DE1951759B - Process for the production of methyl ethyl ketone - Google Patents

Description

The Lrfuuluny refers to a process / ur / lci ^ tc-ΙΙίΐημ son methyl ethyl ketone by converting Hiiicii with an aqueous solution that contains a palladium coating and a salt of a transition melallic occurring in several oxidation steps.

In particular, I ilindimg relates to a method /.in "Production of methyl ethyl ketone on a large scale Malistab with minimal additional product formation.

It is known that monoolefins in carbonyl compounds in the presence of aqueous solutions containing palladium chloride and copper (II) chloride. by a "Carhony! reaction" in which a monoolelin is converted directly into a carbonyl compound, corresponding to the one given below Equation can be derived from:

R Cl! CII

• 2CuC!
■ dC L

RCOCH, + 2CuCl + 2HCI

Herein, R means a hydrogen atom or an alkyl group.

Procedures using those listed above Implementation are referred to as the Hoechst-Wacker process and are for the first time in »Anuewandte Chemistry". Vol. 71, pp. 176 to 182 (Ί959). described. This process has been used on a large scale in the her-healing of acetaldehyde from ethylene and in the Manufacture of acetone from propylene applied. However, the use of this procedure could lead to higher monoolefins with 4 or more carbon atoms, for example euf ßutent. for the formation of Methyl ethyl ketone due to a number of difficulties have not yet been carried out satisfactorily on an industrial scale. With the Hoechst-Wacker process using an aqueous solution containing pelladium chloride and cupric chloride contains, the rate of the carbonyl reaction decreases of the monoolefin with an increase in the carbon number of the monoolefins ebrupt eb. In »Proceedings of the Sixth Petroleum Congress ". Section IV. Pepcr4 (). On page 2 it is reported that the rate of the caronyl reaction when converting monoolefins with 2 to 4 carbon atoms in the aqueous solution v> n Palladium chloride and copper (II) chloride varied considerably at 70 C under atmospheric pressure, like this can be seen in the table below.

Table I.

Moiionk'lin-

Ethylene

Propylene

Butene

I-butene

Mixture of

! -But and

2-butene (molar

ratio of

1-butene too

2-butene = 1.76

2-butt

t ( ₍ irH "M \ I

l'lNlk'l'Ml

about ' ,

about ', 4
about

V ₇ to V ₈

l'ioduklc

acetaldehyde
acetone

i methyl ethyl ketone
I methyl ethyl ketone

fewer

7.4

as '/,.

Methyl ethyl ketone

*) Die- (iesclmiinliykfil der (° iirhonylrc; iklinii des Ailijlcns / ur UilcliiiiL! vein Accliiklciivcl was mil I fcslucscl / l.

From the preferred Table I it can be seen that the rate of the carbonyl reaction of the Butene is very low compared to that with ethylene or propylene. Therefore, the carbonyl reaction requires the butenes a longer period of time, the yield of methyl ethyl ketone per unit volume of the reactor is extremely low. The volume of the reactor must therefore be increased, whereby a large amount of the expensive, aqueous palladium chloride

ίο and copper III chloride containing solution required will. As a result, the large-scale production of methyl ethyl ketone from butenes was previously possible limited to the lioechst-Wacker process. Numerous attempts have already been made with regard to the

is the rate of the carbonony reaction the butenes to a value which is at least equal to or higher than that of ethylene or propylene. executed.

According to a known procedure, aldehydes and Ketones directly from olefins by reaction in the presence of solutions of compounds of Platinum metals and other additional oxidizing agents, especially iron (III) and copper) II (compounds, and prepared in the absence of carriers (cf. Auslelegcschriften 1 080 994 and 1 158 049). Similar working methods are also found in Austrian patent specification 205 476 and in French Patent 1,207,594 and U.S. Patent 3,086,994.

In each of these known modes of operation, it is a question of the carbonony reaction alone. In the Carbon reaction for the formation of methyl ethyl ketone by reacting 1-butene or 2-butene with the aqueous catalyst solution containing a palladium compound and copper! I!) chloride, as in the conventional Hoechst-Wecker method is used, is the extent or the speed the carbonyl reaction of! -Butt.i much faster than that of 2-butene (viii. "Angewandte Chemie".

Vol. 71.1959. P. 180. table) ".

The object of the invention is therefore to create a process for the production of methyl ethyl ketone at a very high reaction rate using a fraction rich in 2-butene as

■ 45 starting points. being pure methyl ethyl ketone is obtained with little by-products.

The process for the preparation of methyl ethyl ketone according to the invention by reacting Butene with an aqueous solution containing a pelladium

zo compound and a salt of a metal which occurs in several oxidation stages, is characterized in that the reaction a) is carried out with a C ₄ -hydrogen mixture rich in 2-butene. by catalytic isomerization of a

S5 C 1-butene-containing C 1 -C hydrocarbon mixtures at 0 to 300 C under a pressure of atmospheric pressure to 50 atm in a known manner is. and b) carried out with an aqueous solution containing a palladium compound and ice (III) sulfate

f'o in the atomic ratio Pd: Fc of 1:10 to 1: 1000 contains.

In the process according to the invention Mcthyläthylkcton is in high yield with only one very minimal formation of by-products, such as

^ 3-chlorobutanone- (2). n-butyraldehyde or the like.

In particular, in the method according to the invention, the extent or the speed is the

I 951 759

. '; irhi »iiylrc: iction of 2-ihiles faster than that of i-huien. This is clear from the drawing .

In the drawing are the (ieschwindigkeile the: aibonylreaklion of l-lkiK'ii and 2-lkilen on the basis of JIT curves Ii and .1, where the 1 immersion is carried out in (essentially an aqueous solution containing palladium sulfate and iron sulfate, and the (ieschwiiuligkeilen the C'arhonylreaktion sun I-you and I 2-Huten of country of the curves C and I) wherein the reaction in the presence of an aqueous palladium chloride and Kupier (II |. -ehlorid enthallenden solution ilen unier same Reaktionshedingungen was carried represented .

