CN118146256A - Method for removing 2-chloropropane in tetramethylsilane raw material - Google Patents
Method for removing 2-chloropropane in tetramethylsilane raw material Download PDFInfo
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- CN118146256A CN118146256A CN202410328578.3A CN202410328578A CN118146256A CN 118146256 A CN118146256 A CN 118146256A CN 202410328578 A CN202410328578 A CN 202410328578A CN 118146256 A CN118146256 A CN 118146256A
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- tetramethylsilane
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- chloropropane
- molecular sieve
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000002994 raw material Substances 0.000 title claims abstract description 61
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 claims abstract description 71
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000010438 heat treatment Methods 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 239000007787 solid Substances 0.000 claims description 54
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- 238000001354 calcination Methods 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 229910021485 fumed silica Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 150000002505 iron Chemical class 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- -1 iron ions Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 20
- 239000006200 vaporizer Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000000746 purification Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 238000005086 pumping Methods 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Abstract
The invention discloses a method for removing 2-chloropropane in a tetramethylsilane raw material, which comprises the following steps: s11, mixing the vaporized tetramethylsilane raw material with a Fe-Na-MOR molecular sieve catalyst under the heating condition for reaction; s12, collecting a reaction product, cooling, liquefying and rectifying to obtain the purified tetramethylsilane. According to the method for removing 2-chloropropane in the tetramethylsilane raw material, disclosed by the invention, the tetramethylsilane raw material and the Fe-Na-MOR molecular sieve catalyst are mixed for reaction, so that the 2-chloropropane in the tetramethylsilane raw material is catalytically reacted into propylene and HCl, and the propylene and the HCl can be easily separated from the tetramethylsilane through rectification, so that the purified tetramethylsilane is obtained, and 2-chloropropane impurities in the tetramethylsilane raw material are removed.
Description
Technical Field
The invention belongs to the technical field of purification of tetramethylsilane, and particularly relates to a method for removing 2-chloropropane in a tetramethylsilane raw material.
Background
Tetramethylsilane (TMS) is an important organosilicon material and has wide application in the fields of medicine, aerospace construction, mechanical materials and the like. TMS is used in the electronics industry as a precursor for Chemical Vapor Deposition (CVD) or Plasma Enhanced Chemical Vapor Deposition (PECVD) for the preparation of high quality silicon carbide films. TMS is a precursor material for low dielectric constant film deposition in the process of ultra-large scale integrated circuits, belongs to a new material in the market, and is mainly used as an etching barrier layer and a copper barrier layer in the process of integrated circuit copper chips below 90 nm. TMS raw material contains about 1-5% of 2-chloropropane, and is difficult to separate in rectification due to azeotropy between the TMS raw material and the 2-chloropropane.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The purpose of the present invention is to provide a method for removing 2-chloropropane from a tetramethylsilane raw material, which can be used.
In order to achieve the above object, a specific embodiment of the present invention provides the following technical solution:
a method for removing 2-chloropropane in tetramethylsilane raw material comprises the following steps:
S11, mixing the vaporized tetramethylsilane raw material with a Fe-Na-MOR molecular sieve catalyst under the heating condition for reaction;
S12, collecting a reaction product, cooling, liquefying and rectifying to obtain the purified tetramethylsilane.
In one or more embodiments of the present invention, in the step S11, the heating temperature is 50 to 80 ℃.
In one or more embodiments of the present invention, the method for preparing the Fe-Na-MOR molecular sieve catalyst comprises the steps of:
s21, obtaining a mixed system of sodium metaaluminate, sodium hydroxide, fumed silica and water;
S22, carrying out hydrothermal reaction on the mixed system, separating, and drying the obtained solid to obtain a solid product;
s23, calcining the solid product to obtain a Na-MOR molecular sieve;
S24, mixing the Na-MOR molecular sieve with an iron salt solution for reaction under the heating condition, separating to obtain a solid, drying and calcining to obtain the Fe-Na-MOR molecular sieve catalyst.
In one or more embodiments of the present invention, the step 21 specifically includes:
dissolving sodium metaaluminate and sodium hydroxide in water, adding fumed silica into the solution, and stirring until white gel is formed, thus obtaining a mixed system of sodium metaaluminate, sodium hydroxide, fumed silica and water.
