CN112390230A - Purification method and purification system of chlorine trifluoride - Google Patents
Purification method and purification system of chlorine trifluoride Download PDFInfo
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- CN112390230A CN112390230A CN202011309109.5A CN202011309109A CN112390230A CN 112390230 A CN112390230 A CN 112390230A CN 202011309109 A CN202011309109 A CN 202011309109A CN 112390230 A CN112390230 A CN 112390230A
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- chlorine trifluoride
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- fluoride
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- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000000746 purification Methods 0.000 title claims description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 38
- 239000003463 adsorbent Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 25
- 238000009833 condensation Methods 0.000 claims abstract description 14
- 230000005494 condensation Effects 0.000 claims abstract description 14
- 150000004673 fluoride salts Chemical group 0.000 claims abstract description 10
- 230000008016 vaporization Effects 0.000 claims abstract description 9
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 22
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 22
- 239000006200 vaporizer Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 11
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 11
- 235000003270 potassium fluoride Nutrition 0.000 claims description 11
- 239000011698 potassium fluoride Substances 0.000 claims description 11
- 235000013024 sodium fluoride Nutrition 0.000 claims description 11
- 239000011775 sodium fluoride Substances 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000047 product Substances 0.000 abstract description 19
- 239000012535 impurity Substances 0.000 abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 239000012043 crude product Substances 0.000 abstract description 6
- 238000012856 packing Methods 0.000 description 10
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 229910020323 ClF3 Inorganic materials 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 229910000792 Monel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004781 supercooling Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- -1 halocarbon hydrocarbon Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/24—Inter-halogen compounds
Abstract
The invention provides a method for purifying chlorine trifluoride, which comprises the following steps: s1) pressurizing and vaporizing the crude chlorine trifluoride, and then performing adsorption treatment by an adsorbent to obtain chlorine trifluoride gas without hydrogen fluoride; the adsorbent is fluoride salt; s2) condensing the chlorine trifluoride gas from which the hydrogen fluoride is removed to obtain a condensed chlorine trifluoride liquid; s3) carrying out two-stage rectification on the condensed chlorine trifluoride liquid to obtain high-purity chlorine trifluoride. Compared with the prior art, the method combines adsorption condensation and two-stage rectification, the chlorine trifluoride crude product is firstly subjected to adsorption to remove part of hydrogen fluoride, and then is subjected to two-stage continuous rectification, so that the hydrogen fluoride, the oxygen, the nitrogen and the metal ions can be removed to high purity, the control on the removal of the metal ion impurities is further increased, the continuous operation can be realized, the operation is stable, and the 3N-purity chlorine trifluoride product meeting the requirements of the semiconductor industry can be obtained.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to a chlorine trifluoride purification method and a purification system.
Background
Chlorine trifluoride (ClF)3) As cleaning gases for semiconductor production, Low Pressure Chemical Vapor Deposition (LPCVD) of polysilicon, SiN and the like, Plasma Chemical Vapor Deposition (PCVD) of amorphous alloy silicon and the like, and the like have been usedThe method is used in various aspects.
Chemical Vapor Deposition (CVD) processes in semiconductor manufacturing use heat or plasma as an energy source to decompose source gases on a silicon substrate. The (LPCVD) film formation reaction in a low pressure chemical vapor deposition process is driven by heat from a silicon wafer (cold wall reactor) or a heating furnace (hot wall reactor). A cold-wall LPCVD reactor is a typical single wafer production facility, while an LPCVD furnace can batch process wafers.
In plasma enhanced chemical vapor deposition processes, the source gas is decomposed by electrons from the heat (-5 eV) in RF (radio frequency) or microwave glow discharge. During CVD, material is deposited not only on the silicon substrate, but also on the chamber walls of the process chamber.
Therefore, the process chamber is periodically cleaned to remove the dislodged particles. In situ cleaning is desirable because the use of such cleaning processes to remove solid residues without disassembling the process chamber, and in situ cleaning of PECVD and LPCVD (cold wall) process chambers with fluorine gas has been used successfully for many years. When cleaned with fluorine gas, the fluorine atoms react with the solid residue to form volatile reaction products, which are pumped from the system. Because there is no thermal energy available, plasma must be used to generate reactive fluorine species.
