the separation effect of the traditional process is limited, and the like), a trace amount of by-products are inevitably generated in the purification process, and the application of the actual high-end product cannot be met. Such as: in the practical application process, especially when the glycerin is used as a medical auxiliary material, trace impurities such as residual fatty acid, aldehyde, polymer and the like in the glycerin (the total content of GC impurity peaks is between 0.06 and 0.2 percent, aldehyde and reducing substances are between 5ppm and 10ppm, and fatty acid and ester are between 0.4 and 2.0 ml) easily influence the key quality index and stability of a downstream preparation. At present, no report related to the removal of trace impurities such as fatty acid, aldehyde and polymer in glycerol is found.
The high-speed counter-current chromatographic technique is a new chromatographic separation and purification technique based on liquid-liquid distribution mechanism developed in the 80 th century, and its principle is that it utilizes multidimensional centrifugal field produced by helical column when it is moved in planet to make two phases which are not mutually soluble continuously mix, at the same time one phase (stationary phase) is retained, and utilizes constant flow pump to continuously input another phase (mobile phase), and the solute which is fed into helical column along with mobile phase is repeatedly distributed between two phases, and according to the order of distribution coefficient, it is successively eluted. The elution is carried out firstly when the proportion of the mobile phase is large, and the elution is carried out after the proportion of the mobile phase is large, so that the separation is realized. At present, although the technology is applied in some fields, the technology is still blank in the separation and purification of impurities such as fatty acid, aldehyde, polyglycerol and the like in the glycerol, so the exploration of raw materials, solvent systems and separation and purification conditions under the system is very important for the industrial development of the high-purity glycerol.
Disclosure of Invention
Based on the technical problems in the background art, the invention aims to provide a deep purification process of high-purity glycerol, which is simple in process, convenient for time operation, thorough in purification process and lower in glycerol impurity content. Namely, on the basis of the traditional crude glycerol purification process, a deep purification step is added, and the glycerol is further refined and purified by utilizing the high-speed counter-current chromatography technology.
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for deep purification of high purity glycerol, comprising the steps of:
step one, performing high-speed counter-current chromatographic separation on a glycerol raw material, collecting elution fractions in different time periods, and collecting the glycerol elution fractions;
and step two, recovering the solvent from the collected glycerin eluate by low-temperature reduced pressure distillation to obtain the high-purity glycerin.
Preferably, in the first step, the quality of the glycerol raw material meets the following requirements: the total amount of miscellaneous peaks is 0.06-0.2%, the aldehyde and reducing substances are 5-10 ppm, and the fatty acid and ester are 0.4-2.0 mL.
Preferably, in the first step, the total amount of miscellaneous peaks in the collected glycerin eluate is less than or equal to 0.01%, the aldehyde and reducing substances are less than or equal to 0.5ppm, and the fatty acid and ester are less than or equal to 0.1mL.
Preferably, in the first step, the solvent used in the high-speed counter-current chromatography is a solvent with a volume ratio of 1-10: 1 to 10:0 to 3 parts by weight of a solvent A, a solvent B and a solvent C; mixing the mixed solvents, uniformly shaking, standing for layering to obtain a two-phase mixed solution, separately collecting an upper phase solvent and a lower phase solvent, and respectively carrying out ultrasonic degassing on the upper phase solvent and the lower phase solvent; adopting a lower phase solvent as a mobile phase of the high-speed countercurrent chromatography, and an upper phase solvent as a stationary phase of the high-speed countercurrent chromatography; the solvent A is any one of n-hexane, n-heptane and petroleum ether; the solvent B is any one of acetonitrile, ethanol and isopropanol; and the solvent C is water or ethyl acetate.
