CN117323738A - Preparation system and preparation method of ultra-high purity titanium tetrachloride - Google Patents

Preparation system and preparation method of ultra-high purity titanium tetrachloride Download PDF

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CN117323738A
CN117323738A CN202311541930.3A CN202311541930A CN117323738A CN 117323738 A CN117323738 A CN 117323738A CN 202311541930 A CN202311541930 A CN 202311541930A CN 117323738 A CN117323738 A CN 117323738A
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adsorption
titanium tetrachloride
adsorption column
high purity
rectification
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张兴毅
郭树虎
万烨
赵雄
赵宇
郭克涛
袁振军
常欣
鲁永洁
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China Silicon Corp ltd
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China Silicon Corp ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
    • B01D15/1864—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns using two or more columns
    • B01D15/1871—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns using two or more columns placed in series
    • 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
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B01D3/146—Multiple effect distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D36/00—Filter circuits or combinations of filters with other separating devices
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention provides a preparation system and a preparation method of ultra-high purity titanium tetrachloride. Comprising the following steps: the device comprises a two-stage liquid phase adsorption device, a rectifying unit and a precise filtering unit, wherein the two-stage liquid phase adsorption device comprises a first adsorption column and a second adsorption column which are arranged in series, the first adsorption column is provided with a first air inlet, the second adsorption column is provided with an adsorption product outlet, the first adsorption column is selected from an activated carbon adsorption column, a modified activated carbon adsorption column, a molecular sieve adsorption column or a zeolite adsorption column, and the second adsorption column is a macroporous adsorption resin adsorption column; the rectification unit is provided with a rectification inlet and a rectification gas outlet, and the rectification inlet is communicated with the adsorption product outlet through an adsorption product conveying pipeline; the precise filtering unit is provided with a rectifying gas inlet and an ultra-high purity titanium tetrachloride outlet, and the rectifying gas inlet is communicated with the rectifying gas inlet. The preparation method of the ultra-high purity titanium tetrachloride by adopting the ultra-high purity titanium tetrachloride preparation system is simple in process, can reduce the process cost and simultaneously improves the quality of products.

Description

Preparation system and preparation method of ultra-high purity titanium tetrachloride
Technical Field
The invention relates to the field of preparation of ultra-high purity titanium tetrachloride, in particular to a preparation system and a preparation method of ultra-high purity titanium tetrachloride.
Background
Ultra-high purity titanium tetrachloride can be used in the production and manufacture of semiconductor integrated memory devices as a liquid phase titanium source material for titanium nitride, titanium dioxide and titanium metal Chemical Vapor Deposition (CVD). As electrode material for capacitors in semiconductor memory fabrication.
The purity requirement of the ultra-high purity titanium tetrachloride applied to the semiconductor is strict, the component requirement is more than or equal to 99.99%, and each impurity is less than 1 ppb. Impurities, particularly metal ion impurities (Sb, as, cu, al, pb, fe, V, sn, ni, etc.), can reduce the insulating properties of thin film layers deposited on semiconductor devices, resulting in circuit boards being scrapped due to short circuits, and organics and particulates in the impurities can affect the uniformity and flatness of the deposited thin film layers. The components of the general industrial grade titanium tetrachloride are 98 to 99 percent, and the titanium tetrachloride contains more ionic impurities (Si, sb, as, cu, al, pb, fe, V, sn, ni and the like) and CCl 4 、CCl 3 COCl、COCl 2 、CS 2 And organic matters and particles, so that the development of the preparation process of the ultra-high purity titanium tetrachloride has positive significance for localization of the electron special gas for semiconductors.
At present, the preparation technology mainly adopted by enterprises at home and abroad is combination of adsorption method-filtration, sub-boiling distillation-rectification-filtration and the like. The prior patent application (JP 2007223877 a) discloses a process for preparing high purity titanium tetrachloride by adsorption-filtration: activated carbon with the burning residue less than 0.01wt% and the metal impurity content less than 30ug/g is filled into an adsorption column made of glass, PTFE, PFA or electropolished 316L under the inert gas environment. Titanium tetrachloride with total metal impurity content below 1000ppb and silicon content below 500ppb is adsorbed by liquid phase with flow rate of 0.5/hr-2/hr (i.e. feed volume per hour to active carbon filling volume) or gas phase with flow rate of 50/hr-200/hr, and if static standing adsorption is performed, the mass ratio of active carbon to titanium tetrachloride is 5-35 wt%, and standing is performed for 24h. After adsorption, the material is filtered with the precision of 0.05 mu m, the metal impurities in the titanium tetrachloride are less than 20ppb, and the silicon content is below 50 ppb. The process has the defects that although the content of metal ions and organic matters in the titanium tetrachloride can be effectively reduced by the activated carbon adsorption, the product quality is not improved enough and the components are not improved because the cleanliness and the adsorption capacity of the activated carbon are limited.
The prior patent application (CN 108178185 a) discloses a process by combination of sub-boiling distillation-rectification-filtration: the titanium tetrachloride is fully mixed with the vanadium removing agent in the vanadium removing device, and is kept to reflux for 2 to 3 hours after being slightly stirred and heated, is filtered by a microporous filter below 0.1 mu m after being cooled, is purified by two sets of rectifying towers connected in series after being subjected to 3 to 5 sets of sub-boiling distillation devices connected in series, and is prepared into a product which is qualified in detection, and the product is filtered and packaged in a local hundred-level purifying environment. All the equipment is high-purity quartz glass products, and the rectifying tower can be a packed tower or a tower plate tower. The product tank is made of high-purity quartz or stainless steel lined with an anti-corrosion material. After purification by this method, w (TiCl 4 ) More than or equal to 99.99999 percent, the total content of metal impurities is less than 100ppb, and single impurities are not more than 2ppb. Although the quality of titanium tetrachloride is obviously improved, the process is complex, the sub-boiling distillation continuity is poor, the production cost is high, and the large-scale production is difficult.
