Production device and method of electronic-grade trimethyl gallium

Abstract

The application discloses a production device and a production method of electronic-grade trimethylgallium, wherein the production device comprises a high-purity gallium-magnesium alloy feeder, a tertiary amine solvent storage tank, a rare gas storage tank, a synthesis kettle reactor, a halogenated alkane storage tank, a microfiltration filter, a vacuum rectifying tower, a high-temperature decomplexing kettle, a high-efficiency rectifying tower, a falling-film evaporator and a finished product receiving tank; the production method specifically comprises the following steps: (1) rare gas is introduced, high-purity gallium-magnesium alloy is added, tertiary amine solvent is added, stirring is carried out, and halogenated alkane is added drop by drop to carry out a synthesis reaction; (2) microfiltration; (3) vacuum rectification; (4) decomplexing; (5) secondary rectification; and (6) evaporation, and the electronic-grade trimethylgallium is obtained. The purity of the electronic-grade trimethylgallium prepared by the application is higher than 99.9999%, and the purity can reach 6N level or even higher; the operation is simple, the reaction is safe and stable, easy to control, the synthesis yield is high, the product loss is small, the technology is mature, no impurities are introduced, and the large-scale industrial production can be realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic industry, more particularly to a production device and method of electronic-grade trimethylgallium. BACKGROUND

[0002] Electronic-grade chemicals are one of the key basic chemical materials in the process of "chip" manufacturing, and the purity and cleanliness thereof have a very important influence on the yield, electrical performance and reliability of integrated circuits. Among them, electronic-grade trimethylgallium is widely used in the front-line industries of integrated circuits, liquid crystal displays, LED lighting, sensors, lasers, photovoltaic cells, etc.

[0003] Trimethylgallium can be used for metal organic chemical vapor deposition (MOCVD) to prepare semiconductor compounds such as gallium nitride, gallium arsenide, gallium aluminum arsenide, etc., and is a gallium source for manufacturing electronic components such as light-emitting diodes. Electronic-grade trimethylgallium is a key MO source raw material for the production of optoelectronic materials such as gallium nitride by MOCVD process technology, and is the most widely used metal organic compound among MO source compounds. MO source, i.e. metal organic compound, is an important metal source in the field of optoelectronic semiconductor materials industry, and is a basic source material for the production and synthesis of new semiconductor optoelectronic compound materials by MOCVD process technology.

[0004] Benefiting from the booming development of downstream integrated circuits, LEDs, photovoltaics, etc., the global demand for trimethylgallium is growing. The purity of electronic-grade trimethylgallium products needs to reach 99.9999% (6N) level, and the high-purity trimethylgallium technology has high barriers and high requirements for the technical strength of production enterprises, so there are fewer enterprises with mass production capacity in the world. Therefore, the research on the preparation of 6N electronic-grade trimethylgallium is imminent. Moreover, the quality of high-purity trimethylgallium products produced by the existing technology is unstable, which is difficult to meet the requirements of the front-line industries such as integrated circuits.

[0005] Therefore, how to develop a production device and method of electronic-grade trimethylgallium is a problem to be solved by those skilled in the art. SUMMARY

[0006] Therefore, the purpose of the present application is to provide a production device and method of electronic-grade trimethylgallium to solve the problems in the prior art.

[0007] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0008] A production device of electronic-grade trimethylgallium comprises a high-purity gallium-magnesium alloy feeder, a tertiary amine solvent storage tank, a rare gas storage tank, a synthesis kettle reactor, a halogenated alkane storage tank, a microfiltration filter, a vacuum rectifying column, a high-temperature decomplexing kettle, a high-efficiency rectifying column, a falling film evaporator and a finished product receiving tank.

[0009] The high-purity gallium-magnesium alloy feeder, the tertiary amine solvent storage tank, the rare gas storage tank, and the halogenated alkane storage tank are respectively connected with the synthesis kettle reactor.

