CN101560138B - Preparation method of pentafluoropropane - Google Patents
Preparation method of pentafluoropropane Download PDFInfo
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- CN101560138B CN101560138B CN2009100277780A CN200910027778A CN101560138B CN 101560138 B CN101560138 B CN 101560138B CN 2009100277780 A CN2009100277780 A CN 2009100277780A CN 200910027778 A CN200910027778 A CN 200910027778A CN 101560138 B CN101560138 B CN 101560138B
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- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 33
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 31
- 238000007259 addition reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- YXEBARDKWGXGRC-UHFFFAOYSA-N 1,1,1-trichloro-2,2-difluoropropane Chemical compound CC(F)(F)C(Cl)(Cl)Cl YXEBARDKWGXGRC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 36
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 36
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 27
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 27
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- DCWQLZUJMHEDKD-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoropropane Chemical compound CC(Cl)(Cl)C(F)(F)F DCWQLZUJMHEDKD-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 claims description 13
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 9
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 9
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 claims description 8
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 8
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 8
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 8
- 229910015900 BF3 Inorganic materials 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 235000019404 dichlorodifluoromethane Nutrition 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 6
- NHCQUJBAMRDYLH-UHFFFAOYSA-N 1,1,2,2-tetrachloro-1-fluoropropane Chemical compound CC(Cl)(Cl)C(F)(Cl)Cl NHCQUJBAMRDYLH-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229940029284 trichlorofluoromethane Drugs 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- FTCVHAQNWWBTIV-UHFFFAOYSA-N 1,1,1,2,2-pentachloropropane Chemical compound CC(Cl)(Cl)C(Cl)(Cl)Cl FTCVHAQNWWBTIV-UHFFFAOYSA-N 0.000 abstract description 8
- -1 alkenyl halide Chemical class 0.000 abstract description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- XHWJTHXIDJSPNF-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2-fluoropropane Chemical compound CC(F)(Cl)C(Cl)(Cl)Cl XHWJTHXIDJSPNF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000004334 fluoridation Methods 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000003513 alkali Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 26
- 238000005406 washing Methods 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 16
- 229910001220 stainless steel Inorganic materials 0.000 description 16
- 239000010935 stainless steel Substances 0.000 description 16
- 238000007599 discharging Methods 0.000 description 15
- 239000012043 crude product Substances 0.000 description 14
- 230000006835 compression Effects 0.000 description 12
- 238000007906 compression Methods 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000013058 crude material Substances 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 229910001339 C alloy Inorganic materials 0.000 description 7
- 230000004913 activation Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 4
- 239000012025 fluorinating agent Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- BBEAZDGZMVABIC-UHFFFAOYSA-N 1,1,1,3,3,3-hexachloropropane Chemical compound ClC(Cl)(Cl)CC(Cl)(Cl)Cl BBEAZDGZMVABIC-UHFFFAOYSA-N 0.000 description 2
- GVWSTOIEDDREHS-UHFFFAOYSA-N 1,1,1-trichloro-3-fluoropropane Chemical compound FCCC(Cl)(Cl)Cl GVWSTOIEDDREHS-UHFFFAOYSA-N 0.000 description 2
- XTRPJEPJFXGYCI-UHFFFAOYSA-N 3-chloro-1,1,1,2,2-pentafluoropropane Chemical compound FC(F)(F)C(F)(F)CCl XTRPJEPJFXGYCI-UHFFFAOYSA-N 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- MDNLZVVUMKSEKO-UHFFFAOYSA-N 1,1,1-trichloro-3,3,3-trifluoropropane Chemical compound FC(F)(F)CC(Cl)(Cl)Cl MDNLZVVUMKSEKO-UHFFFAOYSA-N 0.000 description 1
- AUCISWTVFIKMCZ-UHFFFAOYSA-N 1-chloro-1,1,2,2-tetrafluoropropane Chemical compound CC(F)(F)C(F)(F)Cl AUCISWTVFIKMCZ-UHFFFAOYSA-N 0.000 description 1
- OPLWDQVQIWKMSG-UHFFFAOYSA-N 1-chloro-1-fluoropropane Chemical compound CCC(F)Cl OPLWDQVQIWKMSG-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of pentafluoropropane(245fa), comprising the following steps: preparing alkenyl halide by means of addition reaction between acetylene and halogen hydride in the presence of catalyst, preparing monofluorotetrachloropropane or difluorotrichloropropane or triflurodichloropropane or tetrafluoromonochloropropane by reaction between alkenyl halide and alkanefluoride or fluorine enpara by addition reaction and preparing pentafluoropropane(245fa) by reaction of monofluorotetrachloropropane or difluorotrichloropropane or triflurodichloropropane or tetraflu oromonochloropropane in the presence of the catalyst. The whole technology process of the invention successfully avoids the known process route by which pentachloropropane(240fa) is prepared by telomerization reaction of carbon tetrachloride and chloroethylene and pentafluoropropane(245fa) is prepared by fluoridation of pentachloropropane(240fa), uses most basic ethyne as a raw material, thus greatly decreasing the material cost of the whole technology process and enjoys high yield of the technology process and high purity pentafluoropropane(245fa).
Description
Technical Field
The invention relates to a preparation method of a compound, in particular to a preparation method of pentafluoropropane (HFC245 fa).
Background
1, 1, 1, 3, 3-pentafluoropropane (HFC245fa) has similar properties to CFC11 and HCFC141b, and has become a third generation blowing agent with zero ODP. Currently, HCFC141b is the main blowing agent used in domestic industry, and its molecule still contains chlorine atoms, which destroys the ozone layer. The developed countries have completely prohibited production and application in 2003, China also accelerates the pace of eliminating HCFC141b, and the production of HCFC141b is completely stopped in recent years.
HFC245fa has a lower boiling point and a higher vapor pressure and can improve certain properties of the foam, particularly at low temperatures, to provide the foam with greater mechanical and thermal conductivity over a range of temperatures. HFC245fa foamed polyurethane foam is relatively fine-celled and has thermal insulation properties comparable to HCFC141b foamed foam. HFC245fa has been widely used in Europe and America as a blowing agent for refrigerated foam boards and as a rigid polyurethane blowing agent. It can be seen that HFC245fa has many advantages and wide market prospect when used for replacing HCFC141 b.
At present, the annual yield of HCFC141b in China is 10 ten thousand tons, and the work of replacing HCFC141b is very serious. At present, the manufacturing patent of HFC245fa is almost controlled by European and American companies such as HONEYWELL, DAJIN, DuPont and the like, and the main synthetic route is as follows: firstly, carrying out telomerization reaction on carbon tetrachloride and chloroethylene to generate pentachloropropane, and fluorinating the pentachloropropane into pentafluoropropane through a liquid phase or a gas phase; and secondly, telomerization reaction of the carbon tetrachloride and vinylidene chloride generates hexachloropropane, the hexachloropropane is fluorinated into chloropentafluoropropane through liquid phase or gas phase, and the chloropentafluoropropane is hydrogenated to obtain the pentafluoropropane. Such as documents CN1130614A, CN1128016A, CN1205682A, CN1206394A, CN1166479A, EP0658531a1, EP0703207a1, EP0728720a1, US5821392A, US6291728B1, US6060628A, WO0017137, US2005070746a1, US6316682B1, etc.
In order to avoid the patent technology controlled by European and American companies, the invention successfully opens up a brand new process route. The invention discloses a preparation method of pentafluoropropane (245 fa). The preparation method comprises the steps of preparing vinyl halide by addition reaction of acetylene and hydrogen halide in the presence of a catalyst, preparing tetrachloro-fluoro-propane or trichloro-fluoro-propane or dichlorotrifluoro-propane or tetrafluoro-chloropropane or pentafluoropropane (245fa) by addition reaction of the vinyl halide and fluoroalkane or chlorofluoroalkane, and generating the pentafluoropropane by the tetrachloro-fluoro-propane or trichloro-fluoro-propane or dichlorotrifluoro-chloropropane in the presence of the catalyst. The process takes the most basic acetylene as a raw material route, greatly reduces the raw material cost of the whole process, and has high yield in the process and high purity of the pentafluoropropane (245 fa).
Disclosure of Invention
The technical route of the invention is to provide a brand-new preparation method of pentafluoropropane with low cost and high purity.
The technical scheme adopted by the invention is as follows:
a process for the preparation of pentafluoropropane (HFC245fa), comprising the steps of:
1. acetylene and hydrogen chloride or hydrogen fluoride are subjected to addition reaction under the action of a catalyst according to the molar ratio of 2.5-2.5: 1 to prepare vinyl chloride or vinyl fluoride; the process is described in the' 200810024501 patent.
2(A), carrying out addition reaction on the fluoroethylene obtained in the step (1) and monofluorotrichloromethane according to the molar ratio of 1: 1.1-1.5 under the action of a catalyst to prepare difluorotrichloropropane;
or carrying out addition reaction on the fluoroethylene obtained in the step (1) and difluorodichloromethane according to the molar ratio of 1: 1.1-1.5 under the action of a catalyst to prepare trifluorodichloropropane;
or carrying out addition reaction on the fluoroethylene obtained in the step (1) and trifluoro-monochloromethane according to the molar ratio of 1: 1.1-1.5 under the action of a catalyst to prepare tetrafluoro-monochloropropane;
or carrying out addition reaction on the fluoroethylene obtained in the step (1) and the tetrafluoromethane according to the molar ratio of 1: 1.1-1.5 under the action of a catalyst to prepare the pentafluoropropane.
(B) Performing addition reaction on chloroethylene obtained in the step (1) and trichlorofluoromethane according to the molar ratio of 1: 1.1-1.5 under the action of a catalyst to prepare tetrachlorofluoropropane;
or performing addition reaction on the chloroethylene obtained in the step (1) and difluorodichloromethane according to the molar ratio of 1: 1.1-1.5 under the action of a catalyst to prepare difluorotrichloropropane;
or carrying out addition reaction on the chloroethylene obtained in the step (1) and trifluoro-monochloromethane according to the molar ratio of 1: 1.1-1.5 under the action of a catalyst to prepare trifluoro-dichloropropane;
or carrying out addition reaction on the chloroethylene obtained in the step (1) and the tetrafluoromethane according to the molar ratio of 1: 1.1-1.5 under the action of a catalyst to prepare tetrafluoro-monochloropropane.
3. Reacting the monofluoro tetrachloropropane obtained in the step (2) with hydrogen fluoride according to a molar ratio of 1: 5-7 under the action of a fluorinating agent to generate pentafluoropropane;
or reacting the difluorotrichloropropane obtained in the step (2) with hydrogen fluoride according to the molar ratio of 1: 4-6 under the action of a fluorinating agent to generate pentafluoropropane;
or reacting the trifluorodichloropropane obtained in the step (2) with hydrogen fluoride according to the molar ratio of 1: 3-5 under the action of a fluorinating agent to generate pentafluoropropane;
or reacting the tetrafluorochloropropane obtained in the step (2) with hydrogen fluoride according to the molar ratio of 1: 2-3 under the action of a fluorinating agent to generate the pentafluoropropane.
Wherein the catalyst in the step 2(A) is a mixture of boron trifluoride, aluminum trichloride and ferric trichloride; the solvent is a mixture of ketones and aromatic hydrocarbons; the catalytic reaction temperature is 100-120 ℃, the reaction pressure is 0.5-0.8 MPa, and the reaction time is 3-5 hours.
Wherein the catalyst in the step 2(B) is a mixture of tin dichloride, platinum chloride and ferric trichloride; the solvent is a mixture of straight-chain alcohol and phosphate ester; the catalytic reaction temperature is 120-140 ℃, the reaction pressure is 1.2-1.5 MPa, and the reaction time is 2-3 hours.
The catalyst in the step 3 is a composite catalyst of stannic chloride, cobalt chloride and sulfuric acid, the fluorination reaction temperature is 110-130 ℃, the reaction pressure is 1.0-1.2 MPa, and the reaction time is 5-6 hours.
The reaction formula of the invention is as follows:
HC≡≡CH+HF→H2C＝CHF
H2C＝CHF+CFCl3→CCl3-H2C-CHF2
CCl3-H2C-CHF2+3HF→CF3-H2C-CHF2+3HCl
or,
HC≡≡CH+HF→H2C＝CHF
H2C＝CHF+CF2Cl2→CFCl2-H2C-CHF2
CFCl2-H2C-CHF2+2HF→CF3-H2C-CHF2+2HCl
or,
HC≡≡CH+HF→H2C＝CHF
H2C＝CHF+CF3Cl→CF2Cl-H2C-CHF2
CF2Cl-H2C-CHF2+HF→CF3-H2C-CHF2+HCl
alternatively, HC ≡ CH + HF → H2C＝CHF
H2C＝CHF+CF4→CF3-H2C-CHF2
Or,
HC≡≡CH+HCl→H2C＝CHCl
H2C＝CHCl+CFCl3→CCl3-H2C-CHFCl
CCl3-H2C-CHFCl+4HF→CF3-H2C-CHF2+4HCl
or,
HC≡≡CH+HCl→H2C＝CHCl
H2C＝CHCl+CF2Cl2→CFCl2-H2C-CHFCl
CFCl2-H2C-CHFCl+3HF→CF3-H2C-CHF2+3HCl
or,
HC≡≡CH+HCl→H2C＝CHCl
H2C＝CHCl+CF3Cl→CF2Cl-H2C-CHFCl
CF2Cl-H2C-CHFCl+2HF→CF3-H2C-CHF2+2HCl
or,
HC≡≡CH+HCl→H2C＝CHCl
H2C＝CHCl+CF4→CF3-H2C-CHFCl
CF3-H2C-CHFCl+HF→CF3-H2C-CHF2+HCl
has the advantages that: a preparation step of preparing vinyl halide by addition reaction of acetylene and hydrogen halide in the presence of a catalyst, and preparing monochlorofluoropropane or difluorotrichloropropane or trifluorodichloropropane or tetrafluoromonochloropropane by addition reaction of the vinyl halide and fluoroalkane or fluorochloroalkane; the monofluo-tetrachloropropane or difluoro-trichloropropane or trifluoro-dichloropropane or tetrafluoro-monochloro-propane generates the pentafluoropropane (245fa) under the action of a catalyst. The whole process successfully avoids the well-known process route of telomerizing carbon tetrachloride and vinyl chloride into pentachloropropane (240fa) and fluorinating the pentachloropropane (240fa) into pentafluoropropane (245fa), and the process takes the most basic acetylene as a raw material route, so that the raw material cost of the whole process is greatly reduced, and the yield of the process is high and the purity of the pentafluoropropane (245fa) is high.
Detailed Description
The invention is further illustrated by the following examples. The detection tool for the products of the examples employed an Agilent 6890N/5937(GC/MS) gas chromatography/mass spectrometer.
Example 1:
in thatThe stainless steel tubular reactor was filled with 4 liters of a mixture of activated carbon, platinum chloride and palladium chloride, containing 100 g of palladium chloride and 50 g of platinum chloride. Heating to 400 ℃ with N2The catalyst was activated for 10 hours and then cooled to 100 ℃. Acetylene and hydrogen fluoride are mixed and then put into a tubular reactor, wherein the feeding rate of the acetylene is 3900 g/h, and the feeding rate of the hydrogen fluoride is 2000 g/h. The products of acetylene and hydrogen fluoride in the tubular reactor are directly subjected to water alkali washing and then directly subjected to compression rectification to obtain vinyl fluoride with the purity of 99 percent. The hourly take-up of vinyl fluoride is4305 g, yield of vinyl fluoride 93.58%.
Adding 2000 g of dimethylbenzene and 100 g of cyclohexanone into a 10L stainless steel magnetic stirring autoclave, adding 50 g of aluminum trichloride and 20 g of ferric trichloride into the autoclave, starting stirring, introducing 30 g of boron trifluoride gas into the autoclave, fully stirring for 30 minutes, then pressing 5500 g of fluorotrichloromethane into the autoclave, opening a steam inlet valve of an autoclave jacket, raising the temperature of the autoclave to 100 ℃, then continuously pumping fluoroethylene into the autoclave by using a membrane type compression pump, controlling the pressure of the autoclave system to be 0.5MPa, controlling the feeding speed of the fluoroethylene to be 353.75 g/h, finishing feeding after 4 h, keeping the temperature at 100 ℃ for 1 h, cooling and discharging. The crude material is directly rectified in a rectifying tower to obtain 5003.20 g of difluorotrichloropropane with the purity of 99.2 percent, and the yield of the difluorotrichloropropane is 87.93 percent.
In a 10L Hardgrove C alloy stirring autoclave with 2m2The condenser is internally provided with a water alkali cleaning device and a collecting device. 2100 g of tin tetrachloride, 900 g of cobalt dichloride and 37 g of 98% sulfuric acid are introduced into the autoclave, stirring is started and the autoclave is heated to 50 ℃ with steam. 930 grams of hydrogen fluoride activating catalyst was pressed in. The activation time was 2 hours. And (4) after discharging the hydrogen chloride of the system into the water alkali washing device from the top end of the condenser, closing the exhaust valve. Adding 2500 g of hydrogen fluoride into a reactor, raising the temperature of the autoclave system to 100 ℃, and pumping difluorotrichloropropane into the autoclave by a metering pump, wherein the feeding speed of the difluorotrichloropropane is 1146.9 g/h, and the feeding time is 4 h. Controlling the pressure in the autoclave at 1.0Mpa through an exhaust valve at the top end of the condenser, and preserving the heat for 1 hour after the feeding is finished. After pentafluoropropane (245fa) passes through a water alkali washing system from an exhaust valve at the top end of the condenser, the pentafluoropropane (245fa) is collected into a crude product tank, and the crude product passes through a drying and rectifying device, so that 3006.8 g of pentafluoropropane (245fa) with the purity of 99.5% is obtained, and the yield of pentafluoropropane is 89.31%.
Example 2:
in that
The stainless steel tubular reactor was filled with 4 liters of a mixture of activated carbon, platinum chloride and palladium chloride, containing 100 g of palladium chloride and 50 g of platinum chloride. Heating to 400 ℃ with N2The catalyst was activated for 10 hours and then cooled to 100 ℃. Acetylene and hydrogen fluoride are mixed and then put into a tubular reactor, wherein the feeding rate of the acetylene is 3900 g/h, and the feeding rate of the hydrogen fluoride is 2000 g/h. The products of acetylene and hydrogen fluoride in the tubular reactor are directly subjected to water alkali washing and then directly subjected to compression rectification to obtain vinyl fluoride with the purity of 99 percent. The yield of vinyl fluoride per hour was 4305 g, and the yield of vinyl fluoride was 93.58%.
Adding 2000 g of dimethylbenzene and 100 g of cyclohexanone into a 10L stainless steel magnetic stirring autoclave, adding 50 g of aluminum trichloride and 20 g of ferric trichloride into the autoclave, starting stirring, introducing 30 g of boron trifluoride gas into the autoclave, fully stirring for 30 minutes, then pressing 3630 g of difluorodichloromethane into the autoclave, opening a steam inlet valve of an autoclave jacket, raising the temperature of the autoclave to 110 ℃, then continuously pumping fluoroethylene into the autoclave by using a membrane type compression pump, controlling the pressure of the autoclave system to be 0.6MPa and the feeding speed of the fluoroethylene to be 287.5 g/h, finishing feeding after 4 h, keeping the temperature at 110 ℃ for 1 h, cooling and discharging. The crude material was directly rectified in a rectifying column to obtain 3892.70 g of trifluorodichloropropane with a purity of 99.0% and a yield of 92.31% of trifluorodichloropropane.
In a 10L Hardgrove C alloy stirring autoclave with 2m2The condenser is internally provided with a water alkali cleaning device and a collecting device. 1800 g of tin tetrachloride, 700 g of cobalt dichloride and 35 g of 98% sulfuric acid are introduced into an autoclave, stirring is started and the autoclave is heated to 50 ℃ with steam. 768.50 g of hydrogen fluoride were pressed in to activate the catalyst. The activation time was 2 hours. And (4) after discharging the hydrogen chloride of the system into the water alkali washing device from the top end of the condenser, closing the exhaust valve. 1916 g of hydrogen fluoride is added into the autoclave, the temperature of the autoclave system is raised to 100 ℃, trifluorodichloropropane is pumped into the autoclave by a metering pump, the feeding speed of the trifluorodichloropropane is 1000 g/h, and the feeding time is 4 h. Through the top of the condenserThe pressure in the autoclave is controlled at 1.1Mpa by an exhaust valve, and the temperature is kept for 1 hour after the feeding is finished. After pentafluoropropane (245fa) passes through a water alkali washing system from an exhaust valve at the top end of the condenser, the pentafluoropropane (245fa) is collected into a crude product tank, and the crude product passes through a drying and rectifying device, so that 2815.70 g of pentafluoropropane (245fa) with the purity of 99.6% is obtained, and the yield of the pentafluoropropane (245fa) is 87.38%.
Example 3:
in thatThe stainless steel tubular reactor was filled with 4 liters of a mixture of activated carbon, platinum chloride and palladium chloride, containing 100 g of palladium chloride and 50 g of platinum chloride. Heating to 400 ℃ with N2The catalyst was activated for 10 hours and then cooled to 100 ℃. Acetylene and hydrogen fluoride are mixed and then put into a tubular reactor, wherein the feeding rate of the acetylene is 3900 g/h, and the feeding rate of the hydrogen fluoride is 2000 g/h. The products of acetylene and hydrogen fluoride in the tubular reactor are directly subjected to water alkali washing and then directly subjected to compression rectification to obtain vinyl fluoride with the purity of 99 percent. The yield of vinyl fluoride per hour was 4305 g, and the yield of vinyl fluoride was 93.58%.
Adding 2000 g of dimethylbenzene and 100 g of cyclohexanone into a 10L stainless steel magnetic stirring autoclave, adding 50 g of aluminum trichloride and 20 g of ferric trichloride into the autoclave, starting stirring, introducing 30 g of boron trifluoride gas into the autoclave, fully stirring for 30 minutes, then pressing 3135 g of trifluoro monochloromethane into the autoclave, opening an autoclave jacket steam inlet valve, raising the temperature of the autoclave to 120 ℃, then continuously pumping vinyl fluoride into the autoclave by using a membrane type compression pump, controlling the pressure of the autoclave system to be 0.7MPa, controlling the feeding speed of the vinyl fluoride to be 418.18 g/h, finishing feeding after 3 h, keeping the temperature at 120 ℃ for 1 h, cooling and discharging. The crude material was directly rectified in a rectifying column to obtain 3795.20 g of tetrafluoro-monochloropropane with a purity of 99.5% and a yield of 92.00% of tetrafluoro-monochloropropane.
In a 10L Hardgrove C alloy stirring autoclave with 2m2In the condenser, a water alkali washing device is arrangedAnd a collecting device. 1600 g of tin tetrachloride, 600 g of cobalt dichloride and 78 g of 98% sulfuric acid are introduced into an autoclave, stirring is started and the autoclave is heated to 50 ℃ with steam. 676.26 g of hydrogen fluoride were pressed in to activate the catalyst. The activation time was 2 hours. And (4) after discharging the hydrogen chloride of the system into the water alkali washing device from the top end of the condenser, closing the exhaust valve. 1515 g of hydrogen fluoride is added into the autoclave, the temperature of the autoclave system is raised to 130 ℃, tetrafluoro-monochloropropane is pumped into the autoclave by a metering pump, the feeding speed of the tetrafluoro-monochloropropane is 950 g/h, and the feeding time is 4 h. Controlling the pressure in the autoclave at 1.2Mpa through an exhaust valve at the top end of the condenser, and preserving the temperature for 1 hour after the feeding is finished. After pentafluoropropane (245fa) passes through a water alkali washing system from an exhaust valve at the top end of the condenser, the pentafluoropropane (245fa) is collected into a crude product tank, and the crude product passes through a drying and rectifying device, so that 2957.8 g of pentafluoropropane (245fa) with the purity of 99.5% is obtained, and the yield of pentafluoropropane is 86.98%.
Example 4:
in that
The stainless steel tubular reactor was filled with 4 liters of a mixture of activated carbon, platinum chloride and palladium chloride, containing 100 g of palladium chloride and 50 g of platinum chloride. Heating to 400 ℃ with N2The catalyst was activated for 10 hours and then cooled to 100 ℃. Acetylene and hydrogen fluoride are mixed and then put into a tubular reactor, wherein the feeding rate of the acetylene is 3900 g/h, and the feeding rate of the hydrogen fluoride is 2000 g/h. The products of acetylene and hydrogen fluoride in the tubular reactor are directly subjected to water alkali washing and then directly subjected to compression rectification to obtain vinyl fluoride with the purity of 99 percent. The yield of vinyl fluoride per hour was 4305 g, and the yield of vinyl fluoride was 93.58%.
Adding 2000 g of dimethylbenzene and 100 g of cyclohexanone into a 10L stainless steel magnetic stirring autoclave, adding 50 g of aluminum trichloride and 20 g of ferric trichloride into the autoclave, starting stirring, introducing 30 g of boron trifluoride gas into the autoclave, fully stirring for 30 minutes, then pressing 2640 g of tetrafluoromethane into the autoclave, opening a jacket of the autoclave to feed a steam valve, raising the temperature of the autoclave to 120 ℃, then continuously pumping vinyl fluoride into the autoclave by using a membrane type compression pump, controlling the pressure of the autoclave system to be 0.8MPa, controlling the feeding speed of the vinyl fluoride to be 306.67 g/h, finishing feeding after 3 h, keeping the temperature at 120 ℃ for 1 h, cooling and discharging. The crude material was directly rectified in a rectifying column to obtain 2236.50 g of pentafluoropropane (245fa) with a purity of 99.0% and a yield of pentafluoropropane (245fa) of 82.62%.
Example 5:
in that
The stainless steel tubular reactor was filled with 4 liters of a mixture of activated carbon, platinum chloride and palladium chloride, containing 100 g of palladium chloride and 50 g of platinum chloride. Heating to 400 ℃ with N2The catalyst was activated for 10 hours and then cooled to 170 ℃. Acetylene and hydrogen chloride are mixed and then put into a tubular reactor, wherein the feeding rate of the acetylene is 3900 g/h, and the feeding rate of the hydrogen chloride is 3650 g/h. The products of acetylene and hydrogen chloride in the tubular reactor are directly subjected to water alkali washing and then directly compressed and rectified to obtain vinyl chloride with the purity of 99.3 percent. The yield of vinyl chloride per hour was 5602 g, and the yield of vinyl chloride was 89.63%.
Adding 2500 g of n-butyl alcohol and 300 g of triethyl phosphate into a 10L stainless steel magnetic stirring autoclave, adding 50 g of ferric trichloride, 20 g of platinum chloride and 30 g of tin dichloride into the autoclave, starting stirring, then pressing 5000 g of trichlorofluoromethane into the autoclave, opening a jacket of the autoclave to feed a steam valve, raising the temperature of the autoclave to 120 ℃, then continuously pumping chloroethylene into the autoclave by using a membrane type compression pump, controlling the pressure of the autoclave system to be 1.2MPa and the feeding speed of the chloroethylene to be 473.48 g/h, finishing feeding after 4 h, preserving the temperature at 120 ℃ for 1 h, cooling and discharging. The crude material was directly rectified in a rectifying column to obtain 5303.20 g of monofluoro tetrachloropropane with a purity of 99.3% and a yield of 86.89%.
In a 10L Hardgrove C alloy stirring autoclave with 2m2In the condenserThe device is provided with a water alkali washing device and a collecting device. 2500 g of tin tetrachloride, 900 g of cobalt dichloride and 29 g of 98% sulfuric acid are introduced into the autoclave, stirring is started and the autoclave is heated to 50 ℃ with steam. 1050 grams of hydrogen fluoride activated catalyst was pressed in. The activation time was 2 hours. And (4) after discharging the hydrogen chloride of the system into the water alkali washing device from the top end of the condenser, closing the exhaust valve. 3000 g of hydrogen fluoride is added into a reactor, the temperature of the autoclave system is raised to 130 ℃, a metering pump is adopted to pump the monofluo-tetrachloropropane into the autoclave, the feeding speed of the monofluo-tetrachloropropane is 1250 g/h, and the feeding time is 4 h. Controlling the pressure in the autoclave at 1.2Mpa through an exhaust valve at the top end of the condenser, and preserving the temperature for 1 hour after the feeding is finished. After pentafluoropropane (245fa) passes through a water alkali washing system from an exhaust valve at the top end of the condenser, the pentafluoropropane (245fa) is collected into a crude product tank, and the crude product passes through a drying and rectifying device, so that 2875.8 g of pentafluoropropane (245fa) with the purity of 99.1% is obtained, and the yield of pentafluoropropane is 85.07%.
Example 6:
in that
The stainless steel tubular reactor was filled with 4 liters of a mixture of activated carbon, platinum chloride and palladium chloride, containing 100 g of palladium chloride and 50 g of platinum chloride. Heating to 400 ℃ with N2The catalyst was activated for 10 hours and then cooled to 170 ℃. Acetylene and hydrogen chloride are mixed and then put into a tubular reactor, wherein the feeding rate of the acetylene is 3900 g/h, and the feeding rate of the hydrogen chloride is 3650 g/h. The products of acetylene and hydrogen chloride in the tubular reactor are directly subjected to water alkali washing and then directly compressed and rectified to obtain vinyl chloride with the purity of 99.3 percent. The yield of vinyl chloride per hour was 5602 g, and the yield of vinyl chloride was 89.63%.
Adding 2500 g of n-butanol and 300 g of triethyl phosphate into a 10L stainless steel magnetic stirring autoclave, adding 50 g of ferric trichloride, 20 g of platinum chloride and 30 g of tin dichloride into the autoclave, starting stirring, then pressing 4840 g of difluorodichloromethane into the autoclave, opening a jacket of the autoclave to feed a steam valve, raising the temperature of the autoclave to 130 ℃, then continuously pumping vinyl chloride into the autoclave by using a membrane type compression pump, controlling the pressure of the autoclave system to be 1.3MPa and the feeding speed of the vinyl chloride to be 520.83 g/h, finishing feeding after 4 h, preserving the temperature at 130 ℃ for 1 h, cooling and discharging. The crude material is directly rectified in a rectifying tower to obtain 5611.30 g of difluorotrichloropropane with the purity of 99.3 percent, and the yield of the difluorotrichloropropane is 91.10 percent.
In a 10L Hardgrove C alloy stirring autoclave with 2m2The condenser is internally provided with a water alkali cleaning device and a collecting device. 2000 g of tin tetrachloride, 700 g of cobalt dichloride and 69 g of 98% sulfuric acid are introduced into the autoclave, stirring is started and the autoclave is heated to 50 ℃ with steam. 830 grams of hydrogen fluoride activating catalyst were pressed in. The activation time was 2 hours. And (4) after discharging the hydrogen chloride of the system into the water alkali washing device from the top end of the condenser, closing the exhaust valve. 1962 g of hydrogen fluoride is added into the autoclave, the temperature of the autoclave system is raised to 120 ℃, difluorotrichloropropane is pumped into the autoclave by a metering pump, the feeding speed of the difluorotrichloropropane is 1125 g/h, and the feeding time is 4 h. Controlling the pressure in the autoclave at 1.1Mpa through an exhaust valve at the top end of the condenser, and preserving the temperature for 1 hour after the feeding is finished. Pentafluoropropane (245fa) was passed through a water caustic washing system from an exhaust valve at the top of the condenser, and then collected in a crude product tank, and the crude product was passed through a drying and rectifying apparatus to obtain 2901.70 g of pentafluoropropane (245fa) having a purity of 99.3%, and the yield of pentafluoropropane was 87.68%.
Example 7:
in that
The stainless steel tubular reactor was filled with 4 liters of a mixture of activated carbon, platinum chloride and palladium chloride, containing 100 g of palladium chloride and 50 g of platinum chloride. Heating to 400 ℃ with N2The catalyst was activated for 10 hours and then cooled to 170 ℃. Acetylene and hydrogen chloride are mixed and then put into a tubular reactor, wherein the feeding rate of the acetylene is 3900 g/h, and the feeding rate of the hydrogen chloride is 3650 g/h. Acetylene and hydrogen chloride in a tubular reactorThe product is directly subjected to alkali washing by water and then directly compressed and rectified to obtain the chloroethylene with the purity of 99.3 percent. The yield of vinyl chloride per hour was 5602 g, and the yield of vinyl chloride was 89.63%.
Adding 2500 g of n-butanol and 300 g of triethyl phosphate into a 10L stainless steel magnetic stirring autoclave, adding 50 g of ferric trichloride, 20 g of platinum chloride and 30 g of tin dichloride into the autoclave, starting stirring, then pressing 4500 g of trifluoro-monochloromethane into the autoclave, opening an autoclave jacket and a steam inlet valve, raising the temperature of the autoclave to 140 ℃, then continuously pumping vinyl chloride into the autoclave by using a membrane type compression pump, controlling the pressure of the autoclave system to be 1.5MPa, controlling the feeding speed of the vinyl chloride to be 560.71 g/h, finishing feeding after 4 h, preserving the temperature at 140 ℃ for 1 h, cooling and discharging. The crude material was directly rectified in a rectifying column to obtain 5476.48 g of trifluorodichloropropane with a purity of 99.5% and a yield of 90.94% of trifluorodichloropropane.
In a 10L Hardgrove C alloy stirring autoclave with 2m2The condenser is internally provided with a water alkali cleaning device and a collecting device. 2100 g of tin tetrachloride, 800 g of cobalt dichloride and 18 g of 98% sulfuric acid are introduced into an autoclave, stirring is started and the autoclave is heated to 50 ℃ with steam. 895 g of hydrogen fluoride-activated catalyst were pressed in. The activation time was 2 hours. And (4) after discharging the hydrogen chloride of the system into the water alkali washing device from the top end of the condenser, closing the exhaust valve. 1800 g of hydrogen fluoride is added into a reactor, the temperature of the autoclave system is raised to 130 ℃, trifluorodichloropropane is pumped into the autoclave by a metering pump, the feeding speed of the trifluorodichloropropane is 1002 g/h, and the feeding time is 5 h. Controlling the pressure in the autoclave at 1.2Mpa through an exhaust valve at the top end of the condenser, and preserving the temperature for 1 hour after the feeding is finished. After pentafluoropropane (245fa) passes through a water alkali washing system from an exhaust valve at the top end of the condenser, the pentafluoropropane (245fa) is collected into a crude product tank, and the crude product passes through a drying and rectifying device, so that 3557.18 g of pentafluoropropane (245fa) with the purity of 99.3% is obtained, and the yield of pentafluoropropane is 87.87%.
Example 8:
in that
The stainless steel tubular reactor was filled with 4 liters of a mixture of activated carbon, platinum chloride and palladium chloride, containing 100 g of palladium chloride and 50 g of platinum chloride. Heating to 400 ℃ with N2The catalyst was activated for 10 hours and then cooled to 170 ℃. Acetylene and hydrogen chloride are mixed and then put into a tubular reactor, wherein the feeding rate of the acetylene is 3900 g/h, and the feeding rate of the hydrogen chloride is 3650 g/h. The products of acetylene and hydrogen chloride in the tubular reactor are directly subjected to water alkali washing and then directly compressed and rectified to obtain vinyl chloride with the purity of 99.3 percent. The yield of vinyl chloride per hour was 5602 g, and the yield of vinyl chloride was 89.63%.
Adding 2500 g of n-butanol and 300 g of triethyl phosphate into a 10L stainless steel magnetic stirring autoclave, adding 50 g of ferric trichloride, 20 g of platinum chloride and 30 g of tin dichloride into the autoclave, starting stirring, then pressing 3520 g of tetrafluoromethane into the autoclave, opening a jacket of the autoclave to enter a steam valve, raising the temperature of the autoclave to 140 ℃, then continuously pumping vinyl chloride into the autoclave by using a membrane type compression pump, controlling the pressure of the autoclave system to be 1.5MPa and the feeding speed of the vinyl chloride to be 480.77 g/h, finishing feeding after 4 h, preserving heat at 140 ℃ for 1 h, cooling and discharging. The crude material was directly rectified in a rectifying column to obtain 4047.12 g of tetrafluoro-monochloropropane with a purity of 99.6% and a yield of 87.05% of tetrafluoro-monochloropropane.
In a 10L Hardgrove C alloy stirring autoclave with 2m2The condenser is internally provided with a water alkali cleaning device and a collecting device. 1800 g of tin tetrachloride, 600 g of cobalt dichloride and 49 g of 98% sulfuric acid are introduced into an autoclave, stirring is started and the autoclave is heated to 50 ℃ with steam. 740 grams of hydrogen fluoride activating catalyst was pressed in. The activation time was 2 hours. And (4) after discharging the hydrogen chloride of the system into the water alkali washing device from the top end of the condenser, closing the exhaust valve. 1200 g of hydrogen fluoride is added into a reactor, the temperature of the autoclave system is raised to 130 ℃, tetrafluoro-monochloropropane is pumped into the autoclave by a metering pump, the feeding speed of the tetrafluoro-monochloropropane is 903 g/h, and the feeding time is 5 h. By coolingThe exhaust valve at the top end of the condenser controls the pressure in the autoclave to be 1.2Mpa, and after the feeding is finished, the temperature is kept for 1 hour. After pentafluoropropane (245fa) passes through a water alkali washing system from an exhaust valve at the top end of the condenser, the pentafluoropropane (245fa) is collected into a crude product tank, and the crude product passes through a drying and rectifying device, so that 3605.39 g of pentafluoropropane (245fa) with the purity of 99.7% is obtained, and the yield of pentafluoropropane is 89.42%.
Claims (8)
1. A method for producing pentafluoropropane, comprising the steps of:
(1) acetylene and hydrogen chloride or hydrogen fluoride are subjected to addition reaction to prepare chloroethylene or vinyl fluoride according to the molar ratio of 1.5-2.5: 1 under the action of a first catalyst;
(2) a, adding the fluoroethylene obtained in the step (1) and monofluorotrichloromethane into a first solvent according to the molar ratio of 1: 1.1-1.5, and carrying out addition reaction under the action of a second catalyst to prepare difluorotrichloropropane;
or adding the vinyl fluoride obtained in the step (1) and difluorodichloromethane into a first solvent according to the molar ratio of 1: 1.1-1.5, and carrying out addition reaction under the action of a second catalyst to prepare trifluorodichloropropane;
or adding the fluoroethylene obtained in the step (1) and the trifluoro-monochloromethane into a first solvent according to the molar ratio of 1: 1.1-1.5, and carrying out addition reaction under the action of a second catalyst to prepare tetrafluoro-monochloropropane;
or adding the fluoroethylene obtained in the step (1) and the tetrafluoromethane into a first solvent according to the molar ratio of 1: 1.1-1.5, and carrying out addition reaction under the action of a second catalyst to prepare the pentafluoropropane.
B. Adding the chloroethylene obtained in the step (1) and trichlorofluoromethane into a second solvent according to the molar ratio of 1: 1.1-1.5, and carrying out addition reaction under the action of a third catalyst to prepare tetrachlorofluoropropane;
or adding the chloroethylene and the difluorodichloromethane obtained in the step (1) into a second solvent according to the molar ratio of 1: 1.1-1.5, and carrying out addition reaction under the action of a third catalyst to prepare difluorotrichloropropane;
or adding the chloroethylene obtained in the step (1) and chlorotrifluoromethane into a second solvent according to the molar ratio of 1: 1.1-1.5, and carrying out addition reaction under the action of a third catalyst to prepare the trifluorodichloropropane;
or adding the chloroethylene and the tetrafluoromethane obtained in the step (1) into a second solvent according to the molar ratio of 1: 1.1-1.5, and carrying out addition reaction under the action of a third catalyst to prepare tetrafluoro-monochloropropane.
(3) Reacting the monofluo-tetrachloropropane obtained in the step (2) with hydrogen fluoride according to the molar ratio of 1: 5-7 under the action of a fourth catalyst to generate pentafluoropropane;
or reacting the difluorotrichloropropane obtained in the step (2) with hydrogen fluoride according to a molar ratio of 1: 4-6 under the action of a fourth catalyst to generate pentafluoropropane;
or reacting the trifluorodichloropropane obtained in the step (2) with hydrogen fluoride according to the molar ratio of 1: 3-5 under the action of a fourth catalyst to generate pentafluoropropane;
or reacting the tetrafluorochloropropane obtained in the step (2) with hydrogen fluoride according to the molar ratio of 1: 2-3 under the action of a fourth catalyst to generate the pentafluoropropane.
2. The process for producing pentafluoropropane as claimed in claim 1, wherein said second catalyst in step (2) a is a mixture of boron trifluoride, aluminum trichloride and iron trichloride.
3. The process for producing pentafluoropropane as claimed in claim 1, wherein the first solvent in the step (2) a is a mixture of ketones and aromatic hydrocarbons.
4. The process for producing pentafluoropropane as claimed in claim 1, wherein in the step (2) a, the catalytic reaction temperature is 100 to 120 ℃, the reaction pressure is 0.5 to 0.8MPa, and the reaction time is 3 to 5 hours.
5. The process for producing pentafluoropropane as claimed in claim 1, wherein said third catalyst in step (2) B is a mixture of tin dichloride, platinum chloride and iron trichloride.
6. The process for producing pentafluoropropane as claimed in claim 1, wherein the second solvent in the step (2) B is a mixture of a straight-chain alcohol and a phosphate.
7. The process for producing pentafluoropropane as claimed in claim 1, wherein in the step (2) B, the catalytic reaction temperature is 120 to 140 ℃, the reaction pressure is 1.2 to 1.5MPa, and the reaction time is 2 to 3 hours.
8. The process for producing pentafluoropropane as claimed in claim 1, wherein said fourth catalyst in step (3) is a composite catalyst of tin tetrachloride, cobalt chloride and sulfuric acid, the fluorination reaction temperature is 110 to 130 ℃, the reaction pressure is 1.0 to 1.2MPa, and the reaction time is 5 to 6 hours.
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| CN1152904A (en) * | 1994-07-11 | 1997-06-25 | 联合讯号公司 | Process for preparing 1,1,1,3,3,-pentafluoropropane |
| CN101250086A (en) * | 2008-03-25 | 2008-08-27 | 常熟三爱富氟化工有限责任公司 | Method for preparing monofluo-rodicloroethane |
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| CN1152904A (en) * | 1994-07-11 | 1997-06-25 | 联合讯号公司 | Process for preparing 1,1,1,3,3,-pentafluoropropane |
| CN101250086A (en) * | 2008-03-25 | 2008-08-27 | 常熟三爱富氟化工有限责任公司 | Method for preparing monofluo-rodicloroethane |
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| Title |
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| 蒋琦.1，1，1，3，3－五氟丙烷的研究与应用.化工生产与技术9 6.2002,9(6),4-6. |
| 蒋琦.1,1,1,3,3-五氟丙烷的研究与应用.化工生产与技术9 6.2002,9(6),4-6. * |
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| C06 | Publication | ||
| PB01 | Publication | ||
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