CN111253211B - Separation and purification method of high-purity electronic-grade tetrafluoropropene HFO-1234yf - Google Patents
Separation and purification method of high-purity electronic-grade tetrafluoropropene HFO-1234yf Download PDFInfo
- Publication number
- CN111253211B CN111253211B CN202010183425.6A CN202010183425A CN111253211B CN 111253211 B CN111253211 B CN 111253211B CN 202010183425 A CN202010183425 A CN 202010183425A CN 111253211 B CN111253211 B CN 111253211B
- Authority
- CN
- China
- Prior art keywords
- hfo
- absorption
- raw material
- tetrafluoropropene
- tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 55
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000926 separation method Methods 0.000 title abstract description 14
- 238000000746 purification Methods 0.000 title abstract description 9
- 238000010521 absorption reaction Methods 0.000 claims abstract description 96
- 239000012535 impurity Substances 0.000 claims abstract description 84
- 239000002994 raw material Substances 0.000 claims abstract description 70
- 238000003795 desorption Methods 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims description 41
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 230000000717 retained effect Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000003350 kerosene Substances 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 8
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 16
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 16
- 239000012071 phase Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 5
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 4
- QGYLHZMNVGBXDQ-UHFFFAOYSA-N 1,1-dichloro-2,3,3,3-tetrafluoroprop-1-ene Chemical compound ClC(Cl)=C(F)C(F)(F)F QGYLHZMNVGBXDQ-UHFFFAOYSA-N 0.000 description 4
- COAUHYBSXMIJDK-UHFFFAOYSA-N 3,3-dichloro-1,1,1,2,2-pentafluoropropane Chemical compound FC(F)(F)C(F)(F)C(Cl)Cl COAUHYBSXMIJDK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000004868 gas analysis Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 3
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 description 1
- FTCVHAQNWWBTIV-UHFFFAOYSA-N 1,1,1,2,2-pentachloropropane Chemical compound CC(Cl)(Cl)C(Cl)(Cl)Cl FTCVHAQNWWBTIV-UHFFFAOYSA-N 0.000 description 1
- FDOPVENYMZRARC-UHFFFAOYSA-N 1,1,1,2,2-pentafluoropropane Chemical compound CC(F)(F)C(F)(F)F FDOPVENYMZRARC-UHFFFAOYSA-N 0.000 description 1
- FYIRUPZTYPILDH-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)C(F)(F)F FYIRUPZTYPILDH-UHFFFAOYSA-N 0.000 description 1
- ZDCWZRQSHBQRGN-UHFFFAOYSA-N 1,1,1,2,3-pentafluoropropane Chemical compound FCC(F)C(F)(F)F ZDCWZRQSHBQRGN-UHFFFAOYSA-N 0.000 description 1
- VVWFZKBKXPXGBH-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropane Chemical compound ClC(Cl)CC(Cl)(Cl)Cl VVWFZKBKXPXGBH-UHFFFAOYSA-N 0.000 description 1
- ZEJBFBYYCVJWCZ-UHFFFAOYSA-N 1,1,1,3-tetrachloro-3-fluoropropane Chemical compound FC(Cl)CC(Cl)(Cl)Cl ZEJBFBYYCVJWCZ-UHFFFAOYSA-N 0.000 description 1
- DMUPYMORYHFFCT-UHFFFAOYSA-N 1,2,3,3,3-pentafluoroprop-1-ene Chemical compound FC=C(F)C(F)(F)F DMUPYMORYHFFCT-UHFFFAOYSA-N 0.000 description 1
- GDPWRLVSJWKGPJ-UHFFFAOYSA-N 1-chloro-2,3,3,3-tetrafluoroprop-1-ene Chemical compound ClC=C(F)C(F)(F)F GDPWRLVSJWKGPJ-UHFFFAOYSA-N 0.000 description 1
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- PRDFNJUWGIQQBW-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-yne Chemical compound FC(F)(F)C#C PRDFNJUWGIQQBW-UHFFFAOYSA-N 0.000 description 1
- ZGOMEYREADWKLC-UHFFFAOYSA-N 3-chloro-1,1,1,3-tetrafluoropropane Chemical compound FC(Cl)CC(F)(F)F ZGOMEYREADWKLC-UHFFFAOYSA-N 0.000 description 1
- HXNJCCYKKHPFIO-UHFFFAOYSA-N 3-chloro-1,1,2,3-tetrafluoroprop-1-ene Chemical group FC(Cl)C(F)=C(F)F HXNJCCYKKHPFIO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 102000039935 JUPITER family Human genes 0.000 description 1
- 108091070142 JUPITER family Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000180 cavity ring-down spectroscopy Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000005796 dehydrofluorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling 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
- 239000002904 solvent Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for separating and purifying high-purity electronic grade tetrafluoropropene HFO-1234yf, which comprises the following steps: step S1: removing HF; step S2: and (3) absorption operation: introducing the raw material washed by the water in the step S1 into an absorption tower for absorption operation; step S3: carrying out desorption operation; step S4: rectifying for removing light impurities; step S5: heavy impurity removal rectification operation: and (3) carrying out heavy and light impurity rectification operation on the raw material subjected to the light impurity removal rectification operation, and removing heavy component impurities to obtain the high-purity electronic grade tetrafluoropropene HFO-1234 yf. The separation and purification method can remove impurities which are difficult to separate, does not convert HFO-1234yf into other isomers, and has the characteristics of simple and stable operation and low energy consumption.
Description
Technical Field
The invention belongs to the field of fluorinated olefin separation and purification, and particularly relates to a separation and purification method of high-purity electronic grade tetrafluoropropene HFO-1234 yf.
Background
2,3,3, 3-tetrafluoropropene, also known as HFO-1234yf, with the chemical formula CH 2 ＝CFCF 3 HFO-1234yf is a refrigerant that will replace R-134a for use in automotive air conditioning.
