Production device and production method of electronic-grade trimethyl gallium

Abstract

The invention discloses a production device and a production method of electronic-grade trimethyl gallium. 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 reduced pressure rectifying tower, a high-temperature demixing kettle, an efficient rectifying tower, a falling film evaporator and a finished product receiving tank. The production method specifically comprises the following steps: (1) introducing a rare gas, adding a high-purity gallium magnesium alloy, adding a tertiary amine solvent, stirring, and dropwise adding halogenated alkane to carry out a synthetic reaction; (2) microfiltration; (3) vacuum rectification; (4) decompounding; (5) secondary rectification; and (6) evaporating. The purity of the prepared electronic-grade trimethyl gallium is higher than 99.9999% and can reach the 6N grade or even higher, operation is easy, the reaction is safe and stable, control is easy, the synthesis yield is high, product loss is small, the technology is mature, impurities are not introduced, and large-scale industrial production can be achieved.

Description

Technical Field

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

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

[0003] Trimethylgallium can be used in metal organic chemical vapor deposition (MOCVD) to prepare semiconductor compounds such as gallium nitride, gallium arsenide, and gallium aluminum arsenide. It 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 using 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 source of metals in the optoelectronic semiconductor materials industry and other fields. It is a basic source material for the production and preparation of new semiconductor optoelectronic compound materials using MOCVD process (i.e. metal organic chemical vapor deposition process) and other process technologies.

[0004] Benefiting from the booming development of downstream integrated circuit, LED, photovoltaic and other industries, the global demand for trimethylgallium continues to grow. The purity of electronic-grade trimethylgallium products must reach 99.9999% (6N). The technical barriers to high-purity trimethylgallium are high, and the technical strength of production enterprises is high. There are relatively few companies with mass production capabilities in the world, and research on the preparation of 6N electronic-grade trimethylgallium is imminent. Moreover, the quality of high-purity trimethylgallium products produced by existing technologies is unstable and it is difficult to meet the requirements of cutting-edge industries such as integrated circuits.

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

[0006] In view of this, an object of the present invention is to provide a production device and a production method of electronic grade trimethylgallium to solve the deficiencies in the prior art.

[0007] In order to achieve the above object, the present invention adopts the following technical solution:

[0008] An electronic grade trimethylgallium production device, comprising a high-purity gallium-magnesium alloy feeder, a tertiary amine solvent storage tank, a rare gas storage tank, a synthesis reactor reactor, a halogenated alkane storage tank, a microfiltration filter, a vacuum distillation tower, a high-temperature decomposition kettle, a high-efficiency distillation tower, a falling film evaporator and a finished product receiving tank;

[0009] Among them, a high-purity gallium-magnesium alloy feeder, a tertiary amine solvent storage tank, a rare gas storage tank and a halogenated alkane storage tank are respectively connected to the synthesis reactor reactor;

[0010] The synthesis kettle reactor, the microfiltration filter, the vacuum distillation tower, the high-temperature decomposition kettle, the high-efficiency distillation tower, the falling film evaporator and the finished product receiving tank are connected in sequence;

[0011] The vacuum distillation tower and the high-temperature decomposition kettle are respectively connected to the tertiary amine solvent storage tank.

[0012] Furthermore, the production device of electronic grade trimethylgallium also includes a vacuum distillation tower top condenser and a vacuum distillation tower bottom reboiler, and the vacuum distillation tower top condenser and the vacuum distillation tower bottom reboiler are respectively connected to the vacuum distillation tower in a cycle.

[0013] Furthermore, the above-mentioned electronic grade trimethylgallium production device also includes a high-efficiency distillation tower top condenser and a high-efficiency distillation tower bottom reboiler, and the high-efficiency distillation tower top condenser and the high-efficiency distillation tower bottom reboiler are respectively connected to the high-efficiency distillation tower cycle.

