CN114262281A - Method for separating pyrazoline isomer mixture by using polar solvent-resistant nanofiltration membrane - Google Patents
Method for separating pyrazoline isomer mixture by using polar solvent-resistant nanofiltration membrane Download PDFInfo
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- CN114262281A CN114262281A CN202111563909.4A CN202111563909A CN114262281A CN 114262281 A CN114262281 A CN 114262281A CN 202111563909 A CN202111563909 A CN 202111563909A CN 114262281 A CN114262281 A CN 114262281A
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Abstract
The invention discloses a method for separating pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane, which comprises the following steps: (1) sealing and fixing the polar solvent-resistant nanofiltration membrane in a membrane component, and maintaining the constant temperature by using a heat conductor; (2) pressurizing the raw material by a pump, passing through a membrane module in a cross flow mode, and circulating the concentrated solution to a raw material tank to realize enrichment of pyrazoline; and (4) offline gas phase detection is carried out on the component concentration in the raw material tank every 0.5h, and when the concentration is not changed any more, the separation reaches the end point. The invention provides a high-efficiency polar solvent-resistant nanofiltration membrane separation method by combining the dynamic diameter and polarity difference of isomers aiming at the problems that pyrazoline isomers have similar boiling points and unstable structure, and the separation is difficult to realize by traditional industrial rectification. Meanwhile, the method has simple process and low energy consumption, and has important significance for separating isomers in the pharmaceutical chemical industry.
Description
Technical Field
The invention belongs to the field of chemical separation, and particularly relates to a method for separating pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane.
Technical Field
The hydrocarbon fuel is the most widely used and most energy consuming energy source in the transportation field worldwide, and occupies the dominance in the aspects of aerospace, land transportation, marine transportation and military industry. It is generally accepted that the number of carbon atoms in the compound is greater than 7 (C)7) Is generally referred to as a high carbon number hydrocarbon fuel. Liquid hydrocarbon fuels are a wide variety of sources and are convenient to transport, and are still the main energy source without replacement in the long future. The high-tension cyclic hydrocarbon fuel is a novel hydrocarbon high-energy fuel, and the molecular structure of the high-tension cyclic hydrocarbon fuel takes a tension ring containing cyclopropane as a main structure body, so that the high-tension cyclic hydrocarbon fuel has high tension energy and very excellent combustion performance. Pyrazoline is an important intermediate product for preparing high-energy tension ring fuel, and has strong heat sensitivity and instability. Pyrazolines are currently obtained mainly from the acid-catalyzed isomerization of ketazine. However, ketazine and pyrazoline are isomers of each other, have similar boiling points, and the conventional distillation method has huge energy consumption and difficult effect of achieving the expected separation effect, and more importantly, the yield of the high-energy tension ring prepared by pyrazoline denitrification is greatly reduced. The separation of high-purity pyrazoline and the search for a new separation method are problems to be solved urgently.
The membrane separation technology does not involve phase change in the process of separating substances, has low energy requirement, the cost of the membrane separation technology is about one third of that of the traditional rectification separation, in addition, the membrane separation condition is mild, the membrane separation technology has selective permeability, and the membrane separation technology is suitable for a separation system with complicated heat-sensitive substances, and the two factors enable the membrane separation technology to be applied more and more widely in the biochemical field.
Through simulation calculation, although pyrazoline and ketazine are isomers, the molecular kinetic diameter and the molecular polarity are significantly different, so that the membrane separation technology is considered to be an effective and feasible separation mode for the ketazine and pyrazoline mixed liquor by combining the membrane separation mechanism and the properties. In addition, pyrazoline isomer mixed liquids have a corrosive effect on membranes, so solvent-resistant polar nanofiltration membranes are required.
Disclosure of Invention
Aiming at the practical dilemma of separating and purifying pyrazoline isomer mixtures, the method is combined with simulation data to find that the dynamic diameter and the molecular polarity of pyrazoline and isomers have obvious difference, so that the invention provides a method for separating pyrazoline isomer mixtures by using a polar solvent-resistant nanofiltration membrane, and a feasible path is provided for separating isomers in the field of pharmaceutical and chemical engineering.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for separating pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane comprises the following steps:
(1) sealing and fixing the polar solvent-resistant nanofiltration membrane in a membrane component, and maintaining the constant temperature by using a heat conductor;
(2) the raw material is pressurized by a pump, the raw material passes through a membrane module in a cross flow mode, a ketazine solution containing a small amount of pyrazoline permeates and is detected to flow out from a membrane side port, a concentrated solution containing pyrazoline and ketazine flows out from an outlet end of the membrane module and is circulated to a raw material tank, so that pyrazoline enrichment is realized, components on the membrane permeation side are collected, the component concentration in the raw material tank is detected in an off-line gas phase mode every 0.5h, and when the concentration is not changed any more, the separation reaches the end point.
