CN115591272A - Method and system for purifying silicon-based precursor - Google Patents

Method and system for purifying silicon-based precursor Download PDF

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Publication number
CN115591272A
CN115591272A CN202211323659.1A CN202211323659A CN115591272A CN 115591272 A CN115591272 A CN 115591272A CN 202211323659 A CN202211323659 A CN 202211323659A CN 115591272 A CN115591272 A CN 115591272A
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silicon
based precursor
adsorbent
adsorption
purifying
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CN115591272B (en
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刘颖
裴凯
赵毅
孙良礼
李晓婷
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Dalian Kelide Optoelectronic Mat Co ltd
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Dalian Kelide Optoelectronic Mat Co ltd
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Priority to PCT/CN2022/138262 priority patent/WO2024087340A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to the field of electronic precursor purification, in particular to a method and a system for purifying a silicon-based precursor, wherein the method comprises the following steps: (S.1) dispersing an adsorbent in ionic liquid to obtain adsorption slurry; (S.2) dissolving the industrial-grade silicon-based precursor into the adsorption slurry to enable the industrial-grade silicon-based precursor to be in contact with an adsorbent, so that metal ion impurities in the industrial-grade silicon-based precursor are adsorbed by the adsorbent; and (S.3) after adsorption is finished, rectifying the crude silicon-based precursor, and removing light components and heavy components in the silicon-based precursor to obtain the electronic-grade silicon-based precursor. According to the invention, the environment of the silicon-based precursor in the purification process is changed, so that the silicon-based precursor is effectively separated from the metal ion impurities mixed in the silicon-based precursor, the adsorption of the metal ion impurities is facilitated, and the physical or chemical adsorption effect of the metal ion impurities is improved by combining various means.

Description

Method and system for purifying silicon-based precursor
Technical Field
The invention relates to the field of electronic precursor purification, in particular to a method and a system for purifying a silicon-based precursor.
Background
Advanced integrated circuit manufacturing technology has promoted the continuous development of new materials, and along with the reduction of integrated circuit line width and the increase of transistor density, the application of advanced precursor materials in the ultra-large scale integrated circuit process is more and more the focus of attention of people. The precursor material is mainly used in the key process of manufacturing semiconductor integrated circuit memories and logic chips, such as epitaxy, photoetching, chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD), and forms a thin film with specific electrical properties on the surface of an integrated circuit silicon wafer through chemical reaction and the like, which is important for the quality of the thin film. The silicon-based precursor is one of the important branches in the field of advanced integrated circuit core materials, and has been one of the hot spots in research in recent years, and the main applications of the silicon-based precursor are as follows: selective epitaxial growth of SiGe film, CVD and ALD growth of silicon nitride, silicon oxide, low and high dielectric constant thin film materials, etc. for different purposes.
With the continuous development of semiconductor technology, silicon-based precursor materials become the key to the development of integrated circuit processes, and the quality and performance of chips are directly affected by the technical indexes such as the purity of the materials, the content of metal impurities and the like. In the advanced IC preparation process, the purity of the silicon-based precursor material needs to reach more than 99.99 percent, and the mass fraction of metal impurities is less than 1x10 9 . At present, technologies such as reactive distillation, complex distillation, adsorption distillation and the like are mainly adopted to separate, refine and purify materials so as to meet the development requirements of the semiconductor industry.
Patent application No. 202010256194.7 discloses a process for purifying octamethylcyclotetrasiloxane, comprising the steps of: removing metal impurities in the octamethylcyclotetrasiloxane by an adsorption reaction in a micro-boiling state by using high-purity argon as a carrier gas; rectifying and purifying to separate octamethylcyclotetrasiloxane from adsorbent and remove organic impurities, water and oxygen to obtain an octamethylcyclotetrasiloxane intermediate product; the octamethylcyclotetrasiloxane intermediate product is further purified by secondary rectification to obtain an octamethylcyclotetrasiloxane pure product with the purity of more than 99.999 percent, and the requirement of cladding deposition of an optical fiber preform is met.
The patent with application number 202010256194.7 discloses a purification method of electronic grade octamethylcyclotetrasiloxane, which adopts a rectification mode for purification. The process comprises the following steps: 1) Putting octamethylcyclotetrasiloxane with 99% content into a rectifying tower, and removing a small amount of residual hexamethylcyclotrisiloxane (D3 for short) at the tower top temperature of 90-96 ℃ under the pressure of 0.02-0.03 MPa. 2) And (2) allowing the octamethylcyclotetrasiloxane subjected to D3 removal to flow out of the bottom of the tower and enter a reaction kettle of a de-heavy rectifying tower, adding a special high-efficiency metal complex ligand with the weight ratio of 0.01-0.1%, heating to 90-100 ℃, reacting for 1-10 hours, and performing reduced pressure rectification to obtain the electronic-grade octamethylcyclotetrasiloxane.
Disclosure of Invention
The invention provides a method for purifying a silicon-based precursor so as to overcome the defect that the silicon-based precursor material in the prior art contains more metal impurities and is difficult to meet the requirements of the development of the semiconductor industry.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for purifying a silicon-based precursor, comprising the steps of:
(S.1) dispersing an adsorbent in ionic liquid to obtain adsorption slurry;
(S.2) dissolving the industrial-grade silicon-based precursor into the adsorption slurry to enable the industrial-grade silicon-based precursor to be in contact with an adsorbent, so that metal ion impurities in the industrial-grade silicon-based precursor are adsorbed by the adsorbent;
and (S.3) after adsorption is finished, rectifying the silicon-based precursor, and removing light components and heavy components in the silicon-based precursor to obtain the electronic-grade silicon-based precursor.
The silicon-based precursor in the prior art is usually applied to metal or organic metal catalysts in the synthesis process, for example, a ternary copper catalyst (Cu, cu) is usually adopted in the process of synthesizing chlorosilane 2 O、Cu 2 O) and Cu powder reduced by CuCl as a catalyst. And it has also been proved that zinc, aluminum, selenium, antimony, phosphorus, manganese, etc. can also be used as a cocatalyst for producing chlorosilane by copper catalysis. Meanwhile, impurities such as iron, calcium, lead and the like may also exist in the upstream raw material silicon powder. These impurities often participate in the reaction together in the process of synthesizing the silicon-based precursor, and finally enter the silicon-based precursor finished product. Since these metal impurities are volatile, it is difficult to separate them from the silicon-based precursor by conventional rectification means. These metal impurities do not have a significant impact on conventional organosilicon synthesis and conventional material applications, but for silicon-containing films formed by Chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD), these impurities can have a significant impact on the electrical properties of the silicon-containing films.
