Device for reducing IV-valent germanium into II-valent germanium compound in liquid state
The apparatus for liquid reduction of tetravalent germanium to divalent germanium compounds utilizes an electric heating mantle and a circulating cooling reflux mechanism combined with an absorption bottle to achieve a high germanium utilization rate and lossless conversion and reduction reaction, solving the problem of low germanium utilization and ensuring the safety and environmental friendliness of the reaction.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-30
- Publication Date
- 2026-03-13
AI Technical Summary
In existing technologies, germanium utilization is low and losses are significant, resulting in a low yield of trichlorogermanane.
The apparatus for reducing tetravalent germanium to divalent germanium compounds using liquid includes an electric heating mantle, a three-necked flask, a circulating cooling reflux mechanism, and an absorption bottle. Controllable temperature and stirring are achieved through electric heating and electromagnetic stirring. Gaseous germanium tetrachloride and trichlorogermanane are absorbed during the circulating cooling reflux process, and unreacted gases are absorbed using the absorption liquid to prevent backflow, thus achieving a green and environmentally friendly conversion and reduction reaction.
It achieves high germanium utilization, avoids loss, the reaction system temperature and stirring speed are controllable, the conversion and reduction process is safe, gaseous substances are completely absorbed, and trichlorogermanane has no volatilization loss.
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Figure CN223991126U_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of rare dispersed metal germanium metallurgy technology, and in particular to an apparatus for liquid reduction of IV-valent germanium into II-valent germanium compounds. Background Technology
[0002] Due to the immense potential applications of organogermanium compounds in pharmaceuticals, health products, and food additives, research on them has been exceptionally active in recent decades. Since the synthesis of Ge-132 by Japanese scholars Kazuhiko Asai et al. in 1968, numerous animal and clinical trials have revealed it to be an organogermanium compound with extremely low toxicity and anticancer activity, sparking widespread research interest. In recent years, a series of organogermanium compounds have been synthesized based on Ge-132, demonstrating significant application value in anticancer, anti-inflammatory, and health-promoting applications.
[0003] Trichlorogermanane (GeHCl3) is an important intermediate in the synthesis of Ge-132 and its derivatives. The principle of its synthesis method has been widely recognized. However, due to the lack of high-efficiency synthesis equipment, the utilization rate of germanium is low and the loss is large, resulting in a low yield of trichlorogermanane.
[0004] Therefore, it is essential to provide a device that is highly safe, environmentally friendly, and has a high germanium utilization rate, so as to convert and reduce IV-valent germanium to II-valent germanium compounds. Utility Model Content
[0005] To address or partially address the problems existing in related technologies, this application provides an apparatus for liquid reduction of tetravalent germanium to divalent germanium compounds, which can solve the problems of low germanium utilization, high losses, and low trichlorogermanane yield.
[0006] This application provides an apparatus for liquid reduction of tetravalent germanium to divalent germanium compounds, comprising a heating mantle 1, a three-necked flask 2, a circulating cooling reflux mechanism 3, a primary absorption bottle 5, and a secondary absorption bottle 6. The heating mantle 1 has a concave hemispherical inner cavity. The three-necked flask 2 is placed inside the heating mantle 1. A thermometer is built into the left neck of the three-necked flask 2, the middle neck is the feeding port, and the right neck is connected to the circulating cooling reflux mechanism 3. The upper port of the circulating cooling reflux mechanism 3 is the inlet, and the lower port is the outlet. Its interior is a spiral cooling tube. The circulating cooling reflux mechanism 3 is connected to the primary absorption bottle 5 through a guide tube. The side port of the primary absorption bottle 5 is connected to the secondary absorption bottle 6 through a guide tube. The side port of the secondary absorption bottle 6 is connected to the outside.
[0007] The three-necked flask 2 contains the conversion and reduction material, and the primary absorption bottle 5 and the secondary absorption bottle 6 contain the absorption liquid.
