CN103506056B - Sieve plate-free fluidized bed and preparation method of boron trichloride - Google Patents
Sieve plate-free fluidized bed and preparation method of boron trichloride Download PDFInfo
- Publication number
- CN103506056B CN103506056B CN201210217421.0A CN201210217421A CN103506056B CN 103506056 B CN103506056 B CN 103506056B CN 201210217421 A CN201210217421 A CN 201210217421A CN 103506056 B CN103506056 B CN 103506056B
- Authority
- CN
- China
- Prior art keywords
- carrier gas
- bed
- boron trichloride
- bed body
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000012159 carrier gas Substances 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 35
- 239000012495 reaction gas Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 15
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 15
- 238000011049 filling Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- 239000002893 slag Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 4
- 238000005243 fluidization Methods 0.000 claims description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 16
- 229910052791 calcium Inorganic materials 0.000 description 16
- 239000011575 calcium Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 229910015844 BCl3 Inorganic materials 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- PZKRHHZKOQZHIO-UHFFFAOYSA-N [B].[B].[Mg] Chemical compound [B].[B].[Mg] PZKRHHZKOQZHIO-UHFFFAOYSA-N 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052580 B4C Inorganic materials 0.000 description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910020073 MgB2 Inorganic materials 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 and preferably Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1818—Feeding of the fluidising gas
- B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
- C01B35/061—Halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention provides a sieve plate-free fluidized bed and a preparation method of boron trichloride. The preparation method of the boron trichloride comprises the following steps: filling a powder raw material, namely alkaline earth metal boride into a bed body of a sieve plate-free fluidized bed through a raw material supply device; starting a carrier gas source, and introducing the carrier gas into the bed body of the sieve-plate-free fluidized bed to ensure that the powder raw material alkaline earth metal boride is in a fluidized state in the bed body of the sieve-plate-free fluidized bed; opening a heating device to heat the bed body, and introducing anhydrous hydrogen chloride serving as a reaction gas after the temperature reaches a specified temperature; and after the reaction reaches a specified period of time, opening and starting the separation device to obtain the required boron trichloride. The fluidized bed without the sieve plate is adopted, and the reaction can be carried out at a lower temperature, so that the energy consumption is reduced; the problem of screen plate hole blockage does not exist in the reaction process, so that the equipment is simple, the operation is easy, the reaction can be continuously carried out, the production efficiency is improved, and the impurity gas phosgene which is difficult to separate is not generated.
Description
Technical Field
The invention relates to the field of material synthesis, in particular to a sieve plate-free fluidized bed and a preparation method of boron trichloride.
Background
Boron trichloride can be used in the processes of diffusion, ion implantation, dry etching of silicon semiconductor devices, manufacture of solar cell elements and the like; can also be used as a base material for producing optical fibers and a catalyst in styrene polymerization, and also in purification processes of aluminum, zinc, magnesium and copper alloys to remove nitrides, carbides and oxides from molten metals; as welding fluxes for alloys such as aluminum, iron, zinc, tungsten, and monel; boron trichloride is also used for extinguishing magnesium fire and rocket propellant in the heat treatment furnace; can be used as intermediate for preparing diborane, high temperature resistant metal boride and the like and pyrolytic boron nitride.
At present, boron trichloride is mainly prepared by two process systems, one is a system adopting a molten salt bath, such as U.S. Pat. Nos. 2,097,482, 3,019,089, 3,152,869, 4,125,590 and the like, namely boron-containing salt is converted into boron carbide, the process usually comprises the steps of preparing boron oxide from the boron salt, reacting with carbon to generate a sintered boron carbide block, and finally reacting with chlorine to generate trichlorineThe process of reacting boron, boron oxide and carbon to generate boron carbide needs higher temperature, generally above 800 ℃; another fluidized bed system with sieve plates is adopted, for example, Canadian patent CA 632713 uses boron oxide, carbon powder and chlorine gas to react in a fluidized bed at the temperature of 600 ℃ to prepare boron trichloride, the method has the advantages of more complex control process and low yield, and although the reaction temperature is reduced, a highly toxic byproduct phosgene COCl is generated2Generation, COCl2Boiling point of 8.2 ℃ with BCl3The temperature of the molten raw material is very close to 12.5 ℃, which brings difficulty to the next separation and purification, and the molten raw material easily blocks the sieve plate holes and needs to be cleaned regularly, so that the production cannot be carried out continuously.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a sieve plate-free fluidized bed and a preparation method of boron trichloride, which can overcome the blockage of a sieve plate in the prior art.
