JP2744087B2 - Catalyst for removing peroxide impurities from tertiary butyl alcohol - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tertiary butyl alcohol product containing only a small amount of isobutylene, which is useful as an octane number enhancing component of automotive fuels. A method for removing residual contaminating amounts of tertiary butyl hydroperoxide and ditertiary butyl peroxide from butyl alcohol feedstock. In accordance with the present invention, a source contaminated with peroxide is contacted with a hydrogenation catalyst consisting essentially of nickel, copper, chromium and barium, and without significantly increasing contamination with isobutylene, tertiary butyl hydrochloride. Both peroxide and ditertiary butyl peroxide are substantially selectively reduced to tertiary butyl alcohol.

Prior art a. Method A method for producing a substituted epoxy compound from an α-olefin such as propylene is disclosed in Kollar, US Pat. No. 3,351,653.
The patent discloses that the organic epoxy compound comprises an olefinically unsaturated compound and an organic hydroperoxide, molybdenum, tungsten, titanium,
It is taught that they can be prepared by reacting in the presence of a niobium, tantalum, rhenium, selenium, chromium, zirconium, tellurium or uranium catalyst. When the olefin is propylene and the hydroperoxide is tertiary butyl hydroperoxide, propylene oxide and tertiary butyl alcohol are co-products. U.S. Pat. No. 3,350,422 discloses a similar method using a soluble vanadium catalyst. Molybdenum is a preferred catalyst. Substantial excess of olefin over hydroperoxide is stated to be the usual procedure for this reaction. Also, U.S. Pat.
No. 645 states that it is preferred to add the organic hydroperoxide slowly to the excess olefin.

Stein et al., In U.S. Pat. No. 3,849,451, noted that, among other parameters, close control of the reaction temperature (90-200).
C.) and the need for autogenous pressurization improved the process of Kollar U.S. Pat. Nos. 3,350,422 and 3,351,635. Stein et al. Also proposes the use of several reactors with somewhat elevated temperatures in the final reactor so that a more complete reaction is achieved. The main advantages are said to be increased yield and reduced side reactions.

It is known that isobutane can be oxidized using molecular oxygen to form the corresponding tertiary butyl hydroperoxide, and this oxidation reaction can be promoted, for example, by using an oxidation catalyst (Johnston U.S. Pat. No. 3,825,605 and Worrell U.S. Pat. No. 4,296,263).

Tertiary butyl alcohol can be obtained by a method of reducing tertiary butyl hydroperoxide directly to tertiary butyl alcohol by heat or a catalyst, or by reacting propylene with tertiary butyl peroxide using a catalyst. It can be produced by any method of obtaining an oxide and tertiary butyl alcohol.

It is also known that tertiary butyl alcohol can be used as an octa number enhancing component when added to automotive fuels such as gasoline. Thus, the thermal decomposition of tertiary butyl hydroperoxide and ditertiary butyl peroxide to produce tertiary butyl alcohol has been previously described, for example, as disclosed by Grane in U.S. Pat. No. 3,474,151. Has been proposed. Pyrolysis, as pointed out by Grane, notes that tertiary butyl alcohol initiates dehydration at a temperature of about 450 ° F and accelerates at temperatures above about 475 ° F. Must be done. Moreover, products obtained by pyrolysis usually contain small amounts of tertiary butyl hydroperoxide and ditertiary butyl peroxide. Since they adversely affect the quality of automotive fuels, tertiary butyl alcohol must be substantially completely removed in order to be effective. Grane uses 375 tertiary butyl alcohol containing a small amount of such peroxides.
It has been proposed to achieve this removal by the action of heat by heating for 1-10 minutes at a temperature of ゜ 475 ° F.

This idea was developed by Grane et al. In U.S. Pat. (In the presence of a catalyst), a mixture of tertiary butyl alcohol and tertiary butyl hydroperoxide is obtained, from which a tertiary butyl hydroperoxide-rich fraction can be recovered by distillation. Came to be offered. If this fraction is subjected to pyrolysis for several hours at a temperature of 300 ° F or less under pressure after debutanization, the concentration of tertiary butyl hydroperoxide is greatly reduced. However, the product of this pyrolysis step still contains the balance of tertiary butyl hydroperoxide, most of which was subsequently contaminated with tertiary butyl hydroperoxide, as taught in Grane US Pat. No. 3,474,151. It is removed by the final heat treatment of butyl hydroperoxide.

