CN212315554U - Device for removing carbon-containing impurities in high-purity chlorosilane production - Google Patents
Device for removing carbon-containing impurities in high-purity chlorosilane production Download PDFInfo
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- CN212315554U CN212315554U CN202020204804.4U CN202020204804U CN212315554U CN 212315554 U CN212315554 U CN 212315554U CN 202020204804 U CN202020204804 U CN 202020204804U CN 212315554 U CN212315554 U CN 212315554U
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Abstract
The utility model discloses a device for getting rid of carbonaceous impurity in high-purity chlorosilane production. The device includes: the rectifying device is provided with a material inlet and a material outlet and is used for removing high-boiling point components and low-boiling point components in the trichlorosilane raw material; and the adsorption device is communicated with a material outlet of the rectification device, and the adsorption device is filled with a resin type adsorbent rich in amino and a platinum catalyst. Use the technical scheme of the utility model, utilize inside to fill the adsorption equipment who has resin type adsorbent and platinum catalyst that are rich in amino, remove methyl chlorosilane impurity through adsorption process to reduce the total methyl chlorosilane impurity content that contains of rectification product in the polycrystalline silicon production process to below 50ppb, produce high-purity 4N above, the high-purity chlorosilane of carbon-containing impurity < 50 ppb.
Description
Technical Field
The utility model relates to a chemical industry technical field particularly, relates to a device that is arranged in high-purity chlorosilane production to get rid of carbon-containing impurity.
Background
With the development of the photovoltaic industry, the market has higher and higher requirements on product quality. This puts higher demands on the control of the rectification products in the production process of polysilicon.
The influence of the content of impurities in the rectified product on the quality of the polysilicon product is very important, so that the impurities must be controlled to be low enough, and even completely removed. The separation of impurity components can be realized more thoroughly in the rectification purification process, and most of impurities can be removed in high and low boiling points of a rectification system. However, the trace impurities in the rectification product cannot be completely purified by rectification because the content of the impurities and the trace impurities are basically in ppm, ppb level, such as B, P and the like, and on the other hand, part of the impurities can be close to the boiling point of chlorosilane, even exist in the form of azeotrope, such as C. For the influence and the removal process of P, B impurities, literature reports have been made, and boron and phosphorus impurities are removed by adopting an adsorption method and a zone melting method. There are still not many reports on the removal process of carbon impurities.
Research shows that the minority carrier lifetime of polycrystalline silicon can be obviously reduced due to excessive carbon impurity content, and the conversion efficiency of silicon wafers is reduced. Therefore, the carbon content is also an important factor influencing the quality of the high-purity chlorosilane products. The carbon component in the chlorosilane mainly comes from volatilization of a graphite piece and the like in a reduction furnace, and the total carbon in the chlorosilane mainly exists in the form of methyl chlorosilane, such as methyl dichlorosilane, methyl trichlorosilane, dimethyl chlorosilane, dimethyl dichlorosilane and trimethyl chlorosilane. Wherein the boiling points of the dimethylchlorosilane and the methylchlorosilane are relatively close to that of the trichlorosilane, and azeotrope is easily formed; the boiling points of the trimethylchlorosilane and the methyltrichlorosilane are close to that of the silicon tetrachloride, and an azeotrope is easily formed. Therefore, the carbon-containing impurities in the chlorosilane cannot be deeply removed by adopting the common rectification method. After the carbon is accumulated in the system, the continuous improvement of the product quality is hindered.
SUMMERY OF THE UTILITY MODEL
The utility model aims at providing a device that is arranged in high-purity chlorosilane production to get rid of the carbon-containing impurity's in the chlorosilane technical problem can't be got rid of to the method of ordinary rectification among the solution prior art degree of depth.
In order to achieve the above object, according to one aspect of the present invention, there is provided an apparatus for removing carbon-containing impurities in the production of high-purity chlorosilane. The device includes: the rectifying device is provided with a material inlet and a material outlet and is used for removing high-boiling point components and low-boiling point components in the trichlorosilane raw material; and the adsorption device is communicated with a material outlet of the rectification device, and the adsorption device is filled with a resin type adsorbent rich in amino and a platinum catalyst.
