Catalytic preparation of tertiary butyl alcohol from tertiary butyl hydroperoxide and catalysts therefor

Abstract: The t-butyl hydroperoxide forming a contaminant in a charge stock whose major component is t-butyl alcohol can be converted into tertiary butyl alcohol at a high conversion rate and with high selectivity by a soluble catalyst system comprising a soluble iron compound and a soluble ruthenium compound. The charge stock can be obtained for instance by the reaction of isobutane with molecular oxygen.

Description: This invention relates to the catalytic decomposition of tertiary butyl hydroperoxide. More particularly, this invention relates to a method for the preparation of tertiary butyl alcohol by the catalytic decomposition of tertiary butyl hydroperoxide. Still more particularly, this invention relates to a method wherein a soluble catalyst system composed of a soluble iron compound and a soluble ruthenium compound is used to catalyze the substantially selective decomposition of tertiary butyl hydroperoxide to tertiary butyl alcohol. Said soluble catalyst systems constitute another aspect of this invention. It is known to react isobutane with oxygen, either thermally or catalytically, to form a peroxidation reaction product wherein the principal peroxide that is formed is tertiary butyl hydroperoxide. It is also known to thermally or catalytically decompose the tertiary butyl hydroperoxide to form tertiary butyl alcohol. In the text entitled "Organic Peroxides" edited by Daniel Swern (Wiley Interscience, a Division of John Wiley & Sons, New York), in Vol. II on page 157 it is stated that the metal-ion-catalyzed decomposition of primary hydroperoxides yields mainly alcohols, aldehydes and carboxylic acids, citing as an example the decomposition of hydroxymethyl hydroperoxide with aqueous ferrous sulfate to provide formaldehyde, formic acid and water. Quin U. S. -A- 2,854,487 discloses the hydrogenation of hydrocarbon peroxides in the presence of hydrogen and palladium on activated alumina to provide carbinols. In Massie U. S. -A- 3,775,472 a process is disclosed wherein alkyl substituted aromatic hydrocarbons are oxidized to products such as aromatic alcohols, aldehydes and carboxylic acids in the presence of ruthenium compounds. Vanadium and ruthenium catalysts have been used to prepare saturated vicinal esters by catalyzing the reaction of olefins and the carboxylic acid derivatives thereof with oxygen, as shown by Stapp U. S. -A- 4,221,916. Taylor et al. U. S. -A- 4,551,553 is directed to a process for the formation of alcohols such as tertiary butyl alcohol by the catalytic decomposition of an organic hydroperoxide such as tertiary butyl hydroperoxide using a binary catalyst composed of a mixture of a ruthenium compound with a chromium compound. It is stated that the use of the binary catalyst eliminates the need for stabilizing ligands. Grane U. S. -A- 3,474,151 discloses that tertiary butyl alcohol starts to dehydrate at 232°C (450°F.) and to decompose at a "rapid rate" at temperatures above 246°C (475°F.) Grane discovered, however, that residual quantities of hydroperoxide contaminants present in tertiary butyl alcohol could be thermally decomposed by heating the contaminated tertiary butyl alcohol at a temperature of 190° to 246°C (375° to 475°F.) for 1 to 10 minutes. Grane et al. U. S. -A- 4,294,999 discloses a process wherein isobutane is oxidized in a pressured reactor in the presence of a solubilized molybdenum catalyst to provide a mixture of tertiary butyl alcohol, tertiary butyl hydroperoxide, methanol, acetone, and other oxygen-containing compounds. The tertiary butyl hydroperoxide is thermally decomposed under pressure at 138°C (280°F.) to provide a tertiary butyl alcohol product containing only residual quantities of tertiary butyl hydroperoxide which are then decomposed in accordance with Grane U. S. -A- 3,474,151 by heating the tertiary butyl alcohol at 190° to 246°C (375° to 475°) for 1 to 10 minutes. Heating tertiary butyl alcohol containing small amounts of peroxides at high temperatures for even short periods of time to remove the peroxides produces undesirable products such as isobutylene. Grane et al. U. S. -A- 4,296,262 discloses a related process wherein isobutane is reacted with oxygen in a reaction zone for a residence time of 1 to 10 hours at a temperature of 115° to 171°C (240° to 340°F.) and