CN117401685B - Method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride - Google Patents
Method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride Download PDFInfo
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- 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 title claims abstract description 66
- 239000005049 silicon tetrachloride Substances 0.000 title claims abstract description 66
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000005052 trichlorosilane Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000376 reactant Substances 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000003463 adsorbent Substances 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229920002401 polyacrylamide Polymers 0.000 claims description 12
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- 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 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 49
- 239000000428 dust Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000005046 Chlorosilane Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005484 gravity Effects 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
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
- C01B33/10742—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/10778—Purification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to the technical field of chemical industry, and provides a method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride, which comprises the following steps: s1: introducing hydrogen chloride gas into the silicon powder under the protection of nitrogen, and adding a supported catalyst to react to obtain a reactant; s2: carrying out dry dedusting on the reactant to obtain a dedusted reactant; s3: condensing the dedusted reactant to obtain a condensate; s4: rectifying and separating the condensed product to obtain a first separated product, a second separated product and a third separated product respectively; s5: and respectively adding adsorbents into the second separation product and the third separation product to adsorb impurities, thereby obtaining high-purity trichlorosilane and silicon tetrachloride products. By the technical scheme, the problems that the cost for producing trichlorosilane and silicon tetrachloride in the prior art is high, the process is complex, the industrial production is not facilitated, and the purity of the trichlorosilane and silicon tetrachloride products is low are solved.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride.
Background
Trichlorosilane and silicon tetrachloride are mainly used for synthesizing organic silicon, alkyl, aryl and organic functional chlorosilane, are important production raw materials of polysilicon, are important intermediates for producing organic silicon products such as an organic silane coupling agent and the organic silicon such as the chlorine hydride, and are widely applied to the fields of semiconductors and photovoltaics. The high-purity trichlorosilane and silicon tetrachloride are purified, and the high-purity trichlorosilane and silicon tetrachloride are applied to the production of polysilicon or optical fiber materials, so that the industrial production efficiency is greatly improved.
In the production of trichlorosilane, a certain amount of silicon tetrachloride is produced, and in general, synthetic trichlorosilane contains chlorosilanes such as silicon tetrachloride and dichlorosilane, and impurities such as boron, phosphorus, arsenic and metal chlorides thereof. At present, the preparation of trichlorosilane mainly comprises a reaction method of silicon powder and hydrogen chloride, a silicon tetrachloride thermal hydrogenation method and an improved Siemens method. The silicon tetrachloride thermal hydrogenation method needs to be carried out at a higher temperature, and the reaction conditions are harsh. The improved Siemens method converts byproduct dichlorosilane into trichlorosilane in a reaction rectifying tower, has complex process operation, and has the characteristics of inflammability and explosiveness, thus being not beneficial to industrialized safe production. The reaction method of silicon powder and hydrogen chloride needs to add a metal nickel catalyst to obtain trichlorosilane and silicon tetrachloride products, the used metal nickel catalyst has higher cost, the industrial production is not facilitated, and the purity of the obtained trichlorosilane and silicon tetrachloride is low. Therefore, the development of a method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride, which has low production cost, simple process and high product purity and can be applied to industrial production, is extremely important.
Disclosure of Invention
The invention provides a method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride, which solves the problems that the cost for producing trichlorosilane and silicon tetrachloride is high, the process is complex, the industrial production is not facilitated, and the purity of trichlorosilane and silicon tetrachloride products is low in the prior art.
The technical scheme of the invention is as follows:
the invention provides a method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride, which comprises the following steps:
s1: introducing hydrogen chloride gas into the silicon powder under the protection of nitrogen, and adding a supported catalyst to react to obtain a reactant;
s2: carrying out dry dedusting on the reactant to obtain a dedusted reactant;
s3: condensing the dedusted reactant to obtain a condensate;
s4: rectifying and separating the condensed product to obtain a first separated product, a second separated product and a third separated product respectively, wherein the first separated product is separated at a rectifying temperature of 15-20 ℃, the second separated product is separated at a rectifying temperature of 35-40 ℃, and the third separated product is separated at a rectifying temperature of 60-70 ℃;
s5: and respectively adding adsorbents into the second separation product and the third separation product to adsorb impurities, thereby obtaining high-purity trichlorosilane and silicon tetrachloride products.
As a further technical scheme, the reaction temperature is 300-380 ℃ and the reaction time is 3-5 h.
As a further technical scheme, the addition amount of the supported catalyst is 10% -15% of the mass of the silicon powder.
As a further technical scheme, the pressure of the reaction is 0.1-0.3 MPa.
As a further technical scheme, the introducing speed of the hydrogen chloride gas is 0.25-0.30 m/s.
As a further technical scheme, the supported catalyst takes magnesium chloride as an active component and ZSM-5 molecular sieve as a carrier.
