CN111004088A - Method and device for purifying octafluorocyclobutane gas - Google Patents
Method and device for purifying octafluorocyclobutane gas Download PDFInfo
- Publication number
- CN111004088A CN111004088A CN201911202168.XA CN201911202168A CN111004088A CN 111004088 A CN111004088 A CN 111004088A CN 201911202168 A CN201911202168 A CN 201911202168A CN 111004088 A CN111004088 A CN 111004088A
- Authority
- CN
- China
- Prior art keywords
- tower
- rectifying tower
- rectifying
- component removal
- heavy
- 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.)
- Pending
Links
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000004341 Octafluorocyclobutane Substances 0.000 title claims abstract description 102
- 235000019407 octafluorocyclobutane Nutrition 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 64
- 238000001179 sorption measurement Methods 0.000 claims abstract description 52
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000012071 phase Substances 0.000 claims description 80
- 238000010992 reflux Methods 0.000 claims description 58
- 239000007788 liquid Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000007791 liquid phase Substances 0.000 claims description 45
- 239000012535 impurity Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 25
- 238000000066 reactive distillation Methods 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000428 dust Substances 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000003463 adsorbent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910000792 Monel Inorganic materials 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 29
- 238000000746 purification Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 102
- 239000000047 product Substances 0.000 description 19
- 239000012043 crude product Substances 0.000 description 9
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- DAFIBNSJXIGBQB-UHFFFAOYSA-N perfluoroisobutene Chemical group FC(F)=C(C(F)(F)F)C(F)(F)F DAFIBNSJXIGBQB-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WSJULBMCKQTTIG-OWOJBTEDSA-N (e)-1,1,1,2,3,4,4,4-octafluorobut-2-ene Chemical compound FC(F)(F)C(/F)=C(\F)C(F)(F)F WSJULBMCKQTTIG-OWOJBTEDSA-N 0.000 description 1
- ZVJOQYFQSQJDDX-UHFFFAOYSA-N 1,1,2,3,3,4,4,4-octafluorobut-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)F ZVJOQYFQSQJDDX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002151 riboflavin Substances 0.000 description 1
- 238000000926 separation method Methods 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method and a device for purifying octafluorocyclobutane gas, belonging to the technical field of fine chemical engineering. The method can obtain the high-purity octafluorocyclobutane product with the purity of more than 99.999 percent through the processes of reactive rectification, adsorption, filtration, continuous rectification for two times and filtration, can reduce the cold and heat consumed in the purification process by adopting continuous operation, and has high product yield and good economical efficiency. In addition, the device adopted by the invention has the advantages of less equipment investment and high production capacity, and is suitable for industrial large-scale production.
Description
Technical Field
The invention relates to a method and a device for purifying octafluorocyclobutane gas, belonging to the technical field of fine chemical engineering.
Background
High purity octafluorocyclobutane is a commonly used etching or cleaning gas for semiconductor manufacturing. It can remove the film material such as silicon oxide, silicon nitride, etc., thereby realizing the etching of the semiconductor film material and simultaneously removing the film raw material deposited in the chamber during the film formation. In recent years, with higher performance and smaller size of electronic or electric elements, the requirement for etching precision of semiconductor devices is higher and higher, and the requirement for purity of etching gas is higher and higher. When the octafluorocyclobutane is used as a cleaning gas, a product with a high-density integrated circuit can be defective due to a trace amount of impurities contained in the octafluorocyclobutane. Therefore, the purity requirement of the high-purity octafluorocyclobutane applied to large-scale integrated circuits is more than 99.999 percent.
The preparation method of octafluorocyclobutane mainly comprises a tetrafluoroethylene dimerization method, an electrochemical fluorination method, a pyrolysis method, a byproduct recovery method and the like, and the existing tetrafluoroethylene dimerization method is relatively mature. During the preparation of octafluorocyclobutane, fluorination and high temperature reactions are involved, a large amount of heat is evolved, and bond cleavage and rearrangement occurs, resulting in a large amount of fragments, dimers, polymers or other carbon halogen compounds. The impurities in the crude gas of the octafluorocyclobutane comprise alkene fluorocarbons, other perfluorocarbons and the like. These impurities are of various kinds, and some of them are only 1X 10-6Even 1X 10-9Volume ratio (i.e. ppm or ppb) level, and in addition O2、N2、CO、CO2And H2O and the like, and further purification of the prepared crude gas is required to remove the impurities in order to obtain high-purity octafluorocyclobutane.
The purification method of the octafluorocyclobutane mainly comprises the following steps: (1) a rectification method, which is the most commonly used method, but it is difficult to obtain high-purity octafluorocyclobutane by a rectification method because the boiling points of the olefinic fluorocarbons such as octafluoroisobutylene, octafluoro-1-butene, and octafluoro-2-butene are close to that of octafluorocyclobutane; (2) an adsorption method, which is effective for adsorbing chlorine-containing fluorocarbons, but is difficult to remove impurities such as vinyl fluorocarbons, hydrogen-containing fluorocarbons, perfluorocarbons and the like, and has a high content of octafluoroisobutylene in desorbed gas during desorption, thereby easily causing safety accidents; (3) a catalytic conversion process in which a material having a boiling point close to that of octafluorocyclobutane is converted into a material having a boiling point greatly different from that of octafluorocyclobutane, but this process is effective only for specific impurities; (4) the membrane separation method can only separate substances with larger difference with the molecular size of the octafluorocyclobutane, such as nitrogen, helium and the like, and is more suitable for recovering the octafluorocyclobutane from tail gas containing a large amount of inert gas.
Patent CN101134710A discloses a method for recovering octafluorocyclobutane from the residual liquid of tetrafluoroethylene production process, which comprises subjecting the residual liquid to preliminary distillation to obtain octafluorocyclobutane and components with similar boiling points, and rectifying in an extractive distillation column, wherein the extractant is one or more of carbon tetrachloride, ethylene glycol dimethyl ether, acetone, toluene or methanol, and the components at the top of the column are octafluorocyclobutane. The method is simple and effective, and the purity of the prepared octafluorocyclobutane exceeds 99 percent, but cannot meet the requirement of electronic grade.
Patent CN1220548C discloses a perfluorocarbon adsorbent which can effectively adsorb impurities in octafluorocyclobutane to obtain octafluorocyclobutane gas with purity of more than 99.9999%. Although the method can obtain the octafluorocyclobutane product with high purity, the preparation steps of the adsorbent are complicated, the preparation conditions are harsh, and the types of impurities in the adsorption process are limited, so that the purification process of the octafluorocyclobutane gas is restricted.
Disclosure of Invention
Aiming at the defects in the prior art, one of the purposes of the invention is to provide a method for purifying octafluorocyclobutane gas, which obtains a high-purity octafluorocyclobutane product with the purity of more than 99.999 percent through the processes of reactive distillation, adsorption, filtration, continuous twice distillation and filtration, and has the advantages of simple operation, high product yield and good economy.
