CN117208914A - Preparation and purification method and equipment of high-purity diiodosilane - Google Patents
Preparation and purification method and equipment of high-purity diiodosilane Download PDFInfo
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- AIHCVGFMFDEUMO-UHFFFAOYSA-N diiodosilane Chemical compound I[SiH2]I AIHCVGFMFDEUMO-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000746 purification Methods 0.000 title claims abstract description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000007788 liquid Substances 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 239000002904 solvent Substances 0.000 claims abstract description 41
- 238000007670 refining Methods 0.000 claims abstract description 34
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000077 silane Inorganic materials 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000011049 filling Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 75
- IDIOJRGTRFRIJL-UHFFFAOYSA-N iodosilane Chemical compound I[SiH3] IDIOJRGTRFRIJL-UHFFFAOYSA-N 0.000 claims description 66
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 63
- 239000000463 material Substances 0.000 claims description 59
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 31
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 31
- 229910052740 iodine Inorganic materials 0.000 claims description 31
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 30
- 239000011630 iodine Substances 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 239000006227 byproduct Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 239000002635 aromatic organic solvent Substances 0.000 claims description 16
- 150000002894 organic compounds Chemical class 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- INSWZJAKEHRSPO-UHFFFAOYSA-N benzene silane Chemical compound [SiH4].[SiH4].C1=CC=CC=C1 INSWZJAKEHRSPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- -1 periodate silane Chemical compound 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 5
- 150000002484 inorganic compounds Chemical class 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 238000006192 iodination reaction Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 230000026045 iodination Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 125000001153 fluoro group Chemical class F* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- UJPJVFMGMITNJK-UHFFFAOYSA-N iodo(phenyl)silane Chemical compound I[SiH2]c1ccccc1 UJPJVFMGMITNJK-UHFFFAOYSA-N 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The application relates to the field of inorganic compound preparation and purification methods, in particular to a preparation and purification method and equipment of high-purity diiodosilane. The equipment comprises a first reactor, a first vapor-liquid separator, a second vapor-liquid separator, a benzene-removing silane tower, a diiodosilane refining tower, a mixer and a second reactor; the preparation and purification method comprises the steps of raw material reaction, gas-liquid separation in the first step, gas-liquid separation in the second step, benzene removal, refining and purification and yield filling; the application improves the conversion rate of raw materials, reduces the cost of raw materials, ensures the purity and the yield of diiodosilane simultaneously by matching the device and the process and utilizing the arrangement of multiple recovery cycles, greatly reduces the use cost of the solvent by recycling the solvent, and has high industrial value.
Description
Technical Field
The application relates to the field of inorganic compound preparation and purification methods, in particular to a preparation and purification method and equipment of high-purity diiodosilane.
Background
Diiodosilane (SiH) 2 I 2 DIS), is a pink flammable liquid at normal temperature and pressure, and has a pungent odor. The diiodosilane has active chemical property, releases pyrophoric gas when meeting water, is mixed with air and is easy to explode when heated, reacts with alkali to generate hydrogen under the catalysis of metal platinum, and can react with active metal vigorously. Are commonly used as chemical synthesis intermediates.
Diiodosilane can generate more active silicon free radicals under the enhancement of plasma, is an important silicon precursor for chemical vapor deposition in the integrated circuit process, can adaptively form atomic layer deposition on a plurality of traditional substrates, and has the characteristics of lower temperature and more controllable pressure operation on the premise of keeping high deposition rate. However, diiodosilane for integrated circuits has extremely high purity requirements (mass fraction ≡99.999%), and it is important to obtain high purity diiodosilane by suitable preparation and purification methods.
At present, the preparation method of diiodosilane mainly comprises the following three steps:
1. silane iodination. Maddock et al, published article New Iodine and Fluorine Derivatives of Monosilane (MADDOCK, A., REID, C).&EMELUS, h.new Iodine and Fluorine Derivatives of monosilane.nature 144,328 (1939), uses hydrogen iodide in combination with silane to produce a mixture of silicon-based iodides (SiH) under the catalytic action of aluminum iodide 3 I、SiH 2 I 2 、SiHI 3 、SiI 4 ). The method has the defects that raw material silane is pyrophoric gas, inflammable and explosive, hydrogen iodide gas is difficult to obtain, no supplier exists in China, andand the reaction products are complex.
SiH 4 +HI→SiI x H 4-x
2. Halogen exchange process. And reacting the dichlorosilane with lithium iodide in an organic solvent to obtain diiodosilane and lithium chloride. The insoluble lithium chloride generated by the reaction provides driving force for the reaction and improves the conversion rate. The method has the defects that the reaction raw materials are gas-solid mixed phases, the reaction rate is low, and industrialization is difficult.
