CN117654087A - Device and method for preparing electronic grade silane by catalytic reaction rectification - Google Patents
Device and method for preparing electronic grade silane by catalytic reaction rectification Download PDFInfo
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 239000012535 impurity Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 claims abstract description 32
- 239000000945 filler Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 18
- 238000005498 polishing Methods 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 13
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- 239000003463 adsorbent Substances 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 23
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 21
- 239000005052 trichlorosilane Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 12
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 10
- 239000005049 silicon tetrachloride Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000066 reactive distillation Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 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 2
- 238000005065 mining Methods 0.000 claims 3
- 230000008569 process Effects 0.000 abstract description 15
- 239000005046 Chlorosilane Substances 0.000 abstract description 7
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000006096 absorbing agent Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 239000000460 chlorine Substances 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 7
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 6
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910003902 SiCl 4 Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 229910021332 silicide Inorganic materials 0.000 description 3
- -1 silicon alloy method Chemical compound 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- WIZNWIPCUYSDLF-UHFFFAOYSA-N [B].Cl[SiH](Cl)Cl Chemical compound [B].Cl[SiH](Cl)Cl WIZNWIPCUYSDLF-UHFFFAOYSA-N 0.000 description 1
- GLFAEFVIKYUOJK-UHFFFAOYSA-N [B].[Cl] Chemical compound [B].[Cl] GLFAEFVIKYUOJK-UHFFFAOYSA-N 0.000 description 1
- GJMMXPXHXFHBPK-UHFFFAOYSA-N [P].[Cl] Chemical compound [P].[Cl] GJMMXPXHXFHBPK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 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
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention relates to a device and a method for preparing electronic grade silane by catalytic reaction rectification, which take chlorosilane as a raw material, enter a silane reaction rectifying tower (2) after impurity removal by an absorber (1), and enter a primary refrigerator (3) and a secondary refrigerator (4) for crude separation from the crude silane at the top of the tower, and enter a side line of a silane separating tower (4) for extracting the electronic grade silane. The adsorber (1) is filled with an adsorbent to control the contents of boron, phosphorus, total metals and hydrogen chloride impurities in the chlorosilane raw material; the silane reaction rectifying tower (2) is provided with a plurality of feed inlets, so that the concentration distribution of materials in a reaction section is optimized, and the disproportionation reaction is facilitated; the silane separating tower (4) adopts a discharging mode of liquid phase side extraction at the middle and upper part and performs polishing treatment on the part contacted with the material, so that an electronic grade product can be directly obtained. The invention has the characteristics of high catalytic rectification efficiency, short process flow and long service life of catalytic filler.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a device and a method for producing electronic grade silane by catalytic reaction rectification of trichlorosilane.
Background
Silanes, also known as monosilanes, of the formula SiH 4 . Silane is a colorless gas that reacts strongly with oxygen in different temperature ranges and is unstable and rapidly breaks down into silicon and hydrogen at 600 ℃. Although silane is chemically active, it is the most widely used electron gas with the greatest impact. Silanes can be used to prepare polysilicon. The polysilicon prepared by the silane method has the advantages of high purity and low boron and phosphorus contents, and the process flow is simple, no corrosive gas is generated, equipment corrosion is less, and production cost is low. In the semiconductor microelectronics industry, silanes are useful in the preparation of various microelectronic thin films, such as crystallites, silicon oxides, monocrystalline films, metal silicides, etc., as well as in the preparation of semiconductor devices (silicon carbide, gallium arsenide, etc.) and quantum well materials. Because the metal silicide produced by silane has the characteristics of high purity and fine regulation, the metal silicide becomes an important electron special gas which cannot be replaced by other silicon sources.
SiH 4 There are many methods for preparing (B) silicon, such as silicon alloy method, hydride reduction method, direct hydrogenation synthesis method of silicon and chlorosilane disproportionation method. The chlorosilane disproportionation method is to use trichlorosilane (SiCl) 3 ) Raw material is obtained SiH by disproportionation method 4 At the same time, silicon tetrachloride (SiCl) 4 ). Because SiCl 4 Can be converted into SiCl after hydrogenation 3 The method is used as a raw material, so that the whole process flow is simple, no waste is generated, the method belongs to a green process, and the method becomes a main stream process for preparing the current silane.
