Purification device for high-purity tetrakis (dimethylamino) titanium

Abstract

The utility model discloses a purification device for high-purity tetrakis (dimethylamino) titanium. The purification device comprises a first reaction kettle, a second reaction kettle, an intermediate filter, an evaporation tower, a primary rectifying tower and a secondary rectifying tower which are connected in sequence, the first reaction kettle is used for preparing a dimethylamine lithium salt solution, and the second reaction kettle is used for reacting with titanium tetrachloride to generate a crude product; the evaporation tower is used for realizing gas-liquid separation and recovering an n-hexane solvent; the primary rectifying tower removes low-boiling-point impurities, and the secondary rectifying tower removes high-boiling-point impurities; and a final product enters a finished product storage tank after being filtered by a finished product filter. According to the utility model, impurities such as chlorine, oxygen and the like are effectively removed in a manner of combining multi-stage rectification and precision filtration, and the product purity can reach more than 99.999%; a solvent circulating system and a hot water heat source design are adopted, so that the energy consumption and the production cost are reduced; the whole device is compact in structure and simple and convenient to operate, and can meet the strict requirements of the semiconductor ALD / CVD process on the precursor.

Description

TECHNICAL FIELD

[0001] The utility model relates to gas preparation purification technical field, concretely relates to a kind of high-purity four (dimethylamino) titanium's purification device. BACKGROUND

[0002] Four (dimethylamino) titanium (Ti(NMe2)4) is an important metal organic precursor, and is widely used in the deposition process of High-k thin film in semiconductor industry. Because of its good thermal stability and moderate volatility, it is particularly suitable for atomic layer deposition (ALD) technology. However, the purity of Ti(NMe2)4 directly affects the quality of the thin film. If it contains impurities such as chlorine, oxygen and carbon, it will cause the electrical properties of the thin film to decrease, affecting the reliability of the device.

[0003] Currently, the synthesis of Ti(NMe2)4 usually adopts the reaction route of titanium tetrachloride (TiCl4) and lithium dimethylamide (LiNMe2), but this process has many by-products, and solid impurities such as lithium chloride (LiCl) are easily generated during the reaction process, affecting the subsequent purification efficiency; solvent residues are used in the synthesis process, and if not removed completely, it will affect the purity of the final product; the purification process is complex, and the traditional method relies on multiple distillation and adsorption purification, which has a long equipment process, high energy consumption, and it is difficult to stably obtain high-purity (≥99.999%) products; poor equipment compatibility, the existing device cannot accurately control the reaction temperature and pressure, resulting in poor stability between product batches; to overcome the above problems, some improvement schemes have been proposed in the prior art, such as the combined process of multi-stage rectification + ultrafiltration, but the rectification efficiency is low: the conventional rectification column has limited separation effect on light components (such as residual solvents) and heavy components (such as metal impurities); the filtration precision is insufficient, and general filters cannot remove nano-sized particles, affecting the purity of the product; low solvent recovery rate: solvents such as n-hexane are not effectively recycled, increasing production costs.

[0004] Therefore, the utility model provides a kind of high-purity four (dimethylamino) titanium's purification device, the utility model develops a kind of efficient, energy-saving, stable Ti(NMe2)4 purification device to solve the problems such as incomplete removal of impurities, low solvent recovery rate and complex process in the prior art, to meet the demand of semiconductor industry for high-purity precursor. UTILITY MODEL CONTENTS

[0005] The utility model aims to provide a kind of high-purity four (dimethylamino) titanium's purification device to solve the problems such as incomplete removal of impurities, low solvent recovery rate and complex process in the prior art, to meet the demand of semiconductor industry for high-purity precursor.

[0006] To achieve the above-mentioned purpose, the utility model adopts the technical scheme of:

[0007] A kind of purification device of high purity tetra (dimethylamino) titanium, comprising:

[0008] The first reactor (1) is provided with a nitrogen protection interface, a n-butyllithium and n-hexane mixed solution inlet, a dimethylamine liquid inlet and a kettle bottom outlet, and the reaction temperature of the first reactor (1) is controlled to be-10 to-50 ℃.