[0014] A method for producing electronic-grade trimethylgallium, using the above-mentioned production device for electronic-grade trimethylgallium, specifically comprises the following steps:

[0015] (1) First, a rare gas in a rare gas storage tank is introduced into a synthesis reactor reactor, and then a high-purity gallium-magnesium alloy in a high-purity gallium-magnesium alloy feeder is added, and then a tertiary amine solvent in a tertiary amine solvent storage tank is added, and stirred, and at the same time, a halogenated alkane in a halogenated alkane storage tank is added dropwise to carry out a synthesis reaction to obtain material A;

[0016] (2) transporting material A to a microfiltration filter for microfiltration to remove gallium-magnesium alloy and solid impurities therein to obtain material B;

[0017] (3) transporting material B to a vacuum distillation tower for vacuum distillation, removing the tertiary amine solvent therein and recycling it to a tertiary amine solvent storage tank for recycling, and obtaining material C at the top of the vacuum distillation tower;

[0018] (4) transporting material C to a high-temperature dissolution kettle for dissolution, removing the tertiary amine solvent therein again and recycling it to a tertiary amine solvent storage tank for recycling, thereby obtaining material D;

[0019] (5) transporting material D to a high-efficiency distillation tower for secondary distillation to remove metal ion compounds therein, and obtaining material E at the top of the high-efficiency distillation tower;

[0020] (6) Material E is transported to a falling film evaporator for evaporation to remove impurities therein, and then transported to a finished product receiving tank to obtain electronic grade trimethylgallium.

[0021] Furthermore, in the above step (1), 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 rare gas is helium, neon or argon; the tertiary amine solvent is triethylamine, dimethylaniline, benzyltrimethylamine or tetramethylguanidine; the halogenated alkane is ethyl bromide, ethyl chloride or ethyl iodide; the molar ratio of gallium to halogenated alkane in the high-purity gallium-magnesium alloy is 2:(3-5); the stirring device is a propeller stirring device with a rotation speed of 30-300 r / min; and the dripping acceleration of the halogenated alkane is 2-10 drops / s.

[0022] The further beneficial effect of adopting the above method 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 reactor to replace the air therein, forming a rare gas environment, and then continuing the synthesis reaction. In addition, the metal magnesium in the high-purity gallium-magnesium alloy can promote the smooth progress of the reaction. 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 carry out the synthesis reaction, the particle size of the high-purity gallium-magnesium alloy is controlled in the range of 10-1000μm.

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

[0024] A further beneficial effect of the above method is that the gallium-magnesium alloy and some solid impurities that have not completed the reaction are separated from trimethylgallium by microfiltration, and the gallium-magnesium alloy is recovered and transported to the synthesis kettle reactor to continue participating in the synthesis reaction.

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

[0026] A further beneficial effect of the above method is that, through vacuum distillation, the tertiary amine solvent that does not participate in the synthesis reaction flows out from the bottom of the tower and is transported to the tertiary amine solvent storage tank for recycling, while the complex of trimethylgallium and the tertiary amine solvent is evaporated at the top of the tower.

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

[0028] A further beneficial effect of the above method is that, by dissociation, the combination of trimethylgallium and tertiary amine solvent is broken under high temperature and low pressure conditions, the tertiary amine solvent flows out from the bottom of the kettle and is sent to the tertiary amine solvent storage tank for recycling, and at the same time, gaseous oxygen-free trimethylgallium crude product is evaporated at the top of the kettle.

[0029] Furthermore, in the above step (5), the absolute pressure of the secondary distillation is 0.1-0.3 MPa, the reflux ratio is 5-12, the bottom temperature is 60-100°C, and the top reflux temperature is 60-97°C.

[0030] A further beneficial effect of the above method is that a small amount of metal ion compounds in the crude oxygen-free trimethylgallium product is removed by secondary distillation using multi-stage contact mass transfer, and trimethylgallium is distilled out at the top of the tower with a purity of up to 99.999%, which is 5N grade.

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

[0032] A further beneficial effect of the above method is that, by evaporation, a small amount of impurities can be removed by utilizing the difference in the mean free path of molecular motion at room temperature and low pressure, and the purity of the obtained electronic grade trimethylgallium product can reach 99.9999%, which is 6N grade.