[0010] The synthesis kettle reactor, the microfiltration filter, the vacuum rectifying column, the high-temperature resolving kettle, the high-efficiency rectifying column, the falling film evaporator, and the product receiving tank are sequentially connected.

[0011] The vacuum rectifying column and the high-temperature resolving kettle are respectively connected with the tertiary amine solvent storage tank.

[0012] Further, the electronic-grade trimethylgallium production device further comprises a vacuum rectifying column overhead condenser and a vacuum rectifying column reboiler, and the vacuum rectifying column overhead condenser and the vacuum rectifying column reboiler are respectively connected with the vacuum rectifying column in a circulating manner.

[0013] Further, the electronic-grade trimethylgallium production device further comprises a high-efficiency rectifying column overhead condenser and a high-efficiency rectifying column reboiler, and the high-efficiency rectifying column overhead condenser and the high-efficiency rectifying column reboiler are respectively connected with the high-efficiency rectifying column in a circulating manner.

[0014] A production method of electronic-grade trimethylgallium, which adopts the electronic-grade trimethylgallium production device, and specifically comprises the following steps:

[0015] (1) First, rare gas in the rare gas storage tank is introduced into the synthesis kettle reactor, then high-purity gallium-magnesium alloy in the high-purity gallium-magnesium alloy feeder is added, and then tertiary amine solvent in the tertiary amine solvent storage tank is added, and stirring is performed, and halogenated alkane in the halogenated alkane storage tank is added dropwise for synthesis reaction to obtain material A;

[0016] (2) The material A is transported to the microfiltration filter for microfiltration to remove gallium-magnesium alloy and solid impurities therein, to obtain material B;

[0017] (3) The material B is transported to the vacuum rectifying column for vacuum rectification to remove tertiary amine solvent therein and recycle to the tertiary amine solvent storage tank for circulation, and material C is obtained at the top of the vacuum rectifying column;

[0018] (4) The material C is transported to the high-temperature resolving kettle for resolving to remove tertiary amine solvent therein again and recycle to the tertiary amine solvent storage tank for circulation, to obtain material D;

[0019] (5) The material D is transported to the high-efficiency rectifying column for secondary rectification to remove metal ion compounds therein, and material E is obtained at the top of the high-efficiency rectifying column;

[0020] (6) The material E is transported to the falling film evaporator for evaporation to remove impurities therein, and is sent to the product receiving tank to obtain electronic-grade trimethylgallium.

[0021] Further, in the step (1), the molar ratio of gallium to magnesium in the high-purity gallium-magnesium alloy is 1:(3-6), the particle size is 10-1000 μm; the rare gas is helium, neon or argon; the tertiary amine solvent is triethylamine, dimethylbenzylamine, benzyltrimethylamine or tetramethylguanidine; the haloalkane is bromoethane, chloroethane or iodoethane; the molar ratio of gallium to haloalkane in the high-purity gallium-magnesium alloy is 2:(3-5); the stirring device is a propeller stirring device, and the rotating speed is 30-300 r / min; and the dropping speed of haloalkane is 2-10 drops / s.

[0022] The above further beneficial effect is that the raw materials in the synthesis reaction process are easy to react with the components in the air, so the rare gas is first introduced into the synthesis reactor to replace the air therein and form a rare gas environment, and then the synthesis reaction is continued. In addition, the metallic magnesium in the high-purity gallium-magnesium alloy can promote the smooth progress of the reaction, and in order to ensure the smooth progress of the synthesis reaction, the molar ratio of gallium to magnesium in the high-purity gallium-magnesium alloy should be in the range of 1:(3-6). At the same time, in order to quickly proceed with the synthesis reaction, the particle size of the high-purity gallium-magnesium alloy is controlled in the range of 10-1000 μm.

[0023] Further, in the step (2), the membrane medium of the microfiltration membrane in the microfiltration filter is polypropylene (PP), polyethylene (PE) or polyvinylidene fluoride (PVDF), and the aperture is 0.2 μm; and the operating pressure of the microfiltration is 0.07-0.2 MPa.