It is well known that with the advent of more and more global environmental regulations and policies aimed at reducing the greenhouse effect of hydrofluorocarbons, the fourth generation refrigerant, HFO-1234yf, is receiving attention as a product featuring zero ozone potential (ODP), micro-flammability and low Global Warming Potential (GWP), a new generation of hydrofluoro olefin (HFO) substitute following Hydrochlorofluorocarbons (HCFC) and Hydrofluorocarbons (HFC). With the acceptance of HFO-1234yf by the European Union in recent years, HFO-1234yf is most likely to replace HFC-134a as a new generation of automotive refrigerant. HFO-1234yf is primarily used in automobiles and refrigerators, as well as in many large stationary and commercial refrigeration equipment. At present, international chemical engineering Jupiter family Mu, Honeywell and Akoma have accelerated the pace of factory building in China, and the future development prospect is expected.
Currently, the widely used production process of HFO-1234yf in the prior art mainly comprises the following 5 types: the production process comprises the following steps: using Hexafluoropropylene (HFP) as raw material to produce HFO-1234yf by an addition elimination method; the production process comprises the following steps: the HFO-1234yf is produced by a dehydrofluorination method taking pentafluoropropane (HFC-245cb) as a raw material; production process III: the HFO-1234yf is produced by a fluorine-chlorine exchange method which takes 2-chlorine-3, 3, 3-trifluoropropene (HCFO-1233xf) as a raw material; the production process comprises the following steps: performing pyrolysis by using methane chloride and Tetrafluoroethylene (TFE) as raw materials to prepare tetrafluoropropene (HFO-1234 yf); the production process comprises the following steps: the mixture of hexafluoropropane (HFC-236ea) and pentafluoropropane (HFC-245eb) is used as raw material to prepare the tetrafluoropropene (HFO-1234 yf).
The production process comprises the following specific process flows: firstly, hydrogen and Hexafluoropropylene (HFP) are subjected to catalytic addition reaction to generate hexafluoropropane, and then elimination reaction is carried out to generate pentafluoropropene (HFO-1225 ye); the resulting pentafluoropropene (HFO-1225ye) is subjected to a catalytic addition reaction with hydrogen to produce pentafluoropropane, followed by an elimination reaction to finally produce a tetrafluoropropene (HFO-1234 yf). The conversion rate of raw materials from hexafluoropropylene to pentafluoropropene of the process is 98.2%, the conversion rate of the pentafluoropropene to tetrafluoropropene is 97.1%, and the total conversion rate is 95.2%.
At present, HFO-1234yf is newly applied to an etching process for manufacturing an integrated circuit, and has the characteristics of high selectivity and good etching advantage of silicon oxide and silicon nitride stacked on a high layer.
Patent application CN201711247598.4 by honeywell international corporation discloses a process for the preparation of 1,3,3, 3-tetrafluoropropene. This application provides a simple three-step process for the production of 1,3,3, 3-tetrafluoropropene (HFO-1234 ze). In a first step, carbon tetrachloride is added to vinyl fluoride to give the compound CCl 3 CH 2 CHClF (HCFC-241 fb). Then in a second step, the HCFC-241fb is fluorinated with anhydrous HF to give CF 3 CH 2 CHClF (HCFC-244 fa). In the third step, HCFC-244fa is dehydrochlorinated to give the desired product CF3CH ═ CHF (HFO-1234 ze). According to a similar chemistry, vinyl chloride can be used in place of vinyl fluoride.
Patent application CN201811579269.4 by honeywell international corporation discloses a process for the preparation of tetrafluoropropene. This application describes a process for preparing CF 3 CHF (HFO-1234 ze). The process comprises carbon tetrachloride (CCl) 4 ) Addition with 1, 2-dichloroethylene to form CCl 3 CHClCHCl 2 . Thus the compound CCl 3 CHClCHCl 2 Can be treated with HF to produce CF 3 CHClCHClF as the main product, or it can be converted to CCl by dechlorination 2 ＝CHCHCl 2 (1230za)。CCl 2 ＝CHCHCl 2 Treatment with HF may be carried out so that the main product obtained is CF 3 CHClCHClF。CF 3 CH ═ CHCl is produced as a by-product, but after treatment with HF, it forms the compound CF 3 CHClCHClF. By CF 3 CH 2 Dehydrochlorination of CHClF or from CF 3 Dechlorination of CHClCHClF to give the desired compound CF as a trans/cis mixture 3 CH＝CHF(HFO-1234ze)。
Patent application CN201780036484.7 of arkema french discloses a process for the preparation of 2,3,3, 3-tetrafluoropropene (HFO-1234 yf). The method selects chloro-tetrafluoropropylene to carry out halogen exchange. The method employs three reactors, each reactor including a catalytic bed containing a catalyst or a preliminary catalyst, and including a reaction for independently performing a catalytic reaction or regenerating the catalyst in each reactor, the amount of the catalyst or the preliminary catalyst in the catalytic bed of one of the reactors being 90% to 110% of the amount of the catalyst or the preliminary catalyst contained in the catalytic bed of one of the other two reactors. The invention also relates to a device configured for carrying out the method of the invention.
Patent application cn201180033620.x of arkema french discloses a stable 2,3,3, 3-tetrafluoropropene composition. The invention relates to a stabilising Composition (CS) comprising: at least x% by weight of 2,3,3, 3-tetrafluoropropene (99.8. ltoreq. x < 100); up to y wt% of an unsaturated compound (Ia) (0< y ≦ 0.2) selected from the group consisting of positional isomers of 2,3,3, 3-tetrafluoropropene and 3,3, 3-trifluoropropene (HFO-1243zf), positional isomers of 2,3,3, 3-tetrafluoropropene such as 1,3,3, 3-tetrafluoropropene (isomers Z and E) and 1,1,2, 3-tetrafluoropropene; and optionally up to 500ppm of 3,3, 3-trifluoropropyne and/or up to 200ppm of 1,1,1,2, 3-pentafluoropropene (HFO-1225 ye).
