CN115254050B - Method for removing residual monochlorosilane in trisilicon-based nitrogen - Google Patents

Method for removing residual monochlorosilane in trisilicon-based nitrogen Download PDF

Info

Publication number
CN115254050B
CN115254050B CN202210777731.1A CN202210777731A CN115254050B CN 115254050 B CN115254050 B CN 115254050B CN 202210777731 A CN202210777731 A CN 202210777731A CN 115254050 B CN115254050 B CN 115254050B
Authority
CN
China
Prior art keywords
trisilicon
based nitrogen
adsorbent
polymer
matrix
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210777731.1A
Other languages
Chinese (zh)
Other versions
CN115254050A (en
Inventor
赵毅
赵银凤
吴冬辉
计燕秋
刘颖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Kelide Optoelectronic Mat Co ltd
Original Assignee
Dalian Kelide Optoelectronic Mat Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Kelide Optoelectronic Mat Co ltd filed Critical Dalian Kelide Optoelectronic Mat Co ltd
Priority to CN202210777731.1A priority Critical patent/CN115254050B/en
Publication of CN115254050A publication Critical patent/CN115254050A/en
Application granted granted Critical
Publication of CN115254050B publication Critical patent/CN115254050B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/165—Natural alumino-silicates, e.g. zeolites
    • 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
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Silicon Compounds (AREA)

Abstract

The invention relates to the field of electronic gas purification, in particular to a method for removing residual monochlorosilane in trisilicon-based nitrogen, which comprises the following steps of: (S.1) drying the adsorbent and filling the adsorbent into a packed tower of a rectifying still; (S.2) pumping negative treatment is carried out on the rectifying still, and then inert gas is introduced to replace air in the rectifying still; (S.3) introducing industrial grade trisilicon-based nitrogen into a rectifying still, and heating to enable the trisilicon-based nitrogen to be in contact with the impurity adsorbent in the reflux process; and (S.4) collecting fractions from the top of the packed tower, cooling and filtering to obtain the high-purity trisilicon-based nitrogen. The purification method of the trisilicon-based nitrogen is simpler, and the adsorbent can effectively absorb the chlorosilane impurities through two different physical and chemical methods, so that the residual chlorosilane impurities in the trisilicon-based nitrogen can be removed only by simple rectification of the trisilicon-based nitrogen, and the purification efficiency of the trisilicon-based nitrogen can be effectively improved.

