Process for the Disposal of Aluminum Containing Waste Materials

The following examples indicate preferred embodiments and aspects of the present invention.

To a 500 ml Erlenmeyer flask equipped with a stirrer and heater and in a dry-box was added 0.25 gram of TiCl.sub.3, 0.24 gram of diethyl aluminum chloride, 1.0 gram of Ca(OH).sub.2, 50 ml of n-butanol and 450 ml of hexane. The mixture was heated to 55.degree.-60.degree. C, stirred at that temperature for 30 minutes, and then filtered. The filtration residue weighed 1.61 grams after drying. The initial content of aluminum in the total feed system was 163 ppm. The filtrate contained 2.5 ppm of aluminum. The initial content of titanium in the total feed system was 235 ppm. The filtrate contained 0.9 ppm of titanium. The butanol-hexane mixture was essentially anhydrous and readily separable into the components on distillation.

To a 500 ml Erlenmeyer flask equipped with a stirrer, heater and in a dry-box was added 0.25 gram of TiCl.sub.3, 0.24 gram of diethylaluminum chloride, 1.0 gram of Ca(OH).sub.2 and 500 ml of hexane. The mixture was heated to 45.degree.-58.degree. C, stirred at that temperature for 30 minutes and then filtered. The filtration residue had a dry weight of 1.15 grams. The initial content of aluminum in the total feed system was 163 ppm. The filtrate contained 13.6 ppm of aluminum. The initial content of titanium in the total feed system was 235 ppm. The filtrate contained 0.9 ppm of titanium.

One hundred ten grams of a methyl aluminum sesquichloride heel (MASC) (containing about 50 wt. percent of (CH.sub.3).sub.2 AlCl and CH.sub.3 AlCl.sub.2 in about equimolar proportions plus about 10 wt. percent of aluminum powder and 40 wt. percent of C.sub.12 -C.sub.16 olefins) was diluted to 400 milliliters with kerosene. An equal weight (110 grams) of lime Ca(OH).sub.2, 44 micron size, was slurried with 400 ml of kerosene (25.6 percent slurry). The lime slurry was placed in a 2-liter reactor equipped with a heat exchanger, a turbine-type agitator, and an off-gas absorber containing a 10 percent NaOH solution. The MASC slurry was added to the preheated lime slurry (60.degree. C) slowly over a period of about 4 minutes with the agitator turning at 400 rpm.

The temperature of the reactor increased from the starting 60.degree. C to 100.degree. C in the first 5 minutes of reaction after the addition was completed, heating of the reactor having been discontinued. A maximum of 104.degree. C was reached after ten minutes reaction time. The temperature began to drop after 15 minutes reaction time. The agitator speed was increased from 400 rpm to 500 rpm at this time and the temperature momentarily increased slightly. After 75 minutes reaction time the temperature had dropped to 87.degree. C, at which time 20 grams of lime was added to the reaction mass. The temperature again begin to rise reaching 91.degree. C. Ten milliliters of 25 percent aqueous solution of sodium hydroxide were then added to the mixture, the temperature rising further to 93.degree. C. After 2 hours of reaction time, another 20 grams of lime was added to the mixture. No heat kick was observed this time.

Separate aliquots of the reaction mass were taken at 21/2 hours reaction time. One of these was treated with water and the other with 50 grams of a 25 percent solution of sodium hydroxide in water. There was vigorous but controlled effervescence from both of these tests. Apparently, the aluminum metal had not reacted. After three hours reaction time, aliquots of the reaction mixture were unreactive with water and only slightly reactive with the 25 percent sodium hydroxide solution. An aliquot taken at 41/2 hours reaction time produced only slight gassing when treated with 25 percent sodium hydroxide solution. At this point the residual aluminum appeared substantially dead to water and almost inactive to caustic and hence safe to dump as land-fill.

To separate the hydrolysis product, the mixture was allowed to stand over night (.apprxeq.16 hours) in a separatory funnel producing 437 grams of a heavy grease like sludge and 404 grams of clear kerosene. The sludge consisted of 19 weight percent easily filterable kerosene, 46 percent combustible cloudy liquid and 35 percent solids (residue on ignition). The ignited solid on subsequent analysis by X-ray diffraction pattern analysis was shown to consist of 12 CaO.sup.. 7Al.sub.2 O.sub.3, CaO and CaCO.sub.3 (relative amounts by weight 4:5:1 respectively). The filter cake prior to the ignition contained mostly amorphous material, Ca(OH).sub.2.sup.. CaCl.sub.2 and Ca(OH).sub.2 in about a 1:2 weight ratio.

