Preparation of high surface area metal fluorides and metal oxyfluorides, especially aluminum fluoride extrudates

Abstract

A method is described for the preparation of high surface area metal fluorides and metal oxyfluorides comprising reacting high surface area metal oxides with a fluorocarbon vapor wherein the fluorocarbon is selected from the group consisting of CH.sub.4-Q F.sub.Q wherein Q is 1 to 3 and totally or partially fluorinated C.sub.2 -C.sub.6 alkanes, alkenes and alkynes and C.sub.5 -C.sub.6 cyclic alkanes, preferably fluoroform (CHF.sub.3) wherein the metal oxides and the fluorocarbon vapors are contacted at a temperature of from about 300.degree. to about 800.degree. C., for a time sufficient to effect the essentially complete conversion of the metal oxides into metal fluorides or the partial conversion of the metal oxides into metal oxyfluorides. The metal oxides converted into metal fluorides may be selected from the group consisting of the oxides of sodium, potassium, lithium, cesium, magnesium, calcium, barium, strontium, tin, antimony, bismuth, titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, rhodium, mercury, nickel, copper, silver, zinc, cadmium, lead, uranium, europium, indium, lutetium, neodymium, thallium and mixtures thereof. The metal oxides converted into metal oxyfluorides may be selected from the group recited above and further include silicon, niobium, hafnium, tantalum, molybdenum, tungsten, technetium, rhenium, osmium, iridium, lanthanum and ruthenium. The above metal oxides may also be utilized in combination with alumina and silica. The fluorocarbon partial pressure in the treatment vapor may be in the range of from about 0.001 to about 100 atmosphere. By the practice of the instant invention high surface area metal fluoride extrudates are prepared by the conversion of metal oxide extrudate, particularly aluminum fluoride extrudates from alumina extrudates.

Description

DESCRIPTION OF THE INVENTION

A process is described for the preparation of high surface area metal fluorides comprising reacting high surface area metal oxides selected from the group consisting of the oxides of magnesium, sodium, potassium, lithium, cesium, calcium, barium, strontium, tin, antimony, bismuth, titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, rhodium, mercury, nickel, copper, silver, zinc, lead, cadmium, uranium, europium, indium, lutetium, neodymium, thallium and mixtures thereof, preferably titanium, magnesium, uranium, nickel, cobalt and zirconium, more preferably titanium, magnesium and uranium, most preferably titanium with a fluorocarbon vapor wherein the fluorocarbon is selected from the group consisting of CH.sub.4-Q F.sub.Q wherein Q is 1-3 and totally or partially fluorinated C.sub.2 -C.sub.6 alkanes, alkenes and alkynes and C.sub.5 -C.sub.6 cyclic alkanes, preferably fluoroform and straight and branch chain C.sub.2 -C.sub.6 fluorocarbons of the general formula:

C.sub.A H.sub.2A+2-B F.sub.B wherein A is an integer ranging from 2 to 6 inclusive, preferably 2 to 3, and B is an integer ranging from 1 to 14 and cyclic fluorocarbons of the formula: C.sub.X H.sub.2X-C F.sub.C wherein X is 5 or 6 and C is an integer ranging from 1 to 12, most preferably fluoroform (CHF.sub.3) wherein the metal oxides and the fluorocarbons are contacted at a temperature of from about 300.degree. to about 800.degree. C., preferably about 300.degree. to about 600.degree. C., most preferably about 350 .degree. to about 550.degree. C., at a fluorocarbon partial pressure of from about 0.001 to about 100 atmosphere, preferably about 0.01 to about 10 atmospheres, most preferably about 0.1 to about 1 atmosphere, for a time sufficient to effect the desired level of conversion of the metal oxide into metal fluoride. Alternatively, the metal oxide recited above may be used in combination with alumina or silica to give, for example, metal fluoride-aluminum fluoride mixtures. An inert diluent gas such as hydrogen, helium, nitrogen or argon can be used. When liquid fluorocarbons are used as the source of fluorine, the inert gas may be bubbled through the fluorocarbon liquid resulting in the formation of a fluorocarbon vapor-inert gas mixture which is contacted with the subject metal oxide.

Materials exhibiting the essential complete conversion of the metal oxide into metal fluorides can be obtained by the practice of the instant invention. It is also possible to obtain materials exhibiting lower levels of conversion when such are desired. Such metal oxyfluorides are prepared from the metal oxides recited above and further include the oxides of silicon, niobium, hafnium, tantalum, molybdenum, tungsten, technetium, rhenium, osmium, iridium, lanthanum and ruthenium.

It has also been discovered that by the practice of the instant invention materials such as AlF.sub.3 extrudates having high surface area and high purity are fabricated from Al.sub.2 O.sub.3 extrudates. The AlF.sub.3 extrudates unexpectedly retain the configuration, dimensions, and strength of the Al.sub.2 O.sub.3 extrudate starting material. AlF.sub.3 prepared by prior art methods and available commercially is a fine powder which cannot be extruded or pelletized and consequently cannot be used in commercial catalytic units requiring such configurations and structural strength. Commercially available AlF.sub.3 is also characterized by very low BET surface areas, normally less than about 5 m.sup.2 /gm. By way of contrast, the AlF.sub.3 extrudates prepared by the instant process possesses surface area ranging from 10 to 50 m.sup.2 /gm. The instant invention prepared AlF.sub.3 extrudates are obtained in very high purity (greater than 95%). The AlF.sub.3 extrudates and the other metal fluorides and mixed metal fluorides prepared by the process of the instant invention can be used in solid acid catalyzed hydrocarbon conversion processes with or without the presence of an added metal component. The high surface area AlF.sub.3 in extrudate form (by conversion of Al.sub.2 O.sub.3 extrudates) and other metal fluorides prepared by the conversion of the corresponding metal oxide or mixed metal oxide can be used as a support for a variety of added metals (Groups V, VI, VII, VIII and IB) and would have application in numerous catalytic hydrocarbon conversion processes.