Description

Method for removing residual monochlorosilane in trisilicon-based nitrogen
Technical Field
The invention relates to the field of electronic gas purification, in particular to a method for removing residual monochlorosilane in trisilicon-based nitrogen.
Background
Trisilicon based nitrogen ((SiH) 3 ） 3 Or TSA), also known as trisilylamine, which can be used to deposit high purity silicon oxide films without direct plasma excitation and thus has very important uses in the semiconductor industry, for example, capable of being used in void-filling applications.
The preparation of trisilicon based nitrogen is varied, but it is generally obtained by reacting monochlorosilane with ammonia in industry (related patents such as CN108586515B, CN113912029a and CN 104250007B). However, during the reaction, a part of unreacted monochlorosilane remains in the trisilicon-based nitrogen product, and it is necessary to remove monochlorosilane from the trisilicon-based nitrogen to ensure the final silicon film deposition effect, since monochlorosilane is detrimental to the formation of silicon-containing films by chemical vapor deposition using trisilicon-based nitrogen.
In the prior art, in order to improve the purity of the trisilicon-based nitrogen, the aim of improving the purity of the trisilicon-based nitrogen is generally achieved by adjusting a method and parameters during synthesis in the gas synthesis process. But this approach requires adjustments to the production line from the source, which is costly overall.
Therefore, from the viewpoint of reducing the cost of purification of trisilicon-based nitrogen, the applicant has desired to devise a method capable of obtaining high-purity trisilicon-based nitrogen by purifying trisilicon-based nitrogen of low purity as a starting material to remove the remaining monochlorosilane therefrom.
Disclosure of Invention
The invention aims to overcome the defect that the production cost of high-purity trisilicon-based nitrogen is high in the prior art, and provides a method for removing residual monochlorosilane in trisilicon-based nitrogen with low cost by taking low-purity trisilicon-based nitrogen as a starting material and purifying the low-purity trisilicon-based nitrogen.
In order to achieve the aim of the invention, the invention is realized by the following technical scheme:
in a first aspect of the invention, there is provided an adsorbent,
comprising a mineral matrix, and
a polymer coating on the exterior of the mineral substrate;
the mineral matrix contains structural water;
the polymer coating contains sodium alkoxide groups.
The adsorbent of the present invention has its adsorption part mainly comprising mineral matrix with structural water and polymer coating with sodium alkoxide radical. The mineral substrate can be selected to be in a flake or powder or granular form, so that the mineral substrate has a relatively high specific surface area, and can be used for adsorbing chlorosilanes (such as monochlorosilane or other chlorosilanes containing 1-4 chlorines and other chlorosilanes containing alkyl structures) in a physical manner. Meanwhile, the polymer coating is coated outside the mineral matrix, the polymer coating and the chlorosilane compound are organic compounds, and the polymer coating and the chlorosilane compound can be correspondingly adsorbed through polarity and intermolecular attraction, so that the physical adsorption effect of the mineral matrix on the chlorosilane compound can be improved. Therefore, the physical adsorption of impurities by the adsorbent in the application comprises two different mechanisms, so that the adsorption effect on chlorosilane compounds can be effectively improved.
In addition, the invention can adsorb chlorosilane by chemical adsorption. The principle comprises the following two points:
firstly, in the present invention, due to the presence of structural water in the mineral matrix, it is mainly represented by OH - In the form of a mineral, thereby maintaining the crystal structure of the mineral, and this part of the structural water can react with the chlorosilane-based compound, thereby being capable of immobilizing the chlorosilane-based compound.
Meanwhile, structural water in the minerals is reacted after the structural water is combined with the chlorosilane compounds, so that the crystal lattice of the minerals is damaged, the surface area of a mineral matrix can be rapidly increased after the crystal lattice of the minerals is damaged, and the physical adsorption effect on the chlorosilane compounds is further improved.
In addition, since this part of the structural water is different from ordinary free water, the ordinary free water can have a remarkable decomposition promoting effect on the silicon-nitrogen bond, and particularly in the presence of an acid, the silicon-nitrogen can undergo a remarkable hydrolysis reaction when contacting with the free water. However, the structural water described in the present invention does not react with the silazane bond in the silazane, so that the silazane can be effectively prevented from being decomposed during the purification process.
Secondly, since the polymer coating contains sodium alkoxide groups, the polymer coating has strong alkalinity and can react with chlorosilane compounds, so that chlorosilane is adsorbed. Meanwhile, the hydrogen chloride formed after the chlorosilane compound reacts with the structural water in the minerals can be absorbed by sodium alkoxide groups, so that the pollution of new impurities to trisilicon-based nitrogen is effectively prevented.
Thus, in summary, the adsorbent of the present invention is capable of achieving efficient adsorption of chlorosilane impurities by two different methods, physical and chemical. Meanwhile, the absorption of chlorosilane impurities is effectively promoted by two different absorption mechanisms in the chemical absorption process.
Preferably, the mineral matrix comprises any one or a combination of more of talc, serpentine, kaolinite, hydromica, chlorite.
