CN109569003B - Purification method of trimethylaluminum crude product - Google Patents
Purification method of trimethylaluminum crude product Download PDFInfo
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- CN109569003B CN109569003B CN201811651156.0A CN201811651156A CN109569003B CN 109569003 B CN109569003 B CN 109569003B CN 201811651156 A CN201811651156 A CN 201811651156A CN 109569003 B CN109569003 B CN 109569003B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
Abstract
The invention discloses a method for purifying a trimethylaluminum crude product, which improves the internal structure of a tower of a traditional rectifying tower, replaces a tower plate structure with a concentric column with a micro-channel structure, and enables rising gas to flow down along two spiral grooves after being condensed, so that the two phases are contacted more fully due to the structure, and the rectifying process has high separation efficiency by strengthening the gas-liquid mass transfer and heat transfer processes of the two phases, thereby obtaining high-purity trimethylaluminum.
Description
Technical Field
The invention belongs to the technical field of microelectronic materials, and particularly relates to a method for purifying a trimethylaluminum crude product.
Background
High-purity trimethylaluminum belongs to a high-purity metal organic compound, is a key supporting raw material for preparing a compound semiconductor film material by utilizing an advanced Metal Organic Chemical Vapor Deposition (MOCVD) process or an atomic layer deposition film technology (ALD), and is widely applied to the fields of LED equipment, a new-generation solar cell, a phase change memory, a semiconductor laser, an infrared detector, a super computer and the like.
As a raw material of microelectronic materials, a precursor of aluminum nitride has a relatively high requirement on the purity of trimethylaluminum of 99.9999 percent or even 99.99999 percent, relatively more impurities and a small difference with the boiling point, so great difficulty is brought to separation and purification, which is often a bottleneck restricting the product quality and is also a reason for generating a gap with foreign product performance. Furthermore, because trimethylaluminum is polymerized and decomposed due to long-term high-temperature heating, the process which is quite difficult to separate and purify is more complicated. The method commonly used at present is to use a rectifying tower for purification, which must meet the requirements of providing enough theoretical plates and having low tower pressure drop so as to reduce the temperature of a tower kettle.
The plate column is not suitable for high-purity rectification of trimethylaluminum due to liquid holdup, large pressure drop, long retention time and the like, and the packed column has simple structure and small resistance, so that the research and development of novel efficient packing in recent years become a conventional purification method. In order to obtain higher product purity, the pressure drop and the distribution uniformity of the gas also need to be optimized, and various novel efficient fillers have higher cost and relatively larger liquid holdup.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for purifying a trimethylaluminum crude product, which comprises the following steps:
(1) transferring the trimethylaluminum crude product into a rectifying still by the micro-channel rectifying tower through inert gas exchange;
(2) after the material is transferred, closing the feed valve, and rectifying, wherein the rectifying pressure is as follows: 0.02-0.1 MPa, rectification temperature: 80-128 ℃.
(3) And intercepting the distilled material with the boiling point of 125-127 ℃ under the standard atmospheric pressure, and collecting by using a cold trap to obtain the high-purity trimethylaluminum product.
Furthermore, the purity of the trimethyl aluminum crude product is more than 99.9%.
Further, the microchannel rectifying tower has the structure that:
1) the distillation column in the rectifying tower is in a structure of two concentric columns, and a gap is arranged between the two columns;
2) the inner wall of the outer pipe and the outer wall of the inner pipe of the concentric column are both provided with spiral grooves;
3) the gap between the two concentric columns is a microchannel of the rectifying tower, and the widths of the gaps of the microchannels are the same.
Furthermore, the two concentric column tubes in the microchannel rectifying tower are made of stainless steel, tantalum alloy steel and the like.
Furthermore, the inner wall of the outer pipe and the outer wall of the inner pipe of the concentric column in the microchannel rectifying tower are both provided with spiral grooves, the thread depth, the spiral angle and the thread head number of the spiral grooves on the inner wall of the outer pipe and the outer wall of the inner pipe are the same, and the directions are staggered.