Thus, the removal of traces of tertiary butyl hydroperoxide from automotive grade tertiary butyl alcohol has received considerable attention. However, there appears to be little publication regarding the removal of traces of ditertiary butyl peroxide, the more refractory of the two peroxides. This means that ditertiary butyl peroxide is not always present in trace amounts in automotive grade tertiary butyl alcohol (its presence or absence is a function of the reaction conditions used in the oxidation of the isobutane starting material). , As well as, if present, in relatively small amounts. For example, after a large amount of tertiary butyl hydroperoxide produced by the oxidation of isobutane is decomposed, the residual content of tertiary butyl hydroperoxide is usually
From about 0.1 to about 1% by weight, based on tertiary butyl alcohol, while the content of residual ditertiary butyl peroxide, if any, is from about 0.1 to about 0.5% by weight.
Would just be.

Sanderson et al. In U.S. Pat. No. 4,547,598 disclose a method of decomposing organic hydroperoxides to alcohols using unsupported cobalt borate or cobalt borate supported on titanium dioxide. It has also been proposed to remove residual hydroperoxides from tertiary butyl alcohol using a heterogeneous cobalt oxide catalyst containing a copper oxide promoter, as taught by Coile, for example, in U.S. Patent No. 4,059,598. ing. Al
Lison et al. in U.S. Pat. No. 3,505,360 disclose that alkenyl hydroperoxides are IV-A, VA or VI-
It was more generally taught that catalytic cracking can be achieved by the use of catalysts based on Group A metals or metal compounds.

Other prior art patents relating to the production of hydroperoxides and having no problems with residual tertiary hydroperoxide contamination and tertiary butyl alcohol include Rust U.S. Pat. No. 2,383,919 and Harvey U.S. Pat. issue,
There are US Pat. No. 3,778,382 to Poenisch et al. And US Pat. No. 3,816,548 to Williams et al.

In DE 3248465-A of West Germany, isobutane is oxidized non-catalytically by air to give the corresponding hydroperoxide with a conversion of about 48 to about 90%, which product is obtained under hydrogenation conditions. A two-stage process is disclosed that catalytically cracks in the presence of a supported catalyst such as palladium, platinum, copper, rhenium, ruthenium or nickel to produce tertiary butyl alcohol. The decomposition products obtained using 1.3% palladium on lithium spinel as catalyst contained significant amounts of acetone, water and methanol.

Mabuchi et al. In U.S. Pat. No. 4,112,004 provided a continuous supply of a solution of an organic peroxide (eg, butadiene peroxide) and a suspension of a nickel catalyst to a reactor in a controlled ratio, and the reaction product in the reactor was A process for producing monohydric or polyhydric alcohols from organic peroxides in the presence of a nickel catalyst is disclosed by continuously withdrawing the reaction mixture at a rate appropriate to maintain a constant weight and composition of the alcohol.

U.S. Pat.No. 4,123,616 to Mabuchi et al. Discloses a process for hydrogenating organic peroxides to the corresponding monohydric or polyhydric alcohol by suspension or fluidized bed processes under hydrogen pressure in the presence of a nickel catalyst. I have. The conversion of butanediene peroxide to 1,4-butanediol and 1,2-butanediol and the conversion of tertiary butyl hydroperoxide to tertiary butyl alcohol are illustrated.

Peroxide generated by the uncatalyzed oxidation of isobutane,
For example, a method for decomposing a mixture of tertiary butyl hydroperoxide and tertiary butyl alcohol is disclosed in U.S. Pat. No. 4,551,553 to Taylor et al. In this patent, decomposition is catalyzed using a catalyst system consisting of chromium and ruthenium that is soluble in hydroperoxide.

"Catalystic Purification of" filed on June 27, 1986
Sanderson entitled "Tertiary Butyl Alcohol (Catalytic Purification of Tertiary Butyl Alcohol)" (Document No. 80,577)
No. 06 / 879,660 by U.S. Pat.
When a tertiary butyl alcohol raw material contaminated with peroxide is treated using a nickel, copper, chromium or iron catalyst supported on silica, tertiary butyl alcohol substantially free of peroxide impurities is obtained. It is disclosed that a product is obtained. Although the formation of undesired by-products such as acetone, methanol and isobutylene is largely suppressed by this method, the results obtained are satisfactory, especially with respect to the formation of isobutylene as an undesired contaminating co-product. is not.