The invention also aims to provide a preparation method of boron trichloride, which solves the problem that phosgene serving as an impurity gas is difficult to separate in the reaction process.
To achieve the above object, in a first aspect, the present invention provides a sieve plate-free fluidized bed comprising: a bed body; a carrier gas source for supplying a carrier gas to the bed from a lower portion of the bed toward an upper portion of the bed; the reaction gas supply device is used for supplying reaction gas to the bed body; a raw material supply device for supplying powder raw materials to the bed body; a heating device for heating the bed body; a slag discharge port for discharging reaction slag generated by the reaction in the bed body; and the separation device is connected with the bed body and used for separating the substances reacted in the bed body to obtain the final product.
In order to achieve the above object, in a second aspect, the present invention provides a method for producing boron trichloride using the sieve-plate-free fluidized bed of the first aspect, the method comprising: filling a powder raw material, namely alkaline earth metal boride into a bed body of a sieve plate-free fluidized bed through a raw material supply device; starting a carrier gas source, and introducing the carrier gas into the bed body of the sieve-plate-free fluidized bed to ensure that the powder raw material alkaline earth metal boride is in a fluidized state in the bed body of the sieve-plate-free fluidized bed; opening a heating device to heat the bed body, and introducing anhydrous hydrogen chloride serving as a reaction gas after the temperature reaches a specified temperature; and after the reaction reaches a specified period of time, opening and starting the separation device to obtain the required boron trichloride.
The beneficial effects of the invention are as follows.
The fluidized bed without the sieve plate is adopted, and the reaction can be carried out at a lower temperature, so that the energy consumption is reduced; the improvement of this device structure has solved the problem that the reaction sequence blockked up the sieve pore easily for equipment is simple, easily operation, and the reaction can go on in succession, has improved production efficiency. The alkaline earth metal boride and hydrogen chloride are used as raw materials, so that phosgene which is an impurity gas and is difficult to separate is generated in the reaction process.
Drawings
FIG. 1 is a schematic structural view of a sieve-plate-free fluidized bed according to the present invention;
figure 2 is a schematic horizontal cross-sectional view of the structural relationship of the carrier gas guide and the carrier gas inlet of a sieve-plate free fluidized bed according to the invention;
figure 3 is a schematic vertical cross-sectional view of the structural relationship of the carrier gas guide and the carrier gas inlet of a sieve-plate free fluidized bed according to the invention;
wherein the reference numerals are as follows:
1 bed body 2 carrier gas source 3 reaction gas supply device
4 raw material supply device 5 heating device 6 slag discharge port
7 gas-solid separating device 71 gas-solid separating device 72 gas-gas separating device
73 condensing unit 9 reaction gas processing device
10 carrier gas guide 101 inclined part 103 inner wall
21 vertical axis of carrier gas inlet a
Detailed Description
The invention relates to a sieve-plate-free fluidized bed and a preparation method of boron trichloride.
First, a sieve-plate-free fluidized bed according to the first aspect of the present invention will be described.
As shown in fig. 1, the sieve plate-free fluidized bed according to the present invention comprises: a bed body 1; a carrier gas source 2 for supplying a carrier gas to the bed 1 from the lower part of the bed 1 toward the upper part of the bed 1; a reaction gas supply device 3 for supplying reaction gas to the bed body 1; a raw material supply device 4 for supplying powder raw material to the bed body 4; the heating device 5 is used for heating the bed body 1; a slag discharge port 6 for discharging reaction slag generated by the reaction in the bed body 1; and the separation device 7 is connected to the bed body 1 and is used for separating the substances reacted in the bed body 1 to obtain the final product.
