Method of production of ketones and catalyst for realization of this method

FIELD: main organic synthesis.

SUBSTANCE: proposed method is used for production of ketones, for example dimethyl ketone (CH3COCH3), methyl ethyl ketone (CH3COC2H5) by direct catalytic oxidation of respective alkenes, for example propylene, n-butenes, as well as catalysts for realization of this method. Oxidation of alkenes is performed in the presence of metallocomplex catalysts containing organic component where nitrogen oxide (I) is used as oxidant. Used for process is catalyst on base of peroxopolyoxo metallate complexes of terakis (oxo diperoxo metallate)-phosphate (3-) together with quaternary ammonium cationes having formula Q3{PO4[MeO(O2)2]4}, where Me-Mo, W,V; Q3 is quaternary ammonium catione containing alkyl chains C4-C8 or N-hexadecyl pyridinium.

EFFECT: enhanced selectivity of process.

10 cl, 14 ex

 

The invention relates to the field of organic synthesis, namely the method of production of ketones, such as dimethylketone (DMK, CH3PINES3), methyl ethyl ketone (MEK, CH3SOS2H5) direct catalytic oxidation of the corresponding alkenes, such as propylene, n-butenes, as well as catalysts for its implementation.

DMK and IEC are large-tonnage products industrial organic synthesis. Due to the exceptionally high dissolving ability DMK and IEC find wide industrial application [The Chemical Economics Handbook - New York: SRI International (CEN, 1996]. They are the basis of various paints and adhesives, are used as solvents in the production of polyurethane lacquers, which are used for coating magnetic tapes and audio cassettes and various tools used in the creation of film coating of tablets and capsules medications as extractants in the primary production of medicines. IEC is one of the best deparaffinization fuels and lubricating oils for their frost resistance, is used in the manufacture of foams, artificial leather, PVC skin, epoxy and glyptal resins. As raw materials IEC is used when receiving methylisobutyl-ketone, 2,3-butandione; methyl ethyl ketone oxime, preventing the formation of films during storage cu the juice; to obtain ethylacrylate and isomeric methylcrotonate acids, antioxidants rubbers, for plasticization derivatives of nitrocellulose used in the production of smokeless gunpowder and other Basic applications DMK as reagent is a synthesis of methacrylate, isobutyl ketone, methacrylic acid, cellulose acetate, methylisobutylcarbinol and other.

DMK in the world produce three main synthetic methods. Komorny method, which consists in carrying out the process in two stages: obtaining gidroperekisi cumene and splitting it into phenol and DMK [FR 2050175; US 3803243, US 3839461; GB 1359047; JP 50-1258]. According to this technology cumene oxidized by oxygen in the air to gidroperekisi of cumene in the presence of carbonate and sodium stearate. At this stage produces by-products dimethylbenzylamine alcohol and acetophenone. Oxidation proceeds by a free-radical mechanism and inhibited by unsaturated compounds. Oxidat focus to the content of gidroperekisi 80%, and then subjected to cleavage in the presence of an acidic catalyst. Subsequent improvements in Kumanovo method are reduced to the application of new catalysts, for example composed of polyphthalocyanine copper and heterocyclic amine (pyridine, quinoline, triazine, pyrazine), or carrying out the reaction more gidroperekisi cumene placentas is for multiple reactors at a temperature of from 80 to 120° C. the content of gidroperekisi in the first reactor low-to-2%; in the second to 18-20%in the third 26%, and in the fourth it increased to 31%.

Two-stage process of obtaining DMK from propylene via isopropyl alcohol jointly developed by the two companies in the UK and Germany [Hydrocarbon Process., v.54, No. 11, 1975, R]. In the first stage, propylene and water vapor overheat up to 180°and then pass in the hydration reactor over the catalyst under a pressure of 35 ATM. The second stage of the process is the dehydrogenation of the resulting isopropanol. It is carried out at 450-550°in megatropolis reactor. Acetone fraction is distilled in the column, which is then rectificatum in pure product. Received DMK contains about 0.1% water.