[0033] It can be seen from the above technical solution that compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] The invention effectively reduces the content of metal impurities in trimethylgallium, and the purity of the prepared electronic-grade trimethylgallium is higher than 99.9999%, and the purity can reach 6N level or even higher. In addition, the invention has simple operation, safe and stable reaction, easy control, high synthesis yield, low product loss, mature technology, no impurities are introduced, and is conducive to large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0036] Figure 1 It is a structural schematic diagram of an electronic grade trimethylgallium production device and a process flow chart of its production method.

[0037] Among them, 1-high-purity gallium-magnesium alloy feeder, 2-tertiary amine solvent storage tank, 3-rare gas storage tank, 4-synthesis kettle reactor, 5-halogenated alkane storage tank, 6-microfiltration filter, 7-vacuum distillation tower, 8-vacuum distillation tower top condenser, 9-vacuum distillation tower kettle reboiler, 10-high-temperature decomposition kettle, 11-high-efficiency distillation tower, 12-high-efficiency distillation tower top condenser, 13-high-efficiency distillation tower kettle reboiler, 14-falling film evaporator, 15-finished product receiving tank. DETAILED DESCRIPTION

[0038] Embodiments of the present invention are described in detail below, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and should not be construed as limiting the present invention.

[0039] In the description of the present invention, it is necessary to understand that the terms "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc., indicating the orientation or position relationship are based on the orientation or position relationship shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0040] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0041] In the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0042] In the present invention, unless otherwise clearly specified and limited, a first feature being "above" or "below" a second feature may include that the first and second features are in direct contact, or may include that the first and second features are not in direct contact but are in contact through another feature between them. Moreover, a first feature being "above", "above" and "above" a second feature includes that the first feature is directly above and obliquely above the second feature, or simply indicates that the first feature is higher in level than the second feature. A first feature being "below", "below" and "below" a second feature includes that the first feature is directly below and obliquely below the second feature, or simply indicates that the first feature is lower in level than the second feature.

[0043] Example 1

[0044] The production facilities of 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 reactor 4, a halogenated alkane storage tank 5, a microfiltration filter 6, a vacuum distillation tower 7, a high-temperature decomposition kettle 10, a high-efficiency distillation tower 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 halogenated alkane storage tank 5 are respectively connected to the synthesis reactor reactor 4;

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

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

[0048] Example 2

[0049] The production facilities of 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 reactor 4, a halogenated alkane storage tank 5, a microfiltration filter 6, a vacuum distillation tower 7, a vacuum distillation tower top condenser 8, a vacuum distillation tower kettle reboiler 9, a high-temperature decomposition kettle 10, a high-efficiency distillation tower 11, a high-efficiency distillation tower top condenser 12, a high-efficiency distillation tower kettle 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 halogenated alkane storage tank 5 are respectively connected to the synthesis reactor reactor 4;

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

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

[0053] The vacuum distillation tower top condenser 8 and the vacuum distillation tower kettle reboiler 9 are respectively connected to the vacuum distillation tower 7 in a circular manner;

[0054] The high-efficiency distillation tower top condenser 12 and the high-efficiency distillation tower kettle reboiler 13 are respectively connected to the high-efficiency distillation tower 11 in a circular manner.

[0055] Example 3

[0056] Method for producing electronic grade trimethylgallium, such as Figure 1As shown, the production device of electronic grade trimethylgallium in Example 1 specifically includes the following steps:

[0057] (1) First, argon gas with a purity of 99.999% in the rare gas storage tank 3 is introduced into the synthesis reactor reactor 4. After 300 seconds, 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, and then dimethylaniline with a purity of 99.9% in the tertiary amine solvent storage tank 2 is added. The propulsion stirring device of the synthesis reactor reactor 4 is turned on and stirred at a speed of 200 r / min. At the same time, ethyl bromide with a purity of 99.5% in the halogenated alkane storage tank 5 is added dropwise at a dropping speed of 3 drops / s to carry out a synthesis reaction at room temperature and pressure. The molar ratio of gallium to ethyl bromide in the high-purity gallium-magnesium alloy is 1:2. After the dropwise addition is completed, wait for 180 seconds to obtain material A;

[0058] (2) transporting material A to a microfiltration filter 6 having a membrane medium of polyvinylidene fluoride and a caliber of 0.2 μm for microfiltration at an operating pressure of 0.15 MPa to remove gallium-magnesium alloy and solid impurities therein, thereby obtaining material B;