SiH 2 Cl 2 +2LiI→SiH 2 I 2 +2LiCl
3. Phenylsilane iodination. The phenylsilane iodination route proposed by Fritz and Kummer in 1960 is mature and has industrial prospect (Fritz, g.and Kummer, d. (1960), die Spaltung des C 6 H 5 SiH 3 mit jod und HJ(Eine einfache Darstellung von SiH 3 J) Z.anorg.allg.chem., 304:322-327.). Phenylsilane reacts with iodine under the action of an oxygen-containing organic catalyst to generate monoiodophenylsilane and hydrogen iodide, and the monoiodophenylsilane and the hydrogen iodide continuously react to generate diiodosilane and benzene.
Ph-SiH 3 +I 2 →Ph-SiH 2 I+HI
Ph-SiH 2 I+HI→Ph-H+SiH 2 I 2
The method has the following defects:
(1) The reaction requires a large amount of solvent, and if a continuous reaction process is adopted, a large amount of solvent loss is caused, so that the cost is greatly increased.
(2) There is a side reaction, the intermediate product hydrogen iodide can react with phenylsilane to generate by-product monoiodosilane, so that the yield of diiodosilane is reduced.
Ph-SiH 3 +HI→SiH 3 I+Ph-H
In conclusion, the silane iodination method and the halogen exchange method are only suitable for laboratory experiments due to the factors of inflammable and explosive raw materials, low reaction rate, more byproducts, difficult control of the reaction and the like. The phenylsilane iodination method has industrial prospect, but has the defects of large solvent consumption and side reaction. Therefore, it is necessary to develop an improved, economical process route for producing high purity diiodosilane by phenylsilane iodination which is economical, has high product yield, high product purity, and is safe and reliable.
Disclosure of Invention
In order to overcome various problems in the prior art for preparing diiodosilane, the application provides a preparation and purification method and equipment for high-purity diiodosilane.
In a first aspect, the application provides a preparation device of high-purity diiodosilane, which adopts the following technical scheme:
the preparation equipment of the high-purity diiodosilane comprises a first reactor, a first vapor-liquid separator, a second vapor-liquid separator, a debenzolized silane tower, a diiodosilane refining tower, a mixer and a second reactor; the bottom of the first reactor is communicated with a first vapor-liquid separator, the bottom of the first vapor-liquid separator is communicated with a benzene-removing silane tower, the top of the first vapor-liquid separator is communicated with a second vapor-liquid separator, the bottom of the second vapor-liquid separator is respectively communicated with the first reactor and the second reactor, the bottom of the benzene-removing silane tower is communicated with a diiodosilane refining tower, the top of the benzene-removing silane tower is communicated with the first reactor, the bottom of the diiodosilane refining tower is used for discharging high-purity diiodosilane, the top of the diiodosilane refining tower is communicated with a mixer, the mixer is communicated with the second reactor, and outlet materials at the bottom of the second reactor are communicated with the first vapor-liquid separator through a pipeline.
In a second aspect, based on the above equipment, the application provides a preparation and purification method of high-purity diiodosilane, which adopts the following technical scheme:
the preparation and purification method of the high-purity diiodosilane comprises the following steps:
1. reaction of raw materials
Filling by utilizing inert gas purging, and then introducing a mixed solution of phenylsilane and an oxygen-containing organic catalyst and a mixed solution of iodine and an aromatic organic solvent into a first reactor to complete the reaction, wherein the bottom material of the first reactor is a mixed material of diiodosilane, phenylsilane, monoiodosilane, hydrogen iodide, an oxygen-containing organic catalyst and an aromatic organic solvent;
2. first step vapor-liquid separation
And introducing the materials in the first reactor into a first vapor-liquid separator, wherein the top of the first vapor-liquid separator is used for obtaining mixed gas of an aromatic organic solvent, an oxygen-containing organic catalyst and hydrogen iodide, and the bottom of the first vapor-liquid separator is used for obtaining a crude diiodosilane material containing diiodosilane, phenylsilane and monoiodosilane.
