CN111825058B - Germane preparation method and device based on automatic activation of molecular sieve - Google Patents
Germane preparation method and device based on automatic activation of molecular sieve Download PDFInfo
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Abstract
The invention relates to a germane preparation method based on molecular sieve automatic activation, which comprises the following steps: uniformly mixing magnesium germanide and ammonium chloride according to the mass ratio of 1: 3.5-7, and then loading the mixture into a germane generator; vacuumizing a germane generator to below 8Pa, and introducing liquid ammonia, wherein the introduction amount of the liquid ammonia is 6-12 times of the weight of ammonium chloride, and the reaction time is 45-72 min; after the reaction is completed, purifying the generated mixed gas by a molecular sieve to obtain germane; and acquiring the purification duration of the molecular sieve, and sending an activation instruction when judging that the duration reaches a preset value so as to start an activation system and enter a molecular sieve activation step. The method solves the technical problems of construction period delay and cost increase caused by the fact that the molecular sieve cannot be automatically activated in the germane preparation and purification process in the prior art.
Description
Technical Field
The invention relates to the technical field of molecular sieve activation, in particular to a germane preparation method and device based on molecular sieve automatic activation.
Background
In the semiconductor materials industry, high purity germanium hydride, germane, is commonly used as the substrate doping gas. Commercial use of germanium tetrahydride is steadily increasing by semiconductor and solar cell manufacturers. The semiconductor field requires high purity of produced germanium, less variation of impurity concentration and lower cost than the current manufacturing method. There are many known methods for the production and synthesis of germane. Typical synthesis methods can be classified as chemical reduction, electrochemical reduction, or plasma synthesis. Chemical reduction processes typically involve contacting a germanium-containing compound, such as germanium tetrachloride, germanium oxide, germanide, and/or elemental germanium, with a reducing agent, such as, but not limited to, sodium borohydride, potassium borohydride, lithium aluminum hydride, sodium aluminum hydride, lithium hydride, sodium hydride, or magnesium hydride. Other chemical reduction methods may use organic solvent solutions as the reaction medium rather than aqueous solutions, and may also use the reaction of germanides with acids. On the other hand, the electrochemical reduction method is generally a method in which a voltage is applied to a germanium metal cathode and an anode counter electrode composed of a metal such as molybdenum or cadmium, which are immersed in an aqueous electrolyte solution. Plasma synthesis involves bombarding elemental germanium with hydrogen atoms (H) generated by a high frequency plasma source to provide various reaction products, such as germanes in various states, such as germylane, and the like.
Generally, a large amount of impurities, such as chlorogermane, carbon dioxide, hydrogen and the like, are carried in the synthesis process of germane, so that the crude germane after synthesis is purified. In the prior art, molecular sieves are widely used in gas purification.
Chinese patent CN101486444A discloses a method for purifying germane. According to the adsorption characteristics of the molecular sieve, the crude germane is sequentially passed through adsorption columns filled with the 4A and 5A molecular sieves, and then the pure germane with the purity of 99-99.99% is obtained by a germane collecting system. The molecular sieve adsorption purification method adopted by the invention can effectively remove main impurities in the crude germane, and also has good adsorption capacity on trace impurities in the crude germane, so that the germane purified by the method can obtain high purity more easily; the molecular sieve has stable property and cannot pollute purified gas; the molecular sieve with saturated adsorption can be recycled through activation and regeneration treatment.
Therefore, the molecular sieve adsorption purification method is a high-efficiency, clean and low-cost germane purification method. The molecular sieve is typically a crystalline silicate or aluminosilicate. The molecular sieve has a uniform microporous structure, and the pores have uniform diameter, can adsorb molecules smaller than the diameter of the pores into the pores, and have preferential adsorption capacity for polar molecules and unsaturated molecules, so that the molecular sieve can separate the molecules with different polarity degrees, saturation degrees, molecular sizes and boiling points, namely has the function of sieving the molecules, and is called as the molecular sieve. The molecular sieve has the advantages of high adsorption capacity, strong thermal stability and the like which are not possessed by other adsorbents, so that the molecular sieve can be widely applied.