Further, a material outlet of the rectifying device is communicated with the adsorption device through a centrifugal pump.
Furthermore, the rectifying device comprises a first rectifying tower and a second rectifying tower which are arranged in series, and the adsorption device is communicated with a material outlet of the second rectifying tower through a centrifugal pump.
Furthermore, the first rectifying tower and the second rectifying tower are respectively rectifying towers made of 304 stainless steel materials, the tower diameters are 1.2-1.5 m respectively, the tower heights are 30-40 m respectively, silk screen packing is filled in the towers, the heights of the silk screen packing are 20-30 m, and the tower heights are higher than the heights of the silk screen packing.
Furthermore, the adsorption device comprises two sets of adsorption columns which operate independently.
Further, the column length of the adsorption column was 2 meters and the nominal diameter was DN 250.
Furthermore, the outer wall of the adsorption column is provided with a temperature control interlayer.
Further, the temperature control interlayer is a water temperature control interlayer.
Furthermore, polytetrafluoroethylene coatings are arranged in the two sets of adsorption columns.
Use the technical scheme of the utility model, utilize inside to fill the adsorption equipment who has resin type adsorbent and platinum catalyst that are rich in amino, remove methyl chlorosilane impurity through adsorption process to reduce the total methyl chlorosilane impurity content that contains of rectification product in the polycrystalline silicon production process to below 50ppb, produce high purity more than 4N, the chlorosilane that contains carbon impurity < 50 ppb.
Drawings
The accompanying drawings, which form a part of the present application, 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 and not to limit the invention. In the drawings:
fig. 1 shows a schematic diagram of an apparatus for removing carbon-containing impurities in the production of high-purity chlorosilane according to an embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
"highly pure chlorosilane" as used herein means chlorosilanes having a purity of 4N or more, typically 4N to 9N.
In polysilicon production enterprises, the removal of trace impurities is an important problem to be continuously solved for improving the grade of high-purity chlorosilane products. Carbon-containing impurities are very difficult to remove due to their close boiling points to chlorosilanes. At present, the carbon content of the whole rectification product in the polysilicon industry stays at the ppm level integrally. How to further reduce the carbon content and improve the quality of the rectification product becomes a problem to be continuously solved by polysilicon manufacturers. To this end, the utility model provides the following technical scheme.
According to an exemplary embodiment of the present application, an apparatus for removing carbon-containing impurities in the production of high-purity chlorosilanes is provided. The device comprises a rectifying device and an adsorption device. The rectifying device is provided with a material inlet and a material outlet and is used for removing high-boiling point components and low-boiling point components in the trichlorosilane raw material; the adsorption device is communicated with a material outlet of the rectification device, and the resin type adsorbent rich in amino and a platinum catalyst are filled in the adsorption device.
Use the technical scheme of the utility model, utilize inside to fill the adsorption equipment who has resin type adsorbent and platinum catalyst that are rich in amino, remove methyl chlorosilane impurity through adsorption process to reduce the total methyl chlorosilane impurity content that contains of rectification product in the polycrystalline silicon production process to below 50ppb, produce the chlorosilane more than high-purity 4N, the carbon-containing impurity is < 50 ppb.
The adsorption column is filled with a resin adsorbent rich in amino, the catalyst is a Pt catalyst (which can be a homogeneous platinum catalyst or an immobilized platinum catalyst, the immobilized platinum catalyst is not easy to diffuse into a product, and the catalyst is preferably selected), the methylchlorosilane contains active Si-H bonds and Si-Cl bonds, wherein the Si-Cl bonds have larger bond energy than the Si-H bonds, but are more likely to react due to stronger ionicity, and are similar to acyl chloride bonds. The Si-Cl bond can react with amino in the adsorbent under the action of the catalyst to form methyl silazane, so that the methyl silazane is remained on the adsorbent, and a high-purity trichlorosilane product after adsorption is further obtained, wherein the content of the methyl chlorosilane can be reduced to below 50 ppb.
