CN113735082A - Low-halogen electronic grade red phosphorus purification device and preparation method - Google Patents
Low-halogen electronic grade red phosphorus purification device and preparation method Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 36
- 238000000746 purification Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010453 quartz Substances 0.000 claims abstract description 38
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
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- 238000000034 method Methods 0.000 claims abstract description 29
- 230000007704 transition Effects 0.000 claims abstract description 13
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- 239000000047 product Substances 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 13
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- 238000001914 filtration Methods 0.000 claims description 11
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- 238000001816 cooling Methods 0.000 claims description 7
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- 238000004140 cleaning Methods 0.000 description 28
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- 238000001514 detection method Methods 0.000 description 7
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- 239000002994 raw material Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- KXNLCSXBJCPWGL-UHFFFAOYSA-N [Ga].[As].[In] Chemical compound [Ga].[As].[In] KXNLCSXBJCPWGL-UHFFFAOYSA-N 0.000 description 1
- FTWRSWRBSVXQPI-UHFFFAOYSA-N alumanylidynearsane;gallanylidynearsane Chemical compound [As]#[Al].[As]#[Ga] FTWRSWRBSVXQPI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
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- 238000011985 exploratory data analysis Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 239000000575 pesticide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/04—Purification of phosphorus
- C01B25/043—Purification of phosphorus of red phosphorus
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention relates to the technical field of red phosphorus preparation, and discloses a low-halogen electronic grade red phosphorus purification device and a preparation method thereof, which aim to overcome the technical defect of high-purity red phosphorus halogen residue in the prior art. The low-halogen electronic grade red phosphorus purification device comprises a reaction tube, wherein the reaction tube comprises a charging tube and a condensation tube, and the charging tube is fixedly connected with the condensation tube through a long and narrow steam channel; a quartz boat is arranged in the charging pipe; one end of the charging pipe, which is far away from the steam channel, is provided with a detachable plug; the reaction tube is externally provided with a temperature control structure, and the temperature control structure is sequentially provided with a high-temperature area, a transition temperature area and a low-temperature area along the directions of the charging tube, the steam channel and the condensation tube. The invention provides a method for preparing low-halogen electronic-grade red phosphorus by using the device, which comprises the steps of primary conversion of industrial white phosphorus, sublimation purification of red phosphorus and purification of red phosphorus through solubility difference. The invention purifies red phosphorus to 6N level by multi-step purification method, and the content of halogen impurities is lower than 50 ppb.
Description
Technical Field
The invention relates to the technical field of red phosphorus preparation, in particular to a low-halogen electronic grade red phosphorus purification device and a preparation method thereof.
Background
Red phosphorus at position 15 of the periodic table, element symbol P4. Purplish red or slightly brown amorphous powder, lustrous. Density 2.34g/cm3The heat can sublime, but can melt when heated to 590 ℃ under 4300 kpa. White phosphorus can be obtained by desublimation after vaporization. Red phosphorus is poorly soluble in water and CS2Ethyl ether, ammonia, etc. are slightly soluble in absolute ethyl alcohol, and are non-toxic and odorless, and when they are combusted, they produce white smoke, and the smoke is extremely toxic. Research on the exploratory analysis of explosion reasons in the process of converting white phosphorus into red phosphorus shows that the red phosphorus is ignited when the environmental temperature reaches about 2400 ℃, and when the conversion temperature reaches 3100 ℃ or above, severe explosion can occur if no measures for cooling and oxygen isolation are taken. It is a reducing agent when reacting with halogen and sulfur. Red phosphorus is generally used for producing safe matches, organophosphorus pesticides, flame retardants, phosphorus-containing compound products and the like.
Electronic grade red phosphorus is one of the main materials of compound semiconductors, and can be used for synthesizing compound semiconductors such as indium phosphide (InP), gallium phosphide (GaP), aluminum gallium arsenide phosphide (AlGaAsP), indium gallium arsenide phosphide (InGaAsP), gallium arsenide phosphide (GaAsP), and the like. High purity red phosphorus can also be used as a source of solid doped phosphorus for ICs and the like.
At present, two methods are roughly used in industry to prepare high-purity red phosphorus, which is referred to as fine inorganic chemical manufacturing technology. One method is a phosphorus trichloride reduction method, such as chinese patent documents CN101214935B and CN109850860A, and the core process is to obtain high-purity phosphorus trichloride through multiple rectification, then obtain high-purity white phosphorus through a hydrogen reduction method, and finally bake the white phosphorus in a vacuum glass tube at high temperature to obtain red phosphorus. However, this process scheme suffers from several disadvantages, (1) long cycle time for product production; (2) the halogen residue with higher content is found to be about 400-600 ppb, which affects the subsequent use of electronic-grade industry.