In the sieve-plate-free fluidized bed according to the present invention, the bed 1 is preferably cylindrical in shape. Preferably, the bed 1 is made of high purity quartz, silica, silicon nitride or carbon or silicon carbide coated with said materials.
As shown in fig. 1, in the sieve-plate-free fluidized bed according to the present invention, preferably, the sieve-plate-free fluidized bed further comprises: and a reaction gas treatment device 9 for dehydrating and drying the reaction gas supplied to the bed body 1 by the reaction gas supply device 3 and heating the dehydrated and dried reaction gas.
As shown in fig. 1, in the sieve-plate-free fluidized bed according to the present invention, preferably, the sieve-plate-free fluidized bed further comprises: a carrier gas guide 10 for guiding the carrier gas supplied from the carrier gas source 2 to the bed 1.
In a sieve-less fluidized bed according to the invention, as shown in fig. 1 and 2, the carrier gas guide 10 is preferably provided with a slope 101 tapering towards the bed 1.
As shown in fig. 2, in the sieve plate-less fluidized bed according to the invention, the direction of entry of the carrier gas source 2 into the carrier gas inlet 21 of the carrier gas guide 10 is preferably inclined with respect to the inner wall 103 of the carrier gas guide 10 at the location of the connection to the carrier gas inlet 21.
In the sieve-plate free fluidized bed according to the invention, as shown in fig. 3, preferably the direction of the carrier gas inlet 21 of the carrier gas source 2 into the carrier gas guide 10 is inclined with respect to the inner wall 103 of the carrier gas guide 10 at the location of the connection to the carrier gas inlet 21 and the direction of the carrier gas inlet 21 is inclined upwards with respect to the vertical axis a of the bed 1 in a plane with respect to this vertical axis a.
In the sieve-free fluidized bed according to the invention, as shown in fig. 2, preferably there are at least two carrier gas inlets 21, wherein at least one pair of carrier gas inlets 21 are oppositely arranged along the inner wall 103 of the carrier gas guide 10.
In the sieve plate-free fluidized bed according to the present invention, preferably, the separation device 7 comprises: a gas-solid separation device 71 for separating gaseous substances and solid substances in the substances after the reaction in the bed body 1; a gas-gas separation device 72 for separating a plurality of gaseous substances in the substances after the reaction in the bed body 1; and a condensing device 73 for obtaining said final product by condensation. Preferably, the gas-solid separation device 71 adopts a filtration mode, and preferably adopts a filtration column composed of glass fibers. Preferably, the gas-gas separation device 72 can be operated by means of, for example, but not limited to, chemical reaction or chemical adsorption, depending on the nature of the various gases contained in the reacted material of the bed 1. The condensing unit 73 can obtain the final product by condensation separation according to the nature of the substance to be finally obtained, and more preferably, the condensing unit 73 can be a shell and tube condenser.
Next, a method for producing boron trichloride according to the second aspect of the present invention will be described.
According to a second aspect of the present invention, the method for producing boron trichloride employs the sieve-plate-free fluidized bed of the first aspect, and the method for producing boron trichloride comprises: filling a powder raw material, namely alkaline earth metal boride into a bed body 1 of a sieve plate-free fluidized bed device through a raw material supply device 4; starting a carrier gas source 2, and introducing the carrier gas into a bed body 1 of the fluidized bed device without the sieve plate to ensure that the powder raw material is in a fluidized state in the bed body 1 of the fluidized bed device without the sieve plate; the heating device 5 is turned on to heat the bed body 1, and after the temperature reaches the specified temperature, anhydrous hydrogen chloride serving as reaction gas is introduced; after the reaction reaches a specified period of time, the separation device 7 is opened and started to obtain the required boron trichloride.