In one or more embodiments of the present invention, in the mixed system in S21, the mass ratio of sodium metaaluminate, sodium hydroxide, and fumed silica is 6:80:100.
In one or more embodiments of the present invention, the temperature of the hydrothermal reaction in the step S22 is 170 ℃ and the reaction time of the hydrothermal reaction is 48 to 96 hours.
In one or more embodiments of the present invention, the calcining in step S23 is specifically: heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining for 2-4 h; and/or the number of the groups of groups,
The calcining in the step S24 specifically includes: and (3) heating to 550 ℃ at a heating rate of 2 ℃/min, and then maintaining for 2-4 h.
In one or more embodiments of the present invention, the iron salt solution in the step S24 is at least one of Fe (aqueous solution of NO 3)3, aqueous solution of FeCl 3).
In one or more embodiments of the invention, the concentration of iron ions in the iron salt solution is from 0.5 to 1mol/L.
In one or more embodiments of the present invention, the mixing reaction of the Na-MOR molecular sieve in step S24 with the iron salt solution under heating specifically includes:
Adding Na-MOR molecular sieve into ferric salt solution, stirring and reacting for 3-4 h at 50-80 ℃.
Compared with the prior art, the method for removing the 2-chloropropane in the tetramethylsilane raw material has the advantages that the tetramethylsilane raw material and the Fe-Na-MOR molecular sieve catalyst are mixed and reacted, so that the 2-chloropropane in the tetramethylsilane raw material is catalytically reacted into propylene and HCl, and the propylene and the HCl can be easily separated from the tetramethylsilane through rectification, so that the purified tetramethylsilane is obtained, and the 2-chloropropane impurities in the tetramethylsilane raw material are removed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic flow chart of a method for removing 2-chloropropane from a tetramethylsilane feedstock in accordance with one embodiment of the present invention;
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
As shown in fig. 1, a method for removing 2-chloropropane from a tetramethylsilane raw material according to an embodiment of the present invention comprises the following steps:
s11, mixing the vaporized tetramethylsilane raw material with a Fe-Na-MOR molecular sieve catalyst under the heating condition for reaction.
Specifically, in step S1, the heating temperature is 50-80 ℃.
Wherein, a vaporizer can be used for vaporizing the tetramethylsilane raw material, and the vaporized tetramethylsilane raw material and the Fe-Na-MOR molecular sieve catalyst are contacted and reacted under the heating condition, so that 2-chloropropane in the tetramethylsilane raw material is decomposed under the action of the catalyst, and propylene and HCl are generated by the reaction. Propylene and HCl are not azeotroped with tetramethylsilane in the tetramethylsilane raw material, so that rectification is convenient in the step S12, and the propylene and the HCl can be separated from the tetramethylsilane raw material to obtain purified tetramethylsilane.
In practice, the Fe-Na-MOR molecular sieve catalyst may be packed in a fixed bed reactor, which is purged with an inert gas such as nitrogen, and then the temperature in the fixed bed reactor is raised to 70 ℃. The tetramethylsilane raw material is pumped into a vaporizer through a plunger pump at a certain flow rate, then is introduced from below a fixed bed, and the reacted product (gas) flows out from above the fixed bed reactor.
S12, collecting a reaction product, cooling, liquefying and rectifying to obtain the purified tetramethylsilane.
It will be appreciated that the use of Fe-Na-MOR molecular sieve catalysts in accordance with the present invention may reduce the reaction conditions for the elimination of 2-chloropropane.
In one embodiment, the method for preparing the Fe-Na-MOR molecular sieve catalyst comprises the following steps:
s21, obtaining a mixed system of sodium metaaluminate, sodium hydroxide, fumed silica and water.
Specifically, step 21 may include the steps of: dissolving sodium metaaluminate and sodium hydroxide in water, adding fumed silica into the solution, and stirring until white gel is formed, thus obtaining a mixed system of sodium metaaluminate, sodium hydroxide, fumed silica and water.