Some mineral matrixes listed in the invention contain relatively stable structural water, and can realize effective adsorption of chlorosilane impurities in trisilicon-based nitrogen on the premise of not hydrolyzing the trisilicon-based nitrogen. Meanwhile, the mineral matrixes selected in the invention have larger yield in the nature, so that the price is low, and the consumable cost in the adsorption process can be effectively reduced.
Preferably, the polymer coating comprises a polymer matrix for forming a coating outside the mineral matrix; and a grafting unit attached to the polymer matrix;
the sodium alkoxide groups are located at the end groups of the grafting unit.
The polymer matrix comprises two parts, namely a polymer matrix and a grafting unit, wherein the polymer matrix part is mainly used for firmly coating the mineral matrix, preventing the polymer matrix from falling off from the surface of the mineral matrix, and has a bridging function, so that a base point for connecting the grafting unit is formed, and the stable connection of the grafting unit is facilitated. Meanwhile, as the sodium alkoxide group is positioned at the end group of the grafting unit, the sodium alkoxide group can be directly contacted and adsorbed with chlorosilane impurities in trisilicon-based nitrogen, so that the adsorption effect on the chlorosilane impurities is improved.
Preferably, the polymer matrix is any one of polydopamine and polyglutamic acid.
The polymer matrix is polydopamine or polyglutamic acid, and has more reactive groups, so that the grafting units can be connected favorably, and the more the number of the reactive groups is, the higher the content of the connected grafting units is, so that the adsorption effect on chlorosilane impurities is more obvious. Meanwhile, the formation of polydopamine or polytannic acid is relatively simpler, complex operation steps are not needed, the implementation is facilitated, and the coating difficulty is reduced.
Preferably, the grafting unit is a product obtained by reacting a compound containing at least one hydroxyl group with metallic sodium.
In a second aspect of the invention, there is provided a process for preparing an adsorbent as described above,
the method comprises the following steps:
(1) Dispersing a mineral matrix in a dispersant to form a dispersion;
(2) Adding a polymer monomer to the dispersion and allowing it to polymerize, thereby coating the polymer matrix on the surface of the mineral matrix;
(3) And connecting a grafting unit containing sodium alkoxide groups on the surface of the polymer matrix, thereby obtaining the adsorbent.
The adsorbent provided by the invention has the advantages of simple preparation process steps, realization through simple three-step reaction and good repeatability.
Preferably, the dispersing agent used in the step (1) may be water or other organic solvents (e.g. alcohol solvents, alkane solvents), and in some embodiments of the present invention, water is selected as the dispersing agent, which can be better matched with the polymer monomers used in the present application. When selecting the polymer monomers in addition to those described herein, other solvents may also be selected as dispersants.
Preferably, the polymer monomer in the step (2) is any one of dopamine or tannic acid.
The polymer monomer used in the invention is dopamine or tannic acid, which can rapidly form a layer of polymer matrix completely coating the mineral matrix on the surface of the mineral matrix, and the thickness of the polymer matrix can be adjusted by the concentration of the polymer monomer, thereby improving the adaptability. And the polydopamine and the polyglutamic acid formed after polymerization have more active groups (such as hydroxyl groups) with good reactivity, and the active groups can serve as connecting sites with grafting units, so that the grafting modification of the grafting units containing sodium alkoxide groups is facilitated.
And (2) adding the polymer monomer into the dispersion, stirring at normal temperature for 12-24 hours, centrifugally collecting the precipitate, washing the precipitate with deionized water, and drying to obtain the mineral matrix coated with the polymer matrix.
Preferably, the polymer matrix in the step (3) may be connected in various ways during the connection with the grafting unit containing sodium alkoxide groups, for example, groups capable of reacting with active groups present on the surface of the polymer matrix may be provided on the grafting unit, and grafting may be performed by the reaction between the groups. The hydroxyl group in the reactive group can be grafted to other groups through the compound by modifying the reactive group, and then the hydroxyl group is connected with the grafting unit through the reaction between the groups. Because of the numerous reactions, this is not a list.
In a third aspect of the invention, there is also provided a method of removing residual monochlorosilane from trisilicon based nitrogen,
the method comprises the following steps:
(S.1) drying the adsorbent and filling the adsorbent into a packed tower of a rectifying still;
(S.2) pumping negative treatment is carried out on the rectifying still, and then inert gas is introduced to replace air in the rectifying still;
(S.3) introducing industrial grade trisilicon-based nitrogen into a rectifying still, and heating to enable the trisilicon-based nitrogen to be in contact with the impurity adsorbent in the reflux process;
and (S.4) collecting fractions from the top of the packed tower, cooling and filtering to obtain the high-purity trisilicon-based nitrogen.
The purification method of the trisilicon-based nitrogen is simpler, and the residual monochlorosilane impurity in the trisilicon-based nitrogen can be removed only by simple rectification of the trisilicon-based nitrogen. Meanwhile, batch rectification or continuous rectification can be adopted for purification, so that the purification efficiency of the trisilicon-based nitrogen can be effectively improved.
