CN115254050A - Method for removing residual monochlorosilane in trisilicon-based nitrogen - Google Patents
Method for removing residual monochlorosilane in trisilicon-based nitrogen Download PDFInfo
- Publication number
- CN115254050A CN115254050A CN202210777731.1A CN202210777731A CN115254050A CN 115254050 A CN115254050 A CN 115254050A CN 202210777731 A CN202210777731 A CN 202210777731A CN 115254050 A CN115254050 A CN 115254050A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- nitrogen
- trisilicon
- polymer
- mineral
- 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.)
- Granted
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: (S.1) filling the adsorbent into a packed tower of a rectifying still after the adsorbent is dried; (S.2) carrying out negative pumping treatment on the rectifying still, and introducing inert gas to replace air in the rectifying still; (S.3) introducing industrial grade trisilicon-based nitrogen into a rectifying still, and heating to ensure that the trisilicon-based nitrogen is contacted with an impurity adsorbent in the reflux process; and (S.4) collecting fractions from the top of the packed tower, and cooling and filtering to obtain the high-purity trisilicon-based nitrogen. The method for purifying the trisilyl nitrogen is simple, and the adsorbent can effectively absorb chlorosilane impurities through two different physical and chemical methods, so that residual chlorosilane impurities in the trisilyl nitrogen can be removed only by simply rectifying the trisilyl nitrogen, and the purification efficiency of the trisilyl nitrogen can be effectively improved.
Description
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
Trisilyl nitrogen ((SiH)3）3Or TSA), also known as trisilylamine, can be used to deposit high purity silicon oxide films without the need for direct plasma excitation, and thus has very important applications in the semiconductor industry, such as being able to be used in void-fill applications.
The preparation method of trisilyl nitrogen is various, 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 trisilyl nitrogen product, and since monochlorosilane is harmful to the formation of a silicon-containing film by chemical vapor deposition using trisilyl nitrogen, the monochlorosilane in the trisilyl nitrogen must be removed to ensure the final silicon film deposition effect.
In the prior art, in order to improve the purity of trisilyl nitrogen, the purity of trisilyl nitrogen is generally improved by adjusting the method and parameters during synthesis in the process of gas synthesis. However, this approach requires adjustments to the production line from the source, and the overall cost is significant.
Therefore, from the viewpoint of reducing the cost of purifying trisilyl nitrogen, the present applicant has desired to devise a method capable of obtaining trisilyl nitrogen of high purity by purifying it starting from low purity trisilyl nitrogen to remove the remaining monochlorosilane therein.
Disclosure of Invention
The invention provides a method for removing residual monochlorosilane in trisilicon-based nitrogen at low cost by using low-purity trisilicon-based nitrogen as a starting material and purifying the starting material in order to overcome the defect that the production cost of the high-purity trisilicon-based nitrogen in the prior art is higher.
In order to realize the purpose of the invention, the invention is realized by the following technical scheme:
in a first aspect of the present invention, there is provided an adsorbent,
comprising a mineral matrix, and
a polymer coating coated on the exterior of the mineral substrate;
the mineral matrix contains structural water;
the polymer coating contains sodium alkoxide groups.
The part of the adsorbent for adsorbing mainly consists of a mineral matrix containing structural water and a polymer coating containing sodium alkoxide groups. The mineral matrix can be selected to be in a sheet form or a powder form or a granular form, so that the mineral matrix has a high specific surface area, and can be used for physically adsorbing chlorosilane compounds (such as monochlorosilane in the application, or other chlorosilane containing 1~4 chlorides and other chlorosilane containing alkyl structures). Meanwhile, the outside of the mineral matrix is coated with the polymer coating body, the polymer coating body and the chlorosilane compound are organic compounds, and the polymer coating body 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 adsorbent in the application contains two different mechanisms for the physical adsorption of impurities, so that the adsorption effect on chlorosilane compounds can be effectively improved.
In addition, the invention can adsorb the chlorosilane in a chemical adsorption mode. The principle comprises the following two points:
first, in the present invention, due to the presence of structural water in the mineral matrix, it is predominantly OH-The form of (b) is present in the mineral, so that the crystal structure of the mineral is maintained, and part of the structural water can react with chlorosilane compounds, so that the chlorosilane compounds can be immobilized.