Patent application cn201610543717.x, from AGC co, provides a simple and economical process for producing 1, 1-dichloro-2, 3,3, 3-tetrafluoropropene without purifying the raw material component obtained as an isomer mixture, and a process for producing 2,3,3, 3-tetrafluoropropene from the above product obtained by the process. Specifically, the application provides a process for producing 1, 1-dichloro-2, 3,3, 3-tetrafluoropropene by selectively dehydrofluorinating only 1, 1-dichloro-2, 2,3,3, 3-pentafluoropropane in a mixture of isomers of dichloropentafluoropropane containing 1, 1-dichloro-2, 2,3,3, 3-pentafluoropropane with an aqueous alkaline solution in the presence of a phase transfer catalyst; the present invention also provides a process for producing 2,3,3, 3-tetrafluoropropene from the above-described 1, 1-dichloro-2, 3,3, 3-tetrafluoropropene obtained by the above-described process.
Patent application CN201810568372.2 by AGC co provides a method for stably storing tetrafluoropropene filled in a container for storage or transportation so as not to cause a reaction such as polymerization. The method comprises storing tetrafluoropropene in a gas-liquid state having a gas phase and a liquid phase in a closed container, wherein the oxygen concentration (content ratio) in the gas phase is 3 ppm by volume or more and less than 3000 ppm by volume at a temperature of 25 ℃.
Patent application CN201710976257.4 of Zhejiang thoroughfare fluorine chemistry Limited discloses a co-production method of 2,3,3, 3-tetrafluoropropene and trans-1, 3,3, 3-tetrafluoropropene, wherein a mixture of 1,1,1,2, 2-pentachloropropane and 1,1,1,3, 3-pentachloropropane and anhydrous hydrogen fluoride are preheated and then simultaneously introduced into a first reactor, and La is subjected to fluorination treatment 2 O 3 -Cr 2 O 3 Reacting under the action of a catalyst to obtain a first reactor product; the product of the first reactor is directly introduced into the second reactor without separation, in Ga 2 O 3 -Y 2 O 3 -Cr 2 O 3 Carrying out catalytic fluorination reaction under the action of a catalyst to obtain a reaction product of a second reactor; separating the reaction product of the second reactor to obtain 2,3,3, 3-tetrafluoropropene and trans-1, 3,3,3-tetrafluoropropene products. The invention has the advantages of simple process, less equipment investment, good catalyst activity, high selectivity, long total service life, flexible adjustment of the proportion of two products according to market demands and the like.
Patent application CN201810117773.6 of Asahi glass company provides a method for producing 2,3,3, 3-tetrafluoropropene with high conversion rate stably for a long time. A process for producing 2,3,3, 3-tetrafluoropropene, which comprises reacting at least one starting compound selected from 1, 1-dichloro-2, 3,3, 3-tetrafluoropropene and 1-chloro-2, 3,3, 3-tetrafluoropropene with hydrogen in the presence of a noble metal catalyst supported on activated carbon having an ash content of 3% or less as measured by ASTM D2866.
The patent application CN201810366697.2 by kemueeffex limited is the only patent application for controlling the isomerization of tetrafluoropropene, which discloses the isomerization process and the catalytic isomerization of the corresponding mixtures, in particular 2,3,3, 3-tetrafluoropropene. The process involves contacting 2,3,3, 3-tetrafluoropropene with a suitable catalyst in a reaction zone to produce a product mixture comprising 1,3,3, 3-tetrafluoropropene.
In view of the above, although the patent application of honeywell corporation is for the production of tetrafluoropropene of HFO-1234ze type and the patent application of arkema france corporation for the production of tetrafluoropropene of HFO-1234yf type, the impurities, regardless of the type, contain about 1000ppm of isomers, have very close boiling points and relative volatilities close to 1, and are difficult to separate. The only prior art in which the only isomer control that can be retrieved is the Ke Munich Co., Ltd patent application CN201810366697.2, which is converted to HFO-1234ze by HFO-1234 yf. Because HFO-1234ze is thermodynamically stable and is more prone to form HFO-1234ze, it is very difficult to reverse convert it to HFO-1234 yf. In turn, no research report directed to obtaining high purity HFO-1234yf type tetrafluoropropene exists.
The chemical structures of HFO-1234ze and HFO-1234yf are shown below:
in addition, to meet the requirements of semiconductor manufacturing, HFO-1234yf needs to reach high purity electronic grade, and besides difficult isomers, by-product impurities in synthesis, light component impurities: n is a radical of 2 、O 2 、Ar、HF、CO 2 、CF 4 、C 2 F 6 Heavy component impurities: CF (compact flash) 3 C≡CH、CF 3 -CF＝CFH、CF 3 -CH＝CF 2 、CF 3 -CF＝CF 2 、CF 3 CF 2 CF 3 、CF 3 CFHCF 2 H、CF 3 CF 2 CF 2 H、CF 3 CFHCF 3 . Wherein the substance which is difficult to remove is an azeotrope CF 3 C≡CH。
In summary, the following technical problems are mainly existed in the separation and purification of HFO-1234 yf: the relative volatility of the isomer HFO-1234ze of HFO-1234yf is close to 1, and the separation is very difficult; the CF which is difficult to remove in impurities needs to be particularly considered 3 C is equal to CH azeotrope; the double bond of tetrafluoropropene is very reactive and will be rapidly converted to HFO-1234ze upon contact with an acidic, basic-centered adsorbent material.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for separating and purifying high-purity electronic grade tetrafluoropropene HFO-1234yf, so as to solve the problem that isomers HFO-1234ze and CF cannot be removed in the prior art for separating and purifying HFO-1234yf 3 C is equal to CH azeotrope and the like.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for separating and purifying high-purity electronic grade tetrafluoropropene HFO-1234yf comprises the following steps:
step S1: removing HF: introducing the raw material into a water washing tower to remove HF;
step S2: and (3) absorption operation: the raw material washed by the water in the step S1 is fed into an absorption tower for absorption operation, so that the HFO-1234ze and CF therein 3 C is equal to CH is fully absorbed in the absorption liquid in the absorption tower;
step S3: and (3) desorption operation: introducing the raw material absorbed in the step S2 into a desorption tower to disperse and release gas-phase substances in the raw material, and simultaneously enabling the absorption liquid to be retained in the desorption tower;
step S4: and (3) light impurity removal rectification operation: the raw material after the desorption operation is subjected to light impurity removal rectification operation to remove N 2 、O 2 、Ar、HF、CO 2 、CF 4 、C 2 F 6 Light component impurities;
step S5: heavy impurity removal rectification operation: the raw material after the light impurity removal and rectification operation is subjected to heavy and light impurity rectification operation to remove CF 3 -CF＝CFH、CF 3 -CH＝CF 2 、CF 3 -CF＝CF 2 、CF 3 CF 2 CF 3 、CF 3 CFHCF 2 H、CF 3 CF 2 CF 2 H、CF 3 CFHCF 3 Obtaining high-purity electronic grade tetrafluoropropene HFO-1234yf after heavy component impurities;
wherein the absorption liquid in the step S2 is composed of an extracting agent and a diluent, the extracting agent is acetone, the diluent is aliphatic hydrocarbon, and the volume ratio of the extracting agent to the diluent is 1:3-1: 5.