From the drawing it can be clearly seen that the rate of the carbonyl reaction of 1-butene (KarveCl in the presence of the aqueous palladium chloride and copper (II) chloride containing solution (Hoechst-Wacker process) is higher than that of 2-butene (curve D) (see also "Proceedings of the Sixth Petroleum Congress", Section 'V, Paper 40, I.e.).

In contrast, the rate of the carbonyl reaction of 2-butene (curve A) is about 2 times higher than that of I-butene (curve B) in the presence of an aqueous, a palladium compound, e.g. B. palladium sulfate and iron (III) sulphate-containing solution according to the invention.

It can also be seen that the rates of the carbonyl reactions of both 1-butene and 2-butene (curves A and β) in the presence of the aqueous solution containing the palladium compound and iron 11) sulfate are always greater, for example more than that 2 times that of I-butene and 2-butene (curves C and D) in the presence of the solution containing palladium chloride and cupric chloride. If the concentration of palladium present in both aqueous solutions is adjusted to the same gram atom value and / or the concentration of iron in the first solution is equivalent to the concentration of copper in the second solution, the difference between the curves A or B and the curves C or D even larger than indicated in the drawing.

The reaction rate of 2-butene in the presence of the first solution (curve A) is the greatest of the cases shown and is several times greater than the reaction rate of 1-butene in the second solution (curve D) cis-2-butene is somewhat greater than the reaction rate of trans-2-butene in the presence of the first solution containing iron / di) sulfate, although there are no significant differences and the reaction rates of the two isomers are significantly higher than that of I-butene.

It is completely surprising that the relative position of the reaction rates of I-butene and 2-Butcn when using an aqueous solution containing palladium chloride and copper (II) chloride is completely reversed when an aqueous solution containing palladium compound and ice (FII) sulfate is used. It is also surprising that the rate of the carbonyl reaction of 2-Butcn is extremely high in the presence of the latter aqueous solution.

The reaction time in minutes is entered on the abs'.iss of the drawing, and on the ordinate is the amount of butene absorbed in the solution

in millimeters in the course of the carbonyl reaction unlei application of it) ml of the two aqueous solutions given below at 25 C and I al pressure. The curve.-1 denotes the amount of 2-butene absorbed in the aqueous solution, which contains 1.2 g of PdS (J ₄ · 2ΙΙ _: ϋ and 2KOg Fe, (S () ₄ )., 011.0 per Liier. Curve B indicates the amount of 1-butene absorbed in the same aqueous solution, which was also used to determine curve A. Curve C indicates the amount of 1-butene absorbed in an aqueous solution ;; n, which is 5 g PdC'l · and 70 g CuCK · 2If ₂ O per Liier solution. Curve D indicates the amount of 2-butene absorbed in the same solution as was also used for curve C. The results were obtained, by contacting each butene with the respective aqueous solution under the same reaction conditions.

The fraction rich in 2-butene which is used in the carbonyl reaction according to the invention is obtained by isomerizing a C ₄ hydrocarbon mixture, for example a hydrocarbon mixture which contains hydrocarbons whose carbon number is predominantly four, which is 1- Contains butene, a portion of the I-butene being converted to 2-butene in the hydrocarbon mixture. As a result of this isomerization treatment, the butene in the isomerization product is essentially in the form of 2-butene, which is the most favorable feed material for carrying out the carbonyl reaction according to the invention.

Hin CV hydrocarbon mixture as charge mass, which isobutene, η-butane and / or isobutane can also be used as a starting material for the methods according to the invention can be used. If the Ci hydrocarbon mixture feedstock Contains a large amount of isobutene, removing at least some of the isobutene from the Hydrogen mixture preferred, so that a feed mass is obtained with a reduced content of isobutene. The presence of isobutene in the bulk material the formation of tert-butanol results in addition to the main product methyl ethyl ketone. since the isobutene in the feed has a selective hydration reaction due to the catalytic activity of iron (III) sulfate in the aqueous solution.

Suitable feed stocks for use in the process of the invention are available in the industry. for example a C ₄ fraction that is obtained from the catalytic cracking process in the petroleum refinery, a C ₄ fraction that is obtained from the used gases of the butadic extraction plants, a C ₄ fraction from catalytic hydrogenation plants for η-butane and other industrial raw materials.

Charging compositions originating from the industry often contain 1,3-butadiene and 1,2-butadiene, which are hereinafter referred to as C ₄ -dienes and / or vinyl acetylene, ethyl acetylene, dimethylacetylene and diacetylene, which are hereinafter referred to as Q-acetylene. If the feed _{mass to be used contains C 4} dienes and / or C ₄ acetylenes, a selective hydrogenation should be carried out simultaneously with the isomerization under the same reaction conditions in the presence of hydrogen and a suitable isomerization catalyst, as described below. If both

the isomerization and the selective flydration are carried out at the same time, the C'4-dienes and C ₄ -acetylenes in the feedstock become butenes, e.g. 1-butene and 2-butene. converted by the selective hydrogenation, and all of the 1-butene of the butenes obtained, which was formed as the product of the selective hydrogenation of the C ₄ -dienes and C ₄ -acetylenes, is further isomerized to 2-butene. As a result, the content of 2-butene in the isomerized product can be increased to a greater extent if a simultaneous isomerization and hydrogenation reaction takes place than is only possible when carrying out the isomerization reaction alone. Furthermore, the activity of the isomerization catalyst is not reduced, and there is no formation of carbonaceous material and polymers on the surface of the catalyst during the reaction.