In view of the above-mentioned problems, there is a need to provide a system for preparing ultra-high purity titanium tetrachloride which simultaneously satisfies the requirements of simple preparation process, low impurity content and low cost.
Disclosure of Invention
The invention mainly aims to provide a preparation system and a preparation method of ultra-high purity titanium tetrachloride, so as to solve the problems that the existing preparation process of the ultra-high purity titanium tetrachloride can not simultaneously meet the requirements of simple preparation process, low impurity content and low cost.
In order to achieve the above object, an aspect of the present invention provides a system for preparing ultra-high purity titanium tetrachloride, comprising: the device comprises a two-stage liquid phase adsorption device, a rectifying unit and a precise filtering unit, wherein the two-stage liquid phase adsorption device comprises a first adsorption column and a second adsorption column which are arranged in series, the first adsorption column is provided with a first air inlet, the second adsorption column is provided with an adsorption product outlet, the first adsorption column is selected from an activated carbon adsorption column, a modified activated carbon adsorption column, a molecular sieve adsorption column or a zeolite adsorption column, and the second adsorption column is a macroporous adsorption resin adsorption column; the rectification unit is provided with a rectification inlet and a rectification gas outlet, and the rectification inlet is communicated with the adsorption product outlet through an adsorption product conveying pipeline; the precise filtering unit is provided with a rectifying gas inlet and an ultra-high purity titanium tetrachloride outlet, and the rectifying gas inlet is communicated with the rectifying gas inlet.
Further, the diameters of the first adsorption column and the second adsorption column are independently selected from 25.4-76.2 mm, the aspect ratios are independently selected from (5-10): 1, and the packing coefficients are independently selected from 80-90%.
Further, the granularity of the adsorbent in the first adsorption column is 2-5 mm, the aperture is 2-50 nm, and the specific surface area is 500-1500 m 2 /g; the macroporous adsorption resin adsorption column is selected from a large Kong Yaan group diacetic acid polystyrene resin adsorption column, a large pore amino phosphoric acid polystyrene resin adsorption column or a styrene-divinyl resin adsorption column with the sulfonation degree more than or equal to 60 percent, and the pore diameter of the macroporous adsorption resin adsorption column is 10-50 nm.
Further, the rectification unit includes: the first rectifying device is provided with a rectifying gas inlet, a tower top extraction outlet and an intermediate product outlet; the second rectifying device is provided with an intermediate product inlet, a rectifying gas outlet and a bottom product outlet, and the intermediate product outlet is communicated with the intermediate product inlet.
Further, the first rectifying device and the second rectifying device are both packed towers, and the packing in the packed towers is respectively and independently selected from stainless steel theta-ring packing, triangular spiral packing or glass spring packing.
Further, the packing in the packed tower is independently selected from 5mm double-layer stainless steel theta ring packing or 5mm triangular spiral packing, respectively.
Further, the fine filtration unit includes a first fine filtration device and a second fine filtration device arranged in series, and the filtration precision of the first fine filtration device and the second fine filtration device is independently selected from 0.03 to 0.1 μm, respectively.
Further, the preparation system of ultra-high purity titanium tetrachloride further comprises a pre-filter device which is arranged on the adsorption product conveying pipeline, and preferably, the filtering precision of the pre-filter device is 0.05-0.2 mu m.
In another aspect, the present application further provides a method for preparing ultra-high purity titanium tetrachloride, wherein the purity of the ultra-high purity titanium tetrachloride is greater than or equal to 99.99%, and the method for preparing the ultra-high purity titanium tetrachloride comprises: carrying out two-stage liquid-phase adsorption treatment on industrial-grade titanium tetrachloride to obtain an adsorption product, wherein a first-stage liquid-phase adsorbent adopted in the two-stage liquid-phase adsorption treatment is one or more selected from the group consisting of activated carbon, modified activated carbon, molecular sieve and zeolite, and the second-stage liquid-phase adsorbent is macroporous adsorption resin; rectifying the adsorption product to obtain a rectification product; and (3) carrying out precise filtration on the rectification product to obtain the ultra-high purity titanium tetrachloride.
Further, in the two-stage liquid phase adsorption process, the primary liquid phase adsorbent and the secondary liquid phase adsorbent are sequentially filled in a first adsorption column and a second adsorption column which are arranged in series, wherein the adsorption pressure of the first adsorption column and the second adsorption column is respectively and independently selected from 0.5-5 bar, and the temperature is respectively and independently selected from 10-50 ℃.
Further, the purity of technical grade titanium tetrachloride is > 99%, and the total of all impurities is less than 100ppb.
Further, the granularity of the primary liquid phase adsorbent is 2-5 mm, the aperture is 2-50 nm, and the specific surface area is 500-1500 m 2 Preferably, the molecular sieve adsorbent is selected from ZSM-5 and/or 13X, and the zeolite adsorbent is selected from mordenite and/or chabazite; the macroporous adsorption resin is selected from one or more of macroporous Kong Yaan-based diacetic acid polystyrene resin, macroporous amino phosphoric acid polystyrene resin and styrene-divinyl resin with sulfonation degree more than or equal to 60%.
