CATALYTIC DECOMPOSITION OF IMPURITIES IN TERTIARY BUTYL ALCOHOL

Abstract: Motor-fuel grade tertiary butyl alcohol (which is prepared, for example, by reacting propylene with ter­ tiary butyl hydroperoxide to form propylene oxide and a tertiary butyl alcohol reaction product contaminated with residual amounts of tertiary butyl hydroperoxide and ditertiary butyl peroxide) can be effectively cataly­ tically treated under mild conversion conditions includ­ ing a temperature of about 80° to 280°C with a catalyst composed of iron, copper, chromia and nickel, or the oxides thereof, in order to substantially selectively convert the two peroxide contaminants to tertiary butyl alcohol and to thereby provide a treated tertiary butyl alcohol product substantially free from contaminating quantities of such peroxides.

Description: This invention relates to the catalytic purifica­ tion of tertiary butyl alcohol prepared by the reaction of propylene with tertiary butyl hydroperoxide. More particularly, this invention relates to a method for the removal of residual contaminating quantities of tertiary butyl hydroperoxide and ditertiary butyl peroxide (DTBP) from a tertiary butyl alcohol feedstock which is prepared by the reaction of propylene with tertiary butyl hydro­ peroxide and is useful as an octane-enhancing component for motor fuels. A process for the manufacture of substituted epox­ ides from alpha olefins such as propylene is disclosed in US-A-3,351,653 which teaches that an organic epoxide compound can be made by reacting an olefinically unsatur­ ated compound with an organic hydroperoxide in the pres­ ence of a molybdenum, tungsten, titanium, columbium, tantalum, rhenium, selenium, chromium, zirconium, tellur­ ium or uranium catalyst. When the olefin is propylene and the hydroperoxide is tertiary butyl hydroperoxide, propylene oxide and tertiary butyl alcohol are coproducts. US-A-3,350,422 teaches a similar process using a soluble vanadium catalyst. Molybdenum is the preferred catalyst. A substantial excess of olefin relative to the hydroper­ oxide is taught as the normal procedure for the reaction. See also US-A-3,526,645 which teaches the slow addition of organic hydroperoxide to an excess of olefin as pre­ ferred. It is known that isobutane can be oxidized with molecular oxygen to form a corresponding tertiary butyl hydroperoxide and that the oxidation reaction can be pro­ moted, for example with an oxidation catalyst (see US-A-3,825,605 and 4,296,263. Thus, tertiary butyl alcohol can be prepared either by the direct thermal or catalytic reduction of tertiary butyl hydroperoxide to tertiary butyl alcohol or by the catalytic reaction of propylene with tertiary butyl hydroperoxide to provide propylene oxide and tert­ iary butyl alcohol. It is also known that tertiary butyl alcohol can be used as an octane-enhancing component when added to a motor fuel, such as gasoline. For example, in US-A-­ 3,474,151 it is proposed to thermally decompose tertiary butyl hydroperoxide and ditertiary butyl peroxide to form tertiary butyl alcohol. The thermal decomposition must be conducted with care, as pointed out by the patentee, Grane, in that tertiary butyl alcohol will start to de­ hydrate at a temperature of about 232°C (450°F) and in that the dehydration becomes rapid at temperatures above about 246°C (475°F). Moreover, the product from the thermal decomposition normally contains a minor amount of tertiary butyl hydroperoxide and ditertiary butyl per­ oxide which have an adverse effect upon the quality of motor fuels and must be substantially completely removed if the tertiary butyl alcohol is to be fully effective. Grane proposes to accomplish this thermally by heating tertiary butyl alcohol containing small quantities of such peroxides at a temperature of 190-246°C (375-475°F) for a period of 1 to 10 minutes. The removal of trace quantities of tertiary butyl hydroperoxide from motor grade tertiary butyl alcohol has received appreciable attention. However, little appears to have been published concerning the removal of trace quantities of ditertiary butyl peroxide, the more refractory of the two peroxides. This may be explainable both because ditertiary butyl peroxide is not always present in trace quantities in motor grade tertiary butyl alcohol (its presence or absence being a function of the reaction conditions used in oxidizing the isobutane starting material) and because, when pres­ ent, it is present in significantly lower amounts. For example, after decomposition of the major amount of ter­ tiary butyl hydroperoxide formed by the oxidation of iso­ butane, the tertiary butyl hydroperoxide residual content will normally be about 0.1 to about 1 wt.