Further, the polar solvent-resistant nanofiltration membrane in the step (1) is any one of a modified polyimide solvent-resistant membrane or a modified polyacrylonitrile solvent-resistant membrane, and the molecular weight cut-off is 50-150 Da.
Further, the polar solvent-resistant nanofiltration membrane in the step (1) is an asymmetric nano composite membrane, and the effective thickness of the membrane layer is 0.5-80 μm.
Further, the temperature range of the heat conductor in the step (1) is controlled to be 10-60 ℃.
Further, the raw material in the step (2) is a pyrazoline isomer mixture, specifically any one of acetononoazine/3, 3, 5-trimethyl-2-pyrazoline, 2-butanone-ketazine/3, 5-diethyl-5-methyl-2-pyrazoline, 2-pentanone-ketazine/3, 5-dipropyl-5-methyl-2-pyrazoline, methyl isopropyl ketoazine/3, 5-diisopropyl-5-methyl-2-pyrazoline, 2-hexanone-ketazine/3, 5-dibutyl-5-methyl-2-pyrazoline, cyclopropyl ketoazine/5-methyl-3, 5-dicyclopropylpyrazoline mixture, wherein the mass concentration ratio of pyrazoline to ketazine is (0.001-0.15): 1.
Further, the temperature of the pyrazoline isomer mixture in the step (2) is 25-50 ℃, and 25 ℃ is preferred; the operating pressure of the membrane is 20-40bar, preferably 40 bar; the operation mode is cross-flow filtration.
Further, the off-line gas detection in the step (2) adopts a chromatographic column: HP-5 non-polar column; column temperature procedure: keeping at 50 deg.C for 1min, heating to 120 deg.C at 10 deg.C/min for 1min, heating to 280 deg.C at 15 deg.C/min for 9 min; sample inlet temperature: 300 ℃; the split ratio is as follows: 100: 1; and (3) control mode: flow rate of the column.
The invention has the beneficial effects that: the method is based on the obvious difference of the dynamic diameter and the molecular polarity between the pyrazoline and the isomer, realizes the high-efficiency separation of the pyrazoline isomer mixture by utilizing the steric effect and the electrostatic effect (hydrogen bonds are formed between the pyrazoline and a membrane surface material) of the solvent-resistant nanofiltration membrane, effectively solves the problems of high energy consumption of the traditional rectification separation mode and the thermal sensitivity of the pyrazoline in the rectification process. Meanwhile, a feasible path is provided for the separation of isomers in the pharmaceutical chemical field.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a pyrazoline isomeric mixed liquid membrane separation device;
FIG. 2 is a solvent resistance test (one week soak) for the solvent resistant modified polyacrylonitrile membrane of example 1;
FIG. 3 is the solvent resistance test (one week soak) for the modified polyimide solvent resistant film of example 2;
FIG. 4 is the solvent resistance test (one week soak) for the solvent resistant modified polyacrylonitrile membrane of example 3.
Detailed Description
The following further describes the embodiments of the present invention with reference to the drawings and examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Separation coefficient calculation formula:
the molecular kinetic diameters of ketazine and pyrazoline are shown in table 1.
TABLE 1 molecular kinetic diameter Table of ketazine and pyrazoline
Example 1
By using the separation device shown in fig. 1, the method for separating a pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane of the present embodiment includes the following steps:
(1) the membrane apparatus pressure was set at 20bar and the temperature at 25 ℃. The raw material liquid is a mixed liquid of acetononoazine and 3,3, 5-trimethyl-2-pyrazoline, and the mass concentration ratio of the pyrazoline to the ketazine is 0.15: 1.