Preferably, the volume ratio of the extractant to the diluent is 1: 4.
Further, the aliphatic hydrocarbon is hexane, heptane, octane, nonane, cyclohexane or industrial sulfonated kerosene.
Preferably, the aliphatic hydrocarbon is industrial sulfonated kerosene.
Further, in the step S2, the absorption temperature is-20 to 30 ℃.
Further, the desorption operation temperature in the step S3 is 50-80 ℃.
Further, the rotation speed of stirring in the desorption operation in the step S3 is 200-400 r/min.
Further, the operation temperature of the light component removal rectifying tower in the step S4 is-9 to-11 ℃, and the operation pressure is 3 atm.
Further, the operation temperature of the de-heavy distillation tower in the step S5 is-19 to-21 ℃, and the operation pressure is 2 atm.
Compared with the prior art, the method for separating and purifying high-purity electronic grade tetrafluoropropene HFO-1234yf has the following advantages:
according to the characteristics of strong polarity (F atoms are on one side) of HFO-1234yf and weak polarity of HFO-1234ze, the invention adopts a method combining absorption and rectification to realize separation, and in addition, the absorption liquid in the step S2 can also remove the CF which is difficult to remove 3 C.ident.CH azeotrope. The main component of the non-polar absorption component selected in the absorption liquid is an extracting agent (acetone), and HFO-1234ze can be selectively extracted according to the principle of similar phase solubility. CF 3 C ≡ CH due to CF 3 Strong electron-withdrawing effect, the terminal alkyne is easily acidic to form CF 3 C ≡ C +, with the carbonyl group of acetone to form CF 3 C≡C-O-CH-(CH 3 ) 2 The complex ultimately yields pure HFO-1234 yf. However, since the extractant itself has viscosity, a diluent is required. Wherein the diluent is used for reducing solvent viscosity, and the diluent can be C6-C10 aliphatic hydrocarbon, such as hexane, heptane, octane, nonane, cyclohexane, industrial sulfonated kerosene, etc. Finally, the separation and purification of high-purity electronic grade HFO-1234yf are realized, and the purity reaches 99.999 percent.
The method can remove impurities which are difficult to separate, does not convert HFO-1234yf into other isomers, and has the characteristics of simple and stable operation and low energy consumption.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
Wherein, the content analysis methods of the key impurities in the raw materials and the purified products are all conventional analysis methods in the gas industry. The specific content is according to GB/T3723 industrial chemical product sampling safety rule, GB/T5832.1 gas analysis trace moisture determination part 1: electrolytic method, measurement of trace moisture in GB/T5832.3 gas analysis part 3: cavity ring-down spectroscopy, gas chromatography for measuring carbon monoxide, carbon dioxide and hydrocarbon in GB/T8984 gas, gas chromatography for analyzing helium ionization in GB/T28726 gas, and infrared spectroscopy analysis rule of GB/T6040.
The present invention will be described in detail with reference to examples.
The raw material compositions used in the following examples are shown in the following table:
TABLE 1 composition of the raw materials used in the various examples
| Components | Content (ppm) |
| N 2 | 100 |
| O 2 +Ar | 50 |
| HF | 5 |
| CO 2 | 40 |
| CF 4 | 5 |
| C 2 F 6 | 5 |
| CF 3 C≡CH | 2.9 |
| CF 3 -CF＝CFH | 2.8 |
| CF 3 -CH＝CF 2 | 2.4 |
| CF 3 -CF＝CF 2 | 2.9 |
| CF 3 CF 2 CF 3 | 2.6 |
| CF 3 CFHCF 2 H | 2.5 |
| CF 3 CF 2 CF 2 H | 2.6 |
| CF 3 CFHCF 3 | 2.7 |
| HFO-1234ze | 120 |
| Total content of isomers | 120 |
| Purity of HFO-1234yf | 99.9651％ |
Example 1
A method for separating and purifying high-purity electronic grade tetrafluoropropene HFO-1234yf comprises the following steps:
step S1: removing HF: introducing the raw materials into a water washing tower to remove HF, wherein the meteorological airspeed of the water washing tower is 50m 3 /h；
Step S2: and (3) absorption operation: introducing the raw material washed by the water in the step S1 into an absorption tower for absorption operation, wherein the absorption liquid consists of acetone and hexane in a volume ratio of 1:3, the operation temperature of the absorption tower is-20 ℃, and HFO-1234ze and CF in the absorption liquid are enabled to be in the range of 3 C is equal to CH is fully absorbed in the absorption liquid in the absorption tower;
step S3: and (3) desorption operation: introducing the raw material absorbed in the step S2 into a desorption tower to disperse and release gas-phase substances in the raw material, and simultaneously enabling absorption liquid to be retained in the desorption tower, wherein the operating temperature of the desorption tower is 50 ℃, and the stirring speed is 200 r/min;
step S4: and (3) light impurity removal rectification operation: the raw material after desorption is rectified to remove light impurities, the operation temperature of the rectifying tower is-10 ℃, the operation pressure is 3atm, and N is removed 2 、O 2 、Ar、HF、CO 2 、CF 4 、C 2 F 6 Light component impurities;
step S5: heavy impurity removal rectification operation: rectifying the light and heavy impurities from the raw material with the rectification operation of removing light impurities at-20 deg.C under 2atm to remove CF 3 -CF＝CFH、CF 3 -CH＝CF 2 、CF 3 -CF＝CF 2 、CF 3 CF 2 CF 3 、CF 3 CFHCF 2 H、CF 3 CF 2 CF 2 H、CF 3 CFHCF 3 And obtaining high-purity electronic grade tetrafluoropropene HFO-1234yf after heavy component impurities.