The disproportionation of trichlorosilane is a cascade of reversible reactions, except SiH 4 And SiCl 4 In addition to dichlorosilane (SiH) 2 Cl 2 ) And trichlorosilane (SiH) 3 Cl) intermediate product. In patent US4340574, a process for continuously producing silane by using chlorosilane as a raw material and a fixed bed is proposed, and a disproportionation product is separated and refined by rectification to obtain a silane product. In order to break the limitation of reversible reaction balance and improve the conversion rate of disproportionation reaction, a technological process for continuously producing silane by adopting a reactive distillation technology is proposed for the first time in patent US6905576, and materials extracted from a reactive distillation tower are refined by a silane separation tower to obtain a silane product. Patent CN103172071 uses SiCl based on the characteristics of each component in the disproportionation reaction 4 And (3) taking the mixture as an absorption solvent, and refining the material extracted from the top of the reaction rectifying tower by a fixed bed adsorption process to obtain a silane product. Patent CN103241743 proposes a process for continuously producing silane by a reactive distillation method, wherein raw material purification and product separation equipment are respectively added before and after a silane reactive distillation tower to ensure the purity of a silane product and silicon tetrachloride byproducts. Due to SiH 4 、SiH 2 Cl 2 、SiH 3 The boiling point of Cl is low, the requirement on refrigerant is high during liquefaction, the energy consumption is high, and the patents CN106241813 and CN115321540 utilize the characteristic that the boiling point difference between silane and other components in a reaction system is large, and a multistage condenser is adopted and is matched with cold coals with different temperatures and tastes, so that the gas phase at the top of the reactive rectifying tower is subjected to multistage partial condensation, the cryogenic load is reduced, and the operation cost and the energy consumption are effectively reduced.
The core of the catalytic reaction rectification design is to ensure that the reaction and rectification processes are matched with each other. If the catalytic reaction efficiency is reduced, the single pass conversion is reduced, the amount of unreacted substances is increased, the circulation flow in the reactive distillation system is increased, and the energy consumption of the system is correspondingly increased. The catalytic reaction efficiency of the reaction section is related to the concentration distribution of the reaction section and the activity of the catalyst, but in the process research of preparing silane by catalytic reaction rectification, the core problems are not focused, so that the service life of the catalyst is short, and the single pass conversion rate of a reaction rectifying tower is low. In addition, in the wet process of the electronic industry, electronic chemicals are key materials, and the control of the metal ion content is important to ensure the product yield. The current silane preparation technology cannot control the metal ion content from the source, so that a purification unit is needed to obtain an electronic grade product, which clearly prolongs the process flow and increases the production cost.
Disclosure of Invention
The invention aims at improving the problems existing in the prior art, namely the technical problem to be solved by the invention is a device and a method for preparing electronic grade silane by catalytic reaction rectification, and the technical problems are that the service life of catalytic filler is prolonged, the catalytic rectification efficiency is improved, the content of metal ions is controlled from the source, and the preparation process flow of the electronic grade silane is shortened by optimizing the process and equipment.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the trichlorosilane is used as a raw material, firstly enters a fixed bed adsorption column (1) for adsorption impurity removal, removes boron, phosphorus, metal and hydrogen chloride impurities in the raw material, and then enters a feed inlet at the middle lower part A of a reaction section of a silane reaction rectifying tower (2); the bottom of the silane reaction rectifying tower (2) is provided with a reboiler, the top of the tower is provided with a condenser, the reaction rectifying tower is sequentially provided with a rectifying section, a reaction section and a stripping section from top to bottom, and the reaction section is filled with catalytic filler. SiHCl (SiHCl) 3 The following three-step disproportionation reaction occurs in the reaction section:
2SiHCl 3 ＝SiH 2 Cl 2 +SiCl 4
2SiH 2 Cl 2 ＝SiH 3 Cl+SiHCl 3
2SiH 3 Cl＝SiH 4 +SiH 2 Cl 2
the top steam of the reactive rectifying tower is partially condensed in a condenser, part of the condensate is returned to the tower as reflux liquid, and the other part of the condensate is sent to a feed inlet A at the middle lower part of the reaction section. SiH from overhead condenser 4 、SiH 3 Cl、SiH 2 Cl 2 、SiHCl 3 The mixed gas is sequentially sent into a primary refrigerator (3) and a secondary refrigerator (4), and SiCl is extracted from the bottom of the tower 4 . First-stage deep cooler3) And (3) extracting condensate at the temperature of minus 15-25 ℃, extracting condensate at the temperature of minus 40-minus 15 ℃ by a secondary refrigerator (4), and respectively returning the condensate to different feed inlets at the upper middle part of the reaction section of the silane reaction rectifying tower (2). The produced gas phase material of the secondary refrigerator (4) is pressurized by a compression system (5) and then is sent to a silane separation tower (6); the silane separation tower (6) is provided with a reboiler and a condenser, low-boiling-point light components are extracted from the tower top through vapor-liquid mass transfer in the rectifying tower, electronic-grade silane products are extracted from the upper side line, and chlorosilane components are extracted from the tower bottom and returned to the feed inlet B at the upper part in the reaction section of the silane reaction rectifying tower (2).