The other method is an electronic-grade white phosphorus direct conversion method, and the core process idea is to select high-purity electronic-grade white phosphorus as a conversion raw material, directly heat the high-purity electronic-grade white phosphorus at 350-400 ℃ and convert the high-purity electronic-grade white phosphorus into electronic-grade red phosphorus, such as Chinese invention patent documents CN109081320A and CN106517118A, however, the method has the defect that the main production process of the electronic-grade white phosphorus is still a chlorination reduction method, so that the produced red phosphorus still has a large amount of halogen residues.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-halogen electronic grade red phosphorus purification device and a preparation method thereof, so as to overcome the technical defect of high-purity red phosphorus halogen residue in the prior art.
The research of the invention finds that the purity of the high-purity red phosphorus on the market is basically 5N, most of the high-purity red phosphorus reaching 6N is produced by a chlorine and bromination reduction method, the red phosphorus is affected by intermediate products and has 400-600 ppb chlorine and bromine element residues, but the development of the related microelectronic industry is greatly restricted by the prior art no matter the red phosphorus is developed at the front of research institutions or produced in batches in the electronic industry.
In order to solve the technical problem, in a first aspect, the invention provides a low-halogen electronic-grade red phosphorus purification device, which comprises a reaction tube, a reaction tube and a steam pipe, wherein the reaction tube comprises a charging tube and a condensation tube, and the charging tube is fixedly connected with the condensation tube through an elongated steam channel; a quartz boat is arranged in the charging pipe; a detachable plug is arranged at one end of the charging pipe, which is far away from the steam channel; the reaction tube is externally provided with a temperature control structure, and the temperature control structure is sequentially provided with a high-temperature area, a transition temperature area and a low-temperature area along the directions of the charging tube, the steam channel and the condensation tube.
The plug of the device can close the charging pipe so that the charging pipe, the steam channel and the condensation pipe form a closed space. The device firstly converts the industrial white phosphorus into red phosphorus normally, then heats the industrial white phosphorus to be converted into phosphorus steam, the phosphorus steam is condensed again in the condensing tube, and inorganic impurities in the raw materials are basically removed.
In a preferred embodiment of the purification apparatus for low-halogen electronic grade red phosphorus, the charging pipe and the junction of the condensing pipe and the steam channel are correspondingly located in the transition temperature region, so as to avoid the phosphorus steam from condensing in the steam channel.
As a preferred embodiment of the purification device for low-halogen electronic grade red phosphorus of the present invention, one end of the condensation pipe away from the steam channel is a closed hemisphere, which facilitates uniform condensation of red phosphorus and sufficient removal of red phosphorus. Preferably, the condensation tube is a hemispherical ampoule bottle with a straight tube section.
As the preferred embodiment of the low-halogen electronic grade red phosphorus purification device, the inner diameter of the steam channel is 20-40 mm, and the length of the steam channel is 120-180 mm.
In a preferred embodiment of the purification apparatus for low-halogen electronic grade red phosphorus of the present invention, the reaction tube is made of quartz to avoid introducing impurities.
In a second aspect, the present invention provides a method for preparing low-halogen electronic grade red phosphorus using the apparatus, comprising the steps of:
(1) filling white phosphorus into the quartz boat, packaging the charging tube and vacuumizing, setting a high-temperature area to heat to 320-380 ℃ at a constant heating rate of 10-200 ℃ per minute, and preserving heat for 50-70 hours to obtain a primary conversion product;
(2) heating the temperature control structure for 3-6 hours, heating the high-temperature area to 600-650 ℃, the transition temperature area to 450-500 ℃, and the low-temperature area to 350-400 ℃;
preserving the heat for 18-24 hours;
(3) cooling the temperature control structure to 20-30 ℃ within 6-12 h, and breaking the condensation pipe to obtain a primary product;
(4) and filtering and washing the obtained primary product, and drying to obtain the product.
As a preferred embodiment of the method for preparing the low-halogen electronic grade red phosphorus, in the step (1), the vacuum degree in the charging pipe reaches 1-7 multiplied by 10 during the vacuum pumping-2pa。
In the step (2), the pressure outside the reaction tube is controlled to be 3-5 bar higher than the phosphorus pressure inside the reaction tube during the temperature raising so as to prevent tube explosion.