3. Second step vapor-liquid separation
Introducing the mixed gas at the top of the first vapor-liquid separator into a second vapor-liquid separator, wherein hydrogen iodide and an oxygen-containing organic catalyst are obtained at the top of the second vapor-liquid separator, and a recovered solvent material containing oxygen-containing organic catalyst impurities is obtained at the bottom of the second vapor-liquid separator, wherein the recovered solvent material is used for supplementing the solvent loss of the first reactor and the second reactor;
4. debenzolization process
The bottom material of the first vapor-liquid separator enters a benzene-removing silane tower, and benzene silane extracted from the top of the benzene-removing silane tower is introduced into a first reactor; the tower bottom of the debenzolization silane tower is used for extracting a mixed material of diiodosilane and monoiodosilane;
5. refining and purifying
Feeding tower kettle materials of the debenzolized silane tower into a diiodosilane refining tower; the high-purity periodate silane is extracted from the tower bottom of the diiodo silane refining tower, and the byproduct monoiodosilane is extracted from the tower top.
6. Yield filling
The monoiodo silane extracted from the top of the diiodo silane refining tower is mixed with an oxygen-containing organic matter catalyst through a mixer and is introduced into a second reactor, the second reactor converts byproduct monoiodo silane into diiodo silane to obtain products of diiodo silane, unreacted monoiodo silane, hydrogen iodide, aromatic organic solvent and the oxygen-containing organic matter catalyst, the products of diiodo silane are introduced into a first vapor-liquid separator, and finally the diiodo silane is extracted from the tower bottom of the diiodo silane refining tower.
In a specific embodiment, the first reactor is operated at a reaction temperature of-50 to-10 ℃, at atmospheric pressure, and at a reaction residence time of 8 to 10 hours.
In a specific embodiment, the second reactor is operated at a temperature of-30 to 0℃and at a pressure of normal pressure and a residence time of 8 to 10 hours.
In a specific embodiment, the oxygen-containing organic compound catalyst comprises one or more of ethyl acetate, ethyl formate, butyl acetate, ethanol, and acetone.
In a specific embodiment, the aromatic organic solvent is one or more of benzene, toluene, and xylene.
In a specific embodiment, the operating temperature of the debenzolization column is 50 to 60℃and the operating pressure is 20 to 50kPa, with a theoretical plate count of 5 to 20.
In a specific embodiment, the diiodosilane refining column is operated at a temperature of 60 to 80 ℃, at a pressure of 20 to 50kPa, and at a theoretical plate number of 10 to 20.
The application has the following beneficial effects:
1. firstly, using a phenylsilane mixed solution and an iodine solution as raw materials, and after the raw materials react, the crude diiodosilane material is subjected to debenzolization and refining, the purity can reach more than 99.999 weight percent, the monoiodosilane content is less than 5ppm, the benzene content is less than 3ppm, and the phenylsilane content is less than 2ppm; meanwhile, after the gas at the top of the first gas-liquid separator is subjected to gas-liquid separation, the solvent materials can be recovered and supplemented into the first reactor and the second reactor, so that the use cost of the solvent is greatly reduced; in addition, the tower top material of the debenzolized silane tower after debenzolization can be supplemented into the first reactor, so that the utilization rate of raw materials is increased; finally, the tower top material of the diiodosilane refining tower can be further mixed with an oxygen-containing organic catalyst and pass through a second reactor, so that the recovery of monoiodosilane byproducts can be completed, and the yield of diiodosilane is further increased.
In summary, the application improves the conversion rate of raw materials, reduces the cost of raw materials, ensures the purity and yield of diiodosilane by matching the device and the process and by recycling the solvent, greatly reduces the use cost of the solvent and has high industrial value.
Drawings
FIG. 1 is a process flow diagram of the method provided by the present application.
Reference numerals illustrate: r101, a first reactor; v101, a first vapor-liquid separator; v102, a second vapor-liquid separator; t101, a debenzolization silane tower; t102, diiodosilane refining tower;
m101, a mixer; r102, second reactor.
Wherein, the numbers 1 to 14 represent the logistics, specifically: 1. phenylsilane mixed solution; 2. iodine solution; 3. the material at the outlet of the first reactor; 4. an aromatic organic solvent, an oxygen-containing organic compound catalyst, and a mixed gas of hydrogen iodide; 5. crude diiodosilane material; 6. recovering the solvent material; 7. hydrogen iodide; 8. the top material of the debenzolization tower; 9. a mixture of diiodosilane and monoiodosilane; 10. a byproduct monoiodosilane; 11. high purity diiodosilane; 12. an oxygen-containing organic compound catalyst; 13. iodine solution; 14. the second reactor outlet material.
Detailed Description
The application is described in further detail below with reference to fig. 1 and the examples.