However, in the germane preparation and purification process, the used molecular sieve cannot be automatically activated, and the purification process needs to be interrupted, so that the purification process can be continued after the molecular sieve is activated or replaced, thereby not only delaying the construction period, but also increasing the preparation cost.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a germane preparation method based on automatic activation of a molecular sieve, so as to at least partially solve the technical problems of construction period delay and cost increase caused by the fact that the molecular sieve cannot be automatically activated in the germane preparation and purification process in the prior art.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a germane preparation method based on automatic activation of a molecular sieve comprises the following steps:
uniformly mixing magnesium germanide and ammonium chloride according to the mass ratio of 1: 3.5-7, and then loading the mixture into a germane generator;
vacuumizing a germane generator to below 8Pa, and introducing liquid ammonia, wherein the introduction amount of the liquid ammonia is 6-12 times of the weight of ammonium chloride, and the reaction time is 45-72 min;
after the reaction is completed, purifying the generated mixed gas by a molecular sieve to obtain germane;
and acquiring the purification duration of the molecular sieve, and sending an activation instruction when judging that the duration reaches a preset value so as to start an activation system and enter a molecular sieve activation step.
Further, the molecular sieve activating step comprises:
conveying the molecular sieve particles to a bed layer through an automatic conveying line, and heating to 350-550 ℃ in stages at a speed of 5-20 ℃/min;
continuously flushing the molecular sieve bed layer with ammonia gas while heating;
cooling the regenerated molecular sieve to 20-40 ℃ at the speed of 10-30 ℃/min, and air-cooling and drying;
and conveying the dried molecular sieve particles back to the working position through the automatic conveying line.
Further, heating to 350-:
slowly heating at low temperature for dehydration, and slowly heating from 25 deg.C to 350 deg.C at a rate of 5 deg.C/min;
a rapid heating-up stage, wherein the temperature is rapidly raised from 350 to 550 ℃ at the speed of 20 ℃/min;
and a stage of removing residual water at high temperature, keeping the temperature at 550 ℃ for 1-3 hours.
Further, during the staged heating, the method further comprises:
and acquiring the current temperature of the low-temperature slow heating dehydration stage, and sending a temperature rise instruction when the current temperature reaches 350 ℃, so that the heating device can improve the heating power according to the temperature rise instruction.
Further, during the staged heating, the method further comprises:
and acquiring the current temperature of the rapid heating stage, and sending a constant temperature instruction when the current temperature reaches 550 ℃ so that the heating device maintains the current heating power for 1-3 hours according to the constant temperature instruction.
Further, the method comprises the steps of:
obtaining safety influence parameters in the staged heating process;
if the safety influence parameter is judged to exceed a safety threshold value, an early warning instruction is sent out;
and sending out an early warning signal according to the early warning instruction.
Further, acquiring a safety influence parameter in the staged heating process, judging that the safety influence parameter exceeds a safety threshold, and then sending out an early warning instruction, specifically comprising:
acquiring the current temperature of the reactor;
and if the current temperature in the reactor is judged to be higher than the high-temperature threshold value, an early warning instruction is sent out so that the intelligent terminal can send out an alarm signal according to the early warning instruction.
Further, the early warning instruction comprises a character or voice warning signal pushed to the intelligent terminal.
Further, the molecular sieve purification is continued for a preset value of 6-8 hours.
Meanwhile, the invention also designs a germane preparation device based on automatic activation of the molecular sieve, which comprises the following steps
The component parts are as follows:
a feed vessel comprising a magnesium germanide feed vessel and an ammonium chloride feed vessel;
a germane generator connected to the two raw material containers;
an ammonia water supply assembly comprising an ammonia water tank and a pump, the pump being connected to the germane generator by a pipeline;
the device comprises a filtering tower, a material inlet, a material outlet and a gas outlet at the top end, wherein the filtering tower is internally loaded with a molecular sieve, and comprises a mixed gas inlet connected with a germane generator; the molecular sieve activating and regenerating system includes activating bed layer, automatic conveying lines and drying chamber, and each of the automatic conveying lines is connected to the material inlet and outlet of the filtering tower.
The technical scheme provided by the invention has the following beneficial effects: the invention creatively provides a germane preparation method based on automatic activation of a molecular sieve, which can automatically enter a molecular sieve activation step according to the use duration of the molecular sieve in the germane preparation process, so that the molecular sieve activation can be automatically carried out in the germane preparation process without replacing the molecular sieve, and the technical problems of construction period delay and cost increase caused by the fact that the molecular sieve cannot be automatically activated in the germane preparation and purification process in the prior art are solved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic flow diagram of the germane preparation process based on molecular sieve activation process of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples were purchased from a conventional reagent store unless otherwise specified.