Wherein, the mass ratio of sodium metaaluminate, sodium hydroxide and fumed silica is 6:80:100.
S22, carrying out hydrothermal reaction on the mixed system, separating, and drying the obtained solid to obtain a solid product.
Specifically, the temperature of the hydrothermal reaction in the step S22 is 170 ℃, and the reaction time of the hydrothermal reaction is 48-96 hours.
Specifically, the temperature of the drying may be 120 ℃, and the time of the drying may be 2 hours.
S23, calcining the solid product to obtain the Na-MOR molecular sieve.
Wherein the calcination is specifically as follows: and (3) heating to 550 ℃ at a heating rate of 2 ℃/min, and then maintaining for 2-4 h.
S24, mixing the Na-MOR molecular sieve with an iron salt solution for reaction under the heating condition, separating to obtain a solid, drying and calcining to obtain the Fe-Na-MOR molecular sieve catalyst.
Specifically, the mixing reaction of the Na-MOR molecular sieve and the ferric salt solution under the heating condition specifically comprises the following steps: adding Na-MOR molecular sieve into ferric salt solution, stirring and reacting for 3-4h at 50-80 ℃. This step is to allow the iron to partially replace the sodium in the Na-MOR molecular sieve.
Wherein the ferric salt solution is at least one of Fe (aqueous solution of NO 3)3 and aqueous solution of FeCl 3).
Wherein the concentration of iron ions in the ferric salt solution is 0.5-1 mol/L. The concentration of iron ions can affect the extent to which iron partially displaces sodium in the Na-MOR molecular sieve, thereby affecting the composition of the resulting Fe-Na-MOR molecular sieve catalyst.
Wherein the calcination is specifically as follows: and (3) heating to 550 ℃ at a heating rate of 2 ℃/min, and then maintaining for 2-4 h.
Wherein, the temperature of drying can be 120 ℃, and the time of drying can be 2 hours.
The method for removing 2-chloropropane from a tetramethylsilane raw material of the present invention will be described in detail with reference to specific examples.
Example 1
(1) Preparation of the catalyst
0.6G NaAlO 2, 8g NaOH are dissolved in 200mL deionized water, 10g fumed silica is added to the solution, and the mixture is stirred until a white gel is formed;
putting the mixture (white gel) into a hydrothermal reaction kettle, reacting at 170 ℃ for 96 hours, taking out a reaction product, centrifuging to obtain a solid, and drying the solid at 120 ℃ for 2 hours;
placing the dried solid in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining calcination for 2 hours; obtaining Na-MOR molecular sieve;
10g of Na-MOR molecular sieve is added into Fe (aqueous solution of NO 3)3, stirred and reacted for 3 hours at 80 ℃, wherein Fe (concentration of Fe (NO 3)3) in aqueous solution of NO 3)3 is 0.5 mol/L.) is centrifugally separated, the obtained solid is dried for 2 hours at 120 ℃, then the dried solid is placed in a muffle furnace, and calcination is maintained for 2 hours after the temperature is raised to 550 ℃ at a heating rate of 2 ℃/min, so that the Fe-Na-MOR molecular sieve catalyst is obtained.
(2) Purification of tetramethylsilane starting material
Filling a Fe-Na-MOR molecular sieve catalyst into a fixed bed reactor with an inner diameter of 10mm and a length of 300 mm; the fixed bed reactor was purged with N 2 and then the temperature was raised to 70 ℃; pumping tetramethylsilane raw material into a vaporizer at a certain flow rate (15 mL/h) by a plunger pump, wherein the airspeed is 100h < -1 >, then introducing the tetramethylsilane raw material from below a fixed bed, and collecting a reaction product from above the fixed bed reactor; and cooling and liquefying the collected product at 10 ℃ and rectifying to obtain the purified tetramethylsilane. Wherein the mass percentage of the 2-chloropropane in the purified tetramethylsilane is 0.08 percent.