Unlike other fluorine-containing gases (e.g. NF)3、C2F6And CF4)，ClF3Capable of reacting with the semiconductor material at room temperature. Because of ClF3With this reactive characteristic, it can be used to clean cold-wall CVD process chambers without the need for plasma. By ClF3Cleaning is a chemical etching process without the high energy ion bombardment process like diode RF plasma. Damage to the process chamber is minimized due to the absence of ion bombardment and it has been shown that the time between two wet cleans can be extended.
Albeit ClF3The method is a good semiconductor cleaning agent and fluorinating agent, but because chlorine trifluoride has extremely high reactivity, oxidability and toxicity, the existing method and equipment for purifying chlorine trifluoride are few. Publication No. isCN104555927B discloses a method for purifying chlorine trifluoride, in which chlorine trifluoride raw material is adsorbed and then fed into a batch rectifying tower to collect middle distillate as fine chlorine trifluoride product. Although the process equipment has low investment and simple operation, continuous rectification cannot be carried out, light impurity components (oxygen and nitrogen) and the like and heavy components (hydrogen fluoride) cannot be removed simultaneously, and the content of metal ions in the product is difficult to control.
Disclosure of Invention
In view of the above, the present invention provides a method and a system for purifying chlorine trifluoride, which can be performed continuously and with high purification accuracy.
The invention provides a method for purifying chlorine trifluoride, which comprises the following steps:
s1) pressurizing and vaporizing the crude chlorine trifluoride, and then performing adsorption treatment by an adsorbent to obtain chlorine trifluoride gas without hydrogen fluoride; the adsorbent is fluoride salt;
s2) condensing the chlorine trifluoride gas without hydrogen fluoride to obtain condensed chlorine trifluoride liquid;
s3) carrying out two-stage rectification on the condensed chlorine trifluoride liquid to obtain high-purity chlorine trifluoride.
Preferably, the pressure at the top of the tower is 1.1-1.8 bar and the pressure at the bottom of the tower is 1.2-1.9 bar during the primary rectification in the step S3); the temperature at the top of the tower is 10-20 ℃, and the temperature at the bottom of the tower is 15-25 ℃.
Preferably, the discharge flow of the materials discharged from the top of the primary rectification tower is 0.5-1 kg/h.
Preferably, the pressure at the top of the tower is 1.1-1.4 bar and the pressure at the bottom of the tower is 1.2-1.6 bar during the secondary rectification in the step S3); the temperature at the top of the tower is 8-15 ℃, and the temperature at the bottom of the tower is 10-20 ℃.
Preferably, the extraction flow rate of the tower top product of the secondary rectification is 2-4 kg/h.
Preferably, the pressure during the adsorption treatment in the step S1) is 2.1 to 2.2 bar; the temperature is 25-100 ℃.
Preferably, the fluoride salt is selected from one or more of sodium fluoride, potassium fluoride and calcium fluoride.
Preferably, the adsorbent is spherical fluoride salt with the particle size of 3-15 mm; the adsorbent has a microporous structure; the size of the micropores is 0.3-1.5 nm; the specific surface area of the adsorbent is 500-800 m2/g。
Preferably, the condensation temperature in the step S2) is 5 ℃ to 10 ℃, and the pressure is 2 bar.
The present invention also provides a system for purifying chlorine trifluoride, comprising:
a chlorine trifluoride raw material storage tank;
the pressure booster is communicated with the chlorine trifluoride raw material storage tank;
a vaporizer in communication with the supercharger;
the adsorption tower is communicated with the vaporizer; an adsorbent is arranged in the adsorption tower;
the condenser is communicated with the adsorption tower;
the primary rectifying tower is communicated with the condenser;
and the second-stage rectifying tower is communicated with the first-stage rectifying tower.