%, based on the tertiary butyl alcohol, while the residual ditertiary butyl peroxide content, if any, will only be about 0.1 to 0.5 wt.%. US-A-4,112,004 discloses a process for preparing monohydric or polyhydric alcohols from organic peroxides in the presence of a nickel catalyst by continuously feeding a solution of the organic peroxide (e.g. buta­ diene peroxide) and a suspension of the nickel catalyst to a reactor in a controlled ratio and continuously with­ drawing reaction mixture at a rate adequate to maintain a constant weight and composition of the reaction mixture in the reactor. US-A-3,037,025 discloses the preparation of N-­ alkyl substituted piperazines using catalyst compositions consisting of the metals and oxides of copper, nickel and cobalt (including mixtures thereof) which may also be promoted by the inclusion of a normally non-reducible metal oxide such as chromium, aluminum, iron, calcium, magnesium, manganese and the rare earths. Preferred catalyst compositions are indicated as containing from about 44 to about 74 wt.% of nickel, about 5 to about 55 wt.% of copper and about 1 to about 5 wt.% of chromia. US-A-3,151,112 discloses catalyst compositions useful for the opreparation of morpholines including one or more of copper, nickel, cobalt, chromium, molybdenum, manganese, platinum, palladium and rhodium, which may also be promoted with normally non-reducible oxides such as chromium oxide, molybdenum oxide and manganese oxide. Representative catalyst compositions include those con­ taining from about 60 to about 85 wt.% of nickel, about 14 to about 37 wt.% of copper and about 1 to about 5 wt.% of chromia. Nickel, copper, chromia catalysts are also disclosed in US-A-3,151,115 and 3,152,998. When isobutane is reacted with molecular oxygen the principal products of the reaction are tertiary butyl alcohol and tertiary butyl hydroperoxide. However, minor amounts of other peroxides, including ditertiary butyl peroxide are also formed. Generally speaking, from about 10 to about 100 parts of tertiary butyl hydroperoxide are formed per part of ditertiary butyl peroxide. Minor quantities of other contaminants are also formed. A listing of the components present in a repre­ sentative reaction product, and their nominal boiling points (NBP) is given in Table A. The minor by-products are sometimes difficult to remove. For example, tertiary butyl formate has a higher boiling point than ditertiary butyl hydroperoxide but tends to distill overhead, which suggests that it forms a minimum boiling azeotrope with another component or components. Tertiary butyl hydroperoxide is useful as a raw material for the manufacture of tertiary butyl alcohol either by catalytic decomposition of the tertiary butyl hydroperoxide in the presence of a molybdenum catalyst as taught in US-A-4,249,999 or 4,296,262 or 4,296,263, or by the catalytic reaction of tertiary butyl hydroper­ oxide with an olefin such as propylene to form an epoxide and tertiary butyl alcohol. When the olefin is propylene, the coproduct is propylene oxide. The reaction conditions used for the conversion of tertiary butyl hydroperoxide, by either process, to tertiary butyl alcohol are such that the di­ tertiary butyl peroxide normally is not consumed or des­ troyed and remains in the reaction mixture as an impurity. Only a minor amount of the peroxidation reaction mixture formed by the reaction of molecular oxygen with isobutane will be composed of ditertiary butyl peroxide. However, this minor amount may constitute as much as about 0.5 wt.