Example 2
(1) Preparation of the catalyst
0.6G NaAlO 2, 8g NaOH are dissolved in 200mL deionized water, 10g fumed silica is added to the solution, and the mixture is stirred until a white gel is formed;
putting the mixture (white gel) into a hydrothermal reaction kettle, reacting at 170 ℃ for 96 hours, taking out a reaction product, centrifuging to obtain a solid, and drying the solid at 120 ℃ for 2 hours;
placing the dried solid in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining calcination for 2 hours; obtaining Na-MOR molecular sieve;
10g of Na-MOR molecular sieve is added into Fe (aqueous solution of NO 3)3, stirred and reacted for 3 hours at 80 ℃, wherein Fe (concentration of Fe (NO 3)3) in aqueous solution of NO 3)3 is 1 mol/L) is centrifugally separated, the obtained solid is dried for 2 hours at 120 ℃, then the dried solid is placed in a muffle furnace, and calcination is maintained for 2 hours after the temperature is raised to 550 ℃ at a heating rate of 2 ℃/min, so that the Fe-Na-MOR molecular sieve catalyst is obtained.
(2) Purification of tetramethylsilane starting material
Filling a Fe-Na-MOR molecular sieve catalyst into a fixed bed reactor with an inner diameter of 10mm and a length of 300 mm; the fixed bed reactor was purged with N 2 and then the temperature was raised to 70 ℃; pumping tetramethylsilane raw material into a vaporizer at a certain flow rate (15 mL/h) by a plunger pump, wherein the airspeed is 100h < -1 >, then introducing the tetramethylsilane raw material from below a fixed bed, and collecting a reaction product from above the fixed bed reactor; and cooling and liquefying the collected product at 10 ℃ and rectifying to obtain the purified tetramethylsilane. Wherein the mass percentage of the 2-chloropropane in the purified tetramethylsilane is 0.00%.
Example 3
(1) Preparation of the catalyst
0.6G NaAlO 2, 8g NaOH are dissolved in 200mL deionized water, 10g fumed silica is added to the solution, and the mixture is stirred until a white gel is formed;
putting the mixture (white gel) into a hydrothermal reaction kettle, reacting at 170 ℃ for 96 hours, taking out a reaction product, centrifuging to obtain a solid, and drying the solid at 120 ℃ for 2 hours;
placing the dried solid in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining calcination for 2 hours; obtaining Na-MOR molecular sieve;
10g of Na-MOR molecular sieve is added into Fe (aqueous solution of NO 3)3, stirred and reacted for 3 hours at 80 ℃, wherein Fe (concentration of Fe (NO 3)3) in aqueous solution of NO 3)3 is 1 mol/L) is centrifugally separated, the obtained solid is dried for 2 hours at 120 ℃, then the dried solid is placed in a muffle furnace, and calcination is maintained for 2 hours after the temperature is raised to 550 ℃ at a heating rate of 2 ℃/min, so that the Fe-Na-MOR molecular sieve catalyst is obtained.
(2) Purification of tetramethylsilane starting material
Filling a Fe-Na-MOR molecular sieve catalyst into a fixed bed reactor with an inner diameter of 10mm and a length of 300 mm; the fixed bed reactor was purged with N 2 and then the temperature was raised to 70 ℃; pumping tetramethylsilane raw material into a vaporizer at a certain flow rate (22.5 mL/h) by a plunger pump, wherein the airspeed is 150h < -1 >, then introducing the tetramethylsilane raw material from below a fixed bed, and collecting a reaction product from above the fixed bed reactor; and cooling and liquefying the collected product at 10 ℃ and rectifying to obtain the purified tetramethylsilane. Wherein the mass percentage of the 2-chloropropane in the purified tetramethylsilane is 0.03 percent.
Example 4
(1) Preparation of the catalyst
0.6G NaAlO 2, 8g NaOH are dissolved in 200mL deionized water, 10g fumed silica is added to the solution, and the mixture is stirred until a white gel is formed;
putting the mixture (white gel) into a hydrothermal reaction kettle, reacting at 170 ℃ for 96 hours, taking out a reaction product, centrifuging to obtain a solid, and drying the solid at 120 ℃ for 2 hours;
placing the dried solid in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining calcination for 2 hours; obtaining Na-MOR molecular sieve;
adding 10g of Na-MOR molecular sieve into Fe (NO 3)3 aqueous solution, stirring and reacting for 3 hours at 70 ℃, wherein the concentration of Fe Cl 3 in FeCl 3 aqueous solution is 1mol/L, centrifugally separating, drying the obtained solid at 120 ℃ for 2 hours, placing the dried solid in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining to calcine for 2 hours to obtain the Fe-Na-MOR molecular sieve catalyst.
