Silicon-based electronic chemical purification device and method

Abstract

The present invention provides a device and method for purifying silicon-based electronic chemicals. The device for purifying silicon-based electronic chemicals comprises a heavy removal unit, an azeotropic extraction unit, and a light removal unit connected in sequence, wherein the heavy removal unit is used to remove heavy components from a crude silicon-based compound to obtain a heavy-removed crude silicon-based compound; the azeotropic extraction unit is used to mix the heavy-removed crude silicon-based compound with water for azeotropic extraction to obtain a silicon-based compound fraction and a liquid mixture; the light removal unit is used to remove light components from the silicon-based compound fraction to obtain silicon-based electronic chemicals. The purification device provided in the present application sequentially passes the crude silicon-based compound through the heavy removal unit, the azeotropic extraction unit, and the light removal unit to sequentially remove heavy components, azeotropic extraction with water, and light components, thereby removing metal ions from the crude silicon-based compound. The prepared silicon-based electronic products can meet the purity requirements of silicon-based compounds in fields such as integrated circuits.

Description

Technical Field

[0001] The present invention relates to the technical field of silicon-based electronic chemicals, and in particular to a device and method for purifying silicon-based electronic chemicals. Background Art

[0002] Chemicals and materials used in semiconductor and high-density circuit technology are often referred to as "electronic chemicals." The production of modern semiconductor composite technology typically involves hundreds of electronic chemicals and manufacturing processes. Generally speaking, integrated circuit (IC) manufacturing is a repetitive process involving deposition of specialized materials, photolithography, and etching films.

[0003] In the deposition process, organic silicon, with its excellent dielectric properties, is often used as a material for chemical vapor deposition (CVD). The purity of the organic silicon used is crucial. Impurities, especially metal ions, can easily lead to dislocation, increasing leakage current, causing breakdown, and reducing carrier lifetime. Every order of magnitude increase in organic silicon purity promotes greater integration of integrated circuit devices.

[0004] The purification process for high-purity organosilane primarily involves the removal of organic impurities, metal ions, and solid particulates. Organic impurities are primarily removed by distillation, while solid particulates are typically removed using microfiltration membranes. However, the removal of metal ions remains a production challenge. Integrated circuits (ICs) require increasingly high purity levels for electronic-grade chemicals, and conventional distillation methods are ineffective in removing metal ions. Therefore, a purification technology is needed to produce high-purity silicon-based electronic products.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The main purpose of the present invention is to provide a purification device and method for silicon-based electronic chemicals to solve the problem that in the process of organosilane purification in the prior art, the conventional distillation method is not effective in removing metal ions and cannot meet the purity requirements of electronic-grade chemicals for integrated circuits.

[0007] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, a purification device for silicon-based electronic chemicals is provided, which comprises: a heavy removal unit, which comprises a heavy removal tower, and is used to remove heavy components from a crude silicon-based compound to obtain a heavy-depleted crude silicon-based compound; an azeotropic extraction unit, which comprises an azeotropic extraction tower, and is connected to the heavy removal unit, and is used to mix the heavy-depleted crude silicon-based compound with water for azeotropic extraction to obtain a silicon-based compound fraction and a liquid mixture; and a light removal unit, which is connected to the azeotropic extraction unit, and is used to remove light components from the silicon-based compound fraction to obtain silicon-based electronic chemicals.

[0008] Furthermore, the purification device further comprises a first membrane filter, which is arranged on the pipeline between the deweighting tower and the azeotropic extraction unit. Preferably, the pore size of the membrane in the first membrane filter is 0.005 to 0.5 μm.

[0009] Furthermore, the light-removal unit further comprises a second membrane filter, the inlet of the second membrane filter is connected to the bottom outlet of the light-removal tower, and the pore size of the membrane in the second membrane filter is preferably 0.005 to 0.5 μm.

[0010] Furthermore, the azeotropic extraction unit also includes a tower top decantation storage tank, which is arranged at the top of the azeotropic extraction tower, and the tower top decantation storage tank is arranged on the pipeline between the azeotropic extraction tower and the light removal unit.

[0011] Furthermore, the top decantation tank is provided with a first outlet and a second outlet, the first outlet is connected to the light removal unit, and the second outlet is used to discharge the water separated from the top decantation tank; preferably, the top decantation tank is also provided with a third outlet, and the third outlet is connected to the top inlet of the azeotropic extraction column;

[0012] Furthermore, the azeotropic extraction unit further comprises a second condenser, which is arranged on the pipeline between the azeotropic extraction column and the top decantation tank;

[0013] Furthermore, the second condenser is provided with a fourth outlet, which is connected to the inlet of the top decantation tank; preferably, the second condenser is also provided with a fifth outlet, which is connected to the inlet of the top of the azeotropic extraction tower.

[0014] Furthermore, the azeotropic extraction unit further comprises a bottom extraction pump, which is arranged at the bottom of the azeotropic extraction tower, and the inlet of the bottom extraction pump is connected to the bottom outlet of the azeotropic extraction tower;

[0015] Furthermore, the azeotropic extraction unit further comprises a second tower bottom reboiler, which is arranged on the pipeline between the azeotropic extraction tower and the tower bottom extraction pump;

[0016] Furthermore, the second bottom reboiler has a sixth outlet and a seventh outlet, the sixth outlet is connected to the bottom inlet of the azeotropic extraction column, and the seventh outlet is connected to the inlet of the bottom extraction pump;

[0017] Furthermore, the azeotropic extraction unit further includes a tower bottom decantation storage tank, which is arranged on the pipeline between the second tower bottom reboiler and the tower bottom extraction pump.