[0024] The above further beneficial effect is that the gallium-magnesium alloy which has not completed the reaction and part of the solid impurities are separated from the trimethyl gallium by microfiltration, and the gallium-magnesium alloy is recycled and delivered to the synthesis reactor to continue to participate in the synthesis reaction.

[0025] Further, in the step (3), the absolute pressure of the vacuum rectification is 1-100 mmHg, the reflux ratio is 2-10, the column bottom temperature is 56-150 °C, and the column top reflux temperature is 56-149 °C.

[0026] The above further beneficial effect is that the tertiary amine solvent which does not participate in the reaction in the synthesis reaction is delivered to the tertiary amine solvent storage tank for recycling by the vacuum rectification, and at the same time, the complex of trimethyl gallium and the tertiary amine solvent is distilled out at the column top.

[0027] Further, in the step (4), the pressure of the decomplexation is 20-90 kPa, and the temperature is 150-400 °C.

[0028] The above further beneficial effect is that the combination of trimethyl gallium and the tertiary amine solvent is broken under the conditions of high temperature and low pressure by the decomplexation, the tertiary amine solvent flows out from the bottom of the tank and is delivered to the tertiary amine solvent storage tank for recycling, and at the same time, the gaseous crude trimethyl gallium product is distilled out at the top of the tank.

[0029] Further, in the step (5), the absolute pressure of the secondary rectification is 0.1-0.3 MPa, the reflux ratio is 5-12, the column bottom temperature is 60-100 DEG C, and the column top reflux temperature is 60-97 DEG C.

[0030] The above further beneficial effect is that, by the secondary rectification, the small amount of metal ion compound in the crude trimethyl gallium is removed by the multi-stage contact mass transfer, and the trimethyl gallium is distilled at the column top, and the purity can reach 99.999%.

[0031] Further, in the step (6), the evaporation pressure is 75-90 kPa, and the temperature is 20-30 DEG C.

[0032] The above further beneficial effect is that, by the evaporation, the small amount of impurities is removed by the difference of the mean free path of molecular motion at normal temperature and low pressure, and the purity of the electronic-grade trimethyl gallium product can reach 99.9999%, which is 6N grade.

[0033] According to the above technical solution, compared with the prior art, the beneficial effects of the present application are as follows:

[0034] The present application effectively reduces the content of metal impurities in the trimethyl gallium, and the electronic-grade trimethyl gallium prepared has a purity higher than 99.9999%, which is 6N grade or even higher, and the operation is simple, the reaction is safe and stable, easy to control, the synthesis yield is high, the product loss is small, the technology is mature, no impurities are introduced, and it is beneficial to realize large-scale industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0035] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed in the following embodiment or prior art description will be briefly introduced. Obviously, the drawings in the following description are only embodiments of the present application, and other drawings can be obtained by those skilled in the art without creating laborious work.

[0036] Figure 1 The structure of the electronic-grade trimethyl gallium production device and the process flow chart of the production method thereof.

[0037] Among them, 1-high purity gallium magnesium alloy feeder, 2-tertiary amine solvent storage tank, 3-rare gas storage tank, 4-synthetic kettle reactor, 5-haloalkane storage tank, 6-microfiltration filter, 7-reduced pressure rectification column, 8-reduced pressure rectification column top condenser, 9-reduced pressure rectification column bottom reboiler, 10-high temperature decompounding kettle, 11-high efficiency rectification column, 12-high efficiency rectification column top condenser, 13-high efficiency rectification column bottom reboiler, 14-falling film evaporator, 15-finished product receiving tank. DETAILED DESCRIPTION

[0038] Embodiments of the present application are described below in detail with reference to examples illustrated in the accompanying drawings, wherein the same or similar elements or elements having the same or similar functions are denoted by the same or similar reference numerals throughout. The embodiments described below by reference to the drawings are exemplary and are intended to explain the present application, and cannot be understood as limiting the present application.