[0008] Optionally, in some embodiments, an anti-backflow valve 4 is installed on the guide pipe between the circulating cooling reflux mechanism 3 and the primary absorption bottle 5.
[0009] Optionally, in some embodiments, the inner cavity of the heating mantle 1 is a high-temperature resistant heat-insulating layer, the outer shell is stainless steel, the surface of the stainless steel is provided with a heat-resistant and corrosion-resistant outer layer, the outer shell has a heating adjustment knob, an electromagnetic induction current adjustment knob and a display screen in the center, and an annular electric heating element and a controllable electromagnetic induction element are arranged between the inner cavity and the outer shell of the heating mantle 1.
[0010] Optionally, in some embodiments, the thermometer is a mercury thermometer or a red-line thermometer.
[0011] Optionally, in some embodiments, the three-necked flask 2 is made of transparent borosilicate glass or quartz.
[0012] Optionally, in some embodiments, the conversion reducing material is germanium dioxide and sodium hypophosphite.
[0013] Optionally, in some embodiments, the conversion reducing material is germanium dioxide and hypophosphorous acid.
[0014] Optionally, in some embodiments, the conversion reducing materials are germanium tetrachloride and sodium hypophosphite.
[0015] Optionally, in some embodiments, the conversion reducing materials are germanium tetrachloride and hypophosphorous acid.
[0016] The technical solution provided in this application may include the following beneficial effects:
[0017] This application enables the reduction of IV-valent germanium to II-valent germanium compounds in liquid form. The conversion and reduction reaction process is safe, does not cause backflow, is green and environmentally friendly, and has no exhaust gas emissions due to absorption at two or more levels. The utilization rate of germanium is high, there is no loss, and the reaction system temperature and stirring speed are well controllable.
[0018] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and do not limit this application. Attached Figure Description
[0019] The above and other objects, features and advantages of this application will become more apparent from the more detailed description of exemplary embodiments thereof in conjunction with the accompanying drawings, wherein the same reference numerals generally represent the same components in the exemplary embodiments thereof.
[0020] Figure 1 This is a schematic diagram of the apparatus for liquid reduction of tetravalent germanium to divalent germanium compounds, as shown in the embodiments of this application.
[0021] Figure 2 This is a cross-sectional view of the heating mantle and three-necked flask shown in the embodiments of this application.
[0022] Figure label:
[0023] 1-Heating mantle, 2-Three-necked flask, 3-Circulating cooling reflux mechanism, 4-Anti-backflow valve, 5-First-stage absorption bottle, 6-Second-stage absorption bottle. Detailed Implementation
[0024] Embodiments of this application will now be described in more detail with reference to the accompanying drawings. While embodiments of this application are shown in the drawings, it should be understood that this application may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to make this application more thorough and complete, and to fully convey the scope of this application to those skilled in the art.
[0025] It should be understood that although the terms "first," "second," "third," etc., may be used in this application to describe various information, this information should not be limited to these terms. These terms are only used to distinguish information of the same type from one another. For example, without departing from the scope of this application, first information may also be referred to as second information, and similarly, second information may also be referred to as first information. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, "multiple" means two or more, unless otherwise explicitly specified.
[0026] In the description of this application, it should be understood that the terms "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this application.
[0027] Unless otherwise expressly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.
[0028] To address the aforementioned problems, this application provides an apparatus for liquid reduction of tetravalent germanium to divalent germanium compounds, which can solve the problems of low germanium utilization, high losses, and low trichlorogermanane yield.
[0029] The technical solutions of the embodiments of this application are described in detail below with reference to the accompanying drawings.