In order to remove metal ion impurities in the silicon-based precursor in the prior art, an adsorption step is usually added in the purification process. Generally, in the adsorption step, the metal ion impurities in the silicon-based precursor are adsorbed by the adsorbent by a physical or chemical method, but adsorption can be realized only by contacting the impurity metal ions with the adsorbent in the adsorption process, so that adsorption time is often required to be prolonged to improve the adsorption effect on the impurity metal ions, but a part of the metal ion impurities are still covered by the silicon-based precursor and are difficult to contact with the adsorbent, so that the improvement of the adsorption effect of the conventional adsorbent on the metal ion impurities is limited.
In order to improve the adsorption effect on metal ions in the silicon-based precursor, the applicant specially changes the environment of the silicon-based precursor in the purification process, and unexpectedly discovers that the adsorption effect on the metal ions in the silicon-based precursor is greatly improved after the silicon-based precursor is dissolved in adsorption slurry consisting of ionic liquid and an adsorbent. The reason for this is that: (1) Ionic liquids are liquids that are composed entirely of ions and have good solubility properties for both organic and inorganic substances. The applicants have found that the solubility of metal ions in ionic liquids is much higher than the solubility of metal ions in silicon-based precursors due to the principle of phase-like solubility. (2) The method has the advantage that the silicon-based precursor is purified under the solution condition, so that the contact area between the silicon-based precursor and the adsorption slurry is increased. Therefore, the method provided by the invention innovatively realizes the extraction effect on the metal ions in the silicon-based precursor, so that the metal impurities originally dissolved in the silicon-based precursor are transferred into the ionic liquid, the interaction between the silicon-based precursor and the metal impurity ions is further eliminated, and the physical or chemical adsorption effect of the adsorbent in the adsorption slurry on the metal ion impurities is facilitated, so that the metal ion impurities in the silicon-based precursor can be quickly adsorbed, and the metal ion impurities are prevented from being evaporated into the purified silicon-based precursor in the subsequent rectification process of the silicon-based precursor.
In addition, the ionic liquid has the characteristic of non-volatility, so that the ionic liquid cannot be brought into the rectified ionic liquid in the rectification process of the silicon-based precursor.
Preferably, the ionic liquid comprises one or more of imidazole ionic liquid, quaternary ammonium ionic liquid, quaternary phosphonium ionic liquid, pyrrolidine ionic liquid and piperidine ionic liquid.
Preferably, the cation of the ionic liquid is any one of N-hexylpyridine, N-butylpyridine, N-octylpyridine, N-butyl-N-methylpyrrolidine, 1-butyl-3-methylimidazole, 1-propyl-3-methylimidazole, 1-ethyl-3-methylimidazole, 1-hexyl-3-methylimidazole, 1-octyl-3-methylimidazole, 1-allyl-3-methylimidazole, 1-butyl-2, 3-dimethylimidazole, 1-butyl-3-methylimidazole, tributylmethylphosphine, tributylethylphosphine, tetrabutylphosphine, tributylhexylphosphine, tributyloctylphosphine, tributyldecylphosphine, tributyldodecylphosphine, tributyltetradecylphosphine, triphenylethylphosphine, triphenylbutylphosphine, triphenylmethylphosphine, triphenylpropylphosphine, triphenylpentylphosphine, triphenylacetonylphosphine, triphenylbenzylphosphine, triphenylphosphonium (3-bromopropyl) phosphine, triphenylbromomethylphosphine, triphenylmethoxyphosphine, triphenylethoxycarbonylmethylphosphine, ((3-bromopropyl) phosphine, triphenylvinylphosphine, and tetraphenylphosphine.
Preferably, the anion of the ionic liquid is BF 4 - 、PF 6 - 、CF 3 SO 3 - 、(CF 3 SO 2 ) 2 N - 、C 3 F 7 COO - 、C 4 F 9 SO 3 、CF 3 COO - 、(CF 3 SO 2 ) 3 C - 、(C 2 F 5 SO 2 ) 3 C - 、(C 2 F 5 SO 2 ) 2 N - 、SbF 6 - Any one of them.
Preferably, the ionic liquid includes 1-butyl-3-methylimidazole trifluoromethanesulfonate, 1-butyl-3-methylimidazole dicyanamine salt, 1-ethyl-3-methylimidazole trifluoroacetate, 1-ethyl-3-methylimidazole chloroaluminate, 1-ethyl-2, 3-dimethylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-allyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-ethyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-sulfonic acid butyl-2-methyl-3-hexadecylimidazole hydrogen sulfate salt, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole carbonate, 1-ethyl-3-methylimidazole L-lactate, 1, 3-dimethylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-propyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-hexyl-3-methylimidazole hexafluorophosphate, 1-methyloctylmethyl-3-methylimidazole hexafluorophosphate, 1-tetradecyl-methylimidazole hexafluorophosphate, 1-benzylhexafluorophosphate, 1-methyl imidazole hexafluorophosphate, 1-3-methyl imidazole hexafluorophosphate, 1-decylmethylimidazole hexafluorophosphate, 1-3-methyl imidazole hexafluorophosphate, 1-methyl imidazole benzylhexafluorophosphate, 1-3-methyl imidazole hexafluorophosphate, 1-methyl imidazole, 1-allyl-3-methylimidazolium hexafluorophosphate, 1-vinyl-3-ethylimidazolium hexafluorophosphate, 1-vinyl-3-butylimidazolium hexafluorophosphate, 1-hexadecyl-2, 3-dimethylimidazolium hexafluorophosphate, 1-octyl-2, 3-dimethylimidazolium hexafluorophosphate, 1, 3-dimethylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-decyl-3-methylimidazolium tetrafluoroborate, 1-benzyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-2, 3-dimethylimidazolium tetrafluoroborate, 1-propyl-2, 3-dimethylimidazolium tetrafluoroborate, 1-octyl-2, 3-dimethylimidazolium tetrafluoroborate.
Preferably, the silicon-based precursor includes any one of octamethylcyclotetrasiloxane, trimethylsilane, tetramethylsilane, trimethylsilylamine, tetraethoxysilane, and diethoxymethylsilane.
Preferably, the adsorbent in step (s.1) comprises any one of activated carbon, porous alumina, silica gel powder, zeolite or molecular sieve.
Preferably, the outer surface of the adsorbent in step (s.1) is further coated with a polymer coating;
the polymer coating comprises a nitrogen-doped matrix layer coated on the outer surface of the adsorbent;
and the outside of the nitrogen-doped base layer is chemically bonded with a sodium polyacrylate chain segment.