All common isomerization catalysts. which have double bond migration activity in unsaturated hydrocarbons can be used in the process of the present invention. Preferred isomerization catalysts are sodium metal. Lithium metal. Palladium metal. Platinum metal. Nickel metal. Sodium oxide. Rubidium oxide. Boron oxide, nickel oxide. Chromium oxide. Titanium trichloride. Heteropoly acids. such as phosphotungstic acid and phosphorus vanadic acid 11. The like. These isomerization catalysts are preferably supported on known catalyst supports, such as. B. aluminum oxide. Silicic acid-aluminum oxide. Silica-magnesium oxide. Titanium oxide. Zirconium oxide. Diatomaceous earth. Pumice. Barium carbonate. Activated carbon and the like, sodium metal as a catalyst or lithium metal as a catalyst have a very high activity for isomerizing '5 1-butene into 2-butene. and these catalysts are very useful in isomerizing the C ₄ hydrocarbon mixture as feedstock. When the selective hydrogenation reaction is carried out simultaneously with the isomerization reaction under the same reaction conditions, palladium are metal. Platinum metal or nickel metal are particularly useful as catalysts, since these catalysts have a high activity for selective hydrogenation and for the _{conversion of C 4} -dicnene and C ₄ -acetylenes to butenes in addition to their activity as isomerization catalysts. Of these, a modified palladium catalyst is particularly effective as an isomerization catalyst for the conversion of! - Below in 2-butene and as a selective I Ivdrierimgs- 5 ¹ ^ catalyst to convert tier C ₄ -dienes and C ₄ -actylcne in butenes. This modified palladium catalyst can be prepared by using a palladium metal catalyst at temperatures of 0 to 350 ° C., preferably 50 to 250 ° C., in the presence of elemental sulfur and sulfur-containing compounds such as hydrogen sulfide. Carbon Disulfide Lider Mcrcaptancn. is heated so that at least a portion of the palladium is sulfurized. .! Continues to show it in this way modified palladium catalyst ^h "; ine remarkably long life Katah tables .iuf reason greater resistance to KaUiK- atorvcrgiftuna?.

The isomerization reaction. whereby the vorsteicnd listed (VKohlenwasserstoffbcschickungs- ⁽¹ 5 wet • duction be reacted with a Isomerisierungskatalvsator in loading is known. The Isomeri-.ierunasumsetzunc \ erläuft easily in the presence or absence of hydrogen. However, Ls is not who dig., the reaction system under in a hydrogen atmosphere if isomerization and selective hydrogenation are carried out simultaneously or if the isomerization reaction is carried out solely in the presence of a palladium catalyst. Pure hydrogen or a hydrogen liquor can be used. The amount of hydrogen to be used depends on the total content of C ₄ dienes and d-atoms in the C 1 -hydrogen charge. Usually 0.001 to 50 mol of hydrogen are used per mol of charge. The isomerization is usually carried out at a temperature of 0 to 300 C., preferably between room temperature and 250 C. below a print ck performed from atmospheric pressure up to 50 atm. Under these conditions of temperature and pressure, both the isomerization and the selective hydrogenation can be carried out easily and simultaneously.

The feed mass can enter the isomerization reactor at an hourly space velocity from 0.1 to 40 are supplied, usually the isomerization catalyst is used in a fixed bed, possibly also in a moving bed or in a fluidized bed.

As a result of the isomerization, the C ₄ hydrocarbon mixture is converted into an isomerization product which is rich in 2-butene as a feed mass with a content of 1-butene and, if necessary, by selective hydrogenation in addition to the isomerization of the feed mass. As a result of the selective hydrogenation _{conversion, the C 4} -Dicnc and C ₄ -AcCtVIeIIC. which hinder the carbonyl reaction, selectively hydrogenated and converted into butenes, ie 1-butene and 2-butene. convicted. The 1-butene is further converted to 2-butene through the isomerization reaction.

If contains a large amount of hydrogen and lighter fractions in the isomerization product they can be removed beforehand by customary separation measures, such as distillation. Stripping and the like removed.

If isobutene is also contained in the isomerization product rich in 2-butene. war.rend the carbonyl reaction according to the invention tert- butanol in addition to the formation of Metlulätln! ketone sic forms. If the formation of tert-butanol is not desired. it is necessary to remove the isobutene from the isomerization principle beforehand.

The isobutene can be removed from the isomerization product by conventional methods, for example absorption of the isobutene in an aqueous sulfuric acid solution with a concentration of 50 to "5 percent by weight, by hydration of the isobutene using an isobutene hydration agent, for example Lisen / III sulfate and Sulfuric acid. Removal of isobutene by using crystalline synthetic zeolite and the like so that isobutene is removed and a more concentrated 2-butene fraction is obtained. Isobutene removal is not limited to the above known processes. All processes by isobutene can be selectively removed from the uv, 2-butene-rich isomerization product can be used.

The Isobutylene Absorptic Method Using of sulfuric acid can be carried out.

by the isomerization product, which is rich in 2 bits, with a sulfuric acid of 50 to 75 percent by weight, preferably a sulfuric acid of 55 to 70% at a temperature of 0 to 50 C below a pressure of atmospheric pressure up to 20 atm, so that thereby selectively the isobutene is absorbed in the isomerization product with sulfuric acid. This creates a concentration 2-biiten fraction with a larger 2-bulen content Mis the received Isomcrisicrungsprodukl in the not absorbed fraction obtained. The contact between the isomerization product and the sulfuric acid can for example be performed in countercurrent or in concurrent flow and using each Contact device, provided that intimate contact is achieved between the two reactants will take place in one or more stages.

In the isobutene hydration, the isomerization product rich in 2-butene is treated with an isobulene hydrating agent at a temperature of 0 to 350 ° C. and a pressure of 0.1 to 50 atm. Phosphoric acid, for example, is suitable as isobutene hydrating agent. Nitric acid. Hydrochloric acid. Sulfuric acid. Acetic acid c. Copper-ul-chloride. Copper (cr (l) chloride. Antimony chloride. Stannic chloride. Bismuth chloride. Zinc chloride. Zinc sulfate. I ^J .isen (Il I! Sulfate. Iron phosphate. Boron phosphate. Tin phosphate. Cadmium phosphate. Natriumphosphal and mixtures thereof.

These hydrants must be used in the presence of water or steam. the Contact between the isomerization product and the hydrating agents in the presence of water or Water vapor can, for example, in countercurrent or with concurrent flow and single-stage or can be carried out in multiple stages using any conventional contacting device, as long as intimate contact between the two reaction lines is ensured.

Selective hydration is usually preferred carried out by the isomerization product in an aqueous, the isobutene hydrating agent containing solution, is introduced.