a pressure of 0.8 to 7.0 MPa (100 to 1000 psig.) in the presence of a catalytically effective amount of a soluble molybdenum catalyst. A liquid stream comprising tertiary butyl alcohol is recovered from the reaction mixture and fed to a decomposition zone wherein the tertiary butyl hydroperoxide contained therein is decomposed by "hot aging" at 121° to 176°C (250-350°F.) at a pressure lower than the pressure in the oxidation zone. The tertiary butyl alcohol can be further subjected to a clean-up treatment at 190 - 246°C (375-475°F.) for 1 to 10 minutes. Worrell et al. in U. S. Patent No. -A- disclose a related process wherein the feedstock is a mixture of normal butane with isobutane and wherein the oxidation catalyst is a soluble form of chromium, cobalt, nickel, manganese, molybdenum, or a mixture thereof. 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 contaminants are also formed. In addition, a minor amount of water will be formed, which will normally amount to 0.5 to 1 wt.% of the reactor effluent. The amount of byproduct water that is produced is a function of the severity of the reaction conditions employed and will tend to increase as the severity of the reaction conditions is increased. A listing of the components present in a representative reaction product, and their nominal boiling points is given in Table A. Component NBP (°C) Isobutane -11.7 Methyl formate 31.8 Acetone 56.3 Isobutylene oxide 60.0 Isobutyraldehyde 64.1 Methanol 64.7 Methyl-t-butyl peroxide 74.2 Isopropyl alcohol 82.3 Tertiary butyl alcohol 82.4 Ditertiary butyl peroxide 111.0 t-butyl-i-pr-peroxide 124.0 Tertiary butyl formate 163.8 The minor by-products are sometimes difficult to remove. For example, tertiary butyl formate has a higher boiling point than ditertiary butyl peroxide but tends to distill overhead, which suggests that it forms a minimum boiling azeotrope with another component or components. As indicated, tertiary butyl hydroperoxide is useful as a raw material for the manufacture of tertiary butyl alcohol. The tertiary butyl alcohol can be formed by catalytic decomposition of the tertiary butyl hydroperoxide. In the Williams et al. process disclosed in U. S. -A- 3,472,876, an oxygen-containing gas was charged to a reactor containing isobutane and an oxidation catalyst to provide a reaction mixture comprising tertiary butyl alcohol, tertiary butyl hydroperoxide, acetone, and tertiary butyl ether. The reported results in the patent indicate that there was a comparatively low rate of conversion and a comparatively poor selectivity of the reaction to tertiary butyl alcohol. A feedstock for the present invention is suitably one by the oxidation of isobutane with molecular oxygen to provide an oxidation reaction product containing a solution of tertiary butyl hydroperoxide and tertiary butyl alcohol in unreacted isobutane. The feedstock for the present invention may comprise tertiary butyl hydroperoxide dissolved in tertiary butyl alcohol which is recovered from the isobutane oxidation reaction product. The feedstock is charged to a catalytic decomposition zone wherein the tertiary butyl hydroperoxide is decomposed in the presence of a soluble catalyst system composed of a soluble iron compound and a soluble ruthenium compound to provide a decomposition reaction product characterized by a high conversion rate and a high selectivity of tertiary butyl hydroperoxide to tertiary butyl alcohol. The tertiary butyl alcohol will not be the only decomposition product that is formed. Minor amounts of other oxygen-containing materials such as those listed above will also be formed. The tertiary butyl alcohol that is recovered from the decomposition reaction mixture will be contaminated with the oxygenated impurities. The starting materials for the process of the present invention are a tertiary butyl hydroperoxide feedstock and a catalyst system composed of a soluble iron compound plus a soluble ruthenium compound. The ruthenium-containing compounds employed as a catalyst may take many different forms. For instance, the ruthenium compound may be a salt of a mineral acid, such as ruthenium (III) chloride hydrate, ruthenium (III) bromide, ruthenium (III) iodide, tricarbonylruthenium nitrate, or as the salt of a suitable organic carboxylic acid, for example, ruthenium (III) acetate, ruthenium naphthenate, ruthenium valerate and ruthenium complexes with