The invention also aims to provide a device for purifying the octafluorocyclobutane gas, which has the advantages of less equipment investment and high production capacity and is suitable for industrial large-scale production.
The purpose of the invention is realized by the following technical scheme.
A process for purifying an octafluorocyclobutane gas, comprising the steps of:
reacting and rectifying the crude octafluorocyclobutane through a reaction rectifying tower, sequentially passing gas phase at the top of the reaction rectifying tower through an adsorption tower, a dust remover and a filter in sequence, then feeding the gas phase into a light component removal rectifying tower for rectifying to remove light component impurities, feeding a liquid phase part at the bottom of the light component removal rectifying tower into a heavy component removal rectifying tower for rectifying to remove heavy component impurities, and feeding the gas phase at the top of the heavy component removal rectifying tower through the filter for extracting to obtain high-purity octafluorocyclobutane gas;
SbCl is arranged at the position of a tower kettle of the reaction rectifying tower5Liquid, the temperature of the bottom of the tower is 40-45 ℃, the temperature of the top of the tower is 35-40 ℃, the temperature difference between the bottom of the tower and the top of the tower is not less than 2 ℃, the rectifying pressure is 0.35-0.45 MPa, and the reflux ratio is 1-10;
the adsorbent filled in the adsorption tower is a molecular sieve or active carbon, and the adsorption pressure is 0.35MPa to 0.45 MPa;
the temperature of the bottom of the light component removal rectifying tower is 30-35 ℃, the temperature of the top of the rectifying tower is 25-30 ℃, the temperature difference between the bottom of the rectifying tower and the top of the rectifying tower is not less than 2 ℃, the rectifying pressure is 0.25-0.30 MPa, and the reflux ratio is 5-300;
the temperature of the tower bottom of the heavy component removal rectifying tower is 20-25 ℃, the temperature of the tower top is 15-20 ℃, the temperature difference between the tower bottom and the tower top is not less than 2 ℃, the rectifying pressure is 0.15-0.20 MPa, and the reflux ratio is 1-10;
the reaction rectifying tower, the light component removing rectifying tower and the heavy component removing rectifying tower are all packing rectifying towers, the packing is pall rings, theta rings or Raschig rings, and the material of the packing is polytetrafluoroethylene, stainless steel, nickel or monel alloy.
Further, the reaction rectifying tower, the light component removing rectifying tower and the heavy component removing rectifying tower are arranged into different pressure towers, and the gas phase discharged from the top of the high-pressure tower is used as a heat source to provide heat for a reboiler at the bottom of the low-pressure tower, namely:
the gas phase at the top of the reactive distillation tower is used as a heat source to enter a reboiler at the bottom of the light component removal distillation tower, the gas phase serving as the heat source is partially condensed and liquefied after exchanging heat with materials at the bottom of the tower, the liquid phase is used as reflux liquid at the top of the reactive distillation tower to flow back, and the gas phase is partially introduced into an adsorption tower to be adsorbed;
and the gas phase at the top of the light component removal rectifying tower is used as a heat source to enter a reboiler at the bottom of the heavy component removal rectifying tower, the gas phase serving as the heat source is partially condensed and liquefied after exchanging heat with materials at the bottom of the tower, the liquid phase is used as reflux liquid at the top of the light component removal rectifying tower to flow back, and the gas phase is partially extracted as light component impurities.
Further, the temperature and the flow of the crude octafluorocyclobutane entering the reactive distillation tower are respectively-10 to 50 ℃ and 1kg/h to 100kg/h, and SbCl in the reactive distillation tower5The weight of the heavy component is 10 kg-100 kg, the flow of gas phase extracted from the top of the reactive distillation tower entering the adsorption tower is 1 kg/h-100 kg/h, the feed flow of the light component removal distillation tower is 1 kg/h-100 kg/h, the light component discharge flow of the top of the light component removal distillation tower is 0.05 kg/h-2 kg/h, the feed flow of the heavy component removal distillation tower is 0.95 kg/h-98 kg/h, the heavy component discharge flow of the bottom of the heavy component removal distillation tower is 0.05 kg/h-2 kg/h, and the gas phase extraction rate of the top of the heavy component removal distillation tower is 0.90 kg/h-96 kg/h.
Furthermore, the heights of the reaction rectifying tower, the light component removing rectifying tower and the heavy component removing rectifying tower are respectively and independently 2-15 mm, the diameters of the rectifying columns are respectively and independently 50-500 mm, and the diameters of the fillers are respectively and independently 2-30 mm.
Furthermore, the heights of the reaction rectifying tower, the light component removing rectifying tower and the heavy component removing rectifying tower are respectively and independently 3-8 mm, the diameters of the rectifying columns are respectively and independently 100-300 mm, and the diameters of the fillers are respectively and independently 2-10 mm.
Further, the filtration precision of the filter is 0.003 to 0.5. mu.m.
The device for purifying the octafluorocyclobutane by adopting the method comprises a reaction rectifying tower, an adsorption tower, a dust remover, a filter I, a light component removing rectifying tower, a heavy component removing rectifying tower and a filter II;
the reaction rectifying tower consists of a tower kettle heating device and a tower body, wherein a feed inlet is arranged at the middle lower part of the tower body, and a gas-phase discharge port and a liquid-phase reflux port are arranged at the top of the tower;
the tower bottom of the adsorption tower is provided with a feed inlet, and the tower top is provided with a discharge outlet;
the light component removal rectifying tower consists of a tower bottom reboiler I and a tower body, wherein a feed inlet is formed in the middle of the tower body, a gas phase discharge port and a liquid phase reflux port are formed in the tower top, and a liquid phase discharge port is formed in the tower bottom;
the heavy component removal rectifying tower consists of a tower bottom reboiler II, a tower body and a tower top condenser, wherein a feed inlet is formed in the middle of the tower body, a gas phase discharge port and a liquid phase reflux port are formed in the tower top, and a heavy component removal outlet is formed in the tower bottom;
a gas phase discharge port of the reaction rectifying tower is connected with a feed port of a reboiler I of the light-component removal rectifying tower, a discharge port of the reboiler I of the light-component removal rectifying tower is respectively connected with a liquid phase reflux port of the reaction rectifying tower and a feed port of the adsorption tower, a discharge port of the adsorption tower is connected with a feed port of the light-component removal rectifying tower, a dust remover and a filter I are arranged on a pipeline connecting the adsorption tower and the light-component removal rectifying tower, a liquid phase discharge port of the light-component removal rectifying tower is connected with a feed port of the heavy-component removal rectifying tower, a gas phase discharge port of the light-component removal rectifying tower is connected with a feed port of a reboiler II of the heavy-component removal rectifying tower, a discharge port of the reboiler II of the heavy-component removal rectifying tower is respectively connected with a liquid phase reflux port and a discharge pipe of the light-component removal rectifying tower, a heavy-component discharge outlet of the heavy-component removal rectifying, and a liquid phase reflux port of the heavy component removal rectifying tower is connected with the filter II.
