DEHYDROHALOGENATION REACTOR AND PROCESS
20180297917 ยท 2018-10-18
Assignee
Inventors
- Haluk Kopkalli (Staten Island, NY)
- Ron Joseph Roof (Center Valley, PA)
- Yuon Chiu (Denville, NJ)
- Hsueh Sung Tung (Getzville, NY)
- Robert A. Smith (Kinnelon, NJ)
Cpc classification
B01J16/005
PERFORMING OPERATIONS; TRANSPORTING
B01J19/24
PERFORMING OPERATIONS; TRANSPORTING
C07C17/25
CHEMISTRY; METALLURGY
B01J8/067
PERFORMING OPERATIONS; TRANSPORTING
B01J2208/06
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00132
PERFORMING OPERATIONS; TRANSPORTING
B01J15/005
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00135
PERFORMING OPERATIONS; TRANSPORTING
B01J2208/00415
PERFORMING OPERATIONS; TRANSPORTING
Y02P20/582
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
B01J8/02
PERFORMING OPERATIONS; TRANSPORTING
C07C17/25
CHEMISTRY; METALLURGY
Abstract
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.
Claims
1. A reactor comprising: a.) a reaction chamber having a catalytic surface in contact with reactants in said chamber; and b.) a source for passing electrical current through said catalytic surface.
2. The reactor of claim 1 further comprises an inlet and an outlet, both in fluid communication with said reaction chamber.
3. The reactor of claim 1 wherein the reaction chamber comprises one or more tubes, wherein the one or more tubes are in a shell and tube configuration and wherein the catalytic surface in contact with the reactants is comprised of an inner wall or an outer wall of said one or more tubes, and the one or more tubes is finned.
4. (canceled)
5. (canceled)
6. (canceled)
7. The reactor of claim 1 wherein the catalytic surface in contact with the reactants is comprised of packing, wherein the packing is in the form of metal pellets or metal mesh.
8. (canceled)
9. The reactor of claim 1 wherein the catalytic surface in contact with the reactants is selected from electroless nickel, nickel, a stainless steel, a Monel alloy, an Inconel alloy, an Incoloy alloy, a Hastelloy alloy, and combinations thereof.
10. (canceled)
11. (canceled)
12. The reactor of claim 1 wherein the catalytic surface is comprised of zero valent metal.
13. (canceled)
14. (canceled)
15. The reactor of claim 1 further comprising a superheater zone in fluid communication with the reaction chamber and a vaporizer in fluid communication with the superheater zone.
16. (canceled)
17. (canceled)
18. The reactor of claim 1 wherein the reactor is a dehydrochlorination reactor.
19. The reactor of claim 18 wherein the reactants comprise 2-chloro-1,1,1,2-tetrafluorpropane (HCFC-244bb).
20. A reactor for a dehydrohalogenation reaction comprising an inlet and an outlet in fluid communication with a plurality of reactor tubes, the reactor tubes having a surface in contact with dehydrohalogenation reactants, said surface comprising a material that catalyzes the dehydrohalogenation reaction, the plurality of reactor tubes being connected to an electrical power source for passing electrical current through the reactor tubes to heat the surface to a temperature effective to achieve dehydrohalogenation.
21. The reactor of claim 20 wherein the surface is an inner surface of the reactor tubes or an outer surface of the reactor tubes.
22. The reactor of claim 20 wherein the surface is comprised of packing within the reactor tubes.
23. (canceled)
24. (canceled)
25. (canceled)
26. (canceled)
27. (canceled)
28. (canceled)
29. The reactor of claim 20 further comprising a superheater zone in fluid communication with the inlet.
30. 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; (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.
31. The process of claim 30 where the temperature is about 400? C. to about 500? C.
32. The process of claim 30 wherein the catalytic surface in contact with the composition is selected from electroless nickel, nickel, stainless steel, Monel alloy, Inconel alloy, Incololyalloy, Hastelloy alloy, and combinations thereof.
33. (canceled)
34. The process of claim 30 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.
35. (canceled)
36. 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; b) passing electrical current through said surface to heat said surface to a temperature effective to achieve dehydrohalogenation of the dehydrohalogenation reactant.
