CN115028656A - Method and reaction system for continuously producing high-purity trimethylsilane - Google Patents
Method and reaction system for continuously producing high-purity trimethylsilane Download PDFInfo
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- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 title claims description 25
- 238000001179 sorption measurement Methods 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 29
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 150000004678 hydrides Chemical class 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 22
- 238000010992 reflux Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 10
- 239000003463 adsorbent Substances 0.000 claims description 9
- 238000005194 fractionation Methods 0.000 claims description 8
- 239000012621 metal-organic framework Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 3
- 239000003495 polar organic solvent Substances 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011344 liquid material Substances 0.000 claims description 2
- RSHAOIXHUHAZPM-UHFFFAOYSA-N magnesium hydride Chemical compound [MgH2] RSHAOIXHUHAZPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229940094989 trimethylsilane Drugs 0.000 abstract description 32
- 239000012535 impurity Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910000077 silane Inorganic materials 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract 1
- 230000006872 improvement Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 238000010924 continuous production Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DZPJVKXUWVWEAD-UHFFFAOYSA-N [C].[N].[Si] Chemical compound [C].[N].[Si] DZPJVKXUWVWEAD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a method and a device system for continuously producing electronic grade high-purity trimethylsilane in a large scale. The invention uses the main product of trimethyl chlorosilane in the production process of the organosilicon intermediate as a raw material, uses the hydride of active metal as a reducing agent, generates reduction reaction in a specific solvent to generate trimethyl silane and a plurality of silane impurity gases, and then purifies by combining multi-stage rectification and adsorption, thereby realizing the continuous low-cost batch production of electronic-grade trimethyl silane with organic purity of more than 4N and inorganic purity of more than 6N.
Description
Technical Field
The invention relates to the field of trimethylsilane production, in particular to a method and a reaction system for continuously producing high-purity trimethylsilane.
Background
High purity trimethylsilane is a precursor for depositing silicon carbon nitride (SiCN) and silicon carbide-like films in the semiconductor industry, and is mainly used for depositing a copper diffusion barrier layer or an etching stop layer with a low dielectric constant. In the copper manufacturing process of integrated circuits, copper atoms or copper ions are easily diffused into the low-k dielectric layer under thermal annealing or electric field conditions, and become a main pollution source. In order to prevent copper diffusion and further reduce the effective dielectric constant of the copper interconnection dielectric layer, a low-dielectric-constant silicon carbon nitrogen diffusion barrier layer is deposited on a copper wire to seal the copper wire and simultaneously serve as an etching barrier layer in the process of etching a next metal layer through hole. The silicon-carbon-nitrogen film is generally prepared by taking trimethylsilane as a silicon source and a carbon source precursor and ammonia gas as a nitrogen source through a PECVD (plasma enhanced chemical vapor deposition) process.
At present, high-purity trimethylsilane used in the domestic semiconductor industry mainly depends on import, the report of large-scale production of the high-purity trimethylsilane is not seen, and the preparation is only carried out in laboratory-grade small batches.
The existing laboratory-level preparation method of trimethylsilane mainly takes dimethylchlorosilane and methyl magnesium chloride as raw materials, and methyl iodide as an initiator to initiate a Grignard reaction so as to generate trimethylsilane. The method has the advantages that the Grignard reagent has good selectivity, the trimethylsilane generated by the reaction has low impurity content, and the trimethylsilane is easy to purify to an electronic grade. However, the method relates to the storage and reaction of flammable and explosive materials such as chloromethane, methyl iodide, magnesium powder and the like, and stable control is difficult to realize after amplification of Grignard reaction, and continuous production is difficult to realize only by intermittent operation; meanwhile, the core raw material of the method, namely dimethylchlorosilane, is a trace byproduct generated in the production process of the organosilicon intermediate, and the source of the dimethylchlorosilane is unstable, difficult to purchase in large scale and expensive. For the above reasons, it is difficult to realize large-scale continuous production by this method.