In a preferred technical scheme of the invention, the outer surface of the adsorbent is further coated with a polymer coating body, and the coating body comprises a nitrogen-doped base body layer and a sodium polyacrylate chain segment. The nitrogen-doped matrix layer is doped with nitrogen elements, so that the nitrogen-doped matrix layer can be subjected to coordination complexing with metal ions, and the metal ions can be well adsorbed. And the sodium polyacrylate chain segment can react with divalent and above-divalent metal ions to generate a crosslinking reaction, so that the metal ions are coated and fixed, and the metal ions are prevented from escaping from the adsorption slurry.
Preferably, the preparation method of the adsorbent comprises the following steps:
(1) Coating a layer of resin containing nitrogen atoms on the surface of the adsorbent;
(2) Reacting the adsorbent coated with the nitrogen atom resin with acrylic acid chlorine so as to graft acrylic acid groups on the surface of the adsorbent coated with the nitrogen atom resin, thereby forming a nitrogen-doped matrix layer, namely an intermediate on the adsorbent;
(3) And copolymerizing the intermediate with sodium acrylate to obtain the adsorbent coated with the polymer coating body.
Preferably, the mass ratio of the intermediate in the step (3) to the sodium acrylate is 1: (0.5 to 2).
The applicant of the present invention finds that the mass ratio of the intermediate to the sodium acrylate has an important influence on the final adsorption purification effect, and when the addition amount of the sodium acrylate is too large, the sodium polyacrylate can completely coat the adsorbent, so that the porosity of the final adsorbent is reduced, and the adsorption effect on metal ions is reduced.
Preferably, in the step (2), the contact temperature of the industrial-grade silicon-based precursor and the adsorbent is 0 to 20 ℃.
In the prior art, the adsorption temperature of the silicon-based precursor in the adsorption and purification process is usually under the boiling condition, but the random diffusion motion (namely Brownian motion) speed of metal ions is accelerated under the condition of higher temperature, so that the metal ions are not favorably trapped by the adsorbent. And meanwhile, the energy consumption in the adsorption process is saved.
In a second aspect, the present invention also provides a purification system for purifying a silicon-based precursor, comprising:
the purification unit comprises a purification tank for containing materials, a stirring device for stirring the materials in the purification tank, and a heating device for heating the purification tank;
the rectification unit is arranged at the top of the purification tank and is used for rectifying the tantalum-silicon-based precursor obtained by evaporation in the cavity;
a collection unit comprising a collector in communication with the conduit of the rectification unit for collecting the silicon-based precursor flowing out of the rectification unit;
and the pressure control unit is communicated with the collector pipeline and is used for controlling the internal pressure of the whole purification system.
Preferably, the purification device further comprises a gas supply unit, wherein the gas supply unit comprises a gas tank for introducing inert gas into the purification tank, and a pressure control valve for controlling the flow rate of the conveyed inert gas flow.
Preferably, the collector is externally sleeved with a cold well.
Therefore, the invention has the following beneficial effects:
(1) The method effectively separates the silicon-based precursor from the metal ion impurities mixed in the silicon-based precursor by changing the environment of the silicon-based precursor in the purification process, thereby being beneficial to the adsorption of the metal ion impurities;
(2) The invention improves the physical or chemical adsorption effect on metal ion impurities by combining various means;
(3) Meanwhile, the invention also saves the energy consumption in the adsorption process.
Drawings
FIG. 1 is an electron micrograph of adsorbent A.
FIG. 2 is a gas phase detection diagram of technical grade octamethylcyclotetrasiloxane.
FIG. 3 is a mass spectrum of hexamethylcyclotrisiloxane (D3).
FIG. 4 is a mass spectrum of octamethylcyclotetrasiloxane (D4).
FIG. 5 is a mass spectrum of decamethylcyclopentasiloxane (D5).
FIG. 6 is a gas phase detection diagram of the purified electronic grade octamethylcyclotetrasiloxane.
Fig. 7 is a schematic diagram of a purification system for purifying a silicon-based precursor according to the present invention.
Wherein: purification unit 100, purification tank 110, stirring device 120, driving motor 121, transmission rod 122, stirring paddle 123, heating device 130, rectification unit 200, rectification column 210, rectification packing 220, collection unit 300, collector 310, cold well 320, low-boiling collector 330, pressure control unit 400, gas supply unit 500, gas tank 510, and pressure control valve 520.
Detailed Description
The invention is further described with reference to the drawings and the detailed description. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
[ PREPARATION OF ADSORBENT COATED WITH POLYMER COATING ]
Adsorbent A:
(1) Dispersing 100g of porous alumina in 100ml of deionized water, then adding 50ml of 37% formaldehyde aqueous solution and 0.1g of hexamethylenetetramine into the water, uniformly mixing, then adding 30g of melamine, uniformly stirring, heating to 80 ℃, reacting for 30 minutes, filtering and drying to obtain the porous alumina coated with the melamine-formaldehyde resin;
(2) Dispersing 100g of porous alumina coated with melamine formaldehyde resin in 200ml of dichloromethane, then dropwise adding 4.5g (50 mmol) of acryloyl chloride at 0 ℃, reacting for 1h, and filtering to obtain an intermediate (A);
(3) Adding a certain amount of deionized water and an intermediate (A) accounting for 10% of the total system mass into a 500mL four-neck flask provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, adding a chain transfer agent sodium bisulfite accounting for 4.5% of the system mass, stirring and dispersing, heating to 65 ℃, then dropwise adding monomer acrylic acid accounting for 15% of the system mass and initiator ammonium persulfate accounting for 0.06% of the system mass, preserving heat for 3 hours after dropwise adding is finished, neutralizing by using a sodium hydroxide aqueous solution with the mass fraction of 30% until the pH value is 7-7.5, filtering, washing and drying to obtain an adsorbent A, wherein an electron microscope photo of the adsorbent A is shown in figure 1.
Adsorbent B:
(1) Dispersing 100g of silica gel powder in 200ml of deionized water, then adding 5g of dopamine into the solution, stirring at normal temperature for 8 hours, filtering and drying to obtain the polydopamine-coated silica gel powder;
(2) Dispersing 100g of polydopamine-coated silica gel powder in 200ml of dichloromethane, then dropwise adding 4.5g (50 mmol) of acryloyl chloride at the temperature of 0 ℃, reacting for 1h, and filtering to obtain an intermediate (B);
(3) Adding a certain amount of deionized water and an intermediate (B) accounting for 10% of the total mass of the system into a 500mL four-neck flask provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, adding a chain transfer agent sodium bisulfite accounting for 4.5% of the mass of the system, stirring and dispersing, heating to 65 ℃, then dropwise adding monomer acrylic acid accounting for 15% of the mass of the system and initiator ammonium persulfate accounting for 0.06% of the mass of the system, preserving heat for 3 hours after dropwise adding, neutralizing by using a sodium hydroxide aqueous solution with the mass fraction of 30% until the pH value is 7-7.5, filtering, washing and drying to obtain the adsorbent B.