BACKGROUND OF THE INVENTION

As an article of commerce anhydrous AlF.sub.3 is a white crystalline solid which sublimes at 1290.degree. C./760 mm. It is most conveniently prepared by fluoriding Al.sub.2 O.sub.3 with gaseous or aqueous HF (1)

Al.sub.2 O.sub.3 +6 HF.fwdarw.2AlF.sub.3 +3H.sub.2 O (1) or by allowing an aluminum hydrate to react with ammonium bifluoride (2) Al(OH).sub.3 +3NH.sub.4 HF.sub.2 .fwdarw.AlF.sub.3 +3NH.sub.4 F+3H.sub.2 O (2) in solution or in the solid state. The reactions summarized in equations 1 and 2 are normally conducted at temperatures of about 600.degree. C. and higher. The anhydrous AlF.sub.3 thus produced is typically in the form of a very fine powder. Detailed discussions of the common commercial methods of AlF.sub.3 preparation may be found in either Kirk-Othner Encyclopedia of Chemical Technology, Second Edition, Vol. 9, Wiley, New York, pgs. 527-547; or G. N. Kannan, Indian Chem. J. 4, 22, 1969. Commercially available AlF.sub.3 ranges from 60-90% AlF.sub.3, the major impurities being H.sub.2 O, Al.sub.2 O.sub.3 and mixed aluminum hydroxyfluorides. Commercially available AlF.sub.3 is of limited value in catalytic operations since the fine powder cannot be satisfactorily compacted or extruded into self-supporting pellets. Also in many catalytic applications unreacted Al.sub.2 O.sub.3 cannot be tolerated.

THE INVENTION

High surface area metal fluorides of the formula MF.sub.y wherein M is a metal selected from the group consisting of magnesium, sodium, potassium, lithium, cesium, calcium, barium, strontium, tin, antimony, bismuth, titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, rhodium, mercury, nickel, copper, silver, zinc, cadmium, lead, uranium, europium, indium, lutetium, neodymium, thallium and mixtures thereof, preferably, titanium, magnesium, uranium, nickel, cobalt and zirconium most preferably titanium, magnesium and uranium and y is a number satisfying the valence requirements of the metal, are prepared by reacting a metal oxide selected from the group consisting of the oxides of the metals recited above with a fluorocarbon vapor wherein the fluorocarbon is selected from the group consisting of CH.sub.4-Q F.sub.Q wherein Q is 1-3 and totally and partially fluorinated C.sub.2 -C.sub.6 alkanes, alkenes and alkynes and C.sub.5 -C.sub.6 cyclic alkanes, preferably fluoroform and straight and branch chain, C.sub.2 -C.sub.6 fluorocarbons of the general formula:

C.sub.A H.sub.2A+2-B F.sub.B wherein A is an integer ranging from 2 to 6 inclusive, preferably 2 to 3, and B is an integer ranging from 1 to 14 inclusive and cyclic fluorocarbons of the formula: C.sub.X H.sub.2X-C F.sub.C wherein X is 5 or 6 and C is 1 to 12, most preferably fluoroform wherein the metal oxides and the fluorocarbon vapor are contacted at a temperature of from about 300.degree. to about 800.degree. C., preferably from about 300.degree. to about 600.degree. C., most preferably from about 350.degree. to 550.degree. C. for a time sufficient to effect the essentially complete conversion of the metal oxide into metal fluoride. Metal oxyfluorides of the formula MO.sub.z F.sub.z-y wherein M is a metal selected from the group enumerated above and further including silicon, niobium, tantalum, molybdenum, tungsten, technetium, ruthenium, iridium, hafnium, rhenium, osmium and lanthanum, preferably titanium, magnesium, uranium, tantalum, tungsten, nickel, cobalt and molybdenum, most preferably titanium, magnesium, uranium and tungsten, z is a number satisfying the valence requirements of the metal and y is a number satisfying the valence requirements of the metal are prepared as described above, the contacting of the selected metal oxide with a fluorocarbon source as recited above being conducted at a temperature as stated above for a time sufficient to effect the partial conversion of the metal oxide into the metal oxyfluoride. Alternatively, the enumerated metal oxides may be mixed with added alumina or silica yielding for example, a metal fluoride-aluminum fluoride or metal oxyfluoride-aluminum oxyfluoride-mixture. The fluorocarbon vapor partial pressure may be in the range of from about 0.001 to about 100 atmospheres, preferably about 0.01 to about 10 atmospheres, most preferably about 0.1 to about 1 atmospheres.

In one embodiment of the instant invention, high surface area AlF.sub.3 extrudates are prepared by contacting high surface area Al.sub.2 O.sub.3 extrudates with a fluorocarbon vapor wherein the fluorocarbon is selected from the group consisting of CH.sub.4-Q F.sub.Q wherein Q is 1-3 and fully and partially fluorinated C.sub.2 -C.sub.6 alkanes. alkenes and alkynes and C.sub.5 -C.sub.6 alkanes, preferably fluoroform and straight or branch chain fluorocarbons of the formula:

C.sub.A H.sub.2A+2-B F.sub.B wherein A is an integer ranging from 2 to 6 inclusive, preferably 2 to 3, and B is an integer ranging from 1 to 14 inclusive and cyclic fluorocarbons of the formula: C.sub.X H.sub.2X-C F.sub.C wherein X is 5 or 6 and C is 1 to 12, most preferably fluoroform (CHF.sub.3), wherein the Al.sub.2 O.sub.3 extrudate and the fluorocarbons are contacted at a temperature of from about 300.degree. to about 800.degree. C., preferably about 300.degree. to about 600.degree. C. most preferably about 350.degree. to about 550.degree. C., at a fluorocarbon partial pressure of from 0.001 to 100 atmosphere, preferably 0.01 to 10 atmospheres, most preferably 0.1 to 1.0 atmosphere for a time sufficient to effect the essentially complete conversion of the Al.sub.2 O.sub.3 into AlF.sub.3. A diluent such as hydrogen He, N.sub.2 or Ar can be used. When a liquid fluorocarbon is used as the source of fluorine, the inert gas is bubbled through the fluorocarbon liquid resulting in formation of a fluorocarbon vapor-inert gas mixture which is contacted with the alumina extrudate. Essentially, 100% AlF.sub.3 extrudates are useful and unique as supports for catalytically active metals, for example, as supports for platinum and palladium. The specific benzene hydrogenation activities of Pt/AlF.sub.3 and Pd/AlF.sub.3 catalysts have been found to be comparable to those exhibited by the metals supported on Al.sub.2 O.sub.3 or SiO.sub.2.

EXPERIMENTS

Materials

An 1/6 inch .gamma.-Al.sub.2 O.sub.3 extrudate with a BET surface area of 178 was employed. Trifluoromethane (HCF.sub.3) and tetrafluoromethane (CF.sub.4) were used as supplied by the Matheson Gas Company. Hydrogen (Linde) was passed through a Deoxo unit and a molecular sieve drier prior to use. Helium (Bureau of Mines) was dried by passage through a molecular sieve drier. Aluminum fluoride samples were obtained from commercial sources.

Preparation of Aluminum Fluoride

The fluoridation of .gamma.-Al.sub.2 O.sub.3 with HCF.sub.3 takes place readily at temperatures above 350. The non-toxic and noncorrosive nature of HCF.sub.3 makes this fluoriding technique very attractive from the point of view of convenience and safety. The formation of AlF.sub.3 (rhomohedral form) from .gamma.-Al.sub.2 O.sub.3 is consistent with equation (3).

.gamma.-Al.sub.2 O.sub.3 +2HCF.sub.3 .fwdarw.2AlF.sub.3 +2CO+H.sub.2 O (3) The free energy of formation of AlF.sub.3 according to equation (3) is favorable by 111 kcal/mole. The reaction goes essentially to completion and is not greatly retarded at increasing conversion levels. HCF.sub.3 utilization at temperatures above 450.degree. C. is very nearly stoichiometric. The nearly stoichiometric fluoridation of .gamma.-Al.sub.2 O.sub.3 with HCF.sub.3 at 450.degree.-500.degree. C. and at CHF.sub.3 partial pressures of 0.33 atm to 0.11 atm is clearly illustrated in Table I. TABLE I__________________________________________________________________________FLUORIDATION OF .gamma.-Al.sub.2 O.sub.3 WITH HCF.sub.3.sup.(a) HCF.sub.3.sup.(b) Time Wt. Gm Wt. Gm % AlF.sub.3 BET.sup.(c)No. (cc/min) T .degree.C. (Hr) (Theoretical) (Found) (Theoretical) (m.sup.2 /gm)__________________________________________________________________________1 Starting .gamma.-Al.sub.2 O.sub.3 1782 25 497 0.125 20.3 20.3 3.46 1753 25 499 0.25 20.5 20.5 6.86 1714 50 503 0.25 21.1 20.9 13.3 1655 50 498 0.50 22.2 21.6 25.4 1466 50 450 0.50 22.2 22.1 25.4 1447 50 504 0.75 22.8 22.8 36.2 1358 50 504 1.00 24.4 24.3 46.1 969 50 501 1.50 26.6 26.2 63.5 7910 50 501 2.00 28.8 27.9 78.2 4711 50 501 3.00 32.9 31.7 100 8.712 100 504 1.50 32.9 31.6 100 8.9__________________________________________________________________________ .sup.(a) 20.0 gm of dry Al.sub.2 O.sub.3 extrudate was employed in each fluoridation experiment. The Al.sub.2 O.sub.3 extrudates were prereduced (20% H.sub.2 /He, 500 cc/min) at 500.degree. C. prior to fluoridation. .sup.(b) 200 cc/min of helium was employed as diluent in each fluoridatio experiment. 1.0 atm total pressure .sup.(c) surface areas were determined by the nitrogen BET method.

To further illustrate the method of the instant invention consider the following general procedure.

In a typical quartz tube furnace preparation of AlF.sub.3 100 gm of .gamma.-Al.sub.2 O.sub.3 extrudate was allowed to react with 40% HCF.sub.3 /He (500 cc/min, 1.0 atm) at 500.degree. C. for 5.0 hours. A yield of 158 gm (165 gm theoretical yield) of AlF.sub.3 extrudate was obtained. The progress of the reaction was conveniently monitored by visually following the evolution of H.sub.2 O vapor. Completion of the reaction was signalled by an abrupt cessation of H.sub.2 O vapor. No equipment corrosion problems were encountered. Caution should be exercised, however, as the exit gases may contain small quantities of HF or fluorine. The HCF.sub.3 treatment gas is non-toxic.

Tetrafluoromethane (CF.sub.4) was found to be ineffective in bulk fluoriding Al.sub.2 O.sub.3 at temperatures as high as 600.degree. C. Even in the presence of metals and/or oxygen no bulk fluoridation of Al.sub.2 O.sub.3 occurred at 600.degree. C. using CF.sub.4. Thus, when using fluoromethanes at least one reactive hydrogen must be initially present in the molecule.