Disclosure of Invention
In order to solve the problems, the invention provides a method for continuously producing high-purity trimethylsilane, which comprises the following steps:
the method comprises the following steps: adding a reducing agent and a solvent into a closed mixed feeding tank, uniformly stirring, and introducing the raw material liquid trimethylchlorosilane into the closed raw material feeding tank;
step two: introducing the materials in the mixed feeding tank and the raw material feeding tank in the step I into a closed continuous stirred tank reactor for reaction;
step three: continuously introducing gas generated by the reaction into a coarse fraction rectifying tower for separation, returning liquid materials distilled from the bottom of the tower into a mixed feeding tank, and continuously discharging materials at the bottom of the continuous stirred tank reactor to a slurry tank;
step four: introducing the material distilled from the top of the coarse fraction rectifying tower into a light component removing rectifying tower for purification, and introducing the material distilled from the bottom of the coarse fraction rectifying tower into a heavy component removing rectifying tower for purification;
step six: introducing materials distilled from the bottom of the de-heavy rectification tower into a first-stage adsorption column and a second-stage adsorption column in sequence for purification;
the reducing agent is a hydride containing active metal, and the solvent is furan or ether polar organic solvent with the boiling point range of 30-150 ℃;
wherein the pressure ranges in the mixed feeding tank, the raw material feeding tank, the continuous stirred tank reactor and the coarse fraction rectifying tower are 0.1-0.7 MPa; the pressure range in the light component removal rectifying tower and the heavy component removal rectifying tower is 0.03-0.3 MPa; the pressure range in the first-stage adsorption column and the second-stage adsorption column is 0.05-1 MPa.
The further improvement is that: the reducing agent is one or more of lithium hydride, sodium hydride, magnesium hydride, aluminum hydride, lithium aluminum hydride, sodium aluminum hydride and sodium borohydride.
The further improvement lies in that: the solvent is one of tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether and ethylene glycol dimethyl ether.
The further improvement lies in that: the reaction temperature in the continuous stirred tank reactor is 25-125 ℃.
The further improvement lies in that: the coarse fraction rectifying tower is a packed tower, the number of theoretical plates is 5-15, the operating temperature range is 10-80 ℃, and the reflux ratio is 2: 1-10: 1;
the light component removal rectifying tower is a packed tower, the number of theoretical plates is 25-50, the operating temperature range is-15-55 ℃, and the reflux ratio is 20: 1-200: 1;
the heavy component removal rectifying tower is a packed tower, the number of theoretical plates is 15-30, the operating temperature range is-5-65 ℃, and the reflux ratio is 2: 1-15: 1.
the further improvement lies in that: the adsorbents used in the first-stage adsorption column and the second-stage adsorption column are any two of active carbon, molecular sieves and Metal Organic Framework (MOFs) materials, and the operating temperature is-45 to-5 ℃.
The further improvement lies in that: the Metal Organic Frameworks (MOFs) material is prepared by taking a zirconium base as a core and carrying out self-assembly with nitrogen-containing heterocyclic organic ligands.
A reaction system of a method for continuously producing high-purity trimethylsilane comprises a mixed feeding tank, a raw material feeding tank, a continuous stirring tank type reactor, a rough fractionation rectifying tower, a light component removal rectifying tower, a heavy component removal rectifying tower, a primary adsorption column and a secondary adsorption column; also comprises a slurry tank, a reflux tank, a buffer tank and a crude product tank;
the further improvement is that: the bottom of the mixing and feeding tank is connected with a top feed inlet of the continuous stirring kettle type reactor through a mixing pump, the bottom of the raw material feeding tank is connected with a top feed inlet of the continuous stirring kettle type reactor through the raw material pump, the bottom of the continuous stirring kettle type reactor is connected with a feed inlet of a slag slurry tank through a slag slurry pump, a top gas outlet of the continuous stirring kettle type reactor is connected with a feed inlet of a rough-separating rectifying tower, the bottom of the rough-separating rectifying tower is connected with a top feed inlet of a reflux tank through a reflux pump, the bottom of the reflux tank is connected with a top feed inlet of the continuous stirring kettle type reactor through a reflux pump, the top of the rough-separating rectifying tower is connected with a feed inlet of a light-removing rectifying tower, the bottom of the light-removing rectifying tower is connected with a top feed inlet of a buffer tank through a conveying pump, the top of the heavy-removing rectifying tower is connected with a top feed inlet of the crude tank, and the bottom of the crude tank is sequentially connected with a first-level adsorption column and a second-level adsorption column through a booster pump.