Adsorbent C:
(1) Dispersing 100g of porous alumina in 100ml of deionized water, then adding 20g of polyvinyl alcohol into the water, stirring uniformly, standing for 3 hours, filtering and drying to obtain the porous alumina coated with the polyvinyl alcohol;
(2) Dispersing 100g of polyvinyl alcohol coated porous alumina in 200ml of dichloromethane, then dropwise adding 4.5g (50 mmol) of acryloyl chloride at the temperature of 0 ℃, reacting for 1 hour, and filtering to obtain an intermediate (C);
(3) Adding a certain amount of deionized water and an intermediate (C) accounting for 10% of the total system mass into a 500mL four-neck flask provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, adding a chain transfer agent sodium bisulfite accounting for 4.5% of the system mass, stirring and dispersing, heating to 65 ℃, then dropwise adding monomer acrylic acid accounting for 15% of the system mass and initiator ammonium persulfate accounting for 0.06% of the system mass, preserving heat for 3 hours after dropwise adding, neutralizing by using a sodium hydroxide aqueous solution with the mass fraction of 30% until the pH value is 7-7.5, filtering, washing and drying to obtain the adsorbent C.
Adsorbent D:
(1) Dispersing 100g of porous alumina in 100ml of deionized water, then adding 50ml of 37% formaldehyde aqueous solution and 0.1g of hexamethylenetetramine into the water, uniformly mixing, then adding 30g of melamine, uniformly stirring, heating to 80 ℃, reacting for 30 minutes, filtering and drying to obtain the porous alumina coated with the melamine-formaldehyde resin;
(2) Dispersing 100g of porous alumina coated with melamine formaldehyde resin in 200ml of dichloromethane, then dropwise adding 4.5g (50 mmol) of acryloyl chloride into the mixture at the temperature of 0 ℃, reacting for 1 hour, and filtering to obtain an intermediate (A);
(3) Adding a certain amount of deionized water and an intermediate (A) accounting for 10% of the total mass of the system into a 500mL four-neck flask provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, adding a chain transfer agent sodium bisulfite accounting for 4.5% of the mass of the system, stirring and dispersing, heating to 65 ℃, then dropwise adding monomer acrylic acid accounting for 25% of the mass of the system and initiator ammonium persulfate accounting for 0.06% of the mass of the system, preserving heat for 3 hours after dropwise adding, neutralizing by using a sodium hydroxide aqueous solution with the mass fraction of 30% until the pH value is 7-7.5, filtering, washing and drying to obtain an adsorbent D.
[ purifying System ]
As shown in fig. 2, the present invention also discloses a purification system for purifying a silicon-based precursor, the system at least comprising the steps of:
the purification unit 100 includes a purification tank 110 for holding materials including industrial-grade silicon-based precursor, adsorbent, ionic liquid, and the like, so that the silicon-based precursor can contact with the adsorbent dispersed in the ionic liquid medium inside the purification tank 110, thereby enabling metal ion impurities in the silicon-based precursor to be dissolved in the ionic liquid and adsorbed and purified by the adsorbent.
In order to improve the contact effect of the silicon-based precursor and the adsorbent, a stirring device 120 for stirring the materials in the purification tank 110 is specially arranged on the purification tank 110, the stirring device 120 comprises a driving motor 121 arranged at the top of the purification tank 110 and a transmission rod 122 connected with the driving motor and extending into the purification tank 110, the transmission rod 122 is provided with a stirring paddle 123 for stirring the materials, and when the driving motor 121 is started, the driving motor 121 can drive the transmission rod 122 to rotate, so that the stirring paddle 123 plays a role in shearing the materials, and the stirring effect on the materials is improved.
In order to facilitate the temperature control of the materials inside the purification tank 110, the invention further provides a heating device 130 at the periphery of the purification tank 110, so as to facilitate the heating of the materials inside the purification tank 110.
The top of the purification tank 110 is provided with a set of rectification units 200 communicated with the purification tank, the rectification units 200 comprise a rectification column 210, and the interior of the rectification column 210 is filled with rectification packing 220.
The collecting unit 300 comprises a collector 310 communicated with the pipeline of the rectifying unit 200, a cold well 320 is sleeved outside the collector 310, a cooling medium such as liquid nitrogen can be filled into the cold well 320, when the silicon-based precursor comes out of the rectifying column 210, the silicon-based precursor is used for collecting the silicon-based precursor flowing out, and the collecting unit 300 further comprises a low-boiling collector 330 used for receiving low-boiling-point substances obtained by rectification.
A pressure control unit 400 in line communication with the accumulator 310 for controlling the pressure inside the entire purification system.
And a gas supply unit 500, the gas supply unit 500 including a gas tank 510 for introducing an inert gas into the interior of the purification tank 110, and a pressure control valve 520 for controlling the flow rate of the inert gas flow to be delivered.
[ purification of octamethylcyclotetrasiloxane (D4) ]
Example 1
The purification method of octamethylcyclotetrasiloxane comprises the following steps:
(S.1) putting 10kg of silica gel powder and 100kg of ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) into the purification tank 110, and starting the stirring device 120 to completely disperse the silica gel powder in the ionic liquid, thereby obtaining the adsorption slurry. Starting the air supply unit 500, and introducing nitrogen into the adsorption slurry at a rate of 10L/h, thereby removing air inside the purification tank;
(S.2) controlling the internal temperature of the purification tank 110 at 20 ℃, then putting 50kg of industrial grade octamethylcyclotetrasiloxane (D4) into the purification tank 110, stirring to dissolve the octamethylcyclotetrasiloxane in the adsorption slurry and contact with the adsorbent, and stirring for adsorption for 3 hours, so that metal ion impurities in the industrial grade octamethylcyclotetrasiloxane are adsorbed by the adsorbent;
(S.3) after adsorption is finished, stopping gas supply of the gas supply unit 500, controlling the internal pressure of the purification tank 110 to be 0.05MPa through the pressure control unit 400, heating by programmed temperature rise, collecting fractions with the fraction temperature of 98 ℃ received at the top of the rectification unit 200, removing light components in industrial-grade octamethylcyclotetrasiloxane, controlling the internal pressure of the purification tank 110 to be 0.02MPa, collecting fractions with the fraction temperature of 113 ℃ received at the top of the rectification unit 200, obtaining electronic-grade octamethylcyclotetrasiloxane, and enabling high-boiling-point substances to flow out of the bottom of the purification tank 110.
In order to compare the purity changes of the octamethylcyclotetrasiloxane obtained before and after purification, GC-MS detection is carried out on the industrial-grade octamethylcyclotetrasiloxane and the electronic-grade octamethylcyclotetrasiloxane obtained after purification.