% of the total peroxidation reaction mixture. For example, when tertiary butyl hydroperoxide is recovered from the peroxidation reaction mixture obtained by the reaction of molecular oxygen with iso­ butane, the ditertiary butyl peroxide will also normally be present as a contaminant. Therefore, when the ter­ tiary butyl hydroperoxide is reacted with propylene to form propylene oxide and tertiary butyl alcohol, the di­ tertiary butyl peroxide will be present in the reaction mixture and in the reaction product. The product of the reaction of tertiary butyl hydroperoxide with propylene is normally separated into useful components, usually by distillation, to form, for example, sequential distillate fractions composed of unreacted propylene, propylene oxide and tertiary butyl alcohol. The ditertiary butyl hydroperoxide will nor­ mally be present in the recovered tertiary butyl alcohol as a contaminant together with other contaminants such as residual tertiary butyl hydroperoxide, acetone, methyl formate, methanol, tertiary, butyl formate, isopropyl alcohol, etc. A tertiary butyl alcohol product prepared by either of the processes described above, and contaminated with minor amounts of tertiary butyl hydroperoxide and ditertiary butyl peroxide, may be used as a feedstock for the present invention. Tertiary butyl hydroperoxide can decompose ther­ mally and/or catalytically to form acetone. Tertiary butyl alcohol can be decomposed to form water and iso­ butylene. Accordingly, the tertiary butyl alcohol feed­ stock of the present invention is not entirely satisfac­ tory for use as an octane-enhancing component for motor fuels, such as gasoline, in that tertiary butyl alcohol will normally be considered unsatisfactory for motor fuel use if it contains more than about 3 wt.% of acetone, more than about 1 wt.% of isobutylene, more than about 100 ppm of ditertiary butyl peroxide and more than 100 ppm of tertiary butyl hydroperoxide. Desirably, the ter­ tiary butyl alcohol will contain about 1 wt.% or less of acetone, 0.5 wt.% or less of isobutylene and 10 ppm or less of ditertiary butyl peroxide and 100 ppm or less of tertiary butyl hydroperoxide. According to the present invention there is pro­ vided a method for enhancing the motor fuel quality of a tertiary butyl alcohol feedstock contaminated with residual quantities of tertiary butyl hydroperoxide and ditertiary butyl peroxide, which comprises the steps of: a. contacting said feedstock in a reaction zone with a catalyst at a temperature of from 80° to 280°C for a period of time sufficient to substantially selec­ tively decompose said tertiary butyl hydroperoxide and said ditertiary butyl peroxide to tertiary butyl alcohol; and b. recovering substantially hydroperoxide-free tertiary butyl alcohol from the products of said reac­ tion; and characterised in that c. said catalyst comprises a metals component of metallic iron, copper, chromium and nickel or the oxides of one or more of said metals, in proportions, on an oxygen-free basis, of from 20 to 80 wt.% of iron, from 5 to 40 wt.% of copper, from 0.1 to 10 wt.% of chromium and from 0.01 to 5 wt.% of cobalt. In accordance with the present invention the peroxide-contaminated feedstock is brought into contact with a catalyst which is composed of iron, copper, chromia and cobalt in order to substantially selectively decompose both the tertiary butyl hydroperoxide and the ditertiary butyl peroxide to tertiary butyl alcohol. It has been surprisingly discovered in accordance with the present invention that motor-fuel grade tertiary butyl alcohol which is contaminated with residual amounts of ditertiary butyl peroxide and tertiary butyl hydro­ peroxide can be effectively catalytically treated with a catalyst composed of iron, copper, chromia and cobalt under mild catalytic conditions including a temperature of from 80° to 280°C, preferably 220°C, at a pressure sufficient to maintain a liquid phase reaction mixture (normally, about 1.4 to 5.5 × 10⁶ or 200 to 800 psig, depending on reaction temperature). Higher pressures of up to about 1.4 × 10⁷ Pa (2000 psig) can be used, if desired, but there is no particular advantage in using the higher pressures. This treatment will substantially selectively convert the peroxide contaminants to tertiary butyl alcohol and thereby provide a treated product sub­ stantially free of contaminating quantities of tertiary butyl hydroperoxide and ditertiary butyl peroxide. Thus, the formation of unwanted