Has the advantages that:
(1) the method adopts continuous operation, reduces the cold and heat consumed in the purification process, and has high product yield and good economy;
(2) the method of the invention leads alkene fluorocarbon and SbCl in octafluorocyclobutane to be rectified by reaction5The olefin is added to form chlorinated compound with high boiling point, and the chlorinated compound is left in the reaction rectifying tower to reduce the alkene in octafluorocyclobutane greatlyA fluorocarbon content;
(3) the invention adopts a tertiary rectification process, heats the reboiler at the bottom of the low-pressure tower by the gas phase at the top of the high-pressure tower, can realize secondary utilization of heat, can save energy by more than 30 percent, simultaneously reduces the investment of equipment and saves the use of a low-temperature cooling medium at the top of the tower;
(4) the invention adopts the light component removal rectifying tower to discharge light component impurities and adopts the heavy component removal rectifying tower to discharge heavy component impurities, so that the contents of light component impurities and heavy component impurities in a rectifying system are reduced; the adsorption tower is adopted to adsorb the carbon halogen compound, in particular to the carbon halogen compound containing chlorine and bromine, so that the light discharge weight of the light-weight-removing rectifying tower and the weight discharge in the heavy-weight-removing rectifying tower are reduced, the product yield is improved, and the production capacity and the product quality are improved;
(5) the invention obtains the high-purity octafluorocyclobutane product with the purity of more than 99.999 percent by regulating and controlling the purification process and the process parameters, and is easy to realize large-scale continuous industrial production.
Drawings
FIG. 1 is a schematic diagram of the apparatus involved in purifying octafluorocyclobutane in the example.
The system comprises a T101-reaction rectifying tower, an E101-tower kettle heating device, an A1-adsorption tower, a B1-dust remover, an F1-filter I, a T102-light-component-removal rectifying tower, an E201-reboiler I, a T103-heavy-component-removal rectifying tower, an E301-condenser, an E302-reboiler II and an F2-filter II.
Detailed Description
The invention is further illustrated by the following figures and detailed description, wherein the process is conventional unless otherwise specified, and the starting materials are commercially available from a public disclosure without further specification.
In the following examples:
detecting the components and the content of each component of the octafluorocyclobutane gas by using a gas chromatograph, wherein the gas chromatograph is Shimadzu GC-14C, the carrier gas is nitrogen, the detector is a hydrogen Flame Ionization Detector (FID), and the sample injection amount is 0.2 mL;
the organic carbon halogen compound refers to impurities containing carbon (C) atoms and halogen (F, Cl, Br) atoms;
the device related to the purification of the octafluorocyclobutane gas comprises a reaction rectifying tower T101, an adsorption tower A1, a dust remover B1, a filter IF 1, a light component removal rectifying tower T102, a heavy component removal rectifying tower T103 and a filter II F2, and is shown in figure 1;
the reaction rectifying tower T101 consists of a tower kettle heating device E101 and a tower body, wherein a feed inlet is formed in the middle lower part of the tower body, and a gas phase discharge port and a liquid phase reflux port are formed in the tower top;
the bottom of the adsorption tower A1 is provided with a feed inlet, and the top of the adsorption tower A1 is provided with a discharge outlet;
the light component removal rectifying tower T102 consists of a tower bottom reboiler IE 201 and a tower body, wherein a feed inlet is formed in the middle of the tower body, a gas phase discharge port and a liquid phase reflux port are formed in the top of the tower, and a liquid phase discharge port is formed in the bottom of the tower;
the heavy component removal rectifying tower T103 consists of a tower bottom reboiler IIE 302, a tower body and a tower top condenser E301, wherein a feed inlet is formed in the middle of the tower body, a gas phase discharge port and a liquid phase reflux port are formed in the tower top, and a heavy component removal outlet is formed in the tower bottom;
the gas phase discharge port of a reaction rectifying tower T101 is connected with the feed port of a reboiler IE 201 of a light-weight removal rectifying tower T102, the discharge port of the reboiler IE 201 of the light-weight removal rectifying tower T102 is respectively connected with the liquid phase reflux port of the reaction rectifying tower T101 and the feed port of an adsorption tower A1, the discharge port of an adsorption tower A1 is connected with the feed port of the light-weight removal rectifying tower T102, a dust remover B1 and a filter IF 1 are arranged on a pipeline connecting the adsorption tower A1 and the light-weight removal rectifying tower T102, the liquid phase discharge port of the light-weight removal rectifying tower T102 is connected with the feed port of a reboiler IE 302 of the light-weight removal rectifying tower T103, the gas phase discharge port of the light-weight removal rectifying tower T102 is connected with the feed port of a reboiler IE 302 of a heavy-weight removal rectifying tower T103, the discharge port of the IIE 302 of the heavy-weight removal rectifying tower T103 is respectively connected with the liquid phase reflux port and an emptying pipe of the light-weight removal rectifying tower T102, the heavy-weight removal rectifying tower T103, and a condenser EE 301 of the heavy-weight removal, The liquid phase reflux port of the heavy component removal rectifying tower T103 is connected with a filter IIF 2.