Example 2
A method for separating and purifying high-purity electronic grade tetrafluoropropene HFO-1234yf comprises the following steps:
step S1: removing HF: introducing the raw materials into a water washing tower to remove HF, wherein the meteorological airspeed of the water washing tower is 80m 3 /h；
Step S2: and (3) absorption operation: introducing the raw material washed by the water in the step S1 into an absorption tower for absorption operation, wherein the absorption liquid consists of acetone and heptane in a volume ratio of 1:4, the operation temperature of the absorption tower is 0 ℃, and the HFO-1234ze and CF in the absorption liquid are enabled to be in 3 C.ident.CH is sufficiently absorbed in the adsorptionAbsorbing liquid in the tower;
step S3: and (3) desorption operation: introducing the raw material absorbed in the step S2 into a desorption tower to disperse and release gas-phase substances in the raw material, and simultaneously enabling absorption liquid to be retained in the desorption tower, wherein the operating temperature of the desorption tower is 60 ℃, and the stirring speed is 200 r/min;
step S4: and (3) light impurity removal rectification operation: the raw material after desorption is rectified to remove light impurities, the operation temperature of the rectifying tower is-10 ℃, the operation pressure is 3atm, and N is removed 2 、O 2 、Ar、HF、CO 2 、CF 4 、C 2 F 6 Light component impurities;
step S5: heavy impurity removal rectification operation: rectifying the light and heavy impurities from the raw material with the rectification operation of removing light impurities at-20 deg.C under 2atm to remove CF 3 -CF＝CFH、CF 3 -CH＝CF 2 、CF 3 -CF＝CF 2 、CF 3 CF 2 CF 3 、CF 3 CFHCF 2 H、CF 3 CF 2 CF 2 H、CF 3 CFHCF 3 And obtaining high-purity electronic grade tetrafluoropropene HFO-1234yf after heavy component impurities.
Example 3
A method for separating and purifying high-purity electronic grade tetrafluoropropene HFO-1234yf comprises the following steps:
step S1: removing HF: introducing the raw materials into a water washing tower to remove HF, wherein the meteorological airspeed of the water washing tower is 100m 3 /h；
Step S2: and (3) absorption operation: introducing the raw material washed by the water in the step S1 into an absorption tower for absorption operation, wherein the absorption liquid consists of acetone and octane in a volume ratio of 1:4, the operation temperature of the absorption tower is 10 ℃, and HFO-1234ze and CF in the absorption liquid are enabled to be in 3 C is equal to CH is fully absorbed in the absorption liquid in the absorption tower;
step S3: and (3) desorption operation: introducing the raw material absorbed in the step S2 into a desorption tower to disperse and release gas-phase substances in the raw material, and simultaneously enabling absorption liquid to be retained in the desorption tower, wherein the operating temperature of the desorption tower is 70 ℃, and the stirring speed is 300 r/min;
step S4: and (3) light impurity removal rectification operation: the raw material after desorption is rectified to remove light impurities, the operation temperature of the rectifying tower is-10 ℃, the operation pressure is 3atm, and N is removed 2 、O 2 、Ar、HF、CO 2 、CF 4 、C 2 F 6 Light component impurities;
step S5: heavy impurity removal rectification operation: rectifying the light and heavy impurities from the raw material with the rectification operation of removing light impurities at-20 deg.C under 2atm to remove CF 3 -CF＝CFH、CF 3 -CH＝CF 2 、CF 3 -CF＝CF 2 、CF 3 CF 2 CF 3 、CF 3 CFHCF 2 H、CF 3 CF 2 CF 2 H、CF 3 CFHCF 3 And obtaining high-purity electronic grade tetrafluoropropene HFO-1234yf after heavy component impurities.
Example 4
A method for separating and purifying high-purity electronic grade tetrafluoropropene HFO-1234yf comprises the following steps:
step S1: removing HF: introducing the raw material into a water washing tower to remove HF, wherein the meteorological space velocity of the water washing tower is 130m 3 /h；
Step S2: and (3) absorption operation: introducing the raw material washed by the water in the step S1 into an absorption tower for absorption operation, wherein the absorption liquid consists of acetone and nonane in a volume ratio of 1:4, the operation temperature of the absorption tower is 10 ℃, and HFO-1234ze and CF in the absorption liquid are enabled to be 3 C is equal to CH is fully absorbed in the absorption liquid in the absorption tower;
step S3: and (3) desorption operation: introducing the raw material absorbed in the step S2 into a desorption tower to disperse and release gas-phase substances in the raw material, and simultaneously enabling absorption liquid to be retained in the desorption tower, wherein the operating temperature of the desorption tower is 80 ℃, and the stirring speed is 300 r/min;
step S4: and (3) light impurity removal rectification operation: the raw material after desorption is rectified to remove light impurities, the operation temperature of the rectifying tower is-10 ℃, the operation pressure is 3atm, and N is removed 2 、O 2 、Ar、HF、CO 2 、CF 4 、C 2 F 6 Light component impurities；
Step S5: heavy impurity removal rectification operation: rectifying the light and heavy impurities from the raw material with the rectification operation of removing light impurities at-20 deg.C under 2atm to remove CF 3 -CF＝CFH、CF 3 -CH＝CF 2 、CF 3 -CF＝CF 2 、CF 3 CF 2 CF 3 、CF 3 CFHCF 2 H、CF 3 CF 2 CF 2 H、CF 3 CFHCF 3 And obtaining high-purity electronic grade tetrafluoropropene HFO-1234yf after heavy component impurities.