[0030] See Figure 1-2 The apparatus for liquid reduction of tetravalent germanium to divalent germanium compounds includes a heating mantle 1, a three-necked flask 2, a circulating cooling reflux mechanism 3, a primary absorption bottle 5, and a secondary absorption bottle 6. The heating mantle 1 has a concave hemispherical inner cavity. The three-necked flask 2 is placed inside the heating mantle 1. A thermometer is installed in the left neck of the three-necked flask 2, the middle neck is the feeding port, and the right neck is connected to the circulating cooling reflux mechanism 3. The upper port of the circulating cooling reflux mechanism 3 is the inlet, and the lower port is the outlet. Its interior is a spiral cooling tube. The circulating cooling reflux mechanism 3 is connected to the primary absorption bottle 5 through a guide tube. The side neck of the primary absorption bottle 5 is connected to the secondary absorption bottle 6 through a guide tube. The side neck of the secondary absorption bottle 6 is connected to the outside. The three-necked flask 2 contains the conversion and reduction material, and the primary absorption bottle 5 and the secondary absorption bottle 6 contain the absorption liquid.
[0031] The inner cavity of the electric heating jacket 1 is a high-temperature resistant heat-insulating layer, and the outer shell is made of stainless steel. The stainless steel surface is provided with a heat-resistant and corrosion-resistant outer layer. In the center of the outer shell, there is a heating adjustment knob, an electromagnetic induction current adjustment knob, and a display screen. A ring-shaped electric heating element and a controllable electromagnetic induction element are arranged between the inner cavity and the outer shell of the electric heating jacket 1.
[0032] During operation, the inner cavity of the heating mantle 1 is slightly larger than the outer diameter of the three-necked flask 2. The three-necked flask 2 is placed inside the heating mantle 1, with its bottom in contact with the bottom of the heating mantle 1. This ensures sufficient heat transfer and high energy utilization. The thermometer is inserted into the reaction system inside the three-necked flask 2 to a certain depth. The materials involved in the conversion and reduction reaction system are added sequentially from the middle neck of the three-necked flask 2. The mouth of the primary absorption bottle 5 is connected to the guide tube, which is inserted into the absorbent liquid of the primary absorption bottle. The side opening is connected to the secondary absorption bottle 6 through the guide tube. The mouth of the secondary absorption bottle 6 is connected to the primary absorption bottle through the guide tube, which is inserted into the absorbent liquid of the secondary absorption bottle. The side opening is open to the outside. If tertiary absorption is required, its structure is the same as that of the secondary absorption bottle and they are connected in series.
[0033] The electric heating mantle 1 can simultaneously achieve controllable electric heating and controllable electromagnetic induction stirring. While providing a heat source for the conversion and reduction reaction system, it uses an electromagnetic rod for stirring, avoiding the sealing problems caused by mechanical stirring and preventing the introduction of impurities. The electric heating mantle 1 uses thermal radiation electric heating, and the heating power is continuously adjustable. The electromagnetic induction body controls the rotation speed of the electromagnetic rod by the magnitude of the current.
[0034] The circulating cooling reflux mechanism 3 is placed above the right neck of the three-necked flask 2. During the conversion and reduction reaction, a small amount of gaseous germanium tetrachloride and a trace amount of gaseous trichlorogermanane are produced. Under the action of the cooling liquid (circulating water or cryogenic liquid) in the circulating cooling reflux mechanism, the gaseous germanium tetrachloride and a small amount of gaseous trichlorogermanane exchange heat with the cooling liquid and are transformed into liquid germanium tetrachloride and liquid trichlorogermanane, which fall into the three-necked flask 2. The liquid germanium tetrachloride continues to participate in the reduction reaction, and the liquid trichlorogermanane is collected at the bottom of the three-necked flask 2.
[0035] The guide tube is inserted into the absorption liquid in the primary absorption bottle 5 and the secondary absorption bottle 6, without touching the bottom of the bottle. The absorption liquid in the primary absorption bottle 5 is water or a weak alkaline solution (pH<9). When a trace amount of gaseous germanium tetrachloride that has not become liquid through the circulating cooling reflux mechanism 3 enters the primary absorption bottle 5 through the guide tube, a chemical reaction will occur: GeCl4 + 2H2O → GeO2 + 4HCl and GeO2 + 2NaOH = Na2GeO3 + H2O, thus being fully absorbed.