Meanwhile, after the chlorosilane compounds are combined, structural water in the minerals can be reacted, so that mineral crystal lattices are damaged, the surface area of the mineral matrix can be rapidly increased after the mineral crystal lattices are damaged, and the physical adsorption effect on the chlorosilane compounds is further improved.
In addition, the structural water of the part is different from the common free water in that the common free water can obviously promote the decomposition of the silicon nitrogen bond, and particularly in the presence of acid, the silazane can generate obvious hydrolysis reaction when being contacted with the free water. However, the structural water described in the present invention does not react with the silicon nitrogen bond in the silazane, and thus can effectively prevent the decomposition of the silazane during the purification process.
And secondly, the polymer coating body contains sodium alkoxide groups which have strong basicity and can react with chlorosilane compounds, so that chlorosilane is adsorbed. Meanwhile, hydrogen chloride formed after reaction of chlorosilane compounds and structural water in minerals can be absorbed by sodium alkoxide groups, so that pollution of newly generated impurities to trisilyl nitrogen is effectively prevented.
Thus, in summary, the adsorbent of the present invention can achieve efficient adsorption of chlorosilane impurities by two different methods, physical and chemical. Meanwhile, two different absorption mechanisms are adopted in the chemical absorption process, so that the absorption of chlorosilane impurities is effectively promoted.
Preferably, the mineral substrate comprises any one or combination of talc, serpentine, kaolinite, hydromica, chlorite.
Some mineral matrixes listed in the invention contain stable structural water, and can effectively adsorb chlorosilane impurities in trisilyl nitrogen on the premise of not hydrolyzing the trisilyl nitrogen. Meanwhile, the mineral matrixes selected in the invention have higher yield in nature, so the price is low, and the cost of consumables in the adsorption process can be effectively reduced.
Preferably, the polymeric coating comprises a polymeric matrix for forming a coating on the exterior of the mineral matrix; and a grafting unit attached to the polymer substrate;
the sodium alkoxide groups are located at the end groups of the grafting units.
The polymer matrix comprises a polymer matrix and a grafting unit, wherein the polymer matrix is mainly used for stably coating the mineral matrix and preventing the polymer matrix from falling off from the surface of the mineral matrix, and simultaneously 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, the sodium alkoxide group is positioned at the end group of the grafting unit and can be directly contacted with chlorosilane impurities in the trisilicon-based nitrogen for adsorption, so that the adsorption effect on the chlorosilane impurities is improved.
Preferably, the polymer matrix is any one of polydopamine or polytannic acid.
The polymer matrix in the invention is polydopamine or polytannic acid, which has more reactive groups, so that the grafting units can be connected favorably, and the content of the connected grafting units is higher due to more reactive groups, 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 graft unit is a product obtained by reacting a compound having at least one hydroxyl group with sodium metal.
In a second aspect of the invention, there is provided a process for the preparation of an adsorbent as described above,
the method comprises the following steps:
(1) Dispersing a mineral substrate in a dispersant to form a dispersion;
(2) Adding a polymer monomer to the dispersion and allowing it to polymerize, thereby coating the surface of the mineral substrate with a polymer matrix;
(3) And (3) connecting a grafting unit containing a sodium alkoxide group on the surface of the polymer substrate to obtain the adsorbent.
The adsorbent disclosed by the invention is simple in preparation process steps, and can be realized through simple three-step reaction, so that the adsorbent has the advantage of good repeatability.
Preferably, the dispersant used in step (1) may be water and other organic solvents (e.g., alcohol solvents, alkane solvents), and in some embodiments of the present invention, water is selected as the dispersant, which can be better used with the polymer monomers used in the present document. When selecting other solvents than the polymer monomers described in the present invention, other solvents may also be selected as the dispersing agent.
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 in polydopamine and polytannic acid formed after polymerization, more active groups (such as hydroxyl groups) with good reactivity exist, and the active groups can be used as connecting sites of grafting units, so that the grafting modification of the grafting units containing sodium alkoxide groups is facilitated.
And (3) adding the polymer monomer into the dispersion in the step (2), stirring at normal temperature for 12 to 24h, centrifuging, collecting the precipitate, washing the precipitate with deionized water, and drying to obtain the mineral matrix coated with the polymer matrix.