The further improvement lies in that: the mixed feeding tank, the raw material feeding tank, the continuous stirring kettle type reactor, the rough fractionation rectifying tower, the light component removing rectifying tower, the heavy component removing rectifying tower, the primary adsorption column and the secondary adsorption column are respectively connected with a vacuumizing and replacing pipeline.
The invention has the beneficial effects that: on the basis of a process for preparing high-purity silane by reducing chlorosilane, the invention provides a method for continuously producing high-purity trimethylsilane in a large scale and low cost manner by using metal hydride as a reducing agent, using trimethyl chlorosilane which is a cheap and easily-obtained main product in an organosilicon intermediate production process as a raw material, using a continuous stirred tank reactor as a core reactor and adopting a purification mode of rectification and adsorption.
The method comprises the steps of controlling certain reaction pressure and temperature, utilizing a continuous stirred tank reactor to enable raw materials of trimethyl chlorosilane and metal hydride as reducing agents to generate reduction reaction in a polar organic solvent with the boiling point range of 30-150 ℃ to continuously generate trimethyl silane, vaporizing and separating the trimethyl silane from a reaction system, and continuously purifying the trimethyl silane by a rectifying tower and an adsorption column.
According to the method for continuously producing the high-purity trimethylsilane, the bottleneck of the existing laboratory-grade method for preparing the trimethylsilane in small batches is overcome, and the large-scale continuous production of the trimethylchlorosilane by using the low-cost and easily-obtained trimethylchlorosilane and the active metal hydride as raw materials is realized; meanwhile, the multistage rectification and the adsorption of a special material adsorbent are combined, the defect that more byproducts are generated in the reduction reaction process by the process is overcome, and the full-flow continuous production of the electronic grade high-purity trimethylchlorosilane product is realized.
Drawings
FIG. 1 is a schematic view of a reaction system of the present invention.
Wherein: 1-mixed feed tank, 2-raw material feed tank, 3-continuous stirred tank reactor, 4-coarse fractionating rectifying tower, 5-light-component removing rectifying tower, 6-heavy-component removing rectifying tower, 7-primary adsorption column, 8-secondary adsorption column, 9-slurry tank, 10-reflux tank, 11-buffer tank, 12-crude tank, 13-mixing pump, 14-raw material pump, 15-slurry pump, 16-reflux pump, 17-conveying pump and 18-booster pump.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.
Example one
The embodiment provides a reaction system of a method for continuously producing high-purity trimethylsilane, which comprises a mixed feeding tank 1, a raw material feeding tank 2, a continuous stirring tank type reactor 3, a coarse fraction rectifying tower 4, a light component removal rectifying tower 5, a heavy component removal rectifying tower 6, a primary adsorption column 7 and a secondary adsorption column 8; also comprises a slurry tank 9, a reflux tank 10, a buffer tank 11 and a crude product tank 12; the bottom of the mixed feeding tank 1 is connected with a top feeding hole of a continuous stirring tank type reactor 3 through a mixing pump 13, the bottom of a raw material feeding tank 2 is connected with a top feeding hole of the continuous stirring tank type reactor 3 through a raw material pump 14, the bottom of the continuous stirring tank type reactor 3 is connected with a feeding hole of a slurry tank 9 through a slurry pump 15, a gas outlet at the top of the continuous stirring tank type reactor 3 is connected with a feeding hole of a coarse fraction rectifying tower 4, the bottom of the coarse fraction rectifying tower 4 is connected with a feeding hole at the top of a reflux tank 10, the bottom of the reflux tank 10 is connected with a feeding hole at the top of the continuous stirring tank type reactor 3 through a reflux pump 16, the top of the coarse fraction rectifying tower 4 is connected with a feeding hole of a light-removing rectifying tower 5, the bottom of the light-removing rectifying tower 5 is connected with a feeding hole at the top of a buffer tank 11, the bottom of the buffer tank 11 is connected with a feeding hole of a heavy-removing rectifying tower 6 through a conveying pump 17, the top of the heavy-removing rectifying tower 6 is connected with the top of the crude feeding hole of the heavy-removing rectifying tower 12, the bottom of the crude product tank 12 is sequentially connected with a first-stage adsorption column 7 and a second-stage adsorption column 8 through a booster pump 18. The mixed feeding tank 1, the raw material feeding tank 2, the continuous stirred tank reactor 3, the rough fractionation rectifying tower 4, the light fractionation rectifying tower 5, the heavy fractionation rectifying tower 6, the first-stage adsorption column 7 and the second-stage adsorption column 8 are respectively connected with a vacuumizing and displacement pipeline.