isobutylene and oxygenated der­ ivatives of the peroxide contaminates, including acetone and methanol, is substantially avoided. The results obtained with the process of the pres­ ent invention are surprising and unexpected in several respects. Catalytic or thermal decompositions of ter­ tiary butyl hydroperoxide and ditertiary butyl peroxide normally results in the formation of acetone as the favored decomposition product. Thus, the favorable effect on the quality of motor fuel grade tertiary butyl alcohol that is obtained by the substantially complete elimination of the two peroxides will be largely counter-­ balanced if the decomposition product is principally acetone. Another problem is encountered in the catalytic decomposition of the residual tertiary butyl hydroperox­ ide and ditertiary butyl peroxide contaminants present in the tertiary butyl alcohol in that the catalyst may also catalyze the dehydration of tertiary butyl alcohol to isobutylene. Isobutylene is also an undesired contam­ inant, even when only trace quantities are present. Moreover, we have found that catalysts that are effective for the substantially complete decomposition of tertiary butyl hydroperoxide are normally only part­ ially effective, at best, for the catalytic decomposition of ditertiary butyl peroxide. Thus, the provision of the process of the present invention wherein a motor-fuel grade tertiary butyl alco­ hol feedstock, containing contaminating quantities of both ditertiary butyl peroxide and tertiary butyl hydro­ peroxide, is catalytically treated for the decomposition of the peroxides, so that they are substantially complet­ ely removed without significantly adding to the level of contamination due to the formation of acetone, meth­ anol and isobutylene, constitutes a distinct advantage over the prior art. The starting materials for the process of the present invention include a motor-fuel grade tertiary butyl alcohol feedstock obtained in the manner described above by the reaction of propylene with tertiary butyl hydroperoxide to form propylene oxide and tertiary butyl alcohol by the oxidation of isobutane to form tertiary butyl hydroperoxide. The motor-fuel grade tertiary butyl alcohol feed­ stock obtained by the reaction of propylene with tertiary butyl hydroperoxide to form propylene oxide and tertiary butyl alcohol will contain contaminating quantities of tertiary butyl hydroperoxide, ditertiary butyl peroxide, and acetone, and may also contain contaminating quanti­ ties of methanol and isobutylene. The normal levels of contamination of such materials are such that the ter­ tiary butyl alcohol will normally contain, prior to treatment, from about 0.1 to about 5 wt.% of tertiary butyl hydroperoxide and from about 0.1 to about 5 wt.% of ditertiary butyl peroxide. Minor quantities of other contaminants may also be present. As indicated earlier, the reaction conditions used in the catalytic oxidation of isobutane will sometimes result in the formation of ditertiary butyl peroxide. Thus, the feedstock to be used for the practice of the present invention is an impure motor grade tertiary butyl alcohol containing from about 0.1 to about 5 wt.% of ter­ tiary butyl hydroperoxide and from about 0.1 to about 5 wt.% of ditertiary butyl peroxide. Preferably, the catalyst compositions of the pres­ ent invention contain about 30 to about 50 wt.% of iron and about 10 to about 30 wt.% of copper, about 1 to about 5 wt.% of chromia and about 0.5 to about 2 wt.% of cobalt. The catalyst may also be supported on a suitable inert support such as alumina, silica or titania. The catalysts may be utilized in powdered form in conducting batch reactions, but their utility is enhanced when they are used in pelleted form for catalyz­ ing the reaction in a continuous process. When a cata­ lyst is used in pelleted form for a continuous reaction, it is necessary that the pellets have good physical and chemical properties so that they will not disintegrate or break during the course of the continuous peroxide decomposition. The catalyst compositions of the present invention have such properties. With the present invention, a tertiary butyl alco­ hol feedstock is brought into contact with a catalyst under reaction conditions