In the method for preparing boron trichloride according to the present invention, the method may further include the steps of: and opening a slag discharge port while opening and starting the separation device 7, and discharging reaction slag generated by the reaction in the bed body 1.
In the preparation method of boron trichloride, the alkaline earth metal boride is preferably calcium boride or magnesium boride, and the diameter of the alkaline earth metal boride is 20-200 meshes.
In the method for preparing boron trichloride according to the present invention, preferably, the reaction gas anhydrous hydrogen chloride is dehydrated, dried and heated to raise the temperature through the reaction gas treatment device 9 before being introduced into the bed 1.
In the preparation method of boron trichloride, the reaction process temperature is preferably 550-700 ℃, and the reaction time is preferably 1-2 h.
In the preparation method of boron trichloride, the flow rate of the alkaline earth metal boride is preferably 80-85 g/h, and the flow rate of anhydrous hydrogen chloride is preferably 500-600 g/h.
In the method for producing boron trichloride according to the present invention, it is preferable that the opening and starting of the separation device 7 to obtain the desired boron trichloride includes condensing a substance after the reaction to obtain boron trichloride. Preferably, the condensation temperature is-10 ℃ to-30 ℃.
In the method for producing boron trichloride according to the present invention, the calcium boride is preferably calcium hexaboride.
When the alkaline earth metal boride is calcium hexaboride, the reaction equation is as follows:
CaB6+20HCl=6BCl3+CaCl2+10H2
the reacted substances mainly include: BCl3Carrier gas, hydrogen, BCl3Oxygen, nitrogen, Cl2HCl and the like, and calcium chloride slag, calcium boride and the like. In the gas-solid separation device 71, calcium chloride slag and calcium boride are separated from other gases, preferably by a filter column composed of glass fibers, to achieve gas-solid separation; in the gas-gas separating means 72, it is preferable to use copper powder or carbon powder which is hot and can separate oxygen gas and hydrogen gas, and Cl can be removed by the alkaline solid adsorbent2And HCl, the basic solid preferably being sodium hydroxide or potassium hydroxide; after the gas-solid separation and the gas-gas separation are performed, BCl is condensed by controlling the condensing temperature of the condensing unit in the condensing unit 733Gas condensation to make BCl3Separated from the carrier gas, the carrier gas is discharged from the condensing device 73 and recovered. Preferably, the carrier gas discharged from the condensing unit 73 is recovered by an activated carbon packed column process of an alkaline solution soaking and drying process to improve the purity of the recovered carrier gas. Preferably, the alkaline solution is sodium hydroxide solution or potassium hydroxide solution.
When the alkaline earth metal boride is magnesium boride, the reaction equation is as follows:
MgB2+8HCl=2BCl3+MgCl2+4H2
the reacted substances mainly include: BCl3Carrier gas, hydrogen, BCl3Oxygen, nitrogen, Cl2HCl and the like, and magnesium chloride slag and magnesium boride and the like. The operation of the separation device 7 (gas-solid separation device 71, gas-gas separation device 72, condensing device 73) may be the same as in the above case using calcium hexaboride, and a repeated explanation thereof will be omitted.
In the method for producing boron trichloride according to the present invention, it is preferable that the carrier gas is an inert gas. The inert gas can be nitrogen, argon, helium or a mixed gas of two of the nitrogen, the argon, the helium or the mixed gas, and preferably, nitrogen is selected. Preferably, the flow rate is 0.5m3/h~10m3/h。
In the method for producing boron trichloride according to the present invention, it is preferable that the flow rate of the carrier gas introduced into the bed 1 of the sieve-plate-free fluidized bed after the reaction gas anhydrous hydrogen chloride is introduced is adjusted to an amount that maintains the fluidized state of the alkaline earth metal boride.
Third, an example of the production method of boron trichloride according to the present invention is explained.