Example 1
The composition and the content of each component of the octafluorocyclobutane crude product are detailed in table 1, when the octafluorocyclobutane crude product is purified by adopting the device shown in fig. 1, the material of a reaction rectifying tower T101 is stainless steel, the height of the tower is 2m, the diameter of the tower is 50mm, and a filler is a nickel theta ring with the diameter of 2 mm; the diameter of the adsorption tower A1 is 50mm, the height is 0.5m, and the packed adsorbent is 3A molecular sieve; the light component removal rectifying tower T102 and the heavy component removal rectifying tower T103 are both made of nickel, the tower heights are both 2m, the tower diameters are both 50mm, and stainless steel theta rings with the diameters of 2mm are used as fillers; the filtering precision of the filter I F1 and the filtering precision of the filter II F2 are both 0.003 mu m;
TABLE 1
The procedure for purifying the crude octafluorocyclobutane described in this example was as follows:
(1) 10kg of SbCl was charged into the bottom of the column at a flow rate of 1kg/h by introducing the crude octafluorocyclobutane at-10 DEG C5The liquid reactive distillation tower T101 is used for reactive distillation under the conditions that the tower bottom temperature is 40 ℃, the tower top temperature is 35 ℃ and the distillation pressure is 0.35MPa, a gas phase extracted from the tower top of the reactive distillation tower T101 is used as a heat source and enters a reboiler IE 201, the gas phase which is used as the heat source after heat exchange with materials in the reboiler IE 201 is condensed and liquefied, a liquid phase is used as a tower top reflux liquid and flows back to the reactive distillation tower T101, the reflux ratio is 1, the gas phase part enters an adsorption tower A1 for adsorption at the flow rate of 1kg/h, and the adsorption pressure is 0.35 MPa;
(2) after passing through a dust remover B1 and a filter IF 1, the adsorbed octafluorocyclobutane enters a light component removal rectifying tower T102 at a flow rate of 1kg/h, is rectified under the conditions that the temperature at the bottom of the tower is 30 ℃, the temperature at the top of the tower is 25 ℃ and the rectifying pressure is 0.25MPa, the gas phase extracted from the top of the light component removal rectifying tower T102 enters a reboiler IIE 302 as a heat source, exchanges heat with materials in the reboiler IIE 302 and then is condensed and liquefied as the gas phase part of the heat source, the liquid phase is refluxed to the light component removal rectifying tower T102 as the reflux liquid at the top of the tower, the reflux ratio is 300, and light impurities in the gas phase part are discharged through a emptying pipe at a flow rate of 0.05 kg/h;
(3) the liquid part at the bottom of the light component removal rectifying tower T102 enters a reboiler IE 201, part of the liquid part enters a heavy component removal rectifying tower T103 through a liquid phase discharge port at the bottom of the tower at the flow rate of 0.95kg/h, the liquid part is rectified under the conditions that the temperature at the bottom of the tower is 20 ℃, the temperature at the top of the tower is 15 ℃ and the rectifying pressure is 0.20MPa, the gas phase extracted from the top of the heavy component removal rectifying tower T103 enters a condenser E301 and then is partially condensed and liquefied, the liquid part serving as reflux liquid at the top of the tower flows back to the heavy component removal rectifying tower T103 at the reflux ratio of 10, the gas phase part enters a filter IIF 2 at the flow rate of 0.90kg/h for purification, and then high-purity octafluorocyclobutane gas is obtained, and the heavy impurities at the bottom of the heavy component removal rectifying tower T103. ,
the content of impurities in the purified high-purity octafluorocyclobutane gas was detected by gas chromatography, and the results are shown in table 2. According to the test results, the purity of the purified octafluorocyclobutane gas was calculated to be 99.9996%. Compared with the common rectification process of the octafluorocyclobutane gas, under the conditions of the same treatment capacity, the same product purity and the same product yield, the heat consumption in the process of purifying the octafluorocyclobutane gas is only 65.3 percent of that in the common rectification process, the load of a condenser is 68.0 percent of that in the traditional rectification process, and the consumption of a heating medium and a condensing medium is greatly reduced.
TABLE 2
Example 2
The composition and the content of each component of the crude octafluorocyclobutane are detailed in table 3, when the crude octafluorocyclobutane is purified by adopting the device shown in fig. 1, the material of a reaction and rectification tower T101 is nickel, the height of the tower is 8m, the diameter of the tower is 100mm, and a filler is a stainless steel pall ring with the diameter of 5 mm; the diameter of the adsorption tower A1 is 500mm, the height is 6m, and the filled adsorbent is coconut shell carbon; the light component removal rectifying tower T102 and the heavy component removal rectifying tower T103 are both made of stainless steel, the height of each tower is 15m, the diameter of each tower is 500mm, and nickel Raschig rings with the diameter of 30mm are used as fillers; the filter accuracies of the filter I F1 and the filter II F2 are both 0.5 mu m;
TABLE 3
The procedure for purifying the crude octafluorocyclobutane described in this example was as follows:
(1) the crude octafluorocyclobutane product at 50 ℃ was introduced into the bottom of the column at a flow rate of 100kg/h and 100kg of SbCl was charged5The liquid reaction rectifying tower T101 carries out reaction rectification under the conditions that the tower bottom temperature is 45 ℃, the tower top temperature is 40 ℃ and the rectifying pressure is 0.45MPa, a gas phase extracted from the tower top of the reaction rectifying tower T101 is used as a heat source to enter a reboiler IE 201, the gas phase which is used as the heat source after heat exchange with materials in the reboiler IE 201 is condensed and liquefied, a liquid phase is used as tower top reflux liquid to flow back to the reaction rectifying tower T101, the reflux ratio is 10, the gas phase part enters an adsorption tower A1 for adsorption at the flow rate of 100kg/h, and the adsorption pressure is 0.45 MPa;
(2) after passing through a dust remover B1 and a filter IF 1, the adsorbed octafluorocyclobutane enters a light component removal rectifying tower T102 at a flow rate of 100kg/h, is rectified under the conditions that the temperature at the bottom of the tower is 35 ℃, the temperature at the top of the tower is 30 ℃ and the rectifying pressure is 0.30MPa, the gas phase extracted from the top of the light component removal rectifying tower T102 enters a reboiler IIE 302 as a heat source, exchanges heat with materials in the reboiler IIE 302 and then is condensed and liquefied as the gas phase part of the heat source, the liquid phase is refluxed to the light component removal rectifying tower T102 as the reflux liquid at the top of the tower, the reflux ratio is 12, and light impurities in the gas phase part are discharged through an emptying pipe at a flow rate of 2 kg/h;
(3) the liquid part at the bottom of the light component removal rectifying tower T102 enters a reboiler IE 201, part of the liquid part enters a heavy component removal rectifying tower T103 through a liquid phase discharge port at the bottom of the tower at the flow rate of 98kg/h, the liquid part is rectified under the conditions that the temperature at the bottom of the tower is 25 ℃, the temperature at the top of the tower is 20 ℃ and the rectifying pressure is 0.15MPa, the gas phase extracted from the top of the heavy component removal rectifying tower T103 enters a condenser E301 and then is partially condensed and liquefied, the liquid part serving as reflux liquid at the top of the tower flows back to the heavy component removal rectifying tower T103, the reflux ratio is 1.8, the gas phase part enters a filter II F2 at the flow rate of 96kg/h for purification, and then high-purity octafluorocyclobutane gas is obtained, and the heavy impurities at the bottom of the heavy component removal rectifying tower T.
The content of impurities in the purified high-purity octafluorocyclobutane gas was detected by gas chromatography, and the results are shown in table 4. According to the test results, the purity of octafluorocyclobutane after purification was calculated to be 99.9998%. Compared with the common rectification process of the octafluorocyclobutane gas, under the conditions of the same treatment capacity, the same product purity and the same product yield, the heat consumption in the process of purifying the octafluorocyclobutane gas is only 43.2 percent of that in the common rectification process, the load of a condenser is 43.0 percent of that in the traditional rectification process, and the consumption of a heating medium and a condensing medium is greatly reduced.