The adsorption process using a crystalline synthetic zeolite is to that first the isomerization product with the zeolite at a temperature of 0 to 250 C. is preferred 25 to 200 C. under atmospheric pressure or elevated "pressures in the vapor phase or liquid phase is brought into contact, the non-adlorbicrte fraction is removed and then the .im l! colith adsorbed constituents are dcsorbicrt. A concentrated 2-butene fraction is obtained. All crystalline synthetic ones can be used Zeolites used for the selective adsorption of linear hydrocarbons, such as 2-bulene. i-butene and n-bulan capable of adsorbing hydrocarbons with branched chains, such as isobutene and isobutane, are not capable. The crystalline synthetic Eolite is usually placed in a fixed bed, if desired also in a moving bed or in a bed Fluid bed used.

When the isomerization product rich in 2-butene is treated with the crystalline synthetic zeolite will, become 2-butene. 1-butene and n-Buian adsorbed by the zeolite. Isobutene and isobutane that are not adsorbed are taken by the adsorption system submitted. The adsorbed fractions are then desorbed. so that one focused 2-butene fraction is obtained by conventional methods, for example the heat oscillation method, wherein the desorption is effected by heating the zeolite, the pressure oscillation process, wherein the Desorption is effected by lowering the pressure on the adsorption system, and the stripping process, the desorption using purge gases such as nitrogen. Ammonia or saturated or unsaturated hydrocarbons.

ίο In this way, concentrated 2-butene fractions can be created effectively from the isomerization product using the methods used above can be obtained. However, the above-described removal of the isobutene can be omitted, if the isobutene content in the isomerization product is low. In these cases, the isomerization product can be used directly for the carbonyl reaction according to the invention.

In general, the content of 2-butene in the isomerization product is or in the concentrated 2-butene fraction greater than 25 mol percent, preferably greater than 30 mol percent. from the point of view of Economics. However, a feed lower than 25 mole percent can also be used 2-butene can be used if desired and is within the scope of the invention.

The aqueous solution, with which the 2-butene-rich feed for carrying out the carbonyl reaction is implemented, contains 0.05 to 5 g of palladium compound

-, 0 dung and 50 to 500 g of iron (III) sulfate. based on anhydrous salt per liter of solution. If so desired can the carbonyl use according to the invention using larger concentrations Palladium compound and ferric sulfate or clinker Concentrations as listed above can be carried out. The atomic ratio from palladium to iron in the aqueous solution is between 1:10 and 1: 1000. An atomic ratio> universities of Palladium to iron greater than 1:10 results in the precipitation of metallic palladium in the course of the carbonyl reaction. The formation of metallic palladium results in a decrease in activity of the palladium iron system. An atomic ratio of less than 1: 1000 also lowers the activity in the carbonyl reaction.

All palladium compounds in water are soluble can be used in the process of the invention. Palladium compounds, wii Palladium sulfate. Palladium nitrate. Palladium chloride

^ir; I'alladium potassium chloride. Palladium acetate, are preferred. In addition to these, the inorganic salts of palladium, such as palladium sulfate, are used. Palladia 'initiates palladium chloride. Palladium potassium chloride. particularly preferred.

^ It can be used either the anhydrous salt or the lndratisicrtc salt of the iron Il i-suilais the.

The aqueous, the palladium compound and egg Seniüli sulfate-containing solution can also be a

^ ⁰ contain a small amount of halogen ions. The essential nature of the halide ions in the aqueous solution can be achieved by adding a small amount of an organic halide. Suitable inorganic halides include the halide

' ¹ ^ various metals, such as iron. Copper. Cobal nickel. Chrome. Potassium. Sodium. Calcium. Barine and strontium and the hydrogen halides. The preferred halides consist of a metal

chloride or hydrogen chloride. The halogen ion in the aqueous solution does not act as a reactant. The small amount of the process according to the invention halogen ions used shows a catalytic activity benefit in the carbonyl reaction the olefins and is also very useful in preventing the precipitation of metallic palladium from the aqueous solution during the carbonyl reaction. Thus, the amount of to the aqueous Solution to be added halogen ions only 0.1 g ions or less per mole of iron (III) sulfate. The presence of more than 0.1 g ions is not favorable because it results in a rapid decrease in velocity the carbonyl reaction of 2-butene results in and also a decrease in the yield Methyl ethyl ketone is achieved. If the palladium compound used does not contain halogen, such as. B. Palladium sulfate, or palladium nitrate, must have the entire required amount of halogen ions through a Metal halide or a hydrogen halide can be supplied. On the other hand, they are only supplementary To supply quantities for the total halogen ion required by such halides, if halogen-containing Palladium compounds such as palladium chloride can be used.

In the context of the invention, the aqueous solution is usually preferred in a proportion of 0.1 to 100 l 0.2 to 80 liters per mole of butene in the isomerization product rich in 2-butene or in the concentrated one 2-butene fraction used. If the amount to is less than 0.1 l per mole, the yields are humiliated. Amounts greater than 100 liters per mole give no practical advantage and are uneconomical.

The carbonyl reaction for the production of Mcthyläthylkctons takes place at ordinary temperatures and at atmospheric pressure. The reaction is advantageously carried out at elevated temperatures under pressure in order to increase the rate of the reaction. In practice, the reaction can be carried out at temperatures between room temperature and 200 ° C., preferably from 70 to 120 ° C. under a pressure sufficient to keep the aqueous solution in the liquid phase, usually at a pressure of from atmospheric pressure to 50 atm, preferably from 5 up to 40 atm. be performed. At temperatures higher than 200 ° C., hydrolysis can take place with precipitation of iron (III) hydroxide, which can lower the yield of methyl ethyl ketone. F “s is beneficial. To apply measures that ensure intimate contact between the phases or that increase their miscibility. Intimate contact can be achieved by mechanical measures such as stirring. Shake. Spraying and application of oscillators and also by chemical measures that favor the formation of large surfaces. be achieved.

Inert solvents, for example methanol, can be used as promoters to increase the miscibility. Ethanol. Ethylene glycol. Polyethylene glycol. Dioxane. Dimethylformamide. Acetic acid and propionic acid as well be set. The contact between the aqueous solution and the isomerization product rich in 2-butene or the concentrated 2-butene fraction can, for example, be touched in countercurrent or by contact with a concurrent flow or by blowing in the 2-Butcn charge done in the aqueous solution. The Konlaktzcit between the aqueous solution and the 2-butene π xiicn charge is usually in Range from 0.1 to 20 minutes, preferably 0.5 to 10 minutes. However, they can be shorter or longer Contact times will be applied. Furthermore, the carbonyl reaction can be carried out in a single batch, semicontinuously or be carried out continuously.