Further, in the two-stage liquid phase adsorption treatment, the flow rate of the liquid is 20-200 mL/min, the diameters of the first adsorption column and the second adsorption column are respectively and independently selected from 25.4-76.2 mm, the height-diameter ratio is (5-10): 1, and the filling coefficients are respectively and independently selected from 80-90%; preferably, in the two-stage liquid-phase adsorption treatment, the flow rate of the liquid is 50 to 150mL/min.
Further, the rectification process comprises: carrying out a first rectification process on the adsorption product to obtain an intermediate product; the intermediate product is subjected to a second rectification process to obtain a rectification product; wherein, the pressure at the top of the tower in the first rectification process is 30 kPa-50 kPa, the temperature at the top of the tower is 140-155 ℃, the reflux feed ratio is 5-15, the theoretical plate number is 10-35, and the low-boiling extraction amount accounts for 5-10 wt% of the feed amount; the pressure at the top of the tower in the second rectification process is 30-50 kPa, the temperature at the top of the tower is 140-155 ℃, the reflux feed ratio is 5-15, the theoretical plate number is 10-35, and the high-boiling extraction amount accounts for 5-15 wt.
Further, the reflux feed ratio in the first rectification process is 10-15, and the theoretical plate number is 20-30; the reflux feed ratio of the second rectification process is 10-15, and the theoretical plate number is 20-30.
Further, the fine filtration process includes a first fine filtration process and a second fine filtration process, and the filtration accuracy of the first fine filtration process is smaller than the filtration accuracy of the second fine filtration process; preferably, the filtration precision of the first and second fine filtration processes is selected from 0.03 to 0.1 μm.
Further, the preparation method of the ultra-high purity titanium tetrachloride between the adsorption treatment and the rectification process further comprises the following steps: pre-filtering the adsorption product; preferably, the pre-filtration process has a lower filtration accuracy than the first fine filtration process; more preferably, the prefilter process has a filtration accuracy of 0.05 to 0.2 μm.
By applying the technical scheme of the invention, the organic matters, metal ions and nonmetallic ion impurities in the industrial titanium tetrachloride raw material can be primarily removed by a two-stage liquid phase adsorption device consisting of a specific type of adsorption column and a specific aperture ratio of adsorbent, then the product components are further purified by a rectifying unit, and finally the content of particles in the product can be effectively reduced by a precise filtering unit, so that the effect of improving the quality of the product is realized. In addition, the preparation system has the advantages of simple preparation process, simple device, low preparation cost and the like. On the basis, the ultra-high purity titanium tetrachloride preparation system provided by the application is simple in process, the process cost can be reduced, and the quality of the product is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a block diagram of an ultra-high purity titanium tetrachloride production system according to an exemplary embodiment of the present application.
Wherein the above figures include the following reference numerals:
10. a two-stage liquid phase adsorption device; 11. a first adsorption column; 12. a second adsorption column; 20. a rectification unit; 21. a first rectifying device; 22. a second rectifying device; 30. a fine filtration unit; 31. a first fine filtration device; 32. a second fine filtration device; 40. and a pre-filter device.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As described in the background art, the existing ultra-high purity titanium tetrachloride preparation process cannot simultaneously solve the problems of simple preparation process, low impurity content and low cost. In order to solve the above technical problems, the present application provides a system for preparing ultra-high purity titanium tetrachloride, comprising: a two-stage liquid phase adsorption device 10, a rectification unit 20 and a fine filtration unit 30. The two-stage liquid phase adsorption device 10 comprises a first adsorption column 11 and a second adsorption column 12 which are arranged in series, wherein the first adsorption column 11 is provided with a first air inlet, the second adsorption column 12 is provided with an adsorption product outlet, the first adsorption column 11 is selected from an activated carbon adsorption column, a modified activated carbon adsorption column, a molecular sieve adsorption column or a zeolite adsorption column, and the second adsorption column 12 is a macroporous adsorption resin adsorption column; the rectification unit 20 is provided with a rectification inlet and a rectification gas outlet, and the rectification inlet is communicated with the adsorption product outlet through an adsorption product conveying pipeline; the fine filtration unit 30 is provided with a rectification gas inlet and an ultra-high purity titanium tetrachloride outlet, and the rectification gas inlet is communicated with the rectification gas inlet.
In the above-mentioned ultra-high purity titanium tetrachloride preparation system that this application provided, through the two-stage liquid phase adsorption equipment 10 that specific kind adsorption column and specific aperture ratio's adsorbent are constituteed, can carry out preliminary removal to organic matter, metal ion and nonmetallic ion impurity in the industrial grade titanium tetrachloride raw materials, then carry out further purification to the product component through rectifying element 20, can effectively reduce the particulate matter content in the product through the precision filtration unit 30 at last to the effect of promoting the product quality has been realized. In addition, the preparation system has the advantages of simple preparation process, simple device, low preparation cost and the like. On the basis, the ultra-high purity titanium tetrachloride preparation system provided by the application is simple in process, the process cost can be reduced, and the quality of the product is improved.
The two-stage liquid phase adsorption device 10 filled with the specific adsorbent can effectively reduce the metal ion content and the organic matter content in the titanium tetrachloride and can also effectively improve the purity of the titanium tetrachloride in the product. In a preferred embodiment, the diameters of the first adsorption column 11 and the second adsorption column 12 are independently selected from 25.4 to 76.2mm, respectively, the aspect ratios are independently selected from 5 to 10:1, and the packing coefficients are independently selected from 80 to 90%, respectively. The diameters, the height-to-diameter ratios, and the packing coefficients of the first adsorption column 11 and the second adsorption column 12 include, but are not limited to, the above ranges, and the limitation thereof is advantageous in further improving the throughput of the two-stage liquid phase adsorption apparatus 10 for the raw material gas and the purity of titanium tetrachloride in the product and the safety of the process.
