Patent Grant
10807925
The present invention relates to the dehydrohalogenation of a halogen-containing compound. The present invention further relates to the dehydrochlorination of a hydrochlorofluorocarbon to a fluorinated olefin.
Chlorine-containing compounds, such as chlorofluorocarbons (CFCs), have been employed as refrigerants, foam blowing agents, cleaning agents, solvents, heat transfer media, sterilants, aerosol propellants, dielectrics, fire extinguishing agents, and power cycle working fluids. However, CFCs have proven to be detrimental to the Earth's ozone layer. Conventional substitutes for CFCs include hydrofluorocarbons (HFCs); however, these compounds have been found to contribute to global warming. For these reasons, there is a worldwide effort to develop new compounds that are environmentally benign.
Partly or fully fluorinated olefins, including hydrofluoroolefins, (collectively referred to hereinafter as fluorinated olefins) are potential replacements for HFCs and CFCs. They can be used in some of the aforementioned applications and can also be used as feedstock monomers to synthesize fluoropolymers and other macromolecular compounds.
Various methods for producing certain fluorinated olefins are known, including those involving the dehydrochlorination of hydrochlorofluorocarbons. For example, U.S. patent application Ser. No. 11/619,592 discloses a method for preparing 2,3,3,3-tetrafluoropropene (1234yf) via dehydrochlorination of 1,1,1,2-tetrafluoro-2-chloropropane (244bb) with the aid of a catalyst. The 244bb reactant can be prepared through liquid phase or gas phase catalytic fluorination of 1,1,1-trifluoro-2-chloropropene (1233xf) with HF and 1233xf, in turn, can be made via gas phase fluorination of CCl2═CClCH2Cl (1,1,2,3-tetrachloropropene) with HF. The '592 application also teaches the use of a carbon- and/or metal-based catalyst for the conversion of 244bb to 1234yf. Depending on the reaction conditions, the conversion of 244bb could be as high as 98%, but has a selectivity for 1234yf of only 69% to 86%. Thus, there remains a need to develop a commercially viable catalyst that not only is active, but also is more selective for 1234yf.
However, the conversion of a hydrochlorofluorocarbon to a fluorinated olefin by conventional methods is problematic because by-products often form and undergo a competing dehydrofluorination reaction. Hence, it would be advantageous to develop a catalyst system that can suppress undesirable dehydrofluorination reactions, so that single-pass productivity and yield of the desired fluorinated olefin can be increased.
According to the present invention, provided a process for making a fluorinated olefin via dehydrochlorination of a hydrochlorofluorocarbon having at least one hydrogen atom and at least one chlorine atom on adjacent carbon atoms. The dehydrochlorination is carried out in the presence of a catalyst selected from the group consisting of (i) one or more metal halides, (ii) one or more halogenated metal oxides, (iii) one or more zero-valent metals/metal alloys, and (iv) a combination of two or more of the foregoing. Preferred fluorinated olefin products are the following: 2,3,3,3-tetrafluoropropene (1234yf), 1,3,3,3-tetrafluoropropene (trans/cis-1234ze), 1,2,3,3,3-pentafluoropropene (Z/E-1255ye), 1,1,3,3,3-pentafluoropropene (1225zc), and 1,1,2,3,3,3-hexafluoropropene (1216).
In the present invention, a hydrochlorofluorocarbon having at least one hydrogen and at least one chlorine on adjacent carbons is dehydrochlorinated in the presence of a catalyst to form a product having a fluorinated olefin therein. Table 1 sets forth examples of fluorinated olefins and precursor hydrochlorofluorocarbons from which they can be obtained (i.e., hydrochlorofluorocarbon in left column and corresponding fluorinated olefin in the right column).
In the process of the present invention, selected catalysts are employed to enhance the selectivity and/or conversion of hydrochlorofluorocarbons to fluorinated olefins. The catalysts are more selective for the dehydrochlorination reaction, which produces fluorinated olefin, than for the competing dehydrofluorination side reaction, which produces the undesirable byproduct chlorine-containing olefin.
There are three preferred classes of catalysts useful in the present invention: (i) metal halides, (ii) halogenated metal oxides, and (iii) zero-valent metals/metal alloys.
The first class of catalysts is metal halides, preferably mono-, bi-, and tri-valent metal halides and their mixtures/combinations, and more preferably mono- and bi-valent metal halides and their mixtures/combinations. Component metals include, but are not limited to, Cr3+, Fe3+, Mg2+, Ca2+, Ni2+, Zn2+, Pd2+, Li+, Na+, K+, and Cs+. Component halogens include, but are not limited to, F−, Cl−, Br−, and I−. Examples of useful mono- or bi-valent metal halide include, but are not limited to, LiF, NaF, KF, CsF, MgF2, CaF2, LiCl, NaCl, KCl, and CsCl. The catalyst may be supported or unsupported. A preferred catalyst is a CsCl/MgF2 combination. A particularly preferred catalyst is a CsCl/MgF2 combination wherein CsCl is present in an amount of about 5.0 to about 50 wt % based on the total weight of the catalyst.
The second class of catalysts is halogenated metal oxides, preferably halogenated mono-, bi-, and tri-valent metal oxides and their mixtures/combinations, and more preferably halogenated mono- and bi-valent metal oxides and their mixtures/combinations. Component metals include, but are not limited to, Cr3+, Fe3+, Mg2+, Ca2+, Ni2+, Zn2+, Pd2+, Li+, Na+, K+, and Cs+. Halogenation treatments can include any of those known in the prior art, particularly those that employ HF, F2, HCl, Cl2, HBr, Br2, HI, and I2 as the halogenation source. Examples of useful halogenated mono- and bi-valent metal oxides include, but are not limited to, fluorinated or chlorinated MgO, fluorinated or chlorinated CaO, fluorinated or chlorinated Li2O, fluorinated or chlorinated Na2O, fluorinated or chlorinated K2O, and fluorinated or chlorinated Cs2O. The catalyst may be supported or unsupported.
The third class of catalysts is neutral (i.e., zero valent) metals, metal alloys, and their mixtures. Useful metals include, but are not limited to, Pd, Pt, Rh, Fe, Co, Ni, Cu, Mo, Cr, Mn, and combinations of the foregoing as alloys or mixtures. The catalyst may be supported or unsupported. Useful examples of metal alloys include, but are not limited to, SS 316, Monel 400, Inconel 825, Inconel 600, and Inconel 625.
In addition to the fluorinated olefin, i.e., the hydrofluorocarbon or fluorocarbon, the product mixture may also have unconverted hydrochlorofluorocarbon and hydrogen chloride.
Enhanced or improved selectivity for the target product is an important feature of the present invention. The dehydrochlorination reaction is preferably carried out at a selectivity of at least about 50%, more preferably at least about 70%, and most preferably at least about 80%. Conversion is preferably about 25% or more and most preferably about 40% or more.
Dehydrochlorination may be carried out at a temperature range of about 200° C. to about 800° C., preferably from about 300° C. to about 600° C., and more preferably from about 400° C. to about 500° C. in the presence of a catalyst. It is contemplated that a variety of reaction pressures may be used, such as superatmospheric, atmospheric, and subatmospheric. Atmospheric pressure is preferred.
Dehydrochlorination may optionally be carried out in presence or absence of an oxidizing agent. Useful examples of oxidizing agents include, but are not limited to, oxygen and carbon dioxide. Use of an oxidizing agent can extend the life of the catalyst. The oxidizing agent can be pure or diluted with an inert gas such as nitrogen before being introduced into reactor. The level of oxidizing agent is generally from about 1% to about 10% by volume and preferably from about 2% to 5% by volume based on the volume of the organic feed.
It may also be advantageous to periodically regenerate the catalyst after prolonged use while in place in the reactor. Regeneration of the catalyst may be accomplished by any means known in the art. One method is by passing oxygen or oxygen diluted with nitrogen over the catalyst at temperatures of about 200° C. to about 600° C. (preferably about 350° C. to about 450° C.) for about 0.5 hour to about 3 days followed by either halogenation treatment at temperatures of about 25° C. to about 400° C. (preferably about 200° C. to about 350° C.) for halogenated metal oxide catalysts and metal halide ones or reduction treatment at temperatures of about 100° C. to about 600° C. (preferably about 200° C. to about 350° C.) for metal catalysts.
Dehydrochlorination is preferably carried out in a corrosion-resistant reaction vessel. Examples of corrosion-resistant materials are Hastelloy, Inconel, Monel and fluoropolymer linings. The vessel may have a fixed or a fluidized catalyst bed. If desired, inert gases such as nitrogen or argon may be employed in the reactor during operation.
The following are examples of the present invention and are not to be construed as limiting.
A series of mono-, bi-, and tri-valent metal fluorides and fluorinated bi- and tri-valent metal oxides were used as dehydrohalogenation catalysts. Approximately 20 cc of catalyst pellets was used in a typical run. A mixture containing 97.2 wt. % 244bb and 2.0 wt. % 1233xf was passed through the catalyst bed at a rate of 6 g/h at a temperature that ranged from 200° C. to 600° C. The temperatures at the bottom of catalyst bed and at the top of catalyst bed were measured.
As shown in Table 2, NaF, MgF2, CaF2, and fluorinated MgO were able to provide a selectivity to 1234yf higher than 80%, while FeF3 and fluorinated Cr2O3 exhibited a selectivity to 1233xf higher than 80%. Selectivity is based on mole percent. These results indicate that mono- and bi-valent metal halides as well as halogenated mono- and bi-valent metal oxides are more favorable than their trivalent counterparts as catalysts for 244bb dehydrochlorination. Among NaF, MgF2, CaF2, and fluorinated MgO, MgF2 exhibited the best performance; it provided a conversion of 244bb above 50% and a selectivity to 1234yf above 85% after 8 h (hours) on stream.
A series of alkaline metal chlorides were investigated as an additive to MgF2 with a purpose of improving the selectivity to 1234yf. For comparison purpose, the results obtained over MgF2 catalyst were also reported. Approximately 20 cc of catalyst pellets was used in a typical run. A mixture containing 97.2 wt. % 244bb and 2.0 wt. % 1233xf was passed through catalyst bed at a rate of 6 g/h (grams/hour) at a temperature that ranged from 470° C. to 520° C. The temperatures at the bottom of catalyst bed and at the top of catalyst bed were measured.
As shown in Table 3, the MgF2 provided a 244bb conversion of 53-55%, a 1234yf selectivity of 80-87%, and a 1233xf selectivity of 8-15%; the 10% LiCl/MgF2 provided a 244bb conversion below 45%, a 1234yf selectivity of about 90%, and a 1233xf selectivity of about 5%; the 10% KCl/MgF2 provided a 244bb conversion below 50%, a 1234yf selectivity of about 96%, and a 1233xf selectivity of about 1%; and the 10% CsCl/MgF2 provided a 244bb conversion of 50-52%, a 1234yf selectivity of about 97%, and essentially no formation of 1233xf. CsCl exhibited the best results, while the 10% CsCl/MgF2 catalyst provided activity comparable to MgF2 and the highest 1234yf selectivity while generating no 1233xf.
A series of CsCl/MgF2 catalysts with different loadings of CsCl were investigated with a purpose of optimizing CsCl loading. 20 cc of catalyst pellets was used in a typical run. A mixture containing 97.2 wt. % 244bb and 2.0 wt. % 1233xf was passed through the catalyst bed at a rate of 6 g/h at a temperature that ranged from 470° C. to 520° C. The temperatures at the top and bottom of the catalyst bed were measured. As shown in Table 4, the selectivity to 1233xf decreased with increasing CsCl loading from 0.0 to 5.0 wt %, and no 1233xf was formed over catalysts with CsCl loadings ≥7.5 wt % based on the total weight of the catalyst.
A series of non-precious metals were investigated as additives to MgF2 with a purpose of improving the selectivity to 1234yf. For comparison purposes, the results obtained over MgF2 catalyst were also reported. Approximately 20 cc of catalyst pellets was used in a typical run. A mixture containing 97.2 wt. % 244bb and 2.0 wt. % 1233xf was passed through catalyst bed at a rate of 6 g/h at a temperature that ranged from 440 to 540° C. The temperatures at the top and bottom of the catalyst bed were measured.
As shown in Table 5, the addition of cobalt and especially nickel resulted in the decrease in the selectivity to 1233xf, while the addition of iron resulted in an increase in the selectivity to 1233xf. The 12 wt % Ni/MgF2 catalyst provided a 1234yf selectivity of about 95% with a 1233xf selectivity of about 2%.
A series of supported and unsupported metals as well as metal alloys were used as dehydrohalogenation catalysts. 20 cc of catalyst pellets or a 4 inch-long metal mesh roll was used in a typical run. A mixture containing 97.2 wt. % 244bb and 2.0 wt. % 1233xf was passed through a catalyst bed at a rate of 6 g/h at a temperature ranged from 420° C. to 480° C. The temperatures at the top and bottom of the catalyst bed were measured. As shown in Table 6, all the metal and metal alloy catalysts were active and extremely selective for 244bb dehydrochlorination (1234yf selectivity >95%) while generating no 1233xf. Compared to metal halide and/or halogenated metal oxide catalysts, the metal catalysts did not require as high an operating temperature.
It should be understood that the foregoing description is only illustrative of the present invention. Various alternatives and modifications can be devised by those skilled in the art without departing from the invention. Accordingly, the present invention is intended to embrace all such alternatives, modifications and variances that fall within the scope of the appended claims.
This application is a division of U.S. application Ser. No. 12/167,159, filed Jul. 2, 2008 (now U.S. Pat. No. 9,040,759, issued May 26, 2015), which application claims priority to, and incorporates by reference, U.S. Provisional Application No. 60/958,468, filed Jul. 6, 2007.
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| 2765350 | Conrad | Oct 1956 | A |
| 2774799 | Mantell | Dec 1956 | A |
| 3183277 | Kuhn | May 1965 | A |
| 3444251 | Gardner | May 1969 | A |
| 3691240 | Kircher, Jr. | Sep 1972 | A |
| 5180860 | Fernandez | Jan 1993 | A |
| 8053612 | Wang | Nov 2011 | B2 |
| 8648222 | Wang | Feb 2014 | B2 |
| 9040759 | Wang | May 2015 | B2 |
| 20070112230 | Mukhopadhyay | May 2007 | A1 |
| 20070129579 | Wang | Jun 2007 | A1 |
| Number | Date | Country |
|---|---|---|
| 902682 | Aug 1962 | GB |
| Number | Date | Country | |
|---|---|---|---|
| 20150368169 A1 | Dec 2015 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60958468 | Jul 2007 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12167159 | Jul 2008 | US |
| Child | 14721575 | US |