[0036] The absorbent in the secondary absorption bottle 6 is water or alkaline solution (pH ≮ 10). When the residual trace gaseous germanium tetrachloride that was not absorbed in the primary absorption bottle 5 enters the secondary absorption bottle 6 through the guide tube, a chemical reaction will occur: GeCl4 + 2H2O → GeO2 + 4HCl and GeO2 + 2NaOH = Na2GeO3 + H2O, thus being completely absorbed.
[0037] When the reaction temperature is too high or the reaction system volume is too large, the trace amounts of gaseous germanium tetrachloride that have not been turned into liquid by the circulating cooling reflux mechanism 3 cannot be completely absorbed by the primary absorption bottle 5 and the secondary absorption bottle 6. In such cases, a third or even more absorption bottles can be connected in series at the outlet of the secondary absorption bottle.
[0038] After the conversion and reduction reaction is completed, the liquid is a hydrochloric acid system. Trichlorogermanane, due to its higher density, settles at the bottom. Due to the protection of the hydrochloric acid system, there is no volatilization loss. The trace amounts of gaseous germanium tetrachloride that have not fully reacted during the conversion and reduction reaction can be perfectly absorbed by primary, secondary (or even multi-stage) absorption bottles, and the germanium can be recovered from the absorption liquid. The germanium compounds adhering to the inner walls of the three-necked flask 2, the guide tube, the primary absorption bottle 5, and the secondary absorption bottle 6 exist in the form of germanium tetrachloride or germanium dioxide. They can be washed and absorbed by alkaline solution + hydrogen peroxide, thereby converting them into sodium germanate and recovering the germanium from it.
[0039] An anti-backflow valve 4 is installed on the guide pipe between the circulating cooling reflux mechanism 3 and the primary absorption bottle 5.
[0040] During operation, if the conversion and reduction reaction is vigorous and rapid, the pressure inside the three-necked flask 2 will suddenly drop after germanium tetrachloride is reduced. Under atmospheric pressure, the absorbent in the secondary absorption bottle 6 will be drawn back into the primary absorption bottle 5, and the absorbent in the primary absorption bottle 5 will be drawn back into the three-necked flask 2. Placing the anti-backflow valve 4 between the circulating cooling reflux mechanism 3 connected to the right port of the three-necked absorption bottle 2 and the primary absorption bottle 5, and connecting them through a guide tube, can effectively prevent the absorbent in the absorption bottle from being drawn back into the three-necked flask 2.
[0041] The thermometer in question is a mercury thermometer or a red-line thermometer.
[0042] During operation, the thermometer is inserted to a certain depth into the reaction system inside the three-necked flask 2. Therefore, the thermometer must have a corresponding length. Since the reaction system is a strong acid solution, the thermometer must be corrosion resistant. Therefore, a mercury thermometer or a red-line thermometer is selected.
[0043] The three-necked flask 2 is made of transparent borosilicate glass or quartz.
[0044] During operation, transparent borosilicate glass or quartz materials facilitate the observation of reaction phenomena during the conversion and reduction reaction.
[0045] Example 1
[0046] The conversion and reducing materials are germanium dioxide and sodium hypophosphite.
[0047] In the conversion-reduction reaction, germanium dioxide is used as the raw material and sodium hypophosphite is used as the reducing agent. In the first stage, the conversion reaction 4HCl + GeO2 → GeCl4 + 2H2O occurs. During the reaction, hydrochloric acid converts germanium dioxide into germanium tetrachloride, and water is produced at the same time. In the second stage, the reduction reaction GeCl4 + NaH2PO2 + H2O → GeCl2 + NaH2PO3 + 2HCl and the combination reaction GeCl2 + HCl → GeHCl3 occur. During the reduction reaction, germanium tetrachloride is reduced to germanium dichloride by sodium hypophosphite. During the combination reaction, germanium dichloride and hydrogen chloride combine to form trichlorogermanane.