The adsorption capacity and the product purity improving effect of the adsorption process on the particulate matters in the industrial grade titanium tetrachloride raw material gas can be greatly improved through the cooperation of the first adsorption column 11 and the second adsorption column 12. In order to further improve the purity of the target product, it is preferable that the particle size of the adsorbent in the first adsorption column 11 is 2 to 5mm, the pore diameter is 2nm to 50nm, and the specific surface area is 500 to 1500m 2 /g; the macroporous adsorption resin adsorption column comprises, but is not limited to, a macroporous iminodiacetic acid polystyrene resin adsorption column, a macroporous phosphoramidate polystyrene resin adsorption column or a styrene-divinyl resin adsorption column with the sulfonation degree more than or equal to 60%, and the pore diameter of the macroporous adsorption resin adsorption column is 10-50 nm.
In order to avoid introducing oxygen into the feed gas, the two-stage liquid phase adsorption apparatus 10 is preferably purged with high purity nitrogen before use, so that the oxygen content in the discharged nitrogen is less than or equal to 2ppm, the dew point is less than or equal to-60 ℃, and the purging is terminated.
Further purification of the product components can be achieved by the rectification unit 20. In a preferred embodiment, the rectification unit 20 comprises: a first rectifying device 21 and a second rectifying device 22. The first rectifying device 21 is provided with a rectifying gas inlet, a tower top extraction outlet and an intermediate product outlet; the second rectifying device 22 is provided with an intermediate product inlet, a rectifying gas outlet and a bottom product outlet, and the intermediate product outlet is arranged in communication with the intermediate product inlet. Compared with a single rectifying tower, the two-stage rectifying tower can further improve the purity of titanium tetrachloride in the finally obtained product gas.
To further enhance the rectifying effect, in a preferred embodiment, the first rectifying device 21 and the second rectifying device 22 are each a packed tower, and the packing in the packed tower is independently selected from stainless steel θ -ring packing, triangular spiral packing, or glass spring packing, respectively. Further preferably, the packing in the packed column is independently selected from 5mm double layer stainless steel theta ring packing or 5mm delta spiral packing, respectively.
The fine filtration unit 30 is capable of effectively reducing the particulate content of the distillation product, thereby further increasing the purity of titanium tetrachloride in the product gas. In a preferred embodiment, the fine filtration unit 30 comprises a first fine filtration device 31 and a second fine filtration device 32 arranged in series, and the filtration precision of the first fine filtration device 31 and the second fine filtration device 32 is independently selected from 0.03 to 0.1 μm, respectively. . The filtering accuracy of the first and second fine filtering devices 31 and 32 includes, but is not limited to, the above ranges, and limiting them to the above ranges is advantageous for further improving the filtering efficiency of the fine filtering unit 30 for particulate matters, thereby further improving the purity of titanium tetrachloride in the product gas.
Preferably, the materials of the outer shells of the first and second precise filtering devices 31 and 32 are respectively and independently selected from 316L stainless steel, PTFE (polytetrafluoroethylene), PFA (copolymer of small amount of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene) or PP (polypropylene), preferably electro-polished 316L stainless steel and PTFE; the filter element material is preferably PTFE, more preferably, a 0.05 μm filter element and a 0.03 μm filter element are selected to be used in series, so as to enhance the filtering effect.
In a preferred embodiment, the system for producing ultra-high purity titanium tetrachloride further comprises a pre-filter device 40, the pre-filter device 40 being disposed on the adsorption product delivery line. The pre-filter device 40 is arranged on the adsorption product conveying pipeline, so that the particulate matters in the adsorption product can be further removed, and the purity of the finally obtained product gas can be further improved. In order to further improve the filtering effect, the filter element in the prefilter 40 preferably has a filtering accuracy of 0.05 to 0.2. Mu.m, more preferably 0.05. Mu.m.
Preferably, the shell of the pre-filter device 40 is made of 316L stainless steel, PTFE (polytetrafluoroethylene), PFA (copolymer of small amount of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene) or PP (polypropylene), preferably the inner wall is made of 316L stainless steel and PTFE, and the filter element is made of PTFE.
In another aspect, the present application further provides a method for preparing ultra-high purity titanium tetrachloride, wherein the purity of the ultra-high purity titanium tetrachloride is greater than or equal to 99.99%, and the method for preparing the ultra-high purity titanium tetrachloride comprises: carrying out two-stage liquid-phase adsorption treatment on industrial-grade titanium tetrachloride to obtain an adsorption product, wherein a first-stage liquid-phase adsorbent adopted in the two-stage liquid-phase adsorption treatment is one or more selected from the group consisting of activated carbon, modified activated carbon, molecular sieve and zeolite, and the second-stage liquid-phase adsorbent is macroporous adsorption resin; rectifying the adsorption product to obtain a rectification product; and (3) carrying out precise filtration on the rectification product to obtain the ultra-high purity titanium tetrachloride.
Organic matters, metal ions and nonmetallic ion impurities in the industrial grade titanium tetrachloride raw material can be primarily removed by selecting a specific type of adsorption column and a specific aperture ratio of adsorbent for two-stage liquid phase adsorption treatment, then the product components are further purified by rectification, and finally the content of particulate matters in the product can be effectively reduced by precise filtration, so that the effect of improving the quality of the product is realized. In addition, the preparation process has the advantages of simple preparation process, low preparation cost and the like. On the basis, the preparation method of the ultra-high purity titanium tetrachloride is simple in process, can reduce the process cost and improves the quality of products.