The preferred fluorocarbons for the fluorination of Al.sub.2 O.sub.3 extrudates, are selected from the group consisting of CH.sub.4-Q F.sub.Q wherein Q is 1-3 and straight and branch chain fluorocarbons having the general formula

C.sub.A H.sub.2A+2-B F.sub.B wherein A is an integer ranging from 2 to 6 inclusive and B is an integer ranging from 1 to 14 cyclic fluorocarbons of the formula C.sub.X H.sub.2X-C F.sub.C wherein X is 5 or 6 and C is 1 to 12. The most preferred fluorocarbon, however, is HCF.sub.3.

A typical HCF.sub.3 prepared AlF.sub.3 sample (22.4 m.sup.2 /gm) was subjected to a TGA study in an attempt to determine the exact extent of fluoridation. A 95.1 mg sample was found to lose 89.4 mg between 1000.degree.-1200.degree. under a helium purge (40 cc/min, 1.0 atm). The weight loss was due to the sublimation of AlF.sub.3. The nonsublimable material was determined from an x-ray powder diffraction pattern to be .alpha.-Al.sub.2 O.sub.3. From the weight of the recovered .alpha.-Al.sub.2 O.sub.3 the concentration of AlF.sub.3 in a typical HCF.sub.3 prepared AlF.sub.3 is near 95%. The high purity of the CHF.sub.3 prepared AlF.sub.3 is in contrast to commercially available aluminum fluorides which assay between 60-90% AlF.sub.3. The major impurities present in commercial AlF.sub.3 are H.sub.2 O, Al.sub.2 O.sub.3 and mixed hydroxyfluorides. Such materials are not desired in numerous catalytic applications.

Physical and Chemical Properties of Aluminum Fluoride Physical Form of CHF.sub.3 prepared AlF.sub.3

Unexpectedly the fluoridation of an extruded .gamma.-Al.sub.2 O.sub.3 with HCF.sub.3 yield AlF.sub.3 in the form of an extrudate. The crush strength of the AlF.sub.3 extrudate was found to be comparable with that of starting .gamma.-Al.sub.2 O.sub.3 extrudates. This result is very significant since AlF.sub.3 powders cannot be compacted or extruded into self-supporting pellets without the addition of a binder. The addition of binders is to be avoided in numerous catalytic applications of AlF.sub.3.

The .gamma.-Al.sub.2 O.sub.3 extrudates have average dimensions of 0.073".times.0.4" (nominally 1/16" extrudate). Since the AlF.sub.3 products were found to have average dimensions of 0.071".times.0.4" no change in superficial extrudate volume occurred during fluoridation. This is surprising because the crystal density of AlF.sub.3 is less than that of .gamma.-Al.sub.2 O.sub.3, 3.2 and 3.7 gm/cc, respectively, and also because twice as many fluoride ions as oxide ions are required to complete the AlF.sub.3 crystal lattice. The retention of the .gamma.-Al.sub.2 O.sub.3 extrudate volume upon fluoridation can be accounted for by the following. The relationship between superficial extrudate, crystal and pore volumes is given by equation (4).

superficial extrudate volume=crystal volume+pore volume (4) The crystal volume is calculated from the weight of a given extrudate particle and the known crystal density of the extrudate material. An apparent pore volume is then obtained in a straight forward calculation. The average pore volume of a .gamma.-Al.sub.2 O.sub.3 (178 m.sup.2 /gm) was calculated to be 0.64.+-.0.04 cc/gm. This value is in reasonable agreement with the H.sub.2 O wettability (0.65 cc/gm) and N.sub.2 isotherm pore volume (0.51 cc/gm) of this particular .gamma.-Al.sub.2 O.sub.3. The average pore volume of a series of HCF.sub.3 prepared AlF.sub.3 extrudates (3.74 to 49.7 m.sup.2 /gm) was calculated to be 0.29.+-.0.03 cc/gm. The calculated pore volume agrees very well with the H.sub.2 O wettability (0.3 cc/gm) exhibited by these AlF.sub.3 extrudates. Thus the apparent pore volume of .gamma.-Al.sub.2 O.sub.3 is reduced to about 50% of its original value upon fluoridation. The loss in pore volume results from fluoride ions occupying voids in the Al.sub.2 O.sub.3 crystal lattice. Since the crystal volume occupied by fluoride ions is set by the conversion level, the above analysis indicates that the pore volume of AlF.sub.3 can be systematically varied by utilizing aluminas with different starting pore volumes.

Surface Area

The effect of various reaction conditions on the surface area (nitrogen BET) of HCF.sub.3 prepared AlF.sub.3 is summarized in Tables IIA and IIB. The surface area of AlF.sub.3 was found to decrease substantially upon increasing the fluoriding temperature from 400.degree. to 500.degree. C. while maintaining the space velocity of the treatment gas constant (Table IIA). Longer reaction times and/or higher concentrations of HCF.sub.3 at a given temperature also produced lower surface area AlF.sub.3. The drop in surface area appears to parallel increasing AlF.sub.3 content (Table IIB). This effect is also clearly demonstrated by the data in Table I.