Fig. 1 is a schematic flow chart of germane preparation process based on molecular sieve activation process. Specifically, the method can comprise the following steps:
mixing two raw materials in a magnesium germanide raw material container 1 and an ammonium chloride raw material container 2, then loading the mixture into a germane generator 3, vacuumizing the germane generator 3 to below 8Pa, introducing liquid ammonia in an ammonia water tank 4 into the generator 3 by using a pump 5, introducing the generated mixed gas into a filter tower 6 after the reaction is completed, and purifying by using a molecular sieve to obtain refined germane;
wherein, obtaining the duration of molecular sieve purification, and if the duration is judged to reach a preset value, sending an activation instruction so as to start an activation system and enter a molecular sieve activation step: the automatic control valve 7 is opened, the molecular sieve particles are conveyed to the activation bed layer 9 through the automatic conveying line 8 and are heated to 350-550 ℃ in stages at the speed of 5-20 ℃/min; continuously flushing the molecular sieve bed layer 9 with ammonia gas while heating, wherein the ammonia gas can be generated by heating ammonia water of a pump 5 through a heater 12; drying the regenerated molecular sieve in a drying chamber 10 by air cooling; and (3) transmitting the dried molecular sieve particles to the original working position in the filter tower 6 through the automatic conveying line 11, so as to realize the activation and regeneration of the molecular sieve. The whole process can realize automatic production, the operation is intelligent, and time and labor are saved.
In combination with the above process flow, the invention also includes a germane preparation device based on molecular sieve automatic activation, which comprises the following components:
a feed vessel comprising a magnesium germanide feed vessel and an ammonium chloride feed vessel;
a germane generator connected to the two raw material containers;
the ammonia water supply assembly comprises an ammonia water tank and a pump, wherein the pump is connected to the germane generator through a pipeline;
the device comprises a filtering tower, a material inlet, a material outlet and a gas outlet at the top end, wherein the filtering tower is internally loaded with a molecular sieve, and comprises a mixed gas inlet connected with a germane generator;
the molecular sieve activating and regenerating system includes activating bed layer, automatic conveying lines and drying chamber, and each of the automatic conveying lines is connected to the material inlet and outlet of the filtering tower.
Wherein, above-mentioned automatic transfer chain also can select the auger that can transport the powder granule, and the opening or closing of this auger can be controlled through central processing unit. In the filter column 6, the molecular sieve particles may alternatively be arranged in a close packed arrangement within a vertically arranged baffle. The activation bed layer 9 is provided with a heating element which can heat and dry materials and is provided with a plurality of material and gas inlets and outlets. The drying chamber 10 is provided with an air inlet and with a heating element.
Specifically, the germane preparation method based on automatic activation of the molecular sieve provided by the invention comprises the following steps:
s1: uniformly mixing magnesium germanide and ammonium chloride according to the mass ratio of 1: 3.5-7, and then loading the mixture into a germane generator;
s2: vacuumizing a germane generator to below 8Pa, and introducing liquid ammonia, wherein the introduction amount of the liquid ammonia is 6-12 times of the weight of ammonium chloride, and the reaction time is 45-72 min;
s3: purifying the generated mixed gas by a molecular sieve to obtain germane, wherein the molecular sieve is an ultrafine ZSM-5 molecular sieve based on a porous silicon carbide carrier, the crystal size of the molecular sieve is 3-1000 nanometers, the loading capacity is 0-60 wt%, the thickness of the coating is 0.1-100 micrometers, and the specific surface area of a composite material consisting of the obtained ultrafine ZSM-5 zeolite coating and the porous silicon carbide ceramic carrier is 0.5-300 m2/g；
S4: and acquiring the continuous time of molecular sieve purification, and sending an activation instruction when judging that the continuous time reaches a preset value so as to start an activation system and enter a step of molecular sieve activation, wherein the preset value of the continuous molecular sieve purification is 6-8 hours.