As a preferred embodiment of the method for preparing low-halogen electronic grade red phosphorus of the present invention, in the step (4), the filtration washing employs a quartz washing tank; the solution of the filtration washing is carbon disulfide or an organic solvent, preferably, the organic solvent is at least one of methyl ether, diethyl ether, methanol, ethanol, propanol and acetone. The number of times of filtering and washing is controlled to be 3-6 times, and each time lasts for 30-60 min. Preferably, the filtration and washing is performed by sufficiently soaking and washing with carbon disulfide to remove trace unconverted white phosphorus, and then washing with absolute ethanol to dissolve residual carbon disulfide and other organic impurities.
The drying temperature is controlled to be 50-60 ℃, the drying time is controlled to be 8-12 h, and the air inlet amount is controlled to be 300-1000L/h. The drying is carried out by introducing inert gas (such as helium, neon, argon, krypton and xenon, preferably nitrogen or argon) into the oven and maintaining positive pressure.
Compared with the prior art, the invention has the beneficial effects that:
the invention utilizes a low-halogen electronic grade red phosphorus purification device to normally convert industrial white phosphorus into red phosphorus, then the temperature is raised to convert the red phosphorus into phosphorus vapor, the phosphorus vapor is condensed again in a condensation pipe, and inorganic impurities in the raw materials are basically removed; then placing the red phosphorus which is re-condensed into filtering washing liquid (carbon disulfide solution and ethanol solution) step by step for dissolving and filtering to remove organic impurities; and finally, placing the mixture in a constant-temperature clean nitrogen cabinet for drying, and removing residual filter washing liquid. The invention converts 99.9 percent of industrial white phosphorus into high-purity red phosphorus by a multi-step purification method. The red phosphorus was purified to 6N levels with halogen impurities below 50 ppb.
Drawings
FIG. 1 is a schematic diagram of a device for purifying low-halogen electronic grade red phosphorus in accordance with embodiment 1 of the present invention;
in the figure, 1, a charging tube, 11, a quartz boat, 12 and a plug; 2. a steam channel; 3. a condensation pipe; 4. a temperature control pipe 41, a first temperature zone 42, a second temperature zone 43, a third temperature zone 44, a fourth temperature zone 45 and a fifth temperature zone.
FIG. 2 is a schematic structural view of a quartz cleaning tank in example 2 of the present invention;
in the figure, 5, a cleaning tank, 51, a baffle, 52, a filter screen, 53 and a liquid outlet.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified. The preparation environment of the related products is in a constant-temperature 20 ℃ plant built by stainless steel or other fireproof and explosion-proof materials, and is qualified through testing and inspection. The quartz products involved are high-purity quartz pieces so as to avoid introducing impurities.
Example 1: low-halogen electronic-grade red phosphorus purification device
As shown in fig. 1, the low-halogen electronic grade red phosphorus purification device comprises a reaction tube and a temperature control tube 4.
The reaction tube comprises a charging tube 1 and a condensation tube 3, wherein the charging tube 1 is fixedly connected with the condensation tube 3 through a long and narrow steam channel 2.
The quartz boat 11 is arranged in the charging pipe 1, one end, far away from the steam channel 2, of the charging pipe 1 is an opening, a detachable plug 12 is arranged at the opening, and the plug 12 can seal the charging pipe 1 so that the charging pipe 1, the steam channel 2 and the condensation pipe 3 form a closed space.
The reaction tube is sleeved with a temperature control tube 4; the temperature control pipe 4 is sequentially provided with a high-temperature area, a transition temperature area and a low-temperature area along the directions of the charging pipe 1, the steam channel 2 and the condensation pipe 3; the high temperature region includes a first temperature region 41 and a second temperature region 42, the transition temperature region includes a third temperature region 43, and the low temperature region includes a fourth temperature region 44 and a fifth temperature region 45. Preferably, the temperature control pipe 4 is a heating hearth.
The charging pipe 1 corresponds to a high-temperature area of the temperature control pipe 4; the condensation pipe 3 corresponds to the low-temperature area of the temperature control pipe 4; the charging pipe 1 and the joint of the condensing pipe 3 and the steam channel 3 are correspondingly positioned in the transition temperature area.