TABLE IIA__________________________________________________________________________THE EFFECT OF REACTION CONDITIONS ON THESURFACE AREA AND PORE VOLUME OF AlF.sub.3PREPARED BY FLUORIDING .gamma.-Al.sub.2 O.sub.3 WITH HCF.sub.3 t Minimum (%) Surface Area.sup.(b) Pore Volume.sup.(b)T .degree.C. % HCF.sub.3 /He.sup.(a) (Hr) AlF.sub.3 (m.sup.2 /gm) (cc/gm)__________________________________________________________________________Starting .gamma.-Al.sub.2 O.sub.3.sup.(c) 178 0.513350 33 1.0 No Apparent Reaction400 20 3.0 90.sup.(d) 49.7 0.232450 20 2.0 90.sup.(d) 32.9 0.198450 20 2.5 95.sup.(e) 22.4 0.171500 20 2.5 95.sup.(d) 25.4 0.135500 20 2.5 95.sup.(d) 21.5 0.177500 40 5.0 99.sup.(e) 3.74 0.050Aqueous HF Treated Al.sub.2 O.sub.3 .about.100.sup.(f) 11.8Aqueous HF Treated Al.sub.2 O.sub.3 .about.100.sup.(f) 6.9Aqueous HF Treated Al.sub.2 O.sub.3 96.sup.(f) 1.2Aqueous HF Treated Al.sub.2 O.sub.3 90.sup.(d) 3.25Gaseous HF Treated Al.sub.2 O.sub.3 94.sup.(f) 10Gaseous HF Treated Al.sub.2 O.sub.3 86.sup.(f) 22Gaseous HF Treated Al.sub.2 O.sub.3 70.sup.(f) 63Aqueous NH.sub.4 F Treated Al.sub.2 O.sub.3 71.4.sup.(f) 45__________________________________________________________________________ .sup.(a) 500 cc/min., 1.0 atm. total pressure. .sup.(b) Nitrogen BET method. .sup.(c) Commercial Al.sub.2 O.sub.3. .sup.(d) Minimum AlF.sub.3 content established by xray diffraction measurements. Commercial sample of AlF.sub.3. .sup.(e) AlF.sub.3 content determined by TGA measurements. .sup.(f) Literature values TABLE IIB______________________________________SURFACE AREA AND PORE VOLUME OF ASERIES OF HCF.sub.3 FLUORINATED ALUMINAS Surface Area Pore VolumeFluoriding Agent % AlF.sub.3 (m.sup.2 /gm) (cc/gm)______________________________________HCF.sub.3 0 178 0.513HCF.sub.3 3.46 175HCF.sub.3 6.86 171HCF.sub.3 13.3 165 0.526HCF.sub.3 25.4 146 0.479HCF.sub.3 36.2 135HCF.sub.3 46.1 95.7HCF.sub.3 63.5 79.0HCF.sub.3 78.2 47.1HCF.sub.3 90 49.7 0.232HCF.sub.3 95 22.4 0.171HCF.sub.3 100 8.88 0.050Aqueous NH.sub.4 F.sup.(a) 24.6 51Aqueous NH.sub.4 F.sup.(a) 58.5 43Gaseous HF.sup.(a) 94 10Aqueous HF.sup.(a) 96 1.2Aqueous HF.sup.(b) 95 3.25______________________________________ .sup.(a) Literature values. .sup.(b) Commercial AlF.sub.3 sample.

The CHF.sub.3 prepared AlF.sub.3 --Al.sub.2 O.sub.3 samples generally exhibit higher surface areas than those prepared by fluoriding Al.sub.2 O.sub.3 with either HF or NH.sub.4 F. This is especially apparent in the intermediate (25-75%) AlF.sub.3 content range. (See Tables I and IIB).

A commercial AlF.sub.3 powder assayed at 61% AlF.sub.3. The bulk of the remaining material is H.sub.2 O. The commercial sample reported in Table IIA (3.25 m.sup.2 /gm) was calcined at 650.degree. C. for 5.0 hours under 20% O.sub.2 /He (500 cc/min) prior to the standard BET surface area measurement. The calcined sample was shown by an x-ray diffracton measurement to be essentially rhombohedral AlF.sub.3. Calcining the commercial AlF.sub.3 .degree..times.H.sub.2 O product at 550.degree. C. for 5.0 hours yielded a rhombohedral AlF.sub.3 which was badly contaminated with an AlF.sub.1.96 (OH).sub.1.04 phase. The presence of unreacted Al.sub.2 O.sub.3 is undesirable in many catalytic applications of AlF.sub.3.

The HCF.sub.3 prepared AlF.sub.3 products listed in Table IIA were all found to exhibit an x-ray powder diffraction pattern consistent with that reported for rhombohedral AlF.sub.3. The major diffraction lines of rhombohedral AlF.sub.3 are summarized in Table III. Only the highest surface area AlF.sub.3 (49.7 m.sup.2 /gm) product exhibited discernible weak background diffraction lines from unreacted Al.sub.2 O.sub.3. Addition of incremental amounts of .gamma.-Al.sub.2 O.sub.3 to a high purity AlF.sub.3 has set the minimum x-ray detectable Al.sub.2 O.sub.3 in AlF.sub.3 concentration to be between 5 and 10 wt. %. The minimum AlF.sub.3 content of the HCF.sub.3 prepared samples summarized in Table IIA is estimated from x-ray data to be at least 90 wt. %.

Additional AlF.sub.3 surface area data abstracted from the literature is presented in Tables IIA and IIB for comparative purposes. Within the 90% and higher AlF.sub.3 concentration range the HCF.sub.3 prepared samples exhibit higher surface areas than those prepared by fluoriding Al.sub.2 O.sub.3 with either aqueous or gaseous HF or NH.sub.4 F.

TABLE III______________________________________MAJOR X-RAY DIFFRACTION LINES OFALUMINUM FLUORIDE.sup.(a)d, A.sup.(b) I.sup.(b) d, A.sup.(c)______________________________________3.52 100 3.552.119 19 2.121.759 24 1.7651.587 14 1.5851.560 7 1.566______________________________________ .sup.(a) Rhombohedral AlF.sub.3. .sup.(b) Literature values. .sup.(c) Found for CHF.sub.3 prepared AlF.sub.3.

