CN108178185B - A kind of production method of ultra-high purity titanium tetrachloride - Google Patents
A kind of production method of ultra-high purity titanium tetrachloride Download PDFInfo
- Publication number
- CN108178185B CN108178185B CN201810120467.8A CN201810120467A CN108178185B CN 108178185 B CN108178185 B CN 108178185B CN 201810120467 A CN201810120467 A CN 201810120467A CN 108178185 B CN108178185 B CN 108178185B
- Authority
- CN
- China
- Prior art keywords
- titanium tetrachloride
- rectifying
- sub
- production method
- boiling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
- C01G23/022—Titanium tetrachloride
- C01G23/024—Purification of tetrachloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A kind of production method of ultra-high purity titanium tetrachloride, it is therefore an objective to which preparing purity is 99.99999% titanium tetrachloride, for semiconductor IC industry development service.The method of the present invention includes: that (1) takes technical grade titanium tetrachloride in container, and alumen-removing agent is added, is heated to reflux 3h under stiring, is filtered after being cooled to room temperature with millipore filter；(2) material after filtering is transferred in multistage sub-boiling distillation device, control temperature carries out multistage sub-boiling distillation；(3) gained distillation product import rectifying column and carry out rectifying, collect tower top front-end volatiles after stablizing reflux, take the rectifying again of the second fraction；(4) it takes the second fraction to be sent into finished product storage tank after secondary rectifying, after detection is qualified, filters, packs under environment purification, obtain ultra-high purity titanium tetrachloride product.The present invention in such a way that rectifying combines, is able to produce ultra-high purity titanium tetrachloride using sub-boiling distillation, and process is simple, operation is convenient, highly-safe.Suitable for titanium tetrachloride manufacturer.
Description
Technical field
The present invention relates to the halide with titanium, furthermore, are related to titanium tetrachloride.
Background technique
Ultra-pure titanium tetrachloride is mainly used in semiconductor and integrates in the production and manufacturing process of reservoir, as nitridation
The liquid phase titanium source material of titanium, titanium dioxide and titanium chemical gaseous phase film deposition (CVD).With the hair of IC industry
Exhibition, the continuous development of the technologies such as Preparation of Titanium Nitride by Chemical Vapor Deposition and perfect, the TiCl of ultra-high purity and low-metal content4
Demand increases severely, wherein the purity requirement for titanium tetrachloride is up to 99.9999% or more.
Major impurity has SiCl in industrial titanium tetrachloride4、AlCl3、FeCl3、VOCl3Deng.By impurity and TiCl4The difference of boiling point
It is different to be divided into high-boiling-point impurity, low boiling impurity and the close impurity of boiling point.These impurity are for TiCl4For be all harmful, shadow
The service performance of high-purity titanium tetrachloride is rung.
In Chinese patent database, there is the application part of the production and the purification that are much related to titanium tetrachloride, such as
No. 2009102203122 " the recycling method of purification for preparing olefin polymerization catalysis titanium tetrachloride ", No. 201210572866.0
" Titanium tetrachloride purification system and method ", No. 2012105884029 " technique and system that a kind of purification of titanium tetrachloride removes vanadium ",
No. 2014100755177 " removing the method for foreign matter of vanadium and the method for refining crude titanic chloride in crude titanic chloride ",
No. 2015100539346 " method and system for preparing refined titanic chloride ", No. 2016100493563 " purifications of crude titanic chloride
Hydrolysis process " etc., these patented technologies respectively have feature, can prepare the titanium tetrachloride of certain purity, but final attainable production
Product purity is not high, purity is higher to be also only 99.99%, and not being able to satisfy semiconductor and integrating titanium source in reservoir manufacturing process makes
With requiring.
Summary of the invention
The present invention is intended to provide a kind of production method of ultra-high purity titanium tetrachloride, to prepare purity as 99.99999% 4
Titanium chloride is the development service of semiconductor IC industry.