(2) Adding a raw material liquid into a charging tank, pumping the raw material liquid into the charging tank by a pump under pressure, entering the charging tank from an inlet section of a membrane component, separating the raw material liquid by a modified polyacrylonitrile membrane (GC-PANS solvent-resistant membrane, national institute of science and technology, Ltd.), circulating a concentrated solution containing pyrazoline and ketazine to the charging tank after flowing out of an outlet end of the membrane component, and flowing out of a ketazine solution containing a small amount of pyrazoline from a side port of the membrane. And (4) offline gas phase detection is carried out on the component concentration in the raw material tank every 0.5h, and when the concentration is not changed any more, the separation reaches the end point.
And respectively carrying out GC detection on the raw material solution and the solution at the permeation side, wherein the off-line gas detection adopts a chromatographic column: HP-5 non-polar column; column temperature procedure: keeping at 50 deg.C for 1min, heating to 120 deg.C at 10 deg.C/min for 1min, heating to 280 deg.C at 15 deg.C/min for 9 min; sample inlet temperature: 300 ℃; the split ratio is as follows: 100: 1; and (3) control mode: flow rate of the column. The separation coefficient was calculated as shown in the following table.
Example 2
By using the separation device shown in fig. 1, the method for separating a pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane of the present embodiment includes the following steps:
(1) the membrane apparatus pressure was set at 30bar and the temperature at 25 ℃. The raw material liquid is a mixed liquid of 2-butanone azine and 3, 5-diethyl-5-methyl-2-pyrazoline, and the mass concentration ratio of the pyrazoline to the ketazine is 0.05: 1.
(2) Adding a raw material liquid into a charging tank, pumping the raw material liquid into the charging tank by a pump under pressure, entering the charging tank from an inlet section of a membrane component, separating the raw material liquid by a modified polyacrylonitrile membrane (GC-PANS solvent-resistant membrane, national institute of science and technology, Ltd.), circulating a concentrated solution containing pyrazoline and ketazine to the charging tank after flowing out of an outlet end of the membrane component, and flowing out of a ketazine solution containing a small amount of pyrazoline from a side port of the membrane; and (4) offline gas phase detection is carried out on the component concentration in the raw material tank every 0.5h, and when the concentration is not changed any more, the separation reaches the end point.
And respectively carrying out GC detection on the raw material solution and the solution at the permeation side, wherein the off-line gas detection adopts a chromatographic column: HP-5 non-polar column; column temperature procedure: keeping at 50 deg.C for 1min, heating to 120 deg.C at 10 deg.C/min for 1min, heating to 280 deg.C at 15 deg.C/min for 9 min; sample inlet temperature: 300 ℃; the split ratio is as follows: 100: 1; and (3) control mode: flow rate of the column. The separation coefficient was calculated as shown in the following table.
Example 3
By using the separation device shown in fig. 1, the method for separating a pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane of the present embodiment includes the following steps:
(1) the membrane apparatus pressure was set at 40bar and the temperature at 25 ℃. The raw material liquid is a mixed liquid of cyclopropyl ketoazine and 5-methyl-3, 5-dicyclopropyl pyrazoline, and the mass concentration ratio of the pyrazoline to the ketoazine is 0.03: 1.
(2) Adding a raw material liquid into a charging tank, pumping the raw material liquid into the charging tank by a pump under pressure, entering the charging tank from an inlet section of a membrane assembly, separating by a modified polyimide membrane (GC-PANS solvent-resistant membrane, national institute of science and technology, Ltd.), circulating a concentrated solution containing pyrazoline and ketazine to the charging tank after flowing out from an outlet end of the membrane assembly, flowing out a ketazine solution containing a small amount of pyrazoline from a side port of the membrane, performing off-line gas phase detection on the component concentration in the charging tank every 0.5h, and when the concentration is not changed any more, enabling the separation to reach the end point.
And respectively carrying out GC detection on the raw material solution and the solution at the permeation side, wherein the off-line gas detection adopts a chromatographic column: HP-5 non-polar column; column temperature procedure: keeping at 50 deg.C for 1min, heating to 120 deg.C at 10 deg.C/min for 1min, heating to 280 deg.C at 15 deg.C/min for 9 min; sample inlet temperature: 300 ℃; the split ratio is as follows: 100: 1; and (3) control mode: flow rate of the column. The separation coefficient was calculated as shown in the following table.
Analysis of all the data above shows that: the separation of ketazine and pyrazoline can be realized by using the modified polyacrylonitrile membrane, and the separation effect is obvious.