The end of the condensation pipe 3 far away from the steam channel 2 is a closed hemisphere. Preferably, the condensation tube 3 is a hemispherical ampoule with a straight tube. Preferably, the inner diameter of the steam channel 2 is 20-40 mm, and the length is 150 mm. The reaction tube is made of quartz.
Example 2: preparation method of low-halogen electronic grade red phosphorus
The purification device of example 1 was used to prepare low-halogen electronic grade red phosphorus, the specific steps were as follows:
(1) preliminary conversion of technical white phosphorus
The low-halogen electronic grade red phosphorus purification device is used after being cleaned by a quartz cleaning agent to remove impurities, cleaned by pure water and dried.
Uniformly loading 2-4 kg of industrial-grade white phosphorus (with the purity of 99.9%) into a quartz boat 11, packaging a charging tube 1 through a plug 12, and vacuumizing to make the vacuum degree in a reaction tube reach 1-7 multiplied by 10-2pa (to prevent oxidation and combustion of white phosphorus), welding the charging pipe 1 for pipe sealing, placing the reaction pipe into a heating hearth, setting the first temperature zone 41 and the second temperature zone 42 to raise the temperature of the high-temperature zone to 320-380 ℃ (preferably 350 ℃) at a constant heating rate of 10-200 ℃ per minute, and keeping the temperature for 50-70 hours (not less than 50 hours, preferably 60 hours) to ensure that the industrial white phosphorus in the raw material pipe is basically converted into red phosphorus, thereby obtaining an initial conversion product.
(2) Sublimation purification of red phosphorus
And after the heat preservation is finished, adjusting a thermal field, and slowly raising the temperature for 3-6 h, so that the temperature of the high-temperature zone (the first temperature zone 41 and the second temperature zone 42) is raised to 600-650 ℃ (preferably 600 ℃), the temperature of the transition temperature zone (the third temperature zone 43) is raised to 450-500 ℃ (preferably 480 ℃), and the temperature of the low-temperature zone (the fourth temperature zone 44 and the fifth temperature zone 45) is raised to 350-400 ℃ (preferably 350 ℃). And keeping the temperature for 18-24 hours (preferably 24 hours) under the temperature gradient. The pressure inside and outside the reaction tube is equalized by filling the heating furnace with inert gas (such as helium, neon, argon, krypton, xenon, preferably nitrogen or argon). And adjusting the pressure in the furnace along with the temperature, and keeping the pressure in the furnace to be 3-5 bar higher than the phosphorus pressure in the reaction tube all the time so as to prevent tube explosion accidents.
After the temperature gradient heat preservation, the phosphorus element is basically recondensed in the condensation pipe 3 and converted into red phosphorus, and a small amount of white phosphorus at the condensation end can also be reconverted into red phosphorus. At the moment, the temperature of the first temperature zone 41 to the fifth temperature zone 45 is reduced to 25 ℃, and the time is 6-12 hours, so that the primary product is obtained.
And the air pressure of the hearth is gradually adjusted and exhausted in the cooling process, so that the quartz tube is prevented from being fractured due to overlarge external pressure.
(3) Purification of red phosphorus by solubility difference
As shown in FIG. 2, the quartz cleaning tank comprises a cleaning tank 5, a baffle 51 is arranged on the inner wall of the cleaning tank 5, an extractable stainless steel filter screen 52 is arranged in the cleaning tank 5, and when the filter screen 52 is placed in the cleaning tank 5, the baffle 51 can limit the position of the bottom of the filter screen 52. The bottom of the cleaning tank 5 is provided with a liquid outlet 53. Industrial carbon disulfide (CS) can be contained in the cleaning tank 52) Or absolute ethanol (AR grade ethanol, 95% purity), which can be drained through drain 53 when changing liquids or cleaning.
The quartz cleaning tank is adopted to purify primary products, and product cleaning is carried out in a clean nitrogen cabinet so as to avoid process pollution. The method comprises the following specific steps:
and pouring carbon disulfide into the cleaning tank 5, breaking the condensation pipe 3, taking out the primary product after breaking the pipe, and pouring the primary product into the filter screen 52 for soaking and cleaning. Turning the filter screen 52 up and down, and soaking and washing for 10-30 min (preferably 30min) to remove trace unconverted white phosphorus. After the soaking and washing are finished, the filter screen 52 is lifted out of the liquid level to obtain the soaking and washing red phosphorus particles.