(2) Purification of tetramethylsilane starting material
Filling a Fe-Na-MOR molecular sieve catalyst into a fixed bed reactor with an inner diameter of 10mm and a length of 300 mm; the fixed bed reactor was purged with N 2 and then the temperature was raised to 70 ℃; pumping tetramethylsilane raw material into a vaporizer at a certain flow rate (15 mL/h) by a plunger pump, wherein the airspeed is 100h < -1 >, then introducing the tetramethylsilane raw material from below a fixed bed, and collecting a reaction product from above the fixed bed reactor; and cooling and liquefying the collected product at 10 ℃ and rectifying to obtain the purified tetramethylsilane. Wherein the mass percentage of the 2-chloropropane in the purified tetramethylsilane is 0.04 percent.
Example 5
(1) Preparation of the catalyst
0.6G NaAlO 2, 8g NaOH are dissolved in 200mL deionized water, 10g fumed silica is added to the solution, and the mixture is stirred until a white gel is formed;
Putting the mixture (white gel) into a hydrothermal reaction kettle, reacting at 170 ℃ for 60 hours, taking out a reaction product, centrifuging to obtain a solid, and drying the solid at 120 ℃ for 2 hours;
Placing the dried solid in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining calcination for 3.5h; obtaining Na-MOR molecular sieve;
10g of Na-MOR molecular sieve is added into Fe (aqueous solution of NO 3)3, stirred and reacted for 4 hours at 50 ℃, wherein Fe (concentration of Fe (NO 3)3) in aqueous solution of NO 3)3 is 0.5 mol/L.) is centrifugally separated, the obtained solid is dried for 2 hours at 120 ℃, then the dried solid is placed in a muffle furnace, and calcination is maintained for 3 hours after the temperature is raised to 550 ℃ at a heating rate of 2 ℃/min, so that the Fe-Na-MOR molecular sieve catalyst is obtained.
(2) Purification of tetramethylsilane starting material
Filling a Fe-Na-MOR molecular sieve catalyst into a fixed bed reactor with an inner diameter of 10mm and a length of 300 mm; the fixed bed reactor was purged with N 2 and then the temperature was raised to 50 ℃; pumping tetramethylsilane raw material into a vaporizer at a certain flow rate (15 mL/h) by a plunger pump, wherein the airspeed is 100h < -1 >, then introducing the tetramethylsilane raw material from below a fixed bed, and collecting a reaction product from above the fixed bed reactor; and cooling and liquefying the collected product at 10 ℃ and rectifying to obtain the purified tetramethylsilane. Wherein the mass percent of 2-chloropropane in the purified tetramethylsilane in the present example is similar to the mass percent of 2-chloropropane in the purified tetramethylsilane in example 1.
Example 6
(1) Preparation of the catalyst
0.6G NaAlO 2, 8g NaOH are dissolved in 200mL deionized water, 10g fumed silica is added to the solution, and the mixture is stirred until a white gel is formed;
Putting the mixture (white gel) into a hydrothermal reaction kettle, reacting at 170 ℃ for 48 hours, taking out a reaction product, centrifuging to obtain a solid, and drying the solid at 120 ℃ for 2 hours;
placing the dried solid in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining calcination for 4 hours; obtaining Na-MOR molecular sieve;
10g of Na-MOR molecular sieve was added to an aqueous solution of Fe Cl 3 and reacted at 70℃with stirring for 3.5h. Wherein the concentration of Fe Cl 3 in the aqueous solution of FeCl 3 is 0.5mol/L. Centrifugally separating, drying the obtained solid at 120 ℃ for 2 hours, then placing the dried solid in a muffle furnace, and maintaining calcination for 4 hours after heating to 550 ℃ at a heating rate of 2 ℃/min; obtaining the Fe-Na-MOR molecular sieve catalyst.
