WO2018006695A1 - 高纯度四氯化硅的提纯方法 - Google Patents

高纯度四氯化硅的提纯方法 Download PDF

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WO2018006695A1
WO2018006695A1 PCT/CN2017/088428 CN2017088428W WO2018006695A1 WO 2018006695 A1 WO2018006695 A1 WO 2018006695A1 CN 2017088428 W CN2017088428 W CN 2017088428W WO 2018006695 A1 WO2018006695 A1 WO 2018006695A1
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column
silicon tetrachloride
rectification column
rectification
tray
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PCT/CN2017/088428
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English (en)
French (fr)
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沈祖祥
王姗
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成都蜀菱科技发展有限公司
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/10778—Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof

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  • the invention relates to a method for purifying high-purity silicon tetrachloride, in particular to a method for purifying high-purity silicon tetrachloride by rectification technology.
  • Optical fiber communication materials mainly use high-transparency optical fiber preforms, while high-purity silicon tetrachloride (purity of not less than 99.9999%) is the main raw material for producing high-purity optical fiber preforms.
  • high purity silicon tetrachloride is produced by purifying crude silicon tetrachloride.
  • the purity of optical fiber raw materials directly affects the loss characteristics of optical fibers, which is the key to control the quality of optical fiber products.
  • the content of phosphorus, boron and metal ion impurities such as titanium, copper, iron, etc.
  • the purification of high-purity silicon tetrachloride plays a decisive role in the production process of the entire optical fiber.
  • the crude silicon tetrachloride (purity of 90-99%) prepared by chlorinating industrial silicon or silica may have more than 70 kinds of components, mainly in the form of chloride, and some complexes. .
  • the boron trichloride content is about 1%
  • the trichlorosilane content is about 1.5%
  • the phosphorus trichloride content is about 0.4%.
  • the purification methods of commonly used silicon tetrachloride mainly include rectification method, adsorption method, hydrolysis method, extraction method and complex method.
  • the most commonly used one is the rectification method, which relies on the difference in boiling points of silicon tetrachloride and various impurities to achieve the separation effect.
  • the boiling points of metal chlorides and some non-metal chlorides differ greatly from the boiling points of silicon tetrachloride, which are easily removed as high boiling and low boiling components by rectification.
  • certain polar impurities such as phosphorus chloride, boron trichloride, ferric chloride and other chloride impurities
  • the general rectification column has Big limitations.
  • the invention designs a rectification tower for the purification of high-purity silicon tetrachloride from the physical properties of silicon tetrachloride and its impurity components, thereby realizing continuous industrial production of high-purity tetrachloric acid under relatively simple equipment.
  • the purpose of silicon is to be used to purify high-purity silicon tetrachloride from the physical properties of silicon tetrachloride and its impurity components, thereby realizing continuous industrial production of high-purity tetrachloric acid under relatively simple equipment.
  • the purpose of silicon is a rectification tower for the purification of high-purity silicon tetrachloride from the physical properties of silicon tetrachloride and its impurity components, thereby realizing continuous industrial production of high-purity tetrachloric acid under relatively simple equipment.
  • the invention relates to a method for purifying high-purity silicon tetrachloride, comprising the following steps:
  • the crude silicon tetrachloride is heated and sent to the first rectification column, and the top fraction is refluxed through a first heat exchanger such as a water-cooled heat exchanger, and the other portion is discharged as a low-boiling component;
  • the silicon tetrachloride-containing column liquid is discharged from the bottom of the first rectification column, a part is returned to the bottom of the first rectification column through the reboiler, and the other part is introduced into the second rectification column;
  • the overhead fraction of the second rectification column is refluxed through a second heat exchanger such as a water-cooled heat exchanger, and another portion is produced to obtain high-purity silicon tetrachloride having a purity of not less than 99.9999%.
  • the first rectification column and the second rectification column are respectively a packed column or a tray column.
  • the first rectification column has an operating pressure of from 0.2 to 0.5 MPa, preferably from 0.3 to 0.4 MPa, an operating temperature of from 80 to 120 ° C, preferably from 85 to 90 ° C, most preferably from 86 to 88 ° C.
  • the second rectification column has an operating pressure of from 0.2 to 0.5 MPa, preferably from 0.2 to 0.3 MPa, and an operating temperature of from 80 to 120 ° C, preferably from 80 to 85 ° C, preferably from 82 to 84 ° C.
  • the critical impurity is selected from one or at least two of boron trichloride, phosphorus trichloride, trichlorosilane and dichlorodihydrosilane, for example at least three, or four Kind.
  • the invention further relates to a system for purifying high purity silicon tetrachloride, comprising a first rectification column and a second rectification column.
  • the actual number of plates/package height of the first and second rectification columns is determined by:
  • the key impurities are lighter components with lower boiling points and heavy components with higher boiling points;
  • the invention also relates to a system for purifying high purity silicon tetrachloride, comprising: a first rectification column, a first heat exchanger, a first reboiler, a second rectification column, a second heat exchanger and Second reboiler,
  • the heated crude silicon tetrachloride is sent to the first rectification column comprising a silicon tetrachloride crude feed inlet, the first rectification column being configured such that the first rectification column is The top vapor is returned to the top of the column through the first heat exchanger, and the other portion is discharged as a low boiler, and a portion of the bottom liquid of the first distillation column is heated and evaporated by the first reboiler to Returning to the bottom of the column after the gas phase, and entering the second rectification column; the second rectification column is configured such that the overhead vapor of the second rectification column passes through the second part of the second heat exchanger Returning to the top of the column to continue purification, another part is to produce high-purity silicon tetrachloride; and a part of the bottom liquid of the second rectification column is heated and evaporated into a gas phase by the second reboiler, and then refluxed to the bottom of the column, and the other part Discharge
  • the actual number of plates/package height of the first and second rectification columns is determined by:
  • the key impurity is a light component with a lower boiling point and a heavy component having a higher boiling point than silicon tetrachloride;
  • the first rectification column and the second rectification column are respectively a packed column or a tray column.