Therefore, the invention has the following beneficial effects:
(1) The adsorbent can effectively absorb the chlorosilane impurities by two different physical and chemical methods, and plays an effective promoting role in the absorption of the chlorosilane impurities by a plurality of different absorption mechanisms in the chemical absorption process;
(2) The preparation method of the adsorbent is simple, and the preparation cost is low, so that the method is beneficial to large-scale industrial production;
(3) The method for removing the residual monochlorosilane in the trisilicon-based nitrogen is simple, the residual monochlorosilane impurity in the trisilicon-based nitrogen can be removed only through simple rectification, and meanwhile, the purification efficiency of the trisilicon-based nitrogen is greatly improved compared with that of the prior art.
Detailed Description
The invention is further described below in connection with specific embodiments. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
[ preparation of adsorbent ]
Example 1
A preparation method of an adsorbent comprises the steps of dispersing 10g of talcum powder in 200ml of water, stirring to form a dispersion, adding 1g of dopamine hydrochloride into the dispersion, adjusting the pH value to 8.5, stirring at normal temperature for 24 hours, coating polydopamine on the surface of a mineral matrix, centrifugally collecting precipitate, washing the precipitate with deionized water, and drying to obtain the polydopamine-coated mineral matrix.
10g of polydopamine-coated mineral substrate was dispersed in 200ml of 50% ethanol solution, 5g (28 mmol) of methyltriethoxysilane was added thereto, the pH of the solution was adjusted to 3.5, after stirring for 3 hours, 5g (54 mmol) of glycerin was continuously added thereto, stirring was continued for 3 hours, filtration was carried out, and the precipitate was washed with deionized water and dried to obtain polydopamine-coated mineral substrate having glycerin grafted on the surface.
Dispersing the mineral matrix of the coated polydopamine with the surface grafted with the glycerol in 200ml of toluene, then adding 1.15g (50 mmol) sodium sand, carrying out reflux reaction to enable hydroxyl groups in the glycerol to react with sodium to form sodium alkoxide groups, cooling to room temperature after the reaction is finished, adding 100ml of isopropanol, and obtaining an adsorbent (A1) after no bubble is generated in the reaction, wherein the reaction indicates that metal sodium is completely reacted, centrifuging and collecting sediment, washing the sediment with absolute ethyl alcohol and deionized water, and drying.
Example 2
A preparation method of an adsorbent comprises dispersing 10g of kaolinite powder in 200ml of water, stirring to form a dispersion, adding 1g of tannic acid into the dispersion, stirring at normal temperature for 12h, coating the surface of a mineral matrix with the tannic acid, centrifuging, collecting precipitate, washing the precipitate with deionized water, and drying to obtain the mineral matrix coated with the tannic acid.
10g of a mineral substrate coated with a poly tannic acid was dispersed in 200ml of a 50% ethanol solution, 5.4g (30 mmol) of methyltriethoxysilane was added thereto, the pH of the solution was adjusted to 3.5, after stirring for 5 hours, 10.8g (60 mmol) of glucose was continuously added thereto, after stirring for 3 hours, filtration was continued, and the precipitate was washed with deionized water and dried to obtain a polymer substrate coated with glucose grafted on the surface.
Dispersing the mineral substrate with the polymer substrate grafted with glucose on the surface in 200ml of toluene, then adding 4.6g (0.2 mol) sodium sand, carrying out reflux reaction to enable hydroxyl groups in the glucose to react with sodium to form sodium alkoxide groups, cooling to room temperature after the reaction is finished, adding 100ml of isopropanol, and after no bubble is generated in the reaction, completely reacting metal sodium, centrifugally collecting precipitate, washing the precipitate with absolute ethyl alcohol and deionized water, and drying to obtain the adsorbent (A2).
Example 3
A preparation method of an adsorbent comprises the steps of dispersing 10g of platy hydromica powder in 200ml of water, stirring to form a dispersion, adding 1g of dopamine hydrochloride into the dispersion, stirring for 16 hours at normal temperature, coating a polymer matrix on the surface of a mineral matrix, centrifugally collecting precipitate, washing the precipitate with deionized water, and drying to obtain the mineral matrix coated with polydopamine.
10g of polydopamine-coated mineral substrate and 1.1g of triethylamine are dispersed in 200ml of dichloromethane solution, 1g (10.5 mmol) of dimethylchlorosilane is added into the solution under the protection of nitrogen and at the temperature of minus 10 ℃, stirring is carried out for 3 hours, the temperature is returned to room temperature, stirring is continued for 2 hours, filtration is carried out, the precipitate is washed by deionized water, and drying is carried out, so that the polydopamine-coated mineral substrate with the surface grafted with the silicon-hydrogen structure is obtained.
2.32g (20 mmol) of hydroxyethyl acrylate is dispersed in 50ml of toluene, 0.46g (20 mmol) of sodium sand is added into the toluene for reflux reaction to enable hydroxyl groups in the hydroxyethyl acrylate to react with sodium to form sodium alkoxide groups, after the reaction is finished, the reaction is cooled to room temperature, 10ml of isopropanol is added, no bubbles are generated in the reaction, the reaction solution is poured into absolute ethyl alcohol for alcohol precipitation, and the precipitate is dried after being washed by the absolute ethyl alcohol, and is provided with ethyl acrylate sodium alkoxide.