Specifically, the molecular sieve activating step comprises:
conveying the molecular sieve particles to a bed layer through an automatic conveying line, and heating to 350-550 ℃ in stages at a speed of 5-20 ℃/min; wherein, the heating is carried out to 350-550 ℃ in stages at the speed of 5-20 ℃/min, and the method specifically comprises the following steps: slowly heating at low temperature for dehydration, and slowly heating from 25 deg.C to 350 deg.C at a rate of 5 deg.C/min; a rapid heating-up stage, wherein the temperature is rapidly raised from 350 to 550 ℃ at the speed of 20 ℃/min; and a stage of removing residual water at high temperature, keeping the temperature at 550 ℃ for 1-3 hours.
Continuously flushing the molecular sieve bed layer with ammonia gas while heating;
cooling the regenerated molecular sieve to 20-40 ℃ at the speed of 10-30 ℃/min, and air-cooling and drying;
and conveying the dried molecular sieve particles back to the working position through the automatic conveying line.
The automatic conveying line can also be an auger for conveying powder particles, the opening or closing of the auger is controlled by a central processing unit, when the molecular sieve is continuously used for 6-8 hours, the central processing unit receives time data of a timer and sends an opening instruction to the auger, and the auger is opened according to the instruction; and after activation, keeping the temperature at 550 ℃ for 1-3 hours, and sending a closing instruction to the packing auger by the central processing unit after receiving the time data of the timer.
In order to achieve automatic control over temperature and thus molecular sieve, the method further comprises, during the staged heating:
and acquiring the current temperature of the low-temperature slow heating dehydration stage, and sending a temperature rise instruction when the current temperature reaches 350 ℃, so that the heating device can improve the heating power according to the temperature rise instruction.
And acquiring the current temperature of the rapid heating stage, and sending a constant temperature instruction when the current temperature reaches 550 ℃ so that the heating device maintains the current heating power for 1-3 hours according to the constant temperature instruction.
Further, the method further comprises the steps of:
obtaining safety influence parameters in the staged heating process;
if the safety influence parameter is judged to exceed a safety threshold value, an early warning instruction is sent out;
and sending out an early warning signal according to the early warning instruction.
Specifically, the current temperature of the reactor is obtained; and if the current temperature in the reactor is judged to be higher than the high-temperature threshold value, an early warning instruction is sent out so that the intelligent terminal can send out an alarm signal according to the early warning instruction. The early warning instruction comprises a character or voice warning signal pushed to the intelligent terminal. Therefore, when the reaction temperature is too high, an alarm can be sent out, the substance denaturation or explosion caused by the too high temperature is avoided, and the reaction safety is improved. With high temperature alarm matched with, can set up the shower in the top of reactor, the shower passes through above-mentioned central controller unified control, when sending temperature early warning instruction, sends to the shower motor and opens the instruction, and the shower sprays cooling medium, for example water to reactor top to reduce the temperature rapidly, avoid the conflagration, and can realize spraying at the very first time that the conflagration takes place and put out a fire, avoid the condition of a fire out of control.
The technical solution provided by the present invention is further illustrated below with reference to specific examples.
Example 1
The germane preparation method based on automatic activation of the molecular sieve provided by the embodiment 1 of the invention comprises the following steps:
s11: uniformly mixing magnesium germanide and ammonium chloride according to the mass ratio of 1: 3.7, and then loading the mixture into a germane generator;
s12: vacuumizing a germane generator to below 8Pa, and introducing liquid ammonia, wherein the introduction amount of the liquid ammonia is 8 times of the weight of ammonium chloride, and the reaction time is 50 min;
s13: after the reaction is completed, purifying the generated mixed gas by a molecular sieve to obtain germane; the molecular sieve is an ultrafine ZSM-5 molecular sieve based on a porous silicon carbide carrier, the crystal size of the molecular sieve is 200 nanometers, the loading capacity is 30 wt%, the coating thickness is 20 micrometers, and the specific surface area of a composite material consisting of the obtained ultrafine ZSM-5 type zeolite coating and the porous silicon carbide ceramic carrier is 30m2/g；
S14: when the duration of the molecular sieve purification reaches 6 hours, an activation instruction is sent out so that an activation system can be started and the molecular sieve activation step is carried out;
s15: conveying the molecular sieve particles to a bed layer through an automatic conveying line, slowly heating from 25 ℃ to 350 ℃ at the speed of 5 ℃/min, rapidly heating from 350 ℃ to 550 ℃ at the speed of 20 ℃/min, and keeping the temperature at 550 ℃ for 2 hours;
s16: continuously flushing the molecular sieve bed layer with ammonia gas while heating;
s17: cooling the regenerated molecular sieve to 25 ℃ at the speed of 20 ℃/min, and air-cooling and drying; the dried molecular sieve particles are transported back to the operating location by the automatic conveyor line and step S11 is repeated.