Preferably, the specific process of performing high-speed counter-current chromatography separation on the glycerol raw material comprises the following steps: preheating a high-speed counter-current chromatograph, pumping the stationary phase into the high-speed counter-current chromatograph, starting a main machine of the high-speed counter-current chromatograph when liquid pumped out of a waste liquid bottle reaches 30-50 mL, adjusting the rotating speed, and pumping the mobile phase into the high-speed counter-current chromatograph; when the mobile phase and the fixed phase in the waste liquid bottle are obviously layered, opening a sample injection valve, injecting a glycerol raw material, and collecting the elution components in different time periods.
Preferably, the flow rate of the pumped stationary phase is 5-80 mL/min, the flow rate of the pumped mobile phase is 5-80 mL/min, and the rotating speed is adjusted to be 100-1000 rpm; the flow rate of the sample introduction glycerol raw material is 5-80 mL/min.
Preferably, in the second step, the pressure of the low-temperature reduced pressure distillation is 100-3000 Pa, and the temperature is 130-190 ℃.
Preferably, the total amount of the elution fractions collected in different periods of time in the step one and the total amount of the impurity peaks of the high-purity glycerol obtained in the step three are detected by gas chromatography, and the aldehyde, the reducing substances, the fatty acid and the esters are detected by adopting the '2020 version of Chinese pharmacopoeia'.
The invention utilizes the polarity difference (the polarity is from large to small: -COOH > -OH > -CHO > diglycerol) of aldehyde, alcohol, acid and diglycerol, adopts a high-speed countercurrent technology, and ensures that the separated substance has higher separation degree by reasonably selecting and matching a solvent system; by selectively increasing the chromatographic speed, the two-phase layering time is shortened, and the separation time efficiency is improved. The invention has the following advantages and beneficial effects:
(1) The technical scheme provides a deep purification method of high-purity glycerol, which ensures effective separation of glycerol, reducing substances such as glyceraldehyde and formaldehyde, fatty acid and diglycerol in a crude glycerol product, thereby obtaining the high-purity glycerol, and ensuring that the total amount of miscellaneous peaks in a final glycerol product is less than or equal to 0.01%, the total amount of aldehyde and reducing substances is less than or equal to 0.5ppm, and the total amount of fatty acid and ester is less than or equal to 0.1mL.
(2) Because the stationary phase and the fluidity of the high-speed countercurrent chromatography are both liquid and can be recycled, compared with the traditional chromatographic separation, the process has no solid carrier adsorption loss and high sample recovery rate; no consumption of stationary phase material, and low separation cost.
(3) Compared with the traditional process, the process has the advantages of convenient operation, short production period and high yield.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is the 1# GC detection spectrum of the glycerol feedstock of the present invention;
FIG. 2 is the 2# GC detection spectrum of the glycerol feed of the present invention;
FIG. 3 is a GC detection spectrum of the glycerol feedstock No. 1 after deep purification and solvent recovery in example 1;
FIG. 4 is a GC analysis of the glycerol feed 2# of example 2 after deep purification and solvent recovery.
FIG. 5 is a chemical structural formula of glycerol.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Firstly, commercially available glycerol on the market is selected, and the results of the raw detection of each batch are shown in table 1, wherein GC spectrums are shown in figures 1 and 2.
TABLE 1
From the results of the detection and analysis of the glycerin raw materials 1# and 2#, it can be seen that the raw materials glycerin raw material 1# and 2# contain a small amount of aldehydes, reducing substances, fatty acids, esters, polymerized glycerin, and the like. The distribution coefficients of glycerol, glyceraldehyde, formaldehyde, fatty acid and polyglycerol in a solvent system are different, the glycerol, the glyceraldehyde, the formaldehyde, the fatty acid and the polyglycerol are eluted in a certain sequence through countercurrent chromatography, and the elution sequence is as follows: C6-C18 fatty acid, formaldehyde, glyceraldehyde, glycerol and diglycerol.
