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AssigneePetro-Tex Chemical Corporation
InventorsLouis J. Croce, Laimonis Bajars, Maigonis Gabliks
Estimating the term…
Copper chloride has been employed as a reagent for oxychlorination of hydrocarbons. It has now been found that a non-halide copper compound in combination with a rare earth compound is an excellent oxychlorination catalyst, e.g. a CuCO.sub.3 - CeO.sub.2 catalyst calcined at 900.degree. C. for 1 hour converted 99 mole % of ethylene fed at a selectivity of 100% to chlorinated products, principally vinyl chloride, ethyl chloride and dichloroethane.
In the process of oxychlorination of hydrocarbons comprising contacting in a vapor phase a hydrocarbon, hydrogen chloride or chlorine and oxygen at a temperature range of 200.degree. - 700.degree. C. in the presence of a catalyst wherein the improvement comprises employing a catalyst calcined at 600.degree. - 1100.degree. C. consisting of a non-halide copper component consisting of copper and an element selected from the group consisting of O, S. N. P, As, Sn, Pb, Fe, Cr, Mo, W, V, Ti and mixtures thereof and a rare earth compound component, wherein the rare earth is selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and mixtures thereof and the atomic ratio of rare earth to copper is in the range of 4 to 0.1:1.
Dependencies are inferred from the claim text.
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With oxygen as auxiliary reagent, e.g. oxychlorination: of hydrocarbons
Of the iron group metals or copper: combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
Acyclic or carbocyclic compounds
Chemical or physical processes
Term ended 6 Sep 1994 (estimated)
USPTO file history isn’t available for this patent, so only indexed dates are shown.
The present invention relates to a catalyst and process for oxychlorination of hydrocarbons.
This invention is applicable to the chlorination of paraffins, olefins, cycloolefins, acetylenes and aromatics. The term oxychlorination as used herein refers to a reaction in which the source of chlorine employed for the chlorination is gaseous hydrogen chloride which is made to give up its chlorine in useful form. Copper chloride with various modifiers has been employed to react with hydrogen chloride to make it give up its chlorine through a series of well known reactions. If it is considered that the copper chlorides employed in the prior art oxychlorinations of hydrocarbons are true reagents rather than catalysts, as is generally accepted, then the various chlorides involved in those reactions can be represented in the following typical reaction
Cu.sub.2 Cl.sub.2 +1/2O.sub.2 .fwdarw.CuO . CuCl.sub.2 1
These examples demonstrate the basic concept of the invention and show the improvement of the invention catalysts over the individual components. The conditions and results are set out in Table I. The results are set out as ##STR1## for each run at the indicated temperatures. This indicates:
TABLE I __________________________________________________________________________ Feed.sup.1 Conversion/Selectivity/Yield mole % Ex- Molar at .degree. C. Temperature ample Catalyst Composition Ratio 300 350 400 450 __________________________________________________________________________ 2.5/2.1 6.7/4.6 28/22 1 CuCO.sub.3 C.sub.2 .sup.=/O.sub.2 /HCl/He 1/0.5/2/2 83 95/80 69 97/67 80 76/1 -- 100/83 100/69 99+ /80 0.4/0.1 5.5/1.2 16/4.0 34/11 2 CeO.sub.2 on C.sub.2 .sup.=/O.sub.2 /HCl/He 1/0.5/1/2 23 99+ /23 22 91/20 25 84/21 33 77.25 AMC 99+/23 99/22 98/24 96/32 14/2.9 29/13 3 " C.sub.2 /O.sub.2 /HCl/He 1/1/2/4 -- -- 21 75/16 45 62/28 96/20 83/37 0.3/0.2 1.5/1.4 1.2/1.0 44/33 4 CuCO.sub.3 . C.sub.2 .sup.=/O.sub.2 /HCl/He 1/0.5/2/2 72 99/71 92 92/85 87 72/63 75 55/41 CeO.sub.2 99+/72 99+/91 99+/86 98/73 0.2/0.2 1.0/1.0 1.2/1.2 16/14 5 CuCO.sub.3 . C.sub.2 .sup.=/O.sub.2 /HCl/He 1/0.5/2/2 99 99+ /98 99 96/95 96 71/68 85 35/30 CeO.sub.2.sup. 100/99 100/99 99+/96 99/84 (1 hr at 900.degree. C) __________________________________________________________________________ .sup.1 GHSV = 100 .sup.2 AMC = 4 to 5 mesh alumina supports, Carborundum Company .sup.3 activated at 900.degree. C. for 1 hour in air C.sub.2 .sup.= = ethylene C.sub.2 = ethane
It is readily apparent from Table I that the catalyst composition according to the present invention are superior to the individual components thereof.