Example 1
Filling powder calcium hexaboride with the particle size of 20-30 meshes into a bed body 1 of a sieve-plate-free fluidized bed through a raw material supply device 4 at a flow rate of 80 g/h; starting a carrier gas source 2, and introducing nitrogen into the bed body 1 of the sieve plate-free fluidized bed to ensure that the powder calcium hexaboride is in a fluidized state in the bed body 1 of the sieve plate-free fluidized bed; the heating device 5 is opened to heat the bed body 1, after the temperature reaches 550 ℃, the anhydrous hydrogen chloride of the reaction gas dehydrated and dried by the reaction gas treatment device 9 is introduced into the bed body 1 at the flow rate of 500g/h, and the nitrogen flow rate is continuously reduced to maintain the fluidization state of the calcium boride for reaction for 1 h; then the separation device 7 is opened and started, calcium chloride slag and calcium boride are separated by a filter column consisting of glass fiber in the gas-solid separation device 71,the oxygen and hydrogen gases are then removed by hot copper powder in a gas separator 72, after which the Cl is removed by a solid sodium hydroxide adsorbent2And HCl, and finally condensing in a condenser 73 adopting a tubular condenser at the temperature of minus 10 ℃ to obtain colorless boron trichloride, wherein nitrogen discharged from the condenser 73 is treated by an activated carbon packed column which is soaked in a sodium hydroxide solution and dried.
Example 2
Filling 100-120-mesh powder calcium hexaboride into a bed body 1 of a sieve-plate-free fluidized bed through a raw material supply device 4 at a flow rate of 85 g/h; starting a carrier gas source 2, and introducing argon into the bed body 1 of the sieve plate-free fluidized bed to enable the powder calcium hexaboride to be in a fluidized state in the bed body 1 of the sieve plate-free fluidized bed; the heating device 5 is opened to heat the bed body 1, after the temperature reaches 700 ℃, the anhydrous hydrogen chloride of the reaction gas dehydrated and dried by the reaction gas treatment device 9 is introduced into the bed body 1 at the flow rate of 600g/h, and the flow rate of argon is continuously reduced to maintain the fluidization state of calcium boride for reaction for 1.5 h; then the separation device 7 is opened and started, calcium chloride slag and calcium boride are separated by a filter column consisting of glass fiber in the gas-solid separation device 71, then oxygen and hydrogen are removed by hot carbon powder in the gas-gas separation device 72, and then Cl is removed by a solid potassium hydroxide adsorbent2And HCl; finally, the colorless boron trichloride is obtained by condensation in a condenser 73 adopting a tubular condenser at the temperature of minus 30 ℃, argon gas discharged from the condenser 73 is recovered, and nitrogen gas discharged from the condenser 73 is treated by an active carbon packed column which is soaked by potassium hydroxide solution and dried.
Example 3
Filling powder magnesium boride of 180-200 meshes into a bed body 1 of a sieve-plate-free fluidized bed through a raw material supply device 4 at a flow rate of 82 g/h; starting carrier gas source 2, introducing helium into bed body 1 of sieve-plate-free fluidized bed to make powdered magnesium boride be in sieve-plate-free fluidized bedThe bed body 1 of the fluidized bed is in a fluidized state; the heating device 5 is opened to heat the bed body 1, after the temperature reaches 650 ℃, the anhydrous hydrogen chloride of the reaction gas dehydrated and dried by the reaction gas treatment device 9 is introduced into the bed body 1 at the flow rate of 550g/h, and the flow rate of helium gas is continuously reduced to maintain the fluidization state of calcium boride for reaction for 2 h; then the separation device 7 is opened and started, magnesium chloride slag and magnesium boride are separated by a filter column consisting of glass fiber in the gas-solid separation device 71, then oxygen and hydrogen are removed by hot carbon powder in the gas-gas separation device 72, and then Cl is removed by a solid potassium hydroxide adsorbent2And HCl; finally, the colorless boron trichloride is obtained by condensation in a condenser 73 adopting a shell-and-tube condenser at the temperature of minus 10 ℃, and helium gas discharged from the condenser 73 is treated by an active carbon packed column which is soaked by a sodium hydroxide solution and dried.