The number of industrially important reactions include catalytic oxidation of propylene in DMK using a homogeneous catalyst based on palladium chloride (II) and copper(II) Wacker process. The catalyst employed in relatively mild conditions (temperature 120°C, the pressure of ethylene 5 ATM), has a high activity and selectivity. However, the practical use (PdCl2+CuCl2systems is complicated by a number of disadvantages, which will be explained in detail on the example of obtaining IEC (see reactions 8, 9).

On an industrial scale IEC receive several ways. The main ways the om is a three-stage (1)-(3) processing butylene fraction - a by-product of butadiene plants synthetic rubber. The advantage of this method lies in the cheapness of the raw materials.

Stage (1) and (2) liquid-phase, and phase (3) may be either in liquid-phase and heterogeneous catalytic variant. The disadvantages of this method are:

a large amount of hazardous waste contaminated acidic tars sulfuric acid; highly corrosive environment at stages (1) and (2); high energy stage (3); the complexity of the allocation process the IEC from the reaction mixture, containing many impurities.

One of the modifications of this method is the process in which H2SO4replaced by acetic acid, and the intermediate product is sec-butyl acetate:

As the catalyst stages (2A) and (3A) use sulfonation, which has a small life because of the blocking surface of the formed resin. Contaminated sulfonation is unusable waste production, which seriously affects the environmental and economic performance of the whole process.

Numerous patents suggest that to create effective the th process of obtaining IEC of n-butenes a study was carried out in companies of different countries. Of most interest are two new methods: three-stage, including reactions (4)-(6) [US 5304684, 1994]; the process of direct oxidation of n-butenes in the reaction (7) [Jira R., W. Freiesleben // in: Organometallic Reactions / Ed.: E.I.Becker, M.Tsutsui. Vol.3 - New York et al.: Wiley Intersci., 1972 - P.1-190] and a number of processes using polyoxometallates, the so-called heteropolyacids or their salts [SU 700973; B 01 J 23/44; 1994; SU 822417; B 01 J 23/44, 1994; WO 91/13852, 19.09.1991; SU 1669109, B 01 J 23/44, 1994; SU 1584200, B 01 J 23/44, 1994; SU 1669109, B 01 J 23/44, 1995; JP 07-149685, 1995].

Three-stage method [US 5304684, 1994] based on the reactions (4)-(6), similar to those used in modern industrial method of production of phenol and acetone through Gidropress cumene. However, the stage (5) and the decomposition (6) of the gidroperekisi second-butylbenzene flow with significantly less selective than receiving and decomposition gidroperekisi cumene. Along with the IEC and phenol, in the process formed aldehydes, unsaturated ketones, carboxylic acids, their esters and resins. By-products are removed by alkali, making the process environmentally unfriendly.

One way of obtaining IEC similar Vakker process [Jira R., W. Freiesleben // in: Organometallic Reactions / Ed.: E.I.Becker, M.Tsutsui. Vol.3 - New York et al.: Wiley Intersci., 1972 - P.1-190]:

Homoge the catalytic reduction reaction (7) can be performed in one reactor, giving him a stoichiometric mixture of n-C4H8/About2=2/1 or carried out in two stages: 1) interaction of n-butylene, with a solution of intermediate acting reversible oxidant Oh in the presence of a palladium salt according to equation (8); 2) regeneration Ox oxygen according to equation (9):

Initially as Oh used chlorine copper CuCl2[Jira R., W. Freiesleben, see above], the reduced form of which is ion CuCl-- easily oxidized by oxygen. However, the synthesis of IEC according to reaction (9) in the presence of chloride system (PdCl2+CuCl2) was accompanied by the formation of a large number of side of chlorbutanol (25%). In the absence of Cl-ions or their lack of Cu(II) are not able to serve reversible oxidant. The rate of oxidation of n-butylenes significantly below the rate of oxidation of ethylene and propylene. The speed of delivery of products, expressed in terms of the performance of the catalyst for acetaldehyde, 400 g·l-1·h-1, acetone 130 g·l-1·h-1and for methyl ethyl ketone and 30 g·l-1·h-1. A significant drawback vacarescu system is that due to the presence of chlorine ions severe corrosion of the equipment from an alloy containing iron. Therefore, the GOC is of n-butylenes this process in industry was not implemented.