Pore Volume

The pore volumes of the HCF.sub.3 prepared AlF.sub.3 samples were found to decrease with decreasing surface area (see Tables IIA and IIB). Since the H.sub.2 O wettabilities of these samples were all found to be near 0.3 cc/gm, a large fraction of the total adsorptive capacity must be associated with macropores (pore diameters greater than 1200 A). The average pore diameter within the 1200 A and less range was found to be between 80-100 A. This situation can be contrasted with a typical .gamma.-Al.sub.2 O.sub.3 in which at least 95% of the total pore volume is associated with pores having diameters less than 1200 A. The average pore diameter of the starting 178 m.sup.2 /gm .gamma.-Al.sub.2 O.sub.3 is near 70-75 A.

The physical form and surface characteristics of HCF.sub.3 prepared AlF.sub.3 suggests potential application as a catalyst support. The self-supporting extrudate form would allow usage in a fixed-bed operation. An active metal component supported on AlF.sub.3 would reside primarily on the surface since the pore volume is mainly composed of pores with diameters greater than 1200 A. The latter situation may be desirable in catalytic operations where pore blockage and/or diffusion limitations may be present.

Acidity

Acidity measurements were performed by titration of solid AlF.sub.3 catalysts with standardized n-butylamine/benzene solutions at room temperature using a series of Hammett Indicators. The results of these studies are summarized in Table IV. An anthraquinone indicator (H.sub.o .ltoreq.-8.2) was not converted by any of the 90% and higher AlF.sub.3 catalysts into its acid form. Thus, none of these materials contain acid sites equivalent to 90% H.sub.2 SO.sub.4. AlF.sub.3 --Al.sub.2 O.sub.3 catalysts containing relatively small quantities of AlF.sub.3, 3.3 and 24.6%, respectively, have been reported in the literature to possess H.sub.o .ltoreq.-5.6 (equivalent to 71% H.sub.2 SO.sub.4) acid sites. These acidic sites disappear, however, at higher AlF.sub.3 concentrations. At still higher AlF.sub.3 concentration studies reported in the literature only H.sub.o .ltoreq.-3.0 (equivalent to 48% H.sub.2 SO.sub.4) acid sites were found. The higher number of acidic sites exhibited by the lower wt. % AlF.sub.3 catalysts reported in the literature may be associated with an unreacted Al.sub.2 O.sub.3 component. AlF.sub.3 catalysts containing greater than 90 wt. % AlF.sub.3 (prepared by either aqueous or gaseous HF treatment of Al.sub.2 O.sub.3) have been reported to be devoid of acid sites equivalent to 48% H.sub.2 SO.sub.4. The 25-100% AlF.sub.3 catalysts prepared in this study using CHF.sub.3 are considerably more acidic than the literature AlF.sub.3 and AlF.sub.3 --Al.sub.2 O.sub.3 catalysts listed in Table IV. The differences in acidity between these various AlF.sub.3 preparations is especially apparent when compared on a m.sup.2 basis. The retention of acidity in the HCF.sub.3 prepared AlF.sub.3 catalysts would not be predicted from the results reported in the literature.

The Hammett acidity profile of .gamma.-Al.sub.2 O.sub.3 is included in Table IV for comparative purposes. It is apparent that CHF.sub.3 prepared AlF.sub.3 and partially fluorinated Al.sub.2 O.sub.3 retain much higher acidities than conventionally fluorinated Al.sub.2 O.sub.3. Thus, HCF.sub.3 prepared AlF.sub.3 extrudates and aluminum oxyfluorides of the instant invention would be predicted to be much better solid acid catalysts than materials of the sme fluorine content prepared by conventional fluoriding procedures. The acidity advantage predicted for HCF.sub.3 prepared fluorided aluminas, when compared to aluminas fluorided with aqueous HF is clearly demonstrated in FIG. 1 where cyclohexene isomerization activities are compared. The differences in isomerization activity are especially apparent at higher fluorine levels where the HCF.sub.3 fluorinated aluminas are markedly superior catalysts.

TABLE IV______________________________________ACIDITIES OF A SERIES OFHCF.sub.3 FLUORINATED ALUMINASAcidity (.+-. 25 .mu.mole/gm) pKa Acidity% AlF.sub.3 .ltoreq.-8.2.sup.(a) .ltoreq.-5.6.sup.(b) .ltoreq.-3.0.sup.(c) (.mu.moles/m.sup.2)______________________________________0 325 325 475 2.73.46 325 375 375 2.16.86 300 375 375 2.213.3 275 325 325 2.025.4 275 325 325 2.246.1 175 225 225 2.463.5 125 175 175 2.278.2 75 125 125 2.795 0 0 66 .+-. 12 2.890 0 0 140 .+-. 2.8100 0 25 25 2.83.3.sup.(d) 0 140 300 3.124.6.sup.(d) 0 90 160 3.158.5.sup.(d) 0 0 60 1.471.4.sup.(d) 0 0 30 0.790.sup.(e) 0 0 0 094.sup.(f) 0 0 0 0______________________________________ .sup.(a) Anthraquinone indicator (acidic form requires 90% H.sub.2 SO.sub.4). .sup.(b) Benzolacetophenone indicator (acidic form requires 71% H.sub.2 SO.sub.4). .sup.(c) Dicinnamalacetone indicator (acidic form requires 48% H.sub.2 SO.sub.4). .sup.(d) NH.sub.4 F treated Al.sub.2 O.sub.3 (literature technique). .sup.(e) Aqueous HF treated Al.sub.2 O.sub.3 (literature technique). .sup.(f) Aqueous HF treated Al.sub.2 O.sub.3 (literature technique).