[0018] Furthermore, the heavy removal tower, the azeotropic extraction tower and the light removal tower are each independently a packed tower;

[0019] Furthermore, the theoretical plate numbers of the heavy removal column, the azeotropic extraction column and the light removal column are each independently 10 to 30;

[0020] Furthermore, the main bodies of the heavy removal tower, the azeotropic extraction tower and the light removal tower are independently made of stainless steel.

[0021] According to another aspect of the present invention, a method for purifying silicon-based electronic chemicals is provided, the purification method comprising: step S1, removing heavy components from a crude silicon-based compound to obtain a heavy-free silicon-based compound; step S2, mixing the heavy-free silicon-based compound with water and performing azeotropic extraction to obtain a silicon-based compound fraction and a liquid mixture; step S3, removing light components from the silicon-based compound fraction to obtain silicon-based electronic chemicals.

[0022] Furthermore, in step S1, the heavy component removal treatment is carried out in a deweighting tower, the tower pressure of the deweighting tower is 100-150 kPa, the tower top temperature is 150-200° C., and the reflux ratio is 1-50; preferably, step S1 also includes a first filtration treatment, and the first filtration treatment is provided after the heavy component removal treatment;

[0023] Furthermore, in step S3, light component removal is carried out in a light component removal tower, the tower pressure of the light component removal tower is 100-150 kPa, the temperature of the tower top is 150-200°C, and the reflux ratio is 1-50; preferably, step S3 also includes a second filtration treatment, and the second filtration treatment is arranged after the light component removal.

[0024] Furthermore, in step S2, the azeotropic extraction treatment is carried out in an azeotropic extraction tower, the tower pressure of the azeotropic extraction tower is 100-150 kPa, the tower top temperature is 150-200° C., and the reflux ratio is 1-50;

[0025] Furthermore, step S2 further includes a first phase separation treatment, which is provided after the azeotropic extraction treatment. Preferably, step S2 further includes a condensation treatment, which is provided between the azeotropic extraction treatment and the first phase separation treatment.

[0026] Furthermore, step S2 also includes recycling of the liquid mixture;

[0027] Further, the recovery process includes a reboil process;

[0028] Furthermore, the recovery process further includes a second phase separation process, which is provided after the reboiling process. Furthermore, in step S2, the volume ratio of the deweighted silicon-based compound to water is 1:1-5.

[0029] By applying the technical solution of the present application, the crude silicon-based compound is sequentially passed through a heavy removal unit, an azeotropic extraction unit, and a light removal unit to remove heavy components, azeotropic extraction with water, and light components, thereby removing metal ions from the crude silicon-based compound. This allows the prepared silicon-based electronic products to meet the purity requirements of silicon-based compounds in fields such as integrated circuits, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The accompanying drawings, which constitute part of this application, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0031] Figure 1 It shows a structural block diagram of a purification device for silicon-based electronic products provided in accordance with 1 of the present invention; and

[0032] Figure 2 It shows a structural block diagram of an azeotropic extraction unit in a silicon-based electronic product according to 1 of the present invention;

[0033] Figure 3 It shows a structural block diagram of an azeotropic extraction unit in a silicon-based electronic product according to 2 of the present invention;

[0034] Figure 4 The structure block diagram of the azeotropic extraction unit in the silicon-based electronic product provided in 2 of the present invention is shown.

[0035] The above drawings include the following reference numerals:

[0036] 100, de-weighting tower; 111, first condenser; 121, first tower bottom reboiler; 200, azeotropic extraction tower; 211, tower top decantation storage tank; 212, second condenser; 221, tower bottom extraction pump; 222, second tower bottom reboiler; 223, tower bottom decantation storage tank; 300, de-lighting tower; 311, third condenser; 321, third tower bottom reboiler; 400, first membrane filter; 500, second membrane filter. DETAILED DESCRIPTION

[0037] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments in this application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0038] As analyzed in the background of this application, conventional distillation methods used in the prior art for organosilane purification are ineffective in removing metal ions and are unable to meet the purity requirements of electronic-grade chemicals required for integrated circuits. To address this issue, this application provides a device and method for purifying silicon-based electronic chemicals.

[0039] In a typical embodiment of the present application, a purification device for silicon-based electronic chemicals is provided, which comprises: a deweighting tower unit, the deweighting unit comprising a deweighting tower 100, the deweighting unit being used to remove heavy components from a crude silicon-based compound to obtain a deweighted crude silicon-based compound; an azeotropic extraction unit, the azeotropic extraction unit comprising an azeotropic extraction tower 200, the azeotropic extraction unit being connected to the deweighting unit, and being used to azeotropically extract the deweighted crude silicon-based compound and water to obtain a silicon-based compound fraction and a liquid mixture; and a light removal unit, the light removal unit comprising a light removal tower 300, the light removal unit being connected to the azeotropic extraction unit, and being used to remove light components from the silicon-based compound fraction to obtain silicon-based electronic chemicals.

[0040] In the present application, the silicon-based electronic chemical is at least one of ethyl orthosilicate, octamethylcyclotetrasiloxane, and tetramethylsilane.

[0041] By applying the technical solution of the present application, the crude silicon-based compound is sequentially passed through a heavy removal unit, an azeotropic extraction unit, and a light removal unit to remove heavy components, azeotropic extraction with water, and light components, thereby removing metal ions from the crude silicon-based compound. This allows the prepared silicon-based electronic products to meet the purity requirements of silicon-based compounds in fields such as integrated circuits, and has broad application prospects.