The invention provides a method for purifying chlorine trifluoride, which comprises the following steps: s1) pressurizing and vaporizing the crude chlorine trifluoride, and then performing adsorption treatment by an adsorbent to obtain chlorine trifluoride gas without hydrogen fluoride; the adsorbent is fluoride salt; s2) condensing the chlorine trifluoride gas from which the hydrogen fluoride is removed to obtain a condensed chlorine trifluoride liquid; s3) carrying out two-stage rectification on the condensed chlorine trifluoride liquid to obtain high-purity chlorine trifluoride. Compared with the prior art, the method combines adsorption condensation and two-stage rectification, the chlorine trifluoride crude product is firstly subjected to adsorption to remove part of hydrogen fluoride, and then is subjected to two-stage continuous rectification, so that the hydrogen fluoride, the oxygen, the nitrogen and the metal ions can be removed to high purity, the control on the removal of the metal ion impurities is further increased, the continuous operation can be realized, the operation is stable, and the 3N-purity chlorine trifluoride product meeting the requirements of the semiconductor industry can be obtained.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a chlorine trifluoride purification system, which comprises:
a chlorine trifluoride raw material storage tank;
the pressure booster is communicated with the chlorine trifluoride raw material storage tank;
a vaporizer in communication with the supercharger;
the adsorption tower is communicated with the vaporizer; an adsorbent is arranged in the adsorption tower;
the condenser is communicated with the adsorption tower;
the primary rectifying tower is communicated with the condenser;
and the second-stage rectifying tower is communicated with the first-stage rectifying tower.
According to the invention, the crude chlorine trifluoride to be treated is stored in a chlorine trifluoride raw material tank.
The chlorine trifluoride storage tank is communicated with a supercharger, and the crude chlorine trifluoride product is supercharged through the supercharger.
The outlet of the supercharger is communicated with the vaporizer; and vaporizing the crude chlorine trifluoride product by a vaporizer to obtain chlorine trifluoride gas.
The outlet of the vaporizer is communicated with the adsorption tower; an adsorbent is arranged in the adsorption tower; the adsorbent is preferably spherical; the particle size of the adsorbent is preferably 3-15 mm; the adsorbent has a microporous structure; the size of the micropores is preferably 0.3-1.5 nm; the specific surface area of the adsorbent is preferably 500-800 m2(ii) in terms of/g. In the adsorption tower, the action force of the adsorbent and HF is strong, and HF enters the pore channels of the adsorbent, so that HF is removed from chlorine trifluoride gas. The tower wall of the adsorption tower is preferably provided with a heating device, and more preferably wrapped with a heating jacket for temperature control.
The outlet of the adsorption tower is communicated with a condenser; the HF-removed gas is condensed with chlorine trifluoride in a condenser, whereby oxygen and nitrogen, which are difficult to condense, can be discharged.
The outlet of the condenser is communicated with the primary rectifying tower; the feed inlet of the first-stage rectifying tower is preferably positioned at the middle upper part of the tower; the material of the primary rectifying tower is preferably stainless steel, Monel alloy or nickel alloy and the like; the packing in the primary rectifying tower is preferably one or more of pall ring packing, theta ring packing, triangular spiral packing and Taylor rosette packing; the size of the filler is preferably 3mm multiplied by 3mm to 6mm multiplied by 6 mm; the material of the filler is preferably nickel alloy; the light components of oxygen and nitrogen impurities can be further removed from the tower top through the first-stage rectifying tower.
The primary rectifying tower is communicated with the secondary rectifying tower; the bottom liquid of the primary rectifying tower enters a secondary rectifying tower, the kettle liquid with high metal ion content can be discharged from the bottom of the secondary rectifying tower, and high-purity chlorine trifluoride is collected at the top of the tower; the material of the secondary rectifying tower is preferably stainless steel, Monel alloy or nickel alloy and the like; the packing in the secondary rectifying tower is preferably one or more of pall ring packing, theta ring packing, triangular spiral packing and Taylor rosette packing; the size of the filler is preferably 3mm multiplied by 3mm to 6mm multiplied by 6 mm; the material of the filler is preferably nickel alloy.