correlated to substantially selectively catalytically convert both the tertiary butyl hydroperoxide and ditertiary butyl peroxide contaminants in the tertiary butyl alcohol feedstock to tertiary butyl alcohol with not more than a minor increase in the level of contamination of the acetone, methanol and isobutylene also normally present in the tertiary butyl alcohol as contaminants. The reaction may be conducted batchwise in an autoclave using powdered catalyst or may be conducted on a continuous basis by passing the tertiary butyl alco­ hol through a reactor containing a bed of a catalyst of the present invention under reaction conditions at a tem­ perature preferably from 110° to 180°C. When the reac­ tion is conducted batchwise, contact time may suitably be from about 0.5 to about 4 hours. When the reaction is conducted on a continuous basis, the tertiary butyl alcohol should be passed over the bed of catalyst at a liquid hourly space velocity of about 0.25 to about 5. The reaction product, after being degassed, is suitable for use as an octane-enhancing component of motor fuel, such as gasoline. Thus, for example, the effluent from the reactor may be passed through a phase separation zone in order to permit gaseous reaction components including hydrogen and isobutane to volatilize from the product to thereby provide the desired reaction product. The specific correlation of conditions to be util­ ized with any specific catalyst of the present invention can be determined by one of ordinary skill in the art with comparative ease. Thus, for example, the tertiary butyl alcohol feedstock should be analyzed prior to catalytic treatment to determine the level of contamina­ tion by tertiary butyl hydroperoxide, ditertiary butyl peroxide, acetone, methanol and isobutylene. An insuf­ ficient decomposition of the hydroperoxides such that a significant amount (e.g. more than about 0.1 wt.%) of tertiary butyl hydroperoxide and/or ditertiary butyl per­ oxide is still present is an indication that the reaction conditions are not sufficiently severe, and should be increased by, for example, increasing reaction tempera­ ture or contact time in order to obtain the desired de­ composition of the tertiary butyl hydroperoxide. Conversely, a significant increase in the level of contamination of acetone, isobutylene and/or methanol is an indication that the reaction conditions are too severe for the particular catalyst and should be amelior­ ated (e.g. by reducing contact time or temperature). EXAMPLES Example Set A Catalyst Preparation Catalyst BBB 6098-76 - Preparation of Ni/Cu/Cr/Mo Catalyst A solution of 2856g of H₂O, 1530g of Ni(NO₃)₂.6H₂O, 285.6g of hydrated Cu(NO₃)₂, and 96.9g of Cr(NO₃)₃.9H₂O at 80°C, and a solution of 2400 ml H₂O, 713g of Na₂CO₃, 12.0g of NaOH and 60.0g of ammonium molybdate at 80°C were added simultaneously to 1000 ml of rapidly stirred water at 80°C over a 2¼ hour period at rates such that the pH remained near 7.0. The mixture was filtered hot. The filter cake was stirred with 2500 ml of H₂O at 80°C and filtered hot. This procedure was repeated five more times. The filter cake was dried at 135°C for one day and at 90°C for two more days. Analysis: 40.8% Ni, 10.6% Cu, 1.7% Cr, 4.7% Mo, and 40 ppm Na. The powder was calcined at 400°C for four hours. Analysis: 51.5% Ni, 12.8% Cu, 1.7% Cr, 5.8% Mo, 88 ppm Na. The calcined material was reduced in flowing N₂/H₂ and finally all H₂ at 335-363°C over a six day per­ iod. It was stabilized at room temperature in flowing N₂/air and finally all air. Yield = 456.54g. Analysis: 60.5% Ni, 15.4% Cu, 1.8% Cr, 7.0% Mo, 180 ppm Na. Graphite (3.0 wt.%) was added, and the catalyst powder was made into 3 mm × 3 mm (⅛″ × ⅛″) tablets (260 cc) of 6.8 to 11.4 Kg (15-25 lb) crush strength. Catalyst AAA 6098-40 - Preparation of Fe/Cu/Cr/Co Catalyst A solution containing 3200 ml of H₂O, 1979.7g (4.9 moles) of Fe(NO₃)₃.9H₂O, 413./9g (approx. 