Fig. 2-4 are test pictures of a membrane immersed in a pyrazolone azine mixed solution for one week, demonstrating that the membrane can be used normally in this environment.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. 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. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A method for separating pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane is characterized by comprising the following steps:
(1) sealing and fixing the polar solvent-resistant nanofiltration membrane in a membrane component, and maintaining the constant temperature by using a heat conductor;
(2) the pyrazoline isomer mixture is pressurized by a pump and passes through a membrane component in a cross flow mode, a ketazine solution containing a small amount of pyrazoline permeates and is detected to flow out from a membrane side port, a concentrated solution containing pyrazoline and ketazine flows out from an outlet end of the membrane component and is circulated to a raw material tank, so that enrichment of pyrazoline is realized, the component concentration in the raw material tank is detected in an off-line gas phase mode every 0.5h, and when the concentration is not changed any more, the separation reaches the end point.
2. The method for separating a pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane according to claim 1, wherein the method comprises the following steps: the polar solvent-resistant nanofiltration membrane in the step (1) is any one of a modified polyimide solvent-resistant membrane or a modified polyacrylonitrile solvent-resistant membrane, and the molecular weight cut-off is 50-150 Da.
3. The method for separating a pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane according to claim 1, wherein the method comprises the following steps: in the step (1), the polar solvent-resistant nanofiltration membrane is an asymmetric nano composite membrane, and the effective thickness of the membrane layer is 0.5-80 μm.
4. The method for separating a pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane according to claim 1, wherein the method comprises the following steps: the temperature range of the heat conductor in the step (1) is controlled to be 10-60 ℃.
5. The method for separating a pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane according to claim 1, wherein the method comprises the following steps: and (3) in the step (2), the pyrazoline isomer mixture is a pyrazoline and ketazine mixture.
6. The method for separating a pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane according to claim 5, wherein the method comprises the following steps: the mass concentration ratio of the pyrazoline to the ketazine is (0.001-0.15): 1.
7. The use of polar solvent-resistant nanofiltration membranes as claimed in claim 5 or 6 for the separation of pyrazoline isomer mixtures, wherein: the pyrazoline and ketazine mixture is any one of ketazine/3, 3, 5-trimethyl-2-pyrazoline, 2-butanone ketazine/3, 5-diethyl-5-methyl-2-pyrazoline, 2-pentanoketazine/3, 5-dipropyl-5-methyl-2-pyrazoline, methyl isopropyl ketazine/3, 5-diisopropyl-5-methyl-2-pyrazoline, 2-hexanoketazine/3, 5-dibutyl-5-methyl-2-pyrazoline and cyclopropyl ketazine/5-methyl-3, 5-dicyclopropylpyrazoline.
8. The method for separating a pyrazoline isomer mixture by using a polar solvent-resistant nanofiltration membrane according to claim 2, wherein the method comprises the following steps: in the step (2), the temperature of the pyrazoline isomer mixture is 25-50 ℃, the membrane operation pressure is 20-40bar, and the operation mode is cross-flow filtration.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603313A (en) * | 2004-08-25 | 2005-04-06 | 长沙卷烟厂 | Method for separation purification of polyhydroxy-alkyl-pyrazine from suger amine reaction liquid |
| CN1952015A (en) * | 2005-10-19 | 2007-04-25 | 上海染料研究所有限公司 | Process for preparing lemon chrome |
| US20150119578A1 (en) * | 2013-10-28 | 2015-04-30 | Wincom, Inc. | Filtration process for purifying liquid azole heteroaromatic compound-containing mixtures |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603313A (en) * | 2004-08-25 | 2005-04-06 | 长沙卷烟厂 | Method for separation purification of polyhydroxy-alkyl-pyrazine from suger amine reaction liquid |
| CN1952015A (en) * | 2005-10-19 | 2007-04-25 | 上海染料研究所有限公司 | Process for preparing lemon chrome |
| US20150119578A1 (en) * | 2013-10-28 | 2015-04-30 | Wincom, Inc. | Filtration process for purifying liquid azole heteroaromatic compound-containing mixtures |
Non-Patent Citations (1)
| Title |
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| 常金宇等: "吡唑啉类化合物的典型合成及新应用", 《辽宁化工》 * |
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