Preferably, the amino-rich resin-type adsorbent is a macroporous aminophosphonic acid-type chelating resin having a high affinity for methylchlorosilane.In order to further improve the adsorption effect, it is more preferable that the macroporous amino phosphonic acid type chelate resin has a basic structure of polystyrene grafted divinylbenzene, and has a spherical particle structure, wherein the diameter of the spherical particle is 0.38 to 0.5mm, the specific gravity is 1.13, the expansion reversibility is 50%, and the upper limit of the use temperature is 80 ℃. Grafting an amino group on the surface of the resin by a chemical modification grafting method: ammonium phosphate group (H)6N2O3S), thereby preparing the resin.
In order to further improve the convenience of operation, a material outlet of the rectifying device is communicated with the adsorption device through a centrifugal pump. Typically, the rectifying device comprises a first rectifying tower and a second rectifying tower which are arranged in series, and the adsorption device is communicated with a material outlet of the second rectifying tower through a centrifugal pump. Wherein, the first rectifying tower is used for removing high boiling point components, and the second rectifying tower is used for removing low boiling point components. The utility model discloses an in the embodiment, first rectifying column and second rectifying column are the rectifying column that 304 stainless steel material made respectively, and the tower footpath is 1.2 ~ 1.5 meters respectively, and the tower height is 30 ~ 40 meters respectively, all is equipped with the silk screen packing in the tower, and the height that the silk screen packed is 20 ~ 30 meters, and the tower height is higher than the height that the silk screen packed.
Preferably, the adsorption device comprises two sets of adsorption columns, the two sets of adsorption columns run independently, after one set of adsorption columns is saturated in adsorption, the other set of adsorption columns are switched to adsorb through a valve, and the adsorption columns saturated in adsorption are regenerated, so that the aim of continuous operation is fulfilled. More preferably, polytetrafluoroethylene coatings are arranged in the two sets of adsorption columns, so that the purity of the product is ensured.
In an embodiment of the present invention, the column length of the adsorption column is 2 meters, the nominal diameter is DN250, and the outer wall of the adsorption column is provided with the temperature control interlayer. Preferably, the temperature control interlayer is a water temperature control interlayer.
The following will further illustrate the advantageous effects of the present invention with reference to the following examples.
Example 1
In this embodiment, referring to fig. 1, the apparatus for removing carbon-containing impurities in the production of high-purity chlorosilane mainly includes a first rectification tower 10 (wire mesh packing), a second rectification tower 20 (wire mesh packing), a # 1 adsorption column 30 (lined with ptfe 304 material) and a # 2 adsorption column 40 (lined with ptfe 304 material, and filled with a resin-type adsorbent rich in amino groups and a platinum-based catalyst).
Taking trichlorosilane rectification as an example, the process flow comprises three steps of rectification purification, adsorption and regeneration, and corresponding equipment is a rectification purification tower and an adsorption column respectively. The method comprises the following steps:
1) rectification and purification: using 10-30 m of trichlorosilane 11 (purity is 2-3N, total methyl content is 20-70ppm) containing carbon impurities3The feed amount per second is sent into the first rectifying tower 10 and the second rectifying tower 20 for separation and purification, and the yield is 80 percent. Wherein, the first rectifying tower 10 (pressure is 4-5 Mpa, reflux amount is 60-100 m3The high-boiling-point substances 13 are removed in the/s), the obtained intermediate product 12 is sent into a second rectifying tower 20 (the pressure is 2-3.5 Mpa, the reflux quantity is 50-80 m3And/s) removing the low-boiling-point substances 21 to obtain a rectified product trichlorosilane 22 with the purity of 3-4N, wherein the trichlorosilane contains 3-10 ppm of methyl chlorosilane.
2) Methyl impurity adsorption: the trichlorosilane 22 (8-20 m) obtained in the last step is distilled3And/s) is sent to a parallel 1# adsorption column 30 filled with adsorbent through a centrifugal pump for adsorption, the cooling circulating water flow (circulating inlet water 32 and circulating outlet water 31) is adjusted to ensure that the environmental temperature of the adsorption column is stabilized at 35-45 ℃, and the adsorption pressure is controlled at 3-4 Mpa. At the temperature, methyl chlorosilane in the trichlorosilane can react with amino in the adsorbent under the action of the catalyst to form methyl silazane, so that the methyl silazane is remained on the adsorbent, and further the adsorbed product trichlorosilane is obtained, wherein the content of the methyl chlorosilane can be reduced to below 50ppb, and the high-purity trichlorosilane 50 is obtained.