TABLE 4
Example 3
The composition components and the content of each component of the crude product of the octafluorocyclobutane are detailed in a table 5, when the crude product of the octafluorocyclobutane is purified by adopting the device shown in fig. 1, the material of a reaction and rectification tower T101 is Monel, the height of the tower is 5m, the diameter of the tower is 200mm, and a packing is a polytetrafluoroethylene Raschig ring with the diameter of 10 mm; the diameter of the adsorption tower A1 is 200mm, the height is 2m, and the filled adsorbent is coal carbon; the light component removal tower T102 and the heavy component removal tower T103 are both made of Monel alloy, the tower heights are both 8m, the tower diameters are both 300mm, and polytetrafluoroethylene pall rings with the diameters of 10mm are used as fillers; the filter accuracies of the filter I F1 and the filter II F2 are both 0.1 mu m;
TABLE 5
The procedure for purifying the crude octafluorocyclobutane described in this example was as follows:
(1) 50kg of SbCl were charged into the bottom of a 30 ℃ octafluorocyclobutane crude product at a rate of 30kg/h5The liquid reactive distillation tower T101 carries out reactive distillation under the conditions that the tower bottom temperature is 42 ℃, the tower top temperature is 37 ℃ and the distillation pressure is 0.4MPa, a gas phase extracted from the tower top of the reactive distillation tower T101 is used as a heat source to enter a reboiler IE 201, the gas phase which is used as the heat source after exchanging heat with materials in the reboiler IE 201 is partially condensed and liquefied, and a liquid phase is partially condensed and liquefiedRefluxing to a reactive distillation column T101 as a tower top reflux liquid, wherein the reflux ratio is 10, a gas phase part enters an adsorption tower A1 for adsorption at the flow rate of 30kg/h, and the adsorption pressure is 0.40 MPa;
(2) after passing through a dust remover B1 and a filter IF 1, the adsorbed octafluorocyclobutane enters a light component removal rectifying tower T102 at a flow rate of 30kg/h, is rectified under the conditions that the temperature at the bottom of the tower is 32 ℃, the temperature at the top of the tower is 27 ℃ and the rectifying pressure is 0.27MPa, the gas phase extracted from the top of the light component removal rectifying tower T102 enters a reboiler IIE 302 as a heat source, exchanges heat with materials in the reboiler IIE 302 and then is condensed and liquefied as the gas phase part of the heat source, the liquid phase is refluxed to the light component removal rectifying tower T102 as the reflux liquid at the top of the tower, the reflux ratio is 5, and light impurities in the gas phase part are discharged through a emptying pipe at a flow rate of 0.4 kg/h;
(3) the liquid part at the bottom of the light component removal rectifying tower T102 enters a reboiler IE 201, part of the liquid part enters a heavy component removal rectifying tower T103 through a liquid phase discharge port at the bottom of the tower at the flow rate of 29.6kg/h, the liquid part is rectified under the conditions that the temperature at the bottom of the tower is 22 ℃, the temperature at the top of the tower is 17 ℃ and the rectifying pressure is 0.17MPa, the gas phase extracted from the top of the heavy component removal rectifying tower T103 enters a condenser E301 and then is partially condensed and liquefied, the liquid part serving as reflux liquid at the top of the tower flows back to the heavy component removal rectifying tower T103, the reflux ratio is 1, the gas phase part enters a filter II F2 at the flow rate of 29.2kg/h for purification, and then high-purity octafluorocyclobutane gas is obtained, and the heavy impurities at the bottom of the heavy component removal rectifying tower T103 are.
The content of impurities in the purified high-purity octafluorocyclobutane gas was measured by gas chromatography, and the results are shown in table 6. According to the test results, the purity of octafluorocyclobutane after purification was calculated to be 99.9999%. Compared with the common rectification process of the octafluorocyclobutane gas, under the conditions of the same treatment capacity, the same product purity and the same product yield, the heat consumption in the process of purifying the octafluorocyclobutane gas is only 48.2 percent of that in the common rectification process, the load of a condenser is 48.1 percent of that in the traditional rectification process, and the consumption of a heating medium and a condensing medium is greatly reduced.
TABLE 6
Example 4
The composition and the content of each component of the crude product of octafluorocyclobutane are detailed in table 7, when the crude product of octafluorocyclobutane is purified by using the device shown in fig. 1, the material of the reaction and rectification tower T101 is stainless steel, the height of the tower is 15m, the diameter of the tower is 500mm, and the packing is Monel alloy pall ring with the diameter of 30 mm; the diameter of the adsorption tower A1 is 200mm, the height is 2m, and the packed adsorbent is 5A molecular sieve; the light component removal tower T102 and the heavy component removal tower T103 are both made of stainless steel, the tower heights are both 3m, the tower diameters are both 100mm, and the packing is Monel alloy pall rings with the diameters of 5 mm; the filtering precision of the filter I F1 and the filtering precision of the filter II F2 are both 0.003 mu m;
TABLE 7
The procedure for purifying the crude octafluorocyclobutane described in this example was as follows:
(1) 50kg of SbCl were charged into the bottom of a 30 ℃ octafluorocyclobutane crude product at a rate of 30kg/h5The liquid reaction rectifying tower T101 is used for carrying out reaction rectification under the conditions that the tower bottom temperature is 42 ℃, the tower top temperature is 37 ℃ and the rectifying pressure is 0.4MPa, a gas phase extracted from the tower top of the reaction rectifying tower T101 is used as a heat source and enters a reboiler IE 201, the gas phase which is used as the heat source after heat exchange with materials in the reboiler IE 201 is condensed and liquefied, a liquid phase is used as tower top reflux liquid and flows back to the reaction rectifying tower T101, the reflux ratio is 10, the gas phase part enters an adsorption tower A1 for adsorption at the flow rate of 30kg/h, and the adsorption pressure is 0.40 MPa;
(2) after passing through a dust remover B1 and a filter IF 1, the adsorbed octafluorocyclobutane enters a light component removal rectifying tower T102 at a flow rate of 30kg/h, is rectified under the conditions that the temperature at the bottom of the tower is 32 ℃, the temperature at the top of the tower is 27 ℃ and the rectifying pressure is 0.27MPa, the gas phase extracted from the top of the light component removal rectifying tower T102 enters a reboiler IIE 302 as a heat source, exchanges heat with materials in the reboiler IIE 302 and then is condensed and liquefied as the gas phase part of the heat source, the liquid phase is refluxed to the light component removal rectifying tower T102 as the reflux liquid at the top of the tower, the reflux ratio is 30, and light impurities in the gas phase part are discharged through a emptying pipe at a flow rate of 0.4 kg/h;
(3) the liquid part at the bottom of the light component removal rectifying tower T102 enters a reboiler IE 201, part of the liquid part enters a heavy component removal rectifying tower T103 through a liquid phase discharge port at the bottom of the tower at the flow rate of 29.6kg/h, the liquid part is rectified under the conditions that the temperature at the bottom of the tower is 22 ℃, the temperature at the top of the tower is 17 ℃ and the rectifying pressure is 0.17MPa, the gas phase extracted from the top of the heavy component removal rectifying tower T103 enters a condenser E301 and then is partially condensed and liquefied, the liquid part serving as reflux liquid at the top of the tower flows back to the heavy component removal rectifying tower T103, the reflux ratio is 5, the gas phase part enters a filter II F2 at the flow rate of 29.2kg/h for purification, and then high-purity octafluorocyclobutane gas is obtained, and the heavy impurities at the bottom of the heavy component removal rectifying tower T103 are.