Further, the thread depth of the spiral groove is 100 mu m-3mm, the helix angle is 15-60 degrees, and the number of thread heads is 1-5.
Further, the gap width of the micro-channel is 500 μm-5 mm.
Furthermore, the obtained high-purity trimethylaluminum product is more than 7N (99.99999 percent).
The gaps between the inner wall of the outer pipe and the outer wall of the inner pipe of the whole concentric column of the microchannel rectifying tower are the same, the gaps between the inner pipe and the outer pipe are 500 mu m-5mm, and the heat exchange area can be increased by expanding the surface heat exchange surface in a mode of adopting a small-diameter pipe and a spiral groove; when liquid flows downwards from the vertical flow of the condensation pipe, the liquid flows in the pipe and is guided by the spiral grooves, so that the fluid close to the wall surface flows along the axial direction of the wall surface, and the ascending steam ascends along the zigzag shape of the gap between the inner wall of the outer pipe and the outer wall of the inner pipe of the concentric column, thereby being beneficial to reducing the thickness of the boundary layer and reducing the thermal resistance. The spiral grooves on the pipe wall obviously improve the heat transfer coefficient inside and outside the pipe in the heat transfer process, and play a role in bilateral reinforcement. The heat transfer capacity is improved more than the resistance increases. Compared with other special-shaped pipes and glass pipes, the stainless steel and the tantalum alloy steel have the advantages of good comprehensive performance, corrosion resistance and formability, simple manufacturing process and convenient processing.
In order to maintain lower pressure drop and retention of liquid, the thread pitch, the thread depth, the helix angle and the thread head number of the spiral grooves on the inner wall of the outer pipe and the outer wall of the inner pipe are the same and are staggered in direction.
The invention improves the internal structure of the traditional rectifying tower, the tower plate structure is replaced by a concentric column with a micro-channel structure, the ascending gas flows down along two spiral grooves after being condensed, the structure ensures that two phases are contacted more fully, and the rectifying process has high separation efficiency by strengthening the gas-liquid mass transfer and heat transfer processes, so that the purity of the trimethylaluminum is further improved and can reach more than 7N (99.99999%).
Drawings
FIG. 1 is a schematic structural view of a microchannel rectification column according to the present invention.
Detailed Description
The following is a detailed description with reference to examples:
example 1
A purification method of a trimethylaluminum crude product comprises the following steps:
(1) transferring a trimethylaluminum crude product (with the purity of 99.93%) into a rectifying still by the micro-channel rectifying tower through inert gas exchange;
(2) after the material is transferred, closing the feed valve, and rectifying, wherein the rectifying pressure is as follows: 0.02MPa, rectification temperature: 80 ℃.
(3) And intercepting the distilled material with the boiling point of 125-127 ℃ under the standard atmospheric pressure, and collecting by using a cold trap to obtain the high-purity trimethylaluminum product. The purity of trimethylaluminum obtained by the method of this example was calculated to be 7.0N (99.99999%) by ICP-MS and NMR detection.
The micro-channel rectifying tower has the following structure: the distillation column in the rectifying tower is of a two-concentric-column structure (an inner pipe 2 and an outer pipe 3), the two-concentric-column pipe body is made of stainless steel, and a gap is formed between the two columns; the inner wall of the outer tube 3 and the outer wall of the inner tube 2 of the concentric column are both provided with spiral grooves 5, the thread depth of the spiral grooves on the inner wall of the outer tube and the outer wall of the inner tube is 100 mu m, the helical angle is 15 degrees, the number of threads is single, and the directions are staggered; the gap between the two concentric columns is the micro-channel 4 of the rectifying tower, the width of the gap of the micro-channel 4 is the same and is 500 μm, the length of the concentric column tube is 100cm,
example 2
A method for purifying a trimethylaluminum crude product is characterized by comprising the following steps:
(1) the microchannel rectifying tower is subjected to inert gas exchange, so that the atmosphere with ultra-low water and oxygen content is kept in the tower, and a trimethyl aluminum crude product (with the purity of 99.93%) is transferred into a rectifying kettle in a slight vacuum manner;
(2) after the material is transferred, closing the feed valve, and rectifying, wherein the rectifying pressure is as follows: rectification temperature of 0.05 MPa: at 100 ℃.