  • the tray column is a float valve tower, a sieve tray column, or a bubble column.
  • the system further comprises a preheater connected to the silicon tetrachloride raw material inlet for preheating the silicon tetrachloride coarse material.
  • Figure 1 is a flow chart of a method for purifying high purity silicon tetrachloride.
  • the silicon tetrachloride crude material is heated by the feed preheater 1 and sent to the first rectification column 2; the overhead vapor of the first rectification column is returned to the top of the column after passing through the first water-cooling heat exchanger 4, and the other part As a low boiler discharge; a portion of the bottom liquid of the first rectification column is heated and evaporated into a gas phase by the first reboiler 3, and then returned to the bottom of the column, and another portion enters the second rectification column 5; the tower of the second rectification column
  • the top steam is refluxed to the top of the second water-cooled heat exchanger 6 to continue purification, and the other part is high-purity silicon tetrachloride; the bottom liquid of the second distillation column is heated and evaporated by the second reboiler 7 After the gas phase is formed, it is refluxed to the bottom of the
  • the industrial production of high-purity silicon tetrachloride involves many factors, the type and content of impurities contained in the crude silicon tetrachloride, the process used for purification, the number of distillation columns used in the rectification process, and the height of each distillation column. And structural design, the determination of various operating parameters such as pressure, temperature, reflux ratio, etc. in the rectification process all affect the production efficiency and quality of high-purity silicon tetrachloride.
  • the principle of the conventional rectification method is as follows: the entire rectification process is carried out in a usual rectification column, and the vapor generated by the vaporized liquid in the column flows from the bottom to the top and rises to the top of the column. The steam is cooled again into a liquid flowing from top to bottom. During this continuous gas-liquid two-phase contact process, heat transfer and mass transfer occur, and the latent heat released from the lower steam cooling causes the upper liquid to partially vaporize. The volatile component is transferred from the liquid phase to the gas phase, while the lower vapor releases latent heat to partially condense into a liquid, and the less volatile component changes from a gas phase to a liquid phase.
  • the heat and mass exchange of the gas and liquid phases are carried out in the interior of the rectification column.
  • the volatile components continuously transfer from the liquid phase to the gas phase, and the top portion of the tower
  • the steam is almost entirely a volatile component, that is, a low boiling point.
  • the concentration of the volatile component in the same liquid phase from the top of the column to the bottom of the column is lowered, and the concentration of the less volatile component is increased.
  • the silicon tetrachloride content in the crude silicon tetrachloride is not less than about 97%, about 98%, or about 99%, preferably tetrachlorinated.
  • the silicon content is about 99% or about 99.5%.
  • the crude material of silicon tetrachloride contains various impurity components, including metal chlorides such as phosphorus, boron, titanium, copper, and the like, hydrosilanes, and complexes. Therefore, which one or more impurities are selected as key impurities will directly affect the design of the rectification column, thereby affecting the rectification efficiency.
  • the selection of key impurities takes into account the following criteria:
  • the content of impurities in the crude silicon tetrachloride The content of each impurity in the crude silicon tetrachloride is measured, and the impurity having a large content is a key impurity that must be removed.
  • the content of hydrochlorosilane mainly trichlorosilane and dichlorodihydrosilane
  • the content of phosphorus trichloride is about 0.2. %. Therefore, trichlorosilane, dichlorosilane, and phosphorus trichloride can be used as key impurities.
  • the key impurities may be boron trichloride, phosphorus trichloride, trichlorosilane, dichlorodihydrosilane or a combination thereof.
  • the rectification column is generally divided into a packed column and a plate column, wherein the latter further includes three types of a valve tower, a sieve column, and a bubble column.
  • the packed tower has a relatively small operating range, is difficult to clean, and is more suitable for corrosive materials.
  • cooling or removing heat is needed to remove heat of reaction or heat during gas-liquid contact, it involves liquid uniformity.
  • the structure is complicated, the structure is simple, and the cost is low.
  • the plate type tower has a high liquid holding capacity, a large liquid-gas ratio, a relatively easy installation and maintenance, and a relatively accurate design, and the safety factor can be made smaller.
  • the purification of high purity silicon tetrachloride is carried out in tandem using a rectification column.
  • the first rectification column mainly removes low boilers
  • the second rectification column mainly removes high boilers.
  • the distillation column is a plate column, the number of plates is calculated; when the distillation column is When filling the tower, calculate the packing height).
  • the rectification column designed according to the method of the present invention can effectively remove key impurities, improve the production efficiency of high-purity silicon tetrachloride, and obtain high-purity four.
  • the quality of silicon chloride is relatively stable, achieving the purpose of continuous industrial production of high-purity silicon tetrachloride.