The content of impurities in the purified high-purity octafluorocyclobutane gas was measured by gas chromatography, and the results are shown in table 8. According to the test results, the purity of octafluorocyclobutane after purification was calculated to be 99.9998%. Compared with the common rectification process of the octafluorocyclobutane gas, under the conditions of the same treatment capacity, the same product purity and the same product yield, the heat consumption in the process of purifying the octafluorocyclobutane gas is only 50.2 percent of that in the common rectification process, the load of a condenser is 48.3 percent of that in the traditional rectification process, and the consumption of a heating medium and a condensing medium is greatly reduced.
TABLE 8
Example 5
The composition and the content of each component of the crude octafluorocyclobutane are detailed in table 9, when the crude octafluorocyclobutane is purified by the device shown in fig. 1, the material of a reactive distillation column T101 is nickel, the height of the column is 3m, the diameter of the column is 300mm, and a filler is a stainless steel theta ring with the diameter of 5 mm; the diameter of the adsorption tower A1 is 200mm, the height is 2m, and the packed adsorbent is a carbon molecular sieve; the light component removal tower T102 and the heavy component removal tower T103 are both made of stainless steel, the tower heights are both 5m, the tower diameters are both 200mm, and stainless steel theta rings with the diameters of 5mm are used as fillers; the filter accuracies of the filter I F1 and the filter II F2 are both 0.005 mu m;
TABLE 9
The procedure for purifying the crude octafluorocyclobutane described in this example was as follows:
(1) 50kg of SbCl were charged into the bottom of a 30 ℃ octafluorocyclobutane crude product at a rate of 30kg/h5The liquid reaction rectifying tower T101 is used for carrying out reaction rectification under the conditions that the tower bottom temperature is 42 ℃, the tower top temperature is 37 ℃ and the rectifying pressure is 0.4MPa, a gas phase extracted from the tower top of the reaction rectifying tower T101 is used as a heat source and enters a reboiler IE 201, the gas phase which is used as the heat source after heat exchange with materials in the reboiler IE 201 is condensed and liquefied, a liquid phase is used as tower top reflux liquid and flows back to the reaction rectifying tower T101, the reflux ratio is 10, the gas phase part enters an adsorption tower A1 for adsorption at the flow rate of 30kg/h, and the adsorption pressure is 0.40 MPa;
(2) after passing through a dust remover B1 and a filter IF 1, the adsorbed octafluorocyclobutane enters a light component removal rectifying tower T102 at a flow rate of 30kg/h, is rectified under the conditions that the temperature at the bottom of the tower is 32 ℃, the temperature at the top of the tower is 27 ℃ and the rectifying pressure is 0.27MPa, the gas phase extracted from the top of the light component removal rectifying tower T102 enters a reboiler IIE 302 as a heat source, exchanges heat with materials in the reboiler IIE 302 and then is condensed and liquefied as the gas phase part of the heat source, the liquid phase is refluxed to the light component removal rectifying tower T102 as the reflux liquid at the top of the tower, the reflux ratio is 50, and light impurities in the gas phase part are discharged through a emptying pipe at a flow rate of 0.4 kg/h;
(3) the liquid part at the bottom of the light component removal rectifying tower T102 enters a reboiler IE 201, part of the liquid part enters a heavy component removal rectifying tower T103 through a liquid phase discharge port at the bottom of the tower at the flow rate of 29.6kg/h, the liquid part is rectified under the conditions that the temperature at the bottom of the tower is 22 ℃, the temperature at the top of the tower is 17 ℃ and the rectifying pressure is 0.17MPa, the gas phase extracted from the top of the heavy component removal rectifying tower T103 enters a condenser E301 and then is partially condensed and liquefied, the liquid part serving as reflux liquid at the top of the tower flows back to the heavy component removal rectifying tower T103, the reflux ratio is 10, the gas phase part enters a filter II F2 at the flow rate of 29.2kg/h for purification, and then high-purity octafluorocyclobutane gas is obtained, and the heavy impurities at the bottom of the heavy component removal rectifying tower T103 are.
The content of impurities in the purified high-purity octafluorocyclobutane gas was measured by gas chromatography, and the results are shown in table 10. According to the test results, the purity of octafluorocyclobutane after purification was calculated to be 99.9998%. Compared with the common rectification process of the octafluorocyclobutane gas, under the conditions of the same treatment capacity, the same product purity and the same product yield, the heat consumption in the process of purifying the octafluorocyclobutane gas is only 51.2 percent of that in the common rectification process, the load of a condenser is 49.7 percent of that in the traditional rectification process, and the consumption of a heating medium and a condensing medium is greatly reduced.
Watch 10
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method of purifying an octafluorocyclobutane gas, comprising: the steps of the method are as follows,
reacting and rectifying the crude octafluorocyclobutane through a reaction rectifying tower, sequentially passing gas phase at the top of the reaction rectifying tower through an adsorption tower, a dust remover and a filter in sequence, then feeding the gas phase into a light component removal rectifying tower for rectifying to remove light component impurities, feeding a liquid phase part at the bottom of the light component removal rectifying tower into a heavy component removal rectifying tower for rectifying to remove heavy component impurities, and feeding the gas phase at the top of the heavy component removal rectifying tower through the filter for extracting to obtain high-purity octafluorocyclobutane gas;
SbCl is arranged at the position of a tower kettle of the reaction rectifying tower5Liquid, the temperature of the bottom of the tower is 40-45 ℃, the temperature of the top of the tower is 35-40 ℃, the temperature difference between the bottom of the tower and the top of the tower is not less than 2 ℃, the rectifying pressure is 0.35-0.45 MPa, and the reflux is carried outThe flow ratio is 1-10;
the adsorbent filled in the adsorption tower is a molecular sieve or active carbon, and the adsorption pressure is 0.35MPa to 0.45 MPa;
the temperature of the bottom of the light component removal rectifying tower is 30-35 ℃, the temperature of the top of the rectifying tower is 25-30 ℃, the temperature difference between the bottom of the rectifying tower and the top of the rectifying tower is not less than 2 ℃, the rectifying pressure is 0.25-0.30 MPa, and the reflux ratio is 5-300;
the temperature of the tower bottom of the heavy component removal rectifying tower is 20-25 ℃, the temperature of the tower top is 15-20 ℃, the temperature difference between the tower bottom and the tower top is not less than 2 ℃, the rectifying pressure is 0.15-0.20 MPa, and the reflux ratio is 1-10;
the reaction rectifying tower, the light component removing rectifying tower and the heavy component removing rectifying tower are all packing rectifying towers, the packing is pall rings, theta rings or Raschig rings, and the material of the packing is polytetrafluoroethylene, stainless steel, nickel or monel alloy.