[0059] (3) conveying material B to a vacuum distillation tower 7 for vacuum distillation at an absolute pressure of 50 mmHg, a reflux ratio of 5, a bottom temperature of 95° C., and a top reflux temperature of 92° C. to remove dimethylaniline therein and recover it to a tertiary amine solvent storage tank 2 for recycling, and obtaining material C at the top of the vacuum distillation tower 7;

[0060] (4) Material C is transported to a high-temperature dissolution reactor 10 for dissolution at a pressure of 90 kPa and a temperature of 180° C., and dimethylaniline is removed again and recovered to a tertiary amine solvent storage tank 2 for recycling to obtain material D;

[0061] (5) Material D is transported to a high-efficiency distillation tower 11 for secondary distillation at an absolute pressure of 0.2 MPa, a reflux ratio of 8, a bottom temperature of 80° C., and a top reflux temperature of 78° C. to remove metal ion compounds therein, and obtain material E at the top of the high-efficiency distillation tower 11;

[0062] (6) Material E is transported to a falling film evaporator 14 for evaporation at a pressure of 90 kPa and a temperature of 25° C. to remove impurities therein, and then transported to a finished product receiving tank 15 to obtain electronic grade trimethylgallium.

[0063] Example 4

[0064] Method for producing electronic grade trimethylgallium, such as Figure 1 As shown, the production device of electronic grade trimethylgallium in Example 1 specifically includes the following steps:

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

[0066] (2) transporting material A to a microfiltration filter 6 having a membrane medium of polyvinylidene fluoride and a caliber of 0.2 μm for microfiltration at an operating pressure of 0.1 MPa to remove gallium-magnesium alloy and solid impurities therein, thereby obtaining material B;

[0067] (3) conveying material B to a vacuum distillation tower 7 for vacuum distillation at an absolute pressure of 75 mmHg, a reflux ratio of 4, a bottom temperature of 275° C., and a top reflux temperature of 274° C. to remove triethylamine therein and recover it to a tertiary amine solvent storage tank 2 for recycling, and obtaining material C at the top of the vacuum distillation tower 7;

[0068] (4) Material C is transported to a high temperature dissolution reactor 10 for dissolution at a pressure of 70 kPa and a temperature of 300° C., and triethylamine is removed again and recovered to a tertiary amine solvent storage tank 2 for recycling to obtain material D;

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

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

[0071] Example 5

[0072] Method for producing electronic grade trimethylgallium, such as Figure 1 As shown, the production device of electronic grade trimethylgallium in Example 1 specifically includes the following steps:

[0073] (1) First, argon gas with a purity of 99.999% in the rare gas storage tank 3 is introduced into the synthesis reactor reactor 4. After 480 seconds, high-purity gallium-magnesium alloy with a purity of 99.995%, a gallium-magnesium molar ratio of 2:7, and a particle size of 600 μm in the high-purity gallium-magnesium alloy feeder 1 is added, and then tetramethylguanidine with a purity of 99.9% in the tertiary amine solvent storage tank 2 is added. The propulsion stirring device of the synthesis reactor reactor 4 is turned on and stirred at a speed of 200 r / min. At the same time, iodine with a purity of 99.5% in the halogenated alkane storage tank 5 is added dropwise at a dropping speed of 5 drops / s to carry out a synthesis reaction at room temperature and pressure. The molar ratio of gallium to iodine in the high-purity gallium-magnesium alloy is 1:2. After the dropwise addition is completed, wait for 240 seconds to obtain material A;

[0074] (2) transporting material A to a microfiltration filter 6 having a membrane medium of polypropylene and a caliber of 0.2 μm for microfiltration at an operating pressure of 0.25 MPa to remove gallium-magnesium alloy and solid impurities therein, thereby obtaining material B;

[0075] (3) transporting material B to a vacuum distillation tower 7 for vacuum distillation at an absolute pressure of 75 mmHg, a reflux ratio of 5, a bottom temperature of 178° C., and a top reflux temperature of 177° C., removing tetramethylguanidine therein and recycling it to a tertiary amine solvent storage tank 2 for recycling, and obtaining material C at the top of the vacuum distillation tower 7;