  • Example 1 Determining the actual number of plates in the first rectification column
  • the first rectification column mainly removes low boilers, and the main key impurity is trichlorosilane.
  • the saturated vapor pressure of trichlorosilane is 0.43 MPa
  • the requirement for impurities of 6N grade silicon tetrachloride is to reduce the initial content of about 100 ppm of impurities to 1 ppb (ie 0.001 ppm).
  • the second rectification column mainly removes high boilers, and the main key impurity is phosphorus trichloride.
  • the saturated vapor pressure of silicon tetrachloride is 0.2 MPa
  • the crude silicon tetrachloride having a purity of 99% is preheated and sent to the first rectification column; the temperature of the first rectification column is controlled to be about 87 ° C, the pressure is about 0.3 MPa; the top of the first rectification column After the steam passes through the first water-cooled heat exchanger, a part of the steam is refluxed to the top of the tower, and the other part is discharged as a low-boiling substance, which contains impurities such as trichlorosilane; and a part of the bottom liquid of the first distillation column is heated and evaporated by the first reboiler.
  • the gas phase After the gas phase is formed, it is refluxed to the bottom of the column, and the other portion is introduced into the second rectification column; the temperature of the second rectification column is controlled to be about 83 ° C, the pressure is about 0.2 MPa; and the overhead vapor of the second rectification column is exchanged by the second water cooling After the heater, a part of the heat is refluxed to the top of the tower to continue purification, and the other part is high-purity silicon tetrachloride; the bottom of the second distillation column is passed through the second The boiling device is heated to evaporate into a gas phase and then refluxed to the bottom of the column, and the other portion is discharged as a high-boiling substance containing impurities such as phosphorus trichloride.
  • the first rectification column and the second rectification column are both plate columns, wherein the number of plates in the first rectification column is 63, and the number of plates in the second rectification column is 114.
  • the yield of high purity silicon tetrachloride was 99%. After testing, the content of trichlorosilane in the obtained high-purity silicon tetrachloride product is less than 1 ppb, the content of phosphorus trichloride is less than 1 ppb, and the purity of silicon tetrachloride is greater than 99.9999%.
  • the crude silicon tetrachloride having a purity of 99% is preheated and sent to the first rectification column; the temperature of the first rectification column is controlled to be about 87 ° C, the pressure is about 0.3 MPa; the top of the first rectification column After the steam passes through the first water-cooled heat exchanger, a part of the steam is refluxed to the top of the tower, and the other part is discharged as a low-boiling substance, which contains impurities such as trichlorosilane; and a part of the bottom liquid of the first distillation column is heated and evaporated by the first reboiler.
  • the gas phase After the gas phase is formed, it is refluxed to the bottom of the column, and the other portion is introduced into the second rectification column; the temperature of the second rectification column is controlled to be about 83 ° C, the pressure is about 0.2 MPa; and the overhead vapor of the second rectification column is exchanged by the second water cooling After the heater, a part of the heat is refluxed to the top of the tower to continue purification, and the other part is high-purity silicon tetrachloride; a part of the bottom liquid of the second distillation tower is heated by a second reboiler to be vaporized and returned to the bottom of the column, and One is discharged as a high-boiling substance containing impurities such as phosphorus trichloride.
  • the first rectification column is a plate column, and the actual number of plates is 63.
  • the second rectification column is a packed column having a packing height of 34.2 m.
  • the yield of high purity silicon tetrachloride was 99%. After testing, the content of trichlorosilane in the obtained high-purity silicon tetrachloride product is less than 1 ppb, the content of phosphorus trichloride is less than 1 ppb, and the purity of silicon tetrachloride is greater than 99.9999%.
  • the crude silicon tetrachloride having a purity of 99% is preheated and sent to the first rectification column; the temperature of the first rectification column is controlled to be about 108 ° C, the pressure is about 0.4 MPa; the top of the first rectification column After the steam passes through the first water-cooled heat exchanger, a part of the steam is refluxed to the top of the tower, and the other part is discharged as a low-boiling substance, which contains impurities such as trichlorosilane; and a part of the bottom liquid of the first distillation column is heated and evaporated by the first reboiler.
  • the gas phase After the gas phase, it is refluxed to the bottom of the column, and the other portion enters the second rectification column; the temperature of the second rectification column is controlled to be about 90 ° C, the pressure is about 0.25 MPa; the overhead vapor of the second rectification column is exchanged by the second water cooling After the heater, a part of the heat is refluxed to the top of the tower to continue purification, and the other part is high-purity silicon tetrachloride; a part of the bottom liquid of the second distillation tower is heated by a second reboiler to be vaporized and returned to the bottom of the column, and One is discharged as a high-boiling substance containing impurities such as phosphorus trichloride.
  • the first rectification column is a plate column, and the actual number of plates is 70.
  • the second rectification column is a packed column having a packing height of 22.5 m.
  • the yield of high purity silicon tetrachloride was 99%. After testing, the content of trichlorosilane in the obtained high-purity silicon tetrachloride product is less than 1 ppb, the content of phosphorus trichloride is less than 1 ppb, and the purity of silicon tetrachloride is greater than 99.9999%.