Example 5
A method for separating and purifying high-purity electronic grade tetrafluoropropene HFO-1234yf comprises the following steps:
step S1: removing HF: introducing the raw materials into a water washing tower to remove HF, wherein the meteorological airspeed of the water washing tower is 150m 3 /h；
Step S2: and (3) absorption operation: introducing the raw material washed by the water in the step S1 into an absorption tower for absorption operation, wherein the absorption liquid consists of acetone and sulfonated kerosene in a volume ratio of 1:4, the operation temperature of the absorption tower is 20 ℃, and the HFO-1234ze and CF in the absorption liquid are enabled to be in the range of HFO-1234ze and CF 3 C is equal to CH is fully absorbed in the absorption liquid in the absorption tower;
step S3: and (3) desorption operation: introducing the raw material absorbed in the step S2 into a desorption tower to disperse and release gas-phase substances in the raw material, and simultaneously enabling absorption liquid to be retained in the desorption tower, wherein the operating temperature of the desorption tower is 80 ℃, and the stirring speed is 400 r/min;
step S4: and (3) light impurity removal rectification operation: the raw material after desorption is rectified to remove light impurities, the operation temperature of the rectifying tower is-10 ℃, the operation pressure is 3atm, and N is removed 2 、O 2 、Ar、HF、CO 2 、CF 4 、C 2 F 6 Light component impurities;
step S5: heavy impurity removal rectification operation: rectifying the light and heavy impurities from the raw material with the rectification operation of removing light impurities at-20 deg.C under 2atm to remove CF 3 -CF＝CFH、CF 3 -CH＝CF 2 、CF 3 -CF＝CF 2 、CF 3 CF 2 CF 3 、CF 3 CFHCF 2 H、CF 3 CF 2 CF 2 H、CF 3 CFHCF 3 And obtaining high-purity electronic grade tetrafluoropropene HFO-1234yf after heavy component impurities.
Example 6
A method for separating and purifying high-purity electronic grade tetrafluoropropene HFO-1234yf comprises the following steps:
step S1: removing HF: introducing the raw material into a water scrubber to remove HF, wherein the meteorological airspeed of the water scrubber is 200m 3 /h；
Step S2: and (3) absorption operation: introducing the raw material washed by the water in the step S1 into an absorption tower for absorption operation, wherein the absorption liquid consists of acetone and sulfonated kerosene in a volume ratio of 1:5, the operation temperature of the absorption tower is 30 ℃, and the HFO-1234ze and CF in the absorption liquid are enabled to be in 3 C is equal to CH is fully absorbed in the absorption liquid in the absorption tower;
step S3: and (3) desorption operation: introducing the raw material absorbed in the step S2 into a desorption tower to disperse and release gas-phase substances in the raw material, and simultaneously enabling absorption liquid to be retained in the desorption tower, wherein the operating temperature of the desorption tower is 70 ℃, and the stirring speed is 400 r/min;
step S4: and (3) light impurity removal rectification operation: the raw material after desorption is rectified to remove light impurities, the operation temperature of the rectifying tower is-10 ℃, the operation pressure is 3atm, and N is removed 2 、O 2 、Ar、HF、CO 2 、CF 4 、C 2 F 6 Light component impurities;
step S5: heavy impurity removal rectification operation: rectifying the heavy and light impurities from the raw material with the rectification operation of removing the light and light impurities at the operating temperature of-20 ℃ and the operating pressure of 2atm to remove CF 3 -CF＝CFH、CF 3 -CH＝CF 2 、CF 3 -CF＝CF 2 、CF 3 CF 2 CF 3 、CF 3 CFHCF 2 H、CF 3 CF 2 CF 2 H、CF 3 CFHCF 3 And obtaining high-purity electronic grade tetrafluoropropene HFO-1234yf after heavy component impurities.
Comparative example 1
A method for separating and purifying tetrafluoropropene HFO-1234yf, comprising the following steps:
step S1: and (3) absorption operation: introducing the raw materials into an absorption tower for absorption operation, wherein the absorption liquid is composed of acetone and industrial sulfonated kerosene in a volume ratio of 1:4, the operation temperature of the absorption tower is 20 ℃, and HFO-1234ze and CF in the absorption tower are enabled to be in 3 C is equal to CH is fully absorbed in the absorption liquid in the absorption tower;
step S2: and (3) desorption operation: introducing the raw material absorbed in the step S2 into a desorption tower to disperse and release gas-phase substances in the raw material, and simultaneously enabling absorption liquid to be retained in the desorption tower, wherein the operating temperature of the desorption tower is 70 ℃, and the stirring speed is 400 r/min;
step S3: and (3) light impurity removal rectification operation: the raw material after desorption is rectified to remove light impurities, the operation temperature of the rectifying tower is-10 ℃, the operation pressure is 3atm, and N is removed 2 、O 2 、Ar、HF、CO 2 、CF 4 、C 2 F 6 Light component impurities;
step S4: heavy impurity removal rectification operation: and (3) carrying out heavy and light impurity rectification on the raw material subjected to the light impurity removal rectification operation, wherein the operation temperature of the rectification tower is-20 ℃, and the operation pressure is 2atm, and finally obtaining the tetrafluoropropene HFO-1234 yf.