The production method for the ultra-high purity titanium tetrachloride that inventor provides, includes the following steps:
(1) technical grade titanium tetrachloride is placed in container, alumen-removing agent is added, is heated to reflux 2~3h under gentle agitation, to
It is filtered after being cooled to room temperature with 0.1 μm or less millipore filter；
(2) filtered material is transferred in multistage sub-boiling distillation device, adjusts heating tube voltage and material is kept to be lower than
(material non-boiling state) carries out sub-boiling distillation at 100 DEG C；
(3) gained distillation product import rectifying column and carry out rectifying, after stablizing and flowing back 1h, collect tower top temperature and are lower than 130 DEG C
Front-end volatiles, then 130 DEG C~145 DEG C of fraction is taken to obtain titanium tetrachloride sterling and import after-fractionating tower carrying out rectifying again；
(4) secondary rectifying collects the material lower than 135 DEG C as front-end volatiles, and 135 DEG C~140 DEG C fractions is taken to be sent into finished product storage
Tank is filtered under the environment purification of local laminar flow after detection is qualified, is packed, and obtaining purity is 99.99999% high-purity titanium tetrachloride
Product.
In (1) step of the above method, the alumen-removing agent is the configuration product with aluminium powder and aluminium chloride in 10: 1~3 ratios,
The additional amount of alumen-removing agent is the 1%~3% of inventory；The temperature that is heated to reflux is 130 DEG C~140 DEG C；The millipore filter
It is made of high-purity polytetrafluoroethylene material.
In (2) step of the above method, the multistage sub-boiling distillation device is that 3~5 sets of sub-boiling distillation device tandem compounds form
Distiller；Sub-boiling distillation device is made of pure quartz glass.
In (3) step of the above method, the tower top temperature is lower than 130 DEG C of front-end volatiles, that is, low-boiling-point substance: main component is
SiCl4、VOCl3；The rectifying column is sieve-plate tower or packed tower, and wherein rectifying column is made of pure quartz glass, packed tower
Filler is selected corrosion-resistant and the material of metal impurities is not brought to be made.
In (4) step of the above method, the packaging uses the appearance of high purity quartz or inside lining anti-corrosive material stainless steel material
Device.
Compared with prior art, the present invention having the advantage, that
(1) present invention using sub-boiling distillation in such a way that rectifying combines, by sub-boiling distillation heavy-metal ion removal, institute
It obtains distillation product and passes through rectifying column progress rectifying removal low-boiling-point substance, higher boiling metal and nonmetallic inclusion, gained titanium tetrachloride purity
Up to 99.99999%.
(2) it in technique and production process of the invention, only contacts, packs with extraneous and operator in packaging link material
It is carried out under the environment purification of local laminar flow, product is not contaminated, guarantees the ultra-high purity of product, resultant metal and nonmetallic miscellaneous
Matter total content is lower than 100 ppb, and individual event impurity is no more than 2 ppb, and product quality meets the production that semiconductor integrates reservoir
With the liquid phase titanium source material of titanium nitride, titanium dioxide and titanium chemical gaseous phase film deposition (CVD) in manufacture.
(3) production equipment of the invention is by being composed, and process is simple, operation is convenient, highly-safe, has superelevation
Advantage essential to the purification field of pure titanium tetrachloride.
The present invention is suitable for titanium tetrachloride manufacturer.
Specific embodiment
The following examples further describe technical solution of the present invention, but claimed range is not limited to institute
It states.