Example 2
The germane preparation method based on automatic activation of the molecular sieve provided by the embodiment 2 of the invention comprises the following steps:
s21: uniformly mixing magnesium germanide and ammonium chloride according to the mass ratio of 1: 4, and then loading the mixture into a germane generator;
s22: vacuumizing a germane generator to below 8Pa, and introducing liquid ammonia, wherein the introduction amount of the liquid ammonia is 10 times of the weight of ammonium chloride, and the reaction time is 60 min;
s23: after the reaction is completed, purifying the generated mixed gas by a molecular sieve to obtain germane; the molecular sieve is an ultrafine ZSM-5 molecular sieve based on a porous silicon carbide carrier, the crystal size of the molecular sieve is 300 nanometers, the load capacity is 40 wt%, the coating thickness is 30 micrometers, and the specific surface area of a composite material consisting of the obtained ultrafine ZSM-5 type zeolite coating and the porous silicon carbide ceramic carrier is 50m2/g；
S24: when the duration of the molecular sieve purification reaches 7 hours, an activation instruction is sent out so that an activation system can be started and the molecular sieve activation step is carried out;
s25: conveying the molecular sieve particles to a bed layer through an automatic conveying line, slowly heating from 25 ℃ to 350 ℃ at the speed of 5 ℃/min, rapidly heating from 350 ℃ to 550 ℃ at the speed of 20 ℃/min, and keeping the temperature at 550 ℃ for 2 hours;
s26: continuously flushing the molecular sieve bed layer with ammonia gas while heating;
s27: cooling the regenerated molecular sieve to 25 ℃ at the speed of 30 ℃/min, and air-cooling and drying;
the dried molecular sieve particles are transported back to the operating location by the automatic conveyor line and step S21 is repeated.
Example 3
The germane preparation method based on automatic activation of the molecular sieve provided by the embodiment 3 of the invention comprises the following steps:
s31: uniformly mixing magnesium germanide and ammonium chloride according to the mass ratio of 1: 5, and then loading the mixture into a germane generator;
s32: vacuumizing a germane generator to below 8Pa, and introducing liquid ammonia, wherein the introduction amount of the liquid ammonia is 12 times of the weight of ammonium chloride, and the reaction time is 65 min;
s33: after the reaction is completed, purifying the generated mixed gas by a molecular sieve to obtain germane; the molecular sieve is an ultrafine ZSM-5 molecular sieve based on a porous silicon carbide carrier, the crystal size of the molecular sieve is 400 nanometers, the load capacity is 40 wt%, the coating thickness is 80 micrometers, and the specific surface area of a composite material consisting of the obtained ultrafine ZSM-5 type zeolite coating and the porous silicon carbide ceramic carrier is 100m2/g；
S34: when the duration of the molecular sieve purification reaches 6 hours, an activation instruction is sent out so that an activation system can be started and the molecular sieve activation step is carried out;
s35: conveying the molecular sieve particles to a bed layer through an automatic conveying line, slowly heating from 25 ℃ to 350 ℃ at the speed of 5 ℃/min, rapidly heating from 350 ℃ to 550 ℃ at the speed of 20 ℃/min, and keeping the temperature at 550 ℃ for 3 hours;
s36: continuously flushing the molecular sieve bed layer with ammonia gas while heating;
s37: cooling the regenerated molecular sieve to 30 ℃ at the speed of 30 ℃/min, and air-cooling and drying; the dried molecular sieve particles are transported back to the operating location by the automatic conveyor line and step S31 is repeated.