And (3) pouring absolute ethyl alcohol into the cleaning tank 5, pouring the soaked and washed red phosphorus particles into the filter screen 52, cleaning the red phosphorus particles in the absolute ethyl alcohol for three times, wherein each time is 30-60 min, the absolute ethyl alcohol is replaced by cleaning each time, and the filter screen 52 is required to be turned over up and down during cleaning so as to dissolve residual carbon disulfide and other organic impurities. After cleaning, the filter screen 52 is taken out of the liquid level, the filtered red phosphorus particles are poured on a quartz tray, the quartz tray is transferred to an inert gas oven, preferably nitrogen or argon, the oven is kept at micro-positive pressure, and the temperature is controlled to be 50-60 ℃ (preferably 60 ℃). And (3) air-drying the red phosphorus by nitrogen for 8-12 h (preferably 12h), and completely air-drying the ethanol by the air intake of 300-1000L/h (preferably 800L/h), so that the high-purity electronic grade red phosphorus with the purity of 6N and the halogen level of less than 50ppb can be obtained.
Test example 1:
by adopting the preparation method of the low-halogen electronic-grade red phosphorus in the embodiment 2, the influence of the heat preservation time on the product in the preliminary conversion of the industrial white phosphorus is tested, which is specifically as follows:
the production experiment is carried out by three sets of equipment, and the production batches are CA0001, CA0002 and CA 0003. Each set of equipment is packaged with a quartz boat 11 filled with 3kg of industrial-grade white phosphorus (the purity is 99.9%) in a charging tube 1, and the vacuum degree in the tube is vacuumized to reach 1 multiplied by 10-2pa, welding and sealing the tube, then loading the reaction tube into a heating hearth, setting the temperature of the high-temperature zone to 350 ℃ respectively at a constant heating rate of 15 ℃/min in the first temperature zone 41 and the second temperature zone 42, setting the heat preservation time of the CA0001 device to be 50 hours, the heat preservation time of the CA0002 device to be 60 hours and the heat preservation time of the CA0003 device to be 80 hours. After the heat preservation of the three sets of equipment is finished, the thermal field is adjusted, the temperature is slowly raised for 6 hours, so that the temperature of the high-temperature area (the first temperature area 41 and the second temperature area 42) is raised to 600 ℃, the temperature of the transition temperature area (the third temperature area 43) is raised to 480 ℃, and the temperature of the low-temperature area (the fourth temperature area 44 and the fifth temperature area 45) is raised to 350 ℃. The whole was incubated at this temperature gradient for 24 h. And filling nitrogen or argon into each set of hearth during the heating and condensation periods to balance the internal and external pressures of the ampoule bottles. After the heat preservation time, the temperature of the first temperature zone 41 to the fifth temperature zone 45 of each set of equipment is reduced to 25 ℃ for 12 hours. Gradually regulating and deflating the air pressure of the hearth in the cooling process to avoid overlarge external pressure to fracture the reaction tube, taking out the primary products of each set of equipment in the previous step by breaking the tube, and pouring three sets of primary products into carbon disulfide (CS)2) And (3) soaking and washing the quartz cleaning tank, wherein a filter screen 52 in the quartz cleaning tank is turned up and down for 30min to remove trace unconverted white phosphorus. After the soaking and washing are finished, the filter screen 52 is lifted out of the liquid level, and the soaked and washed red phosphorus particles are poured into an absolute ethyl alcohol quartz washing tank to be washed for three times, 30min each time. After washing, the washing liquid is drained, and the absolute ethyl alcohol is replaced with new absolute ethyl alcohol to dissolve residual carbon disulfide and other organic impurities. After cleaning, the filter screen 52 is lifted out of the liquid level, the filtered red phosphorus particles are poured onto different quartz trays and transferred to a nitrogen oven, and the nitrogen oven maintains the oven temperature of micro-positive pressure of 60 ℃. The ethanol can be completely air-dried by nitrogen at the wind speed of 800L/h for 12h to obtain the product IIIBatch products CA0001, CA0002 and CA 0003.
