Dehydrohalogenation reactor and process
The invention provides a reactor comprising a reaction chamber having a catalytic surface in contact with reactants in said chamber, and a source for passing electrical current through said catalytic surface. The reactor can be used for dehydrohalogentation reactions, such as dehydrochlorination of HCFC-244bb to HFO-1234yf and for reactions where zero valent metals are employed for catalysis. The invention further provides a process to prepare HFO-1234yf from HCFC-244bb using an electrically heated reaction chamber.
1. A process for preparing 2,3,3,3-tetrafluoropropene (HFO-1234yf) comprising:
(a) providing a composition comprising 2-chloro-1,1,1,2-tetrafluorpropane (HCFC-244bb) to a reaction chamber having a catalytic surface in contact with the composition, the reaction chamber being connected to an electrical power source; and
(b) passing electrical current from the power source through the catalytic surface effective to heat the catalytic surface to a temperature effective to catalytically dehydrochorinate at least a portion of the HCFC-244bb to HFO-1234yf.
2. The process of claim 1 wherein the temperature is about 400° C. to about 500° C.
3. The process of claim 2 , wherein the temperature is about 450° C. to about 480° C.
4. The process of claim 1 , wherein the reactor pressure is about 0 psig to about 200 psig.
5. The process of claim 1 wherein the catalytic surface in contact with the composition is selected from the group consisting of electroless nickel, nickel, stainless steel, nickel-copper alloy, nickel-chromium alloy, iron-nickel-chromium alloy, nickel-molybdenum alloy, and combinations thereof.
6. The process of claim 1 wherein the reaction chamber is comprised of one or more tubes in a shell and tube configuration, and wherein the catalytic surface in contact with the composition is comprised of an inner wall or an outer wall of said one or more tubes, and the composition comprising HCFC-244bb is superheated to about 400° C. to about 500° C. prior to being provided to the reaction chamber having the catalytic surface.
7. The process of claim 1 , wherein the current is alternating current.
8. The process of claim 1 , wherein the current is direct current.
9. A process for a dehydrohalogenation reaction comprising
(a) providing at least one dehydrohalogenation reactant to a reaction chamber, the reaction chamber comprising a surface in contact with said dehydrohalogenation reactant, said surface comprising a material that catalyzes the dehydrohaolgenation reaction; and
(b) passing electrical current through said surface to heat said surface to a temperature effective to achieve dehydrohalogenation of the dehydrohalogenation reactant.
10. The process of claim 9 wherein the dehydrohalogenation reaction is selected from the group consisting of reactions A, B, C, and combinations thereof:
A) CHX′X″—CY′Y″—CF 3 →i) CH 2 ═CY—CF 3 , or
ii) CHX═CH—CF 3 , or
iii) combinations of i) and ii)
wherein
X and Y=one of H, Cl, or F,
X′ and X′=one or two of H, Cl, or F, Y′ and Y″=one of H, Cl, or F; or
B) CH 2 ═CY—CF 3 →CH≡C—CF 3
wherein X and Y=one of Cl or F; or
C) CHX═CH—CF 3 CH═C—CF 3
wherein X and Y=one of Cl or F.
11. The process of claim 10 wherein the dehydrohalogenation reaction is selected from the group consisting of:
CH 2 ClCH 2 CF 3 →CH 2 ═CH—CF 3 +HCl (253fb→1243zf+HCl),
CH 3 CHClCF 3 →CH 2 ═CH—CF 3 +HCl (253db→1243zf+HCl),
CH 2 FCH 2 CF 3 →CH 2 ═CH—CF 3 +HF (254fb→1243zf+HF),
CH 3 CHFCF 3 →CH 2 ═CH—CF 3 +HF (254eb→1243zf+HF),
CHCl 2 CH 2 CF 3 →CHCl═CH—CF 3 +HCl (243fa→1233zd+HCl),
CH 3 CCl 2 CF 3 →CH 2 ═CCl—CF 3 +HCl (243ab→1233xf+HCl),
CH 2 ClCHClCF3→CH 2 ═CCl—CF 3 /CHCl ═CH—CF 3 +HCl (243db→1233xf/1233zd+HCl),
CH 2 ClCHFCF 3 →CH 2 ═CF—CF 3 /CHCl ═CH—F 3 +HCl/HF (244eb→1234yf/1233zd+HCl/HF),
CH 2 FCHClCF 3 →CH 2 ═CCl—CF 3 /CHF═CH—CF 3 +HF/HCl (244db→1233xf/1234ze+HF/HCl),
CHFClCH 2 CF 3 →CHF═CH—CF 3 /CHCl ═CH—CF3+HCl/HF (244fa→1234ze/1233zd+HCl/HF),
CH 3 CF 2 CF 3 →CH 2 ═CF—CF 3 +HF (245cb→1234yf+HF),
CH 2 FCHFCF 3 →CH 2 ═CF—CF 3 /CHF═CH—CF 3 +HF (245eb→1234yf/1234ze+HF),
CHF 2 CH 2 CF 3 →CHF═CH—CF 3 +HF (245fa→1234ze+HF),
CH 2 ═CCl—CF 3 →CH≡C—CF 3 +HCl (1233xf→trifluoropropyne+HCl),
CH 2 ═CF—CF 3 →CH≡C—CF 3 +HCl (1234yf→trifluoropropyne+HF),
CHCl ═CH—CF 3 →CH≡C—CF 3 +HCl (1233zd→trifluoropropyne+HCl),
CHF═CH—CF 3 CH≡C—CF 3 +HF (1234ze trifluoropropyne+HF) and combinations thereof.
12. The process of claim 10 , wherein the reactor pressure is about 50 psig to about 100 psig.
13. The process of claim 9 where the temperature is about 400° C. to about 500° C.
14. The process of claim 9 wherein the catalytic surface in contact with the composition is selected from the group consisting of electroless nickel, nickel, stainless steel, nickel-copper alloy, nickel-chromium alloy, iron-nickel-chromium alloy, nickel-molybdenum alloy, and combinations thereof.
15. The process of claim 9 wherein the current is alternating current.
16. The process of claim 9 , wherein the current is direct current.
17. The process of claim 9 , wherein the reactor pressure is about 0 psig to about 200 psig.
18. The process of claim 10 , wherein the reactor pressure is about 50 psig to about 100 psig.