To obtain the Mcthyläthylkclon formed: the reaction mixture of a distillation, the Stripping or other conventional procedures are subjected to so that a product mixture of methyl ethyl ketone and water is obtained, if di < 2-butene-rich feed also contains isobutene, a product mixture of methyl ethyl ketone, tcrt. Butanol and water is separated from the reaction mixture. The consumed aqueous solution dci Palladium compound and the ice (III) -silfate came be combined with water so that the solution is adjusted to the necessary concentration, unc can by conventional regeneration processes, for example oxidation using oxygen or gases containing oxygen, such as air, regenerate and then returned to the reaction zone.

Various common methods can be used for the separation of anhydrous methyl ethyl ketone from the mixture can be used. If z. B. the product mixture contains no tert-butanol, the product mixture a) can with any of the known Dchydratisicrmittcl. treated like anhydrous table salt or rock salt to make anhydrous methyl ethyl ketor to obtain. Also can b). after most of the water has been removed, the mixture continues to distill be taking a small amount of a; azeotropic mixture of methyl ethyl ketone unc Water (the azo-tropic mixture boils at 73.41 C unc contains 88.7 percent by weight of methyl ethyl ketone and 11.3 percent by weight of water) as overhead Mass and anhydrous methyl ethyl ketone ah soil fraction is obtained. Furthermore, c) can Mix the product with a suitable amount of common materials such as cyclohexane. η-hexane. Methylcyclopentane. are added, which modify the relative volatility of methyl ethyl ketone to water. The mixture is then distilled and an anhydrous methyl ethyl ketone is obtained.

If the product mixture contains tert-butanol, can d) the product mixture can be treated with known dehydrating agents to the entire Remove water and anhydrous methyl ethyl ketone and anhydrous ten-butanol after distillation to obtain. Also e) a suitable amount of water / 11 can be added to the mixture and that Mixture are distilled, making the mixtureμπ a first azeoiropes mixture of methyl ethyl ketone and water and a second azeotropic mixture of tcrt.-Buianoi and water is separated (which has azeotropic mixture of tert.-butanol and water a boiling point of 79.9 C and a composition from SS.24 percent by weight tert-butanol and 11.76 percent by weight water. Any arcotropic mixture is treated in the usual way in the manner described above to give anhydrous methyl ethyl ketone or to obtain anhydrous tert-butanol. Furthermore, f). if the content of tert-butane <i! in the Product mix is low. the mixture in the vapor phase with an alcohol vaporization catalyst. such as aluminum oxide or silica-aluminum oxide treated so that selectively the tert -

Butanol is decomposed to isobutylene and water. The The resulting mixture containing methylethyl octone and water can be prepared in the manner described above be treated.

Since the aqueous solution used in the experience according to the invention is somewhat corrosive. should the parts of the device that deal with the aqueous Solution come into contact, formed from corrosion-resistant materials or lined with them being. z. B. titanium. Tantalum, synthetic resins, rubber, Lmail. Glass. Porcelain and ceramics.

As explained in detail above, the process according to the invention allows large-scale production of methylethyl octone at low cost due to the following advantages:

a) The speed of the carbonyl reaction is very high. As a result, the response time are abbreviated, and the yield of methyl ethyl ketone per unit of time and per volume unit of the reactor, hereinafter referred to as space-time yield, can be increased. Furthermore, the volume of the reactor can be reduced to a very manageable size can be reduced, and the amount of the expensive aqueous solution used for the carbonyl reaction can be kept at a minimum

b) In the process according to the invention, 2-butene can be used be used as the cheapest charge. So far, however, 2-butene was considered to be unfavorable Feeding in the usual Hocchst-Wacker process due to its lower reaction rate compared to I-butene.

c) The C ₄ dicnees and the C ₄ / cctylenes. which prevent the carbonyl reaction of the butenes can be converted to 2-butene as a suitable feed for the production of methylethyl octone in the process of the invention.

d) The amount of by-products is very small. As a result, in the method according to the invention the amount of by-products, such as 3-chlorobutanone- (2) and the like very low and is only about a tenth of that in the conventional Hocchst-Wackcr process formed by-products. No complicated procedures for cleaning the product are therefore necessary.

The methyl ethyl ketone thus obtained is a known material and has numerous uses in a variety of fields, for example as a solvent for use in dissolving of coating materials. Solvent for fine waxing of petroleum fractions and for use for pharmaceuticals and former products.

The following examples serve to provide further explanation the invention.

example 1
a) Preparation of the starting mixture

The feed mass used consisted of a Cj hydrocarbon mixture with that in FIG the composition given in Table II below.

Tables salary
(Molpro / cni / iisanimciKiM / unj;
5 _ ....... 12.5
32.8
15.2
39.5 1-butene 2 pictures Isobutene. ο n- and isobutane

The isomerization catalyst used was sodium mclall. worn on aluminum oxide. the Sodium metal aluminum oxide catalyst was

'5 tcr made using the following procedure: Aluminum oxide with a fineness corresponding to a sieve opening of 1.41 to 0.84 mm (14 to 20 mesh) was dried to remove the water. The alumina was mixed with the sodium metaline an amount of 6 percent by weight, based on the total Catalyst weight. mixed in a dry nitrogen atmosphere at about 200 ° C. with stirring and then the alumina was cooled to room temperature under a nitrogen atmosphere.

² ^ 3 l of the isomerization catalyst were introduced into a vertical glass-lined reactor with an internal diameter of 12 cm and a height of 38 cm. The charging mass listed in Table II was in the lower ^P art of the reactor with

An hourly space velocity of 2.0 was initiated and the isomerization reaction was carried out at a temperature of 25 ° C. and a pressure of 5.3 atm, as a result of which the 1-butene in the batch was converted to 2-butene.

■ ^ The isomerization product rich in 2-butene. that was removed from the top of the reactor had the composition listed in Table III below.