[0042] In order to further improve the solid particles in the crude product of the deweighted compound, it is preferred that the deweighting unit also includes a first membrane filter 400, which is arranged on the pipeline between the deweighting tower 100 and the azeotropic extraction unit, so as to facilitate further filtering and removing the solid particles in the crude product of the deweighted compound extracted from the deweighting tower 100 through the first filter, thereby avoiding the solid particles affecting the efficiency of the subsequent azeotropic extraction.

[0043] In order to further improve the filtration efficiency of the first membrane filter 400, the pore size of the membrane in the first membrane filter 400 is preferably 0.005-0.5 μm. Typically, but not limiting, the pore size of the membrane in the first membrane filter 400 is 0.005 μm, 0.01 μm, 0.02 μm, 0.03 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.5 μm, or a range consisting of any two values.

[0044] In order to further improve the yield of azeotropic extraction, it is preferred that the above-mentioned azeotropic extraction unit also includes a top decantation tank 211, which is arranged at the top of the azeotropic extraction tower 200 and on the pipeline between the azeotropic extraction tower 200 and the light removal unit, so as to phase separate the silicon-based compound fraction through the top decantation tank 211 and further remove moisture from the silicon-based compound fraction.

[0045] In order to further improve the phase separation efficiency of the reflux decantation tank, the above-mentioned azeotropic extraction unit preferably also includes a second condenser 212, which is arranged on the pipeline between the azeotropic extraction tower 200 and the top decantation tank 211 to cool the silicon-based compound fraction extracted from the top of the azeotropic extraction tower 200 into a liquid silicon-based compound fraction.

[0046] In some embodiments of the present application, the second condenser 212 and the top decantation tank 211 are connected in the following two ways:

[0047] Method 1: The inlet of the second condenser 212 is connected to the top outlet of the azeotropic extraction column 200, so that the silicon-based compound fraction extracted from the top of the azeotropic extraction column 200 flows into the second condenser 212 for condensation, forming a liquid silicon-based compound fraction. The top decantation tank 211 is provided with a first outlet and a second outlet. The first outlet is connected to the inlet of the lightness removal column 300 for conveying the liquid silicon-based compound fraction after separation of the aqueous phase to the lightness removal column 300 for light component removal. The second outlet is an aqueous phase outlet for discharging water separated from the silicon-based compound fraction out of the top decantation tank 211. The second condenser 212 has a fourth outlet and a fifth outlet. The fourth outlet is connected to the inlet of the top decantation tank 211 to transport the liquid silicon-based compound fraction to the top decantation tank 211 for phase separation. The fifth outlet is a reflux outlet, which is connected to the top inlet of the azeotropic extraction tower 200 to facilitate the reflux of part of the liquid silicon-based compound fraction to the azeotropic extraction tower 200.

[0048] The second method: the inlet of the second condenser 212 is connected to the outlet at the top of the azeotropic extraction tower 200, the second condenser 212 is not provided with a fifth outlet, and the top decantation tank 211 is also provided with a third outlet, which is a reflux outlet, and the third outlet is connected to the top inlet of the azeotropic extraction tower 200.

[0049] In order to further improve the energy utilization rate of the azeotropic extraction unit, the azeotropic extraction unit preferably further includes a bottom extraction pump 221 , which is used to pump out the liquid mixture discharged from the bottom of the azeotropic extraction tower 200 .

[0050] In order to further improve the energy utilization rate of the liquid mixture, the above-mentioned azeotropic extraction unit preferably also includes a second bottom reboiler 222, which is arranged at the bottom of the azeotropic extraction tower 200, and the inlet of the second bottom reboiler 222 is connected to the bottom outlet of the azeotropic extraction tower 200.

[0051] In order to further improve energy utilization, the connection between the second bottom reboiler 222 and the bottom extraction pump 221 is preferably in the following two ways:

[0052] The first method: the inlet of the second bottom reboiler 222 is connected to the outlet at the bottom of the azeotropic extraction tower 200, so that the liquid mixture extracted from the bottom of the azeotropic extraction tower 200 enters the second bottom reboiler 222 for reboiling treatment. The second bottom reboiler 222 is provided with a sixth outlet and a seventh outlet. The sixth outlet is a reflux outlet, and the sixth outlet is connected to the inlet at the bottom of the azeotropic extraction tower 200 so that part of the liquid mixture returns to the azeotropic extraction tower 200. The seventh outlet is connected to the inlet of the bottom extraction pump 221.

[0053] The second method: A bottom decantation tank 223 is also provided on the pipeline between the second bottom reboiler 222 and the bottom extraction pump 221. The inlet of the bottom decantation tank 223 is connected to the seventh outlet of the second bottom reboiler 222. The bottom decantation tank 223 is used to separate the liquid mixture. The bottom decantation tank 223 is provided with an eighth outlet and a ninth outlet, wherein the eighth outlet is used to discharge the water separated from the bottom decantation tank 223, and the ninth outlet is connected to the inlet of the bottom extraction pump 221.

[0054] In order to further improve energy utilization, the bottom production pump 221 is preferably provided with a production pipeline, which is connected to the outlet of the bottom production pump 221. The production pipeline preferably includes a first pipeline and a second pipeline. The first pipeline is connected to the bottom inlet of the azeotropic extraction tower 200 to return part of the production to the azeotropic extraction tower 200, and the second pipeline is used for direct production.