Example 4
The germane preparation method based on automatic activation of the molecular sieve provided by the embodiment 4 of the invention comprises the following steps:
s41: uniformly mixing magnesium germanide and ammonium chloride according to the mass ratio of 1: 6, and then loading the mixture into a germane generator;
s42: vacuumizing a germane generator to below 8Pa, and introducing liquid ammonia, wherein the introduction amount of the liquid ammonia is 10 times of the weight of ammonium chloride, and the reaction time is 60 min;
s43: after the reaction is completed, purifying the generated mixed gas by a molecular sieve to obtain germane; the molecular sieve is an ultrafine ZSM-5 molecular sieve based on a porous silicon carbide carrier, the crystal size of the molecular sieve is 500 nanometers, the load capacity is 55 wt%, the coating thickness is 80 micrometers, and the specific surface area of a composite material consisting of the obtained ultrafine ZSM-5 type zeolite coating and the porous silicon carbide ceramic carrier is 150m2/g；
S44: when the duration of the molecular sieve purification reaches 6 hours, an activation instruction is sent out so that an activation system can be started and the molecular sieve activation step is carried out;
s45: conveying the molecular sieve particles to a bed layer through an automatic conveying line, slowly heating from 25 ℃ to 350 ℃ at the speed of 5 ℃/min, rapidly heating from 350 ℃ to 550 ℃ at the speed of 20 ℃/min, and keeping the temperature at 550 ℃ for 3 hours;
s46: continuously flushing the molecular sieve bed layer with ammonia gas while heating;
s47: cooling the regenerated molecular sieve to 25 ℃ at the speed of 30 ℃/min, and air-cooling and drying;
the dried molecular sieve particles are transported back to the operating location by the automatic conveyor line and step S41 is repeated.
Example 5
The germane preparation method based on automatic activation of the molecular sieve provided by the embodiment 5 of the invention comprises the following steps:
s51: uniformly mixing magnesium germanide and ammonium chloride according to the mass ratio of 1: 5.5, and then loading the mixture into a germane generator;
s52: vacuumizing a germane generator to below 8Pa, and introducing liquid ammonia, wherein the introduction amount of the liquid ammonia is 12 times of the weight of ammonium chloride, and the reaction time is 70 min;
s53: after the reaction is completed, purifying the generated mixed gas by a molecular sieve to obtain germane; the molecular sieve is an ultrafine ZSM-5 molecular sieve based on a porous silicon carbide carrier, the crystal size of the molecular sieve is 800 nanometers, the loading capacity is 45 wt%, the thickness of the coating is 65 micrometers, and the obtained ultrafine ZSM-5 type boiling point zeoliteThe specific surface area of the composite material consisting of the stone coating and the porous silicon carbide ceramic carrier is 200m2/g；
S54: when the duration of the molecular sieve purification reaches 7 hours, an activation instruction is sent out so that an activation system can be started and the molecular sieve activation step is carried out;
s55: conveying the molecular sieve particles to a bed layer through an automatic conveying line, slowly heating from 25 ℃ to 350 ℃ at the speed of 5 ℃/min, rapidly heating from 350 ℃ to 550 ℃ at the speed of 20 ℃/min, and keeping the temperature at 550 ℃ for 2 hours;
s56: continuously flushing the molecular sieve bed layer with ammonia gas while heating;
s57: cooling the regenerated molecular sieve to 30 ℃ at the speed of 30 ℃/min, and air-cooling and drying;
the dried molecular sieve particles are transported back to the operating location by the automatic conveyor line and step S51 is repeated.
The molecular sieve purification effect and the molecular sieve activation effect in examples 1 to 5 of the present invention were systematically evaluated by experiments.
1. Determination of molecular sieve purification effect
Germane mixed gas with the same concentration respectively passes through the molecular sieves described in the embodiments 1 to 5 of the present invention, the control group is germane mixed gas with the concentration before the molecular sieves are not purified, the adopted determination method is a method commonly used in the industry, the germane purity in the test results is 100% of the result of the embodiment 1, the results of other groups are calculated ratios relative to the result of the embodiment 1, and the test results are shown in the following table 1.
TABLE 1 measurement results of molecular sieve purification effect
| Group of | Example 1 | Example 2 | Example 3 |
| Purity of germane | 100.00％ | 99.53％ | 103.21％ |
| Group of | Example 4 | Example 5 | |
| Purity of germane | 98.65％ | 97.28％ | |
| Group of | Control group | ||
| Purity of germane | 62.13％ |
2. Determination of molecular sieve activation Effect
Germane mixed gas with the same concentration respectively passes through the molecular sieves activated in the embodiments 1 to 5 of the invention, a control group passes through the molecular sieves which are not activated, the adopted determination method is a method commonly used in the industry, the germane purity in the test results is 100% of the result of the embodiment 1, the results of other groups are calculated ratios relative to the result of the embodiment 1, and the test results are shown in the following table 2.