Finally, the test results of the examples are explained.
Table 1 shows the results of the tests of examples 1 to 3. During detection, gas input by the condenser 8 (adopting a shell and tube condenser) is detected. The detection method adopts Fourier transform infrared spectrometer (FTIR) and ultraviolet analyzer (UV analyzer)
TABLE 1 examination results of examples 1 to 3
| Example 1 | Example 2 | Example 3 | |
| Purity of boron trichloride | 99.9% | 99.7% | 99.5% |
| N2 | 0.05% | ----- | ----- |
| Ar | ----- | 0.04% | ----- |
| He | ----- | ----- | 0.01% |
| Oxygen gas | 0.005% | 0.006% | 0.007% |
| Total hydrocarbon content (CH4) | 0.005% | 0.004% | 0.013% |
| Carbon dioxide | 0.03% | 0.05% | 0.07% |
| Chlorine | 0.01% | 0.2% | 0.4% |
As can be seen from Table 1, the preparation method of boron trichloride provided by the invention can obtain boron trichloride with high purity.
Claims (10)
1. A screenless fluidized bed for the production of boron trichloride comprising:
a bed body (1);
a carrier gas source (2) which supplies carrier gas to the bed body (1) from the lower part of the bed body (1) to the upper part of the bed body (1);
a reaction gas supply device (3) for supplying reaction gas to the bed body (1);
a raw material supply device (4) for supplying powder raw materials to the bed body (1);
the heating device (5) is used for heating the bed body (1);
a slag discharge port (6) for discharging reaction slag generated by the reaction in the bed body (1);
the separation device (7) is connected with the bed body (1) and is used for separating substances after the reaction of the bed body (1) so as to obtain a final product;
wherein,
the separation device (7) comprises:
a gas-solid separation device (71) for separating gaseous substances and solid substances in the substances after the reaction of the bed body (1);
the gas-gas separation device (72) is used for separating a plurality of gaseous substances in the substances after the bed body (1) is reacted; and
a condensation device (73) for obtaining said final product by condensation.
2. The screenless fluidized bed for producing boron trichloride of claim 1, further comprising: a carrier gas guide (10) for guiding the carrier gas supplied by the carrier gas source (2) to the bed (1).
3. The sieve-free fluidized bed for producing boron trichloride as claimed in claim 2, wherein the carrier gas guide (10) has an inclined portion (101) which tapers toward the bed (1).
4. The sieve-free fluidized bed for producing boron trichloride as claimed in claim 2, wherein the direction in which the carrier gas of the carrier gas source (2) enters the carrier gas inlet (21) of the carrier gas guide (10) is inclined with respect to the inner wall (103) of the carrier gas guide (10) at the position connecting the carrier gas inlet (21).
5. The sieve-free fluidized bed for producing boron trichloride according to claim 2, wherein the direction of entry of the carrier gas source (2) into the carrier gas inlet (21) of the carrier gas guide (10) is inclined with respect to the inner wall (103) of the carrier gas guide (10) at the position where the carrier gas inlet (21) is connected and the direction of the carrier gas inlet (21) is inclined upward with respect to the vertical axis (a) of the bed (1) in a plane with respect to the vertical axis (a).
6. The screenless fluidized bed for production of boron trichloride of claim 4 wherein there are at least two carrier gas inlets (21), and wherein at least one pair of carrier gas inlets (21) are oppositely disposed along the inner wall (103) of the carrier gas guide (10).