(2) Purification of tetramethylsilane starting material
Filling a Fe-Na-MOR molecular sieve catalyst into a fixed bed reactor with an inner diameter of 10mm and a length of 300 mm; the fixed bed reactor was purged with N 2 and then the temperature was raised to 80 ℃; pumping tetramethylsilane raw material into a vaporizer at a certain flow rate (15 mL/h) by a plunger pump, wherein the airspeed is 100h < -1 >, then introducing the tetramethylsilane raw material from below a fixed bed, and collecting a reaction product from above the fixed bed reactor; and cooling and liquefying the collected product at 10 ℃ and rectifying to obtain the purified tetramethylsilane. Wherein the mass percent of 2-chloropropane in the purified tetramethylsilane in the present example is similar to the mass percent of 2-chloropropane in the purified tetramethylsilane in example 1.
Comparative example 1
(1) Preparation of the catalyst
0.6G NaAlO 2, 8g NaOH are dissolved in 200mL deionized water, 10g fumed silica is added to the solution, and the mixture is stirred until a white gel is formed;
putting the mixture (white gel) into a hydrothermal reaction kettle, reacting at 170 ℃ for 96 hours, taking out a reaction product, centrifuging to obtain a solid, and drying the solid at 120 ℃ for 2 hours;
placing the dried solid in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining calcination for 2 hours; obtaining Na-MOR molecular sieve;
10g of Na-MOR molecular sieve is added into Fe (aqueous solution of NO 3)3, stirred and reacted for 3 hours at 80 ℃, wherein Fe (concentration of Fe (NO 3)3) in aqueous solution of NO 3)3 is 1.5 mol/L.) is centrifugally separated, the obtained solid is dried for 2 hours at 120 ℃, then the dried solid is placed in a muffle furnace, and calcination is maintained for 2 hours after the temperature is raised to 550 ℃ at a heating rate of 2 ℃/min, so that the Fe-Na-MOR molecular sieve catalyst is obtained.
(2) Purification of tetramethylsilane starting material
Filling a Fe-Na-MOR molecular sieve catalyst into a fixed bed reactor with an inner diameter of 10mm and a length of 300 mm; the fixed bed reactor was purged with N 2 and then the temperature was raised to 70 ℃; pumping tetramethylsilane raw material into a vaporizer at a certain flow rate (15 mL/h) by a plunger pump, wherein the airspeed is 100h < -1 >, then introducing the tetramethylsilane raw material from below a fixed bed, and collecting a reaction product from above the fixed bed reactor; and cooling and liquefying the collected product at 10 ℃ and rectifying to obtain the purified tetramethylsilane. Wherein the mass percentage of the 2-chloropropane in the purified tetramethylsilane is 0.25%.
Comparative example 2
(1) Preparation of the catalyst
0.6G NaAlO 2, 8g NaOH are dissolved in 200mL deionized water, 10g fumed silica is added to the solution, and the mixture is stirred until a white gel is formed;
putting the mixture (white gel) into a hydrothermal reaction kettle, reacting at 170 ℃ for 96 hours, taking out a reaction product, centrifuging to obtain a solid, and drying the solid at 120 ℃ for 2 hours;
placing the dried solid in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining calcination for 2 hours; obtaining Na-MOR molecular sieve;
10g of Na-MOR molecular sieve is added into Fe (aqueous solution of NO 3)3, stirred and reacted for 3 hours at 80 ℃, wherein Fe (concentration of Fe (NO 3)3) in aqueous solution of NO 3)3 is 2 mol/L) is centrifugally separated, the obtained solid is dried for 2 hours at 120 ℃, then the dried solid is placed in a muffle furnace, and calcination is maintained for 2 hours after the temperature is raised to 550 ℃ at a heating rate of 2 ℃/min, so that the Fe-Na-MOR molecular sieve catalyst is obtained.