2. The method of purifying octafluorocyclobutane gas according to claim 1, wherein: the reaction rectifying tower, the light component removing rectifying tower and the heavy component removing rectifying tower are arranged into different pressure towers, and the gas phase discharged from the top of the high-pressure tower is used as a heat source to provide heat for a reboiler at the bottom of the low-pressure tower, namely:
the gas phase at the top of the reactive distillation tower is used as a heat source to enter a reboiler at the bottom of the light component removal distillation tower, the gas phase serving as the heat source is partially condensed and liquefied after exchanging heat with materials at the bottom of the tower, the liquid phase is used as reflux liquid at the top of the reactive distillation tower to flow back, and the gas phase is partially introduced into an adsorption tower to be adsorbed;
and the gas phase at the top of the light component removal rectifying tower is used as a heat source to enter a reboiler at the bottom of the heavy component removal rectifying tower, the gas phase serving as the heat source is partially condensed and liquefied after exchanging heat with materials at the bottom of the tower, the liquid phase is used as reflux liquid at the top of the light component removal rectifying tower to flow back, and the gas phase is partially extracted as light component impurities.
3. The method of purifying octafluorocyclobutane gas according to claim 1, wherein: the temperature and the flow of the crude octafluorocyclobutane entering the reactive distillation tower are respectively-10 to 50 ℃ and 1kg/h to 100kg/h, and SbCl in the reactive distillation tower5Is 10kg to 100kg by reactionThe flow rate of gas phase extracted from the top of the rectifying tower entering the adsorption tower is 1 kg/h-100 kg/h, the feed flow rate of the light component removing rectifying tower is 1 kg/h-100 kg/h, the light component discharging flow rate of the top of the light component removing rectifying tower is 0.05 kg/h-2 kg/h, the feed flow rate of the heavy component removing rectifying tower is 0.95 kg/h-98 kg/h, the heavy component discharging flow rate of the bottom of the heavy component removing rectifying tower is 0.05 kg/h-2 kg/h, and the gas phase extracting rate of the top of the heavy component removing rectifying tower is 0.90 kg/h-96 kg/h.
4. The method of purifying octafluorocyclobutane gas according to claim 1, wherein: the heights of the reaction rectifying tower, the light component removing rectifying tower and the heavy component removing rectifying tower are respectively and independently 2-15 mm, the diameters of rectifying columns in the rectifying towers are respectively and independently 50-500 mm, and the diameters of fillers are respectively and independently 2-30 mm.
5. The method of purifying octafluorocyclobutane gas according to claim 1, wherein: the heights of the reaction rectifying tower, the light component removing rectifying tower and the heavy component removing rectifying tower are respectively and independently 3-8 mm, the diameters of rectifying columns in the rectifying towers are respectively and independently 100-300 mm, and the diameters of fillers are respectively and independently 2-10 mm.
6. The method of purifying octafluorocyclobutane gas according to claim 1, wherein: the filtration precision of the filter is 0.003-0.5 μm.
7. An apparatus for purifying octafluorocyclobutane by the method according to claims 1 to 6, wherein: the device comprises a reaction rectifying tower, an adsorption tower, a dust remover, a filter I, a light component removal rectifying tower, a heavy component removal rectifying tower and a filter II;
the reaction rectifying tower consists of a tower kettle heating device and a tower body, wherein a feed inlet is arranged at the middle lower part of the tower body, and a gas-phase discharge port and a liquid-phase reflux port are arranged at the top of the tower;
the tower bottom of the adsorption tower is provided with a feed inlet, and the tower top is provided with a discharge outlet;
the light component removal rectifying tower consists of a tower bottom reboiler I and a tower body, wherein a feed inlet is formed in the middle of the tower body, a gas phase discharge port and a liquid phase reflux port are formed in the tower top, and a liquid phase discharge port is formed in the tower bottom;
the heavy component removal rectifying tower consists of a tower bottom reboiler II, a tower body and a tower top condenser, wherein a feed inlet is formed in the middle of the tower body, a gas phase discharge port and a liquid phase reflux port are formed in the tower top, and a heavy component removal outlet is formed in the tower bottom;
a gas phase discharge port of the reaction rectifying tower is connected with a feed port of a reboiler I of the light-component removal rectifying tower, a discharge port of the reboiler I of the light-component removal rectifying tower is respectively connected with a liquid phase reflux port of the reaction rectifying tower and a feed port of the adsorption tower, a discharge port of the adsorption tower is connected with a feed port of the light-component removal rectifying tower, a dust remover and a filter I are arranged on a pipeline connecting the adsorption tower and the light-component removal rectifying tower, a liquid phase discharge port of the light-component removal rectifying tower is connected with a feed port of the heavy-component removal rectifying tower, a gas phase discharge port of the light-component removal rectifying tower is connected with a feed port of a reboiler II of the heavy-component removal rectifying tower, a discharge port of the reboiler II of the heavy-component removal rectifying tower is respectively connected with a liquid phase reflux port and a discharge pipe of the light-component removal rectifying tower, a heavy-component discharge outlet of the heavy-component removal rectifying, and a liquid phase reflux port of the heavy component removal rectifying tower is connected with the filter II.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911202168.XA CN111004088A (en) | 2019-11-29 | 2019-11-29 | Method and device for purifying octafluorocyclobutane gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911202168.XA CN111004088A (en) | 2019-11-29 | 2019-11-29 | Method and device for purifying octafluorocyclobutane gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111004088A true CN111004088A (en) | 2020-04-14 |
Family