As a further technical scheme, in the supported catalyst, the mass loading of the active component is 10%.
As a further technical scheme, the temperature of the condensation is below 10 ℃.
As a further technical scheme, the adsorbent is polyacrylamide loaded on silica gel, and the mass loading capacity of the polyacrylamide is 5%.
As a further technical scheme, the adding amount of the adsorbent is 0.5% -1% of the mass of the silicon powder.
The working principle and the beneficial effects of the invention are as follows:
1. according to the invention, silicon powder is used as a raw material to react with hydrogen chloride gas, the reaction is carried out under the action of a supported catalyst, the reaction rate is obviously improved, the product yield is improved, the production cost is reduced, after the reaction is finished, silicon powder in the mixed product is removed by dry dedusting, unreacted hydrogen chloride and hydrogen are condensed and separated by condensation, mono-chloro-dihydro-silicon, tri-chloro-hydrogen-silicon and silicon tetrachloride are separated, and the condensed product is subjected to rectification separation to separate components, so that the tri-chloro-hydrogen-silicon and silicon tetrachloride products are accurately separated. By adding the adsorbent to adsorb phosphorus and boron impurities in the chlorosilane, the purity of trichlorosilane and silicon tetrachloride products is obviously improved. The whole process is simple, the production cost is low, the purity of the trichlorosilane and silicon tetrachloride products is high, and the industrial production is greatly facilitated.
2. In the invention, trichlorosilane is synthesized at the reaction temperature of 300-380 ℃, so that the decomposition of products caused by overhigh temperature is avoided, the reaction efficiency is improved, and the generation of byproducts is effectively reduced.
3. In the invention, in the reaction of synthesizing trichlorosilane, the supported catalyst with 10 percent of supported mass and active component magnesium chloride supported on a ZSM-5 molecular sieve carrier is catalyzed, so that the yield of trichlorosilane products is improved to be more than 88.92 percent, and the yield of silicon tetrachloride products is improved to be more than 9.13 percent.
4. According to the invention, polyacrylamide loaded on silica gel is used as an adsorbent, so that phosphorus and boron impurities in trichlorosilane and silicon tetrachloride are effectively removed, the purity of the trichlorosilane is improved to more than 99.999wt%, and the purity of the silicon tetrachloride is improved to more than 99.999 wt%.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples:
silicon powder: the mass content of silicon is 99.9%, and the average grain diameter is 1 μm;
ZSM-5 molecular sieve: bulk density is 0.4-0.6 g/mL, grain size is 1-5 mu m, silicon-aluminum ratio is 80mol/mol, and relative crystallinity is more than or equal to 90%;
silica gel: particle size of 125-425 μm, bulk density of more than or equal to 300g/L, pore volume of 0.8-1.3 mL/g, specific surface area of 300-550 m 2 /g；
Activated carbon: bulk specific gravity 0.58g/mL, granularity less than or equal to 200 meshes;
polyacrylamide: the molecular weight of the zwitterionic polyacrylamide is 500-1400 ten thousand, the ionic degree is 5-50%, the pH value is 1-14, and the solid content is more than or equal to 90%.
Example 1
Preparation of a supported catalyst: adding 20g of magnesium chloride into 100mL of ethanol, adding 200g of ZSM-5 molecular sieve carrier, carrying out ultrasonic impregnation for 10h, and drying to obtain the supported catalyst.
Preparing an adsorbent: adding 20g polyacrylamide into 100mL of water, heating to 80 ℃, adding 400g silica gel carrier, soaking for 6h, and drying to obtain the supported adsorbent.
Placing 100g of silicon powder in a reaction furnace under the protection of nitrogen, introducing hydrogen chloride gas at the speed of 0.25m/s, heating to 300 ℃, adding 10g of supported catalyst, and reacting for 5 hours under the pressure of 0.1MPa to obtain a reactant; the method comprises the steps of carrying out dust removal on reactants in a dry dust remover to obtain the reactants after dust removal, condensing the reactants after dust removal at the temperature of 5 ℃ to obtain condensed products, rectifying and separating the condensed products at the temperature of 15 ℃ and the temperature of 35 ℃ to obtain a first separation product (trichlorosilane), a second separation product (trichlorosilane) and a third separation product (silicon tetrachloride), and respectively adding 0.5g of load-type adsorbent into the second separation product and the third separation product to carry out adsorption and impurity removal to obtain 428.97g of trichlorosilane and 55.17g of silicon tetrachloride. The yield of trichlorosilane is 89.05 percent, and the yield of silicon tetrachloride is 9.13 percent. The purity of the trichlorosilane is 99.9999 percent and the purity of the silicon tetrachloride is 99.9998 percent by using a high performance liquid chromatograph for measurement.