Fluoridation of MgO

Dry MgO (187 m.sup.2 /gm) samples were reduced under 20% H.sub.2 /He (500 cc/min) at 500.degree. C. for 1.0 hr and then purged with He (500 cc/min) at 500.degree. C. for 0.5 hr. The pretreated MgO samples were then treated with HCF.sub.3 as follows (see Table V):

TABLE V__________________________________________________________________________HCF.sub.3 FLUORIDATION OF MgOMgO HCF.sub.3 He T t Product Wt (gm) MgF.sub.2 BET(gm) (cc/min) (cc/min) (.degree.C.) (min) (Theo) (found) (%) (m.sup.2 /gm)__________________________________________________________________________A 5.0 49.7 199 500 60 7.7 7.4 100 12B 5.0 49.9 200 450 60 7.7 7.2 100 19C 5.0 49.6 200 500 15 6.0 5.8 51 90D 5.0 49.7 200 500 7.5 5.5 5.3 28 114E 5.0 24.9 200 500 7.5 5.3 5.2 15 130__________________________________________________________________________ The results summarized in the Table V clearly shows that the reaction of MgO with HCF.sub.3 producing MgF.sub.2 is essentially quantitative. The essentially fully fluorinated samples (A) and (B) exhibit x-ray diffraction lines of MgF.sub.2 only, no unreacted MgO was detected. Samples (A) and (B) possess relatively high BET surface areas as commercially available MgF.sub.2 samples display BET surface areas of less than 5.0 m.sup.2 /gm. MgF.sub.2 because of its high thermal stability, chemical inertness and high intrinsic acidity is useful in a wide variety of hydrocarbon conversion reactions which are catalyzed by acidic solids. Such conversions would include catalytic cracking, and hydrocarbon isomerization. MgF.sub.2 as well as partially fluorinated MgO (samples C-E) are useful as supports for Group VIII-metal catalysts. Such catalysts possessing both metal and acidic functions are useful in a wide variety of hydrocarbon conversion reactions. Examples of such conversions would include naphtha reforming, hydrocracking, xylene isomerization, olefin and aromatic hydrogenation, etc.

Fluoridation of TiO.sub.2

Dry TiO.sub.2 is readily fluorinated to TiOF.sub.2 using HCF.sub.3. The following example serves to illustrate the transformation: 1.0 gm of dry TiO.sub.2 was treated with 20% HCF.sub.3 /He (250 cc/min) at 550.degree. C. for 1.0 hr. The crude reaction product was analyzed by x-ray diffraction and was found to contain 45-50% TiOF.sub.2.

Fluoridation of Ta.sub.2 O.sub.5

Dry Ta.sub.2 O.sub.5 is readily fluorinated to TaO.sub.2 F using HCF.sub.3. The following example serves to illustrate the transformation: 3.0 gm of Ta.sub.2 O.sub.5 was allowed to react with 20% HCF.sub.3 /He (250 cc/min) at 550.degree. C. for 2.0 hrs. The crude product was analyzed by x-ray diffraction and was found to contain 50-60% TaO.sub.2 F.

Fluoridation of UO.sub.2

HCF.sub.3 has been found to smoothly convert UO.sub.2 to UF.sub.4 within the temperature range 350.degree.-700.degree. C. The rate of fluoridation in a given time period increasing with increasing temperature. The following example serves to illustrate the process. A 100 mg sample of UO.sub.2 was reduced under 20% H.sub.2 /He (500 cc/min) at 700.degree. C. for 2.0 hours and then treated with 50 cc HCF.sub.3 /min. at 410.degree. C. for 1.0 hour. An x-ray diffraction pattern of the crude product indicated 20-30% conversion of UO.sub.2 into UF.sub.4. The direct fluoridation of UO.sub.2 demonstrated above finds utility in the separation of uranium from crude oxide ores.

Fluoridation of Mixed-Metal Oxides

Mixed-metal oxides such as TiO.sub.2 /Al.sub.2 O.sub.3, TiO.sub.2 /SiO.sub.2, Ta.sub.2 O.sub.5 /Al.sub.2 O.sub.3, Ta.sub.2 O.sub.5 /SiO.sub.2, Nb.sub.2 O.sub.5 /Al.sub.2 O.sub.3, TiO.sub.2 /Ta.sub.2 O.sub.5, TiO.sub.2 /Nb.sub.2 O.sub.5, MgO/Al.sub.2 O.sub.3, MgO/SiO.sub.2, SiO.sub.2 /Al.sub.2 O.sub.3, NO.sub.3 /Al.sub.2 O.sub.3, NO.sub.3 /SiO.sub.2 and ZrO.sub.2 /Al.sub.2 O.sub.3 which are readily prepared by conventional coprecipitation techniques are readily fluorinated with HCF.sub.3. As an example consider the following: 5.0 gm of a dry 12% Ta.sub.2 O.sub.5 /Al.sub.2 O.sub.3 mixed-metal oxide was reduced at 500.degree. C. using 20% H.sub.2 /He (500 cc/min) and then allowed to react with 20% HCF.sub.3 /He (250 cc/min) at 500.degree. C. for 15 mins. The product incorporated a substantial quantity of fluorine as the product was found to weigh 5.9 gms. The crude product displayed x-ray diffraction lines due to AlF.sub.3 and TaO.sub.2 F phases as well as unreacted Al.sub.2 O.sub.3 and Ta.sub.2 O.sub.5. Other mixed-metal oxides behave similarly. Because of their high activity partially fluorinated mixed-metal oxides are useful in acid catalyzed hydrocarbon conversion reactions such as catalytic cracking and isomerization. Partially fluorinated mixed-metal oxides also have utility as supports for Group VIII-metal catalysts which are useful in a wide variety of hydrocarbon conversion reactions such as naphtha reforming, olefin and aromatic hydrogenation, paraffin isomerization, xylene isomerization, hydrocracking, etc.