Table 111

Vcrbinihmc

1-Butcn

2-butene

Isobutene

n- and isobutane

(ichall iMolpro / enl)

2.4 42.9 • 5.2 39.5

^ ₀ b) method of the invention

The isomerization product rich in 2-butene was then. continuously in an amount of 3.2 kg hours to the lower part of a cylindrical titanium reactor with a volume of 6 1 and 2 n "height, which was equipped with a stirrer and baffle plates. together with an aqueous solution. the 1 s PdCl _:. 2S0 g Fe ₂ (SO ₄ I, -9M ₂ O and 7 g of CuCl, containing 2H ₂ C per liter of aqueous solution, added in an amount before 100 1 hour. The carbonvireaction was be

⁽ '° at a temperature of 100 ° C. at a pressure of 30 atm with stirring at 700 revolutions per minute' in contact with a concurrent flow.

The resulting reaction mixture was ii

^ a separation device, wherein the pressure was reduced to atmospheric pressure. At the same time, steam was fed to the bottom part of the reactor to remove the unreacted isomerization product

1 95! 759

A mixture of methyl ethyl ketone. lcri.-Butaiiil liiuI water as vapor phase from the upper part ler separator ahzudeslillicieu. The one found Steam was cooled down and produced a liquid, liquid product the methyl ethyl ketone. teri.-Bulanol .ind VVasse; contained. This liquid product was nil rock salt at room temperature and under atrial pressure treated to remove the water completely / u, n. The anhydrous methyl ethyl ketone was separated from the tert-bulanol by distillation. The consumed aqueous solution was at the bottom Part of the separator removed.

Methyl ethyl ketone was obtained in an amount of 1416 g hr. The space-time degradation of methyl ethyl ketone was 2.Ui g 1 hour. Terl-Butanol was in an amount of 416 g ski. receive.

The gas chromatographic analysis of the product showed the presence of sec-butanol, n-butyric acid. 3-chlorobutanone- (2) and acetone as by-products. The total of the four connections however it was only IS.5 gSld.

Example 2
al preparation of the starting mixture

The vervcr / jete feed mass consisted of a (^ -K -hydrocarbon mixture with that in the the composition listed below in Table IV

Table IV

. "■ hiiuliini; CeIuIi
ι M'llpnvent 1,3-butadiene. 3X.4 Vinvlacelat. . 1 .9 I-butene 14.1 2-butene X 2 lsobuien "M.! n- and isobul; in 1 3.3

The isomerization catalyst used consisted of a modified palladium-aluminum oxide. This catalyst was prepared by supporting the catalyst on aluminum oxide with a 1 unit corresponding to a sieve opening of 1.41 to 0.84 mm with 0.5 percent by weight of palladium, based on the total catalyst weight. The palladium-alumina catalyst (300 ml) was placed in a vertical reactor with an internal diameter of 50 mm. Hinwassloffslrom with a content of 1.0 volume percent hydrogen sulfide was in the reactor in an amount of 300 l / h. at 200 ('under atmospheric pressure for a period of 5 hours, so that at least part of the palladium in the catalyst was sulphurized.

Into the reaction vessel packed with the catalyst prepared above was charged the charge shown in Table IV containing 150 ppm of hydrogen sulfide at a rate of 1800 ml / hour. and 50 mol% of hydrogen, based on the charge mass, introduced. The isomerization reaction of 1-butene to 2-butene and the selective polymerization reaction of the C ₄ -dienes and C ₄ -A,.

peralur of 70 C under a pressure of 35 atm accomplished.

The product table obtained in this way then winds separated from the hydrogen and gave an isoinerization product rich in 2-Buienes. its composition shown in Table V below.

Table V

\ crhnutuiii!

1,3-butadiene

Vinyl acetylene

1-butene

2-butene

Isobutene 23.2

n- and isobutane lf> .2

b) method of the invention

The isomerization product listed in Table V was continuously in an amount of 5 kg hours. In the same reactor as in Example 1 together with an aqueous solution containing 1 g of PdCl. 2X0 g Le ₂ (SOj 9H ₂ C) and 7 g FeCT, · 6H ₂ O per liter Li) SUiIg contained, in an amount of IfK) for 1 hour. The carbonyl reaction was carried out at a temperature of 110 ° C. and a pressure of 30 atm in a concurrent flow with stirring at a speed of 700 revolutions / minute.

The resulting reaction mixture was prepared using the procedure described in Example 1 treated and gave the desired methyl ethyl ketone i.i an amount of 350Og'Std. the The space-time yield of methyl ethyl ketone in this case was 5 × 3.5 g for 1 hour. In addition, terl-butanol in a quantity of 1214 gh. receive. Line rings Amount of by-products from sec-butanol. n-butyric aldehyde. 3-chlorobutanone- (2) and acetone was ascertained.

Example 3

The same procedure was used as in Example 2, but the following four aqueous solutions instead of the aqueous solution with Ig PdCL. 2XOg Le ₂ (SOJ, -9H ₂ C) and 7g LeCl, -6H ₂ O according to Example 2 were used. The following results were obtained in the tests:

L With an aqueous solution containing 0.77 g of Pd (NO,) ,. 2XOg Le ₂ (SO ₁ ), -9H ₂ 0 and 5 g LeCl, · 6H ₂ O per liter of aqueous solution were methyl ethyl ketone and tert-butanol in an amount of 34Ci5 g Sld. or 11X2 g hrs. obtained.

2. Use of an aqueous solution with 0, X g PDSC) ₄ .2H ₂ O, 280g FCj (SO _4)., -9H ₂ O and 5 g FCCI, .6H ₂ OJC liter of solution of methyl ethyl ketone and tert-butanol in Quantities of 3491 or 1210 g / hour. receive.

3. With an aqueous solution containing 1.0 g of PdS 2H ₂ O and 280 g of Fe ₂ (SO ₄ )., · 9H ₂ O per liter of solution, methyl ethyl ketone and tcrt.-Bi in quantities of 3262 or 1130 g / pc. crh .uen.