Example III was repeated. One hundred nine grams of the MASC heel of the type used in Example III were diluted with kerosene to 425 ml total volume (368.0 g). One hundred ten grams of Ca(OH).sub.2 (technical MCB) was mixed with 500 ml of recycled kerosene using an equipment set-up as in Example III.

The lime slurry was preheated to 63.degree. C, the agitator set to 400 rpm. The heel solution was added to the lime slurry over a period of three minutes. The first hour of reaction was as in Example III. An addition of 20 grams of Ca(OH).sub.2 at the 1 hour reaction point produced only a slight heat kick. 80 ml of a 6.25 wt. percent sodium hydroxide-isopropanol-ethanol solution (200 grams isopropanol and 100 grams of ethanol per 20 grams NaOH) was then added, the temperature rising rapidly from 90.degree. C to 120.degree. C. After another 4 minutes reaction time, an additional 20 ml of alcoholic sodium hydroxide solution was added to the mixture, only a slight thermal kick being noted. Another 50 ml of alcoholic sodium hydroxide was added 40 minutes later at which time there was no heat kick but a sample of the solids was still reactive to aqueous caustic. After 21/2 hours of total reaction time, 40 ml of a 25 wt. percent solution of sodium hydroxide in water was added to the mixture. There was a notable heat kick. Even after 51/2 hours the solids were reactive to aqueous caustic. Apparently the alcoholic-caustic treatment did not completely convert the metallic aluminum particles in the heel mass.

The reaction mass was poured out on a coarse fritted filter and allowed to drain five days yielding 493.8 grams of clear kerosene (75 percent of the original amount of kerosene used) and 603 grams of a sludge paste. The sludge was approximately 33 percent solid. The kerosene was free of any active alkyl as shown by the absence of any reactivity thereof with water.

The reaction mass was allowed to drain on a coarse fritted filter for five days yielding 624 grams of clear kerosene and 706.5 grams of sludge. An additional 152 grams of kerosene was drawn from the sludge by subsequent vacuum filtration.

A solution of 23 percent by volume diethyl aluminum chloride (DEAC) in kerosene was slowly poured onto powdered dry Ca(OH).sub.2 in a beaker. There was a very gentle effervescence of gas. No smoke or fog was produced. After ten minutes the oil was decanted from the solids and poured into H.sub.2 O. There was no apparent hydrolysis reaction indicating that the DEAC had been converted to a material that was not reactive with water.

Dry powdered lime was mixed into a 23 percent by volume DEAC-kerosene solution as used in Example VI. A gentle effervescence lasted about two minutes during which time the temperature rose from 25.degree. to 35.degree. C. The resulting mixture was filtered in the air. (There was no evidence of continuing alkyl hydrolysis). The oil filtrate was mixed with H.sub.2 O. There was no evidence of violent reaction; however, a very slight floc was noted in the test aqueous phase. The floc was soluble in added caustic.

The solids were calcined 5 hours at 1000.degree. C. The XRD analysis of the calcined product showed 12 CaO.sup.. Al.sub.2 O.sub.3 and CaO. X-ray diffraction pattern analysis of the uncalcined filter cake indicated the solids to be largely amorphous containing a very small amount of Ca(OH).sub.2.

5 Grams of anhydrous potassium carbonate (K.sub.2 CO.sub.3) was slurried in 25 ml of kerosene in a 100 ml beaker on a hot plate and heated to 70.degree. C.

35 Ml of a 25 percent by weight ethyl aluminum sesquichloride solution in olefin and kerosene as described in Example V were then added to the beaker and the beaker covered with a watch glass. A gentle effervescence of gas occurred, the gas being acid to wet litmus paper. The solids in the beaker turned from white to brown. After 2 hours, the mixture was filtered yielding a filtrate which was substantially unreactive to water. The solids recovered from the filtration showed an amorphous state by X-ray diffraction analysis.