Embodiment 1
Ultra-pure titanium tetrachloride is produced according to the following steps:
(1) it takes technical grade titanium tetrachloride 10L in quartz container of the 20L with condenser, is added in 1% ratio by aluminium
Powder and aluminium chloride press the alumen-removing agent of 10: 2 proportional arrangements, 130 DEG C of reflux 2h are heated under gentle agitation, after being cooled to room temperature
It is filtered with 0.1 μm of millipore filter；
(2) material after filtering is transferred in multistage sub-boiling distillation device, adjusts heating tube voltage and keeps temperature of charge control
In the multistage sub-boiling distillation of 80 DEG C~90 DEG C progress；
(3) gained distillation product import rectifying column made of pure quartz glass and carry out rectifying, after stablizing and flowing back 1h, receive
Integrate main component of the tower top temperature lower than 130 DEG C as SiCl4、VOCl3Front-end volatiles take 130 DEG C~145 DEG C fractions to import secondary fine
It evaporates tower and carries out rectifying again；
(4) secondary rectifying collects lower than 135 DEG C materials as front-end volatiles, and 135 DEG C~140 DEG C fractions is taken to be sent into high-purity
Finished product storage tank made of quartz is filtered under the environment purification of local laminar flow after detection is qualified, is packed, obtains meeting materials quality
And 99.99999% titanium tetrachloride product of packing instructions.
Products obtained therefrom main indicator is as follows under above-mentioned working condition:
Resultant metal content of impurities is lower than 100 ppb, and individual event metal impurities are no more than 2 ppb.
Embodiment 2
Ultra-pure titanium tetrachloride is produced according to the following steps:
(1) it takes technical grade titanium tetrachloride 15L in quartz container of the 20L with condenser, is added in 2% ratio by aluminium
Powder and aluminium chloride press the alumen-removing agent of 10: 1 proportional arrangements, 140 DEG C of reflux 3h are heated under gentle agitation, after being cooled to room temperature
It is filtered with 0.1 μm of millipore filter；
(2) material after filtering is transferred in multistage sub-boiling distillation device, adjusts heating tube voltage and keeps temperature of charge control
In the multistage sub-boiling distillation of 80 DEG C~90 DEG C progress；
(3) gained distillation product import rectifying column made of pure quartz glass and carry out rectifying, after stablizing and flowing back 1h, receive
Collect tower top temperature and be lower than 130 DEG C of front-end volatiles, takes 130 DEG C~145 DEG C fractions to import after-fractionating tower and carry out rectifying again；
(4) secondary rectifying collects lower than 135 DEG C materials as front-end volatiles, takes 135 DEG C~140 DEG C fractions to be sent into liner anti-
Finished product storage tank made of rotten material stainless steel after detection is qualified, is filtered under the environment purification of local laminar flow, is packed, accorded with
Close 99.99999% titanium tetrachloride product of materials quality and packing instructions.
Products obtained therefrom main indicator is as follows under above-mentioned working condition:
| Serial number | Impurity element | Testing result | Serial number | Impurity element | Testing result |
| 1 | Silver-colored (Ag) | 0.04 | 17 | Lithium (Li) | 0.09 |
| 2 | Aluminium (Al) | 0.9 | 18 | Magnesium (Mg) | 0.03 |
| 3 | Arsenic (As) | 1 | 19 | Manganese (Mn) | 0.07 |
| 4 | Golden (Au) | 0.6 | 20 | Molybdenum (Mo) | 0.04 |
| 5 | Barium (Ba) | 0.05 | 21 | Sodium (Na) | 0.03 |
| 6 | Beryllium (Be) | 0.06 | 22 | Nickel (Ni) | 0.01 |
| 7 | Bismuth (Bi) | 0.08 | 23 | Platinum (Pb) | 0.03 |
| 8 | Calcium (Ca) | 1 | 24 | Antimony (Sb) | 0.01 |
| 9 | Cadmium (Cd) | 0.5 | 25 | Tin (Sn) | 0.03 |
| 10 | Cobalt (Co) | 0.04 | 26 | Strontium (Sr) | 0.03 |
| 11 | Chromium (Cr) | 0.3 | 27 | Thorium (Th) | 0.09 |
| 12 | Copper (Cu) | 0.1 | 28 | Uranium (U) | 0.07 |
| 13 | Iron (Fe) | 0.9 | 29 | Vanadium (V) | 0.4 |
| 14 | Gallium (Ga) | 0.1 | 30 | Zinc (Zn) | 0.3 |
| 15 | Mercury (Hg) | 1 | 31 | Yttrium (Zr) | 0.09 |
| 16 | Potassium (K) | 1 |
Resultant metal content of impurities is lower than 100 ppb, and individual event metal impurities are no more than 2 ppb.
