CN110648898B - Mass spectrum device and method for detecting multi-component gas in freeze-drying process - Google Patents
Mass spectrum device and method for detecting multi-component gas in freeze-drying process Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01J49/0027—Methods for using particle spectrometers
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- G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
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- H—ELECTRICITY
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- H01J49/00—Particle spectrometers or separator tubes
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Abstract
The invention provides a mass spectrum device and a method for detecting multi-component gas in a freeze-drying process, wherein the mass spectrum device comprises the following steps: a liner electrode; one end of the sample inlet pipe faces the inner container electrode and introduces gas to be detected into the inner container electrode; the first ionization source faces the inner container electrode and ionizes water molecules, nitrogen molecules or oxygen molecules in the gas to be detected to obtain corresponding positive ions; the second ionization source faces the inner container electrode and ionizes silicon oil neutral molecules in the gas to be detected to obtain corresponding positive ions; a transmission focusing electrode is arranged between the mass analyzer and the inner container electrode; wherein positive ions are drawn by the electric field force generated by the liner electrode and introduced into the mass analyzer through the transmission focusing electrode. The invention can detect and detect the mass spectrum of multi-component gas in the freeze-drying process in real time, and the two ionization modes improve the detection sensitivity and widen the range of analyzing samples.
Description
Technical Field
The invention relates to the field of mass spectrometry, in particular to a mass spectrometry device and a mass spectrometry method for detecting multi-component gas in a freeze-drying process.
Background
The vacuum freeze-drying technique (hereinafter referred to as freeze-drying technique) is a technique of freezing a water-containing material at a low temperature and then sublimating water in the water-containing material directly in a vacuum state without passing through a liquid state. The physical, chemical and form of the material dried by the technology are basically unchanged, the loss of effective components is small, the rehydration performance is good, and the sealing and storage period is long. The freeze-drying technology has wide application, and especially plays an important role in the field of biological pharmacy.
With the continuous improvement of living standard, the environmental protection consciousness and health consciousness of the social public are further enhanced, people put forward higher requirements on the quality of consumer products, and the requirements on various medicines, health care products and freeze-dried foods are increased. The increasing demand for preparing various medicines, biological health products, freeze-dried foods, solid micro-powder and the like can strongly promote the further development of the freeze-drying technology, so that the application scale of the freeze-drying technology is continuously enlarged and the application field is continuously expanded.
The apparatuses for implementing the lyophilization technique are called lyophilizers, and generally speaking, the lyophilizers are composed of a lyophilization chamber, a vacuum system, a refrigeration system and a control system. The freeze-drying box is the main part of freeze dryer, and the freezing and drying of material are accomplished in the freeze-drying box, if be mixed with impurity in the freeze-drying box, the quality of freeze-dried food or medicine will be influenced, therefore the clean degree of freeze-drying box directly influences the quality of material after the freeze-drying. Further, if the food or the pharmaceutical product is not found due to the inclusion of impurities during the lyophilization process, once the food or the pharmaceutical product is taken/eaten as a qualified product and enters the human body, the human health is likely to be affected unpredictably, and therefore, the detection of the impurities during the lyophilization process becomes a focus of attention. The leaked silicone oil in the freeze-drying box is a main source of impurities, so that the real-time online detection of the leaked silicone oil in the freeze-drying machine has important significance for ensuring the quality of freeze-dried products.
Spectroscopic, chromatographic, sensor and mass spectrometric methods can all be used for the detection of silicone oil leaks. The spectrum and the sensor are not high in specificity, only specific target substances can be detected, the detection limit is insufficient, and quantitative analysis cannot be carried out. The detection method of the chromatogram can carry out quantitative analysis on the substances to be detected, but the detection period is too long. The silicon oil in the freeze dryer is mainly used for heat conduction, and the time, content and position of the silicon oil leakage are random, so that the spectrum, sensor and chromatographic methods cannot meet the requirement of on-site real-time online detection of the silicon oil leakage in the freeze dryer.