1.4 moles) of hydrated Cu(NO₃)₂, 160.1g (0.4 moles) of Cr(NO₃)₃.9H₂O, and 29.1g (0.1 moles) of Co(NO₃)₂6H₂O at 80°C, and a sol­ ution containing 3220 ml of H₂O and 1080.7g (10.20 moles) of Na₂CO₃ at 80°C were added simultaneously to 1000 ml of rapidly stirred water at rates such that the pH of the resultant solution remained approximately 7. The addition required 1 hour and 55 minutes. After an addi­ tional half-hour of stirring at 80-83°C, the mixture was filtered. The filter cake was stirred with 3000 ml of H₂O at 80°C and refiltered. This operation was repeated five more times. The final filter cake was dried at 145°C for approximately 18 hours. Analysis: 44.4% Fe, 19.0% Cu, 3.6% Cr and 0.72% Co. The powdered carbonates were calcined at 450°C for five hours. Analysis: 43.2% Fe, 18.1% Cu, 3.5% Cr and 0.82% Co. The calcined powder was reduced at 350°C for 21 hours in a hydrogen stream after prior exposure to flow­ ing N₂H₂ mixtures at 350°Co. Final reduction was in flow­ ing hydrogen at 390-395°C for 1 hours. The powder was cooled and a mixture of flowing N₂/air and finally all air was introduced at 10-22°C. Analysis: 49.5% Fe, 21.5% Cu, 4.2% Cr and 0.95% Co. The reduced and stabilized catalyst was ground to -80 mesh (177 µm opening) particles, mixed with 3% graphite, and formed into 3 mm × 3 mm (⅛″ × ⅛″) tablets of about 19 Kg (42 lb) average crush strength. In all cases, these evaluations were performed in a 100 cc reactor constructed of 13 mm (½ inch) stain­ less steel tubing 43 cm (17 inches) long connected to a 3 mm (⅛ inch) feed and effluent lines with swagelok fittings. The reactor tube was situated inside of a 75 mm square (3 × 3 inch) aluminum block which was heated electrically with four 1000 watt strip heaters. Temper­ ature control was achieved with a Thermoelectric control­ ler monitoring thermocouples attached to the skin of the reactor body. The feed was charged to the reactor system with a Beckman 110A L.C. pump. The reactor effluent was collected in a glass jug and sampled after the system and lined-out at the prescribed temperature for at least 2.5 hours. The catalysts that were used in initial compara­ tive working Examples are listed in Table I together with a brief description of their composition. Example 1-A In a first series of experiments a simulated ter­ tiary butyl alcohol feedstock having the contamination levels listed for notebook (NB) No. 5787-76-1 in Table II was used as the feedstock. In run 6064-60-1, the feedstock was heated in the reactor at a temperature of about 160°C and a gauge pres­ sure of about 3.6 × 10⁶ Pa (520 psig), being passed to the reactor at the rate of about 0.41 kg/hr (0.9 lbs/hr). AS will be noted from Table II, there was a significant reduction in the level of tertiary butyl hydroperoxide contamination, but only a minor decrease in the level of contamination due to ditertiary butyl peroxide. Note also there was a significant increase in the level of contamination due to the formation of acetone. The next series of sets of runs were made using the catalysts, as identified in Table 1, under the reac­ tion conditions noted in Table II and a gauge pressure of 3.48 × 10⁶ Pa (500 psig), with the results that are also there noted. This series of tests was, essentially, a screening test involving a wide variety of commercially available catalyst together with catalysts prepared in our laboratories. Thus, the catalysts included a suppor­ ted cobalt catalyst (catalyst AA), a manganese catalyst (catalyst BB), a tungsten catalyst (catalyst CC), a vanadia catalyst (catalyst DD), a molybdena catalyst (catalyst EE), a copper chromite catalyst (catalyst FF) and a nickel, copper, iron, chromia catalyst (catalyst GG). Turning now to Table II, it will be noted that in all instances there was a reduction in the level of contamination of tertiary butyl hydroperoxide. However, in certain runs (e.g. 6064-84-1, 6064-87-1, 6064-90-1 and 6064-90-2) the contamination level was greater than the level accomplished by straight thermal decomposition at 160°C in run 6064-60-1. Insofar as the reduction of the level of diter­ tiary butyl peroxide is concerned, the only catalyst that reduced the level of ditertiary butyl peroxide below that obtainable by straight thermal decomposition (run 6064-60-1) was catalyst GG. In view of the favorable results obtained at the higher temperature with catalyst GG, three additional runs were made scanning a higher bracket of temperatures ranging from 140°-240°C. Note from run 6089-6, tripli­ cate runs 6089-7 and duplicate runs 6089-12 that