[0055] In order to further reduce the impurities in silicon-based electronic chemicals, the above-mentioned light removal unit preferably also includes a second membrane filter 500, the inlet of which is connected to the bottom outlet of the light removal tower 300, and is used to filter and remove solid particles in the silicon-based electronic chemicals extracted from the light removal tower 300.

[0056] In order to further improve the purification efficiency, the de-weighting unit is preferably further provided with a first condenser 111, which is arranged at the top of the de-weighting tower 100 and on the pipeline between the de-weighting tower 100 and the azeotropic extraction unit, so as to facilitate the condensation of the crude product of the de-light silicon-based compound and then transport it to the azeotropic extraction unit for azeotropic extraction treatment.

[0057] In order to further improve energy utilization efficiency, the de-weighting unit is preferably further provided with a first bottom reboiler 121 . The first bottom reboiler 121 is provided at the bottom of the de-weighting tower 100 to facilitate heating treatment of the de-weighting tower 100 .

[0058] In order to facilitate the recycling of light components, the light removal unit preferably further includes a third condenser 311, which is arranged at the top of the light removal tower 300 and is used to condense the light components discharged from the light removal tower 300.

[0059] In order to further improve energy utilization efficiency, the light removal unit preferably further includes a third bottom reboiler 321 , which is disposed at the bottom of the light removal tower 300 to facilitate heating treatment of the light removal tower 300 .

[0060] In order to further improve the filtration efficiency of the second membrane filter 500, the pore size of the membrane in the second membrane filter 500 is preferably 0.005-0.5 μm. Typically, but not limiting, the pore size of the membrane in the first membrane filter 400 is 0.005 μm, 0.01 μm, 0.02 μm, 0.03 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.5 μm, or a range consisting of any two values.

[0061] In order to further improve the corrosion resistance of the first membrane filter 400 and the second membrane filter 500, preferably, the first membrane filter 400 and the second membrane filter are each independently a PTFE (polytetrafluoroethylene) membrane filter.

[0062] In the present application, in order to further improve the purification efficiency, it is preferred that the above-mentioned de-weighting tower 100, azeotropic extraction tower 200 and de-lightening tower 300 are each independently a packed tower, and the filler in the packed tower is preferably quartz structured packing, quartz random packing, PFA-coated structured packing, PFA-coated random packing, preferably stainless steel structured packing and stainless steel random packing.

[0063] To further improve the corrosion resistance of the weight removal column 100, the azeotropic extraction column 200, and the lightness removal column 300, the main bodies of the weight removal column 100, the azeotropic extraction column 200, and the lightness removal column 300 are preferably each independently constructed of stainless steel. The stainless steel is preferably electrolytically polished stainless steel. Some of the pipes and fittings are also constructed of electrolytically polished stainless steel to enhance corrosion resistance.

[0064] In order to further reduce the metal ion content in silicon-based electronic chemicals, it is preferred that the theoretical plate numbers of the weight removal column 100, the azeotropic extraction column 200, and the lightness removal column 300 are each independently 10 to 30. Typically, but not limiting, the theoretical plate numbers of the weight removal column 100, the azeotropic extraction column 200, and the lightness removal column 300 are each independently 10, 12, 15, 18, 20, 22, 25, 28, or 30.

[0065] In a second typical embodiment of the present application, a method for purifying silicon-based electronic chemicals is also provided, which comprises: step S1, removing heavy components from a crude silicon-based compound to obtain a deheavy silicon-based compound; step S2, mixing the deheavy silicon-based compound with water for azeotropic extraction to obtain a silicon-based compound fraction and a liquid mixture; step S3, removing light components from the silicon-based compound fraction to obtain silicon-based electronic chemicals.

[0066] By applying the technical solution of the present application, the crude silicon-based compound is subjected to the removal of heavy components, azeotropic extraction with water, and light components in sequence, and the metal ions in the crude silicon-based compound are removed, so that the prepared silicon-based electronic products can meet the purity requirements of silicon-based compounds in fields such as integrated circuits, and have broad application prospects.

[0067] In order to further improve the removal rate of heavy components in the crude silicon-based compound, preferably, in step S1, the heavy component removal treatment is carried out in the deweighting tower 100, the tower pressure of the deweighting tower 100 is 100-150 kPa, the tower top temperature is 150-200° C., and the reflux ratio is 1-50.

[0068] Typically but not limitatively, the tower pressure of the deweighting tower 100 is 100 kPa, 105 kPa, 110 kPa, 120 kPa, 130 kPa, 140 kPa, 150 kPa, or a range consisting of any two values; the tower top temperature is 150° C., 160° C., 170° C., 180° C., 190° C., 200° C., or a range consisting of any two values; and the reflux rate is 1, 2, 3, 5, 8, 10, 15, 20, 30, 40, 50, or a range consisting of any two values.

[0069] In order to further reduce the impurities in the deheavy silicon-based compound, step S1 preferably further includes a first filtration process, which is provided after the heavy component removal process. Preferably, the first filtration process is performed in the first membrane filter 400.

[0070] The deweighting tower 100 and the first membrane filter 400 have the same meanings as in the first exemplary embodiment.

[0071] In order to further improve the efficiency of the azeotropic extraction treatment, the azeotropic extraction treatment is preferably carried out in the azeotropic extraction tower 200, wherein the tower pressure of the azeotropic extraction tower 200 is 100-150 kPa, the tower top temperature is 150-200°C, and the reflux ratio is 1-50.