Example 1:
in this embodiment, the solvent used in the high-speed countercurrent chromatography is a mixed solution of n-heptane-isopropanol-water, and the volume ratio of n-heptane: isopropyl alcohol: water =6:6:2, uniformly oscillating, standing and layering to obtain a two-phase mixed solution, separately collecting an upper phase solvent and a lower phase solvent, and respectively placing the two-phase mixed solution in an ultrasonic oscillator for ultrasonic degassing treatment; the lower phase solvent is a mobile phase, and the upper phase solvent is a stationary phase; preheating a high-speed counter-current chromatograph for 30min, pumping the stationary phase at a flow rate of 60mL/min, starting a main machine when the liquid pumped out of a waste liquid bottle reaches 30-50) mL, adjusting the rotating speed to 400rpm, and pumping the mobile phase at a flow rate of 10 mL/min; when the mobile phase and the fixed phase in the waste liquid bottle are obviously layered, opening a sample introduction valve, introducing 80g of sample raw material liquid (glycerol raw material #) at 10mL/min, collecting eluted fractions in a period of 20-50 min, and recovering the solvent under reduced pressure (800pa, 160 ℃); through gas chromatography detection, the purity of the glycerol in the collected fraction is 99.99%, the aldehyde and reducing substances are less than 0.5ppm, and the fatty acid and ester are only 0.1mL; the total amount of the recovered glycerol is 76.3g, and the recovery rate of the glycerol reaches 95.4 percent; the total separation and purification time in this example was 70min.
Fig. 3 is a GC detection spectrum of the glycerin eluate separated from the glycerin raw material 1# in the present example after solvent recovery, and the key index detection parameters of the purified glycerin are shown in table 2:
TABLE 2
The data of the atlas survey of glycerol feed # 1 before purification are shown in table 3:
TABLE 3
The spectrum detection data of the high-purity glycerol product 1# obtained after the raw material 1# is purified and the solvent is recovered is shown in table 4:
TABLE 4
Example 2:
in the embodiment, the solvent adopted by the high-speed countercurrent chromatography is a mixed solution of petroleum ether-ethanol-ethyl acetate, and the volume ratio of the mixed solution is petroleum ether: ethanol: ethyl acetate =6:3:1, uniformly oscillating, standing and layering to obtain a two-phase mixed solution, separately collecting an upper phase solvent and a lower phase solvent, and respectively placing the two-phase mixed solution in an ultrasonic oscillator for ultrasonic degassing treatment. The lower phase of the solvent is used as a mobile phase, and the upper phase of the solvent is used as a stationary phase. Preheating a high-speed counter-current chromatograph for 30min, and pumping the stationary phase at a flow rate of 50 mL/min; when the liquid pumped out of the waste liquid bottle reaches 30-50 mL, starting the main machine, adjusting the rotating speed to 500rpm, and pumping the mobile phase at the flow rate of 15 mL/min; when the mobile phase and the stationary phase in the waste liquid bottle are obviously layered, a sample injection valve is opened, 80g of sample raw material liquid (glycerol raw material No. 2) is injected at 15mL/min, elution fractions in a period of 40-60 min are collected, and the solvent is recovered under reduced pressure (500 pa, 150 ℃). The purity of glycerin in the collected fraction was 99.99%, the aldehyde and reducing substance were less than 0.5ppm, and the amount of fatty acid and ester was only 0.1ml, as determined by gas chromatography. The total amount of the recovered glycerol was 78.3g, and the recovery rate of glycerol reached 97.9%. The total separation and purification time in this example was 80min.
Fig. 4 is a GC detection spectrum of the glycerol eluate separated from the glycerol raw material 2# in the present example after solvent recovery, and the key index detection parameters of the purified glycerol are shown in table 5:
TABLE 5
The data of the 2# atlas of the glycerol feed before purification are shown in table 6:
TABLE 6
The map detection data of the high-purity glycerin product obtained after the glycerin raw material No. 2 is purified and the solvent is recovered are shown in Table 7:
TABLE 7
While embodiments of the invention have been described above, it is not intended to be limited to the details shown, described and illustrated herein, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed, and to such extent that such modifications are readily available to those skilled in the art, and it is not intended to be limited to the details shown and described herein without departing from the general concept as defined by the appended claims and their equivalents.