(3) And intercepting the distilled material with the boiling point of 125-127 ℃ under the standard atmospheric pressure, and collecting by using a cold trap to obtain the high-purity trimethylaluminum product. The purity of trimethylaluminum obtained by the method of this example was calculated to be 7.3N (99.999993%) by ICP-MS and NMR detection.
The micro-channel rectifying tower has the following structure: the distillation column in the rectifying tower is of a two-concentric-column structure (an inner tube 2 and an outer tube 3), the two concentric-column tube bodies are made of tantalum alloy steel materials, and a gap is formed between the two columns; the inner wall of the outer pipe 3 and the outer wall of the inner pipe 2 of the concentric column are both provided with spiral grooves 5, the thread depth of the spiral grooves on the inner wall of the outer pipe and the outer wall of the inner pipe is 1mm, the helical angle is 45 degrees, the number of thread heads is 2, and the directions are staggered; the gap between the two concentric columns is a micro-channel 4 of the rectifying tower, and the width of the gap of the micro-channel 4 is the same and is 2 mm. The concentric cylinder tube is 100cm long.
Example 3
A purification method of a trimethylaluminum crude product comprises the following steps:
(1) the microchannel rectifying tower is subjected to inert gas exchange, so that the atmosphere with ultra-low water and oxygen content is kept in the tower, and a trimethyl aluminum crude product (with the purity of 99.93%) is transferred into a rectifying kettle in a slight vacuum manner;
(2) after the material is transferred, closing the feed valve, and carrying out rectification at the temperature: 128 ℃, rectification pressure: 0.1 MPa.
(3) And intercepting the distilled material with the boiling point of 125-127 ℃ under the standard atmospheric pressure, and collecting by using a cold trap to obtain the high-purity trimethylaluminum product. The purity of trimethylaluminum obtained by the method of this example was calculated to be 7.2N (99.999992%) by ICP-MS and NMR detection.
The micro-channel rectifying tower has the following structure: the distillation column in the rectification tower is of a two-concentric-column structure, the two concentric-column pipes are made of stainless steel materials, and a gap is formed between the two columns; the inner wall of the outer pipe and the outer wall of the inner pipe of the concentric column are both provided with spiral grooves, the thread depth of the spiral grooves on the inner wall of the outer pipe and the outer wall of the inner pipe is 3mm, the helical angle is 60 degrees, the number of thread heads is 5, and the directions are staggered; the gap between the two concentric columns is a micro-channel of the rectifying tower, and the width of the gap of the micro-channel is the same and is 5 mm. The concentric cylinder tube is 100cm long.
Comparative example 1
Experiments show that the purity of the product trimethylaluminum obtained by adopting the concentric column double-spiral groove structure is higher than that of the product trimethylaluminum obtained by adopting the single-spiral groove structure, therefore, the spiral groove structure of the single-layer distillation column is made as a comparison test, and the micro-channel distillation column structure of the comparative example is as follows: the distillation column in the rectifying tower is of a two-concentric-column structure (an inner tube 2 and an outer tube 3), the tube bodies of the two concentric columns are made of stainless steel materials, and a gap is formed between the two columns; the inner wall of the outer tube 3 of the concentric column is provided with a spiral groove 5, the outer wall of the inner tube 2 is of a smooth structure, and the thread depth, the spiral angle and the number of thread heads of the spiral groove on the inner wall of the outer tube are completely the same as those of the inner wall of the outer tube in the embodiment 2; the gap between the two concentric columns is a micro-channel 4 of the rectifying tower, and the width of the gap of the micro-channel 4 is the same and is 2 mm. The concentric cylinder tube is 100cm long.