7. A method for producing boron trichloride using the sieve-plate-free fluidized bed for producing boron trichloride claimed in any one of claims 1 to 6, comprising:
filling a powder raw material alkaline earth metal boride into a bed body (1) of a sieve plate-free fluidized bed for preparing boron trichloride through a raw material supply device (4);
starting a carrier gas source (2), and introducing the carrier gas into a bed body (1) of the sieve-plate-free fluidized bed for preparing boron trichloride so that the powder raw material alkaline earth metal boride is in a fluidized state in the bed body (1) of the sieve-plate-free fluidized bed for preparing boron trichloride;
the heating device (5) is turned on to heat the bed body (1), and after the temperature reaches the specified temperature, the anhydrous hydrogen chloride as the reaction gas is introduced;
after the reaction reaches a specified period of time, the separation device (7) is opened and started to obtain the required boron trichloride.
8. The method of producing boron trichloride according to claim 7, further comprising the steps of: and opening the slag discharge port (6) while opening and starting the separation device (7) to discharge reaction slag generated by the reaction in the bed body (1).
9. The method according to claim 7, wherein the anhydrous hydrogen chloride as the reaction gas is dehydrated, dried and heated to a high temperature before being introduced into the bed (1).
10. A process for the production of boron trichloride as claimed in claim 7, wherein the flow rate of the carrier gas introduced into the bed (1) of the sieve-plate-free fluidized bed for producing boron trichloride is adjusted to an amount at which the fluidization state of the alkaline earth metal boride is maintained after the reaction gas anhydrous hydrogen chloride is introduced.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210217421.0A CN103506056B (en) | 2012-06-28 | 2012-06-28 | Sieve plate-free fluidized bed and preparation method of boron trichloride |
| PCT/CN2013/077478 WO2014000592A1 (en) | 2012-06-28 | 2013-06-19 | Fluidized bed without sieve plate and method for preparing boron trichloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210217421.0A CN103506056B (en) | 2012-06-28 | 2012-06-28 | Sieve plate-free fluidized bed and preparation method of boron trichloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103506056A CN103506056A (en) | 2014-01-15 |
| CN103506056B true CN103506056B (en) | 2015-09-30 |
Family
ID=49782225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210217421.0A Active CN103506056B (en) | 2012-06-28 | 2012-06-28 | Sieve plate-free fluidized bed and preparation method of boron trichloride |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103506056B (en) |
| WO (1) | WO2014000592A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106163628B (en) * | 2014-03-18 | 2019-03-22 | 曼瑟森三汽油公司 | The method and device of silicon tetrachloride is reduced in boron chloride |
| CN103950947B (en) * | 2014-05-20 | 2015-09-09 | 方治文 | The preparation method of high-purity boron trichloride-11 |
| CN106319216B (en) * | 2015-07-06 | 2018-01-23 | 广东先导稀材股份有限公司 | Gas-gas reaction device |
| KR102549706B1 (en) * | 2018-06-26 | 2023-07-03 | 가부시끼가이샤 레조낙 | Method for producing boron trichloride |
| CN114572992B (en) * | 2022-03-09 | 2023-06-23 | 福建福豆新材料有限公司 | Hydrogen chloride removing device for purifying boron trichloride and purification system for boron trichloride |
| CN114570294B (en) * | 2022-04-21 | 2023-10-13 | 金宏气体股份有限公司 | Boron trifluoride continuous production device and method based on ebullated bed reactor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839538A (en) * | 1971-03-20 | 1974-10-01 | Elektroschmelzwerk Kampten Gmb | Process for the manufacture of boron halides |
| CN201390803Y (en) * | 2008-12-02 | 2010-01-27 | 广州有色金属研究院 | Fluidized bed reaction equipment without sieve plate for preparing polysilicon granules |
| CN201431874Y (en) * | 2009-03-20 | 2010-03-31 | 仙桃市中星电子材料有限公司 | Spiral fluidizing chlorination furnace without sieve plates |