[0076] (4) Material C is transported to a high-temperature dissolution reactor 10 for dissolution at a pressure of 75 kPa and a temperature of 190° C., tetramethylguanidine is removed again and recovered to a tertiary amine solvent storage tank 2 for recycling, to obtain material D;

[0077] (5) Material D is transported to a high-efficiency distillation tower 11 for secondary distillation at an absolute pressure of 0.3 MPa, a reflux ratio of 7, a bottom temperature of 75° C., and a top reflux temperature of 73° C. to remove metal ion compounds therein, and obtain material E at the top of the high-efficiency distillation tower 11;

[0078] (6) Material E is transported to a falling film evaporator 14 for evaporation at a pressure of 85 kPa and a temperature of 25° C. to remove impurities therein, and then transported to a finished product receiving tank 15 to obtain electronic grade trimethylgallium.

[0079] Comparative Example 1

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

[0081] In a reactor filled with nitrogen, 580 g of gallium-magnesium alloy and 2100 g of anhydrous methyltetrahydrofuran were added, and 2050 g of methyl iodide (CH3I) was gradually added under stirring conditions. The solvent reflux rate was controlled by controlling the addition rate of methyl iodide (CH3I). After the reaction was completed, reflux was continued for 4 hours, and then the solvent was evaporated, and then under reduced pressure conditions (vacuum degree between 1 and 100 mmgH), a complex of trimethylgallium and ether was obtained, and finally decomposition (decomposition temperature between 70 and 140°C) was performed to obtain 333 g of trimethylgallium, and the yield was 81% (calculated as metallic gallium).

[0082] Comparative Example 2

[0083] Example 1 of the Chinese invention patent with application number 201310280122.6 discloses a method for producing trimethylgallium with high efficiency and low cost, which specifically includes the following steps:

[0084] In a reactor filled with nitrogen, 22 kg of gallium-magnesium alloy and 200 kg of methyltetrahydrofuran were added, heated to above 30°C under stirring conditions, and 0.5 kg of iodomethane (CH3I) was added. The reaction was initiated and the reaction temperature rose. At this time, methyl chloride (CH3Cl) was continuously introduced to maintain the reaction. The reaction rate was controlled by adjusting the speed of introducing methyl chloride. After the reaction was completed, reflux was continued for 4 hours, and then the solvent was evaporated. Under reduced pressure conditions (vacuum degree of 10-400 mmHg), a complex of trimethylgallium and ether was obtained. The complex of trimethylgallium and ether is transferred to a decomposition kettle, and gradually added to 75kg of tri-n-butylamine under stirring conditions. After the addition is completed, the mixture is heated to reflux and kept under reflux for 2 hours, and methyltetrahydrofuran is distilled off. Then, low-boiling impurities are removed under reduced pressure conditions (vacuum degree is between 1 and 100 mmHg), and the trimethylgallium is decomposed by heating (the decomposition temperature is 80 to 200°C, and the decomposition vacuum degree is 1 to 100 mmHg), and 16.3kg of oxygen-free trimethylgallium is obtained, with a yield of 87% (calculated as metallic gallium). The trimethylgallium is then subjected to high-precision distillation to obtain ultra-high-purity trimethylgallium, with a purity of up to 99.99995% (i.e., 6.5N).

[0085] Performance Testing

[0086] The electronic grade trimethylgallium prepared in Examples 3-5 was respectively tested for purity (mass fraction), metal element and other element contents, and compared with Comparative Examples 1-2.

[0087] The results are shown in Table 1.

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

[0089]

[0090]

[0091] It can be seen from Table 1 that the purity of electronic grade trimethylgallium in Examples 3-5 of the present invention is above 99.99996%, which is better than the prior art.

[0092] The above experiments show that the electronic grade trimethylgallium prepared by the present invention has a purity higher than 99.9999%, and the purity can reach 6N level 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 conducive to large-scale industrial production.

[0093] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine different embodiments or examples described in this specification.