[0039] In the description of the present application, it should be understood that the terms "upper", "lower", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the purpose of facilitating the description of the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application.

[0040] In addition, the terms "first", "second" are only for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features. In the description of the present application, the meaning of "a plurality of" is two or more, unless otherwise explicitly specified and limited.

[0041] In the present application, unless otherwise explicitly specified and limited, the terms "mounting", "connection", "connection", "fixing" and the like should be understood broadly, for example, it can be fixed connection, or detachable connection, or integral; it can be mechanical connection, or electrical connection; it can be directly connected, or indirectly connected through intermediate medium, it can be the internal communication of two elements or the interaction relationship between two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0042] In the present application, unless otherwise explicitly specified and limited, the first feature "on" or "under" the second feature can include the first and second features in direct contact, or the first and second features not in direct contact but in contact through another feature between them. Moreover, the first feature "on", "above" and "on" the second feature includes the first feature directly above and obliquely above the second feature, or only indicates that the first feature is higher than the second feature in horizontal height. The first feature "under", "below" and "below" the second feature includes the first feature directly below and obliquely below the second feature, or only indicates that the first feature is lower than the second feature in horizontal height.

[0043] Example 1

[0044] The production device of electronic-grade trimethyl gallium is, for example,Figure 1 As shown, it includes a high-purity gallium-magnesium alloy feeder 1, a tertiary amine solvent storage tank 2, a rare gas storage tank 3, a synthesis reactor 4, a haloalkane storage tank 5, a microfiltration filter 6, a vacuum distillation column 7, a high-temperature decomposition vessel 10, a high-efficiency distillation column 11, a falling film evaporator 14, and a finished product receiving tank 15.

[0045] Among them, the high-purity gallium-magnesium alloy feeder 1, the tertiary amine solvent storage tank 2, the rare gas storage tank 3 and the haloalkane storage tank 5 are respectively connected to the synthesis reactor 4.

[0046] The synthesis reactor 4, microfiltration filter 6, vacuum distillation column 7, high-temperature decomposition vessel 10, high-efficiency distillation column 11, falling film evaporator 14, and finished product receiving tank 15 are connected in sequence.

[0047] The vacuum distillation column 7 and the high-temperature decomposition vessel 10 are respectively connected to the tertiary amine solvent storage tank 2.

[0048] Example 2

[0049] Production facilities for electronic-grade trimethylgallium, such as Figure 1 As shown, it includes a high-purity gallium-magnesium alloy feeder 1, a tertiary amine solvent storage tank 2, a rare gas storage tank 3, a synthesis reactor 4, a haloalkane storage tank 5, a microfiltration filter 6, a vacuum distillation column 7, a vacuum distillation column top condenser 8, a vacuum distillation column bottom reboiler 9, a high-temperature decomposition vessel 10, a high-efficiency distillation column 11, a high-efficiency distillation column top condenser 12, a high-efficiency distillation column bottom reboiler 13, a falling film evaporator 14, and a finished product receiving tank 15;

[0050] Among them, the high-purity gallium-magnesium alloy feeder 1, the tertiary amine solvent storage tank 2, the rare gas storage tank 3 and the haloalkane storage tank 5 are respectively connected to the synthesis reactor 4.

[0051] The synthesis reactor 4, microfiltration filter 6, vacuum distillation column 7, high-temperature decomposition vessel 10, high-efficiency distillation column 11, falling film evaporator 14, and finished product receiving tank 15 are connected in sequence.

[0052] The vacuum distillation column 7 and the high-temperature decomposition vessel 10 are respectively connected to the tertiary amine solvent storage tank 2;

[0053] The vacuum distillation column top condenser 8 and the vacuum distillation column bottom reboiler 9 are respectively connected to the vacuum distillation column 7 in a loop.

[0054] The high-efficiency distillation column top condenser 12 and the high-efficiency distillation column bottom reboiler 13 are respectively connected to the high-efficiency distillation column 11 in a loop.