Preferably, in the step (3), the polymer substrate can be connected in various ways during the connection with the grafting unit containing sodium alkoxide, for example, a group capable of reacting with an active group present on the surface of the polymer substrate can be provided on the grafting unit, and grafting can be performed by reaction between the groups. The active groups can also be modified, and hydroxyl groups in the active groups are connected with other groups through compound grafting in proportion, and then the active groups are connected with grafting units through reaction among the groups. Since these reactions are numerous, they are not listed here.
In a third aspect of the invention, there is also provided a method for removing residual monochlorosilane from trisilicon-based nitrogen,
the method comprises the following steps:
(S.1) filling the dried adsorbent into a packed tower of a rectifying still;
(S.2) carrying out negative pumping treatment on the rectifying still, and introducing inert gas to replace air in the rectifying still;
(S.3) introducing industrial grade trisilicon-based nitrogen into a rectifying still, and heating to ensure that the trisilicon-based nitrogen is contacted with an impurity adsorbent in the reflux process;
and (S.4) collecting fractions from the top of the packed tower, and cooling and filtering to obtain the high-purity trisilicon-based nitrogen.
The purification method of the trisilyl nitrogen is simple, and the residual monochlorosilane impurities in the trisilyl nitrogen can be removed only by simply rectifying the trisilyl 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 realize effective absorption of chlorosilane impurities by two different methods, namely physical method and chemical method, and can play an effective promoting role in the absorption of chlorosilane impurities by multiple different absorption mechanisms in the chemical absorption process;
(2) The preparation method of the adsorbent is simple, the preparation cost is low, and large-scale industrial production can be facilitated;
(3) The method for removing the residual monochlorosilane in the trisilicon-based nitrogen is simple, the residual monochlorosilane impurities in the trisilicon-based nitrogen can be removed only by simple rectification, and meanwhile, the purification efficiency of the trisilicon-based nitrogen is greatly improved compared with the prior art.
Detailed Description
The invention is further described with reference to specific examples. 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 ]
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 to coat polydopamine on the surface of a mineral substrate, centrifuging, collecting precipitates, washing the precipitates with deionized water, and drying to obtain the polydopamine-coated mineral substrate.
Dispersing 10g of polydopamine-coated mineral substrate in 200ml of 50% ethanol solution, adding 5g (28 mmol) of methyltriethoxysilane, adjusting the pH value of the solution to 3.5, stirring for 3h, continuously adding 5g (54 mmol) of glycerol, continuously stirring for 3h, filtering, washing precipitates with deionized water, and drying to obtain the polydopamine-coated mineral substrate with glycerol grafted on the surface.
Dispersing the polydopamine-coated mineral substrate with the surface grafted with glycerol into 200ml of toluene, then adding 1.15g (50 mmol) of sodium sand, carrying out reflux reaction to enable hydroxyl 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, indicating that metal sodium completely reacts when no bubbles are generated in the reaction, then centrifuging to collect precipitates, washing the precipitates with absolute ethyl alcohol and deionized water, and drying to obtain the adsorbent (A1).
Example 2
A preparation method of an adsorbent comprises the steps of dispersing 10g of kaolin powder in 200ml of water, stirring to form a dispersion, adding 1g of tannic acid into the dispersion, stirring for 12 hours at normal temperature to coat the surface of a mineral substrate with the poly-tannic acid, centrifugally collecting precipitates, washing the precipitates with deionized water, and drying to obtain the poly-tannic acid coated mineral substrate.
Dispersing 10g of the mineral substrate coated with the polytannic acid in 200ml of 50% ethanol solution, adding 5.4g (30 mmol) of methyltriethoxysilane, adjusting the pH value of the solution to 3.5, stirring for 5h, continuing to add 10.8g (60 mmol) of glucose, continuing to stir for 3h, filtering, washing the precipitate with deionized water, and drying to obtain the mineral substrate coated with the polymer substrate, the surface of which is grafted with the glucose.