The adsorption capacity and the product purity improving effect of the adsorption process on the particulate matters in the industrial grade titanium tetrachloride raw material gas can be greatly improved through the matched use of the first adsorption column 11 and the second adsorption column 12 containing the specific adsorbent. In a preferred embodiment, in the two-stage liquid phase adsorption process, the first-stage liquid phase adsorbent and the second-stage liquid phase adsorbent are sequentially packed in the first adsorption column 11 and the second adsorption column 12 which are arranged in series, and the adsorption pressures of the first adsorption column 11 and the second adsorption column 12 are respectively and independently selected from 0.5 to 5bar, and the temperatures are respectively and independently selected from 10 ℃ to 50 ℃. By subjecting the first adsorption column 11 and the second adsorption column 12 to the pressure treatment and limiting the temperature within the above-described range, the adsorption efficiency and adsorption effect of the two-stage liquid-phase adsorption process can be advantageously improved, thereby being advantageous in further improving the purity of the product gas.
The purity of the raw material has a great influence on the adsorption effect and the service life of the adsorbent, and in order to prolong the service life of the adsorbent and improve the adsorption effect, the purity of the industrial grade titanium tetrachloride is preferably more than 99 percent, and the total sum of all impurities is less than 100ppb.
In a preferred embodiment, the primary liquid-phase adsorbent has a particle size of 2 to 5mm, a pore size of 2 to 50nm, and a specific surface area of 500 to 1500m 2 And/g. Compared with other adsorbents, the primary liquid-phase adsorbent with the specification is favorable for further improving the removal rate of impurities such as metal ions and the like, so that the purity of the final product is improved. More preferably, the molecular sieve adsorbent includes, but is not limited to, ZSM-5 and/or 13X, and the zeolite adsorbent includes, but is not limited to, mordenite and/or chabazite.
In a preferred embodiment, the macroporous adsorbent resin is selected from one or more of the group consisting of macroporous Kong Yaan-based diacetic polystyrene resin, macroporous phosphoramidate polystyrene resin, styrene-divinylbenzene resin with a sulfonation degree of 60%. Compared with other macroporous adsorption resins, the adoption of the macroporous adsorption resins is beneficial to further improving the adsorption and purification effects of the two-stage liquid phase adsorption process on industrial grade titanium tetrachloride raw material gas.
In the two-stage liquid phase adsorption treatment process, the flow rate of the liquid, the diameters, the height-to-diameter ratio and the packing coefficient of the first adsorbent and the second adsorbent column also have influence on the treatment effect of the two-stage liquid phase adsorption treatment. In order to further enhance the adsorption effect of the two-stage liquid phase adsorption treatment process on the industrial grade titanium tetrachloride raw material gas, in a preferred embodiment, the flow rate of the liquid in the two-stage liquid phase adsorption treatment is 20-200 mL/min, the diameters of the first adsorption column 11 and the second adsorption column 12 are respectively and independently selected from 25.4-76.2 mm, the aspect ratio is (5-10): 1, and the packing coefficients are respectively and independently selected from 80-90%. More preferably, in the two-stage liquid-phase adsorption treatment, the flow rate of the liquid is 50 to 150mL/min.
The impurity components in the adsorbed product can be separated from the titanium tetrachloride gas by the rectification process. In a preferred embodiment, the above-mentioned rectification process comprises: carrying out a first rectification process on the adsorption product to obtain an intermediate product; the intermediate product is subjected to a second rectification process to obtain a rectification product; wherein, the pressure at the top of the tower in the first rectification process is 30 kPa-50 kPa, the temperature at the top of the tower is 140-155 ℃, the reflux feed ratio is 5-15, and the theoretical plate number is 10-35; the pressure at the top of the tower in the second rectifying process is 30-50 kPa, the temperature at the top of the tower is 140-155 ℃, the reflux feed ratio is 5-15, and the theoretical plate number is 10-35. Compared with other rectification processes, the first rectification process and the second rectification process are adopted, so that the purity of the titanium tetrachloride in the product gas is improved. In order to better promote the synergistic effect of the first rectification process and the second rectification process, more preferably, in a preferred embodiment, the reflux feed ratio of the first rectification process is 10 to 15, the theoretical plate number is 20 to 30, and the low-boiling recovery amount accounts for 5 to 10 weight percent of the feed amount; the reflux feed ratio in the second rectification process is 10-15, the theoretical plate number is 20-30, and the high-boiling recovery amount accounts for 5-15 wt% of the feed amount.
The content of particulate matters in the distilled product can be effectively reduced through the precise filtering process, so that the purity of titanium tetrachloride in the product gas is further improved. In order to further enhance the filtering effect thereof, in a preferred embodiment, the fine filtering process includes a first fine filtering process and a second fine filtering process, and the filtering accuracy of the first fine filtering process is smaller than that of the second fine filtering process. This is advantageous in improving the life span and the filtering effect of the fine filtering device. More preferably, the filtration accuracy of the first fine filtration process and the filtration accuracy of the second fine filtration process are selected from 0.03 to 0.1 μm. The combination of the two stages of precise filtration is beneficial to further improving the filtration effect.