[0055] Example 3

[0056] Methods for producing electronic-grade trimethylgallium, such as Figure 1As shown, the production device for electronic-grade trimethylgallium of Example 1 is used, and the production process comprises the following steps:

[0057] (1) First, argon with a purity of 99.999% in the noble gas storage tank 3 is introduced into the synthesis reactor 4, 300 s later, high-purity gallium-magnesium alloy with a purity of 99.99%, a gallium-magnesium molar ratio of 1:4, and a particle size of 500 μm in the high-purity gallium-magnesium alloy feeder 1 is added, then dimethyl aniline with a purity of 99.9% in the tertiary amine solvent storage tank 2 is added, the propelling type stirring device of the synthesis reactor 4 is started, stirring is carried out at a rotating speed of 200 r / min, and bromoethane with a purity of 99.5% in the haloalkane storage tank 5 is added dropwise at a dropping speed of 3 drops / s to carry out a synthesis reaction at normal temperature and pressure, the molar ratio of gallium in the high-purity gallium-magnesium alloy to bromoethane is 1:2, after the dropping is completed, 180 s is waited, and material A is obtained;

[0058] (2) The material A is transported to the microfiltration filter 6 with a polyvinylidene fluoride membrane medium and a caliber of 0.2 μm to carry out microfiltration, the operating pressure is 0.15 MPa, the gallium-magnesium alloy and solid impurities therein are removed, and material B is obtained;

[0059] (3) The material B is transported to the vacuum rectifying tower 7 to carry out vacuum rectification, the absolute pressure is 50 mmHg, the reflux ratio is 5, the column still temperature is 95°C, the reflux temperature at the top of the column is 92°C, the dimethyl aniline therein is removed and recovered to the tertiary amine solvent storage tank 2 for recycling, and material C is obtained at the top of the vacuum rectifying tower 7;

[0060] (4) The material C is transported to the high-temperature decompounding kettle 10 to carry out decompounding, the pressure is 90 kPa, the temperature is 180°C, the dimethyl aniline therein is removed again and recovered to the tertiary amine solvent storage tank 2 for recycling, and material D is obtained;

[0061] (5) The material D is transported to the high-efficiency rectifying tower 11 to carry out secondary rectification, the absolute pressure is 0.2 MPa, the reflux ratio is 8, the column still temperature is 80°C, the reflux temperature at the top of the column is 78°C, the metal ion compound therein is removed, and material E is obtained at the top of the high-efficiency rectifying tower 11;

[0062] (6) The material E is transported to the falling-film evaporator 14 to carry out evaporation, the pressure is 90 kPa, the temperature is 25°C, the impurities therein are removed, and the electronic-grade trimethylgallium is obtained and sent to the finished product receiving tank 15.

[0063] Example 4

[0064] The production method of electronic-grade trimethylgallium is as shown in Figure 1 Example 1, and the production process comprises the following steps:

[0065] (1) First, helium gas with a purity of 99.999% is introduced into the rare gas storage tank 3 of the synthesis reactor 4. After 500s, high-purity gallium-magnesium alloy with a purity of 99.998%, a gallium-magnesium molar ratio of 1:5, and a particle size of 800μm is added to the high-purity gallium-magnesium alloy feeder 1. Then, triethylamine with a purity of 99.95% is added to the tertiary amine solvent storage tank 2. The propeller-type stirring device of the synthesis reactor 4 is turned on and stirred at a speed of 240r / min. At the same time, chloroethane with a purity of 99.7% is added dropwise at a dropping rate of 6 drops / s to carry out the synthesis reaction at room temperature and pressure. The molar ratio of gallium to chloroethane in the high-purity gallium-magnesium alloy is 2:5. After the addition is completed, wait for 300s to obtain material A.

[0066] (2) Material A is transported to a microfiltration filter 6 with polyvinylidene fluoride as the membrane medium and a diameter of 0.2 μm for microfiltration. The operating pressure is 0.1 MPa to remove gallium magnesium alloy and solid impurities, and material B is obtained.

