# Patent

## Title
Selective catalytical dehydrochlorination of hydrochlorofluorocarbons

## Abstract

A dehydrochlorination process is disclosed. The process involves contacting RfCHClCH2Cl with a catalyst in a reaction zone to produce a product mixture comprising RfCCl═CH2, wherein said catalyst comprises MY supported on carbon, and wherein Rf is a perfluorinated alkyl group, M=K, Na or Cs, and Y=F, Cl or Br.

## Background
BACKGROUND
1. Field of the Disclosure
This disclosure relates in general to the selective catalytic dehydrochlorination of hydrochlorofluorocarbons (HCFCs) to make hydrochlorofluoroolefins (HCFOs). More specifically, the catalysts are alkali metal compounds supported on carbon.
2. Description of Related Art
Hydrochlorofluoroolefins (HCFOs), having low ozone depletion potential and low global warming potentials, are regarded as candidates for replacing saturated CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons). HCFOs can be employed in a wide range of applications, including their use as refrigerants, solvents, foam expansion agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishants and power cycle working fluids. For example, HCFO-1233xf (CF3CCl═CH2) can be used as a foam expansion agent, fire extinguishant, refrigerant, et al. HCFO-1233xf is also an intermediate in the production of 2,3,3,3-tetrafluoropropene (HFO-1234yf) which is a refrigerant with zero ozone depletion potential and low global warming potential.
BRIEF SUMMARY OF THE DISCLOSURE
The present disclosure provides a dehydrochlorination process. The process comprises contacting RfCHClCH2Cl with a catalyst in a reaction zone to produce a product mixture comprising RfCCl=CH2, wherein said catalyst comprises MY supported on carbon, and wherein Rf is a perfluorinated alkyl group, M=K, Na or Cs, and Y=F, Cl or Br.