Dispersing the mineral substrate coated with the polymer substrate, the surface of which is grafted with glucose, in 200ml of toluene, then adding 4.6g (0.2 mol) of sodium sand, carrying out reflux reaction to enable hydroxyl 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 until no bubbles are generated in the reaction, indicating that metal sodium completely reacts, then centrifuging to collect precipitates, washing the precipitates 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 flake-shaped 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 to coat a polymer matrix on the surface of a mineral matrix, centrifuging, collecting precipitates, washing the precipitates with deionized water, and drying to obtain the poly-dopamine-coated mineral matrix.
Dispersing 10g of polydopamine-coated mineral substrate and 1.1g of triethylamine in 200ml of dichloromethane solution, adding 1g (10.5 mmol) of dimethylchlorosilane into the solution under the conditions of nitrogen protection and-10 ℃, stirring for 3h, then returning the temperature to room temperature, continuing stirring for 2h, filtering, washing precipitates with deionized water, and drying to obtain the polydopamine-coated mineral substrate with a surface grafted with a hydrosilicon structure.
Dispersing 2.32g (20 mmol) of hydroxyethyl acrylate in 50ml of toluene, adding 0.46g (20 mmol) of sodium sand into the toluene for reflux reaction to enable hydroxyl in the hydroxyethyl acrylate to react with sodium to form sodium alkoxide groups, cooling the mixture to room temperature after the reaction is finished, adding 10ml of isopropanol until no bubble is generated in the reaction, indicating that metal sodium completely reacts, pouring the reaction solution into absolute ethyl alcohol for alcohol precipitation, filtering, washing the precipitate with the absolute ethyl alcohol, and drying to obtain the product with ethyl acrylate sodium alkoxide.
Under the protection of nitrogen, the polydopamine-coated mineral substrate with the surface grafted with the hydrosilation structure is dispersed in 50ml of toluene, then 1.45g (10.5 mmol) of the ethyl acrylate sodium alcoholate salt and 0.1g of a karstedt catalyst are added, the mixture is refluxed for 8 hours, so that the grafted hydrosilation structure and acrylic acid groups are subjected to a hydrosilation reaction, and the mixture is cooled to room temperature after the reaction is finished. And then centrifuging to collect 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 followed, except that talc in preparation example 1 was replaced with titanium dioxide powder having no bound water, to obtain adsorbent (A4).
Comparative example 2
Dissolving 5g (28 mmol) of methyltriethoxysilane in 50ml of 50% ethanol solution, adjusting the pH of the solution to 3.5, stirring and hydrolyzing for 3h to obtain a silane prepolymer, then adding 5g (54 mmol) of glycerol, stirring for 3h, extracting with 100ml of dichloromethane, taking an organic layer, and carrying out rotary evaporation and drying to obtain the polysiloxane grafted with glycerol.
Dispersing the polysiloxane grafted with the glycerol into 200ml of toluene, adding 1.15g (50 mmol) of sodium sand, carrying out reflux reaction to enable hydroxyl 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, indicating that metal sodium completely reacts when no bubbles are generated in the reaction, pouring the solution into 500ml of absolute ethyl alcohol for alcohol precipitation, carrying out centrifugation to collect precipitates, washing the precipitates with the absolute ethyl alcohol and the ionized water, and drying to obtain the adsorbent (A5).
Comparative example 3
A method for preparing adsorbent comprises drying 10g of pulvis Talci at 100 deg.C for 8 hr to obtain adsorbent (A6).
[ Performance test ]
Preparing a standard substance: using a standard addition method of an electronic grade trisilyl nitrogen steel cylinder, trisilyl nitrogen and monochlorosilane are added into the steel cylinder to manufacture a trisilyl nitrogen standard product containing 200ppm of monochlorosilane.
And (3) testing the adsorption performance:
a method for removing residual monochlorosilane in trisilicon-based nitrogen comprises the following steps:
(S.1) the adsorbents (A1) to (A6) prepared in example 1~3 and comparative example 1~3 were dried at 100 ℃ for 3 hours, and then packed in packed columns in a rectifying still, each packed column having a volume of 5m3；
(S.2) carrying out negative pumping treatment on the rectifying still, and then introducing inert gas to replace air in the rectifying still;
(S.3) introducing the prepared trisilyl nitrogen standard substance into a rectifying still at the rate of 100kg/h, and heating at normal pressure to enable the trisilyl nitrogen standard substance to contact with an impurity adsorbent in the reflux process;
and (S.4) collecting fractions at 50-53 ℃ from the top of the packed tower, cooling and filtering to obtain the trisilyl nitrogen.