[0048] Example 2
[0049] The conversion and reducing materials are germanium dioxide and hypophosphorous acid.
[0050] In the conversion-reduction reaction, germanium dioxide is used as the raw material and hypophosphoric acid is used as the reducing agent. In the first stage, the conversion reaction 4HCl + GeO2 → GeCl4 + 2H2O occurs. During the reaction, hydrochloric acid converts germanium dioxide into germanium tetrachloride, and water is produced at the same time. In the second stage, the reduction reaction GeCl4 + H3PO2 + H2O → GeCl2 + H3PO3 + 2HCl and the combination reaction GeCl2 + HCl → GeHCl3 occur. During the reduction reaction, germanium tetrachloride is reduced to germanium dichloride by hypophosphoric acid. During the combination reaction, germanium dichloride and hydrogen chloride combine to form trichlorogermanane.
[0051] Example 3
[0052] The conversion and reduction materials are germanium tetrachloride and sodium hypophosphite.
[0053] In the conversion-reduction reaction, germanium tetrachloride is used as the raw material and sodium hypophosphite is used as the reducing agent. The reduction reaction GeCl4 + NaH2PO2 + H2O → GeCl2 + NaH2PO3 + 2HCl and the combination reaction GeCl2 + HCl → GeHCl3 occur. In the reduction reaction, germanium tetrachloride is reduced to germanium dichloride by sodium hypophosphite. In the combination reaction, germanium dichloride and hydrogen chloride combine to form trichlorogermanane.
[0054] Example 4
[0055] The conversion and reduction materials are germanium tetrachloride and hypophosphorous acid.
[0056] In the conversion-reduction reaction, germanium tetrachloride is used as the raw material and hypophosphoric acid is used as the reducing agent. The reduction reaction GeCl4 + H3PO2 + H2O → GeCl2 + H3PO3 + 2HCl and the combination reaction GeCl2 + HCl → GeHCl3 occur. In the reduction reaction, germanium tetrachloride is reduced to germanium dichloride by hypophosphoric acid. In the combination reaction, germanium dichloride and hydrogen chloride combine to form trichlorogermanane.
[0057] The working process of this application:
[0058] This application uses an electric heating mantle 1 to provide support and a heat source and stirring kinetic energy for the conversion-reduction reaction. The heating element ensures that the conversion-reduction reaction system in the three-necked flask 2 is at a suitable temperature, and electromagnetic stirring ensures that all materials in the conversion-reduction reaction system are in full contact to carry out the conversion-reduction reaction. An appropriate amount of pure water or distilled water can be added to the conversion-reduction material system in this device as needed. This device can convert and reduce IV-valent germanium compounds to II-valent germanium compounds. During the reaction, gaseous germanium tetrachloride, under the action of the circulating cooling reflux mechanism 3, becomes liquid through sufficient heat exchange and returns to the flask to continue the reaction. A small amount of insufficiently cooled gaseous germanium tetrachloride... Germanium tetrachloride is absorbed in the primary and secondary absorption devices. The purpose of the anti-backflow valve 4 in this device is to prevent the liquid in the absorption bottle from being drawn back into the three-necked flask 2 during the conversion and reduction reaction, as a large amount of gaseous germanium tetrachloride is reduced to divalent germanium compounds. The absorption liquid in the primary absorption bottle 5 is a neutral liquid, which can be distilled water, pure water, or an alkaline liquid with a pH value <9. The absorption liquid in the secondary absorption bottle 6 is an alkaline liquid (pH value ≥10). After the conversion and reduction reaction is completed, there is a white precipitate at the bottom of the three-necked flask 2. The upper part of the solution after the reaction is low-density hydrochloric acid, and the lower part is divalent germanium compounds.