37. The process of claim 36 wherein the dehydrohalogenation reaction is selected from reactions A, B, C, or combinations thereof: A) CHXXCYYCF.sub.3.fwdarw. i) CH.sub.2?CYCF.sub.3, or ii) CHX?CHCF.sub.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.sub.2?CYCF.sub.3.fwdarw.CH?CCF.sub.3 wherein X and Y=one of Cl or F; or C) CHX?CHCF.sub.3.fwdarw.CH?CCF.sub.3 wherein X and Y=one of Cl or F.
38. The process of claim 37 wherein the dehydrohalogenation reaction is selected from one or more of the following reactions: CH.sub.2ClCH.sub.2CF.sub.3.fwdarw.CH.sub.2?CHCF.sub.3+HCl (253fb.fwdarw.1243zf+HCl), CH.sub.3CHClCF.sub.3.fwdarw.CH.sub.2?CHCF.sub.3+HCl (253db.fwdarw.1243zf+HCl), CH.sub.2FCH.sub.2CF.sub.3.fwdarw.CH.sub.2?CHCF.sub.3+HF (254fb.fwdarw.1243zf+HF), CH.sub.3CHFCF.sub.3.fwdarw.CH.sub.2?CHCF.sub.3+HF (254eb.fwdarw.1243zf+HF), CHCl.sub.2CH.sub.2CF.sub.3.fwdarw.CHCl?CHCF.sub.3+HCl (243fa.fwdarw.1233zd+HCl), CH.sub.3CCl.sub.2CF.sub.3.fwdarw.CH.sub.2?CClCF.sub.3+HCl (243ab.fwdarw.1233xf+HCl), CH.sub.2ClCHClCF.sub.3.fwdarw.CH.sub.2?CClCF.sub.3/CHCl?CHCF.sub.3+HCl (243db.fwdarw.1233xf/1233zd+HCl), CH.sub.2ClCHFCF.sub.3.fwdarw.CH.sub.2?CFCF.sub.3/CHCl?CHCF.sub.3+HCl/HF (244eb.fwdarw.1234yf/1233zd+HCl/HF), CH.sub.2FCHClCF.sub.3.fwdarw.CH.sub.2?CClCF.sub.3/CHF?CHCF.sub.3+HF/HCl (244db.fwdarw.1233xf/1234ze+HF/HCl), CHFClCH.sub.2CF.sub.3.fwdarw.CHF?CHCF.sub.3/CHCl?CHCF3+HCl/HF (244fa.fwdarw.1234ze/1233zd+HCl/HF), CH.sub.3CF.sub.2CF.sub.3.fwdarw.CH.sub.2?CFCF.sub.3+HF (245cb.fwdarw.1234yf+HF), CH.sub.2FCHFCF.sub.3.fwdarw.CH.sub.2?CFCF.sub.3/CHF?CHCF.sub.3+HF (245eb.fwdarw.1234yf/1234ze+HF), CHF.sub.2CH.sub.2CF.sub.3.fwdarw.CHF?CHCF.sub.3+HF (245fa.fwdarw.1234ze+HF), CH.sub.2?CClCF.sub.3.fwdarw.CH?CCF.sub.3+HCl (1233xf.fwdarw.trifluoropropyne+HCl), CH.sub.2?CFCF.sub.3.fwdarw.CH?CCF.sub.3+HCl (1234yf.fwdarw.trifluoropropyne+HF), CHCl?CHCF.sub.3.fwdarw.CH?CCF.sub.3+HCl(1233zd.fwdarw.trifluoropropyne+HCl), or CHF?CHCF.sub.3.fwdarw.CH?CCF.sub.3+HF (1234ze.fwdarw.trifluoropropyne+HF).
39. (canceled)
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0018]
[0019]
[0020]
[0021]
DETAILED DESCRIPTION
[0022] As described in U.S. Pat. No. 8,058,486, the contents of which are incorporated herein by reference, HCFC-244bb feed can be formed from HCFO-1233xf hydrofluorination in a liquid phase reactor in the presence of a fluorination catalyst. Due to incomplete conversion of HCFO-1233xf and its close boiling point to HCFC-244bb as well as the formation of azeotrope or azeotrope-like composition of HCFC-244bb and HCFO-1233xf under certain conditions, the separation of these two compounds is difficult. For this reason, the HCFC-244bb feed generally contains certain amount of HCFO-1233xf.
[0023] In one practice, the reactor is used in preparing HFO-1234yf by dehydrochlorination of HCFC-244bb.
[0024]
[0025] In
[0026] Generally, catalytic materials of construction for the tubes or the packing depend on the reaction contemplated. For example, in the dehydrochlorination of HCFC-244bb to HFO-1234yf, serviceable materials of tube or packing construction include, without limitation, electroless nickel, nickel, stainless steel, Monel? alloys, Inconel? alloys, Incoloy? alloys, Hastelloy? alloys, and combinations thereof. In an embodiment of the present invention, one or more of the tubular elements are finned, such as depicted in
[0027] In
[0028] In another embodiment of the reactor of the invention,
[0029] While the reaction of HCFC-244bb to HFO-1234yf and HCl is the reaction described above, the apparatus described in this invention is not limited to this chemistry and can be used for other endothermic reactions where zero valent metals are used for catalysis or where a catalyst is not required (e.g. pyrolysis). Examples of other such reactions include, without limitation:
CHXXCYYCF.sub.3.fwdarw.CH.sub.2?CYCF.sub.3 and/or CHX?CHCF.sub.3 [0030] where [0031] X and Y=one of H, Cl, F [0032] X and X=one or two of H, Cl or F [0033] Y and Y=one of H, Cl or F
CH.sub.2?CYCF.sub.3 and/or CHX?CHCF.sub.3.fwdarw.CHCCF.sub.3 [0034] where [0035] X and Y=one of Cl, F
Examples of such reactions include:
CH.sub.2ClCH.sub.2CF.sub.3.fwdarw.CH.sub.2?CHCF.sub.3+HCl (253fb.fwdarw.1243zf+HCl)
CH.sub.3CHClCF.sub.3.fwdarw.CH.sub.2?CHCF.sub.3+HCl (253db.fwdarw.1243zf+HCl)
CH.sub.2FCH.sub.2CF.sub.3.fwdarw.CH.sub.2?CHCF.sub.3+HF (254fb.fwdarw.1243zf+HF)
CH.sub.3CHFCF.sub.3.fwdarw.CH.sub.2?CHCF.sub.3+HF (254eb.fwdarw.1243zf+HF)
CHCl.sub.2CH.sub.2CF.sub.3.fwdarw.CHCl?CHCF.sub.3+HCl (243fa.fwdarw.1233zd+HCl)
CH.sub.3CCl.sub.2CF.sub.3.fwdarw.CH.sub.2?CClCF.sub.3+HCl (243ab.fwdarw.1233xf+HCl)
CH.sub.2ClCHClCF.sub.3.fwdarw.CH.sub.2?CClCF.sub.3/CHCl?CHCF.sub.3+HCl (243db.fwdarw.1233xf/1233zd+HCl)
CH.sub.2ClCHFCF.sub.3.fwdarw.CH.sub.2?CFCF.sub.3/CHCl?CHCF.sub.3+HCl/HF (244eb.fwdarw.1234yf/1233zd+HCl/HF)
CH.sub.2FCHClCF.sub.3.fwdarw.CH.sub.2?CClCF.sub.3/CHF?CHCF.sub.3+HF/HCl (244db.fwdarw.1233xf/1234ze+HF/HCl)
CHFClCH.sub.2CF.sub.3.fwdarw.CHF?CHCF.sub.3/CHCl?CHCF3+HCl/HF (244fa.fwdarw.1234ze/1233zd+HCl/HF)
CH.sub.3CF.sub.2CF.sub.3.fwdarw.CH.sub.2?CFCF.sub.3+HF (245cb.fwdarw.1234yf+HF)
CH.sub.2FCHFCF.sub.3.fwdarw.CH.sub.2?CFCF.sub.3/CHF?CHCF.sub.3+HF (245eb.fwdarw.1234yf/1234ze+HF)
CHF.sub.2CH.sub.2CF.sub.3.fwdarw.CHF?CHCF.sub.3+HF (245fa.fwdarw.1234ze+HF)
CH.sub.2 CClCF.sub.3.fwdarw.CH?CCF.sub.3+HCl (1233xf.fwdarw.trifluoropropyne+HCl)
CH.sub.2?CFCF.sub.3.fwdarw.CH?CCF.sub.3+HCl (1234yf.fwdarw.trifluoropropyne+HF)
CHCl?CHCF.sub.3.fwdarw.CH?CCF.sub.3+HCl (1233zd.fwdarw.trifluoropropyne+HCl)
CHF?CHCF.sub.3.fwdarw.CH?CCF.sub.3+HF (1234ze.fwdarw.trifluoropropyne+HF)
EXAMPLES
Example 1
[0036] In this example, an insulated 1?0.065 Inconel 625 tube reactor with a 7-point thermocouple of ? OD inserted inside of the tube was used. The distance between two neighboring temperature probe points is 4. The reactor served as the pressure containment vessel, the heating element, and the heat transfer surface. A Flex Kraft Rectifier with maximum output of 5 V and 140 A was used to provide DC (Direct Current) power to the Inconel 625 reactor. Once the hot spot temperature of reactor reached its set point, the flow of 244bb feed was started. During reaction, the reactor effluent was periodically sampled for its compositions.
[0037] Table 1 lists its average reactivity under various conditions. An activity higher than that in conventional (externally heated) reactor was observed in this impedance heater reactor. For example, close to 30% 244bb conversion was achieved at temperatures lower than 450? C. In addition, as shown in Table 1, the selectivity to 1234yf was ?98.5%.
TABLE-US-00001 TABLE 1 * Period of Temp. C. P, 244bb Selectivity.sup.#, % time, h T.sub.bottom T.sub.1 T.sub.2 T.sub.3 T.sub.4 T.sub.5 T.sub.top psig conv., % 1234yf Others 14-34 121.0 384.7 444.0 452.9 454.1 419.5 321.5 50.0 23.3 98.8 1.2 36-50 115.0 383.2 441.9 448.7 440.8 395.4 299.9 70.3 25.0 98.5 1.5 52-58 120.3 386.4 441.4 446.6 431.4 383.4 296.4 100.2 28.0 98.9 1.1 68-88 111.9 369.4 436.2 454.7 455.8 430.5 336.0 30.2 14.8 99.4 0.6 91-120 105.8 368.2 433.6 450.4 444.9 405.1 308.2 49.9 14.1 99.0 1.0 132-170 100.9 367.0 461.2 480.5 483.1 441.1 323.3 50.3 52.7 98.8 1.2 220-241 94.2 358.6 454.2 473.8 468.3 412.8 305.1 70.2 41.8 98.7 1.3 * Other conditions: 45 g/h of average feed rate; organic composition - 94A GC area % 244bb/5.2 GC area % 1233xf70.5 GC area % 245cb .sup.#Calculated assuming no 244bb dehydrofluorination occurred
Example 2
[0038] The same reactor and set-up as described in Example 1 were used in Example 2. Speed runs were conducted by doubling the feed rate. In one experiment, the feed rate was doubled but the DC input power supply was kept at the same (2.57 V/118.2 A). As shown in Table 2, the doubled feed rate resulted in significant decrease of both hot-spot temperature (from ?468 to ?453? C.) and 244bb conversion (from ?39 to ?11%). Nevertheless, with input power increasing, both hot-spot temperature and 244bb conversion increased. As shown in Table 2, at 2.76 V/126.2 A, the hot-spot temperature and 244bb conversion increased to ?483? C. and ?40%, respectively. In summary, for the doubled feed rate, comparable 244bb conversion was achieved by increasing electrical input power by about 15%.
TABLE-US-00002 TABLE 2 * Period DC power Flow 244bb of time, Voltage, Current, Temp. ? C. P, rate, conv., h V A T.sub.bottom T.sub.1 T.sub.2 T.sub.3 T.sub.4 T.sub.5 T.sub.top psig g/h % 897- 7.57 118.2 85.6 356.4 447.7 467.7 408.5 309.4 69.9 45.8 39.2 1037 1015- 2.57 118.2 47.7 259.4 397.1 453.2 414.0 324.2 69.7 92.9 10.6 1037 1038- 2.66 122.2 43.6 282.5 419.9 470.0 436.7 343.2 69.9 86.6 24.5 1063 1064- 2.70 124.2 43.8 289.9 430.0 477.0 449.8 354.5 69.6 94.0 34.2 1087 1088- 2.76 126.2 42.6 298.4 438.1 483.6 459.7 362.3 70.1 90.2 40.4 1109 * Organic composition - 0.8 GC area % 245cb194 9 GC area % 244bb/4.1 GC area % 1233x
Example 3
[0039] The same reactor and set-up as described in Example 1 were used in Example 3. The effect of HCl/HF treatments was investigated. The HCl/HF treatments were carried by passing HCl (or HF)/N.sub.2 mixed flow through the reactor maintained at high temperatures (see Table 3 for conditions). As shown in Table 3, slightly higher 244bb conversion was observed after HCl/HF treatments while 1234yf selectivity remained almost unchanged. Note that selectivity changeover from 1234yf to 1233xf occurred after similar HF treatment in conventional reactor.
TABLE-US-00003 TABLE 3 * Period Feed 244bb of Temp. ? C. P, rate, conv., Selectivity.sup.#, % time, h Treatment T.sub.bottom T.sub.1 T.sub.2 T.sub.3 T.sub.4 T.sub.5 T.sub.top psig g/h % 1234yf others 1127- No 87.0 358.2 451.0 473.4 403.9 306.0 68.9 45.2 28.3 99.4 0.6 1165 1169- In 50% 356.7 450.5 472.5 459.4 404.5 312.8 69.8 44.9 30.2 99.3 0.7 1189 HCl/N.sub.2 flow for 16 hat 500? C. 1193- In 5% 357.2 451.1 473.4 463.6 410.2 310.7 70.0 44.0 33.9 99.4 0.6 1363 HF/N.sub.2 flow for 16 h at 480- 490? C. 1366- In 5% 358.3 452.2 475.0 465.0 411.8 313.9 69.5 43.8 32.4 99.5 0.5 1575 HF/N.sub.2 flow for 25 h at 500- 510? C. * Organic composition - 0.8 GC area % 245cb/94.9 GC area % 244bb/4.1 GC area % 1233x #Calculated assuming no 244bb dehydrofluorination occurred
Example 4
[0040] 244bb liquid was vaporized in a steam heated vaporizer at 70 psig pressure and 74? C. It was superheated to 480? C. using an electric superheater, and introduced into the reactor. The reactor consisted of a 2 (51 mm) diameter Alloy 625 tube, directly heated by impedance heating using a 30 volt 3 phase power supply. Watt density was 35 watts/ft.sup.2 tube surface area. The reactor was maintained at 480? C. The reactor produced 100 g/hr of HFO-1234yf. The reactor exit gas was cooled and distilled in a two column separation system. The bottom stream from the first column, consisting of unreacted 244bb, was returned to the vaporizer. The overhead stream from the first column passed to the second column, where HCl was withdrawn via the overheads stream, and the HFO-1234yf product withdrawn via the bottoms stream.
[0041] The present invention relates to an improved process and reactor design for carrying out reactions necessary to manufacture these compounds, or more particularly a novel heating system for such processes and reactors. The reactor may also be used for other chemical processing that requires heating to high temperatures under carefully controlled conditions. The reactor finds particular use in the manufacture of hydrofluoroolefins (HFOs). The reactor of the invention includes a reactor heated by a specially designed electric heating system.
[0042] The foregoing description is by way of example only and is not limiting to the scope of the invention.