in all instances a very low level of contamination of ditertiary butyl peroxide was achieved. However, when the tempera­ ture was more than about 160°C an unacceptable level of isobutylene contamination was obtained. This is shown by run 6089-6-1, 6089-6-2 and 6089-6-3. Longer contact times still further reduced the level of contamination of ditertiary butyl peroxide but resulted in unacceptably high levels of isobutylene contamination as shown by tri­ plicate runs 6089-7 and duplicate runs 6089-12. Example 1-B A series of tests were conducted using a catalyst composition of the present invention together with a ref­ erence catalyst of closely related composition. For this series of tests, however, tertiary butyl hydroperoxide was eliminated from the simulated feedstock because it had already been demonstrated that a catalyst which is effective for reducing the level of contamination of di­ tertiary butyl peroxide will also be effective for reduc­ ing the level of contamination of tertiary butyl hydro­ peroxide. The catalysts tested and the results obtained are summarized in Table III. Again, the pressure used was 3.48 × 10⁶ Pa (500 psig). Note from the results reported in Table III that catalyst AAA of the present invention significantly reduced the contamination level of ditertiary butyl per­ oxide (DTBP) to consistently lower levels of contamina­ tion than those obtained with reference catalyst BBB. Also note the very low isobutylene contamination level obtained with catalyst AAA as compared with catalyst BBB. Compare experiment 6150-28-4 conducted with the catalyst of the present invention which was conducted at 200°C, and a liquid feed rate of 0.454 Kg/hr (1.0 lb/hr) with 6150-30-4 conducted with the reference catalyst under the same conditions. The catalyst of the present inven­ tion gives only 0.0026% isobutylene, whereas the refer­ ence catalyst gives 0.188% isobutylene. Thus, the cata­ lyst of the present invention gives only 0.30% acetone whereas the reference catalyst gives 0.362% acetone. It is also significant to note that although some of the catalysts in Table II gave low yields of isobutyl­ ene, none of the catalysts in Table II was as effective as the catalyst of the present invention insofar as the thermal decomposition of ditertiary butyl peroxide is concerned. Note from Table III that significantly lower levels of ditertiary butyl peroxide were obtained in the product as compared with the amount of ditertiary butyl peroxide present in the product of the examples of Table II.

Claims: 1. A method for enhancing the motor fuel quality of a tertiary butyl alcohol feedstock contaminated with residual quantities of tertiary butyl hydroperoxide and ditertiary butyl peroxide, which comprises the steps of: a. contacting said feedstock in a reaction zone with a catalyst of a temperature of from 80° to 280°C for a period of time sufficient to substantially selec­ tively decompose said tertiary butyl hydroperoxide and said ditertiary butyl peroxide to tertiary butyl alcohol; and b. recovering substantially hydroperoxide-free tertiary butyl alcohol from the products of said reac­ tion; and characterised in that c. said catalyst comprises a metals component of metallic iron, copper, chromium and nickel or the oxides of one or more of said metals, in proportions, on an oxygen-free basis, of from 20 to 80 wt.% of iron, from 5 to 40 wt.% of copper, from 0.1 to 10 wt.% of chromium and from 0.01 to 5 wt.% of cobalt. 2. A method according to claim 1 wherein the reaction is conducted at a temperature of from 110° to 180°C. 3. A method according to claim 1 or 2 wherein the metals component comprises from 30 to 50 wt.% of iron, from 10 to 30 wt.% of copper, from 1 to 5 wt.% of chromia and from 0.05 to 2 wt.% of cobalt. 4. A product tertiary butyl alcohol of a method according to claim 1, which contains not more than 10 ppm of tertiary butyl hydroperoxide, not more than 100 ppm of ditertiary butyl peroxide, not note than 1 wt.% of acetone and not mote that 0.5 wt.% of isobutylene.

Inventors: LARKIN, JOHN MICHAEL, SANDERSON, JOHN RONALD
Applicants: TEXACO DEVELOPMENT CORPORATION
Application year: 1987
Main classification: C07C409
IPC codes: C07C29, B01J23, C07C31, C07C67, C07B61, C07C27