[0009] The second reactor (2) is connected with the first reactor (1) by a delivery pump (19), and the second reactor (2) is provided with a titanium chloride dropping port, a nitrogen protection interface and a stirrer, and the stirring speed of the stirrer is 200-400 rpm.

[0010] The intermediate filter (6) is connected with the second reactor (2) by a delivery pump (20), and the filter pore size of the intermediate filter (6) is 1-10 microns.

[0011] The evaporation tower (3) is connected with the intermediate filter (6) by a delivery pump (21), and the evaporation tower (3) is provided with an evaporation tower overhead condenser (10) and an evaporation tower overhead receiving tank (13) at the top, and an evaporation tower bottom reboiler (16) at the bottom, and the operating pressure of the evaporation tower (3) is normal pressure, and the reaction temperature is 40-60 ℃.

[0012] The first rectifying tower (4) is connected with the evaporation tower (3) bottom outlet by a delivery pump (23), and the first rectifying tower (4) is provided with a first rectifying tower overhead condenser (11) and a first rectifying tower overhead receiving tank (14) at the top, and a first rectifying tower bottom reboiler (17) at the bottom, and the reaction temperature of the first rectifying tower (4) is 50-70 ℃.

[0013] The second rectifying tower (5) is connected with the first rectifying tower (4) bottom, and the second rectifying tower (5) is provided with a second rectifying tower overhead condenser (12) and a second rectifying tower overhead receiving tank (15) at the top, and a second rectifying tower bottom reboiler (18) at the bottom, and the reaction temperature of the second rectifying tower (5) is 35-55 ℃.

[0014] The finished product filter (7) is connected with the upper side line outlet of the second rectifying tower (5), and the filter pore size of the finished product filter (7) is 0.001-0.01 microns.

[0015] The finished product storage tank (9) is provided with a finished product outlet, and the finished product storage tank (9) is connected with the finished product filter (7).

[0016] Further, the gas phase outlet of the evaporation tower overhead condenser (10) is connected with the first reactor (1) for recycling n-hexane.

[0017] Further, the gas phase outlets of the overhead condensers (11) and (12) of the primary and secondary rectification towers are connected to a waste gas treatment system.

[0018] Further, the heat sources of the bottom reboilers (16), (17) and (18) of the evaporation tower, the primary and secondary rectification towers are hot water.

[0019] Further, the heat sources of the overhead condensers (10), (11) and (12) of the evaporation tower, the primary and secondary rectification towers are circulating water.

[0020] Further, the purification device of the high-purity titanium tetrakis (dimethylamide) further comprises an intermediate tank (8) arranged between the bottom of the evaporation tower (3) and the primary rectification tower (4) and connected through a delivery pump four (22) and a delivery pump five (23).

[0021] Further, the bottom of the secondary rectification tower (5) is provided with a residual liquid treatment system.

[0022] Further, the dimethylamine liquid inlet of the first reaction kettle (1) is connected with a condensing system for condensing dimethylamine gas under the conditions of 0.12-0.15 MPa and -10--20℃ into liquid.

[0023] Due to the above technical scheme, the utility model has the following advantages compared with the prior art:

[0024] 1. The utility model adopts a combined process of multi-stage rectification (light component removal tower + heavy component removal tower) + ultra-precision filtration (0.001-0.01 μm), effectively removes impurities such as chlorine, oxygen and carbon, ensures that the purity of Ti (NMe2) 4 is greater than or equal to 99.999%, and meets the requirements of semiconductor ALD / CVD process; the intermediate filter (1-10 μm) removes particulate matter such as LiCl generated in the reaction in advance, avoids blocking the subsequent equipment, improves the rectification efficiency, improves the product purity, and meets the high-end semiconductor process requirements.