carbonyl-containing ligands such as ruthenium (III) acetylacetonate. The ruthenium may also be a carbonyl or hydrocarbonyl derivative. Here, suitable examples include, among others, triruthenium dodecacarbonyl and other hydrocarbonyls such as H₂Ru₂(CO)₁₂, and substituted carbonyl species such as the tricarbonylruthenium (II) chloride dimer, (Ru(CO)₃Cl₂)₂. Additional examples of ruthenium compounds include ruthenium octoate, ruthenium laurate, ruthenium stearate, ruthenium linoleate, ruthenium nitrate, ruthenium sulfate and ruthenium carbonyl. The iron-containing compounds employed as catalysts may also take many different forms, such as ferrous and ferric compounds, including: iron (II) acetate, iron (III) acetate, iron (III) borate, iron (II) bromide, iron (II) chloride, iron (III) chloride, iron (III) 1,3-diphenyl-1,3-propanedionate, iron (III) 2-ethylhexanuate, iron (II) fluoride, iron (III) fluoride, iron (II) gluconate, iron (II) iodide, iron (III) nitrate, iron (III) 2,4-pentanedionate, iron (III) perchlorate, iron (II) sulfate, iron (III) sulfate. The combined ruthenium plus iron compounds may comprise 0.001 to 10 wt.% of the total t-butyl hydroperoxide reactant mix. Preferably the ruthenium plus iron compounds comprise 0.01 to 5.0 wt.% of the total reactants. Said ruthenium plus iron compounds may be charged to the hydroperoxide reactants in a weight ratio of iron to ruthenium of 0.01:1 to 100:1. Preferably this iron/ruthenium compound weight ratio is 1:1 to 10:1. The process of the present invention may be conducted batchwise in kettles or by continuously passing the reactants through a tubular reactor. The catalytic decomposition of the tertiary butyl hydroperoxide is preferably conducted at a temperature within the range of 20° to 100°C. and, more preferably, at a temperature within the range of 30 to about 60°C. The reaction is preferably conducted at autogenous pressure although superatmospheric pressures up to 7.0 MPa (1000 psig.) may be used, if desired. Flow rates of the charge solution to the reaction zone should be adjusted in order to provide an appropriate contact time within the reactor. In a batch process, the holding time may suitably be from 0.5 to 10 hours, and more preferably 1 to 3 hours. In accordance with the most preferred embodiment of the present invention, isobutane is reacted with oxygen in an oxidation zone under oxidation reaction conditions including a temperature of 135 to 155°C., a pressure of 2.2 to 5.6 MPa (300 to 800 psig.), and a holding time of 2 to 6 hours to provide an initial oxidation reaction product comprising unreacted isobutane, tertiary butyl hydroperoxide, tertiary butyl alcohol, and oxygen-containing by-products. The oxidation reaction product is fractionated in any appropriate manner (e.g., by distillation in a distillation zone) to remove the isobutane therefrom for recycle and to provide a solution of tertiary butyl hydroperoxide and tertiary butyl alcohol which will normally contain from 5 to 30 wt.% of tertiary butyl hydroperoxide. If the tertiary butyl hydroperoxide concentration is excessive, additional tertiary butyl alcohol may be added. The solvent solution of tertiary butyl alcohol in organic solvents (e.g., tertiary butyl alcohol solvent solution of tertiary butyl hydroperoxide) is then charged to a catalytic hydroperoxide decomposition zone where it is brought into contact with a catalyst system composed of a soluble ruthenium compound and a soluble iron compound to substantially selectively convert the tertiary butyl hydroperoxide to tertiary butyl alcohol with high yields and selectivities. As indicated, the catalytic decomposition of the tertiary butyl hydroperoxide in the catalytic hydroperoxide decomposition reaction zone may suitably be conducted at a temperature within the range of 20° to 120°C. (and more preferably from 30° to 60°C.) at autogenous pressure or if desired at a superatmospheric pressure up to 7.0 MPa (1000 psig.) for a contact time within the range of 0.5 to 10 hours, and more preferably 1 to 3 hours. The reaction product from the tertiary butyl hydroperoxide decomposition step may then be fractionated in any suitable manner, such as by extractive distillation to recover the tertiary butyl alcohol. The invention will be further illustrated by the following specific examples Procedure: Tube Experiments A 150-ml Fisher-Porter pressure tube equipped