"Catalystic Removal of Pero" filed on November 3, 1986
Sander entitled "Xide Contaminants from Tertiary Butyl Alcohol" Using Catalyst to Remove Peroxide Impurities from Tertiary Butyl Alcohol "(Document No. 80,609)
US co-pending application No. 06 / 926,159 by son et al.
Discloses the use of a base-treated group VIB or VIIIB metal or metal oxide catalyst, such as a base-treated nickel, copper, chromia or iron catalyst, to remove peroxide impurities from t-butyl alcohol. I have.

b.Catalyst Godfrey U.S. Pat.No. 3,037,025 may be promoted by including metal oxides that are normally non-reducing, such as oxides of chromium, aluminum, iron, calcium, magnesium, manganese, and rare earth metals. Disclosed is the preparation of N-alkyl-substituted piperazines using a good catalyst composition consisting of metals and oxides of copper, nickel and cobalt, including mixtures thereof. A preferred catalyst composition comprises about 44 to about 74% by weight nickel and about 5 to about 55% copper.
% And about 1 to about 5% by weight chromium.

U.S. Pat.No. 3,151,112 by Moss describes copper, nickel, cobalt, chromium, molybdenum, manganese, platinum,
Useful for the production of morpholine, containing one or two metals from the group comprising palladium and rhodium, which may be promoted with oxides that are normally non-reducing, such as chromium oxide, molybdenum oxide and manganese oxide. A catalyst composition is disclosed. Exemplary catalyst compositions include those comprising about 60 to about 85% by weight nickel, about 14 to about 37% by weight copper, and about 1 to about 5% by weight chromia. nickel,
Copper and chromia catalysts are also described by Moss in U.S. Pat.
No. 115 and 3,152,998 are also disclosed.

U.S. Pat. No. 3,270,059 to Winderl et al.
Teaches the use of catalysts containing Group B and VIII metals. Examples of suitable catalysts include copper, silver, iron, nickel and especially cobalt.

U.S. Pat. No. 4,014,933 to Boettger et al. Discloses a catalyst promoted by copper and containing cobalt and nickel, such as a catalyst containing about 70 to about 95% by weight of a mixture of cobalt and nickel and about 5 to about 30% by weight of copper. Has been disclosed.

U.S. Pat.No. 4,152,353 to Habermann discloses a catalyst composition comprising nickel, copper and a third component which may be iron, zinc, zirconium or mixtures thereof, e.g., about 20 to about 49% by weight of nickel, About 36 to about 79% by weight and about 1% of iron, zinc, zirconium or a mixture thereof.
Disclosed are catalysts containing from about to about 15% by weight. A similar catalyst composition is mentioned in Habermann, US Pat. No. 4,153,581.

In European Patent Application 00177651, filed October 20, 1980, Haber
Disclosed are catalyst compositions related to the catalyst composition disclosed by Mann, such catalyst compositions comprising nickel or cobalt, copper and iron and zinc or zirconium, for example, 20-90% cobalt, 3-10% copper. 72% and iron,
There are compositions containing 1 to 16% zinc or zirconium and catalyst compositions containing 20 to 49% nickel, 36 to 79% copper and 1 to 16% iron, zinc or zirconium.

West German Patent Application No. 2,721,033 claims nickel 3
A catalyst composition comprising 5%, about 87.5% iron and a small amount of chromia is disclosed.

Johansson et al. In U.S. Pat. No. 3,766,184 disclose a catalyst composition comprising iron and nickel and / or cobalt.

SUMMARY OF THE INVENTION The feedstock of the present invention consists of tertiary butyl alcohol contaminated with tertiary butyl hydroperoxide and ditertiary butyl peroxide.

When isobutane is treated to form tertiary butyl hydroperoxide, the reaction product is usually not only unreacted isobutane, but also tertiary butyl alcohol and other oxygenated by-products such as di-butane. Contains some tertiary butyl peroxide, acetone, etc. After removing the unreacted isobutane by flashing, a fraction mainly consisting of tertiary butyl alcohol may be recovered as a distillate to further concentrate the desired tertiary butyl hydroperoxide reaction product. Tertiary butyl alcohol distillate, which is usually contaminated with tertiary butyl hydroperoxide, ditertiary butyl peroxide, and the like, can be used as a raw material for the method of the present invention.

Tertiary butyl hydroperoxide is suitably reacted with propylene by a method of the type disclosed in U.S. Pat. No. 3,351,635 to Kollar, the primary reaction consisting primarily of unreacted propylene, propylene oxide and tertiary butyl alcohol. Give the product. But usually, the third
Residual butyl hydroperoxide, ditertiary butyl peroxide and other oxygenated impurities present;
It remains dissolved in the tertiary butyl alcohol recovered from the reaction mixture. This tertiary butyl alcohol product can also be used as a raw material for use in the method of the present invention.