| CN101912752A (en) * | 2010-08-20 | 2010-12-15 | 中国航天空气动力技术研究院 | Solid particle player |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2735041B1 (en) * | 1995-06-07 | 1997-07-11 | Gec Alsthom Stein Ind | FLUIDIZED BED REACTOR FOR HEAT TREATMENT OF WASTE |
| DE102004051477B4 (en) * | 2004-10-22 | 2008-10-02 | Alstom Technology Ltd. | Method for regulating the amount of circulating fluid in a circulating fluidized bed reactor system |
| CN102230732B (en) * | 2011-07-01 | 2013-06-19 | 广州有色金属研究院 | Closed automatic slag discharge device for boiling chlorination furnace |
-
2012
- 2012-06-28 CN CN201210217421.0A patent/CN103506056B/en active Active
-
2013
- 2013-06-19 WO PCT/CN2013/077478 patent/WO2014000592A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839538A (en) * | 1971-03-20 | 1974-10-01 | Elektroschmelzwerk Kampten Gmb | Process for the manufacture of boron halides |
| CN201390803Y (en) * | 2008-12-02 | 2010-01-27 | 广州有色金属研究院 | Fluidized bed reaction equipment without sieve plate for preparing polysilicon granules |
| CN201431874Y (en) * | 2009-03-20 | 2010-03-31 | 仙桃市中星电子材料有限公司 | Spiral fluidizing chlorination furnace without sieve plates |
| CN101912752A (en) * | 2010-08-20 | 2010-12-15 | 中国航天空气动力技术研究院 | Solid particle player |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103506056A (en) | 2014-01-15 |
| WO2014000592A1 (en) | 2014-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103506056B (en) | Sieve plate-free fluidized bed and preparation method of boron trichloride | |
| US8778061B2 (en) | Hydrogen gas recovery system and hydrogen gas separation and recovery method | |
| CN105197887B (en) | Steam reforming device and method for producing hydrogen and fixing carbon through coke oven gas in synergic mode | |
| CN101279735A (en) | Production method and apparatus for trichlorosilane | |
| KR102315161B1 (en) | Method for producing chlorine gas through hydrogen chloride catalytic oxidation | |
| CN103864021B (en) | A kind of device and method utilizing chemical chain air separation to prepare oxygen | |
| CN207227001U (en) | Utilize MOCVD tail gas co-producing high-purity hydrogen and the device of high-purity ammon | |
| CN107635913A (en) | The lower adsorbent powerforming hydrogen manufacturing of air calcining | |
| WO2014061666A1 (en) | Method for manufacturing porous carbon material | |
| CN107344100B (en) | Inactivated HgCl2Regeneration method of/AC catalyst | |
| JP5617956B2 (en) | Method for producing high purity boron trichloride | |
| CN106219488B (en) | A kind of method and device preparing hydrochloric acid and purifying quartz sand | |
| CN203959838U (en) | A kind of reaction unit of removing chlorine impurity in boron trichloride | |
| JP2010111550A (en) | High-purity boron trichloride and production method thereof | |
| CN102863312A (en) | Preparation process of carbon tetrafluoride and device implementing same | |
| JP2005060137A (en) | Method for immobilizing carbon dioxide and its system | |
| CN216155477U (en) | Methanol skid-mounted hydrogen production machine | |
| JP5950160B2 (en) | Method for producing lithium oxide | |
| JP2017190275A (en) | Byproduct hydrogen generation device | |
| CN114620731B (en) | Method and device for recovering reduction tail gas of polycrystalline silicon | |
| CN108190950B (en) | Preparation method of zirconium dioxide | |
| CN109422265B (en) | High-temperature modification treatment method for activated carbon raw material | |
| CN112662889B (en) | Preparation method of zinc particles and reaction furnace device | |
| JP2008115046A (en) | Hydrocarbon reforming apparatus | |
| RU2385291C1 (en) | Method of production of high purity crystal silicon (versions) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220520 Address after: No. 1116-1, building 1, Dianzhong Business Plaza, Dianzhong new area, Kunming, Yunnan 650212 Patentee after: Kunming forerunner New Material Technology Co.,Ltd. Address before: 511500 Industrial Zone, wo Yun town, Qingxin County, Qingyuan, Guangdong (beside the fish dam road) Patentee before: FIRST RARE MATERIALS Co.,Ltd. |