[0072] Typically, but not limited to, the tower pressure of the azeotropic extraction tower 200 is 100 kPa, 105 kPa, 110 kPa, 120 kPa, 130 kPa, 140 kPa, 150 kPa, or a range consisting of any two values; the tower top temperature is 150° C., 160° C., 170° C., 180° C., 190° C., 200° C., or a range consisting of any two values; and the reflux rate is 1, 2, 3, 5, 8, 10, 15, 20, 30, 40, 50, or a range consisting of any two values.

[0073] In order to further improve the purity of the silicon-based compound, step S2 preferably also includes a first phase separation treatment, which is arranged after the azeotropic extraction treatment to further remove moisture from the silicon-based compound fraction and reduce the impact of moisture on the removal of light components.

[0074] In order to further improve the efficiency of the first phase separation treatment, step S2 preferably also includes a condensation treatment, which is arranged between the azeotropic extraction treatment and the first phase separation treatment, so as to facilitate the condensation of the gaseous silicon-based compound fraction obtained by the azeotropic extraction into a liquid state before the first phase separation treatment.

[0075] The first phase separation process is preferably performed in a tower top decantation tank, and the condensation process is performed in a second condenser 212. The azeotropic extraction tower 200, tower top decantation tank 211, and second condenser 212 are all the same as those defined in the first exemplary embodiment.

[0076] In order to further improve energy utilization, preferably step S2 also includes a recovery process of the liquid mixture, and the recovery process is to extract the liquid mixture.

[0077] In order to further improve the recovery rate of the liquid mixture, the recovery treatment preferably includes a reboiling treatment, through which a portion of the liquid mixture is returned to the azeotropic extraction tower 200, and another portion of the liquid compound is extracted.

[0078] In order to further improve the utilization rate of the liquid mixture recovery process, the recovery process preferably also includes a second phase separation process, which is arranged after the reboiling process to facilitate the separation and discharge of the water phase in the liquid mixture through the second phase separation.

[0079] The above-mentioned reboiler treatment is preferably carried out in the second bottom reboiler 222, and the second phase separation treatment is preferably carried out in the bottom decantation tank 223. The second bottom reboiler 222 and the bottom decantation tank 223 are respectively the same as the second bottom reboiler 222 and the bottom decantation tank 223 provided in the first typical embodiment.

[0080] In order to further improve the efficiency of azeotropic extraction, the volume ratio of the deweighting silicon-based compound to water is preferably 1:1-5.

[0081] Typically, but not limited to, the volume ratio of the deweighted silicon-based compound to water is 1:1, 1:2, 1:3, 1:4, 1:5 or a range consisting of any two of these values.

[0082] In order to further improve the efficiency of light component removal, step S3 is preferred, and the light component removal is carried out in the light component removal tower 300, the tower pressure of the light component removal tower 300 is 100-150kPa, the temperature of the top of the light component removal tower 300 is 150-200°C, and the reflux ratio is 1-50.

[0083] Typically but not limitatively, the tower pressure of the lightness removal tower 300 is 100 kPa, 105 kPa, 110 kPa, 120 kPa, 130 kPa, 140 kPa, 150 kPa or a range consisting of any two values; the tower top temperature is 150°C, 160°C, 170°C, 180°C, 190°C, 200°C or a range consisting of any two values; the reflux rate is 1, 2, 3, 5, 8, 10, 15, 20, 30, 40, 50 or a range consisting of any two values.

[0084] In order to further reduce the solid particles in the silicon-based electronic chemicals, it is preferred that step S3 further includes a second filtration process, which is arranged after the light components are removed to further improve the purity of the silicon-based electronic chemicals.

[0085] The second filtration treatment is preferably performed in the second membrane filter 500 , and the light removal tower 300 and the second membrane filter 500 are respectively the same as the light removal tower 300 and the second membrane filter 500 provided in the first typical embodiment.

[0086] The beneficial effects of the present application will be further illustrated below with reference to the embodiments.

[0087] Example 1

[0088] like Figure 1 As shown, the present application provides a purification device for silicon-based electronic chemicals, which includes a de-heavy unit, an azeotropic extraction unit and a light removal unit connected in sequence. The de-heavy unit includes a de-heavy tower 100 for removing heavy components from a crude silicon-based compound to obtain a de-heavy silicon-based compound crude product. The azeotropic extraction unit includes an azeotropic extraction tower 200 for azeotropically extracting the de-heavy silicon-based compound crude product and water to obtain a silicon-based compound fraction and a liquid mixture. The light removal unit includes a light removal tower 300 for removing light components from the silicon-based compound fraction to obtain silicon-based electronic chemicals.

[0089] In order to further reduce the solid particles in the deweighted silicon-based compound crude product, the deweighting unit also includes a first membrane filter 400, which is arranged on the pipeline between the deweighting tower 100 and the azeotropic extraction tower 200. The first membrane filter 400 is a PTFE membrane filter, and the pore size of the membrane is 0.005 to 0.5 μm.

[0090] To further reduce solid particles in silicon-based electronic chemicals, the light-removal unit also includes a second membrane filter 500. The inlet of the second membrane filter 500 is connected to the bottom outlet of the light-removal tower 300. This second membrane filter 500 filters out solid particles in the silicon-based electronic chemicals, thereby improving the purity of the silicon-based electronic chemicals. This second membrane filter 500 is a PTFE membrane filter with a pore size of 0.005 to 0.5 μm.