The mass spectrometry is one of important methods in the detection field, can qualitatively and quantitatively analyze complex compounds, can realize in-situ second-level response detection, and becomes a novel method for detecting silicone oil leakage. Likewise, the detection of water vapor during lyophilization is of great importance:
1. and judging whether the freeze-drying process is successful. The production process of the freeze-dried material mainly comprises the stages of pretreatment, freezing, sublimation drying, desorption drying, packaging, storage, rehydration and the like, wherein the three stages of freezing, sublimation drying and desorption drying are the most critical. As shown in fig. 1, during freezing, the temperature and moisture content of the freeze-dried material are continuously reduced with time; in the sublimation drying process, the freeze-dried material is heated at a certain low temperature and vacuum degree, and about 80% of water in the material is directly sublimated from a solid state and removed; in the process of desorption drying, the temperature is raised again for heating, and the water content of the material is reduced to below 5 percent. During the sublimation drying process, if the time is insufficient, the solid water in the material will be melted before being extracted, and at the moment, the water vapor content in the freeze-drying box will be greatly increased, which indicates that the material is failed to be freeze-dried. Therefore, it is important to detect the water vapor content in the freeze-drying box.
2. And (4) quantitatively analyzing the leakage amount of the silicone oil. The traditional foreign mass spectrometer for detecting the leakage of the silicone oil in the freeze dryer judges the leakage amount of the silicone oil by taking the content of water vapor in a freeze drying box, namely the partial pressure of the water vapor as a reference. Therefore, the content of the water vapor in the freeze-drying box can be used as a scale to quantitatively analyze the leakage amount of the silicon oil.
3. The sensitivity of quadrupole mass spectrometry was characterized. The traditional gas analyzer represents the quality of the detection performance of the gas analyzer by using the gas pressure sensitivity, and represents the sensitivity of a mass spectrometer by using the pressure of water vapor, thereby having important significance for the research and development of the gas analyzer and the improvement of the performance.
Therefore, multi-component gases such as silicone oil leakage, water vapor and the like in the freeze dryer are detected on line in real time, the type and the content of the silicone oil leakage are qualitatively and quantitatively analyzed, tracing and tracing are carried out, the reason of the silicone oil leakage is analyzed, and the quality of freeze-dried products is ensured; and moreover, success or failure in the freeze-drying process can be calibrated, and the sensitivity of the instrument can be characterized.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a mass spectrum device and a method for detecting multi-component gas in a freeze-drying process.
According to the invention, the mass spectrum device for detecting the multi-component gas in the freeze-drying process comprises the following components:
a liner electrode;
one end of the sample inlet pipe faces the inner container electrode and introduces gas to be detected into the inner container electrode;
the first ionization source faces the inner container electrode and ionizes water molecules, nitrogen molecules or oxygen molecules in the gas to be detected to obtain corresponding positive ions;
the second ionization source faces the inner container electrode and ionizes silicon oil neutral molecules in the gas to be detected to obtain corresponding positive ions;
a transmission focusing electrode is arranged between the mass analyzer and the inner container electrode;
wherein positive ions are drawn by the electric field force generated by the liner electrode and introduced into the mass analyzer through the transmission focusing electrode.
Preferably, the sampling tube and the second ionization source are respectively perpendicular to the inner container electrode.
Preferably, the sampling tube is arranged on one side of the inner container electrode, and the second ionization source is arranged on the other side of the inner container electrode.
Preferably, the mass analyser comprises a quadrupole mass analyser.
Preferably, the first ionization source comprises an ionization gauge and the second ionization source comprises a single photon ionization source.
Preferably, the method further comprises the following steps:
the ionization chamber, the inner container electrode, the transmission focusing electrode and the mass analyzer are arranged in the ionization chamber;
the first ionization source and the second ionization source are fixed on the side wall of the ionization chamber;
the sample inlet pipe is connected with the ionization chamber and the freeze dryer.
Preferably, the sampling tube comprises:
the connecting pipeline is used for connecting the ionization chamber with the freeze dryer;
and one end of the sample injection capillary is connected with the ionization chamber, and the other end of the sample injection capillary is positioned in the connecting pipeline.
According to the mass spectrum method for detecting the multi-component gas in the freeze-drying process, which is provided by the invention, the mass spectrum device for detecting the multi-component gas in the freeze-drying process is adopted, and the mass spectrum device comprises the following steps:
introducing gas to be detected in the freeze-drying box into the liner electrode through the sample inlet pipe;
ionizing water molecules, nitrogen molecules or oxygen molecules in the gas to be detected through a first ionization source, and ionizing silicon oil neutral molecules in the gas to be detected through a second ionization source to obtain corresponding positive ions;
the resulting positive ions are introduced into the mass analyser via the transmitting focusing electrode.
Preferably, the mass analyzer leads the obtained positive ions out to a detector according to the mass-to-charge ratio for mass spectrometry to obtain a mass spectrogram.