Tertiary butyl hydroperoxide decomposes with heat and / or catalyst to produce acetone. Tertiary butyl alcohol can decompose to produce water and isobutylene. Thus, tertiary butyl alcohol, when initially recovered, is not completely satisfactory for use as an octane boosting component in automotive fuels such as gasoline. Thus, the tertiary butyl alcohol usually contains about 3% by weight of acetone, about 1% by weight of isobutylene, about 100 ppm of ditertiary butyl peroxide and about 100 ppm of tertiary butyl hydroperoxide. It is considered insufficient for use as an automotive fuel. Desirably, the tertiary butyl alcohol is about 1% or less by weight of acetone, 0.5% by weight or less of isobutylene, 10 ppm or less of ditertiary butyl peroxide and 100 ppm or less of tertiary butyl hydroperoxide. It is contained below.

Automotive fuel grade tertiary butyl alcohol contaminated with residual amounts of di- and tertiary butyl peroxide and tertiary butyl hydroperoxide is more useful when the catalyst used comprises a nickel, copper, chromia or barium catalyst. It has been unexpectedly found by the present invention that it can be effectively catalytically purified.

According to the present invention, a tertiary butyl alcohol raw material contaminated with peroxide, such as a raw material contaminated with tertiary butyl hydroperoxide and di-tertiary butyl peroxide, is treated at a temperature of about 80-220 ° C. The catalyst of the present invention is contacted under mild conditions including a pressure sufficient to maintain the phase reaction mixture (typically about 200 to about 800 psig, depending on the reaction temperature). If desired, higher pressures up to about 2000 psig can be used, but there is no particular advantage in using higher pressures.
This treatment substantially selectively converts peroxide impurities to tertiary butyl alcohol, resulting in a substrate substantially free of tertiary butyl hydroperoxide and ditertiary butyl peroxide contamination. A processed product is obtained. Thus, the formation of unwanted oxygenated derivatives of peroxide impurities, such as acetone, methanol and isobutylene, is substantially avoided.

The results obtained by the method of the present invention are surprising and unexpected in several respects. Catalytic or thermal decomposition of tertiary butyl hydroperoxide and ditertiary butyl peroxide usually results in the formation of acetone as the preferred decomposition product. Thus, the favorable effect on the quality of the tertiary butyl alcohol of automotive fuel grade obtained by the substantially complete removal of the two peroxides is that the decomposition product is mainly acetone,
Alternatively, the presence of more than traces of isobutylene will greatly offset.

Furthermore, catalysts that are effective for the substantially complete decomposition of tertiary butyl hydroperoxide are usually at most partially effective for the catalytic decomposition of ditertiary butyl peroxide. If desired, inert carriers such as silica and magnesia may be used.

Thus, an automotive fuel grade tertiary butyl alcohol feedstock containing both polluting amounts of di-tertiary butyl peroxide and tertiary butyl hydroperoxide is treated with a catalyst to decompose peroxides, The peroxide does not substantially increase the level of contamination due to the formation of acetone, methanol and isobutane,
The method of the invention, which is virtually completely eliminated, constitutes a distinct advantage over the prior art.

Starting Materials Starting materials used in the process of the present invention include propylene oxide and tertiary butyl hydroperoxide (by oxidizing isobutane to form tertiary butyl hydroperoxide). There are tertiary butyl alcohol raw materials obtained in the above method by producing butyl alcohol.

Automotive fuel grade tertiary butyl alcohol raw material obtained by reacting propylene with tertiary butyl hydroperoxide to produce propylene oxide and tertiary butyl alcohol has a contaminated amount of tertiary butyl hydroperoxide. , Di-tert-butyl peroxide and acetone, and may also contain contaminating amounts of methanol and isobutylene. The usual level of contamination of such materials is that tertiary butyl alcohol, prior to treatment, reduces tertiary butyl hydroperoxide to about 0.1 to
It is common to have about 5% by weight, and about 0.1 to about 5% by weight of ditertiary butyl peroxide. Other impurities may also be present in small amounts.

As indicated above, the reaction conditions used in the catalytic oxidation of isobutane may lead to the formation of ditertiary butyl peroxide. Thus, the feedstock used in the practice of the present invention is an impure automotive fuel containing about 0.1 to about 5% by weight of tertiary butyl hydroperoxide and about 0.1 to about 5% by weight of ditertiary butyl peroxide. Grade tertiary butyl alcohol.