Further, the fixed bed adsorption column (1) is filled with one or more combined adsorbents selected from resin, activated carbon, molecular sieve and activated alumina;
further, after the trichlorosilane passes through the fixed bed adsorption column (1), the content of the trichlorosilane boron impurities is not higher than 100ppb, the content of the phosphorus impurities is not higher than 50ppb, the content of the total metal impurities is not higher than 100ppb, and the content of the hydrogen chloride impurities is not higher than 10ppm. After the content of the impurities in the raw materials is reduced, the occupation rate of the impurities on active groups of the catalytic filler is obviously reduced, and the service life of the catalytic filler is effectively prolonged.
Further, the boron impurity is a generic name of boron hydrogen compound, boron chlorine compound and other boron-containing compounds, and the boron impurity content after adsorption is not higher than 100ppb, preferably not higher than 10ppb;
further, the phosphorus impurity is a generic name of phosphorus hydrogen compound, phosphorus chlorine compound and other phosphorus-containing compounds, and the content of the phosphorus impurity after adsorption is not higher than 50ppb, preferably not higher than 5ppb;
further, the total metal impurities are the generic names of iron, aluminum, calcium, magnesium, manganese and the like, and the total metal impurity content after adsorption is not higher than 100ppb, preferably not higher than 10ppb;
further, the hydrogen chloride impurity refers to a hydrogen chloride component, and the content of the hydrogen chloride impurity after adsorption is not more than 10ppm, preferably not more than 1ppm.
Further, the silane reaction rectifying tower is sequentially provided with a stripping section of 10-50 theoretical plates, a reaction section of 4 sections filled with catalytic filler and a rectifying section of 4-20 theoretical plates from bottom to top, wherein the catalytic filler of each section is 2-6 m high, and A, B, C feed inlets are arranged between the catalytic filler sections from bottom to top.
Further, part of condensate from the condenser at the top of the silane reaction rectifying tower is returned into the tower from the reflux port, and the ratio of the reflux liquid to the total condensate is 0.5-0.95. A part of the mixture is sent to the feed inlet A at the middle upper part of the reaction section.
Further, the gas phase material from the condenser at the top of the silane reaction rectifying tower passes through the first-stage refrigerator and then is sent to the second-stage refrigerator, the liquid phase condensate of the first-stage refrigerator returns to the reaction rectifying tower from the port C, and the liquid phase condensate of the second-stage refrigerator returns to the reaction rectifying tower from the port B, so that disproportionation reaction is continuously carried out, and the conversion rate of the reaction is improved.
Furthermore, a side sampling port is arranged at the upper part of the feeding port of the silane separation tower, and a liquid phase side sampling discharging mode is adopted to realize light and heavy removal. The light components are discharged from the top of the tower, the components are delivered to the feed inlet B of the reactive rectifying tower from the bottom of the tower,
furthermore, the parts above the side sampling port of the silane separation tower and contacted with materials (comprising the inner wall of the tower, the inner parts of the tower, the inner wall of a gas phase pipe at the top of the tower, the material side of a condenser at the top of the tower, the inner wall of a reflux tank, the inner wall of a reflux pipe and corresponding accessories) are polished.
Further, the polishing treatment includes manual polishing, mechanical polishing, chemical polishing, electrolytic polishing and plasma polishing, and the roughness of the surface after the polishing treatment is required to be not more than 1 μm, preferably not more than 0.4 μm.
Compared with the prior art, the invention has the following effects:
(1) The raw material trichlorosilane is subjected to fixed bed adsorption to remove impurities, the impurity content in the raw material is reduced, the occupancy rate of active groups in the catalytic filler is reduced, and the service life of the catalytic filler is obviously prolonged.