(2) Purification of tetramethylsilane starting material
Filling a Fe-Na-MOR molecular sieve catalyst into a fixed bed reactor with an inner diameter of 10mm and a length of 300 mm; the fixed bed reactor was purged with N 2 and then the temperature was raised to 70 ℃; pumping tetramethylsilane raw material into a vaporizer at a certain flow rate (15 mL/h) by a plunger pump, wherein the airspeed is 100h < -1 >, then introducing the tetramethylsilane raw material from below a fixed bed, and collecting a reaction product from above the fixed bed reactor; and cooling and liquefying the collected product at 10 ℃ and rectifying to obtain the purified tetramethylsilane. Wherein the mass percentage of the 2-chloropropane in the purified tetramethylsilane is 0.83%.
Comparative example 3
(1) Preparation of the catalyst
0.6G NaAlO 2, 8g NaOH are dissolved in 200mL deionized water, 10g fumed silica is added to the solution, and the mixture is stirred until a white gel is formed;
putting the mixture (white gel) into a hydrothermal reaction kettle, reacting at 170 ℃ for 96 hours, taking out a reaction product, centrifuging to obtain a solid, and drying the solid at 120 ℃ for 2 hours;
placing the dried solid in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining calcination for 2 hours; obtaining Na-MOR molecular sieve;
(2) Purification of tetramethylsilane starting material
Filling Na-MOR molecular sieve into a fixed bed reactor with an inner diameter of 10mm and a length of 300 mm; the fixed bed reactor was purged with N 2 and then the temperature was raised to 70 ℃; pumping tetramethylsilane raw material into a vaporizer at a certain flow rate (15 mL/h) by a plunger pump, wherein the airspeed is 100h < -1 >, then introducing the tetramethylsilane raw material from below a fixed bed, and collecting a reaction product from above the fixed bed reactor; and cooling and liquefying the collected product at 10 ℃ and rectifying to obtain the purified tetramethylsilane. Wherein the mass percentage of the 2-chloropropane in the purified tetramethylsilane is 02.32 percent.
Comparative example 4
(1) Preparation of the catalyst
0.6G NaAlO2,8g NaOH was dissolved in 200mL deionized water, 10g fumed silica was added to the above solution and stirred until a white gel formed;
putting the mixture (white gel) into a hydrothermal reaction kettle, reacting at 170 ℃ for 96 hours, taking out a reaction product, centrifuging to obtain a solid, and drying the solid at 120 ℃ for 2 hours;
placing the dried solid in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining calcination for 2 hours; obtaining Na-MOR molecular sieve;
10g of Na-MOR molecular sieve is added into Fe (aqueous solution of NO 3)3, stirred and reacted for 3 hours at 80 ℃, wherein Fe (concentration of Fe (NO 3)3) in aqueous solution of NO 3)3 is 1 mol/L) is centrifugally separated, the obtained solid is dried for 2 hours at 120 ℃, then the dried solid is placed in a muffle furnace, and calcination is maintained for 2 hours after the temperature is raised to 550 ℃ at a heating rate of 2 ℃/min, so that the Fe-Na-MOR molecular sieve catalyst is obtained.
(2) Purification of tetramethylsilane starting material
Filling a Fe-Na-MOR molecular sieve catalyst into a fixed bed reactor with an inner diameter of 10mm and a length of 300 mm; the fixed bed reactor was purged with N 2 and then the temperature was raised to 70 ℃; pumping tetramethylsilane raw material into a vaporizer at a certain flow rate (30 mL/h) by a plunger pump, wherein the airspeed is 200h < -1 >, then introducing the tetramethylsilane raw material from below a fixed bed, and collecting a reaction product from above the fixed bed reactor; and cooling and liquefying the collected product at 10 ℃ and rectifying to obtain the purified tetramethylsilane. Wherein the mass percentage of the 2-chloropropane in the purified tetramethylsilane is 0.96%.
The tetramethylsilane raw materials in examples 1 to 6 and comparative examples 1 to 4 were composed of the following components in mass fraction: 83.42% tetramethylsilane, 12.12% isopentane and 4.46% 2-chloropropane.
As can be seen from the mass percentage of 2-chloropropane in the tetramethylsilane purified in examples 1 to 3, the method for removing 2-chloropropane in the tetramethylsilane raw material of the present invention can effectively reduce the content of 2-chloropropane in the tetramethylsilane raw material to 0.1% or less.