The catalyst composition of the present invention is a catalyst consisting essentially of nickel, copper, chromium and barium. The metal component of the catalyst is usually present during use as an oxide of the metal. Thus, in the peroxide decomposition method of the present invention,
The oxide of the metal is not reduced to its metal form, but the metal, if present, tends to be reduced to the corresponding metal oxide.

A preferred catalyst composition of the present invention is about 1 to about 20% by weight barium and about 1 to about 6% by weight chromium (oxygen free basis), the balance being nickel and copper, the weight ratio being 1 part copper. Nickel or copper, which is 2-3 parts of nickel,
It consists of chromium and barium metals and / or oxides. For example, the composition of the present invention comprises essentially about 30 nickel.
About 60% by weight, copper about 5 to about 40% by weight, chromium about 0.5 to about 1
It may consist of 0% by weight and about 1 to about 30% by weight of barium, wherein the ratio of nickel to copper is as described above.

More preferably, the catalyst composition of the present invention has a barrier of about 1 to 1
It comprises about 20% by weight and about 1 to about 5% by weight chromia, wherein the ratio of nickel to copper is as described above.

The catalyst may also be incorporated in a suitable support, such as silica (eg, Kieselg)
uhr), alumina, titanium dioxide, clay and other similar supports. If a support is used, it preferably comprises from about 30 to about 99.5% of the total weight of the catalyst composition, with the balance (about 0.5 to about 70% by weight)
Consists of metals and / or metal oxides of nickel, copper, chromium and barium.

The catalyst composition of the present invention may be utilized in powder form when performing a batch reaction, but its usefulness when used in pelletized form to catalyze the reaction in a continuous process. Increases.

Contact Treatment of Tertiary Butyl Alcohol According to the present invention, a tertiary butyl alcohol raw material is contacted with the catalyst of the present invention under the correlated reaction conditions as described above, and the tertiary butyl alcohol is similarly converted as an impurity into the tertiary butyl alcohol. The tertiary butyl hydroperoxide and ditertiary butyl peroxide impurities in the tertiary butyl alcohol feedstock are substantially selectively removed by contact without substantially increasing the level of acetone, methanol and isobutylene contamination present. Convert to tertiary butyl alcohol.

The reaction may be carried out batchwise in an autoclave using a powdered catalyst, or the tertiary butyl alcohol of the present invention may be reacted under reaction conditions including a temperature range of about 80 to about 200 ° C. It may be carried out continuously by passing through a reactor containing a bed of catalyst. Reaction is 200-800psig
2,000 ps if desired.
Relatively high pressures up to ig may be used. If the reaction is carried out batchwise, the contact time may preferably be from about 0.5 to about 4 hours. If the reaction is carried out continuously, the tertiary butyl alcohol is passed through the bed of catalyst at a liquid hourly space velocity of about 0.25 to about 5.

After degassing, the reaction product can be suitably used as an octane number improving component of an automobile fuel such as gasoline.

Thus, for example, the effluent from the reactor may be passed through a phase separation zone so that gaseous reactants, including hydrogen and isobutane, volatilize from the product to provide the desired reaction product.

The particular correlation between the particular catalyst of the present invention and the conditions used can be determined relatively easily by techniques common in the art. Thus, for example, a tertiary butyl alcohol feedstock should be analyzed prior to contacting to determine the level of contamination with tertiary butyl hydroperoxide, ditertiary butyl peroxide, acetone, methanol and isobutylene. is there. If a significant amount (eg, about 0.1% by weight or more) of tertiary butyl hydroperoxide and / or ditertiary butyl peroxide is still present due to insufficient reduction of the hydroperoxide,
Since the reaction conditions are not severe enough,
The desired reduction of tertiary butyl hydroperoxide should be achieved by tightening conditions, for example, increasing the reaction temperature or contact time.

On the other hand, if there is a significant increase in the level of contamination of acetone, isobutylene and / or methanol, it means that the reaction conditions are too severe for the particular catalyst and need to be improved (eg shortening the contact time) Or decrease in temperature).

EXAMPLES Procedure The reactor used was a 0.51 inch (inner diameter) x 29 inch stainless steel tube. The liquid feed was pumped into the bottom of the reactor. Before taking a sample for analysis,
The pre-stage was collected at each temperature. To measure moisture percentage
Karl-Fischer titration was used. Other products were determined by GC analysis.