The adsorption effect of the impurity gas adsorbent is compared by testing the impurity content of chlorosilane in the trisilicon-based nitrogen standard before and after purification.
[ results of Performance test ]
Table 1 chlorosilane contaminant gas content table before and after purification for trisilyl nitrogen standards
From the results, the adsorbent prepared by the invention can effectively adsorb the monochlorosilane impurity in the trisilicon-based nitrogen standard product, and the content of the monochlorosilane impurity can be reduced to below 1ppb after purification, so that the adsorbent can be completely applied to the electronic industry.
In comparative example 1, titanium dioxide powder was used instead of talc powder in example 1, and since the titanium dioxide powder contained no bound water, the adsorption effect was poor, and after the purification was completed, the trisilyl nitrogen still contained a relatively large amount of monochlorosilane impurity, indicating that the presence of bound water had a significant effect on the adsorption of monochlorosilane impurity.
The comparative example 2 has poor effect because it does not contain a mineral matrix. The reason for this is as follows: firstly, the adsorption of the monochlorosilane impurities is reduced due to the lack of the existence of the combined water, and meanwhile, the contact time of the monochlorosilane impurities and the adsorbent is shortened due to the lack of the large specific surface area of the mineral substrate, so that the adsorption effect of the monochlorosilane impurities is further reduced.
In comparative example 3, the adsorption effect of the adsorbent used is far better than that of the other adsorbents because the adsorbent used is the talcum powder only containing bound water, and experiments show that the polymer coating containing sodium alkoxide groups plays a dominant role in adsorbing monochlorosilane.
In conclusion, the adsorbent can effectively absorb chlorosilane impurities by two different physical and chemical methods, and the absorption of the chlorosilane impurities is effectively promoted by multiple different absorption mechanisms in the chemical absorption process, meanwhile, the preparation method of the adsorbent is simple, the preparation cost is low, the large-scale industrial production can be facilitated, the purification method is effective, residual monochlorosilane impurities in trisilicon-based nitrogen can be removed only by simple rectification, and meanwhile, the purification efficiency of the trisilicon-based nitrogen is greatly improved compared with the prior art.
Claims (10)
1. An adsorbent, characterized in that,
comprises a mineral substrate, and
a polymer coating coated on the exterior of the mineral substrate;
the mineral matrix contains structural water;
the polymer coating contains sodium alkoxide groups.
2. An adsorbent according to claim 1,
the mineral substrate comprises any one or combination of talc, serpentine, kaolinite, hydromica and chlorite.
3. An adsorbent according to claim 1,
the polymeric coating comprises a polymeric matrix for forming a coating on the exterior of the mineral matrix; and
a graft unit attached to the polymer substrate;
the sodium alkoxide group is located at the end of the grafting unit.
4. An adsorbent according to claim 3,
the polymer matrix is any one of polydopamine or polytannic acid.
5. An adsorbent according to claim 3,
the grafting unit is a product obtained by reacting a compound containing at least one hydroxyl group with metallic sodium.
6. A method of making the adsorbent of any one of claims 1~5,
the method comprises the following steps:
(1) Dispersing a mineral substrate in a dispersant to form a dispersion;
(2) Adding a polymer monomer to the dispersion and allowing it to polymerize, thereby coating the surface of the mineral substrate with the polymer matrix;
(3) And (3) connecting a grafting unit containing a sodium alkoxide group on the surface of the polymer substrate to obtain the adsorbent.
7. The method of claim 6,
in the step (2), the polymer monomer is any one of dopamine or tannic acid.
8. The method according to claim 6 or 7,
and (3) adding a polymer monomer into the dispersion in the step (2), stirring at normal temperature for 12 to 24h, centrifuging, collecting a precipitate, washing the precipitate with deionized water, and drying to obtain the mineral matrix coated with the polymer matrix.