[0025] 2. The overhead condenser of the evaporation tower condenses and circulates the gaseous n-hexane back to the first reaction kettle, realizes efficient recovery of the solvent, reduces the waste of raw materials, and reduces the operating cost; the hot water heat source (bottom reboiler) and the circulating water cold source (overhead condenser) are adopted, the energy consumption is low, and the operation is stable.

[0026] 3. The waste gas treatment system of the utility model centrally processes VOCs (volatile organic compounds) discharged from the overhead of the rectification tower, meets the environmental protection regulations, avoids environmental pollution, meets the requirements of green chemistry, reduces the exposure of materials through closed pipeline transportation, and reduces the safety risk. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the above-mentioned purpose, features and advantages of the present application, the following will be further described in detail in combination with the drawings and specific embodiments. It is obvious that some of the drawings in the following description are some embodiments of the present application, and for those skilled in the art, other drawings can also be prepared without creative labor on the premise that they do not conflict with each other.

[0028] Figure 1 is the process flow chart of the embodiment 1 of the present application;

[0029] 1-First reaction kettle; 2-Second reaction kettle; 3-Evaporation tower; 4-First rectifying tower; 5-Second rectifying tower; 6-Intermediate filter; 7-Finished product filter; 8-Intermediate tank; 9-Finished product storage tank; 10-Evaporation tower overhead condenser; 11-First rectifying tower overhead condenser; 12-Second rectifying tower overhead condenser; 13-Evaporation tower overhead receiving tank; 14-First rectifying tower overhead receiving tank; 15-Second rectifying tower overhead receiving tank; 16-Evaporation tower bottom reboiler; 17-First rectifying tower bottom reboiler; 18-Second rectifying tower bottom reboiler; 19-Conveying pump one; 20-Conveying pump two; 21-Conveying pump three; 22-Conveying pump four; 23-Conveying pump five. DETAILED DESCRIPTION

[0030] In order to more clearly illustrate the above-mentioned purpose, features and advantages of the present application, the following will be further described in detail in combination with the drawings and specific embodiments. It is obvious that some of the drawings in the following description are some embodiments of the present application, and for those skilled in the art, other drawings can also be prepared without creative labor on the premise that they do not conflict with each other.

[0031] In the following description, many specific details are set forth in order to provide a thorough understanding of the present application, but the present application can also be implemented in other ways different from those described herein, therefore, the protection scope of the present application is not limited by the specific embodiments disclosed below.

[0032] Embodiment 1

[0033] Referring to the drawings, Figure 1 The embodiment provides a purification device for high-purity tetra (dimethylamino) titanium, which comprises:

[0034] The first reaction kettle (1) is provided with a nitrogen protection interface, a n-butyl lithium and n-hexane mixed solution inlet, a dimethylamine liquid inlet and a kettle bottom outlet, and the reaction temperature of the first reaction kettle (1) is controlled to be-30 DEG C.

[0035] The second reactor (2) is connected with the first reactor (1) through a delivery pump (19), and is provided with a titanium tetrachloride dropping port, a nitrogen protection interface and a stirrer, wherein the stirring speed of the stirrer is 300 rpm;

[0036] The intermediate filter (6) is connected with the second reactor (2) through a delivery pump (20), and the filter pore size of the intermediate filter (6) is 1-10 microns;

[0037] The evaporation tower (3) is connected with the intermediate filter (6) through a delivery pump (21), and the evaporation tower (3) is provided with an evaporation tower overhead condenser (10) and an evaporation tower overhead receiving tank (13) at the top, and is provided with an evaporation tower bottom reboiler (16) at the bottom, wherein the operating pressure of the evaporation tower (3) is normal pressure, and the reaction temperature is 50℃;

[0038] The primary rectifying tower (4) is connected with the evaporation tower (3) bottom outlet through a delivery pump (23), and the primary rectifying tower (4) is provided with a primary rectifying tower overhead condenser (11) and a primary rectifying tower overhead receiving tank (14) at the top, and is provided with a primary rectifying tower bottom reboiler (17) at the bottom, wherein the reaction temperature of the primary rectifying tower (4) is 60℃;