In the invention [SU 700973, B 01 J 23/44, 1994; SU 822417, B 01 J 23/44, 1994] and later [SU 1669109, B 01 J 23/44, 1994; EN 2230612, B 01 J 23/44, 2004] for the system (Pd+Ox) has been proposed to use as reversible oxidant Mo-V-phosphoric heteroalicyclic (CCP), having the General formula H3+nPVnMo12-nAbout40. With their participation butylene reaction described in equation (8A), and the oxygen in equation (9a):

where HCC is the reduced form of heterophilically with the General formula H3+n+mPVIVmVVn-mMo12-nO40.

In this way the catalytic system Pd2++CCP) did not contain Cl-ions and therefore provides a complete lack of organochlorine compounds in the reaction products. The selectivity of the system was reached 95-98%, while activity in butylene reaction (8A) in 100 times the activity of the chloride system (PdCl2+CuCl2). The process can be arranged in single-stage and two-stage versions. However, in the latter case, there was a deep recovery molecules of the CCP. Therefore, the catalyst (Pd+CCP), as shown by pilot testing, it was impossible to recognize quite stable nor in respect of palladium, either in relation to the CCP. The low stability of this catalyst proved to be its greatest disadvantage.

The placenta is their 30 years there have been many attempts to stabilize the palladium in the catalyst (Pd+CCP), however, all of them for different reasons it was rejected by technology. The easiest way to keep Pd2+in solution the introduction of small concentrations of Cl-ions corresponding to the atomic relations Cl-/Pd=5÷50, was proposed in the patent firm Catalytica Inc. (USA) [WO 91/13852, 19.09.1991]. However, even with such concentrations of chlorine from a solution of the catalyst quickly passed into the reaction products with the formation of organochlorine compounds. Required continuous addition of hydrochloric acid in the solution, and purifying products from organochlorine compounds. Therefore mallorey catalyst (PdCl2+CCP) has not found industrial application.

The use of palladium in the form of complexes with pyridylcarbonyl acids (α-pikolinos or dipicolinate) increases its stability [SU 1584200, B 01 J 23/44, 1994; SU 1669109, B 01 J 23/44, 1995]. However, 10 or more times the reduced activity of the catalyst in the reaction (7a) due to excessive stabilization of palladium, and therefore, decreases the efficiency of the process as a whole. Therefore, this method turned out to be-low-tech.

In the invention [JP 07-149685, 1995] catalysts (Pd+CCP) was used in mixed solvents containing less than 50% water. As such used dioxane, ethanol, tetrahydrofuran, γ-butyrolactone or sulfolan. Reaction (7) conducted a single-stage: RAS is voennyi α -butene at 80°and a pressure of About29 kg/cm2oxidized in the IEC. The stability of the palladium ensured by the fact that reaction (8A) and (9a) proceeded simultaneously in one reactor). However, conversion α-butene in the IEC was small: 21% per hour in aqueous dioxane and 14% in aqueous ethanol. The idea of using non-aqueous solvents for the reaction (7) was unpromising, since this reaction proceeds through the stages (8A) and (9a), in which water is acetalization reaction (7), and the decrease of its content dramatically reduces the reaction rate.

This reason allows us to understand low activity in the reaction (7) heterogenizing catalysts (Pd+CCP)deposited on a solid carrier [Stobbe-Kreemers A.W., van der Zon M., Makkee M., J.J.F. Scholten // J. Molec. Cat.; Stobbe-Kreemers A.W., M. Makkee, J.J.F. Scholten // Appl. Catal.]. When using such catalysts were used not liquid water, and water vapor, which could give water only condense in the pores of the support. Therefore, reaction (8) in a heterogeneous version was very slow.