Comparative example 2
A method for separating and purifying tetrafluoropropene HFO-1234yf, comprising the following steps:
step S1: and (3) absorption operation: introducing the raw materials into an absorption tower for absorption operation, wherein the absorption liquid is composed of toluene and industrial sulfonated kerosene in a volume ratio of 1:4, the operation temperature of the absorption tower is 20 ℃, and HFO-1234ze and CF in the absorption tower are enabled to be in 3 C is equal to CH is fully absorbed in the absorption liquid in the absorption tower;
step S2: and (3) desorption operation: introducing the raw material absorbed in the step S2 into a desorption tower to disperse and release gas-phase substances in the raw material, and simultaneously enabling absorption liquid to be retained in the desorption tower, wherein the operating temperature of the desorption tower is 70 ℃, and the stirring speed is 400 r/min;
step S3: and (3) light impurity removal rectification operation: carrying out light impurity removal rectification operation on the raw material subjected to desorption operation, wherein the operation temperature of the rectification tower is-10 ℃, and the operation pressure is 3 atm;
step S4: heavy impurity removal rectification operation: and (3) carrying out heavy and light impurity rectification on the raw material subjected to the light impurity removal rectification operation, wherein the operation temperature of the rectification tower is-20 ℃, and the operation pressure is 2atm, and finally obtaining the tetrafluoropropene HFO-1234 yf.
The tetrafluoropropene HFO-1234yf obtained in examples 1 to 6 and comparative examples 1 and 2 were subjected to the test of impurity content and purity, and the test results are shown in table 2.
TABLE 2 impurity content and purity (in ppm) of each of the examples and comparative examples
As can be seen from Table 2, the purity of HFO-1234yf of examples 1-6 reaches above 99.998%, and the purity of HFO-1234yf of example 5 reaches as high as 99.999%, which indicates that the purity of HFO-1234yf can be obviously improved by the purification method of the present invention. The embodiment 5 has the best effect, and the mass transfer resistance is effectively reduced mainly because the proportion of the diluent and the extracting agent is better, and the prepared viscosity is more appropriate. In addition, the absorption efficiency is improved and the separation effect is achieved by more proper gas phase airspeed, reaction temperature, stirring speed and stirring pressure.
Comparative example 1 eliminated the HF water wash step and comparative example 2 replaced the extractant acetone with toluene. The separation effect is not ideal. This is because the effective absorption liquid of choice in the present invention is acetone and the remaining extractant (e.g., toluene) is not effective in removing impurities. Meanwhile, trace amounts of impurity HF contained in HFO-1234yf are easily partially complexed with acetone, rendering acetone decomposition ineffective, and therefore it is necessary to remove HF before proceeding to step S2.
In addition, the invention innovatively selects the absorption liquid compounded by acetone and aliphatic hydrocarbon, and integrally improves the separation purity of HFO-1234yf by controlling parameters such as gas phase airspeed, reaction temperature, stirring speed, pressure and the like. The separation and purification method has strong operability and low cost, and the obtained HFO-1234yf reaches a high-grade electronic grade and can completely meet the requirements of semiconductor manufacturing.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A method for separating and purifying high-purity electronic grade tetrafluoropropene HFO-1234yf is characterized by comprising the following steps: the method comprises the following steps:
step S1: removing HF: introducing the raw material into a water washing tower to remove HF;
step S2: and (3) absorption operation: the raw material washed by the water in the step S1 is fed into an absorption tower for absorption operation, so that the HFO-1234ze and CF therein 3 C is equal to CH is fully absorbed in the absorption liquid in the absorption tower;
step S3: and (3) desorption operation: introducing the raw material absorbed in the step S2 into a desorption tower to disperse and release gas-phase substances in the raw material, and simultaneously enabling the absorption liquid to be retained in the desorption tower;
step S4: and (3) light impurity removal rectification operation: carrying out light impurity removal rectification operation on the raw material subjected to desorption operation to remove light component impurities;
step S5: heavy impurity removal rectification operation: carrying out heavy and light impurity rectification operation on the raw material subjected to the light impurity removal rectification operation, and removing heavy component impurities to obtain high-purity electronic grade tetrafluoropropene HFO-1234 yf;
wherein the absorption liquid in the step S2 is composed of an extracting agent and a diluent, the extracting agent is acetone, the diluent is aliphatic hydrocarbon, and the volume ratio of the extracting agent to the diluent is 1:3-1: 5;
the aliphatic hydrocarbon is hexane, heptane, octane, nonane, cyclohexane or industrial sulfonated kerosene;
in the step S2, the absorption temperature is-20-30 ℃;
the desorption operation temperature in the step S3 is 50-80 ℃.
2. The method for separating and purifying high purity electronic grade tetrafluoropropene HFO-1234yf of claim 1, characterized in that: the volume ratio of the extracting agent to the diluting agent is 1: 4.
3. The method for separating and purifying high purity electronic grade tetrafluoropropene HFO-1234yf of claim 1, characterized in that: the aliphatic hydrocarbon is industrial sulfonated kerosene.
4. The method for separating and purifying high purity electronic grade tetrafluoropropene HFO-1234yf of claim 1, characterized in that: and stirring in the desorption operation process in the step S3, wherein the stirring speed is 200-400 r/min.
5. The method for separating and purifying high purity electronic grade tetrafluoropropene HFO-1234yf of claim 1, characterized in that: the operation temperature of the light component removing rectifying tower in the step S4 is-9 to-11 ℃, and the operation pressure is 3 atm.