(2) The condensate of the tower top condenser, the first-stage deep cooler and the second-stage deep cooler of the reaction rectifying tower and the kettle liquid of the silane separation tower are respectively returned to different feed inlet positions of the silane reaction rectifying tower, so that the concentration distribution of materials in a reaction section is optimized, the disproportionation reaction is facilitated, and the single pass conversion rate can be improved by 8-15%.
(3) The raw material trichlorosilane is pretreated by adopting fixed bed adsorption, the metal content is controlled from the source, an electronic grade silane product can be obtained without a subsequent purification unit, and the process flow is shortened.
(4) All equipment surfaces contacted with silane are polished, so that the influence of external equipment factors on electronic grade silane products can be greatly reduced, and the metal impurity content of the silane products is ensured not to exceed the standard.
Drawings
FIG. 1 is a process flow diagram for preparing electronic grade silane by catalytic reactive distillation;
wherein, 1 is a fixed bed adsorption column, 2 is a silane reaction rectifying tower, 3 is a primary refrigerator, 4 is a secondary refrigerator, 5 is a compression system, and 6 is a silane separation tower.
Detailed Description
In order to make the above features and advantages of the present invention more comprehensible, embodiments accompanied with figures (fig. 1) are described in detail below.
The production process flow for preparing electronic grade silane by catalytic reaction rectification as shown in fig. 1 comprises a fixed bed adsorption column 1, a silane reaction rectification column 2, a primary refrigerator 3, a secondary refrigerator 4, a compression system 5, a silane separation column 6 and rectification column auxiliary equipment (reboiler and condenser), and the specific flow is as follows.
Firstly, introducing trichlorosilane raw materials into a fixed bed adsorption column 1 for adsorption impurity removal, removing boron, phosphorus, metal and hydrogen chloride impurities in the raw materials, and then introducing the raw materials into a feed inlet A of a silane reaction rectifying tower; the bottom of the silane reaction rectifying tower 2 is provided with a reboiler, the top of the tower is provided with a condenser, the reaction rectifying tower is sequentially provided with a rectifying section, a reaction section and a stripping section from top to bottom, and the reaction section is filled with catalytic filler. Trichlorosilane undergoes three-step serial disproportionation reaction in the silane reaction rectifying tower 2.
The top steam of the reactive rectifying tower is partially condensed in a condenser, part of the condensate is returned to the tower as reflux liquid, and the other part of the condensate is sent to a feed inlet A at the middle lower part of the reaction section. SiH from overhead condenser 4 、SiH 3 Cl、SiH 2 Cl 2 、SiHCl 3 The mixed gas is sequentially sent to a primary refrigerator 3 and a secondary refrigerator 4, and silicon tetrachloride is extracted from the bottom of the tower. The condensate of the primary refrigerator 3 returns to the C feed inlet of the silane reaction rectifying tower, and the condensate of the secondary refrigerator 4 returns to the B feed inlet of the silane reaction rectifying tower.
The gas phase materials produced by the secondary refrigerator 4 are pressurized by the compression system 5 and then sent to the silane separation tower 6. The silane separation tower 6 is provided with a reboiler and a condenser, low-boiling-point light components are extracted from the top of the rectifying tower through vapor-liquid mass transfer, electronic-grade silane products are extracted from the upper side line, and chlorosilane components are extracted from the bottom of the rectifying tower and returned to the feed inlet B of the silane reaction rectifying tower 2.
Example 1:
the trichlorosilane raw material is from a trichlorosilane synthesis device, is analyzed by an ICP-MS analysis method, the boron impurity content is 315ppb, the phosphorus impurity content is 193ppb, the total metal impurity content is 1398ppb, and the GC analysis method is used for analysis, so that the hydrogen chloride content is 83ppm.
500kg/h of trichlorosilane continuously enters a fixed bed adsorption column (phi 400mm multiplied by 4000 mm), the effective volume is 525L, 4-level adsorption beds are arranged, and the first level is filled with 80L of chelating resin; the second level is filled with 100L of modified activated carbon; the third stage is filled with ion resin 80L; and the fourth stage is filled with active carbon 100L. After stable flow, the sample was analyzed by ICP-MS analysis with 48ppb of boron impurity, 17ppb of phosphorus impurity, 87ppb of total metal impurity, and by GC analysis with undetected hydrogen chloride.