Preferably, each component and the corresponding content in the gas to be detected are qualitatively/quantitatively analyzed according to the obtained mass spectrogram.
Compared with the prior art, the invention has the following beneficial effects:
1. makes up the defects of the existing products and technologies, and has important significance for the sustainable development of the technology.
2. The ionization gauge provided by the invention can ionize water and nitrogen in a sample, can be used as a vacuum gauge to provide the vacuum degree of a mass spectrometer, does not need to additionally install the vacuum gauge, saves the cost while increasing the functions, and can effectively improve the profit margin of products.
3. Meanwhile, an ionization gauge and a single-photon ionization source are used as double ionization sources, so that the detection sensitivity is improved, the range of analyzing samples is widened, and the quadrupole mass analyzer is taken as a core, so that the method is an optimal scheme for combining two advantages of different ionization characteristics and high sensitivity of quadrupole mass spectrometry.
4. The method and the device for detecting the leakage of the silicone oil can realize real-time online detection of the leakage of the silicone oil and can also independently provide detection of water, nitrogen and oxygen. The device is not only limited in the field of silicone oil detection, but also can detect the constant quantities of water, nitrogen and oxygen in any space and time, so that the application range of the product is expanded, a new application direction is developed, and the device has pioneering significance for product development.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic diagram showing changes in material temperature and water content during lyophilization;
FIG. 2 is a schematic structural view of the present invention;
FIG. 3 is a water vapor mass spectrum of an embodiment of the present invention;
FIG. 4 is a mass spectrum of silicone oil in an embodiment of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
As shown in fig. 2, the mass spectrometer for detecting multi-component gas in the freeze-drying process provided by the invention comprises:
a liner electrode 23;
a sample inlet tube 24, one end of which faces the inner container electrode 23 and introduces the gas to be measured into the inner container electrode 23;
the first ionization source 21 faces the inner container electrode 23 and ionizes water molecules, nitrogen molecules or oxygen molecules in the gas to be detected to obtain corresponding positive ions;
the second ionization source 22 faces the inner container electrode 23 and ionizes silicon oil neutral molecules in the gas to be detected to obtain corresponding positive ions;
a mass analyzer 26 having a transmission focusing electrode 25 provided between the inner container electrode 23 and the mass analyzer;
an ionization chamber, wherein the inner container electrode 23, the transmission focusing electrode 25 and the mass analyzer 26 are arranged in the ionization chamber;
wherein positive ions are drawn by the electric field force generated by the liner electrode 23 and introduced into the mass analyzer 26 through the transmission focusing electrode 25.
The first ionization source 21 and the second ionization source 22 are fixed on the side wall of the ionization chamber, and the sampling tube connection 24 connects the ionization chamber with the freeze dryer.
In this embodiment, the sample injection tube 24 and the second ionization source 22 are perpendicular to the inner container electrode 23, respectively, the sample injection tube 24 is disposed on one side of the inner container electrode 23, and the second ionization source 22 is disposed on the other side of the inner container electrode 23. The purpose of this arrangement is to make the gas to be measured entering from the sample inlet tube 24 be sufficiently ionized by the first ionization source 21 and the second ionization source 22, and then be extracted under the action of the electric field force of the inner container electrode 23.
In this embodiment, the mass analyzer is a quadrupole mass analyzer, the first ionization source is an ionization gauge, and the second ionization source comprises a single photon ionization source.
The sampling tube 24 includes:
the connecting pipeline is connected with the ionization chamber and the freeze dryer;
one end of the sample injection capillary is connected with the ionization chamber, and the other end of the sample injection capillary is positioned in the connecting pipeline.
According to the mass spectrum method for detecting the multi-component gas in the freeze-drying process, which is provided by the invention, the mass spectrum device for detecting the multi-component gas in the freeze-drying process is adopted, and the mass spectrum device comprises the following steps:
introducing gas to be detected in the freeze-drying box into the liner electrode through the sample inlet pipe;
ionizing water molecules, nitrogen molecules or oxygen molecules in the gas to be detected through a first ionization source, and ionizing silicon oil neutral molecules in the gas to be detected through a second ionization source to obtain corresponding positive ions;
the resulting positive ions are introduced into the mass analyser via the transmitting focusing electrode.
And the mass analyzer leads the obtained positive ions out to a detector according to the mass-to-charge ratio for mass spectrometry to obtain a mass spectrogram.