9. A method for removing residual monochlorosilane in trisilicon-based nitrogen is characterized in that,
the method comprises the following steps:
(s.1) filling a packed column of a rectifying still after drying the adsorbent of any one of claims 1~5;
(S.2) carrying out negative pumping treatment on the rectifying still, and introducing inert gas to replace air in the rectifying still;
(S.3) introducing industrial grade trisilicon-based nitrogen into a rectifying still, and heating to ensure that the trisilicon-based nitrogen is contacted with an impurity adsorbent in the reflux process;
and (S.4) collecting fractions from the top of the packed tower, and cooling and filtering to obtain the trisilyl nitrogen.
10. The method for removing residual monochlorosilane from trisilyl nitrogen as claimed in claim 9,
the rectification pressure in the step (S.3) is normal pressure rectification;
and (S.4) the collection temperature of the distillate in the step (S.4) is 50-53 ℃.
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 true CN115254050A (en) | 2022-11-01 |
| CN115254050B 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) |
Citations (5)
| 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 |
| CA2727442A1 (en) * | 2008-06-19 | 2009-12-23 | Evonik Degussa Gmbh | Method for removing boron-containing impurities from halogen silanes and apparatus for performing said method |
| 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 |
| CN213623299U (en) * | 2020-11-16 | 2021-07-06 | 天津大学 | Device of chlorosilane purification system |
-
2022
- 2022-07-04 CN CN202210777731.1A patent/CN115254050B/en active Active
Patent Citations (5)
| 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 |
| CA2727442A1 (en) * | 2008-06-19 | 2009-12-23 | Evonik Degussa Gmbh | Method for removing boron-containing impurities from halogen silanes and apparatus for performing said method |
| CN112250073A (en) * | 2020-11-16 | 2021-01-22 | 天津大学 | Method and device of chlorosilane purification system |
| CN213623299U (en) * | 2020-11-16 | 2021-07-06 | 天津大学 | 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 |
|---|---|
| CN115254050B (en) | 2023-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108912269B (en) | Polyimidazole ionic liquid-based copolymer and preparation method and application thereof | |
| CN104826582A (en) | Preparation method of graphene-mesoporous silica aerogel | |
| CN110745834B (en) | Green production process and application of aerogel | |
| CN113817116B (en) | Preparation of covalent organic framework material and application of covalent organic framework material in rare earth separation | |
| WO2023236316A1 (en) | Impurity gas adsorbent and preparation method therefor, and application | |
| CN115254050B (en) | Method for removing residual monochlorosilane in trisilicon-based nitrogen | |
| KR100347254B1 (en) | Synthesis Method of Mesoporous Silicas with Chelating Ligands for Heavy Metal Ion Removal in Aqueous Solutions | |
| CN108084219B (en) | Synthesis method of bis (diethylamino) silane | |
| CN1401687A (en) | Method for mfg. controllable structure inorganic nanoparticle/polymer composite superthin film | |
| KR20240060518A (en) | Purification method and purification system for silicon-based precursors | |
| WO2023236317A1 (en) | Impurity adsorbent, preparation method and method for using adsorbent to purify trimethylaluminium | |
| CN106517094B (en) | The method that purifying has High Purity Hydrogen or high-purity chlorosilane containing phosphorus impurities | |
| JP2019147099A (en) | CO2 adsorbent | |
| JP2958338B2 (en) | Method for manufacturing carrier for nucleic acid synthesis | |
| CN1164595C (en) | Prepn of alpha-chloro-hydrocarbon siloxane | |
| CN105498698B (en) | A kind of preparation method of the bridged polysilsesquioxane of the nitrogenous long flexible chain of porous type | |
| CN1304397C (en) | Active alkylated silica gel and preparation method | |
| JP2006089588A (en) | Method for producing organic silica composite material | |
| CN104549503B (en) | A kind of support type organic tin catalyst and its preparation method and application | |
| CN117563558B (en) | Modified porous spherical silica gel and preparation method thereof | |
| CN115228437B (en) | Surface modification method for making active carbon surface positive | |
| CN118122383A (en) | Preparation method of modified graphene oxide catalyst and application of modified graphene oxide catalyst in preparation of diisopropylamino silane | |
| KR20070114667A (en) | Metal-coated aerogel of nanoporous materials and preparing method thereof | |
| CN116328746A (en) | Terpyridine-silica gel composite material and preparation method thereof | |
| CN117019025A (en) | Process for purifying OLED material by utilizing silicon dioxide |
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 |