According to the invention, a subcooler and a collecting device are preferably also included; the subcooler is communicated with the top of the secondary rectifying tower; the collecting device is communicated with the subcooler; the high-purity chlorine trifluoride obtained from the top of the secondary rectifying tower can enter a collecting device for collection after passing through a cooler.
According to the invention, it is preferred to further include a vacuum pump; the vacuum pump is respectively communicated with the supercharger, the vaporizer, the absorption tower, the condenser, the primary rectifying tower and the secondary rectifying tower; for evacuating the whole system before purification to remove gaseous impurities contained in the system.
The present invention also provides a method for purifying chlorine trifluoride using the above purification system, comprising: s1) pressurizing and vaporizing the crude chlorine trifluoride, and then performing adsorption treatment by an adsorbent to obtain chlorine trifluoride gas without hydrogen fluoride; the adsorbent is fluoride salt; s2) condensing the chlorine trifluoride gas without hydrogen fluoride to obtain condensed chlorine trifluoride liquid; s3) carrying out two-stage rectification on the condensed chlorine trifluoride liquid to obtain high-purity chlorine trifluoride.
The present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.
Pressurizing and vaporizing the crude chlorine trifluoride, and then performing adsorption treatment by using an adsorbent to obtain chlorine trifluoride gas without hydrogen fluoride; the crude chlorine trifluoride is preferably chlorine trifluoride with the purity of more than or equal to 98 percent; the pressurizing vaporization preferably enables the pressure of the vaporized gas to be 2.1-2.2 bar, and more preferably 2.2 bar; during pressurization vaporization, the flow of the chlorine trifluoride crude product is preferably 4-6 kg/h, and more preferably 5 kg/; the adsorbent used in the adsorption treatment is fluoride salt, preferably one or more of sodium fluoride, potassium fluoride and calcium fluoride, and more preferably sodium fluoride, potassium fluoride and calcium fluoride; the mass ratio of the sodium fluoride to the potassium fluoride to the calcium fluoride is preferably (2-8): (1-5): 2, more preferably (3-6): (2-3): 2; in some embodiments provided herein, the mass ratio of sodium fluoride, potassium fluoride and calcium fluoride is preferably 5: 3: 2; in some embodiments provided herein, the mass ratio of sodium fluoride, potassium fluoride and calcium fluoride is preferably 6: 2: 2; in other embodiments provided by the present invention, the mass ratio of the sodium fluoride, the potassium fluoride and the calcium fluoride is preferably 3: 2: 2; the adsorbent is preferably spherical; the particle size of the adsorbent is preferably 3-15 mm, more preferably 3-12 mm, still more preferably 3-10 mm, still more preferably 3-8 mm, and most preferably 4-5 mm; the adsorbent has a microporous structure; the average size of the micropores is preferably 0.3-1.5 nm, more preferably 0.3-1.2 nm, still more preferably 0.3-1 nm, still more preferably 0.3-0.8 nm, still more preferably 0.4-0.6 nm, and most preferably 0.4 nm; the specific surface area of the adsorbent is preferably 500-800 m2(ii)/g, more preferably 600 to 700m2(ii)/g; the pressure during the adsorption treatment is preferably 2.1-2.2 bar, and more preferably 2.1 bar; the temperature is from 25 ℃ to 100 ℃, more preferably from 35 ℃ to 80 ℃, even more preferably from 35 ℃ to 60 ℃, and most preferablyIs 40 ℃ to 50 ℃; the time of the adsorption treatment is preferably 16-28 s, more preferably 18-25 s, and further preferably 20 s; the flow rate of the gas during the adsorption treatment is preferably 4-6 kg/h, and more preferably 5 kg/h.
Condensing the chlorine trifluoride gas without hydrogen fluoride to obtain condensed chlorine trifluoride liquid; the condensation is preferably carried out in a condenser; during the condensation, the temperature of the condensed chlorine trifluoride liquid is preferably controlled to be 5-10 ℃, more preferably 7-9 ℃, and further preferably 7-8 ℃; the outlet pressure is preferably controlled to 2bar during the condensation.