It can be seen from the mass percentage of 2-chloropropane in the purified tetramethylsilane of example 1, comparative example 1 and comparative example 2 that the increase in the Fe content of the Fe-Na-MOR molecular sieve catalyst results in poor removal of 2-chloropropane.
As can be seen from the mass percentage of 2-chloropropane in the purified tetramethylsilane in example 1 and comparative example 3, the removal effect of 2-chloropropane becomes super-grade without Fe element in the molecular sieve catalyst.
As can be seen from the mass percent of 2-chloropropane in the purified tetramethylsilane in example 1 and comparative example 4, excessive flow rate (flow velocity) and space velocity of the tetramethylsilane feed resulted in insufficient contact and reaction of the Fe-Na-MOR molecular sieve catalyst of the present invention with 2-chloropropane, which resulted in an increase in the mass percent of 2-chloropropane in the purified tetramethylsilane.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. The method for removing the 2-chloropropane in the tetramethylsilane raw material is characterized by comprising the following steps of:
S11, mixing the vaporized tetramethylsilane raw material with a Fe-Na-MOR molecular sieve catalyst under the heating condition for reaction;
S12, collecting a reaction product, cooling, liquefying and rectifying to obtain the purified tetramethylsilane.
2. The method for removing 2-chloropropane from a tetramethylsilane raw material according to claim 1, wherein the heating temperature in step S11 is 50 to 80 ℃.
3. The method for removing 2-chloropropane from a tetramethylsilane raw material according to claim 1, wherein said method for preparing a Fe-Na-MOR molecular sieve catalyst comprises the steps of:
s21, obtaining a mixed system of sodium metaaluminate, sodium hydroxide, fumed silica and water;
S22, carrying out hydrothermal reaction on the mixed system, separating, and drying the obtained solid to obtain a solid product;
s23, calcining the solid product to obtain a Na-MOR molecular sieve;
S24, mixing the Na-MOR molecular sieve with an iron salt solution for reaction under the heating condition, separating to obtain a solid, drying and calcining to obtain the Fe-Na-MOR molecular sieve catalyst.
4. The method for removing 2-chloropropane from a tetramethylsilane raw material according to claim 3, wherein said step 21 comprises:
dissolving sodium metaaluminate and sodium hydroxide in water, adding fumed silica into the solution, and stirring until white gel is formed, thus obtaining a mixed system of sodium metaaluminate, sodium hydroxide, fumed silica and water.
5. The method for removing 2-chloropropane from a tetramethylsilane raw material according to claim 3, wherein in the mixed system in S21, the mass ratio of sodium metaaluminate, sodium hydroxide and fumed silica is 6:80:100.
6. The method for removing 2-chloropropane from a tetramethylsilane raw material according to claim 3, wherein the hydrothermal reaction in step S22 is carried out at a temperature of 170 ℃ for a reaction time of 48 to 96 hours.
7. The method for removing 2-chloropropane from a tetramethylsilane raw material according to claim 3, wherein the calcination in step S23 is specifically: heating to 550 ℃ at a heating rate of 2 ℃/min, and maintaining for 2-4 h; and/or the number of the groups of groups,
The calcining in the step S24 specifically includes: and (3) heating to 550 ℃ at a heating rate of 2 ℃/min, and then maintaining for 2-4 h.
8. The method for removing 2-chloropropane from a tetramethylsilane raw material according to claim 3, wherein the iron salt solution in step S24 is at least one of Fe (aqueous solution of NO 3)3 and aqueous solution of FeCl 3).
9. The method for removing 2-chloropropane from a tetramethylsilane raw material according to claim 3, wherein the concentration of iron ions in said iron salt solution is 0.5 to 1mol/L.
10. The method for removing 2-chloropropane from a tetramethylsilane raw material according to claim 1, wherein the mixing reaction of the Na-MOR molecular sieve in step S24 with the iron salt solution under heating specifically comprises:
Adding Na-MOR molecular sieve into ferric salt solution, stirring and reacting for 3-4 h at 50-80 ℃.
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