[0091] like Figure 2 As shown, in order to further improve the purity of the silicon-based compound fraction, the azeotropic extraction unit provided in this embodiment also includes a top decantation tank 211, which is arranged at the top of the azeotropic extraction tower 200 and on the pipeline between the azeotropic extraction tower 200 and the light removal unit, and the top decantation tank 211 is provided with a first outlet, a second outlet and a third outlet, the first outlet is connected to the light removal unit, the second outlet is used to discharge the aqueous phase separated by the top decantation tank 211, and the third outlet is a reflux outlet, which is connected to the top inlet of the azeotropic extraction tower 200 to return part of the silicon-based compound fraction to the azeotropic extraction tower 200.

[0092] In order to facilitate phase separation in the top decantation tank 211, the azeotropic extraction unit also includes a second condenser 212, which is arranged on the pipeline between the azeotropic extraction tower 200 and the top decantation tank 211. The inlet of the second condenser 212 is connected to the top outlet of the azeotropic extraction tower 200, and the second condenser 212 is provided with a fourth outlet, which is connected to the inlet of the top decantation tank 211.

[0093] In order to further improve the efficiency of azeotropic extraction, the azeotropic extraction unit also includes a bottom extraction pump 221, which is arranged at the bottom of the azeotropic extraction tower 200, and the inlet of the bottom extraction pump 221 is connected to the outlet of the azeotropic extraction tower 200 to facilitate the extraction of the liquid mixture discharged from the bottom of the azeotropic extraction tower 200.

[0094] In order to further improve the recovery and processing efficiency of the liquid phase mixture, the azeotropic extraction unit preferably also includes a second bottom reboiler 222, which is arranged on the pipeline between the azeotropic extraction tower 200 and the bottom extraction pump 221. The second bottom reboiler 222 is provided with a sixth outlet and a seventh outlet. The sixth outlet is a reflux outlet, and the sixth outlet is connected to the bottom inlet of the azeotropic extraction tower 200 to facilitate the return of part of the liquid phase mixture to the azeotropic extraction tower 200 for recovery. The seventh outlet is connected to the inlet of the bottom extraction pump 221 to facilitate extraction through the bottom extraction pump 221.

[0095] In order to facilitate the extraction of materials through the tower bottom extraction pump 221, the outlet of the tower bottom extraction pump 221 is connected to a extraction pipeline.

[0096] In order to further improve the mixing efficiency of the crude product of the deweighted silicon-based compound and water, water is fed from the top of the azeotropic extraction tower 200 , and the crude product of the deweighted silicon-based compound is fed from the bottom of the azeotropic extraction tower 200 .

[0097] In order to further improve the purification efficiency, a first condenser 111 is provided on the pipeline between the de-weighting tower 100 and the azeotropic extraction tower 200, so as to facilitate condensing the crude product of the de-light silicon-based compound and then transporting it to the azeotropic extraction tower 200 for azeotropic extraction treatment.

[0098] In order to maintain the top temperature of the deweighting tower 100 , a first bottom reboiler 121 is provided at the bottom of the deweighting tower 100 to facilitate heating treatment of the deweighting tower 100 .

[0099] In order to facilitate the recycling of the light components discharged from the light removal tower 300, a third condenser 311 is provided on the top of the light removal tower 300 for condensing the light components discharged from the light removal tower 300.

[0100] In order to further improve energy utilization efficiency, a third bottom reboiler 321 is provided at the bottom of the light-removal tower 300 to facilitate heating treatment of the light-removal tower 300.

[0101] In order to further improve the purification efficiency, the above-mentioned de-heavy tower 100, azeotropic extraction tower 200 and light-removal tower 300 are each independently a packed tower, and the packing in the packed tower includes but is not limited to quartz structured packing, quartz random packing, PFA-coated structured packing, PFA-coated random packing, preferably stainless steel structured packing and stainless steel random packing.

[0102] To further enhance the corrosion resistance of the weight removal column 100, azeotropic extraction column 200, and lightness removal column 300, the main bodies of the weight removal column 100, azeotropic extraction column 200, and lightness removal column 300 are each independently constructed of stainless steel. The stainless steel is preferably electropolished stainless steel. Some of the pipes and fittings are also constructed of electropolished stainless steel to enhance corrosion resistance.

[0103] In order to further improve the purification efficiency, the theoretical plate numbers of the heavy removal tower 100, the azeotropic extraction tower 200 and the light removal tower 300 are all 10 to 30.

[0104] Example 2

[0105] like Figure 3As shown, the difference between this embodiment and Example 1 is that the purification device further includes a bottom decantation tank 223, which is arranged on the pipeline between the second bottom reboiler 222 and the bottom extraction pump 221. The bottom decantation tank 223 is used to separate the liquid mixture. The bottom decantation tank 223 is provided with an eighth outlet and a ninth outlet, wherein the eighth outlet is used to discharge the water separated from the bottom decantation tank 223, and the ninth outlet is connected to the inlet of the bottom extraction pump 221.

[0106] In order to further improve the recycling efficiency of the liquid mixture, the extraction pipeline includes a first pipeline and a second pipeline. The outlet of the first pipeline is connected to the inlet of the bottom of the azeotropic extraction tower 200, and the second pipeline is used to extract the liquid phase material pumped out by the bottom extraction pump 221.