First, the present application provides an apparatus (product line) for producing high purity diiodosilane, which comprises a first reactor R101, a first vapor-liquid separator V101, a second vapor-liquid separator V102, a debenzolization column T101, a diiodosilane refining column T102, a mixer M101, and a second reactor R102, as shown in fig. 1. The first reactor R101 comprises a phenylsilane mixed liquid feeding pipeline and an iodine solution feeding pipeline, the bottom of the first reactor R101 is connected with a first vapor-liquid separation pipeline, the bottom of the first vapor-liquid separator V101 is connected with a phenylsilane stripping tower T101, the top of the first vapor-liquid separator V101 is connected with a second vapor-liquid separator V102, the bottom of the second vapor-liquid separator V102 is respectively connected with the first reactor R101 and the second reactor R102 through valves, the bottom of the phenylsilane stripping tower T101 is connected with a diiodosilane refining tower T102, the top of the phenylsilane stripping tower T101 is connected with a phenylsilane mixed liquid feeding pipeline in the first reactor R101, the bottom of the diiodosilane refining tower T102 is used for discharging high-purity diiodosilane, the top of the diiodosilane tower T102 is connected with a mixer M101, the mixer M101 is used for mixing an oxygen-containing organic matter catalyst with a material at the top of the diiodosilane refining tower T102 and finally injecting the mixture into the second reactor R102, the top of the second reactor R102 is further provided with an iodine solution feeding pipeline at the top of the second reactor R102, and the bottom of the second reactor R101 is connected with a material through a second reactor V101.
Based on the equipment, the application also provides a preparation and purification method of the high-purity diiodosilane, which comprises the following steps:
the preparation and purification method of the high-purity diiodosilane provided by the application comprises the following steps:
(1) And (3) filling the whole product line by using nitrogen to purge and replace the air of the product line. The volume ratio is 1:0.03 phenylsilane and an oxygen-containing organic compound catalyst to obtain phenylsilane mixed solution. The mass ratio is 1:1 and an aromatic organic solvent to obtain an iodine solution.
(2) And introducing 25-40kg/h of phenylsilane solution and 40-60kg/h of iodine solution into the first reactor R101 to carry out phenylsilane iodination reaction, wherein phenylsilane in the reaction products is excessive so as to lead the iodine reaction to be complete. The reaction temperature is-50 to-10 ℃, the reaction pressure is normal pressure, and the reaction residence time is 8-10 hours. The output material of the first reactor R101 containing diiodosilane, phenylsilane, monoiodosilane, hydrogen iodide, aromatic organic solvent and oxygen-containing organic compound catalyst is obtained.
(3) The material at the outlet of the first reactor R101 is introduced into a first vapor-liquid separator V101 to remove the solvent and terminate the reaction, the operating pressure is 0.8-1bar, and the operating temperature is 60-100 ℃. The mixed gas of aromatic organic solvent, oxygen-containing organic compound catalyst and hydrogen iodide is obtained at the top. The crude diiodosilane material containing diiodosilane, phenylsilane and monoiodosilane is obtained at the bottom.
(4) The mixed gas at the top of the first vapor-liquid separator V101 is introduced into the second vapor-liquid separator V102 to recover the solvent, the operation pressure is 0.8-1bar, and the operation temperature is 50-70 ℃. The hydrogen iodide and the oxygen-containing organic compound catalyst are obtained at the top. The bottom is obtained with a recovered solvent material in which a small amount of oxygen-containing organic compound catalyst impurities are dissolved. The recovered solvent feed may be used to make up for solvent losses in the first reactor R101 and the second reactor R102.
(5) The crude diiodosilane material obtained at the bottom of the first vapor-liquid separator V101 enters a debenzolization column T101 for removing phenylsilane. The operation temperature is 50-60 ℃, the operation pressure is 20-50kPa, the theoretical plate number is 5-20, and the reflux ratio is 25. Phenylsilane is withdrawn overhead and recycled to the first reactor R101 to increase phenylsilane conversion. And (3) extracting a mixed material of diiodosilane and monoiodosilane from the tower bottom.
(6) The tower bottom material of the debenzolization tower T101 enters a diiodosilane refining tower T102 for removing byproduct monoiodosilane. The operation temperature is 60-80 ℃, the operation pressure is 20-50kPa, the theoretical plate number is 10-20, and the reflux ratio is 25. And (3) extracting monoiodo silane as a byproduct from the tower top, and extracting high-purity diiodosilane with purity of more than 99.999wt% from the tower bottom.