The production method of 99.99999% titanium tetrachloride disclosed in this invention, is completed preferable case study on implementation, related personnel
Any simple modification or variation are carried out not departing from the content of present invention, implementation method and purifying technique as described herein, is regarded
For included in the content of present invention.
Claims (5)
1. a kind of production method of ultra-high purity titanium tetrachloride, it is characterised in that this method comprises the following steps:
(1) technical grade titanium tetrachloride is placed in container, alumen-removing agent is added, 2~3h is heated to reflux under gentle agitation, it is to be cooled
It is filtered after to room temperature with 0.1 μm or less millipore filter；
(2) filtered material is transferred in multistage sub-boiling distillation device, adjusts heating tube voltage and material is kept to be lower than 100 DEG C
Lower carry out sub-boiling distillation；
(3) gained distillation product import rectifying column and carry out rectifying, after stablizing and flowing back 1h, before collecting tower top temperature lower than 130 DEG C
Fraction, then take 130 DEG C~145 DEG C of fraction to obtain titanium tetrachloride sterling and import after-fractionating tower progress rectifying again；
(4) secondary rectifying collects the material lower than 135 DEG C as front-end volatiles, and 135 DEG C~140 DEG C fractions is taken to be sent into finished product storage tank,
It filters, pack under the environment purification of local laminar flow after detection is qualified, obtaining purity is that 99.99999% high-purity titanium tetrachloride produces
Product.
2. production method as described in claim 1, it is characterised in that in (1) step, the alumen-removing agent is with aluminium powder and chlorination
For aluminium in the configuration product of 10: 1~3 ratios, the additional amount of alumen-removing agent is the 1%~3% of inventory；The temperature that is heated to reflux is 130
DEG C~140 DEG C；The millipore filter is made of high-purity polytetrafluoroethylene material.
3. production method as described in claim 1, it is characterised in that in (2) step, the multistage sub-boiling distillation device is 3~5
Cover distiller made of sub-boiling distillation device tandem compound；Sub-boiling distillation device is made of pure quartz glass.
4. production method as described in claim 1, it is characterised in that in (3) step, before the tower top temperature is lower than 130 DEG C
Fraction, that is, low-boiling-point substance: main component SiCl4、VOCl3；The rectifying column is sieve-plate tower or packed tower, and wherein rectifying column is using high
Pure quartz glass is made, and the filler of packed tower is selected corrosion-resistant and the material of metal impurities is not brought to be made.