Dispersing the mineral matrix of the coated polydopamine with the grafted silicon-hydrogen structure on the surface in 50ml of toluene under the protection of nitrogen, then adding 1.45g (10.5 mmol) of ethyl acrylate alcohol sodium salt and 0.1g of 1% Karstedt catalyst, carrying out reflux reaction for 8h, enabling the grafted silicon-hydrogen structure and an acrylic acid group to carry out silicon-hydrogen addition reaction, and cooling to room temperature after the reaction is finished. And then centrifugally collecting the precipitate, washing the precipitate with absolute ethyl alcohol and deionized water, and drying to obtain the adsorbent (A3).
Comparative example 1
Preparation example 4 the same procedure as in preparation example 1 was conducted except that the talc in preparation example 1 was replaced with titanium dioxide powder having no bound water to obtain an adsorbent (A4).
Comparative example 2
5g (28 mmol) of methyltriethoxysilane was dissolved in 50ml of 50% ethanol solution, the pH of the solution was adjusted to 3.5, and the solution was stirred and hydrolyzed for 3 hours to obtain a silane prepolymer, then 5g (54 mmol) of glycerin was continuously added thereto, stirring was continued for 3 hours, extraction was performed with 100ml of methylene chloride, and an organic layer was taken and spin-evaporated and dried to obtain glycerin-grafted polysiloxane.
Dispersing the polysiloxane grafted with glycerol in 200ml of toluene, then adding 1.15g (50 mmol) sodium sand, carrying out reflux reaction to enable hydroxyl groups in the glycerol to react with sodium to form sodium alkoxide groups, cooling to room temperature after the reaction is finished, adding 100ml of isopropanol, completely reacting the metallic sodium when no bubble is generated in the reaction, pouring the solution into 500ml of absolute ethyl alcohol for alcohol precipitation, centrifugally collecting the precipitate, washing the precipitate with absolute ethyl alcohol and ionized water, and drying to obtain the adsorbent (A5).
Comparative example 3
A process for preparing the adsorbent comprises drying 10g of talcum powder at 100deg.C for 8 hr to obtain adsorbent (A6).
[ Performance test ]
Preparing a standard substance: a trisilicon-based nitrogen standard containing 200ppm of monochlorosilane was prepared by adding trisilicon-based nitrogen and monochlorosilane to the cylinders using standard addition methods for electronic grade trisilicon-based nitrogen cylinders.
Adsorption performance test:
a method for removing residual monochlorosilane in trisilicon based nitrogen, comprising the steps of:
(S.1) the adsorbents (A1) to (A6) obtained in examples 1 to 3 and comparative examples 1 to 3 were dried at 100℃for 3 hours and then packed in packed columns of a rectifying still, each packed column having a capacity of 5m 3 ；
(S.2) pumping negative treatment is carried out on the rectifying still, and then inert gas is introduced to replace air in the rectifying still;
(S.3) introducing the prepared trisilicon-based nitrogen standard product into a rectifying kettle at the rate of 100kg/h, and heating at normal pressure to enable the trisilicon-based nitrogen standard product to be in contact with the impurity adsorbent in the reflux process;
and (S.4) collecting a fraction at 50-53 ℃ from the top of the packing tower, and cooling and filtering to obtain the trisilicon-based nitrogen.
And comparing the adsorption effect of the impurity gas adsorbent by testing the impurity content of the monochlorosilane before and after purification of the trisilicon-based nitrogen standard.
[ Performance test results ]
TABLE 1 content of chlorosilane impurity gas before and after purification of trisilicon-based Nitrogen Standard
Figure DEST_PATH_IMAGE002
。
From the results, the adsorbent prepared by the method can effectively adsorb the monochlorosilane impurity in the trisilicon-based nitrogen standard substance, and the content of the monochlorosilane impurity after purification can be reduced to below 1ppb, so that the adsorbent can be completely applied to the electronic industry.
In comparative example 1, since titanium dioxide powder was used instead of the talc in example 1, the titanium dioxide powder contained no bound water, resulting in poor adsorption, and after purification, trisilicon based nitrogen still contained a relatively large amount of monochlorosilane impurities, indicating that the presence of bound water has a significant effect on the adsorption of monochlorosilane impurities.
In comparative example 2, the effect was poor because it did not contain a mineral matrix. The reason for this is as follows: firstly, the adsorption of the monochlorosilane impurity is reduced due to the lack of the combined water, and meanwhile, the contact time of the monochlorosilane impurity and the adsorbent is shortened due to the lack of the large specific surface area of the mineral matrix, so that the adsorption effect of the monochlorosilane impurity is further reduced.
In comparative example 3, since the adsorbent used is talcum powder only containing bound water, the adsorption effect of the adsorbent is far smaller than that of the rest adsorbents, and experiments show that the polymer coating containing sodium alkoxide groups plays a dominant role in adsorbing the monochlorosilane.
In summary, the adsorbent can effectively absorb the chlorosilane impurities through two different physical and chemical methods, and plays an effective promoting role in the absorption of the chlorosilane impurities through a plurality of different absorption mechanisms in the chemical absorption process, meanwhile, the preparation method of the adsorbent is simple, the preparation cost is low, large-scale industrial production can be facilitated, and the purification method is effective, and the residual chlorosilane impurities in the trisilicon-based nitrogen can be removed only through simple rectification, so that the purification efficiency of the trisilicon-based nitrogen is greatly improved compared with the prior art.