The diameter of the silane reaction rectifying tower is 500mm, 15 theoretical plates of the rectifying section and 20 theoretical plates of the stripping section are arranged, 22m catalytic filler in the form of bundling is filled in the middle, the heights of the catalytic filler in each section from top to bottom are 5m, 6m and 6m respectively, and the total height of the catalytic filler is 4.32m 3 . The feed inlet A is positioned between the third section catalytic filler and the fourth section catalytic filler from top to bottom, the feed inlet B is positioned between the second section catalytic filler and the third section catalytic filler from top to bottom, and the feed inlet C is positioned between the first section catalytic filler and the second section catalytic filler from top to bottom.
The diameter of the silane separation tower is 200mm, 30 theoretical plates of the rectifying section are arranged, 30 theoretical plates of the stripping section are arranged, and the side sampling port is positioned in the middle of the rectifying section. The tower top is directly connected with a vertical fixed tube plate condenser, and freon at-45 ℃ is used as a cold source. Polishing the inner wall of the rectifying tower above the feed inlet, the inner wall of a tube array, which is in contact with materials, of a flow-through sieve tray, a condenser, a side line extraction pipeline and the inner wall of a silane product receiving tank, wherein the roughness is 0.4 mu m.
After the silane reaction rectifying tower and the silane separating tower stably run, the condenser non-condensing flow rate at the top of the silane reaction rectifying tower is 123.3kg/h, wherein the trichlorosilane content is 23.3wt%, and the single pass conversion rate of the silane reaction rectifying tower is 94.5 percent.
TABLE 1 example 1 Material information for the main stream (I)
TABLE 2 example 1 Material information for the main stream (II)
The upper side line of the middle-upper part of the silane separating tower is used for extracting 29.31kg/h of electronic grade silane product. After stable operation for 360 hours, samples were analyzed by ICP-MS analysis, and the total metal impurity content in the silane product was 0.163ppb.
After 100 days of continuous operation, the average value of the yield of the electronic grade silane product is reduced from the original 29.31kg/h to 28.82kg/h, and the absolute value of the yield reduction is 0.49kg/h. When the yield drops to 70% of the design value, the catalytic packing is considered to need replacement, from which the service life of the catalyst is calculated to be 4.9 years.
Example 2:
the trichlorosilane raw material is from a trichlorosilane crude distillation device, and is analyzed by an ICP-MS analysis method, the boron impurity content is 43ppb, the phosphorus impurity content is 38ppb, the total metal impurity content is 219ppb, and the hydrogen chloride content is 0.0036% by adopting a GC analysis method.
400kg/h of trichlorosilane continuously enters a fixed bed adsorption column with the size of 400mm multiplied by 4000mm and the effective volume of 525L, and 200L of resin, 100L of activated carbon and 160L of activated alumina are filled in the fixed bed adsorption column by adopting a mixed loading scheme. After stable flow, the sample was analyzed by ICP-MS analysis, the boron impurity content in the outlet material was 22ppb, the phosphorus impurity content was 35ppb, the total metal impurity content was 69ppb, and the sample was analyzed by GC analysis, the hydrogen chloride content was 0.0005%.
The diameter of the silane reaction rectifying tower is 500mm, 18m regular catalytic filler forms of catalytic filler are filled in the tower, and the heights of each section of catalytic filler from top to bottom are 3m, 5m and 5m respectively, and the total height of the catalytic filler is 3.54m 3 . The arrangement of the feed port ABC is the same as in example 1.
The diameter of the silane separation tower is 200mm, 30 theoretical plates of the rectifying section are arranged, 30 theoretical plates of the stripping section are arranged, and the side sampling port is arranged in the middle of the rectifying section. The tower top is directly connected with a vertical fixed tube plate condenser, and freon at-45 ℃ is used as a cold source. Polishing the inner wall of the rectifying tower above the feed inlet, the inner wall of a tube array, a side line extraction pipeline and the inner wall of a silane product receiving tank, wherein the tube array is in contact with materials, the tube array is in contact with a condenser, and the roughness is 0.25 mu m.
After the silane reaction rectifying tower and the silane separating tower stably run, the condenser non-condensing flow rate at the top of the silane reaction rectifying tower is 123.9kg/h, wherein the trichlorosilane content is 13.7wt%, and the single pass conversion rate of the silane reaction rectifying tower is calculated to be 95.8%.