Claims (2)
1. The deep purification method of the glycerol is characterized by comprising the following steps:
step one, performing high-speed counter-current chromatographic separation on a glycerol raw material, collecting elution fractions in different time periods, and collecting the glycerol elution fractions;
step two, recovering the solvent from the collected glycerin eluate by low-temperature reduced pressure distillation to obtain glycerin;
in the first step, the quality of the glycerol raw material meets the following requirements: the total amount of miscellaneous peaks is 0.06 to 0.2 percent, the aldehyde and reducing substances are 5ppm to 10ppm, and the fatty acid and ester are 0.4 to 2.0mL;
in the first step, the total amount of the miscellaneous peaks of the collected glycerin elution part is less than or equal to 0.01 percent, the aldehyde and reducing substances are less than or equal to 0.5ppm, and the fatty acid and ester are less than or equal to 0.1mL;
in the first step, the solvent adopted by the high-speed countercurrent chromatography is a solvent with a volume ratio of 1 to 10:1 to 10:0 to 3 of a mixed solvent of a solvent A, a solvent B and a solvent C; mixing the mixed solvents, uniformly shaking, standing for layering to obtain a two-phase mixed solution, separately collecting an upper phase solvent and a lower phase solvent, and respectively carrying out ultrasonic degassing on the upper phase solvent and the lower phase solvent; adopting a lower phase solvent as a mobile phase of the high-speed countercurrent chromatography, and an upper phase solvent as a stationary phase of the high-speed countercurrent chromatography; the solvent A is any one of n-hexane, n-heptane and petroleum ether; the solvent B is any one of acetonitrile, ethanol and isopropanol; the solvent C is water or ethyl acetate;
the specific process of performing high-speed countercurrent chromatographic separation on the glycerol raw material comprises the following steps: preheating a high-speed counter-current chromatograph, pumping the stationary phase into the high-speed counter-current chromatograph, starting a high-speed counter-current chromatograph host when liquid pumped out of a waste liquid bottle reaches 30-50 mL, adjusting the rotating speed, and pumping the mobile phase into the high-speed counter-current chromatograph host; when the mobile phase and the stationary phase in the waste liquid bottle are obviously layered, opening a sample injection valve, injecting a feed liquid prepared from a glycerol raw material, and collecting elution fractions at different time intervals;
the flow rate of the pumped stationary phase is 5 to 80mL/min, the flow rate of the pumped mobile phase is 5 to 80mL/min, and the rotating speed is adjusted to be 100 to 1000rpm; the flow rate of the sample introduction glycerol raw material is 5 to 80mL/min.
2. The method for the deep purification of glycerol according to claim 1, wherein in the second step, the pressure of the low-temperature reduced pressure distillation is 100 to 3000Pa, and the temperature is 130 to 190 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759526A (en) * | 2010-01-13 | 2010-06-30 | 肖志红 | Refining production method of glycerin |
| WO2017119007A1 (en) * | 2016-01-07 | 2017-07-13 | Institute Of Chemical Technology | Process for purification and refining of glycerol |
| WO2019138338A1 (en) * | 2018-01-09 | 2019-07-18 | Universidade Do Porto | Process of separation and purification of glycerol derivatives |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759526A (en) * | 2010-01-13 | 2010-06-30 | 肖志红 | Refining production method of glycerin |
| WO2017119007A1 (en) * | 2016-01-07 | 2017-07-13 | Institute Of Chemical Technology | Process for purification and refining of glycerol |
| WO2019138338A1 (en) * | 2018-01-09 | 2019-07-18 | Universidade Do Porto | Process of separation and purification of glycerol derivatives |
Non-Patent Citations (2)
| Title |
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| "高速逆流色谱分离纯化脂肪酸的研究进展";荣辉等;《食品工业科技》;2017;第38卷(第13期);319-323 * |
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