4. With an aqueous solution containing 2 g of PdSO ₄ 2H ₂ O, 420 g of Fe ₂ (SO ₄ ), -9H ₂ O and 6 g of salt

sau den gen

the ι icli .-. ll Table iMnlpro / aiii 0.009 0 3.0 57.0 1-Bui

2-But Isobi n ur

AO

acid (37 percent by weight) per Liier solution, methyl ethyl ketone and lcrl-bulanol were added in quantities of 3450 or 12 (K) g hrs. obtained.

Example 4

a) Preparation of the mixture

The feed mass used has the composition listed in Table VI.

Table VI

\ L-i '

1-butene

2-butene

Isobutene

n- and isobutane

(icli.ih
I Mnlprii / cn'i

12.5
32.8
15.2
39.5

The feedstock listed in Table VI had previously been treated with an isobutene hydrator to reduce the isobutene content of the feedstock. The hydration treatment of the isohutacn was carried out according to the following procedure: The charge mass according to Table VI was in an amount of IC kg / hour. fed to the lower part of a stainless steel reactor 2 m high and an internal volume of 15 l, which was equipped with a stirrer and baffle plates. Ii) the top of the reactor was an aqueous isobutene hydrator. which contained 200 g of 1-C ₂ (SO ₄ )., · 9HjO 'and 20 g of H ₂ SO ₄ per liter of aqueous solution, in an amount of 200 1 / Sld. brought in. The above reactants were continuously introduced and treated in countercurrent at a temperature of 110 ° C. and a pressure of 30 atm with stirring at 700 revolutions / minute, so that the isobutene in the feed mass was selectively hydrated to tert-butanol. The mixture was then withdrawn from the system together with the aqueous solution of the isobutene hydrating agent. Tert-butanol was used in an amount of 1431 g / hour. receive. The fraction that had not been hydrated. was treated with silica gel to completely remove the water. The composition of this fraction is shown in Table VII below.

Table VII

1-Bulcn

2-butene

Isobutene

n- and isobutane

(k-lial;
iMulpro / cnli

13.8

36.9

5.1

44.2

The fraction listed in Table VIl was added at an hourly space velocity of 2.2 the lower part of a vertical glass-lined reactor with an internal diameter of 12 cm and 38 cm height introduced, the naked with 3 l of the sodium metal-aluminum oxide catalysis used in Example 1 was. The leomerization reaction to

The conversion of 1-butene into 2-butene was carried out in a temperature of 25 C and a pressure of 5.3 atm.

The isomerization product removed from the top of the reactor is shown in the following Table listed composition.

Table VIII

\ L-r

1-butene

2-butene

Isobutene

n- and isobutane

(i.ill

2, X
47 »

5.1
44.2

b) Method of Invention

The isomerization product described in Table VIII was then continuously fed into a reactor as used in Example 1 in an amount of 4.0 kg / hour. together with an aqueous solution containing 2 g of PdCl ₂ . 320 g Fe ₂ (SO ₄ ), · 9H ₂ O and 7 g FeCl., · 6H ₂ O per liter of solution in an amount of 100 1 / hour. fed. The carbonyl reaction was carried out at a temperature of 100 ° C. and a pressure of 30 atm with stirring at 700 revolutions / minute in cocurrent.

.ίο The reaction mixture obtained was treated as in Example 1 and gave methyl ethyl ketone in an amount of U.72 g hours. The space-time yield of methyl ethyl ketone was 312 g / l / Sld. In addition, tert-butanol was obtained in an amount of 174 g / hr.

Example 5
a) Preparation of the starting mixture

That described in Table Hi: Example I. Isomerisicrunijsprodukt is rich in 2-butene Stirred tank supplied and there with a sulfuric acid of 65 "(i at a temperature voii '5 C below Pressure treated, with the weight ratio: vr »n Isomerization product to the sulfuric acid of 65 weight percent was about 1: 1. The not absorbed Fraction was treated sequentially with fresh 65% sulfuric acid.

F-iicMC absorption cycles were performed three times each carried out in the opposite direction unabsorbed traction consisted of concentrated 2-butene traction with that in the following "Composition listed in Table IX.

Table IX connection (icliall
(Molpro / cnl I-butene 2.8
50.2
47.0 2-butt n- and isobutane

b) method of the invention

^The concentrated 2-butene fraction listed in Table IX in an amount of 5.5 kg / hour and an aqueous solution with 1 g of PdCl ₂ , 280 g, were continuously fed into the reactor used in Example I

I 951

he

Fe ₂ (SO.,), - ¹ JIhO and 5 μl, -6IhO per liter of aqueous solution in an amount wtn 100 I hours. In this case, the ammonia aclion was carried out at 110 ° C. at a pressure of 30 atm with stirring at 700 revolutions, minule in cocurrent.

The reaction mixture obtained was treated as in Example I. The milestone you want was obtained in an amount of 3133 g hours. Here space-time today on methyl ethyl ketone was 522 g / L Sid. No partial bulanol was formed.

Example 6
a) Preparation of the starting mixture

The 2-Buien-rich isomerization product described in Table V for Example 2 was in one Kettle treated with sulfuric acid of 65 "u at a temperature of 15 C under pressure, the weight ratio \; mi isomerization product to Sulfuric acid was about ΐ: I. The unabsorbed fraction was successively countercurrent Treated with fresh 65 "sulfuric acid. After the absorption operation was repeated three times, the resultant had not absorbed Fraction has the composition listed in Table X.

Table X

connection

Butadiene

1-butene

2-butene

n- and isobutane ....

[ Salary

I I Molpro / enl I

4.6
73.9
21.5

b) Method of discovery

In the reactor used in Example I, the concentrated 2-butene fraction listed in Table X was continuously fed in an amount of 5.5 kg hours and an aqueous solution containing I u PdCi ,. 2SOg Le ₂ (SO ₄ ), - 9H ₂ O and 7g LeCl, 6H ₂ O per liter of aqueous solution in an amount of 100 1 / hour. introductory. The carbonyl reaction was carried out at 110 ° C. under a pressure of 30 atm with stirring at 700 revolutions / minute in cocurrent.