The yields of the products were weighed and calculated as shown in table 1:
TABLE 1 Effect of varying soak times on products at changeover
The element content of the CA0002 product is shown in Table 2 by Glow Discharge Mass Spectrometry (GDMS):
TABLE 2 CA0002 product element detection results
Test example 2:
by adopting the preparation method of the low-halogen electronic grade red phosphorus of the embodiment 2, the influence of different temperature gradients on the product during sublimation and purification of the red phosphorus is tested, which is specifically as follows:
four sets of equipment production experiments are carried out, and the production batches are CA0008, CA0009, CA0010 and CA 0011. Each set of equipment is packaged with a quartz boat containing 3kg of industrial-grade white phosphorus (the purity is 99.9%) in a high-temperature region charging tube 1, and the vacuum degree in the tube is pumped to 1 multiplied by 10-2pa, welding and sealing the tube, then loading the reaction tube into a heating hearth, setting the first temperature zone 41 and the second temperature zone 42 to respectively heat the temperature of the high-temperature zone to 350 ℃ at a constant heating rate of 15 ℃/min, and setting the heat preservation time of each set of equipment to be 60 hours at the moment. Adjusting a thermal field after the four sets of equipment are insulated, and slowly raising the temperature for 6 hours to set the temperature gradient of CA0008 to be 650-450-400 ℃; the temperature gradient of CA0009 is set to 600-450-400 ℃; the temperature gradient of CA0010 is set to be 600-450-350 ℃; the temperature gradient of C0011 is set to 600-480-350 ℃. The four sets of equipment are all insulated for 24 hours under the temperature gradient. And during heating and coagulationAnd filling nitrogen or argon into each hearth to balance the pressure inside and outside the reaction tube. After the heat preservation time, the temperature of the first temperature zone 41 to the fifth temperature zone 45 of each set of equipment is reduced to 25 ℃ for 12 hours. Gradually regulating and deflating the air pressure of the hearth in the cooling process to avoid overlarge external pressure to fracture the reaction tube, taking out the primary products of each set of equipment in the previous step by breaking the tube, and pouring four sets of primary products into carbon disulfide (CS)2) And (3) soaking and washing the quartz cleaning tank, wherein a filter screen 52 of the quartz cleaning tank is turned up and down for 30min to remove trace unconverted white phosphorus. After the soaking and washing are finished, the stainless steel filter screen 52 is lifted out of the liquid level, and the soaked and washed red phosphorus particles are poured into an absolute ethyl alcohol quartz washing tank to be washed for three times, 30min each time. After washing, the washing liquid is drained, and the absolute ethyl alcohol is replaced with new absolute ethyl alcohol to dissolve residual carbon disulfide and other organic impurities. After the cleaning, the stainless steel filter screen 52 is lifted out of the liquid level, the filtered red phosphorus particles are poured onto different quartz trays and transferred to a nitrogen oven, and the nitrogen oven keeps the oven temperature of micro-positive pressure of 60 ℃. The ethanol can be completely air-dried by air-drying the nitrogen for 12 hours at the wind speed of 800L/h to obtain four batches of products of CA0008, CA0009, CA0010 and CA 0011.
The yields of the products were weighed and calculated as shown in table 3:
TABLE 3 Effect of varying temperature gradient on product
When the Glow Discharge Mass Spectrometry (GDMS) method is adopted for detection, the element contents of CA0008, CA0009, CA0010 and CA0011 products are shown in tables 4-7:
TABLE 4 CA0008 product element detection results
TABLE 5 CA0009 product element detection results
TABLE 6 CA0010 product element detection results
TABLE 7 CA0011 product element detection results
Test example 3:
by adopting the preparation method of the low-halogen electronic grade red phosphorus in the embodiment 2, the influence of the heat preservation time in the optimal temperature gradient on the product during sublimation and purification of the red phosphorus is tested, and the method specifically comprises the following steps:
four sets of equipment production experiments are carried out, and the production batches are CA0004, CA0005, CA0006 and CA 0007. Uniformly loading 3kg of industrial-grade white phosphorus (purity of 99.9%) in a quartz boat 11, packaging in a high-temperature region charging tube 1 of each equipment, and vacuumizing to make the vacuum degree in the tube reach 1 × 10-2pa, welding and sealing the tube, then loading the reaction tube into the heating furnace of each device, and setting the first temperature zone 41 and the second temperature zone 42 to respectively heat the temperature of the high-temperature zone to 350 ℃ at a constant heating rate of 15 ℃/min and keep the temperature for 60 hours. After the heat preservation is finished, the thermal field is adjusted, the temperature is slowly raised for 6 hours, the temperature of the high-temperature area (the first temperature area 41 