[0067] (3) Material B is transported to vacuum distillation column 7 for vacuum distillation. The absolute pressure is 75 mmHg, the reflux ratio is 4, the column bottom temperature is 275℃, and the column top reflux temperature is 274℃. Triethylamine is removed and recycled to tertiary amine solvent storage tank 2 for recycling. Material C is obtained at the top of vacuum distillation column 7.

[0068] (4) Material C is transported to the high-temperature decomposition vessel 10 for decomposition at a pressure of 70 kPa and a temperature of 300 °C. Triethylamine is removed from it and recycled to the tertiary amine solvent storage tank 2 for reuse, resulting in material D.

[0069] (5) The material D is transported to the high-efficiency distillation column 11 for secondary distillation. The absolute pressure is 0.25 MPa, the reflux ratio is 6, the bottom temperature is 90°C, and the top reflux temperature is 88°C to remove the metal ion compounds. Material E is obtained at the top of the high-efficiency distillation column 11.

[0070] (6) The material E is transported to the falling film evaporator 14 for evaporation at a pressure of 75 kPa and a temperature of 25°C to remove impurities and is then sent to the finished product receiving tank 15 to obtain electronic grade trimethylgallium.

[0071] Example 5

[0072] Methods for producing electronic-grade trimethylgallium, such as Figure 1 As shown, the production apparatus for electronic-grade trimethylgallium using Example 1 specifically includes the following steps:

[0073] (1) first, the argon gas with purity of 99.999% in the noble gas storage tank 3 is introduced into the synthesis reactor 4, after 480s, the high purity gallium-magnesium alloy with purity of 99.995%, gallium-magnesium molar ratio of 2:7 and particle size of 600μm in the high purity gallium-magnesium alloy feeder 1 is added, then the tetramethylguanidine with purity of 99.9% in the tertiary amine solvent storage tank 2 is added, the propelling type stirring device of the synthesis reactor 4 is started, the stirring is carried out at a rotating speed of 200r / min, the iodomethane with purity of 99.5% in the halogenated alkane storage tank 5 is added dropwise at a dropping speed of 5 drops / s at normal temperature and pressure to carry out the synthesis reaction, the molar ratio of gallium in the high purity gallium-magnesium alloy to the iodomethane is 1:2, after the dropping is completed, 240s is waited, and material A is obtained;

[0074] (2) the material A is transported to the microfiltration filter 6 with polypropylene as the membrane medium and the aperture of 0.2μm to carry out the microfiltration, the operating pressure is 0.25MPa, the gallium-magnesium alloy and the solid impurities in the material A are removed, and material B is obtained;

[0075] (3) the material B is transported to the vacuum rectifying tower 7 to carry out the vacuum rectification, the absolute pressure is 75mmHg, the reflux ratio is 5, the tower kettle temperature is 178℃, the reflux temperature at the top of the tower is 177℃, the tetramethylguanidine in the material B is removed and recycled to the tertiary amine solvent storage tank 2 for circulation, and the material C is obtained at the top of the vacuum rectifying tower 7;

[0076] (4) the material C is transported to the high-temperature decompounding kettle 10 to carry out the decompounding, the pressure is 75kPa, the temperature is 190℃, the tetramethylguanidine in the material C is removed again and recycled to the tertiary amine solvent storage tank 2 for circulation, and the material D is obtained;

[0077] (5) the material D is transported to the high-efficiency rectifying tower 11 to carry out the secondary rectification, the absolute pressure is 0.3Mpa, the reflux ratio is 7, the tower kettle temperature is 75℃, the reflux temperature at the top of the tower is 73℃, the metal ion compound in the material D is removed, and the material E is obtained at the top of the high-efficiency rectifying tower 11;

[0078] (6) the material E is transported to the falling-film evaporator 14 to carry out the evaporation, the pressure is 85kPa, the temperature is 25℃, the impurities in the material E are removed, and the electronic-grade trimethylgallium is obtained and sent to the finished product receiving tank 15.