A prototype of the proposed method and catalyst to obtain a ketone (DMK, IEC) is a method [SU 1584200, B 01 J 23/44,1994], in which the catalyst using an aqueous solution of salt of palladium 10-4-1,5·10-2M, a derivative of pyridine, 10-4-4,5·10-2M aqueous solution of oxometallic acid salt postrm libdevinfo heteroalicyclic (CCP) 0,05-03 M with the General formula IU andH3+n-aRMO12-nVn-4O40where Me is an alkaline or alkaline earth metal; n=2-7; 06 n≅and<n, obtained by the interaction of decavanadate metal metavanadates of the same metal, molybdenum trioxide and phosphorus pentoxide or phosphoric acid when the molar ratio [(n-a)/4]/[5-3n)/2]/[12-n]/[0.5 or 1] or decavanadate metal with molybdenum trioxide and phosphorus pentoxide or phosphoric acid when a molar ratio of 0,1n/(12-n)/(0.5 or 1) when boiling. The oxidation reaction is carried out by interaction of the catalyst with n-butylene, at temperatures of 50-70°and after the separation of ketone oxidize the recovered form of the catalyst with oxygen or air at temperatures 130-160°With (two-stage version).

The main significant disadvantages of the method are the instability of palladium in the solution - precipitation of metallic palladium butylene reactor (stage 8A) with incomplete return it to the solution in the air reactor (stage 9); even more serious disadvantage is the instability of the molecules of the CCP, due to the loss of part of vanadium, drop-down in the form of a brown solid V3O7·2H2O, which trudnookislyaemymi waste production.

The invention solves the problem of increasing the efficiency of the method of producing ketones.

The task resetsession obtain ketones by oxidation of alkenes in the presence of metal complex catalysts contains organic component, an oxidizer used nitrous oxide (I). The oxidation reaction is carried out in the liquid phase, the liquid phase may contain not more than 10% of water.

The oxidation reaction of alkenes is carried out in one reactor, feeding a mixture of reactants consisting of alkenes, nitric oxide (I) and light alkanes.

The oxidation reaction of alkenes is carried out in the liquid hydrocarbon, which can be used aromatic hydrocarbons.

The oxidation reaction of alkenes is carried out at a temperature of 20÷150°and the total pressure of the gas mixture 1÷3.5 ATM.

Use the catalyst on the basis of peroxomonosulfate complexes - tetrakis(oxodiperoxotungsto)-phosphate(3-) in combination with Quaternary ammonium cations, with General formula Q3{PO4[MeO(O2)2]4}, where Me - Mo, W, V; Q3- Quaternary ammonium cation containing alkyl chains C4-C8or N-hexadecylpyridinium.

The concentration of the catalytic complex is 1·10-2÷1·10-4M

The problem is solved also by the composition of the catalyst obtain ethyl ketone oxidation of butenes nitrogen oxide (I) in the liquid hydrocarbon, which is peroxomonosulfate complex - tetrakis(oxodiperoxotungsto)-phosphate(3-) in combination with the Quaternary ammo avimi cations, with General formula Q3{PO4[MeO(O2)2]4}, where Me - Mo, W, V; Q3- Quaternary ammonium cation containing alkyl chains C4-C8or N-hexadecylpyridinium. The concentration of the catalytic complex is 1·10-2÷1·10-4M

The catalyst was synthesized analogously to known methods [C. Venturello, Alneri E., Ricci M. // J. Org. Chem. 1983. Vol.48. R; C. Venturello, Ricci M. // J. Org. Chem. 1986. Vol.51. No. 9. P.1599; Ishii Y., Yamawaki K., Ura T., Yamada H., Yoshida T., Ogawa M. // J. Org. Chem. 1988. Vol.53. No. 15. P.3587; R. Noyori, M. Aoki, and K. Sato // Chem. Commun. 2003. No. 16. P.1977; Pai Z.P., Tolstikov A.G., P.V. Berdnikova, Kustova G.N., Khlebnikova T.B., Selivanova N.V., Shangina A.B., Kostrovsky V.G., " Izv. An. Ser. chem. 2005. No. 8].

The main difference of the proposed process of obtaining ketones are:

a) use as an oxidant nitric oxide (I), which improves the selectivity of the process;

b) carrying out the process in a single reactor in accordance with, for example, reaction (10) reduces capital costs for the production of the corresponding ketone;

C) conducting the reaction in the liquid phase - liquid hydrocarbons containing not more than 10% water, this helps to improve the solubility of gases and, in particular, nitric oxide (I);

g) carrying out the process under relatively mild conditions when 20-150°and bsem the pressure of the gas mixture 1÷ 3.5 atmospheres, and the use of alkenes containing light alkanes, allows to make the process safe;

d) the use as catalysts of peroxomonosulfate with organic component and the General formula Q3{PO4[MeO(O2)2]4}, where Me - Mo, W, V; Q3- Quaternary ammonium cation containing alkyl groups of C4-C8or N-hexadecylpyridinium, for example: n-Bu4N+C5H5N(n-C16H33)+CH3N(n-C8H17)3+etc. Peroxomonosulfate complexes have greater activity in various oxidation reactions of organic substrates than catalysts based oxometalates process of the prototype, where the system (Pd+CCP) stable phthalocyanine ligands (RS).