[0059] Finally, it should be noted that in this document, relationships such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "include," "contain," or any other variations are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus.
[0060] The units described as separate components may or may not be physically separate. The components shown as units may or may not be physical units; that is, they may be located in one place or distributed across multiple network units. Some or all of the units can be selected to achieve the purpose of this embodiment according to actual needs.
[0061] The various embodiments of this application have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or improvement of the technology in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.
Claims
1. An apparatus for reducing germanium in the +4 oxidation state to a compound of germanium in the +2 oxidation state in the liquid state, characterized by: The device for reducing liquid germanium of the fourth valence into germanium compound of the second valence comprises an electric heating jacket (1), a three-neck flask (2), a circulating cooling reflux mechanism (3), a first absorption bottle (5) and a second absorption bottle (6); the inner cavity of the electric heating jacket (1) is a concave semispherical shape, the three-neck flask (2) is placed in the inner cavity of the electric heating jacket (1), a thermometer is placed in the left neck of the three-neck flask (2), the middle neck is a charging port, and the right neck is connected with the circulating cooling reflux mechanism (3); the upper end of the circulating cooling reflux mechanism (3) is an inlet, the lower end is an outlet, and the inner part is a spiral cooling pipe; the circulating cooling reflux mechanism (3) is connected with the first absorption bottle (5) through a flow guide pipe, the side neck of the first absorption bottle (5) is connected with the second absorption bottle (6) through a flow guide pipe, and the side neck of the second absorption bottle (6) is connected with the outside. The three-neck flask (2) is filled with conversion reduction materials, and the first absorption bottle (5) and the second absorption bottle (6) are filled with absorption liquid.
2. The apparatus for reducing a compound of germanium in the tetravalent state to a compound of germanium in the divalent state in the liquid state according to claim 1, characterized in that: A backflow prevention valve (4) is installed on the flow guide pipe between the circulating cooling reflux mechanism (3) and the first absorption bottle (5).
3. An apparatus for the liquid reduction of germanium (IV) to germanium (II) compounds according to claim 1 or 2, characterised in that: The inner cavity of the electric heating jacket (1) is a high-temperature-resistant heat-insulating layer, the shell is made of stainless steel, a heat-resistant and corrosion-resistant outer layer is arranged on the surface of the stainless steel, a heating adjustment knob, an electromagnetic induction current adjustment knob and a display screen are arranged in the middle of the shell, and annular electric heating elements and controllable electromagnetic induction elements are arranged between the inner cavity of the electric heating jacket (1) and the shell.
4. An apparatus for the liquid reduction of germanium (IV) to germanium (II) compounds according to claim 1 or 2, characterised in that: The thermometer is a mercury thermometer or a red line thermometer.
5. An apparatus for the liquid reduction of germanium (IV) to germanium (II) compounds according to claim 1 or 2, characterised in that: The three-neck flask (2) is made of transparent borosilicate glass or quartz material.
6. The apparatus for reducing a compound of germanium in the tetravalent state to a compound of germanium in the divalent state in the liquid state according to claim 5, characterized by: The conversion reduction materials are germanium dioxide and sodium hypophosphite.
7. The apparatus for reducing a compound of germanium in the tetravalent state to a compound of germanium in the divalent state in the liquid state according to claim 5, characterized by: The conversion reduction materials are germanium dioxide and hypophosphorous acid.
8. The apparatus for reducing a compound of germanium in the tetravalent state to a compound of germanium in the divalent state in the liquid state according to claim 5, characterized by: The conversion reduction materials are germanium tetrachloride and sodium hypophosphite.
9. The apparatus for reducing a compound of germanium in the tetravalent state to a compound of germanium in the divalent state in the liquid state according to claim 5, characterized by: The conversion reduction materials are germanium tetrachloride and hypophosphorous acid.