Wherein, fig. 3 is a gas phase detection spectrogram of industrial grade octamethylcyclotetrasiloxane, wherein a peak at 6.209min is hexamethylcyclotrisiloxane (D3), a mass spectrogram thereof is shown in fig. 4, a peak at 7.550min is octamethylcyclotetrasiloxane (D4), a mass spectrogram thereof is shown in fig. 5, a peak at 10.401min is decamethylcyclopentasiloxane (D5), a mass spectrogram thereof is shown in fig. 6, and the rest peaks are high boiling point substances.
The gas-phase detection spectrum of the electronic grade octamethylcyclotetrasiloxane obtained after purification is shown in fig. 7, and it can be seen that the electronic grade octamethylcyclotetrasiloxane only contains octamethylcyclotetrasiloxane (D4) after purification.
Example 2
The purification method of octamethylcyclotetrasiloxane comprises the following steps:
(S.1) putting 10kg of adsorbent A and 100kg of ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) into a purification tank 110, and starting a stirring device 120 to completely disperse silica gel powder in the ionic liquid to obtain adsorption slurry. Starting the air supply unit 500, and introducing nitrogen into the adsorption slurry at a rate of 10L/h, thereby removing air inside the purification tank;
(S.2) controlling the internal temperature of the purification tank 110 at 20 ℃, then putting 50kg of industrial grade octamethylcyclotetrasiloxane (D4) into the purification tank 110, stirring to dissolve the octamethylcyclotetrasiloxane in the adsorption slurry and contact with the adsorbent, and stirring for adsorption for 3 hours, so that metal ion impurities in the industrial grade octamethylcyclotetrasiloxane are adsorbed by the adsorbent;
(S.3) after adsorption is finished, stopping gas supply of the gas supply unit 500, controlling the internal pressure of the purification tank 110 to be 0.05MPa through the pressure control unit 400, heating by programmed temperature rise, collecting fractions with the fraction temperature of 98 ℃ received at the top of the rectification unit 200, removing light components (D3) in industrial-grade octamethylcyclotetrasiloxane, controlling the internal pressure of the purification tank 110 to be 0.02MPa, collecting fractions with the fraction temperature of 113 ℃ received at the top of the rectification unit 200, obtaining electronic-grade octamethylcyclotetrasiloxane, and enabling high-boiling-point substances to flow out of the bottom of the purification tank 110.
Example 3
A method for purifying octamethylcyclotetrasiloxane, comprising the steps of:
(S.1) 10kg of the adsorbent B and 100kg of an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) were put into the purification tank 110, and the stirring device 120 was started to completely disperse the silica gel powder in the ionic liquid, thereby obtaining an adsorption slurry. Starting the air supply unit 500, and introducing nitrogen into the adsorption slurry at a rate of 10L/h, thereby removing air inside the purification tank;
(S.2) controlling the internal temperature of the purification tank 110 at 20 ℃, then putting 50kg of industrial-grade octamethylcyclotetrasiloxane (D4) into the purification tank 110, stirring to dissolve the octamethylcyclotetrasiloxane in the adsorption slurry and contact with the adsorbent, and stirring for adsorption for 3 hours, so that metal ion impurities in the industrial-grade octamethylcyclotetrasiloxane are adsorbed by the adsorbent;
(S.3) after adsorption is finished, stopping gas supply of the gas supply unit 500, controlling the internal pressure of the purification tank 110 to be 0.05MPa through the pressure control unit 400, heating by programmed temperature rise, collecting fractions with the fraction temperature of 98 ℃ received at the top of the rectification unit 200, removing light components (D3) in industrial-grade octamethylcyclotetrasiloxane, controlling the internal pressure of the purification tank 110 to be 0.02MPa, collecting fractions with the fraction temperature of 113 ℃ received at the top of the rectification unit 200, obtaining electronic-grade octamethylcyclotetrasiloxane, and enabling high-boiling-point substances to flow out of the bottom of the purification tank 110.
Example 4
A method for purifying octamethylcyclotetrasiloxane, comprising the steps of:
(S.1) 20kg of adsorbent B and 100kg of ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) are put into a purification tank 110, and a stirring device 120 is started to completely disperse silica gel powder in the ionic liquid, so that adsorption slurry is obtained. Starting the air supply unit 500, and introducing nitrogen into the adsorption slurry at a rate of 10L/h, thereby removing air inside the purification tank;
(S.2) controlling the internal temperature of the purification tank 110 at 20 ℃, then putting 50kg of industrial grade octamethylcyclotetrasiloxane (D4) into the purification tank 110, stirring to dissolve the octamethylcyclotetrasiloxane in the adsorption slurry and contact with the adsorbent, and stirring for adsorption for 3 hours, so that metal ion impurities in the industrial grade octamethylcyclotetrasiloxane are adsorbed by the adsorbent;
(S.3) after adsorption is finished, stopping gas supply of the gas supply unit 500, controlling the internal pressure of the purification tank 110 to be 0.05MPa through the pressure control unit 400, heating by programmed temperature rise, collecting fractions with the fraction temperature of 98 ℃ received at the top of the rectification unit 200, removing light components (D3) in industrial-grade octamethylcyclotetrasiloxane, controlling the internal pressure of the purification tank 110 to be 0.02MPa, collecting fractions with the fraction temperature of 113 ℃ received at the top of the rectification unit 200, obtaining electronic-grade octamethylcyclotetrasiloxane, and enabling high-boiling-point substances to flow out of the bottom of the purification tank 110.
Comparative example 1
The purification method of octamethylcyclotetrasiloxane comprises the following steps:
(S.1) putting 10kg of porous alumina coated with melamine formaldehyde resin and 100kg of ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) into a purification tank 110, and starting a stirring device 120 to completely disperse silica gel powder in the ionic liquid to obtain adsorption slurry. Starting the air supply unit 500, and introducing nitrogen into the adsorption slurry at a rate of 10L/h, thereby removing air inside the purification tank;
(S.2) controlling the internal temperature of the purification tank 110 at 20 ℃, then putting 50kg of industrial grade octamethylcyclotetrasiloxane (D4) into the purification tank 110, stirring to dissolve the octamethylcyclotetrasiloxane in the adsorption slurry and contact with the adsorbent, and stirring for adsorption for 3 hours, so that metal ion impurities in the industrial grade octamethylcyclotetrasiloxane are adsorbed by the adsorbent;
(S.3) after adsorption is finished, stopping gas supply of the gas supply unit 500, controlling the internal pressure of the purification tank 110 to be 0.05MPa through the pressure control unit 400, heating by programmed temperature rise, collecting fractions with the fraction temperature of 98 ℃ received at the top of the rectification unit 200, removing light components (D3) in industrial-grade octamethylcyclotetrasiloxane, controlling the internal pressure of the purification tank 110 to be 0.02MPa, collecting fractions with the fraction temperature of 113 ℃ received at the top of the rectification unit 200, obtaining electronic-grade octamethylcyclotetrasiloxane, and enabling high-boiling-point substances to flow out of the bottom of the purification tank 110.