Claims (9)

1. An adsorbent, which is characterized in that,
comprising a mineral matrix, and
a polymer coating on the exterior of the mineral substrate;
the mineral matrix contains structural water;
the polymer coating comprises sodium alkoxide groups;
the polymer coating comprises a polymer matrix for forming a coating outside the mineral matrix; and
grafting units attached to the polymer matrix;
the sodium alkoxide groups are located at the end groups of the grafting unit.
2. An adsorbent according to claim 1, characterized in that,
the mineral matrix comprises any one or a combination of more of talcum, serpentine, kaolinite, hydromica and chlorite.
3. An adsorbent according to claim 1, characterized in that,
the polymer matrix is any one of polydopamine or polyglutamic acid.
4. An adsorbent according to claim 1, characterized in that,
the grafting unit is a product obtained by reacting a compound containing at least one hydroxyl group with metal sodium.
5. A process for preparing an adsorbent according to any one of claims 1 to 4,
the method comprises the following steps:
(1) Dispersing a mineral matrix in a dispersant to form a dispersion;
(2) Adding a polymer monomer to the dispersion and allowing it to polymerize, thereby coating the polymer matrix on the surface of the mineral matrix;
(3) And connecting a grafting unit containing sodium alkoxide groups on the surface of the polymer matrix, thereby obtaining the adsorbent.
6. The method of claim 5, wherein the step of determining the position of the probe is performed,
the polymer monomer in the step (2) is any one of dopamine or tannic acid.
7. The method according to claim 5 or 6, wherein,
and (2) adding the polymer monomer into the dispersion, stirring at normal temperature for 12-24 hours, centrifugally collecting the precipitate, washing the precipitate with deionized water, and drying to obtain the mineral matrix coated with the polymer matrix.
8. A method for removing residual monochlorosilane in trisilicon-based nitrogen is characterized in that,
the method comprises the following steps:
(s.1) drying the adsorbent according to any one of claims 1 to 4, and filling the adsorbent in a packed column of a rectifying still;
(S.2) pumping negative treatment is carried out on the rectifying still, and then inert gas is introduced to replace air in the rectifying still;
(S.3) introducing industrial grade trisilicon-based nitrogen into a rectifying still, and heating to enable the trisilicon-based nitrogen to be in contact with the impurity adsorbent in the reflux process;
and (S.4) collecting fractions from the top of the packed tower, cooling and filtering to obtain the trisilicon-based nitrogen.
9. The method for removing residual monochlorosilane from trisilicon based nitrogen of claim 8, wherein,
the rectification pressure in the step (S.3) is normal pressure rectification;
and (4) collecting the fraction in the step (S.4) at a temperature of 50-53 ℃.
CN202210777731.1A 2022-07-04 2022-07-04 Method for removing residual monochlorosilane in trisilicon-based nitrogen Active CN115254050B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210777731.1A CN115254050B (en) 2022-07-04 2022-07-04 Method for removing residual monochlorosilane in trisilicon-based nitrogen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210777731.1A CN115254050B (en) 2022-07-04 2022-07-04 Method for removing residual monochlorosilane in trisilicon-based nitrogen