The invention is illustrated by the following examples.

Example 1. In the reactor-type catalytic duck" 220 ml, fixed on the rocking chair, placed 50 ml of a solution containing 0,542 g (0,240 mmol) of the catalyst having the composition: [CH3(n-C8H17)3N]3{PO4[WO(O2)2]4}. The reactor thermostatic at 50°remove air using a vacuum pump and filled with a mixture gas composition, vol.%: N2O - 50,0, α-C4H8- 48,15, the sum of CIS - and TRANS-β-C4H8- 0,7, n-butane - 1,1, although the white admixture -≅ 0,05. Connect the reactor burette filled with gas having the composition: α-C4H8- 96,3, the sum of CIS - and TRANS-β-C4H8to 1.4, n-butane - 2,2, heavy impurities is 0.1, and with vigorous shaking of the reactor to carry out the oxidation of C4H8according to reaction (10). 8 min the solution containing the catalyst oxidizes 68 ml of butylene. The yield of methyl ethyl ketone, established on the basis of chromatographic analysis of the reaction mixture, equal 74,0%.

Example 2. In example 1, characterized in that the catalyst used [C5H5N(n-C16H33)]3{PO4[WO(O2)2]4}. 6 min oxidize 76 ml C4H8. The yield of methyl ethyl ketone is 73%.

Example 3. In example 1, characterized in that the catalyst used [(n-Bu)4N]3{PO4[WO(O2)2]4for 15 min oxidize 102 ml C4H8. The yield of methyl ethyl ketone 72%.

Example 4. In example 1, characterized in that add 0,271 mmol catalyst, for 10 min oxidize 90 ml C4H8. The yield of methyl ethyl ketone and 67.8%.

Example 5. In example 1, characterized in that add 0,048 mmol of catalyst. For 20 minutes oxidize 87 ml C4H8. The yield of methyl ethyl ketone was 69.7%.

Example 6. In example 1, characterized in that the reaction temperature is 70°C. For 20 min oxidize 152 ml C4H8. Ihad methyl ethyl ketone to 47.8%.

Example 7. In example 1, characterized in that the reaction temperature is 90°C. For 20 min oxidize 184 ml C4H8. The yield of methyl ethyl ketone 52%.

Example 8. In example 1, characterized in that the composition of the gas mixture to fill the reactor was as follows,%: N2O - 50,0, α-C4H8- 46,0, the sum of CIS - and TRANS-β-C4H8of 0.4, n-butane - 3,1, ethane - 0.2, a heavy admixture of 0.3, and the burette was filled with gas composition: α-C4H8- of 92.7, sum of CIS - and TRANS-β-C4H8- 0,7, n-butane - 6,0, ethane and 0.5, ISO-butane - 0.03, heavy admixture of 0.07. 15 min oxidize 54 ml C4H8. The yield of methyl ethyl ketone 70,8%.

Example 9. In example 8, characterized in that the reaction (10) is carried out in metal temperature-controlled autoclave, which is connected with an exemplary monometr. In an autoclave was placed a solution of toluene with a catalyst, the autoclave vacuum, then fill butylene fraction composition, vol.%: α-C4H8and 88.8, the sum of CIS - and TRANS-β-C4H8- 0,1, n-butane - 5,6, ethane - 5,4, ISO-butane is 0.1 to 1.5 ATM and nitric oxide (I) to 3.0 ATM. Stirring of the solution is performed using a magnetic stirrer. Of the reaction is measured by pressure drop in time. For 10 min oxidize 206 ml C4H8. The yield of methyl ethyl ketone is of 87.8%.