Comparative example 2
A method for purifying octamethylcyclotetrasiloxane, comprising the steps of:
(S.1) putting 10kg of adsorbent C and 100kg of ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) into a purification tank 110, and starting a stirring device 120 to completely disperse silica gel powder in the ionic liquid to obtain adsorption slurry. Starting the air supply unit 500, and introducing nitrogen into the adsorption slurry at a rate of 10L/h, thereby removing air inside the purification tank;
(S.2) controlling the internal temperature of the purification tank 110 at 20 ℃, then putting 50kg of industrial grade octamethylcyclotetrasiloxane (D4) into the purification tank 110, stirring to dissolve the octamethylcyclotetrasiloxane in the adsorption slurry and contact with the adsorbent, and stirring for adsorption for 3 hours, so that metal ion impurities in the industrial grade octamethylcyclotetrasiloxane are adsorbed by the adsorbent;
(S.3) after adsorption is finished, stopping gas supply of the gas supply unit 500, controlling the internal pressure of the purification tank 110 to be 0.05MPa through the pressure control unit 400, heating by programmed temperature rise, collecting fractions with the fraction temperature of 98 ℃ received at the top of the rectification unit 200, removing light components (D3) in industrial-grade octamethylcyclotetrasiloxane, controlling the internal pressure of the purification tank 110 to be 0.02MPa, collecting fractions with the fraction temperature of 113 ℃ received at the top of the rectification unit 200, obtaining electronic-grade octamethylcyclotetrasiloxane, and enabling high-boiling-point substances to flow out of the bottom of the purification tank 110.
Comparative example 3
The purification method of octamethylcyclotetrasiloxane comprises the following steps:
(S.1) 10kg of the adsorbent D and 100kg of an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) were put into the purification tank 110, and the stirring device 120 was started to completely disperse the silica gel powder in the ionic liquid, thereby obtaining an adsorption slurry. Starting the air supply unit 500, and introducing nitrogen into the adsorption slurry at a rate of 10L/h, thereby removing air inside the purification tank;
(S.2) controlling the internal temperature of the purification tank 110 at 20 ℃, then putting 50kg of industrial grade octamethylcyclotetrasiloxane (D4) into the purification tank 110, stirring to dissolve the octamethylcyclotetrasiloxane in the adsorption slurry and contact with the adsorbent, and stirring for adsorption for 3 hours, so that metal ion impurities in the industrial grade octamethylcyclotetrasiloxane are adsorbed by the adsorbent;
(S.3) after adsorption is finished, stopping gas supply of the gas supply unit 500, controlling the internal pressure of the purification tank 110 to be 0.05MPa through the pressure control unit 400, heating by temperature programming, collecting fractions with the fraction temperature of 98 ℃ received at the top of the rectification unit 200, removing light components (D3) in industrial-grade octamethylcyclotetrasiloxane, controlling the internal pressure of the purification tank 110 to be 0.02MPa, collecting fractions with the temperature of 113 ℃ received at the top of the rectification unit 200, obtaining electronic-grade octamethylcyclotetrasiloxane, and enabling high-boiling-point substances to flow out of the bottom of the purification tank 110.
[ purification of tetraethoxysilane ]
Example 5
The method for purifying tetraethoxysilane comprises the following steps:
(S.1) 10kg of the adsorbent A and 100kg of an ionic liquid (1, 3-dimethylimidazolium tetrafluoroborate) were put into a purification tank 110, and a stirring device 120 was started to completely disperse silica gel powder in the ionic liquid, thereby obtaining an adsorption slurry. Starting the air supply unit 500, and introducing nitrogen into the adsorption slurry at a rate of 10L/h, thereby removing air inside the purification tank;
(S.2) controlling the internal temperature of the purification tank 110 to be 10 ℃, then putting 50kg of industrial tetraethoxysilane into the purification tank 110, stirring to dissolve the tetraethoxysilane in the adsorption slurry and contacting with the adsorbent, and stirring to adsorb for 5 hours, so that metal ion impurities in the industrial tetraethoxysilane are adsorbed by the adsorbent;
(S.3) after adsorption is finished, stopping gas supply of the gas supply unit 500, controlling the internal pressure of the purification tank 110 to be 0.05MPa through the pressure control unit 400, heating by programmed temperature rise, collecting fractions with the temperature of 93-95 ℃ received by the top of the rectification unit 200, removing light components in industrial octamethylcyclotetrasiloxane, controlling the internal pressure of the purification tank 110 to be 0.02MPa, collecting fractions with the temperature of 108-110 ℃ received by the top of the rectification unit 200, obtaining electronic tetraethoxysilane, and enabling high-boiling-point substances to flow out of the bottom of the purification tank 110.
[ purification of Tetramethylsilane ]
Example 6
The method for purifying tetramethylsilane comprises the following steps:
(S.1) 10kg of the adsorbent A and 100kg of an ionic liquid (1, 3-dimethylimidazolium tetrafluoroborate) were put into a purification tank 110, and a stirring device 120 was started to completely disperse silica gel powder in the ionic liquid, thereby obtaining an adsorption slurry. Starting the air supply unit 500, and introducing nitrogen into the adsorption slurry at a rate of 10L/h, thereby removing air inside the purification tank;
(S.2) controlling the internal temperature of the purification tank 110 at 0 ℃, then putting 50kg of industrial tetramethylsilane into the purification tank 110, stirring to dissolve the tetramethylsilane in the adsorption slurry and contact the adsorbent, and stirring for adsorption for 5 hours, so that metal ion impurities in the industrial tetramethylsilane are adsorbed by the adsorbent;
(S.3) after adsorption is finished, stopping gas supply of the gas supply unit 500, controlling the internal pressure of the purification tank 110 to be one atmospheric pressure through the pressure control unit 400, heating by temperature programming, collecting fractions at 26-28 ℃ received by the top of the rectification unit 200 to obtain electronic-grade tetramethylsilane, and allowing high-boiling-point substances to flow out of the bottom of the purification tank 110.