[0107] Example 3

[0108] like Figure 4 As shown, the difference between this embodiment and embodiment 1 is that, in the purification device, the second condenser 212 is further provided with a fifth outlet, the fifth outlet is connected to the top inlet of the azeotropic extraction tower 200, and the top decantation tank 211 is not provided with a third outlet.

[0109] Example 4

[0110] This embodiment provides a method for purifying crude industrial ethyl orthosilicate, which uses the silicon-based electronic chemical purification device provided in Example 1 for purification. The crude industrial ethyl orthosilicate has the following component contents: 99.87% ethyl orthosilicate, 0.02% ethanol, 0.03% water, 0.08% unknown high boiling point, and a total metal impurity content of 2.68 ppm. The purification method comprises the following steps:

[0111] (1) introducing ethyl orthosilicate into a deweighting column 100 for slight positive pressure distillation, controlling the column pressure at 120 kPa, the top temperature at 180° C., and the reflux ratio at 30, and filtering the top distillate through a first membrane filter 400 to obtain a crude deweighted ethyl orthosilicate;

[0112] (2) The crude product of the deweighted ethyl orthosilicate is introduced into an azeotropic extraction tower 200 and mixed with water in a volume ratio of 1:3, and subjected to slight positive pressure distillation. The tower pressure is controlled at 120 kPa, the top temperature is 180° C., and the reflux ratio is 30. Water is used as both an azeotropic agent and an extractant to further purify the crude product of the deweighted ethyl orthosilicate. The fraction extracted from the top of the azeotropic extraction tower 200 is sequentially passed through a second condenser 212 and a tower top decanting tank for phase separation to obtain a ethyl orthosilicate fraction.

[0113] (3) The ethyl orthosilicate fraction is passed into the lightness removal tower 300 and subjected to slight positive pressure distillation. The tower pressure is controlled at 120 kPa, the top temperature is 180° C., and the reflux ratio is 30. The fraction extracted from the top of the tower is filtered through the second membrane filter 500 to obtain a silicon-based electronic-grade product.

[0114] The number of plates of the de-heavy column 100, the azeotropic extraction column 200 and the light-removal column 300 are all 20, the pore size of the first membrane filter 400 is 0.1 μm, and the pore size of the membrane in the second membrane filter 500 is 0.01 μm.

[0115] Example 5

[0116] The difference between this embodiment and embodiment 4 is that the number of plates of the weight removal tower 100, the azeotropic extraction tower 200 and the light removal tower 300 are all 10, the reflux ratio is all 50, the tower pressure of the weight removal tower 100, the azeotropic extraction tower 200 and the light removal tower 300 are all 150 kPa, and the top temperature is all 200°C.

[0117] Example 6

[0118] The difference between this embodiment and embodiment 4 is that the number of plates of the weight removal tower 100, the azeotropic extraction tower 200 and the light removal tower 300 is 30, the reflux ratio is 1, the tower pressure of the weight removal tower 100, the azeotropic extraction tower 200 and the light removal tower 300 is 100 kPa, and the top temperature is 150°C.

[0119] Example 7

[0120] The difference between this embodiment and embodiment 4 is that in step (2), the volume ratio of the crude deweighted ethyl orthosilicate to water is 1:1.

[0121] Example 8

[0122] The difference between this embodiment and embodiment 4 is that in step (2), the volume ratio of the crude deweighted ethyl orthosilicate to water is 1:5.

[0123] Example 9

[0124] The difference between this embodiment and embodiment 4 is that in step (2), the volume ratio of the crude deweighted ethyl orthosilicate to water is 1:0.5.

[0125] Example 10

[0126] The difference between this embodiment and embodiment 4 is that industrial-grade octamethylcyclotetrasiloxane is used instead of industrial-based ethyl orthosilicate as a raw material. The industrial-based octamethylcyclotetrasiloxane contains the following components: 0.09% hexamethylcyclotrisiloxane, 99.83% octamethylcyclotetrasiloxane, 0.08% decamethylcyclopentasiloxane, and 2.07 ppm of metal impurities.

[0127] Test example

[0128] The total metal ion content and purity of the silicon-based electronic-grade products provided in Examples 4-10 were respectively tested, and the results are shown in Table 1 below.

[0129] Among them, the total metal ion content was determined by inductively coupled mass spectrometry;

[0130] The purity was determined by gas chromatography.

[0131] Table 1

[0132]

[0133]

[0134] From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: by applying the technical solution of the present application, the crude silicon-based compound is sequentially passed through a heavy removal unit, an azeotropic extraction unit and a light removal unit to remove heavy components, azeotropic extraction with water and light components, and remove metal ions in the crude silicon-based compound, so that the prepared silicon-based electronic products can meet the requirements for the purity of silicon-based compounds in fields such as integrated circuits, and have broad application prospects.

[0135] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A purification device for silicon-based electronic chemicals, characterized in that: The purification device comprises: A de-weighting unit, comprising a de-weighting tower (100), and configured to remove heavy components from the crude silicon-based compound to obtain a de-weighted crude silicon-based compound; An azeotropic extraction unit, comprising an azeotropic extraction tower (200), connected to the de-weighting unit, for mixing the de-weighted silicon-based compound crude product with water for azeotropic extraction to obtain a silicon-based compound fraction and a liquid mixture; A light removal unit, comprising a light removal tower (300), connected to the azeotropic extraction unit, for removing light components from the silicon-based compound fraction to obtain the silicon-based electronic chemicals; Wherein, the silicon-based electronic chemical is at least one of ethyl orthosilicate, octamethylcyclotetrasiloxane and tetramethylsilane.