and the second temperature area 42) is raised to 600 ℃, the temperature of the transition temperature area (the third temperature area 43) is raised to 480 ℃, and the temperature of the low-temperature area (the fourth temperature area 44 and the fifth temperature area 45) is raised to 350 ℃. Under the temperature gradient, the CA0004 is kept warm for 18h, the CA0005 is kept warm for 21h, the CA0006 is kept warm for 24h, and the CA0007 is kept warm for 27 h. Meanwhile, each set of equipment is heated up and nitrogen or argon is filled into the hearth during the condensation period to balance the internal and external pressures of the ampoule bottle. After the heat preservation time, the temperature of the first temperature zone 41 to the fifth temperature zone 45 is reduced to 25 ℃ for 12 hours. The air pressure of the hearth is gradually adjusted and deflated in the cooling process, so that the phenomenon that the external pressure is too large is avoidedFracturing a reaction tube, taking out four batches of primary products in the last step by four sets of equipment respectively through breaking the tubes, and pouring the primary products into carbon disulfide (CS) in batches2) And (3) soaking and washing the quartz cleaning tank, wherein a filter screen 52 in the quartz cleaning tank is turned up and down for 30min to remove trace unconverted white phosphorus. After the soaking and washing are finished, the filter screen 52 is lifted out of the liquid level, and the soaked and washed red phosphorus particles are poured into an absolute ethyl alcohol quartz washing tank to be washed for three times, 30min each time. After washing, the washing liquid is drained, and the absolute ethyl alcohol is replaced with new absolute ethyl alcohol to dissolve residual carbon disulfide and other organic impurities. After the cleaning, the stainless steel filter screen 52 is lifted out of the liquid level, the filtered red phosphorus particles are poured onto respective quartz trays, and the quartz trays are transferred to a nitrogen oven, and the nitrogen oven is kept at a micro-positive pressure and an oven temperature of 60 ℃. The ethanol can be completely air-dried by air-drying the nitrogen at the wind speed of 800L/h for 12h, and four batches of products CA0004, CA0005, CA0006 and CA0007 are obtained.
The yields of the products were weighed and calculated as shown in table 8:
TABLE 8 Effect of varying incubation time within optimum temperature gradient on product
| Production batch number | Incubation time (h) | Raw material weight (g) | Coagulation output (g) | Yield of |
| CA0004 | 18 | 3000.9 | 2097.03 | 69.89％ |
| CA0005 | 21 | 3001.2 | 2165.1 | 72.14％ |
| CA0006 | 24 | 3001.6 | 2260.5 | 75.31％ |
| CA0007 | 27 | 3000.6 | 2286.7 | 76.21％ |
The element contents of the CA0006 product, as detected by Glow Discharge Mass Spectrometry (GDMS), are shown in Table 9:
TABLE 9 CA0006 product element detection results
In summary, the embodiment of the invention utilizes the low-halogen electronic-grade red phosphorus purification device to normally convert industrial white phosphorus into red phosphorus, then the temperature is raised to convert the red phosphorus into phosphorus vapor, the phosphorus vapor is condensed again in the condensation pipe, and inorganic impurities in the raw materials are basically removed; then placing the red phosphorus which is re-condensed into a carbon disulfide solution and an ethanol solution step by step for dissolving and filtering to remove organic impurities; and finally, placing the mixture in a constant-temperature clean nitrogen cabinet for drying, and removing residual ethanol. The invention converts 99.9 percent of industrial white phosphorus into high-purity red phosphorus by a multi-step purification method. As shown in tables 2, 4-7 and 9, the total impurity content of the red phosphorus obtained after purification is less than 1000ppb, chlorine and bromine are basically kept at about 20ppb, and the red phosphorus is purified to the level of 6N and the content of halogen impurities is less than 50 ppb.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The purification device for the low-halogen electronic-grade red phosphorus is characterized by comprising a reaction tube, wherein the reaction tube comprises a charging tube and a condensation tube, and the charging tube is fixedly connected with the condensation tube through an elongated steam channel; a quartz boat is arranged in the charging pipe; a detachable plug is arranged at one end of the charging pipe, which is far away from the steam channel; the reaction tube is externally provided with a temperature control structure, and the temperature control structure is sequentially provided with a high-temperature area, a transition temperature area and a low-temperature area along the directions of the charging tube, the steam channel and the condensation tube.
2. The device for purifying low-halogen electronic-grade red phosphorus according to claim 1, wherein the charging pipe and the junction of the condensing pipe and the steam passage are located in the transition temperature region.
3. The device as claimed in claim 2, wherein the end of the condensing tube remote from the vapor channel is a closed hemisphere.