The preparation method of the ultra-high purity titanium tetrachloride between the adsorption treatment and the rectification process further comprises the following steps: the adsorbed product was pre-filtered. The pre-filtering device for the adsorption product can further remove the particulate matters in the adsorption product, so that the purity of the finally obtained product gas is further improved. In order to improve the service life of the filter, the filter precision of the pre-filtering process is lower than that of the first precise filtering process. In order to further improve the filtering effect, the prefilter preferably has a filtering accuracy of 0.05 to 0.2 μm.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
According to the process flow shown in FIG. 1, 99.000wt% technical grade titanium tetrachloride is pressurized with nitrogen and then fed into a two-stage liquid phase adsorption apparatus 10. In the two-stage liquid phase adsorption device 10, the adsorbent in the first adsorption column 11 is modified activated carbon (particle size 2-4 mm, pore diameter 2-50 nm, specific surface area 1500m 2 And/g, manufacturer: jacobi, model: CS12X 30), the above-mentioned technical grade titanium tetrachloride is adsorbed by the first adsorption column 11 and then enters the second adsorption column 12. The adsorbent in the second adsorption column 12 is of the type D001, brand of Bluet. Wherein the diameters of the first adsorption column 11 and the second adsorbent are 2 inches, the lengths are 20 inches, the material is 316L stainless steel, and the inner walls are subjected to electrolytic polishing; the adsorption pressure was 2bar, and the flow rate was controlled to 100mL/min.
And (3) adsorbing by a two-stage liquid phase adsorption device 10 to obtain an adsorption product. Then the adsorption product is introduced into a pre-filter device 40, the shell of the pre-filter device 40 is made of 316L stainless steel, the filter element is made of PTFE, and the filtering precision is 0.1 mu m.
The material adsorbed by the pre-filter 40 is condensed and fed to the rectifying unit 20. The rectifying unit 20 includes a first rectifying device 21 and a second rectifying device 22 arranged in series. Wherein the tower pressure of the first rectifying device 21 is 50kPa, the top temperature is 152 ℃, the reflux feed ratio is 10, the theoretical plate number is 30, the low-boiling recovery accounts for 10% of the feed amount, and the pressure difference is controlled to be 3-5 kPa. The intermediate product of the first rectifying tower is pressurized by a pump and then enters the second rectifying tower. The column pressure of the second rectifying device 22 is 50kPa, the top temperature is 152 ℃, the reflux feed ratio is 10, the theoretical plate number is 30, the pressure difference is controlled to be 3-5 kPa, the high-boiling extraction accounts for 15% of the total feed amount, and the total system yield is 75%. And (5) taking out the product from the top of the second rectifying tower.
And (3) feeding the product obtained from the top of the second rectifying tower into a precise filtering unit 30 for precise filtering to obtain a qualified product. Wherein the rectification filter unit is a series two-stage precise filter device, the shell of the two-stage precise filter device is made of 316L stainless steel, the filter element is made of PTFE, the primary precise filter precision is 0.05 mu m, and the secondary precise filter precision is 0.03 mu m.
After the GC-MS detection, the titanium tetrachloride treated by the process has the components of 99.995 percent. After ICP-MS detection, the total impurity content of the product is 2ppbw; after being detected by a particle meter, the granularity of the product is as follows: 10 particles/mL or less of 0.1 mu m, 5 particles/mL or less of 0.2 mu m, and 1 particle/mL or less of 0.5 mu m.
Example 2
The differences from example 1 are: the adsorbent in the first adsorption column 11 is a molecular sieve adsorbent which is UOP company 5A molecular sieve, the diameter of spherical particles is 2-3 mm, and the specific surface area is 700m 2 /g。
The purity of the titanium tetrachloride obtained by the process is 99.992%wt after being detected by GC-MS. After ICP-MS detection, the total impurity content of the product is 1.9ppbw; after being detected by a particle meter, the granularity of the product is as follows: 10 particles/mL or less of 0.1 mu m, 4 particles/mL or less of 0.2 mu m, and 1 particle/mL or less of 0.5 mu m.
Example 3
The differences from example 1 are: the adsorbent in the first adsorption column 11 is Zeolite adsorbent ZSM-5 Zeolite of Zeolite company, the particle size is 2-3 mm, the silicon-aluminum ratio is not less than 200, and the specific surface area is 500m 2 /g。
After being detected by GC-MS, the titanium tetrachloride obtained by the process has the purity of 99.991 percent by weight. After ICP-MS detection, the total impurity content of the product is 1.8ppbw; after being detected by a particle meter, the granularity of the product is as follows: 9 particles/mL or less with 0.1 μm or less, 4 particles/mL or less with 0.2 μm or less, and 1 particle/mL or less with 0.5 μm or less.
Example 4
The differences from example 1 are: the adsorbent in the first adsorption column 11 is unmodified ACF shell activated carbon of DAIZEN company, with particle diameter of 2-5 mm and specific surface area of 500m 2 /g。
After being detected by GC-MS, the titanium tetrachloride obtained by the process has the purity of 99.991 percent by weight. After ICP-MS detection, the total impurity content of the product is 5ppbw; after being detected by a particle meter, the granularity of the product is as follows: 15 particles/mL or less with 0.1 mu m, 6 particles/mL or less with 0.2 mu m, 2 particles/mL or less with 0.5 mu m.
Example 5
The differences from example 1 are: the macroporous adsorption resin in the second adsorption column 12 is Langsheng Lewatit iminodiacetic acid polystyrene resin, the particle diameter is 2-4 mm, and the specific surface area is 200m 2 And/g, exchange capacity 2eq/L.
The purity of the titanium tetrachloride obtained by the process is 99.993%wt after being detected by GC-MS. After ICP-MS detection, the total impurity content of the product is 4ppbw; after being detected by a particle meter, the granularity of the product is as follows: 15 particles/mL or less with 0.1 mu m, 8 particles/mL or less with 0.2 mu m, 2 particles/mL or less with 0.5 mu m.