[0079] Comparative Example 1

[0080] The Example 7 of the Chinese patent for invention with the application number of 201010600017.2 discloses a method for industrial preparation of trimethylgallium, which specifically comprises the following steps:

[0081] In a reaction kettle filled with nitrogen, put in gallium-magnesium alloy 580g, add anhydrous methyl tetrahydrofuran 2100g, gradually add iodomethane (CH3I) 2050g under stirring, control the solvent refluxing speed by controlling the adding speed of iodomethane (CH3I), after the reaction is completed, continue to maintain refluxing for 4 hours, then evaporate the solvent, obtain the complex of trimethyl gallium and ether under reduced pressure (vacuum degree is between 1-100mmHg), finally decomplex (decomplex temperature is between 70-140℃) to obtain trimethyl gallium 333g, the yield is 81% (calculated according to metallic gallium).

[0082] Comparative Example 2

[0083] Example 1 of Chinese patent application No. 201310280122.6 discloses a method for efficiently and low-cost producing trimethyl gallium, which specifically comprises the following steps:

[0084] In a reaction kettle filled with nitrogen, put in gallium-magnesium alloy 580g, add anhydrous methyl tetrahydrofuran 2100g, gradually add iodomethane (CH3I) 2050g under stirring, control the solvent refluxing speed by controlling the adding speed of iodomethane (CH3I), after the reaction is completed, continue to maintain refluxing for 4 hours, then evaporate the solvent, obtain the complex of trimethyl gallium and ether under reduced pressure (vacuum degree is between 1-100mmHg), finally decomplex (decomplex temperature is between 70-140℃) to obtain trimethyl gallium 333g, the yield is 81% (calculated according to metallic gallium).

[0085] Performance test

[0086] Each of the electronic-grade trimethyl gallium prepared in Examples 3-5 is detected for purity (mass fraction), content of metal elements and other elements, and compared with Comparative Examples 1-2.

[0087] The results are shown in Table 1.

[0088] Table 1 Purity, content of metal elements and other elements of electronic-grade trimethyl gallium in Examples 3-5

[0089]

[0090]

[0091] From Table 1, it can be seen that the purity of the electronic-grade trimethylgallium of the present application in Examples 3-5 is above 99.99996%, which is superior to the prior art.

[0092] The above experiments show that the electronic-grade trimethylgallium prepared by the present application has a purity of above 99.9999%, up to 6N level or even higher, and has the advantages of simple operation, safe and stable reaction, easy control, high synthesis yield, small product loss, mature technology, no introduction of impurities, and being conducive to large-scale industrial production.

[0093] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in the present specification.

[0094] Although the embodiments of the present application have been shown and described above, it should be understood that the above embodiments are exemplary and should not be construed as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above embodiments within the scope of the present application.

Claims

1. A production apparatus for electronic-grade trimethylgallium, characterized in that, The device comprises a high-purity gallium-magnesium alloy feeder, a tertiary amine solvent tank, a rare gas tank, a synthesis kettle reactor, a halogenated alkane tank, a microfiltration filter, a vacuum rectifying tower, a high-temperature resolving kettle, a high-efficiency rectifying tower, a falling film evaporator and a product receiving tank. The high-purity gallium-magnesium alloy feeder, the tertiary amine solvent tank, the rare gas tank and the halogenated alkane tank are connected with the synthesis kettle reactor. The synthesis kettle reactor, the microfiltration filter, the vacuum rectifying tower, the high-temperature resolving kettle, the high-efficiency rectifying tower, the falling film evaporator and the product receiving tank are connected in sequence. The vacuum rectifying tower and the high-temperature resolving kettle are connected with the tertiary amine solvent tank. The molar ratio of gallium to magnesium in the high-purity gallium-magnesium alloy is 1: (3-6), and the particle size is 10-1000 μm. The tertiary amine solvent is triethylamine, dimethyl aniline, benzyl trimethylamine or tetramethyl guanidine. The halogenated alkane is bromoethane, chloroethane or iodoethane. The molar ratio of gallium to halogenated alkane in the high-purity gallium-magnesium alloy is 2: (3-5).