Carrying out two-stage rectification on the condensed chlorine trifluoride liquid; the pressure at the top of the tower during the primary rectification is preferably 1.1-1.8 bar, more preferably 1.3-1.7 bar, and still more preferably 1.5-1.6 bar; the temperature at the top of the column is preferably 10 to 20 ℃, and more preferably 14 to 20 ℃; the pressure at the bottom of the tower is preferably 1.2-1.9 bar, more preferably 1.4-1.8 bar, and still more preferably 1.6-1.7 bar; the temperature at the bottom of the column is preferably from 15 to 25 ℃ and more preferably from 18 to 25 ℃. Removing light components (including oxygen, nitrogen and the like) at the tower top through primary rectification; the flow rate for removing the light components is preferably 0.5-1 kg/h.
The tower bottom material of the first-stage rectification enters a second-stage rectification tower to be subjected to second-stage rectification; the pressure at the top of the tower during the secondary rectification is preferably 1.1-1.4 bar, more preferably 1.1-1.3 bar, and still more preferably 1.2 bar; the temperature at the top of the tower is preferably 8-15 ℃, and more preferably 12-15 ℃; the pressure at the bottom of the tower is preferably 1.2-1.6 bar, more preferably 1.3-1.5 bar, and still more preferably 1.3-1.4 bar; the temperature at the bottom of the column is preferably 10 to 20 ℃ and more preferably 16 to 20 ℃. Heavy component halocarbon hydrocarbon impurities are removed from the tower bottom during secondary rectification; the discharge flow rate of heavy components at the bottom of the tower is preferably 0.5-1.5 kg/h; high-purity chlorine trifluoride is obtained at the top of the tower, and the extraction flow of the product at the top of the tower is preferably 2-4 kg/h, and more preferably 3-4 kg/h.
According to the invention, adsorption condensation and two-stage rectification are combined, a chlorine trifluoride crude product is subjected to adsorption to remove part of hydrogen fluoride, and then is subjected to two-stage continuous rectification, so that hydrogen fluoride, oxygen, nitrogen and metal ions can be removed to high purity, the control of metal ion impurity removal can be further increased, the continuous operation can be realized, the operation is stable, and the 3N-purity chlorine trifluoride product meeting the requirements of the semiconductor industry can be obtained.
In order to further illustrate the present invention, the following will describe the purification method and purification system of chlorine trifluoride provided by the present invention in detail with reference to the examples.
The reagents used in the following examples are all commercially available. Example 1
And purging and replacing the whole system by using high-purity nitrogen, and vacuumizing the system by using a vacuum pump until the negative pressure is 0.5 Pa.
Helium leak detection is carried out on the system, because the toxicity of the chlorine trifluoride active agent is extremely high, the leakage of the system must be ensured to be free, and the leakage rate of the system is lower than 1.0 multiplied by 10-9mbarL/s；
The crude liquid chlorine trifluoride (the composition of which is shown in Table 2) from the chlorine trifluoride raw material storage tank is pressurized to 2.2barg by a booster pump, and the outlet gas pressure is controlled to be 2.2barg by gasifying a vaporizer, wherein the flow rate is controlled to be 5 kg/h;
the pressurized chlorine trifluoride gas enters a DN50mm multiplied by 2000mm adsorption tower to adsorb hydrogen fluoride (the mass ratio of sodium fluoride to potassium fluoride to calcium fluoride is 5: 3: 2; the adsorbent is spherical, the particle size is 4-5 mm; the average micropore size is 0.4 nm; and the specific surface area is 600-700 m)2The pressure of the adsorption tower is controlled to be 2.1barg, the outer wall of the adsorption tower is wrapped by a heating sleeve for temperature control, and the adsorption temperature is 40 ℃;
the chlorine trifluoride gas after absorbing and removing hydrogen fluoride enters a condenser for condensation, the temperature of the outlet of chlorine trifluoride liquid is controlled to be 8 ℃, the pressure is 2barg, the condensed liquid enters a primary rectifying tower, and the impurities of the gas which is difficult to condense are discharged to a tail gas treatment system;
after condensation, chlorine trifluoride liquid enters a two-stage rectifying tower for rectification, firstly enters a first-stage rectifying tower to control the pressure at the top of the tower to be 1.5barg, the pressure at the bottom of the tower to be 1.6barg, the temperature at the top of the tower to be 15 ℃ and the temperature at the bottom of the tower to be 20 ℃, light components (including oxygen, nitrogen and the like) are removed at the top of the tower, and the discharge flow is controlled to be 0.5kg/h by a mass flow meter controller; then the tower bottom material enters a secondary rectifying tower to control the pressure at the top of the tower to be 1.2barg, the pressure at the bottom of the tower to be 1.3barg, the temperature at the top of the tower to be 13 ℃ and the temperature at the bottom of the tower to be 18 ℃, heavy component halocarbon impurities are separated from the tower bottom, and the discharge flow at the bottom of the tower is controlled to be 0.5kg/h by a mass flow meter controller; 3N qualified products are obtained at the top of the rectifying tower, the flow of the products is controlled to be 4kg/h by a mass flow controller, and the yield is 80 percent.