(7) The volume ratio of the byproduct monoiodosilane extracted from the top of the diiodosilane refining tower T102 to the oxygen-containing organic compound catalyst is 1:0.03 to obtain a monoiodo silane mixed solution. Mixing monoiodosilane mixed solution and iodine solution according to a mass flow ratio of 1: (1.5-2) introducing into a second reactor R102 to convert the byproduct monoiodo silane into product diiodosilane, so as to improve the yield of diiodosilane. The monoiodosilane in the reaction was in excess to complete the iodine reaction. The reaction temperature is-30-0 ℃, the reaction pressure is normal pressure, and the reaction residence time is 8-10 hours. The output material of the second reactor R102 containing diiodosilane, monoiodosilane, hydrogen iodide, aromatic organic solvent and oxygen-containing organic compound catalyst is obtained, and the material is circulated to the first vapor-liquid separator V101 to remove the solvent and terminate the reaction.
Based on the above-described apparatus and preparation and purification methods, the following description will be made with reference to specific examples.
Example 1
And (3) filling the whole product line by using nitrogen to purge and replace the air of the product line. The volume ratio is 1:0.03 phenylsilane and ethyl acetate to obtain a phenylsilane mixed solution. The mass ratio is 1:1 is mixed with benzene to be dissolved to obtain iodine solution. 30kg/h of phenylsilane solution and 55kg/h of iodine solution are fed into the first reactor R101 for phenylsilane iodination, and phenylsilane in the reaction mixture is excessive so as to complete the iodine reaction. The reaction temperature is-50 ℃, the reaction pressure is normal pressure, and the reaction residence time is 8 hours. The output from the first reactor R101 was obtained, which contained 16.6% by weight of diiodosilane, 7.5% by weight of phenylsilane, 14.3% by weight of monoiodosilane, 4.5% by weight of hydrogen iodide, 56.8% by weight of benzene and 0.3% by weight of ethyl acetate. The material at the outlet of the first reactor R101 was fed to a first vapor-liquid separator V101 to remove the solvent, terminate the reaction, operating at a pressure of 0.8bar and at a temperature of 60 ℃. The mixed gas of benzene, ethyl acetate and hydrogen iodide is obtained at the top. The crude diiodosilane material containing diiodosilane, phenylsilane and monoiodosilane is obtained at the bottom. The mixed gas at the top of the first vapor-liquid separator V101 is introduced into the second vapor-liquid separator V102 to recover the solvent, and the operation pressure is 0.8bar and the operation temperature is 60 ℃. Hydrogen iodide and ethyl acetate were obtained on top. The benzene recovery solvent material dissolved with a small amount of ethyl acetate impurity is obtained at the bottom. The recovered solvent feed may be used to make up for solvent losses in the first reactor R101 and the second reactor R102. The crude diiodosilane material obtained at the bottom of the first vapor-liquid separator V101 enters a debenzolization column T101 for removing phenylsilane. The operating temperature is 50 ℃, the operating pressure is 20kPa, the theoretical plate number is 5, and the reflux ratio is 25. Phenylsilane is withdrawn overhead and recycled to the first reactor R101 to increase phenylsilane conversion. And (3) extracting a mixed material of diiodosilane and monoiodosilane from the tower bottom. The tower bottom material of the debenzolization tower T101 enters a diiodosilane refining tower T102 for removing byproduct monoiodosilane. Operating temperature 60 ℃, operating pressure 20kPa, theoretical plate number 10, reflux ratio 25. The byproduct monoiodo silane is extracted from the tower top, 34.47kg/h of high-purity diiodosilane with the purity of 99.9995wt% is extracted from the tower bottom, the monoiodo silane content is 2ppm, the benzene content is 2ppm, and the phenylsilane content is 1ppm. The volume ratio of monoiodosilane and ethyl acetate which are byproducts extracted from the top of the debenzolization silane tower T101 is 1:0.03 to obtain a monoiodo silane mixed solution. Mixing monoiodosilane mixed solution and iodine solution according to a mass flow ratio of 1:1.5 is introduced into a second reactor R102 to convert the byproduct monoiodo silane into product diiodosilane, so as to improve the yield of diiodosilane. The monoiodosilane in the reaction was in excess to complete the iodine reaction. The reaction temperature is minus 30 ℃, the reaction pressure is normal pressure, and the reaction residence time is 8 hours. The output from the second reactor R102 containing 36.5% by weight of diiodosilane, 9.4% by weight of monoiodosilane, 5.6% by weight of hydrogen iodide, 48.2% by weight of benzene, 0.3% by weight of ethyl acetate was obtained and recycled to the first vapor-liquid separator V101 to remove the solvent and terminate the reaction.