The method for purifying the trimethylaluminum crude product by using the micro-channel rectifying tower comprises the following steps:
(1) the microchannel rectifying tower is subjected to inert gas exchange, so that the atmosphere with ultra-low water and oxygen content is kept in the tower, and a trimethyl aluminum crude product (with the purity of 99.93%) is transferred into a rectifying kettle in a slight vacuum manner;
(2) after the material is transferred, closing the feed valve, and rectifying, wherein the rectifying pressure is as follows: 0.05MPa, rectification temperature: at 100 deg.C.
(3) And intercepting the distilled material with the boiling point of 125-127 ℃ under the standard atmospheric pressure, and collecting by using a cold trap to obtain the high-purity trimethylaluminum product. The purity of trimethylaluminum obtained by the method of this example was calculated to be 5.4N (99.9994%) by ICP-MS and NMR detection.
Comparative example 2
A distillation column without a spiral groove structure is manufactured as a comparative test, and the micro-channel distillation column of the comparative example has the following structure: the distillation column in the rectifying tower is of a two-concentric-column structure (an inner tube 2 and an outer tube 3), the tube bodies of the two concentric columns are made of stainless steel materials, and a gap is formed between the two columns; the inner wall of the outer pipe 3 and the outer wall of the inner pipe 2 of the concentric columns are both of smooth structures, the gap between the two concentric columns is a micro-channel 4 of the rectifying tower, and the widths of the gaps of the micro-channel 4 are the same and are both 2 mm. The concentric cylinder tube is 100cm long.
The method for purifying the trimethylaluminum crude product by using the micro-channel rectifying tower comprises the following steps:
(1) the microchannel rectifying tower is subjected to inert gas exchange, so that the atmosphere with ultra-low water and oxygen content is kept in the tower, and a trimethyl aluminum crude product (with the purity of 99.93%) is transferred into a rectifying kettle in a slight vacuum manner;
(2) after the material is transferred, closing the feed valve, and rectifying, wherein the rectifying pressure is as follows: 0.05MPa, rectification temperature: at 100 ℃.
(3) And intercepting the distilled material with the boiling point of 125-127 ℃ under the standard atmospheric pressure, and collecting by using a cold trap to obtain the high-purity trimethylaluminum product. The purity of trimethylaluminum obtained by the method of this example was calculated to be 5.8N (99.9998%) by ICP-MS and NMR detection.
Comparative example 3
The self-made single-tube distillation column is used as a comparison test, and the rectifying tower structure of the comparison example is as follows: the distillation column of the distillation column is of a single-tube structure, the tube body of the distillation column is made of stainless steel materials, the inner wall of the tube is provided with spiral grooves, and the thread depth, the spiral angle and the number of thread heads of the spiral grooves on the inner wall of the tube are completely the same as those of the spiral grooves on the inner wall of the outer tube in the embodiment 2. The concentric cylinder tube is 100cm long.
The method for purifying the trimethylaluminum crude product by using the rectifying tower in the comparative example comprises the following steps:
(1) the rectifying tower is subjected to inert gas exchange, so that the atmosphere with ultra-low water and oxygen content is kept in the tower, and a trimethyl aluminum crude product (with the purity of 99.93%) is transferred into a rectifying kettle in a slight vacuum manner;
(2) after the material is transferred, closing the feed valve, and rectifying, wherein the rectifying pressure is as follows: 0.05MPa, rectification temperature: at 100 deg.C.
(3) And intercepting the distilled material with the boiling point of 125-127 ℃ under the standard atmospheric pressure, and collecting by using a cold trap to obtain the high-purity trimethylaluminum product. The purity of trimethylaluminum obtained by the method of this example was calculated to be 4.5N (99.995%) by ICP-MS and NMR detection.