Example 10. In example 9, characterized in that the total pressure of the MCA and gases in the autoclave - 2.0 ATM. For 10 min oxidizes to 78.3 ml C4H8. The yield of methyl ethyl ketone 85,3%.

Example 11. In example 9, characterized in that the reaction temperature is 70°C. For 10 min oxidize 239,8 ml C4H8. The yield of methyl ethyl ketone of 92.7%.

Example 12. In example 1, characterized in that the filling of the reactor using a gas mixture containing propylene and nitric oxide (I) of the following composition,%: N2O - 50,0,3H6- 49,9, the amount of alkanes ≅ 0,1, and fill the burette 99.8% of propylene. 15 min oxidize 125 ml3H6. The output of acetone (DMK) 78%.

Example 13. In example 9, characterized in that the filling of the autoclave to a pressure of 1.5 ATM use 99.8% of propylene(C3H6). For 10 min oxidize 180 ml3H6. The output of acetone (DMK) to 86.3%.

Example 14. In example 3, characterized in that the catalyst used [(n-Bu)4N]3{PO4[VO(O2)2]4}, for 20 min oxidize 80 ml C4H8. The yield of methyl ethyl ketone 42%.

1. The method of obtaining ketones by oxidation of alkenes in the presence of metal complex catalysts containing organic component, characterized in that as the oxidant used nitrous oxide (I) and use the catalyst on the basis of peroxomonosulfate complexes - tetrakis(oxodiperoxotungsto)-phosphate(3-) in combination with the Quaternary the Quaternary ammonium cations with General formula Q 3{PO4[MeO(O2)2]4}, where Me - Mo, W, V; Q3- Quaternary ammonium cation containing alkyl chains C4-C8or N-hexadecylpyridinium.

2. The method according to claim 1, characterized in that the oxidation reaction is carried out in the liquid phase.

3. The method according to claim 1, characterized in that the oxidation reaction of alkenes is carried out in one reactor, feeding a mixture of reactants consisting of alkenes, nitric oxide (I) and light alkanes.

4. The method according to claim 2, characterized in that the oxidation reaction of alkenes is carried out in the liquid hydrocarbon.

5. The method according to claim 4, characterized in that as the liquid hydrocarbon using an aromatic hydrocarbon.

6. The method according to claim 2, characterized in that the liquid phase may contain not more than 10% of water.

7. The method according to claim 1, characterized in that the oxidation reaction of alkenes is carried out at a temperature of 20÷150°C.

8. The method according to claim 1, characterized in that the oxidation reaction of alkenes is carried out at the total pressure of the gas mixture 1÷3.5 ATM.

9. The method according to claim 1, characterized in that the fact that the concentration of the catalytic complex is 1·10-2÷1·10-4M

10. The catalyst for the process of obtaining ketones by oxidation of alkenes-based metal complexes containing organic component, characterized in that it is peroxomonosulfate - tetrakis(oxodiperoxotungsto)-phosphate(3-) in combination with Quaternary ammonium cations with General formula Q3{PO4[MeO(O2)2]4}, where Me - Mo, W, V; Q3- Quaternary ammonium cation containing alkyl chains With4-C8or N-hexadecylpyridinium.



 

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FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention relates to a methyl ethyl ketone production process via catalytic oxidation of n-butenes with oxygen and/or oxygen-containing gas. Catalyst is based on (i) palladium stabilized with complexing ligand and (ii) heteropolyacid and/or its acid salts, in particular molybdo-vanado-phosphoric heteropolyacid having following composition: H11P4Mo18V7O87 and/or acid salt Na1.2H9.3Mo18V7O87, said complexing ligand being notably phthalocyanine ligand. Catalyst is regenerated by making it interact with oxygen and/or oxygen-containing gas at 140-190°C and oxygen pressure 1 to 10 excessive atmospheres. Oxidation of n-butenes is conducted continuously in two-stage mode at 15 to 90°C in presence of above-defined catalyst.

EFFECT: enhanced process efficiency due to increased stability of catalyst resulting in considerably increased productivity and selectivity.

7 cl, 1 dwg, 3 tbl, 8 ex

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FIELD: chemical industry; methods of production of phenol and acetone.

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