Example 2
And (3) filling the whole product line by using nitrogen to purge and replace the air of the product line. The volume ratio is 1:0.03 phenylsilane and ethyl acetate to obtain a phenylsilane mixed solution. The mass ratio is 1:1 is mixed with benzene to be dissolved to obtain iodine solution. 30kg/h of phenylsilane solution and 55kg/h of iodine solution are fed into the first reactor R101 for phenylsilane iodination, and phenylsilane in the reaction mixture is excessive so as to complete the iodine reaction. The reaction temperature is minus 30 ℃, the reaction pressure is normal pressure, and the reaction residence time is 9 hours. The first reactor R101 outlet material containing 14.5wt% diiodosilane, 9.5wt% phenylsilane, 12.8wt% monoiodosilane, 3.7wt% hydrogen iodide, 59.2wt% benzene, 0.3wt% ethyl acetate was obtained. The material at the outlet of the first reactor R101 was fed to a first vapor-liquid separator V101 to remove the solvent, terminate the reaction, operating at a pressure of 0.8bar and at a temperature of 60 ℃. The mixed gas of benzene, ethyl acetate and hydrogen iodide is obtained at the top. The crude diiodosilane material containing diiodosilane, phenylsilane and monoiodosilane is obtained at the bottom. The mixed gas at the top of the first vapor-liquid separator V101 is introduced into the second vapor-liquid separator V102 to recover the solvent, and the operation pressure is 0.8bar and the operation temperature is 50 ℃. Hydrogen iodide and ethyl acetate were obtained on top. The benzene recovery solvent material dissolved with a small amount of ethyl acetate impurity is obtained at the bottom. The recovered solvent feed may be used to make up for solvent losses in the first reactor R101 and the second reactor R102. The crude diiodosilane material obtained at the bottom of the first vapor-liquid separator V101 enters a debenzolization column T101 for removing phenylsilane. The operating temperature is 55 ℃, the operating pressure is 35kPa, the theoretical plate number is 10, and the reflux ratio is 25. Phenylsilane is withdrawn overhead and recycled to the first reactor R101 to increase phenylsilane conversion. And (3) extracting a mixed material of diiodosilane and monoiodosilane from the tower bottom. The tower bottom material of the debenzolization tower T101 enters a diiodosilane refining tower T102 for removing byproduct monoiodosilane. The operating temperature is 70 ℃, the operating pressure is 40kPa, the theoretical plate number is 15, and the reflux ratio is 25. The byproduct monoiodo silane is extracted from the tower top, and the high-purity diiodosilane with the purity of 99.9992wt% is extracted from the tower bottom, wherein the monoiodo silane content is 5ppm, the benzene content is 2ppm and the phenylsilane content is 1ppm. The volume ratio of monoiodosilane and ethyl acetate which are byproducts extracted from the top of the debenzolization silane tower T101 is 1:0.03 to obtain a monoiodo silane mixed solution. Mixing monoiodosilane mixed solution and iodine solution according to a mass flow ratio of 1:1.5 is introduced into a second reactor R102 to convert the byproduct monoiodo silane into product diiodosilane, so as to improve the yield of diiodosilane. The monoiodosilane in the reaction was in excess to complete the iodine reaction. The reaction temperature is-20 ℃, the reaction pressure is normal pressure, and the reaction residence time is 9 hours. The output from the second reactor R102 containing 35.2% by weight of diiodosilane, 8.9% by weight of monoiodosilane, 5.0% by weight of hydrogen iodide, 50.6% by weight of benzene, 0.3% by weight of ethyl acetate was obtained and recycled to the first vapor-liquid separator V101 to remove the solvent and terminate the reaction.