Example 6
The differences from example 1 are: the macroporous adsorption resin in the second adsorption column 12 is Rogowski UP6040 styrene ion exchange resin with the particle diameter of 2-3 mm and the specific surface area of 200m 2 And/g, exchange capacity 2eq/L.
The purity of the titanium tetrachloride obtained by the process is 99.994%wt after the titanium tetrachloride is detected by GC-MS. After ICP-MS detection, the total impurity content of the product is 5ppbw; after being detected by a particle meter, the granularity of the product is as follows: 13 particles/mL or less with 0.1 mu m, 8 particles/mL or less with 0.2 mu m, 2 particles/mL or less with 0.5 mu m.
Example 7
The differences from example 1 are: the pressure at the top of the first rectification process is 30Pa, the temperature at the top of the column is 155 ℃, the reflux feed ratio is 5, and the theoretical plate number is 35;
the top pressure of the tower in the second rectification process is 50kPa, the top temperature of the tower is 155 ℃, the reflux feed ratio is 15, and the theoretical plate number is 10.
The purity of the titanium tetrachloride obtained by the process is 99.990%wt after the detection of GC-MS. After ICP-MS detection, the total impurity amount of the product is 1.9.Ppbw; after being detected by a particle meter, the granularity of the product is as follows: 10 particles/mL or less of 0.1 mu m, 5 particles/mL or less of 0.2 mu m, and 1 particle/mL or less of 0.5 mu m.
Example 8
The differences from example 1 are: the pressure at the top of the first rectification process is 50kPa, the temperature at the top of the column is 140 ℃, the reflux feed ratio is 15, and the theoretical plate number is 10;
the top pressure of the tower in the second rectification process is 30KPa, the top temperature is 155 ℃, the reflux feed ratio is 5, and the theoretical plate number is 35.
After being detected by GC-MS, the titanium tetrachloride obtained by the process has the purity of 99.991 percent by weight. After ICP-MS detection, the total impurity content of the product is 2.1ppbw; after being detected by a particle meter, the granularity of the product is as follows: 10 particles/mL or less of 0.1 mu m, 5 particles/mL or less of 0.2 mu m, and 1 particle/mL or less of 0.5 mu m.
Comparative example 1
The differences from example 1 are: a single modified activated carbon adsorption column was used instead of the two-stage liquid phase adsorption apparatus 10, and the modified activated carbon in the modified activated carbon adsorption column was the same as in example 1.
The purity of the titanium tetrachloride obtained by the process is 99.900wt% after the titanium tetrachloride is detected by GC-MS. After ICP-MS detection, the total impurity content of the product is 20ppbw; after being detected by a particle meter, the granularity of the product is as follows: 10 particles/mL or less of 0.1 mu m, 5 particles/mL or less of 0.2 mu m, and 1 particle/mL or less of 0.5 mu m.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: compared with the prior art, the method provided by the application has the advantages that the purity of the titanium tetrachloride component is obviously improved, the impurity removal efficiency of the product is improved, and the product quality improvement effect is obvious.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described herein.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (17)

1. A system for preparing ultra-high purity titanium tetrachloride, the system comprising:
the two-stage liquid phase adsorption device (10), wherein the two-stage liquid phase adsorption device (10) comprises a first adsorption column (11) and a second adsorption column (12) which are arranged in series, the first adsorption column (11) is provided with a first air inlet, the second adsorption column (12) is provided with an adsorption product outlet, the first adsorption column (11) is selected from an activated carbon adsorption column, a modified activated carbon adsorption column, a molecular sieve adsorption column or a zeolite adsorption column, and the second adsorption column (12) is a macroporous adsorption resin adsorption column;
the rectification unit (20) is provided with a rectification inlet and a rectification gas outlet, and the rectification inlet is communicated with the adsorption product outlet through an adsorption product conveying pipeline;
the precise filtering unit (30) is provided with a rectification gas inlet and an ultra-high purity titanium tetrachloride outlet, and the rectification gas inlet is communicated with the rectification gas inlet.
2. The system for producing ultra-high purity titanium tetrachloride according to claim 1, wherein the diameters of the first adsorption column (11) and the second adsorption column (12) are independently selected from 25.4 to 76.2mm, the aspect ratios are independently selected from (5 to 10): 1, and the packing coefficients are independently selected from 80 to 90%, respectively.
3. The production system of ultra-high purity titanium tetrachloride according to claim 1 or 2, wherein,
the granularity of the adsorbent in the first adsorption column (11) is 2-5 mm, the aperture is 2-50 nm, and the specific surface area is 500-1500 m 2 /g；
The macroporous adsorption resin adsorption column is selected from a macroporous Kong Yaan-based diacetic acid polystyrene resin adsorption column, a macroporous amino phosphoric acid polystyrene resin adsorption column or a styrene-divinyl resin adsorption column with the sulfonation degree more than or equal to 60%, and the aperture of the macroporous adsorption resin adsorption column is 10-50 nm.
4. The system for preparing ultra-high purity titanium tetrachloride according to claim 1, wherein said rectification unit (20) comprises:
a first rectifying device (21), wherein the first rectifying device (21) is provided with the rectifying gas inlet, a tower top extraction outlet and an intermediate product outlet;
the second rectifying device (22) is provided with an intermediate product inlet, a rectifying gas outlet and a tower bottom product outlet, and the intermediate product outlet is communicated with the intermediate product inlet.