Example 2
Preparation of a supported catalyst: 20g of magnesium chloride is added and dissolved in 100mL of ethanol, 200g of ZSM-5 molecular sieve carrier is added, the impregnation is carried out for 10 hours, and the supported catalyst is obtained after drying.
Preparing an adsorbent: adding 20g polyacrylamide into 100mL of water, heating to 80 ℃, adding 400g silica gel carrier, soaking for 6h, and drying to obtain the supported adsorbent.
Placing 100g of silicon powder in a reaction furnace under the protection of nitrogen, introducing hydrogen chloride gas at the speed of 0.25m/s, heating to 350 ℃, adding 12g of supported catalyst, and reacting for 4 hours under the pressure of 0.2MPa to obtain a reactant; the method comprises the steps of carrying out dust removal on reactants in a dry dust remover to obtain the reactants after dust removal, condensing the reactants after dust removal at the temperature of 0 ℃ to obtain condensed products, rectifying and separating the condensed products at the temperature of 15 ℃ and the temperature of 35 ℃ to obtain a first separation product (mono-chloro-dihydro-silicon), a second separation product (tri-chloro-hydro-silicon) and a third separation product (silicon tetrachloride), and respectively adding 0.8g of load type adsorbent into the second separation product and the third separation product to carry out adsorption and impurity removal to obtain 434.90g of tri-chloro-hydro-silicon and 56.07g of silicon tetrachloride. The yield of trichlorosilane is 90.28 percent, and the yield of silicon tetrachloride is 9.28 percent. The purity of the trichlorosilane is 99.9998 percent and the purity of the silicon tetrachloride is 99.9999 percent by using a high performance liquid chromatograph for measurement.
Example 3
Preparation of a supported catalyst: 20g of magnesium chloride is added and dissolved in 100mL of ethanol, 200g of ZSM-5 molecular sieve carrier is added, the impregnation is carried out for 10 hours, and the supported catalyst is obtained after drying.
Preparing an adsorbent: adding 20g polyacrylamide into 100mL of water, heating to 80 ℃, adding 400g silica gel carrier, soaking for 6h, and drying to obtain the supported adsorbent.
Placing 100g of silicon powder in a reaction furnace under the protection of nitrogen, introducing hydrogen chloride gas at the speed of 0.30m/s, heating to 380 ℃, adding 15g of supported catalyst, and reacting for 3 hours under the pressure of 0.3MPa to obtain a reactant; the method comprises the steps of carrying out dust removal on reactants in a dry dust remover to obtain the reactants after dust removal, condensing the reactants after dust removal at the temperature of 5 ℃ to obtain condensed products, respectively rectifying and separating at the temperature of 20 ℃,40 ℃ and 70 ℃ to obtain a first separation product (mono-chloro-dihydro-silicon), a second separation product (tri-chloro-hydro-silicon) and a third separation product (silicon tetrachloride), and respectively adding 1g of load type adsorbent into the second separation product and the third separation product to carry out adsorption and impurity removal to obtain 436.29g of tri-chloro-hydro-silicon and 56.50g of silicon tetrachloride. The yield of trichlorosilane is 90.57 percent, and the yield of silicon tetrachloride is 9.35 percent. The purity of the trichlorosilane is 99.9999 percent and the purity of the silicon tetrachloride is 99.9999 percent by using a high performance liquid chromatograph for measurement.
Example 4
Preparation of a supported catalyst: 20g of magnesium chloride is added and dissolved in 100mL of ethanol, 200g of ZSM-5 molecular sieve carrier is added, the impregnation is carried out for 10 hours, and the supported catalyst is obtained after drying.
Placing 100g of silicon powder in a reaction furnace under the protection of nitrogen, introducing hydrogen chloride gas at the speed of 0.25m/s, heating to 300 ℃, adding 10g of supported catalyst, and reacting for 3 hours under the pressure of 0.1MPa to obtain a reactant; the method comprises the steps of carrying out dust removal on reactants in a dry dust remover to obtain the reactants after dust removal, condensing the reactants after dust removal at the temperature of 5 ℃ to obtain condensed products, rectifying and separating at the temperature of 15 ℃ and the temperature of 35 ℃ and the temperature of 70 ℃ to obtain a first separation product (mono-chloro-dihydro-silicon), a second separation product (tri-chloro-hydro-silicon) and a third separation product (silicon tetrachloride), and adding 0.5g polyacrylamide into the second separation product and the third separation product respectively to carry out adsorption and impurity removal to obtain 428.38g of tri-chloro-hydro-silicon and 62.06g of silicon tetrachloride. The yield of trichlorosilane is 88.92 percent and the yield of silicon tetrachloride is 10.27 percent. The purity of trichlorosilane is 99.9913 percent and the purity of silicon tetrachloride is 99.9945 percent by using a high performance liquid chromatograph for measurement.