ID=70113628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911202168.XA Pending CN111004088A (en) | 2019-11-29 | 2019-11-29 | Method and device for purifying octafluorocyclobutane gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111004088A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111470940A (en) * | 2020-04-16 | 2020-07-31 | 北京宇极科技发展有限公司 | Method for preparing high-purity 3,3,4,4,5, 5-hexafluorocyclopentene |
| CN111978145A (en) * | 2020-08-27 | 2020-11-24 | 上海化工研究院有限公司 | Purification device for low-boiling-point perfluorocarbon and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996040606A1 (en) * | 1995-06-07 | 1996-12-19 | E.I. Du Pont De Nemours And Company | Manufacture of 1,1-difluoroethane by reactive distillation |
| JP2001247493A (en) * | 2000-03-08 | 2001-09-11 | Nippon Zeon Co Ltd | Method for producing octafluorocyclopentene |
| US6333440B1 (en) * | 2000-04-07 | 2001-12-25 | E. I. Du Pont De Nemours And Company | Process for perfluorocyclobutane purification |
| JP2002212118A (en) * | 2001-01-15 | 2002-07-31 | Showa Denko Kk | Method for purifying octafluolocyclobutane and method for producing the same, and use thereof |
| CN1503770A (en) * | 2001-01-15 | 2004-06-09 | �Ѻ͵繤��ʽ���� | Process for purifying octafluorocyclobutane process for preparing the same and use thereof |
| CN104529691A (en) * | 2014-12-30 | 2015-04-22 | 中国船舶重工集团公司第七一八研究所 | Catalytic conversion method for impurities in perfluoroalkane |
| CN105358510A (en) * | 2013-07-19 | 2016-02-24 | 日本瑞翁株式会社 | Method for purifying 2-fluorobutane |
| CN105777483A (en) * | 2016-01-28 | 2016-07-20 | 广东华特气体股份有限公司 | High-purity octafluorocyclobutane purification method and system |
| CN107759439A (en) * | 2017-10-25 | 2018-03-06 | 西安近代化学研究所 | A kind of method of the trifluoro propene of 2 chlorine of hydrofluorination 3,3,3 |
-
2019
- 2019-11-29 CN CN201911202168.XA patent/CN111004088A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996040606A1 (en) * | 1995-06-07 | 1996-12-19 | E.I. Du Pont De Nemours And Company | Manufacture of 1,1-difluoroethane by reactive distillation |
| JP2001247493A (en) * | 2000-03-08 | 2001-09-11 | Nippon Zeon Co Ltd | Method for producing octafluorocyclopentene |
| US6333440B1 (en) * | 2000-04-07 | 2001-12-25 | E. I. Du Pont De Nemours And Company | Process for perfluorocyclobutane purification |
| JP2002212118A (en) * | 2001-01-15 | 2002-07-31 | Showa Denko Kk | Method for purifying octafluolocyclobutane and method for producing the same, and use thereof |
| CN1503770A (en) * | 2001-01-15 | 2004-06-09 | �Ѻ͵繤��ʽ���� | Process for purifying octafluorocyclobutane process for preparing the same and use thereof |
| CN105358510A (en) * | 2013-07-19 | 2016-02-24 | 日本瑞翁株式会社 | Method for purifying 2-fluorobutane |
| CN104529691A (en) * | 2014-12-30 | 2015-04-22 | 中国船舶重工集团公司第七一八研究所 | Catalytic conversion method for impurities in perfluoroalkane |
| CN105777483A (en) * | 2016-01-28 | 2016-07-20 | 广东华特气体股份有限公司 | High-purity octafluorocyclobutane purification method and system |
| CN107759439A (en) * | 2017-10-25 | 2018-03-06 | 西安近代化学研究所 | A kind of method of the trifluoro propene of 2 chlorine of hydrofluorination 3,3,3 |
Non-Patent Citations (2)
| Title |
|---|
| 张浩等: "八氟环丁烷的制备与纯化", 当代化工, vol. 48, no. 01, pages 98 - 101 * |
| 袁淑筠等: "八氟环丁烷的纯化", 低温与特气, vol. 34, no. 06, pages 289 - 290 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111470940A (en) * | 2020-04-16 | 2020-07-31 | 北京宇极科技发展有限公司 | Method for preparing high-purity 3,3,4,4,5, 5-hexafluorocyclopentene |
| CN111470940B (en) * | 2020-04-16 | 2022-09-09 | 北京宇极科技发展有限公司 | Method for preparing high-purity 3,3,4,4,5, 5-hexafluorocyclopentene |
| CN111978145A (en) * | 2020-08-27 | 2020-11-24 | 上海化工研究院有限公司 | Purification device for low-boiling-point perfluorocarbon and application thereof |
| CN111978145B (en) * | 2020-08-27 | 2023-03-28 | 上海化工研究院有限公司 | Purification device for low-boiling-point perfluorocarbon and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2008538213A5 (en) | ||
| CN109251124B (en) | Purification process of monofluoromethane | |
| CN111004088A (en) | Method and device for purifying octafluorocyclobutane gas | |
| CN113735683B (en) | Purification device and purification method of electronic grade difluoromethane | |
| CN110980648A (en) | Hydrogen bromide purification device and method | |
| CN211871827U (en) | Device for purifying octafluorocyclobutane gas | |
| CN113321184B (en) | High-purity electronic-grade chlorine purification production device and technology thereof | |
| CN215101986U (en) | High-purity electronic grade chlorine purification apparatus for producing | |
| CN112591711B (en) | High-purity high-yield FTrPSA separation and purification extraction method for HF/HCl mixed gas | |
| EP2942324B1 (en) | Carbonyl fluoride purification method | |
| CN105753635B (en) | A kind of production method of perfluoroethane | |
| CN104262376A (en) | TMSOTf (trimethylsilyl trifluoromethanesulfonate) purifying method | |
| CN100374184C (en) | A process and apparatus for purifying hydrogen bromide | |
| CN114478172B (en) | Ultra-high purity olefin purification method | |
| CN111138240B (en) | Water removal device and water removal method for hexafluorobutadiene | |
| CN212687558U (en) | Hydrogen bromide's purification device | |
| CN101070144B (en) | Method for removing carbon tetrafluoride foreign matter in nitrogen trifluoride gas | |
| TW201632485A (en) | Process for producing propane, and propane production device | |
| CN112642259A (en) | Method for recovering FTrPSA (fluorine substituted PSA) tail gas generated in epitaxial process of chlorine-based SiC-CVD (chemical vapor deposition) by alkane and silane reaction | |
| CN105037079A (en) | Rectification technique of 1,1,1,2-tetrafluoroethane | |
| CN112094172B (en) | Method and device for purifying crude trichlorobromomethane | |
| CN112573991B (en) | Method for preparing vinyl chloride by using tail gas FTrPSA (fluorine-doped plasma-enhanced pressure swing adsorption) in growth process of vinyl-containing chlorine-based CVD (chemical vapor deposition) crystal film | |
| CN217854618U (en) | Recovery and purification device for octafluorocyclobutane | |
| CN112279234B (en) | Azeotropic compositions of carbonyl fluoride and carbon dioxide | |
| CN220758036U (en) | Device for producing electronic grade monofluoromethane by utilizing extractive distillation mode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 057550 No. five Weir Road, chemical industry gathering area, Feixiang District, Handan, Hebei, 1 Applicant after: China shipbuilding (Handan) Perry Special Gas Co.,Ltd. Address before: No.1 Weiwu Road, chemical industry gathering area, Feixiang County, Handan City, Hebei Province Applicant before: PERIC SPECIAL GASES Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200414 |
|
| WD01 | Invention patent application deemed withdrawn after publication |