And qualitatively/quantitatively analyzing each component and corresponding content in the gas to be detected according to the obtained mass spectrogram.
The first embodiment is as follows: certain domestic brand freeze dryer (1 m)2) The mass spectrometer is used together with the mass spectrometer in the invention, and can simulate the detection of multi-component gases such as leaked silicone oil, water vapor and the like on line in real time.
First, the gas in the lyophilization chamber is introduced into the mass spectrometer apparatus of the present invention by capillary injection.
Secondly, the ionization gauge in the device ionizes water, nitrogen and oxygen molecules in the gas to be detected into water, nitrogen and oxygen positive ions; the single photon ionization source ionizes silicon oil neutral molecules in the detected gas into silicon oil positive ions.
And thirdly, introducing positive ions of water, nitrogen, oxygen and silicon oil into the quadrupole mass analyzer through the transmission focusing electrode.
Next, the mass spectrum peaks of water, nitrogen, oxygen and silicone oil were obtained by mass analysis using a quadrupole mass analyzer, as shown in fig. 3 and 4.
And finally, quantitatively analyzing the corresponding content of each substance according to mass spectrograms of the mass water, the nitrogen, the oxygen and the silicone oil.
In the description of the present application, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present application and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (9)
1. A mass spectrometer device for detecting multi-component gases in a lyophilization process, comprising:
a liner electrode;
one end of the sample inlet pipe faces the inner container electrode and introduces gas to be detected into the inner container electrode;
the first ionization source faces the inner container electrode and ionizes water molecules, nitrogen molecules or oxygen molecules in the gas to be detected to obtain corresponding positive ions;
the second ionization source faces the inner container electrode and ionizes silicon oil neutral molecules in the gas to be detected to obtain corresponding positive ions;
a transmission focusing electrode is arranged between the mass analyzer and the inner container electrode;
wherein positive ions are drawn by the electric field force generated by the liner electrode and are introduced into the mass analyzer through the transmission focusing electrode;
the first ionization source comprises an ionization gauge and the second ionization source comprises a single photon ionization source.
2. The mass spectrometer device for detecting multi-component gases in a freeze-drying process according to claim 1, wherein the sample introduction tube and the second ionization source are respectively perpendicular to the inner container electrode.
3. The mass spectrometer apparatus for detecting multi-component gases in a freeze-drying process according to claim 1, wherein the sample injection tube is disposed on one side of the inner container electrode, and the second ionization source is disposed on the other side of the inner container electrode.
4. The mass spectrometry apparatus for detecting multi-component gases during lyophilization according to claim 1, wherein the mass analyzer comprises a quadrupole mass analyzer.
5. The mass spectrometer apparatus for detecting multi-component gases during lyophilization according to claim 1, further comprising:
the ionization chamber, the inner container electrode, the transmission focusing electrode and the mass analyzer are arranged in the ionization chamber;
the first ionization source and the second ionization source are fixed on the side wall of the ionization chamber;
the sample inlet pipe is connected with the ionization chamber and the freeze dryer.
6. The mass spectrometer apparatus for detecting multi-component gases in a lyophilization process of claim 5, wherein the sample tube comprises:
the connecting pipeline is used for connecting the ionization chamber with the freeze dryer;
and one end of the sample injection capillary is connected with the ionization chamber, and the other end of the sample injection capillary is positioned in the connecting pipeline.
7. A mass spectrometry method for detecting multi-component gas in a freeze-drying process, which is characterized in that the mass spectrometry device for the multi-component gas in the freeze-drying process of any one of claims 1 to 6 is adopted, and the mass spectrometry method comprises the following steps:
introducing gas to be detected in the freeze-drying box into the liner electrode through the sample inlet pipe;
ionizing water molecules, nitrogen molecules or oxygen molecules in the gas to be detected through a first ionization source, and ionizing silicon oil neutral molecules in the gas to be detected through a second ionization source to obtain corresponding positive ions;
the resulting positive ions are introduced into the mass analyser via the transmitting focusing electrode.
8. The mass spectrometry method for detecting multi-component gases in a freeze-drying process according to claim 7, wherein the mass analyzer leads the obtained positive ions to a detector according to the mass-to-charge ratio for mass spectrometry to obtain a mass spectrogram.
9. The mass spectrometry method for detecting multi-component gases in a freeze-drying process according to claim 8, wherein each component and corresponding content in the gas to be detected are qualitatively/quantitatively analyzed according to the obtained mass spectrogram.
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