2. The apparatus for producing electronic-grade trimethylgallium according to claim 1, wherein The device further comprises a vacuum rectifying tower overhead condenser and a vacuum rectifying tower kettle reboiler, which are connected with the vacuum rectifying tower in circulation.

3. The apparatus according to claim 1, wherein The device further comprises a high-efficiency rectifying tower overhead condenser and a high-efficiency rectifying tower kettle reboiler, which are connected with the high-efficiency rectifying tower in circulation.

4. A method for producing electronic grade trimethylgallium, characterized by, The device for producing electronic-grade trimethyl gallium as claimed in claim 1 comprises the following steps: (1) First, rare gas in the rare gas tank is introduced into the synthesis kettle reactor, then high-purity gallium-magnesium alloy in the high-purity gallium-magnesium alloy feeder is added, and then tertiary amine solvent in the tertiary amine solvent tank is added, and the mixture is stirred, and halogenated alkane in the halogenated alkane tank is added dropwise for synthesis reaction to obtain material A; The molar ratio of gallium to magnesium in the high-purity gallium-magnesium alloy is 1: (3-6), and the particle size is 10-1000 μm. The tertiary amine solvent is triethylamine, dimethyl aniline, benzyl trimethylamine or tetramethyl guanidine. The halogenated alkane is bromoethane, chloroethane or iodoethane. The molar ratio of gallium to halogenated alkane in the high-purity gallium-magnesium alloy is 2: (3-5). (2) Material A is delivered to the microfiltration filter for microfiltration to remove gallium-magnesium alloy and solid impurities therein to obtain material B; (3) Material B is delivered to the vacuum rectifying tower for vacuum rectification to remove tertiary amine solvent therein and recycle to the tertiary amine solvent tank for circulation, and material C is obtained at the top of the vacuum rectifying tower; (4) Material C is delivered to the high-temperature resolving kettle for resolving to remove tertiary amine solvent therein and recycle to the tertiary amine solvent tank for circulation, and material D is obtained; (5) Material D is delivered to the high-efficiency rectifying tower for secondary rectification to remove metal ion compounds therein, and material E is obtained at the top of the high-efficiency rectifying tower; (6) Material E is delivered to the falling film evaporator for evaporation to remove impurities therein, and is delivered to the product receiving tank to obtain the electronic-grade trimethyl gallium.

5. The method of producing electronic grade trimethylgallium according to claim 4, wherein In step (1), the rare gas is helium, neon or argon; the stirring device is a propeller stirring device, and the rotating speed is 30-300 r / min; the dropping speed of the halogenated alkane is 2-10 drops / s.

6. The method of producing electronic grade trimethylgallium according to claim 4, wherein In step (2), the membrane medium of the microfiltration membrane in the microfiltration filter is polypropylene, polyethylene or polyvinylidene fluoride, and the aperture is 0.2 μm; the operation pressure of the microfiltration is 0.07-0.2 MPa.

7. The method of producing electronic grade trimethyl gallium according to claim 4, wherein In step (3), the absolute pressure of the vacuum rectification is 1-100 mmHg, the reflux ratio is 2-10, the column bottom temperature is 56-150 ℃, and the column top reflux temperature is 56-149 ℃.

8. The method of producing electronic grade trimethyl gallium according to claim 4, wherein In step (4), the pressure of the decomplexation is 20-90 kPa, and the temperature is 150-400 ℃.

9. The method of producing electronic grade trimethyl gallium according to claim 4, wherein In step (5), the absolute pressure of the secondary rectification is 0.1-0.3 MPa, the reflux ratio is 5-12, the column bottom temperature is 60-100 ℃, and the column top reflux temperature is 60-97 ℃.

10. The method of producing electronic grade trimethyl gallium according to claim 4, wherein In step (6), the pressure of the evaporation is 75-90 kPa, and the temperature is 20-30 ℃.

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