2. The purification device according to claim 1, characterized in that The purification device further comprises a first membrane filter (400), the first membrane filter (400) being arranged on the pipeline between the deweighting tower (100) and the azeotropic extraction unit, and the pore size of the membrane in the first membrane filter (400) being 0.005-0.5 μm.

3. The purification device according to claim 2, characterized in that The light removal unit further comprises a second membrane filter (500), the inlet of the second membrane filter (500) is connected to the bottom outlet of the light removal tower (300), and the pore size of the membrane in the second membrane filter (500) is 0.005-0.5 μm.

4. The purification device according to claim 1, characterized in that The azeotropic extraction unit further includes a tower top decantation storage tank (211), which is arranged at the top of the azeotropic extraction tower (200), and the tower top decantation storage tank (211) is arranged on the pipeline between the azeotropic extraction tower (200) and the light removal unit.

5. The purification device according to claim 4, characterized in that The tower top decantation storage tank (211) is provided with a first outlet and a second outlet, the first outlet is connected to the light removal unit, and the second outlet is used to discharge the water separated by the tower top decantation storage tank (211); the tower top decantation storage tank (211) is also provided with a third outlet, and the third outlet is connected to the tower top inlet of the azeotropic extraction tower (200); The azeotropic extraction unit further includes a second condenser (212), which is arranged on a pipeline between the azeotropic extraction tower (200) and the tower top decantation storage tank (211); The second condenser (212) is provided with a fourth outlet, which is connected to the inlet of the top decantation storage tank (211); the second condenser is also provided with a fifth outlet, which is connected to the inlet of the top of the azeotropic extraction tower (200).

6. The purification device according to claim 1, characterized in that The azeotropic extraction unit further comprises a bottom extraction pump (221), which is arranged at the bottom of the azeotropic extraction tower (200), and an inlet of the bottom extraction pump (221) is connected to a bottom outlet of the azeotropic extraction tower (200).

7. The purification device according to claim 6, characterized in that The azeotropic extraction unit further includes a second tower bottom reboiler (222), and the second tower bottom reboiler (222) is arranged on the pipeline between the azeotropic extraction tower (200) and the tower bottom extraction pump (221); The second bottom reboiler (222) has a sixth outlet and a seventh outlet, the sixth outlet is connected to the bottom inlet of the azeotropic extraction tower (200), and the seventh outlet is connected to the inlet of the bottom extraction pump (221); The azeotropic extraction unit further includes a tower bottom decantation storage tank (223), and the tower bottom decantation storage tank (223) is arranged on the pipeline between the second tower bottom reboiler (222) and the tower bottom extraction pump (221).

8. The purification device according to any one of claims 1 to 7, characterized in that The weight removal tower (100), the azeotropic extraction tower (200) and the lightness removal tower (300) are each independently a packed tower.

9. The purification device according to claim 8, characterized in that The theoretical plate numbers of the de-weighting tower (100), the azeotropic extraction tower (200) and the lightness removal tower (300) are each independently 10 to 30; The main bodies of the de-weighting tower (100), the azeotropic extraction tower (200) and the lightness removal tower (300) are each independently made of stainless steel.

10. A method for purifying silicon-based electronic chemicals, characterized in that: The purification method comprises: Step S1, removing heavy components from the crude silicon-based compound to obtain a deheavy silicon-based compound; Step S2, mixing the deweighted silicon-based compound and water to perform azeotropic extraction to obtain a silicon-based compound fraction and a liquid mixture; Step S3, removing light components from the silicon-based compound fraction to obtain the silicon-based electronic chemicals; Wherein, the silicon-based electronic chemical is at least one of ethyl orthosilicate, octamethylcyclotetrasiloxane and tetramethylsilane.

11. The purification method according to claim 10, characterized in that In the step S1, the heavy component removal treatment is performed in a deweighting tower (100), the tower pressure of the deweighting tower (100) is 100-150 kPa, the tower top temperature is 150-200° C., and the reflux ratio is 1-50.

12. The purification method according to claim 11, characterized in that The step S1 further includes a first filtration process, which is provided after the heavy component removal process.

13. The purification method according to claim 11, characterized in that In the step S3, the light component removal is carried out in a light component removal tower (300), the tower pressure of the light component removal tower (300) is 100-150 kPa, the tower top temperature is 150-200° C., and the reflux ratio is 1-50.

14. The purification method according to claim 13, characterized in that The step S3 further includes a second filtration process, which is provided after the light component is removed.

15. The purification method according to claim 10, characterized in that In step S2, the azeotropic extraction treatment is performed in an azeotropic extraction tower (200), wherein the tower pressure of the azeotropic extraction tower (200) is 100-150 kPa, the tower top temperature is 150-200° C., and the reflux ratio is 1-50.

16. The purification method according to claim 15, characterized in that The step S2 further includes a first phase separation treatment, which is provided after the azeotropic extraction treatment. The step S2 further includes a condensation treatment, which is provided between the azeotropic extraction treatment and the first phase separation treatment.

17. The purification method according to claim 10, characterized in that The step S2 also includes recycling the liquid mixture.

18. The purification method according to claim 17, characterized in that The recovery process includes a reboil process; The recovery process further includes a second phase separation process, which is provided after the reboiling process.

19. The purification method according to any one of claims 10 to 18, characterized in that In step S2, the volume ratio of the deweighted silicon-based compound to water is 1:1-5.

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