Special Fluoridation of Al.sub.2 O.sub.3 With HCF.sub.3

It has been stated in GB No. 969863 that freons are ineffective fluoriding agents in the presence of a reducing atmosphere such as H.sub.2. We have shown that Al.sub.2 O.sub.3 is readily fluorinated with HCF.sub.3 in the presence of H.sub.2. Consider the following example.

______________________________________ HCF.sub.3 H.sub.2 Product BETAl.sub.2 O.sub.3 (cc/ (cc/ T t wt (gm) AlF.sub.3 (m.sup.2 /(gm) min) min) (.degree.C.) (min) theo found (%) gm)______________________________________20.0 50 200 500 180 32.9 31.0 100 12______________________________________ An x-ray diffraction pattern of the product was devoid of any Al.sub.2 O.sub.3 lines. Thus essentially complete fluoridation has been affected in the presence of hydrogen.

Claims

1. A process for the preparation of metal oxyfluorides of the formula:

MO.sub.z-y F.sub.y

wherein M is a metal selected from the group consisting of sodium, potassium, lithium, cesium, magnesium, calcium, barium, strontium, tin, antimony, bismuth, titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, rhodium, mercury, nickel, copper, silver, zinc, cadmium, lead, uranium, europium, indium, lutetium, neodymium, thallium, silicon, niobium, hafnium, tantalum, molybdenum, rhenium, tungsten, osmium, iridium, lanthanum, technetium and ruthenium and mixtures thereof, z is a number satisfying the valence requirements of the metal and y is a number satisfying the valence requirements of the metal, which comprises reacting a metal oxide selected from the group consisting of the oxides of the metals recited above with a fluorocarbon selected from the group consisting of CH.sub.4-Q F.sub.Q wherein Q is 1 to 3 and partially and totally fluoridated C.sub.2 -C.sub.6 alkanes, alkenes, alkynes and C.sub.5 -C.sub.6 cyclic alkenes wherein the metal oxide and the fluorocarbon are contacted at a temperature of from about 300.degree. to about 800.degree. C. at a fluorocarbon partial pressure of from about 0.001 to about 1 atmosphere for a time sufficient to effect the desired degree of conversion of the metal oxide into the metal oxyfluoride.

2. The process of claim 1 wherein the fluorocarbon is selected from the group consisting of CH.sub.4-Q F.sub.Q wherein Q is 1 to 3, straight and branch chain C.sub.2 -C.sub.6 fluorocarbons of the general formula

C.sub.A H.sub.2A+2-B F.sub.B

wherein A is an integer ranging from 2 to 6 inclusive and B is an integer ranging from 1 to 14 inclusive, and cyclic fluorocarbon of the formula

C.sub.X H.sub.2X-C F.sub.C

wherein X is 5 or 6 and C is an integer ranging from 1 to 12.

3. The process of claim 1 wherein the metal oxide is selected from the group consisting of the oxides of titanium, magnesium, uranium, tantalum, tungsten, nickel, cobalt and molybdenum.

4. The process of claim 1 wherein the metal oxide is selected from the group consisting of the oxides of tungsten.

5. The process of claim 1 wherein A ranges from 2 to 3.

6. The process of claim 1 wherein the fluorocarbon is trifluoromethane.

7. The process of claim 1 wherein the metal oxide is further in admixture with alumina.

8. The process of claim 1 wherein the metal oxide is titania and the fluorocarbon is trifluoromethane.

9. The process of claim 1 wherein the temperature ranges from about 300.degree. to about 600.degree. C.

10. The process of claim 1 wherein the temperature ranges from about 350.degree. to about 550.degree. C.

11. The process of claim 1 wherein the fluorocarbon partial pressure ranges from about 0.1 to about 1 atmosphere.

12. Metal oxyfluorides of the formula:

MO.sub.z-y F.sub.y

wherein M is a metal selected from the group consisting of sodium, potassium, lithium, cesium, magnesium, calcium, barium, strontium, tin, antimony, bismuth, titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, rhodium, mercury, nickel, copper, silver, zinc, cadmium, lead, uranium, europium, indium, lutetium, neodymium, thallium, silicon, niobium, hafnium, tantalum, molybdenum, rhenium, tungsten, osmium, iridium, lanthanum, technetium and ruthenium and mixtures thereof, z is a number satisfying the valence requirements of the metal and y is a number satisfying the valence requirements of the metal prepared by reacting a metal oxide selected from the group consisting of the oxides of the metals recited above with a fluorocarbon selected from the group consisting of CH.sub.4-Q F.sub.Q l wherein Q is 1 to 3 and partially and totally fluoridated C.sub.2 -C.sub.6 alkanes, alkenes, alkynes and C.sub.5 -C.sub.6 cyclic alkanes wherein the metal oxide and fluorocarbon are contacted at a temperature of from 300.degree. to 800.degree. C. at a fluorocarbon partial pressure of from 0.001 to 1 atmosphere for a time sufficient to effect the desired degree of conversion of the metal oxide onto the metal oxyfluoride.

13. The metal oxyfluoride prepared as in claim 12 wherein the fluorocarbon is selected from the group consisting of fluoroform, straight and branch chain C.sub.2 -C.sub.6 fluorocarbons of the general formula:

C.sub.A H.sub.2A+2-B F.sub.B

wherein A is an integer ranging from 2 to 6 inclusive and B is an integer ranging from 1 to 14 and cyclic fluorocarbons of the formula

C.sub.X H.sub.2X-C F.sub.C

wherein X is 5 or 6 and C is an integer ranging from 1 to 12.

14. The metal oxyfluorides of claim 12 wherein M is selected from the group consisting of tungsten, nickel, cobalt and molybdenum.

15. The metal oxyfluorides of claim 12 wherein M is tungsten.

16. The metal oxyfluorides of claim 12 wherein the enumerated metal oxides are further in combination with alumina.