DETAILED DESCRIPTION
The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims. Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, and from the claims.
As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and/or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
The term “dehydrochlorination”, as used herein, means a process during which hydrogen and chlorine on adjacent carbons in a molecule are removed.
The term “hydrochlorofluoroolefin”, as used herein, means a molecule containing hydrogen, carbon, fluorine, chlorine, and at least one carbon-carbon double bond. Exemplary hydrochlorofluoroolefins in this disclosure include HCFO-1233xf.
The term “alkyl”, as used herein, either alone or in compound words such as “perfluorinated alkyl group”, includes cyclic or acyclic and straight-chain or branched alkyl groups, such as, methyl, ethyl, n-propyl, i-propyl, or the different isomers thereof.
The term “perfluorinated alkyl group”, as used herein, means an alkyl group wherein all hydrogens on carbon atoms have been substituted by fluorines. Examples of a perfluorinated alkyl group include —CF3 and —CF2CF3.
The term “product selectivity to RfCCl═CH2”, as used herein, means the molar percentage of RfCCl═CH2 obtained in the process compared to the total molar amounts of all products obtained.
The term “dehydrochlorination selectivity to RfCCl═CH2”, as used herein, means the molar percentage of RfCCl═CH2 based on the total molar amount of RfCCl═CH2 and RfCH═CHCl obtained in the dehydrochlorination reaction of RfCHClCH2Cl.
The term “an elevated temperature”, as used herein, means a temperature higher than the room temperature.
Disclosed is a dehydrochlorination process comprising contacting RfCHClCH2Cl with a catalyst in a reaction zone to produce a product mixture comprising RfCCl═CH2, wherein said catalyst comprises MY supported on carbon, and wherein Rf is a perfluorinated alkyl group, M=K, Na or Cs, and Y=F, Cl or Br.
In some embodiments of this invention, Rf is —CF3 or —CF2CF3. In some embodiments of this invention, RfCHClCH2Cl is CF3CHClCH2Cl (HCFC-243db), and RfCCl═CH2 is CF3CCl═CH2 (HCFO-1233xf).
Some hydrochlorofluoroolefins of this disclosure, e.g., CF3CH═CHCl (HCFO-1233zd), exist as different configurational isomers or stereoisomers. When the specific isomer is not designated, the present disclosure is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For instance, HCFO-1233zd is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.
The starting materials for the dehydrochlorination processes in this disclosure, i.e., RfCHClCH2Cl, can be synthesized by methods known in the art. For example, HCFC-243db may be prepared by chlorinating CF3CH═CH2 or by the addition reaction of CF2═CHCl with CFClH2.
The dehydrochlorination process can be carried out in liquid phase or vapor phase using well-known chemical engineering practice, which includes continuous, semi-continuous or batch operations. The temperature in the reaction zone is typically from about 140° C. to about 400° C. In some embodiments of this invention, the temperature in the reaction zone is from about 150° C. to about 250° C. In some embodiments of this invention, the temperature in the reaction zone is from about 175° C. to about 225° C. The dehydrochlorination process can be conducted at superatmospheric, atmospheric, or subatmospheric pressures. The contact time of the starting material RfCHClCH2Cl with the catalyst can be largely varied. Typically, the contact time is from about 10 seconds to about 150 seconds. In some embodiments of this invention, the contact time is from about 40 seconds to about 100 seconds. The contacting step of this invention may be carried out by methods known in the art. In some embodiments of this invention, starting material RfCHClCH2Cl, optionally with an inert gas, is fed to a reactor containing the catalyst. In some embodiments of this invention, starting material RfCHClCH2Cl, optionally with an inert gas, is passed through the catalyst bed in a reactor. In some embodiments of this invention, starting material
RfCHClCH2Cl, optionally together with an inert gas, may be mixed with the catalyst in a reactor with stir or agitation.
The dehydrochlorination process may be conducted in the presence of an inert gas such as He, Ar, or N2. In some embodiments of this invention, the inert gas is co-fed into the reactor with the starting material.
In accordance with this invention, catalysts suitable for dehydrochlorination are provided. Said catalysts comprise carbon supported alkali metal halide salt represented by the formula MY, wherein M=K, Na or Cs, and Y=F, Cl or Br. In some embodiments of this invention, MY is KF. In some embodiments of this invention, MY is KCl.
The alkali metal halide salt can be deposited on the carbon support using deposit techniques well known in the art. For example, alkali metal halide salt can be dissolved in deionized water and then mixed with freshly dried acid washed activated carbon. The mixture can be gently stirred until the solution of the alkali metal halide salt is completely absorbed by the activated carbon. Finally, the loaded activated carbon is dried at an elevated temperature and stored in a sealed container for use as a catalyst. In some embodiments of this invention, the catalyst contains from about 5 wt % (weight percent) to about 40 wt % alkali metal halide salt based on the total amount of alkali metal halide salt and carbon. In some embodiments of this invention, the catalyst contains from about 10 wt % to about 30 wt % alkali metal halide salt based on the total amount of alkali metal halide salt and carbon.
Carbon used in the embodiments of this invention may come from any of the following sources: wood, peat, coal, coconut shells, bones, lignite, petroleum-based residues and sugar. Commercially available carbons which may be used include those sold under the following trademarks: Barneby & SutcliffeTM, DarcoTM, Nucharm, Columbia JXNTM Columbia LCKTM, CalgonTM PCB, CalgonTM BPL, WestvacoTM, NoritTM, TakedaTM and Barnaby Cheny NBTM The carbon also includes three dimensional matrix porous carbonaceous materials. Examples are those described in U.S. Pat. No. 4,978,649. In one embodiment of the invention, carbon includes three dimensional matrix carbonaceous materials which are obtained by introducing gaseous or vaporous carbon-containing compounds (e.g., hydrocarbons) into a mass of granules of a carbonaceous material (e.g., carbon black); decomposing the carbon-containing compounds to deposit carbon on the surface of the granules; and treating the resulting material with an activator gas comprising steam to provide a porous carbonaceous material. A carbon-carbon composite material is thus formed. Carbon includes unwashed and acid-washed carbons. In some embodiments of this invention, suitable catalysts may be prepared by treating the carbon used as catalyst support with acids such as HNO3, HCl, HF, H2SO4, HClO4, CH3COOH, and combinations thereof. Acid treatment is typically sufficient to provide carbon that contains less than 1000 ppm of ash. Some suitable acid treatments of carbon are described in U.S. Pat. No. 5,136,113. In some embodiments of this invention, an activated carbon is dried at an elevated temperature and then is soaked for 8 to 24 hours with occasional stirring in 1 to 12 weight percent of HNO3. The soaking process can be conducted at temperatures ranging from room temperature to 80° C. The activated carbon is then filtered and washed with deionized water until the washings have a pH greater than 4.0 or until the pH of the washings does not change. Finally, the activated carbon is dried at an elevated temperature.
In some embodiments of this invention, carbon is an activated carbon. In some embodiments of this invention, carbon is an acid washed activated carbon. The carbon can be in the form of powder, granules, or pellets, et al.
The effluent from the reaction zone typically includes residual starting materials RfCHClCH2Cl, desired hydrochlorofluoroolefin product RfCCl═CH2, dehydrochlorination byproduct RfCH═CHCl and some other byproducts. The desired product RfCCl═CH2 may be recovered from the product mixture by conventional methods. In some embodiments of this invention, product RfCCl═CH2 may be purified or recovered by distillation.
It was found through experiments that the catalytic dehydrochlorination processes of this disclosure produced desired products with high selectivity. In some embodiments of this invention, the product selectivity to RfCCl═CH2 is at least 90 mole %. In some embodiments of this invention, the product selectivity to RfCCl═CH2 is at least 96 mole %.
It was also found through experiments that the dehydrochlorination reaction of this disclosure is highly selective. The dehydrochlorination reaction of RfCHClCH2Cl may generate both isomers RfCCl═CH2 and RfCH═CHCl. It was found that the dehydrochlorination processes of this disclosure generate substantially more RfCCl═CH2 than RfCH═CHCl. In some embodiments of this invention, the dehydrochlorination selectivity to RfCCl═CH2 is at least 95 mole %. In some embodiments of this invention, the dehydrochlorination selectivity to RfCCl═CH2 is at least 98 mole %.
The reactors, distillation columns, and their associated feed lines, effluent lines, and associated units used in applying the processes of embodiments of this invention may be constructed of materials resistant to corrosion. Typical materials of construction include TeflonTM and glass.
Typical materials of construction also include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as MonelTM nickel-copper alloys, HastelloyTM nickel-based alloys and, InconelTM nickel-chromium alloys, and copper-clad steel.
Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.
EXAMPLES
The concepts described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims.
Example 1
Example 1 demonstrates that contacting HCFC-243db with KCl supported on acid washed TakedaTM carbon generates HCFO-1233xf.
Preparation of HNO3 Washed TakedaTM Carbon
TakedaTM activated carbon with surface area ranging from about 1000 m2/g to about 1200 m2/g was soaked in 1 wt % HNO3 aqueous solution at room temperature for 12 hours before being fully washed with deionized water and dried at 120° C. for 12 hours. The HNO3 washed TakedaTM carbon was then loaded with KCl and used below.
Dehydrochlorination Reaction
10 cc (cubic centimeter) of catalyst granules of 25 wt % KCl/acid washed TakedaTM carbon were loaded into a 0.43 inch I. D. MonelTM reactor tube to form a catalyst bed. Gaseous HCFC-243db was passed through the catalyst bed at a rate of 1.1 g/hr together with 4.3 ml/min N2.
The effluent from the reactor tube was analyzed by GC and GC-MS. The conversion rate of the starting material HCFC-243db, the product selectivity to HCFO-1233xf and HCFO-1233zd, and the dehydrochlorination selectivity to HCFO-1233xf were listed in the Table 1 below which shows both good product selectivity and good dehydrochlorination selectivity to HCFO-1233xf.











TABLE 1









Dehydro-




Product
Product
chlorination



Conversion
Selectivity
Selectivity
Selectivity


Temp
Mole %
Mole %
Mole %
Mole %


° C.
HCFC-243db
HCFO-1233xf
HCFO-1233zd
HCFO-1233xf



















145
9.17
92.34
0.49
99.47


176
45.47
98.64
0.74
99.26


176
53.66
98.83
0.81
99.19


202
89.83
98.61
1.18
98.82


197
94.57
98.59
1.28
98.72


226
98.19
97.59
2.10
97.89


230
98.13
97.55
1.93
98.06


254
99.06
96.32
3.04
96.94


247
98.99
96.66
2.76
97.22


217
98.48
97.55
2.01
97.98


224
98.13
98.05
1.74
98.26


222
98.20
98.07
1.77
98.23









Example 2 (Comparative)
Example 2 demonstrates that the HCFC-243db conversion rate and the selectivity to HCFO-1233xf were low without a catalyst.
10cc HastelloyTM 276 turnings were loaded into a 0.43 inch I. D. MonelTM reactor tube to form a bed. Gaseous HCFC-243db was passed through the bed at a rate of 1.1 g/hr together with 4.3 ml/min N2. The effluent from the reactor tube was analyzed by GC and GC-MS. The results are listed in the Table 2 below.











TABLE 2









Dehydro-




Product
Product
chlorination



Conversion
Selectivity 
Selectivity
Selectivity


Temp
Mole %
Mole %
Mole %
Mole %


° C.
HCFC-243db
HCFO-1233xf 
HCFO-1233zd
HCFO-1233xf



















401
5.92
12.10
26.60
31.27


403
4.16
19.79
48.45
29.00


429
13.06
24.66
64.97
27.51


423
12.82
25.23
66.79
27.42


450
40.75
25.62
70.35
26.70


449
42.37
25.62
71.01
26.51


476
73.35
24.53
68.81
26.28


471
74.01
25.18
70.71
26.26


500
84.00
22.17
60.92
26.68


499
73.92
23.26
65.47
26.21









Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed are not necessarily the order in which they are performed. In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.
Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.
It is to be appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.

## Claims

1. A dehydrochlorination process comprising contacting RfCHClCH2Cl with a catalyst in a reaction zone to produce a product mixture comprising RfCCl═CH2, wherein said catalyst comprises an alkali metal halide salt of the formula MY supported on carbon, and wherein Rf is a perfluorniated alkyl group, M=K, Na or Cs, and Y=F, Cl or Br and wherein the catalyst contains from about 5wt % to about 40wt % alkali metal halide salt based on the total amount of alkali metal halide salt and carbon.

2. The dehydrochlorination process of claim 1 wherein the carbon is an activated carbon.

3. The dehydrochlorination process of claim 2 wherein the carbon is an acid washed activated carbon.

4. The dehydrochlorination process of claim 1 wherein M is K and Y is F or Cl.

5. The dehydrochlorination process of claim 1 wherein the temperature in the reaction zone is from about 140° C. to about 400° C.

6. The dehydrochlorination process of claim 5 wherein the temperature in the reaction zone is from about 150° C. to about 250° C.

7. The dehydrochlorination process of claim 6 wherein the temperature in the reaction zone is from about 175° C. to about 225° C.

8. The dehydrochlorination process of claim 1 wherein the product selectivity to RfCCl═CH2 is at least 90 mole %.

9. The dehydrochlorination process of claim 1 wherein the product selectivity to RfCCl═CH2 is at least 96 mole %.

10. The dehydrochlorination process of claim 1 wherein the dehydrochlorination selectivity to RfCCl═CH2 is at least 95 mole %.

11. The dehydrochlorination process of claim 1 wherein Rf is CF3.

12. The dehydrochlorination process according to claim 1 wherein the catalyst contains from about 10 wt % to about 30 wt % alkali metal halide salt based on the total amount of alkali metal halide salt and carbon.

13. A dehydrochlorination process comprising contacting RfCHClCH2Cl with a catalyst in a reaction zone to produce a product mixture comprising RfCCl═CH2, wherein said catalyst comprises MY supported on carbon, and wherein Rf is a perfluorniated alkyl group, M=K, Na or Cs, and Y=F, Cl or Br, wherein the product selectivity to RfCCl═CH2 is at least 90 mole %.

14. The dehydrochlorination process of claim 13 wherein the carbon is an activated carbon.

15. The dehydrochlorination process of claim 14 wherein the carbon is an acid washed activated carbon.

16. The dehydrochlorination process of claim 13 wherein M is K and Y is F or Cl.

17. The dehydrochlorination process of claim 13 wherein the temperature in the reaction zone is from about 140° C. to about 400° C.

18. The dehydrochlorination process of claim 17 wherein the temperature in the reaction zone is from about 150° C. to about 250° C.

19. The dehydrochlorination process of claim 18 wherein the temperature in the reaction zone is from about 175° C. to about 225° C.

20. The dehydrochlorination process of claim 13 wherein the product selectivity to RfCCl═CH2 is at least 96 mole %.

21. The dehydrochlorination process of claim 13 wherein the dehydrochlorination selectivity to RfCCl═CH2 is at least 95 mole %.

22. The dehydrochlorination process of claim 13 wherein Rf is CF3.