[0039] The secondary rectifying tower (5) is connected with the primary rectifying tower (4) bottom, and the secondary rectifying tower (5) is provided with a secondary rectifying tower overhead condenser (12) and a secondary rectifying tower overhead receiving tank (15) at the top, and is provided with a secondary rectifying tower bottom reboiler (18) at the bottom, wherein the reaction temperature of the secondary rectifying tower (5) is 45℃;

[0040] The finished product filter (7) is connected with the upper side line outlet of the secondary rectifying tower (5), and the filter pore size of the finished product filter (7) is 0.001-0.01 microns;

[0041] The finished product storage tank (9) is provided with a finished product outlet, and is connected with the finished product filter (7);

[0042] Further, the gas phase outlet of the evaporation tower overhead condenser (10) is connected with the first reactor (1) for recycling n-hexane;

[0043] Further, the gas phase outlets of the primary rectifying tower overhead condenser (11) and the secondary rectifying tower overhead condenser (12) are connected to a waste gas treatment system;

[0044] Further, the heat sources of the evaporation tower bottom reboiler (16), the primary rectifying tower bottom reboiler (17) and the secondary rectifying tower bottom reboiler (18) are all hot water;

[0045] Furthermore, the cold source for the evaporator top condenser (10), the first-stage distillation column top condenser (11), and the second-stage distillation column top condenser (12) is circulating water;

[0046] Furthermore, the purification device for high-purity tetra(dimethylamino)titanium also includes an intermediate tank (8), which is located between the bottom of the evaporation tower (3) and the primary distillation tower (4), and is connected by a fourth transfer pump (22) and a fifth transfer pump (23).

[0047] Furthermore, the bottom of the secondary distillation column (5) is equipped with a residual liquid treatment system;

[0048] Furthermore, the dimethylamine liquid inlet of the first reactor (1) is connected to a condensation system for condensing dimethylamine gas into liquid under conditions of 0.14 MPa and -15°C.

[0049] In summary, this invention employs a multi-stage distillation process (light weight removal tower + heavy weight removal tower) combined with ultra-precision filtration (0.001–0.01 μm) to effectively remove impurities such as chlorine, oxygen, and carbon, ensuring a Ti(NMe2)4 purity ≥ 99.999%, meeting the requirements of semiconductor ALD / CVD processes. An intermediate filter (1–10 μm) pre-removes particulate matter such as LiCl generated during the reaction, preventing clogging of subsequent equipment, improving distillation efficiency, and increasing product purity to meet the demands of high-end semiconductor processes. The evaporator top condenser condenses and recycles gaseous n-hexane back to the first reaction vessel, achieving efficient solvent recovery, reducing raw material waste, and lowering operating costs. The use of a hot water heat source (bottom reboiler) and a circulating water cooling source (top condenser) results in low energy consumption and stable operation. The waste gas treatment system centrally treats VOCs (volatile organic compounds) discharged from the top of the distillation tower, complying with environmental regulations, avoiding environmental pollution, and meeting green chemistry requirements. Closed-loop pipeline transportation reduces material exposure and lowers safety risks.

[0050] In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to fixed connections, detachable connections, or integral connections; they can refer to mechanical connections or electrical connections; they can refer to direct connections or indirect connections through an intermediate medium; and they can refer to the internal communication between two components. Those skilled in the art will understand the specific meaning of the above terms in this application based on the specific circumstances.