Publications (2)

Publication Number Publication Date
CN115254050A CN115254050A (en) 2022-11-01
CN115254050B true CN115254050B (en) 2023-06-30

Family

ID=83763195

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210777731.1A Active CN115254050B (en) 2022-07-04 2022-07-04 Method for removing residual monochlorosilane in trisilicon-based nitrogen

Country Status (1)

Country Link
CN (1) CN115254050B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1132229A (en) * 1995-03-31 1996-10-02 湘潭市中南化工研究所 Toughened wall paint
DE102008002537A1 (en) * 2008-06-19 2009-12-24 Evonik Degussa Gmbh Process for the removal of boron-containing impurities from halosilanes and plant for carrying out the process
CN213623299U (en) * 2020-11-16 2021-07-06 天津大学 Device of chlorosilane purification system
CN112250073A (en) * 2020-11-16 2021-01-22 天津大学 Method and device of chlorosilane purification system
CN112979223A (en) * 2021-02-08 2021-06-18 上海力阳道路加固科技股份有限公司 Heat-conducting anti-cracking high-ductility geopolymer composite material and preparation method thereof

Also Published As

Publication number Publication date
CN115254050A (en) 2022-11-01

Similar Documents

Publication Publication Date Title
CN110745834B (en) Green production process and application of aerogel
WO2006123802A1 (en) Method for producing silicon
CN115591272B (en) Method and system for purifying silicon-based precursor
CN107253724A (en) Amino-functional resin is used to be disproportionated halogenated silanes and method and application for removing extraneous metal
TWI755148B (en) Process for removing an impurity from a chlorosilane mixture
CN114849671B (en) Impurity adsorbent, preparation method and method for purifying trimethylaluminum by using impurity adsorbent
CN115254050B (en) Method for removing residual monochlorosilane in trisilicon-based nitrogen
CN113402640A (en) Adsorption resin for impurity removal of chlorosilane and preparation method thereof
CN108084219B (en) Synthesis method of bis (diethylamino) silane
CN1401687A (en) Method for mfg. controllable structure inorganic nanoparticle/polymer composite superthin film
CN1164595C (en) Preparation method of alpha-chloro alkyl siloxane
CN105498698B (en) A kind of preparation method of the bridged polysilsesquioxane of the nitrogenous long flexible chain of porous type
CN117563558B (en) Modified porous spherical silica gel and preparation method thereof
CN117903185A (en) Method for preparing tetramethoxysilane and tetraethoxysilane from hexa-ligand organosilicon compound
CN104549503B (en) A kind of support type organic tin catalyst and its preparation method and application
CN112898185B (en) Fluorine-containing compound for immersion photoresist, preparation method thereof and photoresist
CN118122383A (en) Preparation method of modified graphene oxide catalyst and application of modified graphene oxide catalyst in preparation of diisopropylamino silane
CN116328746A (en) Terpyridine-silica gel composite material and preparation method thereof
JPH0480848B2 (en)
CN108516986B (en) Benzocyclobutene-functionalized tetrakis (dimethylsiloxy) silane, method for preparing same, and method for preparing resin containing same
JPH02131489A (en) Silylating agent
CN117736235A (en) Purification method of methyltrichlorosilane
CN117903187A (en) Method for preparing tetramethoxysilane and tetraethoxysilane from penta-ligand organosilicon compound
CN118580265A (en) Synthesis method of high-purity trimethylsilane without participation of halogen
WO2022160356A1 (en) Porous crosslinked material, preparation method for same, and applications thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant