Claims
- 1. A process for removing an unsaturated hydrocarbon containing at least one non-aromatic unsaturated bond from a feedstream containing said unsaturated hydrocarbon and saturated hydrocarbons, said process comprising contacting said feedstream with a mixture consisting essentially of an organic solvent or diluent and a compound of the formula: ##STR22## wherein R.sub.1 is trichloromethyl or R.sub.F ; R.sub.F is C.sub.n F.sub.2n+1 and n is 1-8; R.sub.2 is H or hydrocarbyl of 2-20 carbon atoms having at least one olefinic unsaturated bond; R.sub.3 is hydrocarbyl of 2-20 carbon atoms having at least one olefinic unsaturated bond and M.sup.I is Cu.sup.I or Ag.sup.I, whereby said compound selectively absorbs the unsaturated hydrocarbon.
- 2. A process in accordance with claim 1 wherein said compound is present in an organic solvent.
- 3. A process in accordance with claim 2 wherein said organic solvent is selected from the group consisting of ethylbenzene, toluene and cymene.
- 4. A process in accordance with claim 1 wherein said compound is present in an inert diluent.
- 5. A process in accordance with claim 1, wherein the feedstream is contacted with copper(I) 1,1,1-trifluoro-8,12-dimethyl-trans-7,11-tridecadiene-2,4-dioneate in an organic solvent.
- 6. A process in accordance with claim 1 wherein the feedstream is contacted with cooper(I), 1,1,1-trifluoro-8-methyl-7-nonene-2,4-dioneate in an organic solvent.
- 7. A process in accordance with claim 1 wherein the unsaturated hydrocarbon is 1-alkene.
- 8. A process in accordance with claim 1 wherein the unsaturated hydrocarbon is propylene.
- 9. A process in accordance with claim 1 wherein the unsaturated hydrocarbon is acetylene.
CROSS REFERENCE TO PARENT APPLICATION
This is a continuation-in-part of U.S. application Ser. No. 07/167,605 filed 14 Mar. 1988 now U.S. Pat. No. 4,845,254, which is a divisional of U.S. application Ser. No. 07/083,742 filed 7 Aug. 1987, now abandoned. The subject matter of both which is hereby incorporated by reference.
This invention relates to novel metal-containing complexes, which selectively absorb carbon monoxide or olefinically-unsaturated compounds from feedstreams.
Carbon monoxide is produced in a variety of incomplete oxidation processes. It appears in refinery off gas, methanol plant purge gas, blast furnace gas, water gas, coke oven gas and the gaseous effluent of steam reforming of methane. It would be highly desirable to isolate and use this carbon monoxide as a feedstock for other processes, for example, in making acetic acid. Methods for separating carbon monoxide from gas mixtures have been developed, including cryogenic distillation methods. These procedures are expensive. Therefore, there is a need for economical chemical processes for removing carbon monoxide from feed streams and recovering relatively pure carbon monoxide at the end of the separation process. Chemical separation processes are accordingly based on reversible binding of carbon monoxide with an absorbent, which will release carbon monoxide under appropriate conditions.
The separation of olefins from other hydrocarbons, including saturated hydrocarbons and aromatic hydrocarbons, is also of commercial interest. Although this can be accomplished by distillation, there is considerable interest in chemical processes, depending on selective complexation of one of a mixture of unsaturated hydrocarbons with an absorbent, which will release the hydrocarbon of interest under selected conditions.
The use of various metallic complexes has been investigated for the separation of both carbon monoxide and olefins from feed streams.
Doyle (U.S. Pat. No. 4,385,005) has proposed the use of a mixture of copper(I) or silver(I) oxide and a perfluorinated acetylacetonate to remove unsaturated hydrocarbons from feedstreams.
Carbon monoxide and alkene derivatives of copper(I) and silver(I) beta-diketonates hae been reported by Doyle et al., Organometallics, vol. 4 (1985), pages 830-835. These complexes are of varying stability with respect to air oxidation and disproportionation, but are insensitive to moisture.
Doyle has proposed in U.S. Pat. No. 4,279,874, using Cu(I) halogenated acetylacetonate complexes for the separation of carbon monoxide from a gas stream.
The use os Cu(I) complexes of fluorinated acetylacetone in an organic solvent for the removal of unsaturated hydrocarbons from feedstreams has been proposed by Doyle et al. in U.S. Pat. Nos. 4,434,317 and 4,508,694. The use of a stabilized cuprous fluorinated acetonylacetonate is proposed by Doyle et al. in U.S. Pat. No. 4,471,152.
Long et al. (U.S. Pat. No. 3,592,865) have recited using cuprous aluminum halide complexes to remove complexible ligands from feedstreams.
Walker, "Making and using CO," Chemtech (May, 1975), pages 308-311, has described the Cosorb purification process for separating carbon monoxide from gaseous mixtures, including streams rich in nitrogen. The process relies on stabilization of the active component, cuprous tetrachloroaluminate, in an aromatic solvent.
Dunlop et al, in U.S. Pat. No. 3,401,112, have recited separating hydrocarbons of various kinds of unsaturation using cuprous salts of oxyacids.
References suggesting the state of the art of metal complexes, using organic or inorganic copper(I) or silver(I) compounds, include:
In one aspect, this invention relates to novel unsaturated trichloromethyl or perfluoroalkyl diketones of the formula ##STR2## wherein R.sub.1 is trichloromethyl or R.sub.F ; R.sub.F is C.sub.n F.sub.2n+1 and n is 1-8; and R.sub.3 is hydrocarbyl of 2-20 carbon atoms having at least one olefinic unsaturated bond.
In another aspect, this invention relates to Cu.sup.I or Ag.sup.I complexes of perfluoroalkyl diketonate compounds, having the formula ##STR3## wherein R.sub.1 and R.sub.3 are as above, M.sup.I is Cu.sup.I or Ag.sup.I and R.sub.2 is H or hydrocarbyl of 2-20 carbon atoms having at least one olefinic unsaturated bond.
This invention further relates to a process for removing carbon monoxide or an unsaturated hydrocarbon containing at least one olefinic unsaturated bond from a feedstream by contacting the feedstream with a metal-diketonate compound, as above, in an inert organic solvent or vehicle.
In yet another aspect, this invention relates to compounds of the formula ##STR4## wherein R.sub.F' and R.sub.F" are independently selected from perfluoroalkyl of 1-8-carbon atoms and R is hydrocarbyl of 2-20 carbon atoms having at least one olefinic unsaturated bond.
This invention further relates to novel metal-diketone compounds of the formula ##STR5## wherein R.sub.F', R.sub.F", R and M.sup.I are as above, as well as to their use as absorbents for carbon monoxide and olefins in feed streams.
In a further aspect, this invention relates to a process for making compounds of the formula ##STR6## wherein R.sub.1, R.sub.2 and R.sub.3 are as above, comprising the steps of:
The trichloromethyl or perfluoroalkyl diketones of this invention can exist in two tautomeric forms, enol or ketone, corresponding to ##STR7## and ##STR8## Alternatively, the tautomeric mixture can be represented by the formula ##STR9##
The perfluoroalkyl or trichloromethyl diketones are made from an unsaturated ketone of the formula R.sub.2 CH.sub.2 COR.sub.3, wherein R.sub.2 and R.sub.3 are as above. This is converted to a lithio derivative, represented by the formula R.sub.2 CHLiCOR.sub.3 by reaction with lithium diisopropylamide under anhydrous conditions. The resulting anion .sup.- R.sub.2 CHCOR.sub.3 adds to the carbonyl of R.sub.F COOalk or CCl.sub.3 COOalk to produce a beta-diketonate, which is protonated to the desired product, that is, to R.sub.1 COCHR.sub.2 COR.sub.3.
Preferred diketone derivatives of this invention are those derived from trifluoroacetylacetone. It is therefore preferred to react a lithiated unsaturated ketone with a trifluoracetate ester, most preferably with ethyl trifluoroacetate. It is preferred to carry out reactions in which R.sub.2 CCH.sub.2 COR.sub.3 is 5-hexen-2-one, 6-methyl-5-hepten-2-one, geranyl acetone, neryl acetone, 3-prenyl-2-decanone or farnesyl acetone. In each of these cases, R.sub.2 is H.
Preferred compounds of this invention include, but are not limited to:
1,1,1-trifluoro-7-octene-2,4-dione (ATFAC, allyltrifluoroacetoacetate), R.sub.1 is CF.sub.3, R.sub.2 is H and R.sub.3 is 1-butenyl, having the structure (enol form) ##STR10##
1,1,1-trifluoro-8-methyl-7-nonene-2,4-dione (OTFAC, olefin-trifluoroacetoacetate), R.sub.1 is CF.sub.3, R.sub.2 is H and R.sub.3 is 2-methyl-2-pentenyl, having the structure ##STR11##
1,1,1-trifluoro-5-prenyl-dodecane-2,4-dione (HOTFAC, heptylated olefin-trifluoroacetoacetate), R.sub.1 is CF.sub.3, R.sub.2 is H and R.sub.3 is 5-(2-methyl-2-dodecenyl), having the structure ##STR12##
1,1,1-trifluoro-8,12-dimethyl-trans-7,11-tridecadiene-2,4-dione (GTFAC, geranyltrifluoroacetoacetate), R.sub.1 is CF.sub.3, R.sub.2 is H and R.sub.3 is (E)-2,6-dimethyl-2,6-nonadienyl, having the structure ##STR13##
1,1,1-trifluoro-8,12-dimethyl-cis-7,11-tridecadiene-2,4-dione (NTFAC, neryltrifluoroacetetoacetate), R.sub.1 is CF.sub.3, R.sub.2 is H and R.sub.3 is (Z)-2,6-dimethyl-2,6-nonadienyl, having the structure ##STR14## and 1,1,1-trifluoro-8,12,16-trimethyl-7,11,15-heptadecatriene-2,4-dione (FTFAC, farnesyltrifluoroacetoacetate), R.sub.1 is CF.sub.3, R.sub.2 is H and R.sub.3 is 2,6,10-trimethyl-2,6,10-tridecatrienyl (mixed EE, EZ, ZE and ZZ isomers), having the structure ##STR15## It will be understood that many of the compounds of this group contain a prenyl substituent and that compounds, containing a prenyl fragment, --CH.sub.2 CH.dbd.C(CH.sub.3).sub.2, are among preferred TFAC-derived diketones.
The TFAC-derived diketones are converted to corresponding M.sup.I salts by reaction with a monovalent metal compound, preferably a compound of Cu.sup.I or Ag.sup.I. It is preferred to use cuprous oxide, Cu.sub.2 O, of very high purity. It is most preferred to use Cu.sub.2 O exceeding 99.9% purity. In order to obtain good yields of corresponding Cu.sup.I -diketone compounds, it is preferred to use about half an equivalent of Cu.sup.I compound to TFAC-derived diketone. The structure of the monovalent metal salts can be represented by the formula: ##STR16##
The M.sup.I complexes of R.sub.1 COCHR.sub.2 COR.sub.3 are useful as absorbents for carbon monoxide and for hydrocarbons having at least one olefinically-unsaturated bond. The Cu.sup.I complexes are particularly preferred for the absorption of carbon monoxide, olefins or acetylenes from feedstreams.
Solutions or slurries of the absorbent complexes in an organic solvent are contacted with a stream containing carbon monoxide, an olefin or an acetylenic compound. The complexes bind carbon monoxide, the olefin or the acetylenic compound. The complexes, containing bound carbon monoxide, olefin or acetylenic compound, are isolated from the feed stream and further treated by heating or pressure reduction, or both, to liberate bound carbon monoxide, olefin or acetylenic compound. The complexes of this invention therefore provide an effective means for removal of carbon monoxide, olefins or acetylenic compounds from feed streams especially for the removal of unsaturated hydrocarbons from saturated hydrocarbons.
Most preferred absorbent compounds are Cu.sup.I complexes from 1,1,1-trifluoro-8,12-dimethyl-trans-7,11-tridecadiene-2,4-dione (GTFAC) and from 1,1,1-trifluoro-8-methyl-7-nonene-2,4-dione (OTFAC). The M.sup.I complexes are used for absorption of carbon monoxide or olefins in an inert organic solvent or diluent, particularly in ethylbenzene, toluene, cymene or the like.
An unexpected feature of the Cu.sup.I+- R.sub.1 COCR.sub.2 COR.sub.3 complexes is the low heat of absorption, about -2 to -3 kcal/mol. The complexes are therefore very acceptable absorbents for carbon monoxide and olefins in feed streams.
Other compounds of this invention, useful as absorbents for carbon monoxide and olefins or other non-aromatic unsaturated hydrocarbons are those derived from diketones of the formula ##STR17##
Compounds of this group can be made from a silver salt of a perfluorodiketone and an unsaturated halide, for example, allyl bromide. The following is typical of processes for making compounds of this type: ##STR18##
The diketones can be converted to Cu.sup.I or Ag.sup.I complexes by the same methods used for the TFAC-derived diketones. A most preferred compound of this series is a compound in which R.sub.F' and R.sub.F" each are trifluoromethyl and R is allyl. A most preferred metal derivative is the Cu.sup.I derivative.
US Referenced Citations (7)
Non-Patent Literature Citations (12)
| Entry |
| Doyle (et al.), Organometallics, 1985, vol. 4, 830-835. |
| Doyle et al., "Alkene and Carbon Monoxide Derivatives of Copper(I) and Silver(I) B-Diketonates"-Organometallics, 1985, vol. 4, pp. 830-835. |
| D. G. Walker, "Making and Using CO", CHEMTECH, May 1975, pp. 308-311. |
| M. Bertholef, "Observation Relatives a Lasction des Sels Cuivreux sur les Carbures D'hychogene et sur L'oryde de Carbon," Ann. de Chim. et de Phys., 7th Series, vol. XXIII (May, 1901), pp. 32-39. |
| M. I. Bruce, "Carbonyl Chemistry of the Group IB Metals," J. Organometal Chem., vol. 44 (1972), pp. 209-228. |
| I. R. Gilliland et al, "Reaction of Olefins with Solid Cuprous Halides," J. Am. Chem. Soc., vol. 61 (1939), pp. 1960-1962; ibid., vol. 63 (1941), pp. 2088-2090. |
| R. J. Hurtada, "Copper (I) Nitrile Complexes Part III, Reversible Olefin Complex Formation with Acetonitrilecopper (I) Trifluoromethanesulfonate", Transition Met. Chem., vol. 2 (1977), pp. 91-94. |
| F. R. Hartley et al, "Influence of Solvent on the Stability of Silver(1)-Olefin Complexes", J. Chem. Soc. Dalton (1977), pp. 469-477. |
| J. Liebig, "Ueber die Constitution des Aethers und Seiner Vrbendungen", Ann. der Pharmacie, vol. IX (1834), pp. 1-39; Uever die Aethertheorie, in besonderer Rucksicht auf die vorhergrende Abhandlung Zeise's, ibid, vol. 23 (1837) pp. 12-42. |
| M. A. Ture et al, "Separation of 1,3 Butadiene from a Mixture of Other Hydrocarbons Using Cuprous Chloride," Sinet, Kauchuk, vol. 3, No. 6 (1934), pp. 19-29. |
| S. Winstein et al., "The Coordination of Silver Ion with Unsaturated Compounds", J. Am. Chem. Soc., vol. 60 (19328), pp. 836-847. |
| Y. Kanritori et al, "A New Convenient Synthetic Method for 3-Allyl-1,1,1-Trifluoroacetylacetone and Its Derivatives," Synthesis, Apr. 1986, pp. 340-342. |
Divisions (1)
|
Number |
Date |
Country |
| Parent |
83742 |
Aug 1987 |
|
Continuations (1)
|
Number |
Date |
Country |
| Parent |
167605 |
Mar 1988 |
|
Patent Grant
4943673