Comparative example 1
Comparative example 1 differs from example 1 only in that the supported catalyst was a ZSM-5 molecular sieve as the support and copper metal as the active component. 396.66g of trichlorosilane and 53.54g of silicon tetrachloride were finally obtained. The yield of trichlorosilane is 82.34 percent, and the yield of silicon tetrachloride is 8.86 percent. The purity of trichlorosilane is 99.9981 percent and the purity of silicon tetrachloride is 99.9978 percent by using a high performance liquid chromatograph for measurement.
Comparative example 2
Comparative example 2 differs from example 1 only in that the supported catalyst is in delta-Al 2 O 3 As a carrier, magnesium chloride as an active ingredient. 402.29g of trichlorosilane and 51.91g of silicon tetrachloride were finally obtained. The yield of trichlorosilane is 83.51 percent, and the yield of silicon tetrachloride is 8.59 percent. The purity of trichlorosilane is 99.9987 percent and the purity of silicon tetrachloride is 99.9984 percent by using a high performance liquid chromatograph for measurement.
Comparative example 3
Comparative example 3 differs from example 1 only in that 10g of unsupported catalyst magnesium chloride are directly added. 388.52g of trichlorosilane and 45.44g of silicon tetrachloride were finally obtained, the yield of trichlorosilane was 80.65%, and the yield of silicon tetrachloride was 7.52%. The purity of trichlorosilane is 99.9976 percent and the purity of silicon tetrachloride is 99.9971 percent by using a high performance liquid chromatograph for measurement.
Comparative example 4
Comparative example 4 differs from example 1 only in that no adsorbent was added. 427.66g of trichlorosilane, 54.75g of silicon tetrachloride were finally obtained, the yield of trichlorosilane was 88.76%, and the yield of silicon tetrachloride was 9.06%. The purity of trichlorosilane is 99.9805 percent and the purity of silicon tetrachloride is 99.9816 percent by using a high performance liquid chromatograph for measurement.
Comparative example 5
Comparative example 5 differs from example 1 only in that the supported adsorbent was activated carbon as a carrier and polyacrylamide as an adsorbent, yielding 428.51g of trichlorosilane, 53.60g of silicon tetrachloride. The yield of trichlorosilane is 88.95 percent, and the yield of silicon tetrachloride is 8.87 percent. The purity of trichlorosilane is 99.9953 percent and the purity of silicon tetrachloride is 99.9967 percent by using a high performance liquid chromatograph for measurement.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (4)
1. A method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride, which is characterized by comprising the following steps:
s1: introducing hydrogen chloride gas into the silicon powder under the protection of nitrogen, and adding a supported catalyst to react to obtain a reactant; the reaction temperature is 300-380 ℃, the reaction time is 3-5 h, and the reaction pressure is 0.1-0.3 MPa; the addition amount of the supported catalyst is 10% -15% of the mass of the silicon powder; the supported catalyst takes magnesium chloride as an active component and takes ZSM-5 molecular sieve as a carrier, and the mass loading capacity of the active component is 10%;
s2: carrying out dry dedusting on the reactant to obtain a dedusted reactant;
s3: condensing the dedusted reactant to obtain a condensate;
s4: rectifying and separating the condensed product to obtain a first separated product, a second separated product and a third separated product respectively, wherein the first separated product is separated at a rectifying temperature of 15-20 ℃, the second separated product is separated at a rectifying temperature of 35-40 ℃, and the third separated product is separated at a rectifying temperature of 60-70 ℃;
s5: respectively adding adsorbents into the second separation product and the third separation product to adsorb impurities, so as to obtain high-purity trichlorosilane and silicon tetrachloride products; the purity of the trichlorosilane is improved to be more than 99.999 weight percent, and the purity of the silicon tetrachloride is improved to be more than 99.999 weight percent; the adsorbent is polyacrylamide loaded on silica gel, and the mass loading capacity of the polyacrylamide is 5%.
2. The method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride according to claim 1, wherein the introducing speed of the hydrogen chloride gas is 0.25-0.30 m/s.
3. The method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride according to claim 1, wherein the condensation temperature is 10 ℃ or lower.
4. The method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride according to claim 1, wherein the adding amount of the adsorbent is 0.5% -1% of the mass of the silicon powder.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311703687.0A CN117401685B (en) | 2023-12-13 | 2023-12-13 | Method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride |
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| CN116272684A (en) * | 2022-11-08 | 2023-06-23 | 江西蓝星星火有机硅有限公司 | System and method for preparing trimethylchlorosilane |
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| EP0027733A1 (en) * | 1979-10-19 | 1981-04-29 | Arco Polymers, Inc. | Process for polymerisation of alpha-mono olefins, supported catalyst therefor and method of preparing said catalyst |
| WO2014116341A1 (en) * | 2013-01-25 | 2014-07-31 | Dow Corning Corporation | Mehtod for preparing a trihalosilane |
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