The technical solutions provided by the present invention are described in detail above, and for those skilled in the art, the ideas according to the embodiments of the present invention may be changed in the specific implementation manners and the application ranges, and in summary, the content of the present description should not be construed as limiting the present invention.
Claims (6)
1. A method for purifying a trimethylaluminum crude product is characterized by comprising the following steps:
(1) the microchannel rectifying tower is subjected to inert gas exchange, so that the atmosphere with ultra-low water and oxygen content is kept in the tower, and the trimethylaluminum crude product is transferred to a rectifying kettle;
(2) after the material is transferred, closing the feed valve, and rectifying, wherein the rectifying pressure is as follows: 0.02-0.1 MPa, rectification temperature: 80-128 ℃;
(3) intercepting distilled materials with the boiling point of 125-127 ℃ under the standard atmospheric pressure, and collecting by using a cold trap to obtain a high-purity trimethylaluminum product;
the micro-channel rectifying tower has the following structure:
1) the distillation column in the rectifying tower is in a structure of two concentric columns, and a gap is arranged between the two columns;
2) the inner wall of the outer pipe and the outer wall of the inner pipe of the concentric column are both provided with spiral grooves;
3) the gap between the two concentric columns is a microchannel of the rectifying tower, and the widths of the gaps of the microchannels are the same.
2. The method for purifying a trimethylaluminum crude product according to claim 1, wherein the purity of the trimethylaluminum crude product is 99.9% or higher.
3. The method for purifying the crude product of trimethylaluminum as set forth in claim 1, wherein the two concentric column tubes inside the microchannel rectification column are made of stainless steel or tantalum alloy steel.
4. The method for purifying a trimethylaluminum crude product as set forth in claim 1, wherein the inner wall of the outer tube and the outer wall of the inner tube of the concentric column inside the microchannel rectification column are both provided with helical grooves, and the helical grooves of the inner wall of the outer tube and the outer wall of the inner tube have the same pitch, the same depth, the same helix angle and the same number of thread starts, and have alternating directions.
5. The method for purifying a crude trimethylaluminum product as set forth in claim 1, wherein the width of the gap of the microchannel is 500 μm to 5 mm.
6. The method for purifying a trimethylaluminum crude product according to claim 1, wherein the obtained high-purity trimethylaluminum product is 7N (99.99999%) or more.
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| NL107050C (en) * | 1956-03-15 | |||
| US4490104A (en) * | 1982-11-22 | 1984-12-25 | Borg-Warner Chemicals, Inc. | Apparatus for separating a low viscosity material from a high _viscosity material |
| US20100282680A1 (en) * | 2009-05-06 | 2010-11-11 | University Of Central Florida Research Foundation, Inc. | Superhydrophobic membrane distillation for water purification |
| CN205216250U (en) * | 2015-12-24 | 2016-05-11 | 河北荣特化工有限公司 | Rectifier unit of using in crude benzene hydrogenation production technology |
| CN108371826A (en) * | 2018-05-07 | 2018-08-07 | 金溪遥遥领先高科有限公司 | A kind of distillation column equipment |
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|---|---|---|---|---|
| GB594900A (en) * | 1944-06-20 | 1947-11-21 | Distillation Products Inc | Improvement in high vacuum distillation process and apparatus |
| CN101126564A (en) * | 2007-06-15 | 2008-02-20 | 清华大学 | Gas-liquid separation type sleeve evaporator |
| CN101555059A (en) * | 2009-05-05 | 2009-10-14 | 西安交通大学 | Porous evaporation wall device used for supercritical water treatment of waste organic matters |
| CN104353259A (en) * | 2014-11-04 | 2015-02-18 | 李桂芳 | Combined rectifying column and application thereof |
| CN108579116A (en) * | 2018-07-03 | 2018-09-28 | 衢州市鼎盛化工科技有限公司 | A kind of bead tube, rectifying column and rectifying plate |
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