Example 3
And (3) filling the whole product line by using nitrogen to purge and replace the air of the product line. The volume ratio is 1:0.03 phenylsilane and ethyl acetate to obtain a phenylsilane mixed solution. The mass ratio is 1:1 is mixed with benzene to be dissolved to obtain iodine solution. 30kg/h of phenylsilane solution and 55kg/h of iodine solution are fed into the first reactor R101 for phenylsilane iodination, and phenylsilane in the reaction mixture is excessive so as to complete the iodine reaction. The reaction temperature is-10 ℃, the reaction pressure is normal pressure, and the reaction residence time is 10 hours. The output from the first reactor R101 was obtained containing 17.1% by weight of diiodosilane, 7.0% by weight of phenylsilane, 15.8% by weight of monoiodosilane, 3.7% by weight of hydrogen iodide, 56.1% by weight of benzene and 0.3% by weight of ethyl acetate. The material at the outlet of the first reactor R101 was fed to a first vapor-liquid separator V101 to remove the solvent, terminate the reaction, operating at a pressure of 0.8bar and at a temperature of 60 ℃. The mixed gas of benzene, ethyl acetate and hydrogen iodide is obtained at the top. The crude diiodosilane material containing diiodosilane, phenylsilane and monoiodosilane is obtained at the bottom. The mixed gas at the top of the first vapor-liquid separator V101 is introduced into the second vapor-liquid separator V102 to recover the solvent, and the operation pressure is 0.8bar and the operation temperature is 50 ℃. Hydrogen iodide and ethyl acetate were obtained on top. The benzene recovery solvent material dissolved with a small amount of ethyl acetate impurity is obtained at the bottom. The recovered solvent feed may be used to make up for solvent losses in the first reactor R101 and the second reactor R102. The crude diiodosilane material obtained at the bottom of the first vapor-liquid separator V101 enters a debenzolization column T101 for removing phenylsilane. Operating temperature 60 ℃, operating pressure 50kPa, theoretical plate number 20, reflux ratio 25. Phenylsilane is withdrawn overhead and recycled to the first reactor R101 to increase phenylsilane conversion. And (3) extracting a mixed material of diiodosilane and monoiodosilane from the tower bottom. The tower bottom material of the debenzolization tower T101 enters a diiodosilane refining tower T102 for removing byproduct monoiodosilane. The operating temperature is 80 ℃, the operating pressure is 50kPa, the theoretical plate number is 20, and the reflux ratio is 25. The byproduct monoiodo silane was recovered at the top of the column, and 34.91kg/h of high-purity diiodosilane having a purity of 99.9994wt% was recovered at the bottom of the column, 3ppm monoiodo silane, 2ppm benzene and 1ppm phenylsilane. The volume ratio of monoiodosilane and ethyl acetate which are byproducts extracted from the top of the debenzolization silane tower T101 is 1:0.03 to obtain a monoiodo silane mixed solution. Mixing monoiodosilane mixed solution and iodine solution according to a mass flow ratio of 1:1.5 is introduced into a second reactor R102 to convert the byproduct monoiodo silane into product diiodosilane, so as to improve the yield of diiodosilane. The monoiodosilane in the reaction was in excess to complete the iodine reaction. The reaction temperature is 0 ℃, the reaction pressure is normal pressure, and the reaction residence time is 10 hours. The output from the second reactor R102 containing 36.1% by weight of diiodosilane, 9.3% by weight of monoiodosilane, 6.2% by weight of hydrogen iodide, 48.1% by weight of benzene, 0.3% by weight of ethyl acetate was obtained and recycled to the first vapor-liquid separator V101 to remove the solvent and terminate the reaction.
The specific reaction equation involved in the application is as follows:
a first reactor:
Ph-SiH 3 +I 2 →Ph-SiH 2 I+HI
Ph-SiH 2 I+HI→Ph-H+SiH 2 I 2
Ph-SiH 3 +HI→SiH 3 I+Ph-H (side reaction)
A second reactor:
SiH 3 I+I 2 →SiH 2 I 2 +HI
in the above embodiments, benzene is used as the aromatic organic solvent, but the method is not limited to benzene, benzene homologues such as toluene, xylene, etc., and the solvent substitution is a common technical means for those skilled in the art, and the specific embodiments are not supplemented herein; similarly, in the above embodiments, the oxygen-containing organic compound catalyst is ethyl acetate, but is not limited to ethyl acetate, and one or more of ethyl formate, butyl acetate, ethanol and acetone can play a catalytic role.
In the embodiment of the present application, the reflux ratio of the debenzolization column and diiodosilane purification column is preferably 25, and may be any reflux ratio of 5 to 100.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (8)
1. A preparation device of high-purity diiodosilane is characterized in that: comprises a first reactor (R101), a first vapor-liquid separator (V101), a second vapor-liquid separator (V102), a debenzolization silane tower (T101), a diiodosilane refining tower (T102), a mixer (M101) and a second reactor (R102); the bottom of the first reactor (R101) is communicated with the first vapor-liquid separator (V101), the bottom of the first vapor-liquid separator (V101) is communicated with the deironing silane tower (T101), the top of the first vapor-liquid separator (V101) is communicated with the second vapor-liquid separator (V102), the bottom of the second vapor-liquid separator (V102) is respectively communicated with the first reactor (R101) and the second reactor (R102), the bottom of the deironing silane tower (T101) is communicated with the diiodo silane refining tower (T102), the top of the deironing silane tower (T101) is communicated with the first reactor (R101), the bottom of the diiodo silane refining tower (T102) is used for discharging high-purity diiodosilane, the top of the diiodo silane refining tower (T102) is communicated with the mixer (M101), the mixer (M101) is communicated with the second reactor (R102), and the outlet material at the bottom of the second reactor (R102) is communicated with the first reactor through a pipeline.