3) Desorption and regeneration: when the adsorption saturation of the No. 1 adsorption column 30, the adsorption column is switched to the No. 2 adsorption column 40 (circulating inlet water 32 and circulating outlet water 31) through a valve for adsorption, and the adsorbent and the catalyst of the No. 1 adsorption column 30 are replaced, so that the aim of continuous operation is fulfilled.
From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: the method has the advantages that the simple and efficient adsorption filtration method is adopted to efficiently remove methyl chlorosilane impurities in the chlorosilane in the polycrystalline silicon production system, so that the chlorosilane product with PPb-level carbon content is obtained. The process is simple and efficient, reliable in operation and high in practicability.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A device for removing carbon-containing impurities in high-purity chlorosilane production is characterized by comprising the following components:
the rectifying device is provided with a material inlet and a material outlet and is used for removing high-boiling point components and low-boiling point components in the trichlorosilane raw material; and
and the adsorption device is communicated with a material outlet of the rectification device, and is internally filled with a resin type adsorbent rich in amino and a platinum catalyst, and the resin type adsorbent rich in amino is macroporous amino phosphonic acid type chelate resin.
2. The apparatus of claim 1, wherein the material outlet of the rectification apparatus is in communication with the adsorption apparatus via a centrifugal pump.
3. The device as claimed in claim 2, wherein the rectification device comprises a first rectification tower and a second rectification tower which are arranged in series, and the adsorption device is communicated with a material outlet of the second rectification tower through a centrifugal pump.
4. The apparatus according to claim 3, wherein the first rectifying tower and the second rectifying tower are respectively rectifying towers made of 304 stainless steel materials, the tower diameters are respectively 1.2-1.5 m, the tower heights are respectively 30-40 m, wire mesh packing is filled in the towers, the height of the wire mesh packing is 20-30 m, and the tower heights are higher than the height of the wire mesh packing.
5. The apparatus of claim 1, wherein the adsorption device comprises two sets of adsorption columns, and the two sets of adsorption columns operate independently.
6. The apparatus of claim 5, wherein the column length of the adsorption column is 2 meters and the nominal diameter is DN 250.
7. The device of claim 5, wherein the outer wall of the adsorption column is provided with a temperature control interlayer.
8. The device of claim 7, wherein the temperature control interlayer is a water temperature control interlayer.
9. The device of claim 5, wherein a polytetrafluoroethylene coating is arranged in each of the two sets of adsorption columns.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113214304A (en) * | 2021-04-23 | 2021-08-06 | 洛阳中硅高科技有限公司 | Preparation system and method of tetramethylsilane |
| CN116553559A (en) * | 2023-05-31 | 2023-08-08 | 宁夏润阳硅材料科技有限公司 | Method and system for controlling content of carbon impurities in disilicon for reduction process |
| CN116715242A (en) * | 2023-05-31 | 2023-09-08 | 宁夏润阳硅材料科技有限公司 | Method and system for controlling content of carbon impurities in hydrogen for reduction process |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113214304A (en) * | 2021-04-23 | 2021-08-06 | 洛阳中硅高科技有限公司 | Preparation system and method of tetramethylsilane |
| CN116553559A (en) * | 2023-05-31 | 2023-08-08 | 宁夏润阳硅材料科技有限公司 | Method and system for controlling content of carbon impurities in disilicon for reduction process |
| CN116715242A (en) * | 2023-05-31 | 2023-09-08 | 宁夏润阳硅材料科技有限公司 | Method and system for controlling content of carbon impurities in hydrogen for reduction process |
| CN116715242B (en) * | 2023-05-31 | 2024-02-02 | 宁夏润阳硅材料科技有限公司 | Method and system for controlling content of carbon impurities in hydrogen for reduction process |
| CN116553559B (en) * | 2023-05-31 | 2024-02-02 | 宁夏润阳硅材料科技有限公司 | Method and system for controlling content of carbon impurities in disilicon for reduction process |
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