The 3N purity product at the top of the secondary rectifying tower is supercooled into liquid by a subcooler and then is filled into a steel cylinder, and the analysis result is shown in the following table 1.
Example 2
And (4) purging and replacing the whole system by using high-purity nitrogen, and vacuumizing the system by using a vacuum pump until the negative pressure is 1 pa.
Helium leak detection is carried out on the system, because the toxicity of the chlorine trifluoride active agent is extremely high, the leakage of the system must be ensured to be free, and the leakage rate of the system is lower than 1.0 multiplied by 10-9mbarL/s；
Pressurizing the liquid chlorine trifluoride crude product from a chlorine trifluoride raw material storage tank to 2.2barg by a booster pump, controlling the pressure of outlet gas to be 2.2barg by gasifying a vaporizer, and controlling the flow to be 5 kg/h;
the pressurized chlorine trifluoride gas enters an adsorption tower of DN50mm multiplied by 2000mm to adsorb hydrogen fluoride (the mass ratio of sodium fluoride to potassium fluoride to calcium fluoride is 6: 2: 2, the spherical particle size is 4-5 mm, the average micropore size is 0.4nm, and the specific surface area is 600-700 m2The pressure of the adsorption tower is controlled to be 2.1barg, the outer wall of the adsorption tower is wrapped by a heating sleeve for temperature control, and the adsorption temperature is 50 ℃;
the chlorine trifluoride gas after absorbing and removing hydrogen fluoride enters a condenser for condensation, the temperature of the outlet of chlorine trifluoride liquid is controlled to be 7 ℃, the pressure is 2barg, the condensed liquid enters a primary rectifying tower, and the impurities of the gas which is difficult to condense are discharged to a tail gas treatment system;
after condensation, chlorine trifluoride liquid enters a two-stage rectifying tower for rectification, firstly enters a first-stage rectifying tower to control the pressure at the top of the tower to be 1.2barg, the pressure at the bottom of the tower to be 1.4barg, the temperature at the top of the tower to be 14 ℃ and the temperature at the bottom of the tower to be 18 ℃, light components (including oxygen, nitrogen and the like) are removed from the top of the tower, and the discharge flow is controlled to be 0.6kg/h by a mass flow meter controller; then the tower bottom material enters a secondary rectifying tower to control the pressure at the top of the tower to be 1.1barg, the pressure at the bottom of the tower to be 1.2barg, the temperature at the top of the tower to be 12 ℃, the temperature at the bottom of the tower to be 16 ℃, heavy component halocarbon impurities are separated from the tower bottom, and the discharge flow at the bottom of the tower is controlled to be 0.6kg/h by a mass flow meter controller; 3N qualified products are obtained at the top of the rectifying tower, the flow of the products is controlled to be 3.8kg/h by a mass flow controller, and the yield is 76%.
Supercooling the 3N purity product at the top of the secondary rectifying tower through a subcooler into liquid, filling the liquid into a steel cylinder, and enabling the analysis result to meet the requirements of the table 1.
Example 3
And purging and replacing the whole system by using high-purity nitrogen, and vacuumizing the system by using a vacuum pump until the negative pressure is 1 Pa.