2. A process for the preparation and purification of high purity diiodosilane, based on the apparatus of claim 1, characterized in that it comprises the following steps:
1. reaction of raw materials
Filling by utilizing inert gas purging, and then introducing a mixed solution of phenylsilane and an oxygen-containing organic catalyst and a mixed solution of iodine and an aromatic organic solvent into a first reactor (R101) to complete the reaction, wherein the bottom material of the first reactor (R101) is a mixed material of diiodosilane, phenylsilane, monoiodosilane, hydrogen iodide, the oxygen-containing organic catalyst and the aromatic organic solvent;
2. first step vapor-liquid separation
Introducing the materials in the first reactor (R101) into a first vapor-liquid separator (V101), obtaining a mixed gas of an aromatic organic solvent, an oxygen-containing organic catalyst and hydrogen iodide at the top of the first vapor-liquid separator (V101), and obtaining a crude diiodosilane material containing diiodosilane, phenylsilane and monoiodosilane at the bottom of the first vapor-liquid separator (V101);
3. second step vapor-liquid separation
Introducing the mixed gas at the top of the first vapor-liquid separator (V101) into a second vapor-liquid separator (V102), obtaining hydrogen iodide and an oxygen-containing organic catalyst at the top of the second vapor-liquid separator (V102), obtaining a recovered solvent material containing oxygen-containing organic catalyst impurities at the bottom, wherein the recovered solvent material is used for supplementing the solvent loss of the first reactor (R101) and the second reactor (R102);
4. debenzolization process
The bottom material of the first vapor-liquid separator (V101) enters a benzene-removing silane tower (T101), and benzene silane extracted from the top of the benzene-removing silane tower (T101) is introduced into a first reactor (R101); the tower kettle of the debenzolization tower (T101) is used for extracting a mixed material of diiodosilane and monoiodosilane;
5. refining and purifying
The tower kettle material of the debenzolized silane tower (T101) enters a diiodosilane refining tower (T102); the tower bottom of the diiodosilane refining tower (T102) is used for extracting high-purity periodate silane, and the tower top is used for extracting byproduct monoiodosilane;
6. yield filling
The monoiodo silane extracted from the top of the diiodo silane refining tower (T102) is mixed with an oxygen-containing organic matter catalyst through a mixer (M101) and is introduced into a second reactor (R102), the second reactor (R102) converts byproduct monoiodo silane into diiodo silane to obtain products of diiodo silane, unreacted monoiodo silane, hydrogen iodide, an aromatic organic solvent and the oxygen-containing organic matter catalyst, the products of diiodo silane are introduced into a first vapor-liquid separator (V101), and finally the diiodo silane is extracted from the tower kettle of the diiodo silane refining tower (T102).
3. The method for preparing and purifying high-purity diiodosilane according to claim 2, wherein the method comprises the following steps: the reaction temperature of the first reactor (R101) is-50 to-10 ℃, the reaction pressure is normal pressure, and the reaction residence time is 8-10 hours.
4. The method for preparing and purifying the high-purity diiodosilane according to claim 2, wherein the method is characterized in that: the reaction temperature of the second reactor (R102) is-30-0 ℃, the reaction pressure is normal pressure, and the reaction residence time is 8-10 hours.
5. The method for preparing and purifying high-purity diiodosilane according to claim 2, wherein the method comprises the following steps: the oxygen-containing organic compound catalyst comprises one or more of ethyl acetate, ethyl formate, butyl acetate, ethanol and acetone.
6. The method for preparing and purifying high-purity diiodosilane according to claim 2, wherein the method comprises the following steps: the aromatic organic solvent is one or more of benzene, toluene and xylene.
7. The method for preparing and purifying high-purity diiodosilane according to claim 2, wherein the method comprises the following steps: the operating temperature of the debenzolization silane tower (T101) is 50-60 ℃, the operating pressure is 20-50kPa, and the theoretical plate number is 5-20.
8. The method for preparing and purifying high-purity diiodosilane according to claim 2, wherein the method comprises the following steps: the diiodosilane refining tower (T102) has the operating temperature of 60-80 ℃, the operating pressure of 20-50kPa and the theoretical plate number of 10-20.
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