The reaction mixture obtained was then according to Treated Example 1 and obtained the desired Me- so Ihyläthylkcton. The methyl ethyl kelon was in an amount of vein 46 ^ 0 g hrs. received what one Space-line yield of 773 g / l / hour. is equivalent to. Fs no tert-butanol was formed.

B ice ρ ic 1 7
a) Preparation of the starting mixture

The feed weight had the composition listed in Table XI. ,

IH

\ Li ΙιιιΐιΙιιιιμ

2-Huien

Isobutene

n- and isobuta.

1 Mnlpiii / L'iu 1

Ui.ll
41.S.
13.2

In a vertical reaction vessel with an internal diameter of 50 mm. the mn 300 ml of the in example 2 used modified l'al ladiuni -Alumini iimo \ y d catalyst was packed. If the in table XI listed 'charge mass, the 250 ppm AlInI-meicaplan contained in a lot of ISDiImI skis. and 10 mole pro / enl hydrogen on a charge weight basis. introduced to simultaneously the Isonierunusreaktion and to conduct selective llydrieruni. After removal of the hydrogen, the isomerization product was as follows Table XII listed composition:

Table XII

connection

1,3-butadiene

I-butene

2-butene

Isobutene

n- and isobutane

Table XI

connection

1,3-butadiene
I-rods

salary
(Molpro / enl)

1.7
27.3

salary
iMolpro / en'.l

2.5
42.1
41.6
1 3rd p

The isomerization product according to Table XI! was continuously fed into the bottom of a stainless steel reactor 2 m high, equipped with a stirrer and baffle plates. in an amount of 10 kg / hour. initiated. At the same time, an isobutylene hydration system was used. which consisted of an aqueous solution containing 200 g of Fc ₂ (SO ₄ ), · 9H ₂ O and 20 g of H ₂ SO ₄ per liter of the aqueous solution, continuously introduced into the top of the reactor in an amount of 200 1 hour. The hydration reaction of the isobutene to give tert-butanol was carried out in the reactor at a temperature of 110 ° C. and a pressure of 30 atm with stirring at 700 revolutions / minute in countercurrent. The tert-butanol was removed from the hydration system together with the aqueous solution of the isobutene hydration agent. From this aqueous solution, tert.-butanol was obtained in an amount of 4543 g / h.

The fraction that had not received hydration provided the concentric 2-butene fraction with the composition listed in Table XIII.

Table XIII salary
(Mole percentage connection 3.5 1-butene 66.1 2-butene 8.5 Isobutene 21.9 n- and isobutane

Claims (1)

h | Procedure of LiTmdung In the reactor used in Example I, the concentrated 2-Bule; ii-IT action according to Table XIII in a menu ", e of 5.5 ky SuL and a wäl.irige solution with 1 g Pd (L, 2S0 g le , | S () ₄ ), ■ ¹ JIi ₂ O and 7 g IeCl, 611.0 per Liier solution in an amount of 100 I Sld. Initiated and the carbonyl reaction at a temperature of 110 C and a pressure of 30 atm carried out with stirring at 700 revolutions Minule in cocurrent. The resulting reaction mixture was separated using the procedure of Example 1 and gave the desired methyl ethyl ketone in an amount of> 74 g, Sid., which is a space-time yield from 662 gTStcl. is equivalent to. There were also 444 g 'pc. terl.-butanol obtained. Example 8
a) Production of the original sound The isolation product described in Table III of Example I. was in an amount of 30.4 l / h. by one with 1.1 1 of a crystalline synthetic Zeolilhs (with the pore size of 5 Å) packed Adsorption column out. The temperature of the adsorption column was then increased to 75.degree. The unabsorbed components were continuously withdrawn from the adsorption column. The adsorption column was then heated to 300 C and SlickstofTges in an amount of 30 1 / hour. at a pressure of! atm passed through the column in order to desorb the material absorbed on zeolite. After the nitrogen had been removed, the desorbed fraction produced the concentrated 2-Bulenl'raklion with the ingredients listed in Table XIV. Table XIV connection I-butene 2-butene Isobutene ti- and isobutane Ciehnlt
(Molpro / cnl 3.6 64.5 1.6 29.7 h | Procedure of the iliiulung The concentrated 2-Uulen ITaklion according to the table XIV was continuously in the example I S used reactor Mi an amount of 5.5 kg / Sld. together with a walky solution with I g IVR L, 2SOg Lc (SO ₄ ), ¹ JII ₂ (J and 7g le ( ¹ I., 6 I ί, Ο per Liier solution in an amount of K) OI / hour . initiated. The (arhonylreaktion was at a temperature door of 110 C with a pressure of 3OaIm below Stirring carried out at 700 revolutions minute in cocurrent. The resulting reaction mixture was then applied using; the method according to Example 1 treat and he read the desired methyl ethyl ketone. The Methyl ethyl ketone was used in an amount of 3950 g. Hrs. Get what a rajm-time bulge from g, l / h is equivalent to. Terl.-Üulanol was also obtained in an amount of 83 g / hr. Patent claims: 1. Process for the preparation of methyl ethyl ketone by reacting butene with a aqueous solution containing a palladium compound and contains a salt of a transition metal occurring in several oxidation states, thereby marked that one the Implementation a) with a CV hydrocarbon mixture rich in 2-butene, which is Table isomerization of a 1-butene-containing (V-hydrocarbon mixture at 0 to 3 (H) C has been prepared under a pressure of atmospheric pressure to 50 atm in a known manner. and b) carried out with an aqueous solution which contains a palladium compound and ice (III) sulfate in an atomic ratio of Pd: Fe of 1:10 to 1: 1000. 2. The method according to claim 1, characterized in that the aqueous solution in an amount from 0.5 to 100 l per mole of butene in the 2-butene-rich C ^ hydrocarbon mixture used w'rd. 3. The method according to claim 1 or 2, characterized in that an aqueous solution is used del, which additionally contains halogen ions in a concentration of less than 0.1 g-ions per mole of L ^: isene (III! -sulfate. 4. Seduction according to claim L, characterized in that that the implementation with i-inern - ^S ° 2-butene-rich C ^ -hydrocarbon mixture is carried out, from which the isobutene has been removed in a known manner after the Isomcrisicrungsstufc. 1 sheet of drawings