  • the crude silicon tetrachloride having a purity of 99% is preheated and sent to the first rectification column; the temperature of the first rectification column is controlled to be about 116 ° C, the pressure is about 0.5 MPa; the top of the first rectification column After the steam passes through the first water-cooling heat exchanger, a part of the steam is refluxed to the top of the tower, and the other part is discharged as a low-boiling substance, which contains impurities such as trichlorosilane; and a part of the tower liquid of the first distillation column is passed through After the first reboiler is heated to evaporate into a gas phase, it is refluxed to the bottom of the column, and the other portion is introduced into the second rectification column; the temperature of the second rectification column is controlled to be about 105 ° C, and the pressure is about 0.4 MPa; the second rectification column is The steam at the top of the tower is refluxed to the top of the tower through the
  • the first rectification column is a plate column, and the actual number of plates is 65.
  • the second rectification column is a packed column with a packing height of 24 m.
  • the yield of high purity silicon tetrachloride was 99%. After testing, the content of trichlorosilane in the obtained high-purity silicon tetrachloride product is less than 1 ppb, the content of phosphorus trichloride is less than 1 ppb, and the purity of silicon tetrachloride is greater than 99.9999%.

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Abstract

一种使用精馏塔来提纯高纯度四氯化硅的方法，其中所述精馏塔的塔板数或填料高度根据关键杂质的选择来计算确定。

Description

高纯度四氯化硅的提纯方法 技术领域
本发明涉及一种高纯度四氯化硅的提纯方法，尤其涉及利用精馏技术提纯高纯度四氯化硅的方法。
背景技术
在信息化时代，因光纤传导容量大、效率高、损失小，光纤通讯成为首选。光纤通讯材料主要使用高透明度的光纤预制棒，而高纯度四氯化硅(纯度不低于99.9999％)则是生产高纯度光纤预制棒的主要原料。通常，高纯度四氯化硅通过提纯四氯化硅粗料制得。众所周知，光纤原料的纯度直接影响光纤的损耗特性，是控制光纤产品质量的关键。一般要求磷、硼和金属离子杂质例如钛、铜、铁等的含量低于1ppb，氢氧根离子的含量低于1ppb。提纯的目的则是最大限度地除去这些引起光纤吸收损耗的杂质。因此高纯度四氯化硅的提纯在整个光纤的生产过程中起着决定性的作用。