[ purification of trimethylsilane ]
Example 7
The method for purifying trimethylsilane comprises the following steps:
(S.1) 10kg of the adsorbent A and 100kg of an ionic liquid (1, 3-dimethylimidazolium tetrafluoroborate) were put into a purification tank 110, and a stirring device 120 was started to completely disperse silica gel powder in the ionic liquid, thereby obtaining an adsorption slurry. Starting the air supply unit 500, and introducing nitrogen into the adsorption slurry at a rate of 10L/h, thereby removing air inside the purification tank;
(S.2) reducing the internal temperature of the purification tank 110 to-10 ℃, then putting 50kg of industrial-grade trimethylsilane into the purification tank 110, stirring to dissolve the trimethylsilane into the adsorption slurry and contact with the adsorbent A, and stirring for adsorption for 5 hours to adsorb metal ion impurities in the industrial-grade trimethylsilane by the adsorbent A;
(S.3) after adsorption is finished, stopping gas supply of the gas supply unit 500, controlling the internal pressure of the purification tank 110 to be one atmospheric pressure through the pressure control unit 400, heating by temperature programming, collecting fractions of 6-7 ℃ received at the top of the rectification unit 200 to obtain the electronic-grade trimethylsilane, and enabling high-boiling-point substances to flow out of the bottom of the purification tank 110.
[ results of Performance test ]
The metal ion impurity contents of the octamethylcyclotetrasiloxane purified in examples 1 to 4 and comparative examples 1 to 3, the tetraethoxysilane obtained in example 5, the tetramethylsilane prepared in example 6, and the trimethylsilane prepared in example 7 are shown in table 1 below.
TABLE 1
Figure 718304DEST_PATH_IMAGE002
。
From the data in the table above, the preparation method of the present invention can achieve a good purification effect on the silicon-based precursor, and can effectively remove metal ion impurities and high and low boiling point substances in the silicon-based precursor.
Comparing example 1 with examples 1 to 4, it is found that the adsorption effect of the present invention on metal ion impurities inside the silicon-based precursor can be effectively improved by coating the polymer coating outside the adsorbent.
Comparing example 2 with comparative examples 1 to 2, it is found that the adsorption effect on metal ion impurities inside the silicon-based precursor can be improved to a certain extent after the nitrogen-doped matrix layer is coated outside the adsorbent, but the adsorption effect on the metal ion impurities can be greatly improved after the sodium polyacrylate chain segment is chemically bonded outside the nitrogen-doped matrix layer. The nitrogen-doped matrix layer and the sodium polyacrylate chain segment can form a synergistic effect.
After comparing the example 2 with the comparative example 3, it is found that the adsorbent D in the comparative example 3 has a sealing effect on the pores of the adsorbent due to an excessively large addition amount of sodium acrylate in the synthesis process, so that the porosity is reduced, and the adsorption effect on the metal ion impurities is further influenced.

Claims (10)

1. The method for purifying the silicon-based precursor is characterized by comprising the following steps of:
(S.1) dispersing an adsorbent in ionic liquid to obtain adsorption slurry;
(S.2) dissolving the industrial-grade silicon-based precursor into the adsorption slurry to enable the industrial-grade silicon-based precursor to be in contact with an adsorbent, so that metal ion impurities in the industrial-grade silicon-based precursor are adsorbed by the adsorbent;
and (S.3) after adsorption is finished, rectifying the crude silicon-based precursor, and removing light components and heavy components in the silicon-based precursor to obtain the electronic-grade silicon-based precursor.
2. The method of purifying a silicon-based precursor according to claim 1,
the silicon-based precursor comprises any one of octamethylcyclotetrasiloxane, trimethylsilane, tetramethylsilane, trisilylamine, tetraethoxysilane and diethoxymethylsilane.
3. The method of purifying a silicon-based precursor according to claim 1,
the adsorbent in the step (S.1) comprises any one of activated carbon, porous alumina, silica gel powder, zeolite or molecular sieve.
4. The method of purifying a silicon-based precursor according to claim 1 or 3,
the outer surface of the adsorbent in the step (S.1) is further coated with a polymer coating body;
the polymer coating comprises a nitrogen-doped matrix layer coated on the outer surface of the adsorbent;
and the outside of the nitrogen-doped base layer is chemically bonded with a sodium polyacrylate chain segment.
5. The method of purifying a silicon-based precursor according to claim 4,
the preparation method of the adsorbent comprises the following steps:
(1) Coating a layer of resin containing nitrogen atoms on the surface of the adsorbent;
(2) Reacting the adsorbent coated with the nitrogen atom resin with acryloyl chloride so as to graft acrylic acid groups on the surface of the adsorbent coated with the nitrogen atom resin, thereby forming a nitrogen-doped matrix layer, namely an intermediate body, on the adsorbent;
(3) And copolymerizing the intermediate with sodium acrylate to obtain the adsorbent coated with the polymer coating.
6. The method of purifying a silicon-based precursor according to claim 4,
the mass ratio of the intermediate in the step (3) to the sodium acrylate is less than 1:2.
7. the method of purifying a silicon-based precursor according to claim 1,
in the step (2), the contact temperature of the industrial-grade silicon-based precursor and the adsorbent is 0-20 ℃.
8. A purification system for purifying a silicon-based precursor, comprising:
the purification unit (100) comprises a purification tank (110) for containing materials, a stirring device (120) for stirring the materials in the purification tank (110), and a heating device (130) for heating the purification tank (110);
the rectification unit (200) is arranged at the top of the purification tank (110) and is used for rectifying the silicon-based precursor obtained by evaporation in the cavity (110);
a collection unit (300) comprising a collector (310) in communication with the conduit of the rectification unit (200) for collecting the silicon-based precursor flowing out of the rectification unit (200);
a pressure control unit (400) in line communication with the accumulator (310) for controlling the pressure within the entire purification system.
9. A purification system for purifying a silicon-based precursor according to claim 8,
the device also comprises a gas supply unit (500), wherein the gas supply unit (500) comprises a gas tank (510) for introducing inert gas into the purification tank (110), and a pressure control valve (520) for controlling the flow rate of the conveyed inert gas flow.
10. A purification system for purifying a silicon-based precursor according to claim 8,
the outside of the collector (310) is sleeved with a cold well (320).