Helium leak detection is carried out on the system, because the toxicity of the chlorine trifluoride active agent is extremely high, the leakage of the system must be ensured to be free, and the leakage rate of the system is lower than 1.0 multiplied by 10-9mbarL/s；
Pressurizing the liquid chlorine trifluoride crude product from a chlorine trifluoride raw material storage tank to 2.2barg by a booster pump, controlling the pressure of outlet gas to be 2.2barg by gasifying a vaporizer, and controlling the flow to be 5 kg/h;
the pressurized chlorine trifluoride gas enters an adsorption tower of DN50mm multiplied by 2000mm to adsorb hydrogen fluoride (the mass ratio of sodium fluoride to potassium fluoride to calcium fluoride is 3: 2: 2, the spherical particle size is 4-5 mm, the average micropore size is 0.4nm, and the specific surface area is 600-700 m2The pressure of the adsorption tower is controlled to be 2.1barg, the outer wall of the adsorption tower is wrapped by a heating sleeve for temperature control, and the adsorption temperature is 50 ℃;
the chlorine trifluoride gas after absorbing and removing hydrogen fluoride enters a condenser for condensation, the temperature of the outlet of chlorine trifluoride liquid is controlled to be 8 ℃, the pressure is 2barg, the condensed liquid enters a primary rectifying tower, and the impurities of the gas which is difficult to condense are discharged to a tail gas treatment system;
after condensation, chlorine trifluoride liquid enters a two-stage rectifying tower for rectification, firstly enters a first-stage rectifying tower to control the pressure at the top of the tower to be 1.6barg, the pressure at the bottom of the tower to be 1.7barg, the temperature at the top of the tower to be 20 ℃ and the temperature at the bottom of the tower to be 25 ℃, light components (including oxygen, nitrogen and the like) are removed at the top of the tower, and the discharge flow is controlled to be 0.8kg/h through a mass flow meter controller; then the tower bottom material enters a secondary rectifying tower to control the pressure at the top of the tower to be 1.4barg, the pressure at the bottom of the tower to be 1.5barg, the temperature at the top of the tower to be 15 ℃, the temperature at the bottom of the tower to be 20 ℃, heavy component halocarbon impurities are separated from the tower bottom, and the discharge flow at the bottom of the tower is controlled to be 0.3kg/h by a mass flow meter controller; 3N qualified products are obtained at the top of the rectifying tower, the flow of the products is controlled to be 3.9kg/h by a mass flow controller, and the yield is 78 percent.
Supercooling the 3N purity product at the top of the secondary rectifying tower through a subcooler into liquid, filling the liquid into a steel cylinder, and enabling the analysis result to meet the requirements of the table 1.
TABLE 13N product composition and Metal ion content
| Serial number | Item | Index (I) |
| 1 | ClF3 | 99.9％ |
| 2 | O2 | 20ppmv |
| 3 | N2 | ＜50ppmv |
| 4 | HF | 700ppmv |
| 6 | Fe | ＜1ppmw |
| 7 | Ni | ＜1ppmw |
| 8 | Cr | ＜1ppmw |
| 9 | Na | ＜1ppmw |
| 10 | K | ＜1ppmw |
| 11 | Ca | ＜1ppmw |
| 12 | Cu | ＜1ppmw |
| 13 | Co | ＜1ppmw |
TABLE 2 crude chlorine trifluoride composition and Metal ion content
Claims (10)
1. A method for purifying chlorine trifluoride, comprising:
s1) pressurizing and vaporizing the crude chlorine trifluoride, and then performing adsorption treatment by an adsorbent to obtain chlorine trifluoride gas without hydrogen fluoride; the adsorbent is fluoride salt;
s2) condensing the chlorine trifluoride gas without hydrogen fluoride to obtain condensed chlorine trifluoride liquid;
s3) carrying out two-stage rectification on the condensed chlorine trifluoride liquid to obtain high-purity chlorine trifluoride.