通过氯化工业硅或二氧化硅制备的四氯化硅粗料(纯度为90-99％)可能存在的组分约有70多种，其主要以氯化物的形式存在，也有一些络合物。例如，纯度为97％的四氯化硅粗料中，三氯化硼含量为约1％，三氯氢硅含量为约1.5％，三氯化磷含量为约0.4％。目前常用的四氯化硅的提纯方法主要有精馏法、吸附法、水解法、萃取法以及络合法等。其中最常用的是精馏法，其依靠四氯化硅与各种杂质的沸点不同来实现分离效果。金属氯化物和一些非金属氯化物的沸点和四氯化硅的沸点相差很大，通过精馏法容易将它们作为高沸点和低沸点组分除去。然而，对于沸点与四氯化硅非常接近的组分，特别是某些极性杂质，例如三氯化磷、三氯化硼、三氯化铁等氯化物杂质，一般的精馏塔具有较大的局限性。尤其是要进一步彻底分离四氯化硅中的杂质硼、磷卤化物难度更大，而硼、磷对光纤质量及硅材料的导电性起主要作用，必须彻底加以分离。此外，含氢氯硅烷对光纤危害也很大，必须彻底除去。
目前国内生产高纯度四氯化硅工艺产品质量不稳定，不能实现连续工业化生产，无法满足光纤领域的使用要求。因此需要一种设备简单并能实现高纯度四氯化硅连续生产的方法。
本发明从四氯化硅及其杂质组分的物性出发，特意针对高纯度四氯化硅的提纯设计精馏塔，从而实现在设备相对简单的情况下，能连续工业化生产高纯度四氯化硅的目的。
发明内容
本发明涉及一种高纯度四氯化硅的提纯方法，包括以下步骤：
a.将四氯化硅粗料加热后输送至第一精馏塔，塔顶馏分经第一换热器如水冷换热器后一部分回流，另一部分作为低沸物组分排出；
b.将含四氯化硅的塔釜液从第一精馏塔的塔底排出，一部分通过再沸器回流至第一精馏塔底部，另一部分进入第二精馏塔；
c.将第二精馏塔的塔釜液从塔底排出，一部分通过再沸器回流至第二精馏塔，另一部分作为高沸物组分排出；和
d.第二精馏塔的塔顶馏分经第二换热器如水冷换热器后一部分回流，另一部分采出得到纯度不低于99.9999％的高纯度四氯化硅。
根据本发明的一个实施方案，第一精馏塔和第二精馏塔分别是填料塔或板式塔。
根据本发明的一个实施方案，第一精馏塔的操作压力为0.2-0.5MPa，优选0.3-0.4MPa，操作温度为80-120℃，优选85-90℃，最优选86-88℃。
根据本发明的一个实施方案，第二精馏塔的操作压力为0.2-0.5MPa，优选0.2-0.3MPa，操作温度为80-120℃，优选80-85℃，优选82-84℃。
根据本发明的一个实施方案，所述关键杂质选自三氯化硼、三氯化磷、三氯氢硅和二氯二氢硅中的一种或至少两种，例如至少三种，或四种。
本发明还涉及一种用于高纯度四氯化硅提纯的系统，包括第一精馏塔和第二精馏塔。
根据本发明的实施方案中，第一精馏塔和第二精馏塔的实际塔板数/填料高度通过以下方式确定：
(1)根据高纯度四氯化硅的用途以及四氯化硅粗料中杂质的含量，确定四氯化硅产品中的关键杂质；
(2)根据以下公式计算相对挥发度α：
α＝重组分的饱和蒸汽压/轻组分的饱和蒸汽压
其中，关键杂质和四氯化硅相比，沸点较低的为轻组分，沸点较高的为重组分；
(3)根据αn＝ω/ω0计算理论塔板数n，其中ω0是关键杂质的最初含量，ω是关键杂质的最终要求含量；
(4)根据N＝n/b计算板式塔的实际塔板数，其中b是塔板效率；或根据M＝N*c计算填料塔的填料高度M，其中c是等板高度。
本发明还涉及一种用于高纯度四氯化硅提纯的系统，包括：第一精馏塔，第一换热器，第一再沸器，第二精馏塔，第二换热器和第二再沸器，
其中，经加热的四氯化硅粗料被输送至所述第一精馏塔包括四氯化硅粗料入口，所述第一精馏塔被构造成使得所述第一精馏塔的塔顶蒸汽经所述第一换热器后一部分回流至塔顶，另一部分作为低沸物排出，并且使得所述第一精馏塔的塔釜液一部分经过所述第一再沸器加热蒸发成气相后回流至塔底，另一部分进入所述第二精馏塔；所述第二精馏塔被构造成使得所述第二精馏塔的塔顶蒸汽经所述第二换热器后一部分回流至塔顶继续提纯，另一部分采出高纯度四氯化硅；并且使得第二精馏塔的塔釜液一部分经过所述第二再沸器加热蒸发成气相后回流至塔底，另一部分作为高沸物排出。
根据本发明的一个实施方案，所述第一精馏塔和第二精馏塔的实际塔板数/填料高度通过以下方式来确定：
(1)根据高纯度四氯化硅的用途以及四氯化硅粗料中杂质的含量，确定四氯化硅产品中的关键杂质；
(2)根据以下公式计算相对挥发度α：
α＝重组分的饱和蒸汽压/轻组分的饱和蒸汽压
其中，所述关键杂质和四氯化硅相比，沸点较低的为轻组分，沸点较高的为重组分；
(3)根据αn＝ω/ω0计算理论塔板数n，其中ω0是所述关键杂质的最初含量，ω是所述关键杂质的最终要求含量；
(4)根据N＝n/b计算板式塔的实际塔板数，其中b是塔板效率；或根据M＝N*c计算填料塔的填料高度M，其中c是等板高度。
根据本发明的一个实施方案，所述第一精馏塔和第二精馏塔分别是填料塔或板式塔。
根据本发明的一个实施方案，所述板式塔为浮阀塔、筛板塔、或泡罩塔。
根据本发明的一个实施方案，所述系统还包括预热器，所述预热器连接至所述四氯化硅粗料入口用于预热四氯化硅粗料。
附图说明
图1是高纯度四氯化硅的提纯方法的流程图。四氯化硅粗料经进料预热器1加热后输送至第一精馏塔2；第一精馏塔的塔顶蒸汽经第一水冷换热器4后一部分回流至塔顶，另一部分作为低沸物排出；第一精馏塔的塔釜液一部分经过第一再沸器3加热蒸发成气相后回流至塔底，另一部分进入第二精馏塔5；第二精馏塔的塔顶蒸汽经第二水冷换热器6后一部分回流至塔顶继续提纯，另一部分则采出高纯度四氯化硅；第二精馏塔的塔釜液一部分经过第二再沸器7加热蒸发成气相后回流至塔底，另一部分作为高沸物排出。