5. production method as described in claim 1, it is characterised in that in (4) step, the packaging uses high purity quartz or interior
Serve as a contrast the container of anti-corrosion material stainless steel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810120467.8A CN108178185B (en) | 2018-02-07 | 2018-02-07 | A kind of production method of ultra-high purity titanium tetrachloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810120467.8A CN108178185B (en) | 2018-02-07 | 2018-02-07 | A kind of production method of ultra-high purity titanium tetrachloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108178185A CN108178185A (en) | 2018-06-19 |
| CN108178185B true CN108178185B (en) | 2019-10-29 |
Family
ID=62552250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810120467.8A Active CN108178185B (en) | 2018-02-07 | 2018-02-07 | A kind of production method of ultra-high purity titanium tetrachloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108178185B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357150A (en) * | 2019-08-08 | 2019-10-22 | 中国恩菲工程技术有限公司 | Titanium tetrachloride rectificating method |
| CN113247947A (en) * | 2021-06-08 | 2021-08-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for removing vanadium from crude titanium tetrachloride |
| CN113461049A (en) * | 2021-08-11 | 2021-10-01 | 贵阳精一科技有限公司 | Preparation method of ultrahigh-purity titanium dioxide |
| CN113912107B (en) * | 2021-11-08 | 2023-03-28 | 贵州威顿晶磷电子材料股份有限公司 | High-purity titanium tetrachloride purification manufacturing process |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU292457A1 (en) * | 1969-09-25 | 1983-07-30 | Brudz V G | Method for purifying titanium tetrachloride |
| CN100418887C (en) * | 2006-06-12 | 2008-09-17 | 北京有色金属研究总院 | Method of removing vanadium from titanium tetrachloride by aluminum powder as direct reducer |
| CN101891218B (en) * | 2010-06-12 | 2012-05-23 | 贵州威顿晶磷电子材料有限公司 | Production method for high-purity boron tribromide |
| CN102070189A (en) * | 2010-11-23 | 2011-05-25 | 金川集团有限公司 | Method for removing vanadium from titanium tetrachloride |
| CN104229880A (en) * | 2014-09-12 | 2014-12-24 | 天津市风船化学试剂科技有限公司 | Method for preparing high-purity titanium dioxide |
-
2018
- 2018-02-07 CN CN201810120467.8A patent/CN108178185B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108178185A (en) | 2018-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108178185B (en) | A kind of production method of ultra-high purity titanium tetrachloride | |
| CN100494426C (en) | Method for producing high-purity arsenic | |
| US20200189928A1 (en) | Ultra-High Purity Tungsten Chlorides | |
| TW539646B (en) | Production of high purity hydrochloric acid | |
| JP2017141150A (en) | Purification method of fluorine compound gas | |
| DE102006049156A1 (en) | Dry etching gas for semiconductor processes and manufacturing method thereof | |
| CN104925759A (en) | Continuous production method of sulfuric acid with ultrahigh purity | |
| KR102165773B1 (en) | Fluorine gas purification method | |
| DE102011112662B4 (en) | Process for treating metallurgical silicon | |
| WO2017138366A1 (en) | Method for purifying fluorine compound gas | |
| CN112028023B (en) | Method and device for purifying and pulverizing metal chloride | |
| CN101264889B (en) | Method and apparatus for producing solid product | |
| CN109399644A (en) | The preparation method of disilane | |
| CN108751201A (en) | The preparation facilities of disilane | |
| CN108862282A (en) | The preparation method of disilane | |
| CN1958445A (en) | Method for producing high purity silicon tetrachloride in optical fiber level | |
| CN109646979B (en) | High-purity oxygen-free selenium vacuum rectification device | |
| CN110589784A (en) | Fine series purification system and purification method for laboratory-grade ultrapure nitric acid | |
| US8906340B2 (en) | Purification of TiCl4 through the production of new co-products | |
| JP7029325B2 (en) | Manufacturing method of TiCl4 or titanium sponge | |
| US20220153606A1 (en) | Tungsten hexafluoride manufacturing method, tungsten hexafluoride purification method, and tungsten hexafluoride | |
| Luo et al. | Sustainable and Clean Approach to Remove High Toxicity Element from High-Value Waste Selenium Material | |
| KR20020086865A (en) | Method for purification of tungsten hexafluoride | |
| AU2012220664B2 (en) | Purification of TiCl4 through the production of new co-products | |
| US4966763A (en) | Direct vapor/solid synthesis of mercuric iodide using compounds of mercury and iodine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xiang Dong Inventor after: Shu Xiaoji Inventor after: Pan Xianwei Inventor after: Zhou Jiagui Inventor after: Xu Hu Inventor before: Xiang Dong Inventor before: Su Xiaoji Inventor before: Pan Xianwei Inventor before: Zhou Jiagui Inventor before: Xu Hu |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |