US20120203036A9 - Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene - Google Patents
Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene Download PDFInfo
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- US20120203036A9 US20120203036A9 US12/265,335 US26533508A US2012203036A9 US 20120203036 A9 US20120203036 A9 US 20120203036A9 US 26533508 A US26533508 A US 26533508A US 2012203036 A9 US2012203036 A9 US 2012203036A9
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- 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 25
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title description 5
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012467 final product Substances 0.000 claims abstract description 8
- -1 titanium halides Chemical class 0.000 claims abstract description 8
- 239000007858 starting material Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 8
- 239000000047 product Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CAQPTDOAJUMIAI-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)C(F)(F)F CAQPTDOAJUMIAI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- 229910000792 Monel Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910010342 TiF4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
Definitions
- This invention relates to methods of synthesizing hydrofluoroolefins. More particularly, the invention relates to catalytic synthesis of 2,3,3,3-tetrafluoro-1-propene.
- hydrofluoroolefin 2,3,3,3-tetrafluoro-1-propene which can be used as a low global warming potential (GWP) refrigerant, blowing agent, etc.
- GWP global warming potential
- U.S. Pat. No. 2,931,840 describes concurrently passing 55 cc/min of MeCl and 110 cc/min CHClF 2 through a platinum tube (6 mm ⁇ 24 in) that is heated to about 800° C.
- the gaseous product synthesized by this process is scrubbed to remove HCl and dried, but yields only a small amount (14.8 mole %) of 2,3,3,3-tetrafluoropropene. This low yield correlates to almost 90% of the starting material being lost to unimportant byproducts including a significant amount of carbon black, which tends to deactivate the reaction's catalyst.
- JP 06072925 describes the synthesis of 2,3,3,3-tetrafluoro-1-propanol by reacting tetrafluoroethylene, formaldehyde, and HF in the presence of a TiF 4 catalyst and limonene as a polymer inhibitor.
- the 2,3,3,3-tetrafluoro-1-propanol in turn, can serve as a starting material to synthesize 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf).
- the process of JP 06072925 involves feeding a 1:3 (mol/mol) gaseous mixture of HOCH 2 (CF 2 ) 4 H and H 2 into a tube reactor packed with activated carbon and heated to 500° C.
- a residence time of 4 seconds yields CH 2 ⁇ CF(CF 2 ) 3 H at a monomer conversion of 64% and a selectivity of 82%. Although this is a high-yield process, commercial handling of H 2 at high temperature is exceptionally hazardous. In addition, the process of JP 06072925 requires a costly on-site generation of H 2 .
- Applicants have found a commercially viable process for manufacturing HFC-1234yf from HFO-1233xd that results in a conversion of over 90% and a selectivity of up to about 80%. More particularly, Applicants have found a two-step continuous gas-phase process for the production of HFO-1234yf wherein (1) relatively inexpensive HFO-1233xd is reacted with HF in the presence of a first catalyst to form an intermediate composition comprising, for example, CF 3 CFClCH 3 and/or CF 3 CF 2 CH 3 , and (2) in the presence of a second catalyst, transforming the intermediate composition into a product comprising the desired HFO-1234yf.
- an aspect of the invention involves a process for preparing 2,3,3,3-tetrafluoro-1-propene comprising: (a) contacting a starting material comprising 2-chloro-3,3,3-trifluoro-1-propene with hydrogen fluoride in the presence of a first activated catalyst selected from the group consisting of antimony-halides, iron-halides, titanium halides, and tin-halides, to produce an intermediate composition; and (b) contacting at least a portion of the intermediate composition with a second activated catalyst comprising carbon to produce a final product comprising 2,3,3,3-tetrafluoro-1-propene.
- a first activated catalyst selected from the group consisting of antimony-halides, iron-halides, titanium halides, and tin-halides
- FIG. 1 shows a schematic diagram of a preferred 2,3,3,3-tetrafluoro-1-propene synthesis process according to the invention.
- a multi-step process for preparing 2,3,3,3-tetrafluoro-1-propene comprising two catalytic reactions.
- the two catalytic reactions of the process are conducted separate reactors that are arranged in series.
- the shown preferred process for 2,3,3,3-tetrafluoro-1-propene synthesis 1 involves one or more feed stream(s) 10 of HFC-1233xd and HF that are introduced into a first reactor 12 , having a first catalyst bed 14 , to produce an intermediate composition steam 20 comprising, for example, CF 3 CFClCH 3 and/or CF 3 CF 2 CH 3 .
- This intermediate composition stream 20 exits from the first reactor 12 and is then passed through column 26 which is packed with an HF scavenger 26 , such as NaF, KF, or Al 2 O 3 , to remove a majority of, and preferably substantially all, the unreacted HF exiting the first reactor 12 .
- the resulting cleaned intermediate composition stream 21 is then fed into a second reactor 22 having a second catalyst bed 24 to produce a final product stream 30 comprising HFO-1234yf.
- the final product steam 30 recovered from the second reactor 22 may optionally be passed through a scrubber 38 containing, for example, a KOH solution 36 , to scrub HF and/or HCl from the steam, thereby yielding a cleaned final product stream 31 .
- Preferred catalysts for the first reaction include, but are not limited to, antimony halides, iron halides, titanium halides, and tin halides. More preferred catalysts are SbCl 5 , FeCl 3 , TiCl 4 , and SnCl 4 .
- Preferred antimony halides include antimony pentahalides, particularly those having the formula: SbX 5 , wherein X is independently selected from Cl and F, with SbCl 5 being most preferred.
- the first catalyst is supported by a substrate, such as carbon. Also, preferably the catalyst is arranged as bed that is disposed within the first reactor.
- the first catalyst is pretreated (i.e., activated) with Cl 2 and/or HF, and more preferably with both Cl 2 and HF, prior to use in the synthesis reaction.
- an SbCl 5 catalyst supported on a carbon substrate can be activated by exposing the catalyst to 50 g/h of HF at 65° C. for 4 hours, then with the combination of about 50 g/h of HF and about 200 sccm of Cl 2 at about 65° C. for about 4 hours.
- free chloride is preferably removed from the catalyst surface.
- free chloride is preferably removed from the catalyst surface.
- about 50 sccm of N 2 can be passed over the catalyst bed for about 40 minutes to remove substantially all of the free chloride.
- the intermediate composition stream After the intermediate composition stream exits the first reactor, it preferably is processed to remove residual and/or unreacted HF from the stream.
- the intermediate composition stream can be passed through a column packed with NaF, KF, or Al 2 O 3 .
- the temperature of the packed column is preferably maintained at about 50-75° C. for high HF absorption efficiency.
- Preferred catalysts for the second reaction are activated carbons.
- Acceptable activated carbons include those produced by Takeda Chemical Industries (marketed under the trade name SHIRO SAGI), Calgon Carbon Corp. (marketed under the trade name CARBOSORBTM), Norit Americas Inc., and Aldrich (marketed under the trade name DARCO®).
- the second catalysts is preferably arranged as a bed that is disposed within the second reactor.
- the flow of material through the reactors is controlled by regulating the flow of the exit gases from the second reactor via a control valve, thus establishing a pressure drop though the system. That is, the flow of materials through the system is controlled by limiting the amount of material exiting the last second reactor and, thus, controlled pressure drops between subsequent components in the system is achieved.
- the pressure in the first reactor is maintained at between about 40 and about 100 psig, more preferably from about 40 to 50 psig
- the pressure in the second reactor is maintained at between about 0 and about 100 psig, more preferably from about 5 to 10 psig, provided that the pressure in the second reactor is lower than the pressure in the first reactor.
- the temperature of the first reaction is maintained at about 140 to 200° C., more preferably from about 150 to 185° C.
- the temperature of the second reactor is preferably maintained at about 400 to 600° C., more preferably from about 450 to 550° C.
- the reactor was mounted inside a heater to maintain the reactor temperature.
- the temperature of the reaction was monitored by a thermocouple disposed at the middle inside of the reactor.
- the inlet of the reactor was connected to an electrical pre-heater, which maintained the inlet at 300° C.
- the pressure inside the reactor was maintained at about 45 psig.
- a stream of HFO-1233xf at 70° C. and 150 sccm was fed from a cylinder through a regulator, needle valve, and a gas mass-flow-meter, and into the first reactor. This feed stream kept at a constant temperature of 73° C. by electrical heating to avoid condensation.
- a stream of liquid HF was fed from a cylinder pressurized with N 2 at a constant pressure of 45 psig.
- the liquid HF flowed through a dip tube, needle valve, liquid mass flow meter, a research control valve, and a gate valve and then into the reactor at a rate of 50 g/h.
- the product mixtures coming out of the first reactor were passed through a packed column containing NaF to separate HF from the stream.
- the packed column was kept at 50-75° C. for high HF adsorption efficiency.
- the HF-free gas stream thus obtained, was then passed into a second 22-inch (1 ⁇ 2-inch diameter) Monel tube reactor containing 120 cc of Calgon Activated Carbon.
- the interior temperature of the reactor was maintained at different temperatures from 400 to 550° C. (see Table A).
- the pressure of the second reactor was maintained at about 6 psig.
- the exit gases from the second reactor were then passed through a 20-60-wt % aq. KOH scrubber solution to trap HF or HCl.
- the exit gases from the scrubber were condensed into a cylinder that was chilled with dry ice.
- the products were then isolated by distillation.
- the process described herein can be used to produce HFO-1234yf from HFO-1233xf at a conversion of over 90% and a selectivity of about 80%.
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Abstract
Description
- 1. Field of Invention
- This invention relates to methods of synthesizing hydrofluoroolefins. More particularly, the invention relates to catalytic synthesis of 2,3,3,3-tetrafluoro-1-propene.
- 2. Description of Related Art
- The hydrofluoroolefin 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), which can be used as a low global warming potential (GWP) refrigerant, blowing agent, etc., has been synthesized by the catalytic pyrolysis of methyl chloride and either tetrafluoroethylene or chlorodifluoromethane. For example, U.S. Pat. No. 2,931,840 describes concurrently passing 55 cc/min of MeCl and 110 cc/min CHClF2 through a platinum tube (6 mm×24 in) that is heated to about 800° C. The gaseous product synthesized by this process is scrubbed to remove HCl and dried, but yields only a small amount (14.8 mole %) of 2,3,3,3-tetrafluoropropene. This low yield correlates to almost 90% of the starting material being lost to unimportant byproducts including a significant amount of carbon black, which tends to deactivate the reaction's catalyst.
- EP 328148 discloses that fluorine-containing olefins having the formula CH2═CFRf[Rf=(per) halo alkyl group)] can be prepared at low cost and with low toxic waste generation by high-temperature dehydrohalogenation and dehydration of fluoroalcohols such as HOCH2CF2Rf in the presence of H2 gas.
- JP 06072925 describes the synthesis of 2,3,3,3-tetrafluoro-1-propanol by reacting tetrafluoroethylene, formaldehyde, and HF in the presence of a TiF4 catalyst and limonene as a polymer inhibitor. The 2,3,3,3-tetrafluoro-1-propanol, in turn, can serve as a starting material to synthesize 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf). The process of JP 06072925 involves feeding a 1:3 (mol/mol) gaseous mixture of HOCH2(CF2)4H and H2 into a tube reactor packed with activated carbon and heated to 500° C. A residence time of 4 seconds yields CH2═CF(CF2)3H at a monomer conversion of 64% and a selectivity of 82%. Although this is a high-yield process, commercial handling of H2 at high temperature is exceptionally hazardous. In addition, the process of JP 06072925 requires a costly on-site generation of H2.
- Therefore, there is a need for alternative commercial processes for producing HFO-1234yf that involving more economical and less hazardous starting materials which also result in higher conversion rates and selectivity.
- Applicants have found a commercially viable process for manufacturing HFC-1234yf from HFO-1233xd that results in a conversion of over 90% and a selectivity of up to about 80%. More particularly, Applicants have found a two-step continuous gas-phase process for the production of HFO-1234yf wherein (1) relatively inexpensive HFO-1233xd is reacted with HF in the presence of a first catalyst to form an intermediate composition comprising, for example, CF3CFClCH3 and/or CF3CF2CH3, and (2) in the presence of a second catalyst, transforming the intermediate composition into a product comprising the desired HFO-1234yf.
- Accordingly, an aspect of the invention involves a process for preparing 2,3,3,3-tetrafluoro-1-propene comprising: (a) contacting a starting material comprising 2-chloro-3,3,3-trifluoro-1-propene with hydrogen fluoride in the presence of a first activated catalyst selected from the group consisting of antimony-halides, iron-halides, titanium halides, and tin-halides, to produce an intermediate composition; and (b) contacting at least a portion of the intermediate composition with a second activated catalyst comprising carbon to produce a final product comprising 2,3,3,3-tetrafluoro-1-propene.
-
FIG. 1 shows a schematic diagram of a preferred 2,3,3,3-tetrafluoro-1-propene synthesis process according to the invention. - Provided is a multi-step process for preparing 2,3,3,3-tetrafluoro-1-propene comprising two catalytic reactions. Preferably, the two catalytic reactions of the process are conducted separate reactors that are arranged in series. Referring to
FIG. 1 , the shown preferred process for 2,3,3,3-tetrafluoro-1-propene synthesis 1 involves one or more feed stream(s) 10 of HFC-1233xd and HF that are introduced into afirst reactor 12, having afirst catalyst bed 14, to produce anintermediate composition steam 20 comprising, for example, CF3CFClCH3 and/or CF3CF2CH3. This intermediate composition stream 20 exits from thefirst reactor 12 and is then passed throughcolumn 26 which is packed with anHF scavenger 26, such as NaF, KF, or Al2O3, to remove a majority of, and preferably substantially all, the unreacted HF exiting thefirst reactor 12. The resulting cleanedintermediate composition stream 21 is then fed into asecond reactor 22 having asecond catalyst bed 24 to produce afinal product stream 30 comprising HFO-1234yf. Thefinal product steam 30 recovered from thesecond reactor 22 may optionally be passed through ascrubber 38 containing, for example, aKOH solution 36, to scrub HF and/or HCl from the steam, thereby yielding a cleanedfinal product stream 31. - Preferred catalysts for the first reaction include, but are not limited to, antimony halides, iron halides, titanium halides, and tin halides. More preferred catalysts are SbCl5, FeCl3, TiCl4, and SnCl4. Preferred antimony halides include antimony pentahalides, particularly those having the formula: SbX5, wherein X is independently selected from Cl and F, with SbCl5 being most preferred. Preferably, the first catalyst is supported by a substrate, such as carbon. Also, preferably the catalyst is arranged as bed that is disposed within the first reactor.
- In highly preferred embodiments, the first catalyst is pretreated (i.e., activated) with Cl2 and/or HF, and more preferably with both Cl2 and HF, prior to use in the synthesis reaction. For example, an SbCl5 catalyst supported on a carbon substrate can be activated by exposing the catalyst to 50 g/h of HF at 65° C. for 4 hours, then with the combination of about 50 g/h of HF and about 200 sccm of Cl2 at about 65° C. for about 4 hours.
- After pretreatment, free chloride is preferably removed from the catalyst surface. For example, after pretreatment about 50 sccm of N2 can be passed over the catalyst bed for about 40 minutes to remove substantially all of the free chloride.
- After the intermediate composition stream exits the first reactor, it preferably is processed to remove residual and/or unreacted HF from the stream. For example the intermediate composition stream can be passed through a column packed with NaF, KF, or Al2O3. The temperature of the packed column is preferably maintained at about 50-75° C. for high HF absorption efficiency.
- Preferred catalysts for the second reaction are activated carbons. Acceptable activated carbons include those produced by Takeda Chemical Industries (marketed under the trade name SHIRO SAGI), Calgon Carbon Corp. (marketed under the trade name CARBOSORB™), Norit Americas Inc., and Aldrich (marketed under the trade name DARCO®). The second catalysts is preferably arranged as a bed that is disposed within the second reactor.
- In one embodiment, the flow of material through the reactors is controlled by regulating the flow of the exit gases from the second reactor via a control valve, thus establishing a pressure drop though the system. That is, the flow of materials through the system is controlled by limiting the amount of material exiting the last second reactor and, thus, controlled pressure drops between subsequent components in the system is achieved. Preferably, the pressure in the first reactor is maintained at between about 40 and about 100 psig, more preferably from about 40 to 50 psig, whereas the pressure in the second reactor is maintained at between about 0 and about 100 psig, more preferably from about 5 to 10 psig, provided that the pressure in the second reactor is lower than the pressure in the first reactor.
- Preferably, the temperature of the first reaction is maintained at about 140 to 200° C., more preferably from about 150 to 185° C. The temperature of the second reactor is preferably maintained at about 400 to 600° C., more preferably from about 450 to 550° C.
- Certain aspects of the present invention are further illustrated, but are not limited by, the following examples.
- A 22-inch (½-inch diameter) Monel tube reactor, serving as the first reactor, was charged with about 120 cc of a 50-wt % SbCl5/C catalyst. The reactor was mounted inside a heater to maintain the reactor temperature. The temperature of the reaction was monitored by a thermocouple disposed at the middle inside of the reactor. The inlet of the reactor was connected to an electrical pre-heater, which maintained the inlet at 300° C. The pressure inside the reactor was maintained at about 45 psig.
- A stream of HFO-1233xf at 70° C. and 150 sccm was fed from a cylinder through a regulator, needle valve, and a gas mass-flow-meter, and into the first reactor. This feed stream kept at a constant temperature of 73° C. by electrical heating to avoid condensation.
- A stream of liquid HF was fed from a cylinder pressurized with N2 at a constant pressure of 45 psig. The liquid HF flowed through a dip tube, needle valve, liquid mass flow meter, a research control valve, and a gate valve and then into the reactor at a rate of 50 g/h.
- All feed cylinders were mounted on scales to monitor their weight by difference.
- Samples of the gas mixtures exiting the first reactor were analyzed by on-line GC and GC/MS to determine their composition. It was found that the intermediate composition contained mainly CF3CF2CH3 and CF3CFClCH3. The conversion of HFO-1233xf was about 50 to about 100% and the combined selectivity for CF3CF2CH3 and CF3CFClCH3 was 90-97% depending on the temperature which was varied from about 148 to 175° C. (see Table A).
- The product mixtures coming out of the first reactor were passed through a packed column containing NaF to separate HF from the stream. The packed column was kept at 50-75° C. for high HF adsorption efficiency.
- The HF-free gas stream, thus obtained, was then passed into a second 22-inch (½-inch diameter) Monel tube reactor containing 120 cc of Calgon Activated Carbon. The interior temperature of the reactor was maintained at different temperatures from 400 to 550° C. (see Table A). The pressure of the second reactor was maintained at about 6 psig.
- The exit gases from the second reactor were then passed through a 20-60-wt % aq. KOH scrubber solution to trap HF or HCl. The exit gases from the scrubber were condensed into a cylinder that was chilled with dry ice. The products were then isolated by distillation.
- The results of the these tests are provided in Table A
-
TABLE A Con- version Selectivity (Reactor 1) (Reactor 2) HFO- HFO- Temp. Temp. 1233xf 1234yf Catalyst (° C.) Catalyst (° C.) (%) (%) 1 50 wt % SbCl5/C 152 Calgon 400 83 55 2 50 wt % SbCl5/C 155 Calgon 450 86 57 3 50 wt % SbCl5/C 153 Calgon 500 89 59 4 50 wt % SbCl5/C 148 Calgon 500 88 60 5 50 wt % SbCl5/C 156 Calgon 550 90 77 6 50 wt % SbCl5/C 175 Calgon 550 93 79 - As seen in the data presented in Table A, the process described herein can be used to produce HFO-1234yf from HFO-1233xf at a conversion of over 90% and a selectivity of about 80%.
- The separation of HF from the gas stream coming out off the first reactor is highly preferred for achieving high selectivity. Only 49% selectivity for HFO-1234yf was obtained when the exiting gas-stream of the first reactor was sent directly into the second reactor compare with 79% selectivity when HF separation was utilized.
- Having thus described a few particular embodiments of the invention, it will be apparent to those skilled in the art, in view of the teachings contained herein, that various alterations, modifications, and improvements not specifically described are available and within the scope of the present invention. Such alterations, modifications, and improvements, as are made obvious by this disclosure, are intended to be part of this description though not expressly stated herein, and are intended to be within the spirit and scope of the invention. Accordingly, the foregoing description is by way of example only, and not limiting. The invention is limited only as defined in the following claims and equivalents thereto.
Claims (19)
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US12/265,335 US8324436B2 (en) | 2006-01-03 | 2008-11-05 | Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene |
ES08168778T ES2381885T3 (en) | 2007-11-09 | 2008-11-10 | Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene |
KR1020080111026A KR20090048378A (en) | 2007-11-09 | 2008-11-10 | Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene |
JP2008287911A JP5462469B2 (en) | 2007-11-09 | 2008-11-10 | Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene |
CN2008101779703A CN101440017B (en) | 2007-11-09 | 2008-11-10 | Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene |
EP20080168778 EP2062866B1 (en) | 2007-11-09 | 2008-11-10 | Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene |
AT08168778T ATE551314T1 (en) | 2007-11-09 | 2008-11-10 | GAS PHASE SYNTHESIS OF 2,3,3,3-TETRAFLUORINE-1-PROPENE FROM 2-CHLORINE-3,3,3-TRIFLUORO-1-PROPENE |
KR1020150145173A KR20150122110A (en) | 2007-11-09 | 2015-10-19 | Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene |
KR1020160175475A KR20170000378A (en) | 2007-11-09 | 2016-12-21 | Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene |
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US11/619,592 US8084653B2 (en) | 2004-04-29 | 2007-01-03 | Method for producing fluorinated organic compounds |
US98659907P | 2007-11-09 | 2007-11-09 | |
US12/265,335 US8324436B2 (en) | 2006-01-03 | 2008-11-05 | Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene |
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US9024092B2 (en) * | 2006-01-03 | 2015-05-05 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
US20230150900A1 (en) * | 2004-04-29 | 2023-05-18 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
US20090182179A1 (en) * | 2008-01-15 | 2009-07-16 | Honeywell International Inc. | Hydrofluorination of 2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropane with catalysts of sbcl3, sbcl5, sbf5, ticl4, sncl4, cr2o3 and fluorinated cr2o3 |
US8952208B2 (en) * | 2006-01-03 | 2015-02-10 | Honeywell International Inc. | Method for prolonging a catalyst's life during hydrofluorination |
US9493384B2 (en) | 2007-07-06 | 2016-11-15 | Honeywell International Inc. | Process for producing 2,3,3,3-tetrafluoropropene |
US9035111B2 (en) * | 2007-08-22 | 2015-05-19 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
LT2634231T (en) | 2008-05-07 | 2022-08-25 | The Chemours Company Fc, Llc | Compositions |
US8916733B2 (en) * | 2008-06-17 | 2014-12-23 | Honeywell International Inc. | Processes for hydrofluorination of 2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropane |
FR2935700B1 (en) * | 2008-09-11 | 2013-05-10 | Arkema France | PROCESS FOR THE PREPARATION OF TRIFLUORO AND TETRAFLUORO COMPOUNDS |
JP5581858B2 (en) | 2009-07-21 | 2014-09-03 | セントラル硝子株式会社 | Process for producing 2-chloro-3,3,3-trifluoropropene |
HUE031899T2 (en) * | 2009-12-23 | 2017-08-28 | Arkema France | Catalytic gas phase fluorination of 1233xf to 1234yf |
US8426656B2 (en) | 2010-04-05 | 2013-04-23 | Honeywell International Inc. | Integrated process to co-produce trans-1-chloro-3,3,3-trifluoropropene and trans-1,3,3,3-tetrafluoropropene |
US8927791B2 (en) * | 2010-04-29 | 2015-01-06 | Honeywell International Inc. | Method for producing tetrafluoropropenes |
US8436218B2 (en) | 2010-05-27 | 2013-05-07 | Honeywell International Inc. | Azeotrope-like composition of hexafluoropropane, hexafluoropropene and hydrogen fluoride |
CN102199071B (en) * | 2011-04-08 | 2013-05-01 | 北京宇极科技发展有限公司 | Method for synthesizing 2,3,3,3-tetrafluoropropene |
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KR20140071456A (en) * | 2011-09-30 | 2014-06-11 | 허니웰 인터내셔날 인코포레이티드 | Process for producing 2,3,3,3-tetrafluoropropene |
IN2014DN06917A (en) | 2012-02-10 | 2015-05-15 | Haiyou Wang | |
JP6043415B2 (en) * | 2015-08-20 | 2016-12-14 | アルケマ フランス | Method for producing 2,3,3,3-tetrafluoropropene |
US9856193B2 (en) | 2015-11-12 | 2018-01-02 | Honeywell International Inc. | Process for the production of fluorinated cyclobutane |
US9790151B2 (en) | 2015-11-12 | 2017-10-17 | Honeywell International Inc. | Process for making 2,3,3,3-tetrafluoropropene and/or vinylidine fluoride |
US10005705B2 (en) | 2015-11-12 | 2018-06-26 | Honeywell International Inc. | Process for the production of fluorinated cyclobutane |
EP3538503B1 (en) | 2016-11-08 | 2021-08-18 | Honeywell International Inc. | A process for the production of fluorinated cyclobutane |
US11555001B2 (en) | 2018-06-06 | 2023-01-17 | Honeywell International Inc. | Method for dehydrochlorination of HCFC-244bb to manufacture HFO-1234yf |
CA3110479A1 (en) | 2018-08-24 | 2020-02-27 | Honeywell International Inc. | Processes for producing trifluoroiodomethane and trifluoroacetyl iodide |
JP2022514907A (en) | 2018-12-21 | 2022-02-16 | ハネウェル・インターナショナル・インコーポレーテッド | Foaming agent composition containing 1,2,2-trifluoro-1-trifluoromethylcyclobutane, and foaming method |
US11554956B2 (en) | 2019-04-16 | 2023-01-17 | Honeywell International Inc. | Integrated process and catalysts for manufacturing hydrogen iodide from hydrogen and iodine |
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WO2024040222A1 (en) | 2022-08-19 | 2024-02-22 | Generation Bio Co. | Cleavable closed-ended dna (cedna) and methods of use thereof |
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US2931840A (en) * | 1958-11-25 | 1960-04-05 | Du Pont | Process for preparing 2, 3, 3, 3-tetrafluoropropene |
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JP2755530B2 (en) | 1992-08-28 | 1998-05-20 | 株式会社トクヤマ | Method for producing fluorinated alcohol |
US8084653B2 (en) * | 2004-04-29 | 2011-12-27 | Honeywell International, Inc. | Method for producing fluorinated organic compounds |
US9024092B2 (en) * | 2006-01-03 | 2015-05-05 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
US7189884B2 (en) * | 2004-04-29 | 2007-03-13 | Honeywell International | Processes for synthesis of tetrafluoropropene |
US8664455B2 (en) * | 2008-08-08 | 2014-03-04 | Honeywell International Inc. | Process to manufacture 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) |
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