具体实施方式
高纯四氯化硅的工业化生产涉及很多因素，四氯化硅粗料中所含杂质的类型和含量，提纯所用的工艺，使用精馏法时精馏塔的数量，各精馏塔的高度和结构设计，精馏工艺中各操作参数如压力、温度、回流比等的确定，均影响高纯四氯化硅的生产效率和质量。
就提纯工艺而言，常用的精馏法的原理如下：整个精馏过程在通常的精馏塔内进行，在塔内被汽化的液体所产生的蒸汽自下而上流动，而升入塔顶蒸汽又被冷却成液体自上而下流动，在这种连续的气液两相接触过程中就产生传热和传质的现象，来自下方的蒸汽冷却时放出的潜热使上方的液体部分汽化，易挥发的组分从液相转入气相，而同时下方蒸汽放出潜热就部分凝为液体，难挥发的组分从气相变为液相。这样在精馏塔的内部随处进行着气液相的热量和质量的交换，当塔身有一定的高度，经过一定时间的回流，易挥发的组分不断从液相向气相转移，塔顶部分的蒸汽几乎全是易挥发的组分，也就是低沸点，同样的液相从塔顶到塔底易挥发的组分浓度降低，难挥发的组分浓度上升，塔底最后得到的几乎全是难挥发的组分，也就是高沸点部分，这时整个精馏塔内部达到一个动态平衡，不同的高度由不同的组分组成的组分层，从而达到分离提纯混合液的目的。
在现有的工业生产中，对高纯四氯化硅提纯工艺的改进主要集中于操作参数的优化以及精馏工艺的改进，例如使用多于两个的精馏塔串联来提高效率。据发明人所知，目前还没有专门针对高纯度四氯化硅的提纯设计的精馏塔。由于四氯化硅粗料中杂质组分的特异性以及高纯度四氯化硅对杂质含量的高要求，由针对性涉设计的精馏塔不仅能简化提纯工艺(例如减少精馏塔的数量，不需要与其他提纯法例如吸附法结合)，更能提高生产效率，降低生产成本。
关键杂质
一般四氯化硅粗料中四氯化硅含量不低于约97％、约98％、或约99％，优选四氯化 硅含量为约99％或约99.5％。四氯化硅的粗料含有各种杂质组分，包括磷、硼、钛、铜等金属氯化物、含氢硅烷以及络合物等杂质。因此，选择哪一种或几种杂质作为关键杂质将直接影响精馏塔的设计，从而影响精馏效率。关键杂质的选择综合考虑以下标准：
(1)根据高纯四氯化硅的用途，产品对杂质的要求。例如，硼极大影响半导体和光纤的导电性，因此对于用于制备半导体或光纤的高纯四氯化硅而言，即使是ppm范围的痕量硼也是不可接受的。因此，高纯四氯化硅中必须除去硼化物，例如三氯化硼。
(2)四氯化硅粗料中杂质的含量。测量四氯化硅粗料中各杂质的含量，含量较大的杂质则是必须除去的关键杂质。例如，在纯度为99％的四氯化硅粗料中，含氢氯硅烷(主要是三氯氢硅和二氯二氢硅)的含量约为0.7％，三氯化磷的含量约为0.2％。因此，可以将三氯氢硅、二氯氢硅、三氯化磷作为关键杂质。
在可以除去难以分离的关键杂质的操作参数下，沸点差异较大的一般杂质必然也可以除去。在本发明的高纯度四氯化硅的提纯方法中，关键杂质可以是三氯化硼、三氯化磷、三氯氢硅、二氯二氢硅或其组合。
精馏塔
根据本发明的方法可使用本领域技术人员熟知的任何类型的精馏塔。通常，精馏塔一般分为填料塔和板式塔，其中后者又包括浮阀塔、筛板塔、泡罩塔三种。填料塔与板式塔相比，操作范围相对较小，清洗难度大，更适合腐蚀性物系，当气液接触过程中需要冷却以移除反应热或溶解热时，其因涉及液体均布问题而使结构复杂化，结构简单、造价便宜。但板式塔持液量较高，液气比适应范围大，安装检修比较容易，而且设计比较准确，安全系数可取得更小。
在本发明的一种实施方案中，采用精馏塔串联的方式进行高纯四氯化硅的提纯。第一精馏塔主要除去低沸物，第二精馏塔主要除去高沸物。
在本发明的一种实施方案中，需要根据关键杂质的选择以及其物性特点计算精馏塔的塔板数或填料高度(当精馏塔为板式塔时，计算塔板数；当精馏塔为填料塔时，计算填料高度)。
当关键杂质选定后，其相对挥发度可以根据公式α＝重组分的饱和蒸汽压/轻组分的饱和蒸汽压来确定。然后根据αn＝ω/ω0计算理论塔板数n，其中ω0是关键杂质的最初含量，ω是关键杂质的最终要求含量；并根据N＝n/b计算板式塔的实际塔板数N，其中b是塔板 效率；或根据M＝N*c计算填料塔的填料高度M，其中c是等板高。
基于针对高纯四氯化硅的用途及其杂质物性的特异性，根据本发明的方法设计的精馏塔能有效除去关键杂质，提高高纯四氯化硅的生产效率，获得的高纯四氯化硅质量比较稳定，实现连续工业化生产高纯四氯化硅的目的。
实施例
为了进一步理解本发明，下面结合实施例对本发明提供的工业化生产四氯化硅的方法进行说明。本发明的保护范围不受以下实施例的任何限制。
实施例1.确定第一精馏塔的实际塔板数
第一精馏塔主要去除低沸物，其中主要的关键杂质是三氯氢硅。在操作条件下，三氯氢硅的饱和蒸汽压是0.43MPa，四氯化硅的饱和蒸汽压是0.21MPa。因此，三氯氢硅与四氯化硅的相对挥发度α＝0.21/0.43＝0.49。6N级四氯化硅对杂质的要求是要将最初含量为约100ppm的杂质降低至1ppb(即0.001ppm)以下，根据αn＝1ppb/100ppm＝10-5计算得到理论板数17。第一精馏塔的塔板效率为0.27，因此最终确定第一精馏塔的最终实际塔板数为17/0.27＝63。