[0051] The above description of disclosed embodiments enables one of ordinary skill in the art to make or use the application. Various modifications to the above described embodiments will be readily apparent to those of ordinary skill in the art and the generic principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A purification apparatus for high purity tetra(dimethylamino)titanium, characterized by comprising: The application relates to a preparation method of dimethylamine. The first reaction kettle (1) is provided with a nitrogen protection interface, a n-butyl lithium and n-hexane mixed solution inlet, a dimethylamine liquid inlet and a kettle bottom outlet, the reaction temperature of the first reaction kettle (1) is controlled to be -10 to -50 DEG C; The second reaction kettle (2) is connected with the first reaction kettle (1) through a conveying pump one (19), the second reaction kettle (2) is provided with a titanium tetrachloride dropping opening, a nitrogen protection interface and a stirrer, the stirring speed of the stirrer is 200 to 400 rpm; The intermediate filter (6) is connected with the second reaction kettle (2) through a conveying pump two (20), the filter aperture of the intermediate filter (6) is 1 to 10 microns; The evaporation tower (3) is connected with the intermediate filter (6) through a conveying pump three (21), the evaporation tower (3) is provided with an evaporation tower overhead condenser (10) and an evaporation tower overhead receiving tank (13) at the top, the evaporation tower (3) is provided with an evaporation tower bottom reboiler (16) at the bottom, the operation pressure of the evaporation tower (3) is normal pressure, and the reaction temperature is 40 to 60 DEG C; The primary rectifying tower (4) is connected with the evaporation tower (3) bottom outlet through a conveying pump five (23), the primary rectifying tower (4) is provided with a primary rectifying tower overhead condenser (11) and a primary rectifying tower overhead receiving tank (14) at the top, the primary rectifying tower (4) is provided with a primary rectifying tower bottom reboiler (17) at the bottom, and the reaction temperature of the primary rectifying tower (4) is 50 to 70 DEG C; The secondary rectifying tower (5) is connected with the primary rectifying tower (4) bottom, the secondary rectifying tower (5) is provided with a secondary rectifying tower overhead condenser (12) and a secondary rectifying tower overhead receiving tank (15) at the top, the secondary rectifying tower (5) is provided with a secondary rectifying tower bottom reboiler (18) at the bottom, and the reaction temperature of the secondary rectifying tower (5) is 35 to 55 DEG C; The finished product filter (7) is connected with the upper side line outlet of the secondary rectifying tower (5), and the filter aperture of the finished product filter (7) is 0.001 to 0.01 microns; The finished product storage tank (9) is provided with a finished product outlet and is connected with the finished product filter (7).

2. The purification apparatus for high purity tetra (dimethylamino) titanium according to claim 1, wherein The gas phase outlet of the evaporation tower overhead condenser (10) is connected with the first reaction kettle (1) and is used for recovering n-hexane.

3. The purification apparatus for high purity titanium tetra( dimethylamide) according to claim 1, wherein The gas phase outlets of the primary rectifying tower overhead condenser (11) and the secondary rectifying tower overhead condenser (12) are connected to a waste gas treatment system.

4. The purification apparatus for high purity titanium tetra( dimethylamide) according to claim 1, wherein The heat sources of the evaporation tower bottom reboiler (16), the primary rectifying tower bottom reboiler (17) and the secondary rectifying tower bottom reboiler (18) are all hot water.

5. The purification apparatus for high purity tetra (dimethylamino) titanium according to claim 1, wherein The cold sources of the evaporation tower overhead condenser (10), the primary rectifying tower overhead condenser (11) and the secondary rectifying tower overhead condenser (12) are all circulating water.

6. The purification apparatus for high purity tetra (dimethylamino) titanium according to claim 1, wherein An intermediate tank (8) is further arranged between the evaporation tower (3) bottom and the primary rectifying tower (4) and is connected through a conveying pump four (22) and a conveying pump five (23).

7. The purification apparatus for high purity titanium tetra( dimethylamide) according to claim 1, wherein The secondary rectifying tower (5) bottom is provided with a residual liquid treatment system.

8. The purification apparatus for high purity titanium tetra( dimethylamide) according to claim 1, wherein The dimethylamine liquid inlet of the first reaction kettle (1) is connected with a condensation system and is used for condensing dimethylamine gas under the conditions of 0.12 to 0.15 MPa and -10 to -20 DEG C into liquid.

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