[0094] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A production device for electronic grade trimethylgallium, characterized in that: Including high-purity gallium-magnesium alloy feeder, tertiary amine solvent storage tank, rare gas storage tank, synthesis reactor reactor, halogenated alkane storage tank, microfiltration filter, vacuum distillation tower, high-temperature decomposition kettle, high-efficiency distillation tower, falling film evaporator and finished product receiving tank; 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 to the synthesis reactor reactor; The synthesis kettle reactor, the microfiltration filter, the vacuum distillation tower, the high-temperature decomposition kettle, the high-efficiency distillation tower, the falling film evaporator and the finished product receiving tank are connected in sequence; The vacuum distillation tower and the high-temperature decomposition kettle are respectively connected to the tertiary amine solvent storage tank.

2. The production device of electronic grade trimethylgallium according to claim 1, characterized in that: It also includes a vacuum distillation tower top condenser and a vacuum distillation tower kettle reboiler, and the vacuum distillation tower top condenser and the vacuum distillation tower kettle reboiler are respectively connected to the vacuum distillation tower in a cycle.

3. The production device of electronic grade trimethylgallium according to claim 1, characterized in that: It also includes a high-efficiency distillation tower top condenser and a high-efficiency distillation tower bottom reboiler, and the high-efficiency distillation tower top condenser and the high-efficiency distillation tower bottom reboiler are respectively connected to the high-efficiency distillation tower in a cycle.

4. A method for producing electronic grade trimethylgallium, characterized in that: The production device of electronic grade trimethylgallium as claimed in claim 1 specifically comprises the following steps: (1) First, a rare gas in a rare gas storage tank is introduced into a synthesis reactor reactor, and then a high-purity gallium-magnesium alloy in a high-purity gallium-magnesium alloy feeder is added, and then a tertiary amine solvent in a tertiary amine solvent storage tank is added, and stirred, and at the same time, a halogenated alkane in a halogenated alkane storage tank is added dropwise to carry out a synthesis reaction to obtain material A; (2) transporting material A to a microfiltration filter for microfiltration to remove gallium-magnesium alloy and solid impurities therein to obtain material B; (3) transporting material B to a vacuum distillation tower for vacuum distillation, removing the tertiary amine solvent therein and recycling it to a tertiary amine solvent storage tank for recycling, and obtaining material C at the top of the vacuum distillation tower; (4) transporting material C to a high-temperature dissolution kettle for dissolution, removing the tertiary amine solvent therein again and recycling it to a tertiary amine solvent storage tank for recycling, thereby obtaining material D; (5) transporting material D to a high-efficiency distillation tower for secondary distillation to remove metal ion compounds therein, and obtaining material E at the top of the high-efficiency distillation tower; (6) Material E is transported to a falling film evaporator for evaporation to remove impurities therein, and then transported to a finished product receiving tank to obtain the electronic grade trimethylgallium.

5. The method for producing electronic grade trimethylgallium according to claim 4, characterized in that: In step (1), 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 rare gas is helium, neon or argon; the tertiary amine solvent is triethylamine, dimethylaniline, benzyltrimethylamine or tetramethylguanidine; the halogenated alkane is ethyl bromide, ethyl chloride or ethyl iodide; the molar ratio of gallium to halogenated alkane in the high-purity gallium-magnesium alloy is 2:(3-5); the stirring device is a propeller stirring device with a rotation speed of 30-300 r / min; the dripping acceleration of the halogenated alkane is 2-10 drops / s.

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

7. The method for producing electronic grade trimethylgallium according to claim 4, characterized in that: In step (3), the absolute pressure of the vacuum distillation is 1-100 mmHg, the reflux ratio is 2-10, the bottom temperature is 56-150°C, and the top reflux temperature is 56-149°C.

8. The method for producing electronic grade trimethylgallium according to claim 4, characterized in that: In step (4), the debonding pressure is 20-90 kPa and the temperature is 150-400°C.

9. The method for producing electronic grade trimethylgallium according to claim 4, characterized in that: In step (5), the absolute pressure of the secondary distillation is 0.1-0.3Mpa, the reflux ratio is 5-12, the bottom temperature is 60-100°C, and the top reflux temperature is 60-97°C.

10. The method for producing electronic grade trimethylgallium according to claim 4, characterized in that: In step (6), the evaporation pressure is 75-90 kPa and the temperature is 20-30°C.

Images