实施例2.确定第二精馏塔的填料高度
第二精馏塔主要去除高沸物，其中主要的关键杂质是三氯化磷。在操作条件下，四氯化硅的饱和蒸汽压是0.2MPa，三氯化磷的饱和蒸汽压是0.14MPa。因此，三氯化磷与四氯化硅的相对挥发度α＝0.14/0.2＝0.7。根据αn＝10-5计算得到理论板数32，塔板效率为0.28，则实际塔板数为32/0.28＝114。四氯化硅精馏工艺中的等板高度为0.3m，因此最终确定第二精馏塔的最终填料高度为114*0.3＝34.2m。
实施例3.高纯度四氯化硅的提纯方法
将纯度为99％的四氯化硅粗料预加热后输送至第一精馏塔；控制第一精馏塔的温度为约87℃，压力为约0.3MPa；第一精馏塔的塔顶蒸汽经第一水冷换热器后一部分回流至塔顶，另一部分作为低沸物排出，其中含有三氯氢硅等杂质；第一精馏塔的塔釜液一部分经过第一再沸器加热蒸发成气相后回流至塔底，另一部分进入第二精馏塔；控制第二精馏塔的温度为约83℃，压力为约0.2MPa；第二精馏塔的塔顶蒸汽经第二水冷换热器后一部分回流至塔顶继续提纯，另一部分则采出高纯度四氯化硅；第二精馏塔的塔釜液一部分经过第二再 沸器加热蒸发成气相后回流至塔底，另一部作为高沸物排出，其中含有三氯化磷等杂质。第一精馏塔和第二精馏塔均为板式塔，其中第一精馏塔的塔板数是63，第二精馏塔的塔板数是114。高纯度四氯化硅的产率为99％。经检测，所得高纯度四氯化硅产品中三氯氢硅含量小于1ppb，三氯化磷含量小于1ppb，四氯化硅纯度大于99.9999％。
实施例4.高纯度四氯化硅的提纯方法
将纯度为99％的四氯化硅粗料预加热后输送至第一精馏塔；控制第一精馏塔的温度为约87℃，压力为约0.3MPa；第一精馏塔的塔顶蒸汽经第一水冷换热器后一部分回流至塔顶，另一部分作为低沸物排出，其中含有三氯氢硅等杂质；第一精馏塔的塔釜液一部分经过第一再沸器加热蒸发成气相后回流至塔底，另一部分进入第二精馏塔；控制第二精馏塔的温度为约83℃，压力为约0.2MPa；第二精馏塔的塔顶蒸汽经第二水冷换热器后一部分回流至塔顶继续提纯，另一部分则采出高纯度四氯化硅；第二精馏塔的塔釜液一部分经过第二再沸器加热蒸发成气相后回流至塔底，另一部作为高沸物排出，其中含有三氯化磷等杂质。第一精馏塔是板式塔，其实际板数是63。第二精馏塔是填料塔，其填料高度是34.2m。高纯度四氯化硅的产率为99％。经检测，所得高纯度四氯化硅产品中三氯氢硅含量小于1ppb，三氯化磷含量小于1ppb，四氯化硅纯度大于99.9999％。
实施例5.高纯度四氯化硅的提纯方法
将纯度为99％的四氯化硅粗料预加热后输送至第一精馏塔；控制第一精馏塔的温度为约108℃，压力为约0.4MPa；第一精馏塔的塔顶蒸汽经第一水冷换热器后一部分回流至塔顶，另一部分作为低沸物排出，其中含有三氯氢硅等杂质；第一精馏塔的塔釜液一部分经过第一再沸器加热蒸发成气相后回流至塔底，另一部分进入第二精馏塔；控制第二精馏塔的温度为约90℃，压力为约0.25MPa；第二精馏塔的塔顶蒸汽经第二水冷换热器后一部分回流至塔顶继续提纯，另一部分则采出高纯度四氯化硅；第二精馏塔的塔釜液一部分经过第二再沸器加热蒸发成气相后回流至塔底，另一部作为高沸物排出，其中含有三氯化磷等杂质。第一精馏塔是板式塔，其实际板数是70。第二精馏塔是填料塔，其填料高度是22.5m。高纯度四氯化硅的产率为99％。经检测，所得高纯度四氯化硅产品中三氯氢硅含量小于1ppb，三氯化磷含量小于1ppb，四氯化硅纯度大于99.9999％。
实施例6.高纯度四氯化硅的提纯方法
将纯度为99％的四氯化硅粗料预加热后输送至第一精馏塔；控制第一精馏塔的温度为约116℃，压力为约0.5MPa；第一精馏塔的塔顶蒸汽经第一水冷换热器后一部分回流至塔顶，另一部分作为低沸物排出，其中含有三氯氢硅等杂质；第一精馏塔的塔釜液一部分经 过第一再沸器加热蒸发成气相后回流至塔底，另一部分进入第二精馏塔；控制第二精馏塔的温度为约105℃，压力为约0.4MPa；第二精馏塔的塔顶蒸汽经第二水冷换热器后一部分回流至塔顶继续提纯，另一部分则采出高纯度四氯化硅；第二精馏塔的塔釜液一部分经过第二再沸器加热蒸发成气相后回流至塔底，另一部作为高沸物排出，其中含有三氯化磷等杂质。第一精馏塔是板式塔，其实际板数是65。第二精馏塔是填料塔，其填料高度是24m。高纯度四氯化硅的产率为99％。经检测，所得高纯度四氯化硅产品中三氯氢硅含量小于1ppb，三氯化磷含量小于1ppb，四氯化硅纯度大于99.9999％。
以上所述仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (16)

  1. 一种高纯度四氯化硅的提纯方法，包括以下步骤：
    a.将四氯化硅粗料加热后输送至第一精馏塔，塔顶馏分经第一换热器如水冷换热器后一部分回流，另一部分作为低沸物组分排出；