Example two
The embodiment provides a method for continuously producing high-purity trimethylsilane, which comprises the steps of taking lithium hydride as a reducing agent, ether as a solvent, controlling the reaction temperature at 45 ℃, controlling the pressure of a reaction kettle and a crude distillation column to be 0.35MPa, controlling the pressure of a light component removal distillation column to be 0.2MPa, controlling the operation temperature to be 15-25 ℃, controlling the pressure of a heavy component removal distillation column to be 0.3MPa, controlling the operation temperature to be 20-30 ℃, adopting active carbon with the particle size of 3mm as an adsorbent in a first-stage adsorption column, controlling the pressure to be 0.7MPa, controlling the temperature to be-30 ℃, adopting a 4A molecular sieve as an adsorbent in a second-stage adsorption column, controlling the pressure to be 0.5MPa and controlling the temperature to be-20 ℃; the feeding amount of the reducing agent is 0.5kg/h, the feeding amount of the solvent is 10L/h, the feeding amount of the trimethylchlorosilane is 6.5kg/h, the operation is continuously carried out for 100 hours, and the results are as follows:
the total yield of the trimethylsilane is 203kg, and the yield is 45.8 percent;
the total impurity content is 72650ppb, wherein the total content of the alkyl substituted silane impurities is about 72050 ppb.
EXAMPLE III
The embodiment provides a method for continuously producing high-purity trimethylsilane, lithium aluminum hydride is used as a reducing agent, tetrahydrofuran is used as a solvent, the reaction temperature is controlled at 40 ℃, the pressure of a reaction kettle and a crude distillation tower is 0.25MPa, the pressure of a light component removal distillation tower is 0.15MPa, the operation temperature range is 10-18 ℃, the pressure of a heavy component removal distillation tower is 0.15MPa, the operation temperature range is 13-20 ℃, activated carbon with the particle size of 3mm is used as an adsorbent in a first-stage adsorption column, the pressure is 0.1MPa, the temperature is-40 ℃, zirconium-based MOFs materials are used as adsorbents in a second-stage adsorption column, the pressure is 0.08MPa, and the temperature is 0 ℃; the feeding amount of the reducing agent is 0.6kg/h, the feeding amount of the solvent is 10L/h, the feeding amount of the trimethylchlorosilane is 6.5kg/h, the operation is continuously carried out for 100 hours, and the results are as follows:
the total yield of the trimethylsilane is 231kg, and the yield is 52.1 percent;
the total impurity content is 58330ppb, wherein the total content of the alkyl substituted silane impurities is about 57960 ppb.
Example four
The embodiment provides a method for continuously producing high-purity trimethylsilane, sodium aluminum hydride is used as a reducing agent, ethylene glycol dimethyl ether is used as a solvent, the reaction temperature is controlled to be 65 ℃, the pressure of a reaction kettle and a crude distillation tower is 0.1MPa, the pressure of a light component removal distillation tower is 0.08MPa, the operation temperature range is 2-8 ℃, the pressure of a heavy component removal distillation tower is 0.1MPa, the operation temperature range is 5-12 ℃, a 5A molecular sieve is used as an adsorbent in a first-stage adsorption column, the pressure is 0.1MPa, the temperature is-50 ℃, a zirconium-based MOFs material is used as an adsorbent in a second-stage adsorption column, the pressure is 0.08MPa, and the temperature is 0 ℃; the feeding amount of the reducing agent is 0.6kg/h, the feeding amount of the solvent is 10L/h, the feeding amount of the trimethylchlorosilane is 6.5kg/h, the operation is continuously carried out for 100 hours, and the results are as follows:
the total yield of the trimethylsilane was 324kg, and the yield was 73.1%;
the total impurity content is 87210ppb, wherein the total content of the alkyl substituted silane impurities is about 86490 ppb.
