Method for dehydrochlorination of HCFC-244BB to manufacture HFO-1234YF

Patent metadata

Field	Value
Publication number	US-12304880-B2
Application number	US-202218079677-A
Country	US
Kind code	B2
Filing date	Dec 12, 2022
Priority date	Jun 6, 2018
Publication date	May 20, 2025
Grant date	May 20, 2025

Abstract

A process for making 2,3,3,3-tetrafluoropropene (HFO-1234yf) includes providing a composition including 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) to a reactor including a heater surface at a surface temperature greater than about 850° F. (454° C.), and then bringing the composition into contact with the heater surface for a contact time of less than 10 seconds to dehydrochlorinate a portion of the HCFC-244bb to make HFO-1234yf.

First claim

What is claimed is:

1. A process for making 2,3,3,3-tetrafluoropropene (HFO-1234yf), the process comprising:
providing a composition including at least 96 wt. % 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) to a reactor including a heater surface at a surface temperature from about 975° F. (524° C.) to about 1,005° F. (541° C.); and
bringing the composition into contact with the heater surface for a contact time of less than 10 seconds to dehydrochlorinate a portion of the HCFC-244bb to make a final product stream comprising HFO-1234yf, wherein the HFO-1234yf includes 1,1,1,2-tetrafluoroethane (HFC-134a) at a concentration from 0.0001 wt. % to 0.010 wt. % on an HCFC-244bb-free basis.

2. The process of claim 1 , wherein the contact time is from 0.1 seconds to 9 seconds.

3. The process of claim 1 , wherein the heater surface includes a catalytic surface.

4. The process of claim 3 , wherein the catalytic surface includes electroless nickel, nickel, stainless steel, nickel-copper alloy, nickel-chromium-iron alloy, nickel-chromium alloy, nickel-chromium-molybdenum, or combinations thereof.

5. The process of claim 3 , wherein the catalytic surface comprises nickel-chromium-iron alloy.

6. The process of claim 3 , wherein the catalytic surface comprises nickel-chromium-molybdenum alloy.

7. The process of claim 1 , wherein the heater surface is not a catalytic surface.

8. The process of claim 1 , further including:
vaporizing the composition; and
heating the vaporized composition to a temperature from about 575° F. (302° C.) to 1,200° F. (649° C.) before providing the composition to the reactor.

9. The process of claim 1 , wherein the dehydrochlorination of the portion of the HCFC-244bb produces hydrogen chloride (HCl) and wherein the final product stream comprises HFO-1234yf, HCl, and unreacted HCFC-244bb, the process further comprising:
separating the HFO-1234yf and the HCl from at least a portion of the HCFC-244bb in the distillation column;
recycling the separated HCFC-244bb forming a recycle stream and combining the recycle stream with the composition forming a combined stream and providing the combined stream into the reactor including the heater surface and vaporizing the combined stream to form a vaporized composition;
providing the HFO-1234yf and the HCl to an HCl separation unit; and

separating the HCl from the HFO-1234yf to form a final product stream including the HFO-1234yf.

10. The process of claim 9 , wherein the final product stream comprises the HFO-1234yf at a concentration greater than 99.1 wt. % on an HCFC-244bb-free basis.

11. The process of claim 1 , wherein the final product stream comprises the HFO-1234yf at a concentration greater than 99.1 wt. % on an HCFC-244bb-free basis.

12. The process of claim 1 , wherein the final product stream comprises the HFO-1234yf at a concentration greater than 99.5 wt. % on an HCFC-244bb-free basis.

13. The process of claim 1 , wherein the final product stream comprises the HFO-1234yf at a concentration greater than 99.8 wt. % on an HCFC-244bb-free basis.

14. The process of claim 1 , wherein the HFO-1234yf includes 1,1,1,2-tetrafluoroethane (HFC-134a) at a concentration from 0.001 wt. % to 0.010 wt. % on an HCFC-244bb-free basis.

15. The process of claim 1 , wherein the HFO-1234yf includes 1,1,1,2-tetrafluoroethane (HFC-134a) at a concentration from 0.05 wt. % to 0.010 wt. % on an HCFC-244bb-free basis.

16. The process of claim 1 , wherein the contact time is less than 8 seconds.

17. The process of claim 1 , wherein the contact time is less than 6 seconds.

18. The process of claim 1 , wherein the contact time is less than 4 seconds.

19. The process of claim 1 , wherein the reactor comprises a tubular body enclosing electrical resistance wires.

Assignees

• Honeywell Int Inc

Inventors

• Kopkalli Haluk
• Navar Carlos
• Chiu Yuon
• Wang Haiyou

Classifications

• C07C17/383

  by distillation · CPC title

• C07C17/38

  Separation; Purification; Stabilisation; Use of additives · CPC title

• C07C19/10

  and chlorine · CPC title

• C07C17/04

  to unsaturated halogenated hydrocarbons · CPC title

• C07C21/18

  containing fluorine · CPC title