Catalyst XX was prepared in a manner substantially similar to catalyst GGG. However, barium was not used in the preparation of catalyst XX.

Preparation of Catalyst (6141-12-3) Two solutions were prepared as follows.

First _{solution: Ni (NO 3) 2 ·} 6H 2 O 1405g, Cu (NO 3) 2 XH 2 O 3
_{00g, Cr (NO 3) 3} · 9H 2 O 96g, Ba (NO 3) 2 140g and H ₂ O
2500 ml 2nd solution: 800 g of NaCO ₃ and 2500 ml of H ₂ O Both solutions were heated to 80 ° C., and H ₂ O (1
000 ml) at 80 ° C. over 1 hour at a rate such that the pH value stays between 6.85 and 7.45. When the addition was completed, 280 g of the second solution remained unconsumed. The resulting mixture was stirred at 80 ° C. for another hour and filtered hot. The filter cake was stirred at 80 ° C. with 2600 ml of H ₂ O and refiltered. This operation was repeated five more times (the filtration was performed for a total of 7 times).
Times). After drying at 155 ° C. for one day, the filter cake weighed 840.7 g. This was baked at 400 ° C. for 4.5 hours to yield 535.2 g. This is first reduced in a nitrogen / hydrogen mixture stream and finally at about 335 ° C. in a hydrogen-only stream.
Was reduced. The resulting powder was stabilized at 25-29 ° C. by gradually adding an air stream to the nitrogen stream, and finally by adding only the air stream. Analysis of this powder showed that Ni was 55.0% and Cu was 15.6%.
%, 1.8% of Cr and 9.3% of Ba, and 2400 ppm of Na. This is mixed with graphite (3% by weight) and has a crush strength of 20%.
1/8 inch x 1/8 inch tablet weighing ~ 30lb.

I. Equipment and Methods In all cases, each measurement was made of a 1/2 inch diameter by 17 inch long stainless steel connected to a 1/8 inch line for feed and effluent equipped with swagelok fittings. Performed in a tube 100 cc reactor. 100 reactor tubes
It was mounted inside a 3 inch × 3 inch aluminum block electrically heated with four 0 watt strip heaters. The temperature was controlled using a thermoelectric controller that monitors a thermocouple attached to the surface of the reactor body. The feed was replenished to the reactor apparatus using a Beckman 110A LC pump. The effluent from the reactor was collected in a glass head and a sample was taken after the system had been lined out at the given temperature for at least 2.5 hours.

The catalysts used in the examples are tabulated as Table I, with a brief description of their composition.

Experiments 6196-30-4 and 6129-39-4 are compared (both experiments performed at 160 ° C with a feed rate of 0.2 lb / h). Catalyst XX produced 0.214% isobutylene (IB), while catalyst GGG produced only 0.004% isobutylene. Comparing similar experiments performed at different temperatures showed similar results-the catalyst GGG always produced less isobutylene.

Even higher yields of isobutylene were obtained with catalysts DD and EE containing molybdenum and vanadium (known peroxide decomposition catalysts).

The foregoing embodiments have been performed for the purpose of illustrating the invention only and are not intended to limit the scope of the claims as defined by the appended claims.

Claims (3)

(57) [Claims] 1. A tertiary butyl hydroperoxide, ditertiary
A method for improving the quality of a tertiary butyl alcohol raw material automotive fuel contaminated with tert-butyl peroxide, acetone, methanol and isobutylene, comprising the steps of: ,
Contact with a catalyst consisting of chromium and barium, whereby tertiary butyl hydroperoxide is less than 100 ppm, ditertiary butyl peroxide is less than 100 ppm, isobutylene is less than 1% by weight and acetone and methanol are less than 3 ppm each.
A method comprising obtaining a tertiary butyl alcohol product containing less than or equal to% by weight. 2. The catalyst according to claim 1, wherein the catalyst contains 10 to 90% by weight of nickel, 1 to 25% by weight of copper, 0.5 to 3% by weight of barium, based on oxygen.
(1) containing 0% by weight and 1 to 10% of chromium.
The method described in. 3. The catalyst produces an aqueous solution of nickel, copper, chromium and barium nitrate and precipitates a mixture of nickel, copper, chromium and barium compounds by adding a hot solution of an alkali metal carbonate. And then,
The method according to claim 1, prepared by recovering, drying, reducing, calcining and pelletizing the obtained nickel, copper, chromia and barrier composition.