4. The device for purifying low-halogen electronic-grade red phosphorus according to claim 1, wherein the steam channel has an inner diameter of 20 to 40mm and a length of 120 to 180 mm.
5. The device for purifying low-halogen electronic-grade red phosphorus according to claim 1, wherein the reaction tube is made of quartz.
6. A method of producing low halogen electronic grade red phosphorus using the apparatus of any one of claims 1 to 5, comprising the steps of:
(1) filling white phosphorus into the quartz boat, packaging the charging tube and vacuumizing, setting a high-temperature area to heat to 320-380 ℃ at a constant heating rate of 10-200 ℃ per minute, and preserving heat for 50-70 hours to obtain a primary conversion product;
(2) heating the temperature control structure for 3-6 hours, heating the high-temperature area to 600-650 ℃, the transition temperature area to 450-500 ℃, and the low-temperature area to 350-400 ℃; preserving the heat for 18-24 hours;
(3) cooling the temperature control structure to 20-30 ℃ within 6-12 h, and breaking the condensation pipe to obtain a primary product;
(4) and filtering and washing the obtained primary product, and drying to obtain the product.
7. The production method according to claim 6, wherein in the step (1), the degree of vacuum in the charging tube reaches 1 to 7X 10 when the vacuum is applied-2pa。
8. The production method according to claim 6, wherein in the step (2), the temperature is raised by controlling the pressure outside the reaction tube to be higher than the phosphorus pressure inside the reaction tube by 3 to 5 bar.
9. The production method according to claim 6, wherein in the step (4), the filter washing employs a quartz washing tank; the solution of filtering and washing is carbon disulfide or an organic solvent; the number of times of filtering and washing is controlled to be 3-6 times, and each time lasts for 30-60 min.
10. The preparation method according to claim 6, wherein in the step (4), the drying temperature is controlled to be 50-60 ℃, the nitrogen time is controlled to be 8-12 h, and the air intake amount is controlled to be 300-1000L/h.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4185081A (en) * | 1978-07-31 | 1980-01-22 | The United States Of America As Represented By The Secretary Of The Air Force | Procedure for the synthesis of stoichiometric proportioned indium phosphide |
| US4764350A (en) * | 1986-10-08 | 1988-08-16 | The United States Of America As Represented By The Secretary Of The Air Force | Method and apparatus for synthesizing a single crystal of indium phosphide |
| JP2002160911A (en) * | 2000-11-20 | 2002-06-04 | Showa Denko Kk | METHOD FOR MANUFACTURING InP POLYCRYSTAL |
| US20120263630A1 (en) * | 2011-04-12 | 2012-10-18 | Zhi He | Vertical high temperature and high pressure stove structure |
| CN207943874U (en) * | 2017-09-13 | 2018-10-09 | 南京金美镓业有限公司 | A kind of composite heat shield structure of indium phosphide synthesizer |
| CN112374474A (en) * | 2020-11-13 | 2021-02-19 | 广东先导先进材料股份有限公司 | Preparation method of compact ultrahigh-purity material |
-
2021
- 2021-10-14 CN CN202111200556.1A patent/CN113735082A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4185081A (en) * | 1978-07-31 | 1980-01-22 | The United States Of America As Represented By The Secretary Of The Air Force | Procedure for the synthesis of stoichiometric proportioned indium phosphide |
| US4764350A (en) * | 1986-10-08 | 1988-08-16 | The United States Of America As Represented By The Secretary Of The Air Force | Method and apparatus for synthesizing a single crystal of indium phosphide |
| JP2002160911A (en) * | 2000-11-20 | 2002-06-04 | Showa Denko Kk | METHOD FOR MANUFACTURING InP POLYCRYSTAL |
| US20120263630A1 (en) * | 2011-04-12 | 2012-10-18 | Zhi He | Vertical high temperature and high pressure stove structure |
| CN207943874U (en) * | 2017-09-13 | 2018-10-09 | 南京金美镓业有限公司 | A kind of composite heat shield structure of indium phosphide synthesizer |
| CN112374474A (en) * | 2020-11-13 | 2021-02-19 | 广东先导先进材料股份有限公司 | Preparation method of compact ultrahigh-purity material |
Non-Patent Citations (2)
| Title |
|---|
| 天津化工研究设计院: "《无机精细化学品手册》", 31 January 2001, 化学工业出版社 * |
| 湖北省卫生防疫站: "《环境保护监测工作手册 第一册》", 31 January 1975, 湖北省卫生防疫站编印 * |
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