6. The method for separating and purifying high purity electronic grade tetrafluoropropene HFO-1234yf of claim 1, characterized in that: the operation temperature of the de-heavy rectifying tower in the step S5 is-19 to-21 ℃, and the operation pressure is 2 atm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010183425.6A CN111253211B (en) | 2020-03-16 | 2020-03-16 | Separation and purification method of high-purity electronic-grade tetrafluoropropene HFO-1234yf |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010183425.6A CN111253211B (en) | 2020-03-16 | 2020-03-16 | Separation and purification method of high-purity electronic-grade tetrafluoropropene HFO-1234yf |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111253211A CN111253211A (en) | 2020-06-09 |
| CN111253211B true CN111253211B (en) | 2022-08-05 |
Family
ID=70946023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010183425.6A Active CN111253211B (en) | 2020-03-16 | 2020-03-16 | Separation and purification method of high-purity electronic-grade tetrafluoropropene HFO-1234yf |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111253211B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340459B (en) * | 2021-05-13 | 2023-12-26 | 中昊晨光化工研究院有限公司 | Industrial method for removing impurities in trifluoromethyl fluoacid ester |
| CN115286482B (en) * | 2022-09-06 | 2024-06-11 | 天津绿菱气体有限公司 | Purification method of electronic grade hexafluoroisobutylene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102971280A (en) * | 2010-07-23 | 2013-03-13 | 大金工业株式会社 | Purification method of 2,3,3,3-tetrafluoropropene |
| CN105612139A (en) * | 2013-10-09 | 2016-05-25 | 旭硝子株式会社 | Method for purifying 2,3,3,3-tetrafluoropropene |
| WO2019220454A1 (en) * | 2018-05-16 | 2019-11-21 | Srf Limited | Process for purification of olefin feed comprising 1234yf |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2948362B1 (en) * | 2009-07-23 | 2012-03-23 | Arkema France | PROCESS FOR THE PREPARATION OF FLUORINATED COMPOUNDS |
| EP2799415B2 (en) * | 2011-12-28 | 2019-06-12 | AGC Inc. | Method for purifying 2,3,3,3-tetrafluoropropene and process for producing same |
| WO2014103582A1 (en) * | 2012-12-27 | 2014-07-03 | 旭硝子株式会社 | Method for purifying tetrafluoropropene |
-
2020
- 2020-03-16 CN CN202010183425.6A patent/CN111253211B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102971280A (en) * | 2010-07-23 | 2013-03-13 | 大金工业株式会社 | Purification method of 2,3,3,3-tetrafluoropropene |
| CN105612139A (en) * | 2013-10-09 | 2016-05-25 | 旭硝子株式会社 | Method for purifying 2,3,3,3-tetrafluoropropene |
| WO2019220454A1 (en) * | 2018-05-16 | 2019-11-21 | Srf Limited | Process for purification of olefin feed comprising 1234yf |
Non-Patent Citations (1)
| Title |
|---|
| 2,3,3,3-四氟丙烯的合成研究进展;王玉林等;《化工生产与技术》;20160625(第03期);1-12 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111253211A (en) | 2020-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9862660B2 (en) | Method for purifying fluid that includes trifluoroethylene, and method for producing trifluoroethylene | |
| EP2170788B1 (en) | Preparation of halogen and hydrogen containing alkenes over metal fluoride catalysts | |
| JP5477011B2 (en) | (Z) Purification method of 1-chloro-3,3,3-trifluoropropene | |
| CN108368011B (en) | Process for producing hydrofluoroolefin | |
| CN101665405A (en) | Method for producing 2,3,3,3-tetrafluoropropene | |
| US10011553B2 (en) | Method for producing dry etching gas | |
| EP3442935A1 (en) | Process for the manufacture of 2,3,3,3-tetrafluoropropene | |
| CN111253211B (en) | Separation and purification method of high-purity electronic-grade tetrafluoropropene HFO-1234yf | |
| KR102689473B1 (en) | How to remove acidic impurities from halogenated propene | |
| US11661387B2 (en) | High-purity 1,1,1,2,3,3-hexafluoropropane, method for producing same and use thereof | |
| CN105218300B (en) | The preparation method of Fluorine containing olefine compound | |
| JP5859659B2 (en) | Process for preparing 2,3,3,3-tetrafluoropropene | |
| EP3699164A1 (en) | Co-production method for 2,3,3,3-tetrafluoropropylene and trans-1,3,3,3-tetrafluoropropylene | |
| WO2011162335A1 (en) | Process for preparation of 1,1-dichloro-2,2,3,3,3-penta- fluoropropane | |
| JP7287391B2 (en) | Method for producing fluorine-containing propene | |
| JP2023052523A (en) | Process for reducing 3,3,3-trifluoropropyne in 2,3,3,3-tetrafluoropropene | |
| CN113527038B (en) | Process for preparing cis-1, 3-tetrafluoropropene | |
| JP2010090045A (en) | Separation method of hydrogen fluoride | |
| KR100543253B1 (en) | Production and use of hexafluoroethane | |
| TWI266759B (en) | Process for the production of fluoroethane and use of the produced fluoroethane | |
| CN111511708B (en) | Method for removing 2-chloro-1, 3-tetrafluoropropene and method for producing 1-chloro-2, 3-tetrafluoropropene | |
| TW200401760A (en) | Process for purifying pentafluoroethane, process for producing the same, and use thereof | |
| US20040242943A1 (en) | Process for the production of fluoroethane and use of the produced fluoroethane | |
| KR20240118069A (en) | High purity HFO-E-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze) and method for producing the same | |
| JP4458784B2 (en) | Method for producing pentafluoroethane and use thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 300000 south of GANGDA Road, Nangang Industrial Zone, economic and Technological Development Zone, Binhai New Area, Tianjin and west of Zhonghe Haifeng project Patentee after: Tianjin Green Ling Gas Co.,Ltd. Country or region after: China Address before: 300000 south of GANGDA Road, Nangang Industrial Zone, economic and Technological Development Zone, Binhai New Area, Tianjin and west of Zhonghe Haifeng project Patentee before: Tianjin Lvling Gas Co.,Ltd. Country or region before: China |