TABLE 3 example 2 Material information for the main stream (I)
TABLE 4 example 2 Material information for the main stream (II)
The upper side line of the middle-upper part of the silane separating tower is used for extracting 23.45kg/h of electronic grade silane product. After stable operation for 360 hours, samples were analyzed by ICP-MS analysis, and the total metal impurity content in the silane product was 0.135ppb.
After 100 days of continuous operation, the average value of the yield of the electronic grade silane product is reduced from the original 23.45kg/h to 23.08kg/h, and the absolute value of the yield reduction is 0.37kg/h. When the yield drops to 70% of the design value, the catalytic packing is considered to need replacement, from which the service life of the catalyst is calculated to be 5.2 years.
While the present invention has been described with reference to the embodiments, it will be apparent to those skilled in the art that the present invention may be practiced with modification and alteration and combination of the systems and methods described herein without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be included within the spirit, scope and content of the invention.
Claims (8)
1. The method for preparing the electronic grade silane by catalytic reaction rectification is characterized by comprising the following steps of:
(1) Raw material trichlorosilane is fed from the lower part of the fixed bed adsorption column, and then discharged from the upper part; the fixed bed adsorption column is filled with an adsorbent for removing impurities such as boron, phosphorus, metal, hydrogen chloride and the like in the raw materials;
(2) Delivering the material at the outlet of the fixed bed adsorption column to a middle feed inlet of a silane reaction rectifying tower, and performing a series of disproportionation reaction on trichlorosilane under the action of a catalyst to generate dichlorosilane, trichlorosilane, silicon tetrachloride and silane; after passing through a part of condenser at the top of the reactive rectifying tower, a part of the material is sent to a reflux port at the top of the reactive rectifying tower to be used as reflux liquid, and a part of the material is sent to a feeding port at the middle part; the gas phase material from the tower top condenser is sent to a subsequent primary deep cooler, and silicon tetrachloride is extracted from the tower bottom;
(3) The gas phase material which is not condensed at the top of the silane reaction rectifying tower is further condensed in a first-stage cryocooler, and the gas phase material which comes out of the first-stage cryocooler is sent to a second-stage cryocooler for continuous condensation; liquid phase materials from the primary refrigerator and the secondary refrigerator are respectively returned to corresponding feed inlets of the silane reaction rectifying tower;
(4) The gas phase outlet material from the secondary refrigerator is compressed and pressurized and then sent to a silane separation tower; light components are extracted from the top of the silane separation tower, electronic grade silane products are extracted from the upper middle part of the tower, and materials extracted from the tower bottom are returned to the silane reaction rectifying tower.
2. The method of claim 1, wherein the adsorbent in step (1) is one or a combination of several of resin, activated carbon, molecular sieve, activated alumina.
3. The method according to claim 1, wherein the silane reaction rectifying tower in the step (2) is provided with a stripping section of 10-50 theoretical plates, 4 reaction sections filled with catalytic filler and 4-20 rectifying sections of theoretical plates from bottom to top, and the catalytic filler in each section is 2-6 m high.
4. A method according to claim 1 or 3, characterized in that the catalytic packing section of the silane reaction rectifying column is provided with A, B, C three feed openings from bottom to top, the material from the fixed bed adsorption column being fed from opening a.
5. The method according to claim 1, wherein in the step (2), a part of liquid phase material of a top condenser of the reactive distillation column is returned into the column from a reflux port, the ratio of reflux liquid to total condensate is 0.5-0.95, and a part of liquid phase material is returned into the column from an A port; the liquid phase material of the primary refrigerator is fed from the C port, and the liquid phase material of the secondary refrigerator is fed from the B port.
6. The method according to claim 1, wherein the material extracted from the bottom of the silane separation column is returned to the feed inlet of the reactive distillation column B.
7. The method according to claim 1, wherein the upper part of the feed inlet of the silane separation tower is provided with a side mining port, and the part above the side mining port, which is in contact with the material, is subjected to polishing treatment; the part above the side mining port contacted with the materials comprises a tower inner wall, a tower inner part, a tower top gas phase pipe inner wall, a tower top condenser material side, a reflux tank, a reflux pipe inner wall and corresponding accessories.
8. The method of claim 7, wherein the polishing treatment comprises one or more of manual polishing, mechanical polishing, chemical polishing, electrolytic polishing, and plasma polishing, and the roughness requirement of the polishing treatment is not greater than 1 μm.
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