with pressure gauge, rupture disk, and shut-off valve was charged with 15.0g of a 20% TBHP solution in TBA, and catalyst(s). The tube was suspended in a constant temperature bath (+ or - 0.2°C.) for the desired period of time at the required temperature. The tube was then placed in cold water (15-20°C.) for 15 minutes after which the pressure was slowly released. The liquid contents were analyzed by GC. The results are shown in the attached Table I. No. Catalyst(s) Time (Hr) Temp (°C) Conv. TBHP% Selectivity, % TBA Acetone MeOH DTBP 1 Ru(AcAc)₃ [.005g] 1.0 100.0 99.87 78.56 19.75 5.65 0.91 2 Ru(AcAc)₃ [.005g] 1.5 80.0 99.85 83.43 14.63 3.02 1.30 3 Ru(AcAc)₃ [.005g] 4.0 60.0 99.92 86.49 10.91 1.57 1.99 4 Ru(AcAc)₃ [.005g] 1.0 60.0 99.88 86.22 11.31 1.64 1.88 5 Ru(AcAc)₃ [.005g] 1.0 60.0 99.64 87.53 9.78 1.33 2.07 Fe(AcAc)₃ [.01g] 6 Ru(AcAc)₃ [.002g] 2.0 60.0 98.88 88.50 9.03 1.10 1.75 Fe(AcAc)₃ [.018g] 7 Ru(AcAc)₃ [.004g] 2.0 60.0 98.48 88.51 9.29 1.32 1.57 Fe(AcAc)₃ [.036g] 8 Ru(AcAc)₃ [.005g] 2.0 60.0 99.75 87.33 10.51 1.32 1.60 Cr(AcAc)₃ [.01g] 9 Ru(AcAc)₃ [.004g] 2.0 40.0 89.84 91.13 4.78 <0.5 3.30 Fe(AcAc)₃ [.036g] With reference to the table, it will be noted that essentially equivalent conversions of the tertiary butyl hydroperoxide were obtained with the ruthenium catalyst, the reference ruthenium-chromium catalyst and the ruthenium-iron catalysts of the present invention and that essentially equivalent selectivities to tertiary butyl alcohol were also obtained. However, there was a significant and desirable reduction in the selectivity of the reaction to acetone with the ruthenium-iron catalysts of the present invention. Thus when the acetone selectivity for Run No. 4 using a ruthenium catalyst is compared with the acetone selectivity for Run No. 5 of the present invention, it will be noted that the acetone selectivity was reduced by about 15%. Acetone selectivities were also lower in Run No. 6 and Run No. 7 where reductions of about 20% and about 17%, respectively, were obtained. In Run No. 9 , conducted at a temperature of only about 40°C., there was a loss in the conversion of the tertiary butyl hydroperoxide which was offset by about a 5% increase in the selectivity to tertiary butyl alcohol and by about a 60% reduction in the selectivity to acetone. Iron compounds are, in general, more economical and less toxic than similar chromium compounds. In addition, iron compounds do not have the handling and disposal problems that some chromium compounds have.

Claims: A method for decomposing t -butyl hydroperoxide into decomposition products, principally t -butyl alcohol, wherein a charge stock containing t -butyl hydroperoxide in t -butyl alcohol is brought into contact with a hydroperoxide decomposition catalyst in liquid phase with agitation, characterized in that the hydroperoxide decomposition catalyst comprises a soluble iron compound and a soluble ruthenium compound. A method according to Claim 1 characterized in that the weight ratio of iron compound to ruthenium compound in the soluble catalyst system is from 1:1 to 10:1. A method according to Claim 1 or 2 characterized in that the iron compound is ferrous acetylacetonate and the ruthenium compound is ruthenium acetylacetonate. A method according to any one of Claims 1 to 3 characterized in that the catalyst is employed in an amount from 0.01 to 5 wt.%, based on the weight of the charge stock. A method according to any one of Claims 1 to 4 characterized in that the charge stock and catalyst are contacted for 0.5 to 10 hours, at a temperature of 20° to 100°C and autogenous pressure. A method according to Claim 5 characterized in that the reaction time is from 1 to 3 hours and the temperature is from 30 to 60°C. A catalyst system useful in the catalytic decomposition of t -butyl hydroperoxide which comprises a mixture of a soluble iron compound with a soluble ruthenium compound in a weight ratio of 1 to 10 parts of said iron compound per part of said ruthenium compound. A composition according to Claim 7 characterized in that the iron compound is ferrous acetylacetonate and the ruthenium compound is ruthenium acetylacetonate.

Inventors: KNIFTON JOHN FREDERICK, SANDERSON JOHN RONALD, KNIFTON, JOHN FREDERICK, SANDERSON, JOHN RONALD
Applicants: TEXACO CHEMICAL, TEXACO CHEMICAL COMPANY
Application year: 1991
Main classification: C07C29
IPC codes: C07C29, C07C31, B01J31, C07B61