In the second to fourth embodiments, trimethylchlorosilane is used as a raw material, a hydrogenation reduction process is adopted to continuously produce trimethylsilane, and multistage rectification and adsorption are combined to purify the trimethylsilane, so that large-scale continuous production of electronic grade high-purity trimethylsilane with annual capacity of more than 10 tons can be realized; the total content of organic impurities in the product is less than 100000ppb (purity is more than or equal to 4N), and the total content of inorganic impurities is less than 1000ppb (purity is more than or equal to 6N).
Although particular embodiments of the invention have been described and illustrated in detail, it should be understood that various equivalent changes and modifications could be made to the above-described embodiments in accordance with the teachings of the present invention, and its functional operation would still fall within the scope of the present invention, without departing from the spirit covered by the present specification.
Claims (10)
1. A method for continuously producing high-purity trimethylsilane is characterized by comprising the following steps:
the method comprises the following steps: adding a reducing agent and a solvent into a closed mixed feeding tank, uniformly stirring, and introducing the raw material liquid trimethylchlorosilane into the closed raw material feeding tank;
step two: introducing the materials in the mixed feeding tank and the raw material feeding tank in the step I into a closed continuous stirred tank reactor for reaction;
step three: continuously introducing gas generated by the reaction into a coarse fraction rectifying tower for separation, returning liquid materials distilled from the bottom of the tower into a mixed feeding tank, and continuously discharging materials at the bottom of the continuous stirred tank reactor to a slurry tank;
step four: introducing the material distilled from the top of the coarse fractionating rectifying tower into a light component removing rectifying tower for purification, and introducing the material distilled from the bottom of the tower into a heavy component removing rectifying tower for purification;
step six: introducing materials distilled from the bottom of the de-heavy rectification tower into a first-stage adsorption column and a second-stage adsorption column in sequence for purification;
the reducing agent is a hydride containing active metal, and the solvent is furan or ether polar organic solvent with the boiling point range of 30-150 ℃;
wherein the pressure ranges in the mixed feeding tank, the raw material feeding tank, the continuous stirring tank reactor and the coarse fraction rectifying tower are 0.1-0.7 MPa; the pressure range in the light component removal rectifying tower and the heavy component removal rectifying tower is 0.03-0.3 MPa; the pressure range in the first-stage adsorption column and the second-stage adsorption column is 0.05-1 MPa.
2. The method for continuously producing high-purity trimethylsilane according to claim 1, characterized in that: the reducing agent is one or more of lithium hydride, sodium hydride, magnesium hydride, aluminum hydride, lithium aluminum hydride, sodium aluminum hydride and sodium borohydride.
3. The method for continuously producing high-purity trimethylsilane according to claim 1, characterized in that: the solvent is one of tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether and ethylene glycol dimethyl ether.
4. The method for continuously producing high-purity trimethylsilane according to claim 1, wherein: the reaction temperature in the continuous stirred tank reactor is 25-125 ℃.
5. The method for continuously producing high-purity trimethylsilane according to claim 1, characterized in that: the crude distillation tower is a packed tower, the number of theoretical plates is 5-15, the operating temperature range is 10-80 ℃, and the reflux ratio is 2: 1-10: 1;
the light component removal rectifying tower is a packed tower, the number of theoretical plates is 25-50, the operating temperature range is-15-55 ℃, and the reflux ratio is 20: 1-200: 1;
the heavy component removal rectifying tower is a packed tower, the number of theoretical plates is 15-30, the operating temperature range is-5-65 ℃, and the reflux ratio is 2: 1-15: 1.