    b.将含四氯化硅的塔釜液从所述第一精馏塔的塔底排出，一部分通过再沸器回流至第一精馏塔底部，另一部分进入第二精馏塔；
    c.将所述第二精馏塔的塔釜液从塔底排出，一部分通过再沸器回流至所述第二精馏塔，另一部分作为高沸物组分排出；和
    d.所述第二精馏塔的塔顶馏分经第二换热器如水冷换热器后一部分回流，另一部分采出得到纯度不低于99.9999％的高纯度四氯化硅。
  2. 如权利要求1所述的方法，其特征在于，所述第一精馏塔和第二精馏塔分别是填料塔或板式塔。
  3. 如权利要求1或2所述的方法，其特征在于，所述第一精馏塔和第二精馏塔的实际塔板数/填料高度通过以下方式确定：
    (1)根据高纯度四氯化硅的用途以及四氯化硅粗料中杂质的含量，确定四氯化硅产品中的关键杂质；
    (2)根据以下公式计算相对挥发度α：
    α＝重组分的饱和蒸汽压/轻组分的饱和蒸汽压
    其中，所述关键杂质和四氯化硅相比，沸点较低的为轻组分，沸点较高的为重组分；
    (3)根据αn＝ω/ω0计算理论塔板数n，其中ω0是所述关键杂质的最初含量，ω是所述关键杂质的最终要求含量；
    (4)根据N＝n/b计算板式塔的实际塔板数，其中b是塔板效率；或根据M＝n*c计算填料塔的填料高度M，其中c是等板高度。
  4. 如权利要求1所述的方法，其特征在于，所述第一精馏塔的操作压力为0.2-0.5MPa，优选0.3-0.4MPa，操作温度为80-120℃，优选85-90℃，最优选86-88℃。
  5. 如权利要求1所述的方法，其特征在于，所述第二精馏塔的操作压力为0.2-0.5MPa，优选0.2-0.3MPa，操作温度为80-120℃，优选80-85℃，优选82-84℃。
  6. 如权利要求3所述的方法，其中所述关键杂质选自三氯化硼、三氯化磷、三氯氢硅和二氯二氢硅中的一种或至少两种。
  7. 如权利要求3所述的方法，其特征在于，所述板式塔为浮阀塔、筛板塔、或泡罩塔。
  8. 一种用于高纯度四氯化硅提纯的系统，包括第一精馏塔和第二精馏塔。
  9. 权利要求8所述的系统，其特征在于，所述第一精馏塔和第二精馏塔的实际塔板数/填料高度通过以下方式确定：
    (1)根据高纯度四氯化硅的用途以及四氯化硅粗料中杂质的含量，确定四氯化硅产品中的关键杂质；
    (2)根据以下公式计算相对挥发度α：
    α＝重组分的饱和蒸汽压/轻组分的饱和蒸汽压
    其中，所述关键杂质和四氯化硅相比，沸点较低的为轻组分，沸点较高的为重组分；
    (3)根据αn＝ω/ω0计算理论塔板数n，其中ω0是所述关键杂质的最初含量，ω是所述关键杂质的最终要求含量；
    (4)根据N＝n/b计算板式塔的实际塔板数，其中b是塔板效率；或根据M＝N*c计算填料塔的填料高度M，其中c是等板高度。
  10. 如权利要求8所述的系统，其特征在于，所述第一精馏塔和第二精馏塔分别是填料塔或板式塔。
  11. 如权利要求9所述的系统，其特征在于，所述板式塔为浮阀塔、筛板塔、或泡罩塔。
  12. 一种用于高纯度四氯化硅提纯的系统，包括：第一精馏塔，第一换热器，第一再沸器，第二精馏塔，第二换热器和第二再沸器，
    其中，所述第一精馏塔包括四氯化硅粗料入口，所述第一精馏塔被构造成使得所述第一精馏塔的塔顶蒸汽经所述第一换热器后一部分回流至塔顶，另一部分作为低沸物排出，并且使得所述第一精馏塔的塔釜液一部分经过所述第一再沸器加热蒸发成气相后回流至塔底，另一部分进入所述第二精馏塔；所述第二精馏塔被构造成使得所述第二精馏塔的塔顶蒸汽经所述第二换热器后一部分回流至塔顶继续提纯，另一部分采出高纯度四氯化硅；并且使得第二精馏塔的塔釜液一部分经过所述第二再沸器加热蒸发成气相后回流至塔底，另一部作为高沸物排出。
  13. 权利要求12所述的系统，其特征在于，所述第一精馏塔和第二精馏塔的实际塔板数/填料高度通过以下方式确定：
    (1)根据高纯度四氯化硅的用途以及四氯化硅粗料中杂质的含量，确定四氯化硅产品中的关键杂质；
    (2)根据以下公式计算相对挥发度α：
    α＝重组分的饱和蒸汽压/轻组分的饱和蒸汽压
    其中，所述关键杂质和四氯化硅相比，沸点较低的为轻组分，沸点较高的为重组分；
    (3)根据αn＝ω/ω0计算理论塔板数n，其中ω0是所述关键杂质的最初含量，ω是所述关键杂质的最终要求含量；
    (4)根据N＝n/b计算板式塔的实际塔板数，其中b是塔板效率；或根据M＝N*c计算填料塔的填料高度M，其中c是等板高度。
  14. 如权利要求12或13所述的系统，其特征在于，所述第一精馏塔和第二精馏塔分别是填料塔或板式塔。
  15. 如权利要求12或13所述的系统，其特征在于，所述板式塔为浮阀塔、筛板塔、或泡罩塔。
  16. 如权利要求12所述的系统，其特征在于，所述系统还包括预热器，所述预热器连接至所述四氯化硅粗料入口用于预热四氯化硅粗料。
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