5. The system for producing ultra-high purity titanium tetrachloride according to claim 4, wherein the first rectifying device (21) and the second rectifying device (22) are each a packed column, and the packing in the packed column is each independently selected from stainless steel θ -ring packing, delta spiral packing, or glass spring packing.
6. The system for producing ultra-high purity titanium tetrachloride according to claim 5, wherein the packing in the packed tower is independently selected from 5mm double-layer stainless steel θ -ring packing and 5mm triangle spiral packing, respectively.
7. The system for producing ultra-high purity titanium tetrachloride according to claim 1, wherein the fine filtration unit (30) comprises a first fine filtration device (31) and a second fine filtration device (32) arranged in series, and the filtration precision of the first fine filtration device (31) and the second fine filtration device (32) is independently selected from 0.03 to 0.1 μm, respectively.
8. The system for producing ultra-high purity titanium tetrachloride according to claim 7, further comprising a pre-filter device (40), wherein the pre-filter device (40) is provided on the adsorption product delivery line, and preferably, the pre-filter device (40) has a filtration accuracy of 0.05 to 0.2 μm.
9. The preparation method of the ultra-high purity titanium tetrachloride is characterized by comprising the following steps of:
performing two-stage liquid-phase adsorption treatment on industrial-grade titanium tetrachloride to obtain an adsorption product, wherein a first-stage liquid-phase adsorbent adopted in the two-stage liquid-phase adsorption treatment is one or more selected from the group consisting of activated carbon, modified activated carbon, molecular sieve and zeolite, and the second-stage liquid-phase adsorbent is macroporous adsorption resin;
rectifying the adsorption product to obtain a rectification product;
and (3) carrying out precise filtration on the rectification product to obtain the ultra-high purity titanium tetrachloride.
10. The method for preparing ultra-high purity titanium tetrachloride according to claim 9, wherein in the two-stage liquid phase adsorption process, the primary liquid phase adsorbent and the secondary liquid phase adsorbent are sequentially packed in a first adsorption column (11) and a second adsorption column (12) which are arranged in series, and adsorption pressures of the first adsorption column (11) and the second adsorption column (12) are respectively and independently selected from 0.5 to 5bar, and temperatures are respectively and independently selected from 10 ℃ to 50 ℃.
11. The method for producing ultra-high purity titanium tetrachloride according to claim 9, wherein the technical grade titanium tetrachloride has a purity of > 99% and the total of impurities is less than 100ppb.
12. The method for preparing ultra-high purity titanium tetrachloride according to claim 9, wherein the primary liquid phase adsorbent has a particle size of 2 to 5mm, a pore diameter of 2 to 50nm, and a specific surface area of 500 to 1500m 2 Preferably, the molecular sieve adsorbent is selected from ZSM-5 and/or 13X, and the zeolite adsorbent is selected from mordenite and/or chabazite;
the macroporous adsorption resin is selected from one or more of large Kong Yaan group diacetic acid polystyrene resin, large pore amino phosphate polystyrene resin and styrene-divinyl resin with the sulfonation degree more than or equal to 60 percent.
13. The method for producing ultra-high purity titanium tetrachloride according to claim 10, wherein in the two-stage liquid phase adsorption treatment, the flow rate of the liquid is 20 to 200mL/min, the diameters of the first adsorption column (11) and the second adsorption column (12) are independently selected from 25.4 to 76.2mm, the aspect ratio is (5 to 10): 1, and the packing coefficients are independently selected from 80 to 90%, respectively;
preferably, in the two-stage liquid-phase adsorption treatment, the flow rate of the liquid is 50-150 mL/min.
14. The method for producing ultra-high purity titanium tetrachloride according to claim 9, wherein the rectification process comprises:
carrying out a first rectification process on the adsorption product to obtain an intermediate product;
subjecting the intermediate product to a second rectification process to obtain the rectification product;
wherein the pressure at the top of the tower in the first rectification process is 30 kPa-50 kPa, the temperature at the top of the tower is 140-155 ℃, the reflux feed ratio is 5-15, the theoretical plate number is 10-35, and the low-boiling extraction amount accounts for 5-10wt% of the feed amount;
the pressure at the top of the second rectifying process is 30-50 kPa, the temperature at the top of the second rectifying process is 140-155 ℃, the reflux feed ratio is 5-15, the theoretical plate number is 10-35, and the high-boiling recovery amount accounts for 5-15 wt% of the feed amount.
15. The method for producing ultra-high purity titanium tetrachloride according to claim 14, wherein the reflux feed ratio of the first rectification process is 10 to 15 and the theoretical plate number is 20 to 30;
the reflux feed ratio of the second rectification process is 10-15, and the theoretical plate number is 20-30.
16. The method for producing ultra-high purity titanium tetrachloride according to claim 9, wherein the fine filtration process comprises a first fine filtration process and a second fine filtration process, and wherein the first fine filtration process has a filtration accuracy that is less than the filtration accuracy of the second fine filtration process;
preferably, the filtration precision of the first and second fine filtration processes is selected from 0.03 to 0.1 μm.
17. The method for producing ultra-high purity titanium tetrachloride according to any one of claims 9 to 16, further comprising, between the adsorption treatment and the rectification process: pre-filtering the adsorption product; preferably, the filtering precision of the pre-filtering process is lower than that of the first precise filtering process; more preferably, the prefilter process has a filtration accuracy of 0.05 to 0.2 μm.
CN202311541930.3A 2023-11-20 2023-11-20 Preparation system and preparation method of ultra-high purity titanium tetrachloride Pending CN117323738A (en)

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