2. The purification method according to claim 1, wherein the pressure at the top of the column in the primary rectification in the step S3) is 1.1 to 1.8bar, and the pressure at the bottom of the column is 1.2 to 1.9 bar; the temperature at the top of the tower is 10-20 ℃, and the temperature at the bottom of the tower is 15-25 ℃.
3. The purification method according to claim 2, wherein the discharge flow rate of the overhead material of the primary rectification is 0.5-1 kg/h.
4. The purification method according to claim 1, wherein the pressure at the top of the column in the secondary rectification in the step S3) is 1.1 to 1.4bar, and the pressure at the bottom of the column is 1.2 to 1.6 bar; the temperature at the top of the tower is 8-15 ℃, and the temperature at the bottom of the tower is 10-20 ℃.
5. The purification method according to claim 4, wherein the extraction flow rate of the overhead product of the secondary rectification is 2-4 kg/h.
6. The purification method according to claim 1, wherein the pressure in the adsorption treatment in step S1) is 2.1 to 2.2 bar; the temperature is 25-100 ℃.
7. The purification method according to claim 1, wherein the fluoride salt is selected from one or more of sodium fluoride, potassium fluoride, and calcium fluoride.
8. The purification method according to claim 1, wherein the adsorbent is a spherical fluoride salt having a particle size of 3 to 15 mm; the adsorbent has a microporous structure; the size of the micropores is 0.3-1.5 nm; the specific surface area of the adsorbent is 500-800 m2/g。
9. The purification method according to claim 1, wherein the temperature of the condensation in step S2) is 5 ℃ to 10 ℃ and the pressure is 2 bar.
10. A system for purifying chlorine trifluoride, comprising:
a chlorine trifluoride raw material storage tank;
the pressure booster is communicated with the chlorine trifluoride raw material storage tank;
a vaporizer in communication with the supercharger;
the adsorption tower is communicated with the vaporizer; an adsorbent is arranged in the adsorption tower;
the condenser is communicated with the adsorption tower;
the primary rectifying tower is communicated with the condenser;
and the second-stage rectifying tower is communicated with the first-stage rectifying tower.
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| CN113371681A (en) * | 2021-06-29 | 2021-09-10 | 鹤壁德瑞科技有限公司 | Purification method and preparation method of high-purity chlorine trifluoride |
| CN113562699A (en) * | 2021-06-29 | 2021-10-29 | 鹤壁德瑞科技有限公司 | Purification system and preparation system of high-purity chlorine trifluoride |
| CN113562700A (en) * | 2021-07-17 | 2021-10-29 | 鹤壁德瑞科技有限公司 | Preparation method of chlorine trifluoride |
| CN113926282A (en) * | 2021-10-19 | 2022-01-14 | 中船重工（邯郸）派瑞特种气体有限公司 | Purification and separation device for efficiently preparing high-purity chlorine trifluoride |
| CN114470866A (en) * | 2022-01-26 | 2022-05-13 | 中船(邯郸)派瑞特种气体股份有限公司 | Method for purifying hydrogen fluoride in trifluoromethanesulfonyl fluoride |
| CN115321486A (en) * | 2022-07-23 | 2022-11-11 | 四川红华实业有限公司 | Electronic grade chlorine trifluoride purification method |
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| CN113371681A (en) * | 2021-06-29 | 2021-09-10 | 鹤壁德瑞科技有限公司 | Purification method and preparation method of high-purity chlorine trifluoride |
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| CN113926282A (en) * | 2021-10-19 | 2022-01-14 | 中船重工（邯郸）派瑞特种气体有限公司 | Purification and separation device for efficiently preparing high-purity chlorine trifluoride |
| CN114470866A (en) * | 2022-01-26 | 2022-05-13 | 中船(邯郸)派瑞特种气体股份有限公司 | Method for purifying hydrogen fluoride in trifluoromethanesulfonyl fluoride |
| CN115321486A (en) * | 2022-07-23 | 2022-11-11 | 四川红华实业有限公司 | Electronic grade chlorine trifluoride purification method |
| CN115321486B (en) * | 2022-07-23 | 2023-11-17 | 四川红华实业有限公司 | Method for purifying electronic grade chlorine trifluoride |
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