6. the method for continuously producing high-purity trimethylsilane according to claim 1, wherein: the adsorbents used in the first-stage adsorption column and the second-stage adsorption column are any two of active carbon, molecular sieves and Metal Organic Framework (MOFs) materials, and the operating temperature is-45 to-5 ℃.
7. The method for continuously producing high-purity trimethylsilane according to claim 6, characterized in that: the Metal Organic Frameworks (MOFs) material is prepared by taking a zirconium base as a core and carrying out self-assembly with nitrogen-containing heterocyclic organic ligands.
8. A reaction system based on the method for continuously producing high-purity trimethylsilane of claims 1 to 7, characterized in that: comprises a mixed feeding tank (1), a raw material feeding tank (2), a continuous stirred tank reactor (3), a coarse fractionating rectifying tower (4), a light component removing rectifying tower (5), a heavy component removing rectifying tower (6), a primary adsorption column (7) and a secondary adsorption column (8); also comprises a slurry tank (9), a reflux tank (10), a buffer tank (11) and a crude product tank (12).
9. The reaction system of the method for continuously producing high-purity trimethylsilane according to claim 8, wherein: the bottom of the mixed feeding tank (1) is connected with the top feed inlet of the continuous stirring tank reactor (3) through a mixing pump (13), the bottom of the raw material feeding tank (2) is connected with the top feed inlet of the continuous stirring tank reactor (3) through a raw material pump (14), the bottom of the continuous stirring tank reactor (3) is connected with the feed inlet of a slurry tank (9) through a slurry pump (15), a gas outlet at the top of the continuous stirring tank reactor (3) is connected with the feed inlet of a coarse fraction rectifying tower (4), the bottom of the coarse fraction rectifying tower (4) is connected with the top feed inlet of a reflux tank (10), the bottom of the reflux tank (10) is connected with the top feed inlet of the continuous stirring tank reactor (3) through a reflux pump (16), the top of the coarse fraction rectifying tower (4) is connected with the feed inlet of a lightness-removing rectifying tower (5), the bottom of the lightness-removing rectifying tower (5) is connected with the top feed inlet of a buffer tank (11), the bottom of the buffer tank (11) is connected with the gravity-removing rectifying tower (6) through a conveying pump (17), the top of the de-heavy rectifying tower (6) is connected with a feed inlet at the top of a crude product tank (12), and the bottom of the crude product tank (12) is sequentially connected with a first-stage adsorption column (7) and a second-stage adsorption column (8) through a booster pump (18).
10. The reaction system of the method for continuously producing high-purity trimethylsilane according to claim 8, wherein: the device comprises a mixing feeding tank (1), a raw material feeding tank (2), a continuous stirring kettle type reactor (3), a rough fractionation rectifying tower (4), a light fractionation rectifying tower (5), a heavy fractionation rectifying tower (6), a first-stage adsorption column (7) and a second-stage adsorption column (8) which are connected with a vacuumizing and displacement pipeline respectively.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115636846A (en) * | 2022-11-02 | 2023-01-24 | 洛阳中硅高科技有限公司 | Preparation method and device of high-purity trisilylamine |
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| JP2004331549A (en) * | 2003-05-07 | 2004-11-25 | Mitsui Chemicals Inc | Method for producing hydrogenated organosilane |
| JP2004331572A (en) * | 2003-05-08 | 2004-11-25 | Mitsui Chemicals Inc | Method for producing hydrogenated organosilane and hydrocarbon in combination, and hydrogenated organosilane composition |
| CN113214304A (en) * | 2021-04-23 | 2021-08-06 | 洛阳中硅高科技有限公司 | Preparation system and method of tetramethylsilane |
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| JP2004331549A (en) * | 2003-05-07 | 2004-11-25 | Mitsui Chemicals Inc | Method for producing hydrogenated organosilane |
| JP2004331572A (en) * | 2003-05-08 | 2004-11-25 | Mitsui Chemicals Inc | Method for producing hydrogenated organosilane and hydrocarbon in combination, and hydrogenated organosilane composition |
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