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116770581A (en) * 2023-08-28 2023-09-19 烟台奥森制动材料有限公司 Method for preparing antioxidant carbon fiber solid felt by adopting metal ion purifying agent

Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005120029A (en) * 2003-10-17 2005-05-12 Jsr Corp Method of purifying silane compound
CN101736157A (en) * 2009-12-14 2010-06-16 北京有色金属研究总院 Process for absorbing and extracting valuable metal ions in leachate of laterite nickel ore by applying immobilized room temperature ionic liquid
CN102092720A (en) * 2009-02-13 2011-06-15 李明成 Continuous preparation device for high-purity silane gas
CN102225981A (en) * 2011-04-27 2011-10-26 浙江卫星石化股份有限公司 Preparation method of porous sodium acrylate super absorbent resin
CN102513064A (en) * 2011-12-23 2012-06-27 广东工业大学 Preparation method and application of ionic liquid bonded silica adsorbent
CN103788124A (en) * 2014-01-16 2014-05-14 上海爱默金山药业有限公司 Method for purifying electronic grade octamethylcyclotetrasiloxane
CN103922434A (en) * 2014-04-10 2014-07-16 北京工业大学 Preparation method of adsorption-flocculating agent of natural porous base material
CN103933950A (en) * 2014-05-07 2014-07-23 济南大学 Method for preparing loofah sponge immobilized ionic liquid adsorbent
CN105712351A (en) * 2016-04-18 2016-06-29 张玲 Method for adsorption purification of silicane
CN105732694A (en) * 2016-03-04 2016-07-06 张玲 Method for adsorbing and purifying 1, 1, 1, 3, 5, 5, 5-heptamethyltrisiloxane
CN111097190A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Method for extracting and recovering organic solvent by ionic liquid
CN111574551A (en) * 2020-04-02 2020-08-25 有研国晶辉新材料有限公司 Purification process of octamethylcyclotetrasiloxane
CN112678829A (en) * 2021-01-26 2021-04-20 大连科利德光电子材料有限公司 High-purity disilane continuous production system and preparation process
CN113368826A (en) * 2021-07-06 2021-09-10 江阴市锦绣江南环境发展有限公司 Adsorbent for heavy metal wastewater treatment and preparation method thereof
CN113603096A (en) * 2021-05-26 2021-11-05 中国科学院过程工程研究所 Method for adsorbing trace boron and phosphorus impurities in chlorosilane system
CN215139813U (en) * 2021-03-29 2021-12-14 大连科利德光电子材料有限公司 Trisilicon based nitrogen alkane purification device
CN113797568A (en) * 2021-08-20 2021-12-17 洛阳中硅高科技有限公司 Synthesis device and synthesis method of electronic grade tri (dimethylamino) silane
CN114349966A (en) * 2022-03-03 2022-04-15 江门市胜鹏化工实业有限公司 Preparation method of high-purity methyl silicone oil
CN114783641A (en) * 2022-03-29 2022-07-22 华中科技大学 Application method of polyion liquid gel material in uranium rhenium adsorption separation
CN114849671A (en) * 2022-06-10 2022-08-05 大连科利德光电子材料有限公司 Impurity adsorbent, preparation method and method for purifying trimethylaluminum by using impurity adsorbent

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE869189C (en) * 1949-12-22 1953-03-02 Metallgesellschaft Ag Method and device for the continuous countercurrent extraction of liquids with liquids
US7638058B2 (en) * 2005-04-07 2009-12-29 Matheson Tri-Gas Fluid storage and purification method and system
US8277768B2 (en) * 2008-11-14 2012-10-02 Texas Instruments Incorporated System and method for production of high purity silicon solids and solids therefrom
CN110745831B (en) * 2019-11-14 2021-09-10 李龙飞 Method and device for removing impurities from silicon tetrachloride
CN111298834A (en) * 2020-03-27 2020-06-19 孙桂霞 Preparation method of pharmaceutical intermediate for department of respiration
CN112759608B (en) * 2020-12-31 2023-05-02 有研国晶辉新材料有限公司 Device and process for removing metal impurities in octamethyl cyclotetrasiloxane

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005120029A (en) * 2003-10-17 2005-05-12 Jsr Corp Method of purifying silane compound
CN102092720A (en) * 2009-02-13 2011-06-15 李明成 Continuous preparation device for high-purity silane gas
CN101736157A (en) * 2009-12-14 2010-06-16 北京有色金属研究总院 Process for absorbing and extracting valuable metal ions in leachate of laterite nickel ore by applying immobilized room temperature ionic liquid
CN102225981A (en) * 2011-04-27 2011-10-26 浙江卫星石化股份有限公司 Preparation method of porous sodium acrylate super absorbent resin
CN102513064A (en) * 2011-12-23 2012-06-27 广东工业大学 Preparation method and application of ionic liquid bonded silica adsorbent
CN103788124A (en) * 2014-01-16 2014-05-14 上海爱默金山药业有限公司 Method for purifying electronic grade octamethylcyclotetrasiloxane
CN103922434A (en) * 2014-04-10 2014-07-16 北京工业大学 Preparation method of adsorption-flocculating agent of natural porous base material
CN103933950A (en) * 2014-05-07 2014-07-23 济南大学 Method for preparing loofah sponge immobilized ionic liquid adsorbent
CN105732694A (en) * 2016-03-04 2016-07-06 张玲 Method for adsorbing and purifying 1, 1, 1, 3, 5, 5, 5-heptamethyltrisiloxane
CN105712351A (en) * 2016-04-18 2016-06-29 张玲 Method for adsorption purification of silicane
CN111097190A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Method for extracting and recovering organic solvent by ionic liquid
CN111574551A (en) * 2020-04-02 2020-08-25 有研国晶辉新材料有限公司 Purification process of octamethylcyclotetrasiloxane
CN112678829A (en) * 2021-01-26 2021-04-20 大连科利德光电子材料有限公司 High-purity disilane continuous production system and preparation process
CN215139813U (en) * 2021-03-29 2021-12-14 大连科利德光电子材料有限公司 Trisilicon based nitrogen alkane purification device
CN113603096A (en) * 2021-05-26 2021-11-05 中国科学院过程工程研究所 Method for adsorbing trace boron and phosphorus impurities in chlorosilane system
CN113368826A (en) * 2021-07-06 2021-09-10 江阴市锦绣江南环境发展有限公司 Adsorbent for heavy metal wastewater treatment and preparation method thereof
CN113797568A (en) * 2021-08-20 2021-12-17 洛阳中硅高科技有限公司 Synthesis device and synthesis method of electronic grade tri (dimethylamino) silane
CN114349966A (en) * 2022-03-03 2022-04-15 江门市胜鹏化工实业有限公司 Preparation method of high-purity methyl silicone oil
CN114783641A (en) * 2022-03-29 2022-07-22 华中科技大学 Application method of polyion liquid gel material in uranium rhenium adsorption separation
CN114849671A (en) * 2022-06-10 2022-08-05 大连科利德光电子材料有限公司 Impurity adsorbent, preparation method and method for purifying trimethylaluminum by using impurity adsorbent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATRICK A TAYLOR: "对高纯度硅烷中气态杂质和金属杂质的纯化技术和分析方法" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116770581A (en) * 2023-08-28 2023-09-19 烟台奥森制动材料有限公司 Method for preparing antioxidant carbon fiber solid felt by adopting metal ion purifying agent
CN116770581B (en) * 2023-08-28 2023-10-20 烟台奥森制动材料有限公司 Method for preparing antioxidant carbon fiber solid felt by adopting metal ion purifying agent

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