TABLE 2 measurement results of molecular sieve activation effect
| Group of | Example 1 | Example 2 | Example 3 |
| Purity of germane | 100.00％ | 99.53％ | 103.21％ |
| Group of | Example 4 | Example 5 | |
| Purity of germane | 98.65％ | 97.28％ | |
| Group of | Control group | ||
| Purity of germane | 86.27％ |
According to the test results, the invention creatively provides a germane preparation method based on automatic activation of a molecular sieve, which can automatically enter a molecular sieve activation step according to the use duration of the molecular sieve in the germane preparation process, so that the molecular sieve activation can be automatically carried out in the germane preparation process without replacing the molecular sieve, and the technical problems of construction period delay and cost increase caused by the fact that the molecular sieve cannot be automatically activated in the germane preparation and purification process in the prior art are solved.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains. Unless specifically stated otherwise, the relative steps, numerical expressions, and values of the components and steps set forth in these embodiments do not limit the scope of the present invention. In all examples shown and described herein, unless otherwise specified, any particular value should be construed as merely illustrative, and not restrictive, and thus other examples of example embodiments may have different values.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. A germane preparation method based on automatic activation of a molecular sieve is characterized by comprising the following steps:
mixing magnesium germanide and ammonium chloride according to the mass ratio of 1: 3.5-7, and then loading into a germane generator;
vacuumizing a germane generator to below 8Pa, and introducing liquid ammonia, wherein the introduction amount of the liquid ammonia is 6-12 times of the weight of ammonium chloride, and the reaction time is 45-72 min;
after the reaction is completed, purifying the generated mixed gas by a molecular sieve to obtain germane;
obtaining the purification duration of the molecular sieve, and sending an activation instruction when judging that the duration reaches a preset value so as to start an activation system and enter a molecular sieve activation step, wherein the molecular sieve is an ultrafine ZSM-5 molecular sieve based on a porous silicon carbide carrier, and the molecular sieve activation step comprises the following steps:
the molecular sieve particles are conveyed to the bed layer through an automatic conveying line and are heated to 350-550 ℃ in stages at the speed of 5-20 ℃/min, and the method specifically comprises the following steps: slowly heating at low temperature for dehydration, and slowly heating from 25 deg.C to 350 deg.C at a rate of 5 deg.C/min; a rapid heating-up stage, wherein the temperature is rapidly raised from 350 to 550 ℃ at the speed of 20 ℃/min; removing residual water at high temperature, and keeping the temperature at 550 ℃ for 1-3 hours;
continuously flushing the molecular sieve bed layer with ammonia gas while heating;
cooling the regenerated molecular sieve to 20-40 ℃ at the speed of 10-30 ℃/min, and air-cooling and drying;
and conveying the dried molecular sieve particles back to the working position through the automatic conveying line.
2. The method of claim 1, wherein during the staged heating, the method further comprises:
and acquiring the current temperature of the low-temperature slow heating dehydration stage, and sending a temperature rise instruction when the current temperature reaches 350 ℃, so that the heating device can improve the heating power according to the temperature rise instruction.
3. The method of claim 1, wherein during the staged heating, the method further comprises:
and acquiring the current temperature of the rapid heating stage, and sending a constant temperature instruction when the current temperature reaches 550 ℃ so that the heating device maintains the current heating power for 1-3 hours according to the constant temperature instruction.
4. The method for preparing germane based on automatic activation of molecular sieves according to claim 1, comprising the steps of:
obtaining safety influence parameters in the staged heating process;
if the safety influence parameter is judged to exceed a safety threshold value, an early warning instruction is sent out;
and sending out an early warning signal according to the early warning instruction.
5. The method for preparing germane based on automatic activation of molecular sieve according to claim 3, wherein a safety influence parameter in a staged heating process is obtained, and if the safety influence parameter is judged to exceed a safety threshold, an early warning instruction is issued, specifically comprising:
acquiring the current temperature of the reactor;
and if the current temperature in the reactor is judged to be higher than the high-temperature threshold value, an early warning instruction is sent out so that the intelligent terminal can send out an alarm signal according to the early warning instruction.
6. The method for preparing germane based on automatic activation of molecular sieve according to claim 5, wherein the early warning instruction comprises a text or voice alarm signal to be pushed to the intelligent terminal.
7. The method for preparing germane based on automatic activation of molecular sieve according to claim 1, wherein the purification of molecular sieve is continued for a preset value of 6-8 hours.
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