Catalyst and method for producing methyl ethyl ketone

 

The invention relates to the field of organic synthesis, namely the method of producing ethyl ketone by catalytic oxidation of n-butenes with oxygen, and the catalyst for its implementation. The invention solves the problem of increasing the efficiency of the process by increasing the stability of the catalyst components (Pd + CCP) that will significantly improve the performance of the catalyst and its activity in both reactions. The problem is solved by the method of producing ethyl ketone by oxidation of n-butenes by oxygen and/or oxygen-containing gas using a catalytic system, which consists of an aqueous solution of HPC-z - molybdovanadophosphoric heteroalicyclic or mixture of heteropolyacids and/or their salts and palladium with a concentration of 510-4-110-2M, stable phtalocyanines ligand RS at a molar ratio of [Pd]:[MS]=0.5 to 2. Use Mo-V-phosphoric GPK-z composition of HaPxMoyVzObwhere 1x3; 820; 2z12; 40b

The invention relates to the field of organic synthesis, namely the method of producing methyl ethyl ketone (MEK, CH3SOS2H5) catalytic oxidation of n-butenes with oxygen, and the catalyst for its implementation.

Due to the exceptionally high dissolving ability of the methyl ethyl ketone-MEK finds wide industrial application [The Chemical Economics Handbook New York: SRI International (CEN, 1996]. It is used in the production of polyurethane lacquers, which are used for coating magnetic tapes, computers, tools, audio - and videotapes, is the best deparaffinization lubricating oils, providing them with frost, is a solvent in the production of foams, various paints, epoxy and glyptal resins, PVC skin, artificial skin, serves as the basis ink for Pecatonica, preventing the formation of films during storage of paints. Used to get ethylacrylate and isomeric methylcrotonate acids, antioxidants rubbers, for plasticization derivatives of nitrocellulose used in the manufacture of smokeless powders, finds use as a solvent for the film coating of tablets and capsules drugs, as a reagent and solvent in many pharmaceutical industries. Peroxide MAC and is the initiator of the polymerization of unsaturated polyesters in the manufacture of reinforced plastics.

On an industrial scale IEC receive several ways. One of them is based on liquid-phase free-radical oxidation of n-butane according to the scheme (1), where IEC is one of the target products:

In this way the output of the IEC does not exceed 23%, while it turns and acetic acid. The advantage of this method is the low cost of raw materials, lack of abundance of by-products, greatly complicating and more expensive process of allocating the IEC.

The main industrial method for the synthesis of the IEC is a three-stage processing butylene fraction, which is a byproduct of the production of butadiene plants synthetic is

Of these reactions (2) and (3) is liquid, and reaction (4) is a heterogeneous catalyst, and in some embodiments is a liquid. The disadvantages of this method are: the abundance of harmful neobespechenii waste contaminated acidic tars sulfuric acid; highly corrosive environment in reactions (2) and (3); high energy intensity of the reaction (4); the complexity of the process of separation of the IEC from numerous impurities.

A variation of this method is the process in which instead of H2SO4use acetic acid as an intermediate product is sec-butyl acetate:

The catalyst stages (2A) and (3A) is sulfonation, which quickly becomes clogged with resin and therefore has a limited service life. Used sulfonation is also harmful waste production, seriously impairing its ecology.

Have recently been proposed and other acidic catalysts of these stages, such as heteroalicyclic [Tianxi Cai, Huang He, Lin Jinlong, He Min, Zhang Suofang, Li Luhui // Shiyou Huagong, 1988, V. 17, n 9, p. 565-567], however they did not provide a significant improvement in the way. In the second-butylacetate method of obtaining DOE is larger capital investments and recurring costs per unit of output due to the corrosive properties of aqueous acetic acid.

In recent years there had been multiple attempts to create new technologies for the IEC of n-butenes. This is evidenced by numerous patents. Of most interest are two new methods: three-stage, including reactions (5)-(7) with an intermediate receiving gidroperekisi second-butylbenzene [U.S. Pat. USA 5304684, 1994 company Sumimoto Chem. Ltd.] and the direct oxidation of n-butenes according to reaction (8):

Three-stage method is based on reactions, similar to those used in modern industrial method of production of phenol and acetone through Gidropress cumene. However, obtaining and decomposition gidroperekisi second-butylbenzene stages (6) and (7) runs with less selectivity than receiving and decomposition gidroperekisi cumene. In reactions (6) and (7) together with the IEC and the phenol formed carboxylic acids, their esters, aldehydes, unsaturated ketones, resin. By-products are removed by alkali, which significantly impairs the production ecology. Method (5)-(7) could be promising for the industry, provided a substantial increase in the selectivity stages (6) and (7) receive and decomposition getoperation reaction accurascope oxidation of ethylene to acetaldehyde [Jira R., Freiesleben W // in: Organometallic Reactions / Ed.: E. I. Becker, M. Tsutsui. Vol. 3 - New York et al.: Wiley Intersci., 1972, p.1-190]:

Reaction (8) can be carried out in one reactor, giving it a stoichiometric mixture of n-C4H8: O2=2: 1, which was previously considered non-explosive [chemist's Handbook. 2nd ed. Additional volume. - L.: Chemistry, 1968,S. 434]. However, to improve the selectivity and risk reduction reaction should be 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 (9); 2) regeneration of Oh with oxygen according to the equation (10):

Initially as Oh used chlorine copper CuCl2[Jira R., W. Freiesleben, see above], the reduced form of which is ion ul-2- 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. Therefore, for the oxidation of n-butylenes this system proved with the USSR 1669109, B 01 J 23/44, 1994] was first proposed for use as reversible oxidant (Oh) Mo-V-phosphoric heteroalicyclic patterns of Keggin having the General formula H3+nPVnMo12-nO40marked us through the CCP1. With their participation butylene reaction described in equation (9a), and the oxygen in equation (10A):

In this way (Oh=CPC1) catalytic system PdII+GPK1) 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 (9a) 100 times the activity of the chloride system (PdCl2+CuCl2). The catalytic system Pd+GPK1) could successfully be used for stoichiometric oxidation of a mixture of n-C4H8: O2=2:1 in IEC (one option), and for carrying out reactions (9a) and (10A) in different reactors (two-stage version). The last option was to exclude the contact of oxygen or air with butenes and MAC ohms and ensure production safety. However, in the latter case, there was a deep recovery molecules GPKmolecules GPK1. This option (non-stationary) catalysis was associated with a decrease in stability of the catalytic system Pd+GPK1).

The stability of the catalyst in respect of ions Pd2+and molecules GPK1different depended on the number of vanadium atoms in the molecule GPC1(n) and m:n relationship (degree of recovery molecules GPK1). For small values of n (1n3) and mn unstable turned out to be palladium, which stood out on the surface of the recovered solution in the form of thin metal films, Pilipovich to the walls of the reactor. When a large number of atoms of vanadium (4<n6) and mn, except for the formation of films of palladium was observed precipitation from solution is also part of the vanadium in the form of a brown solid V3About72H2O. After oxidation in air reactor restored form CCP1according to reaction (10A) metallic palladium was dissolved and returned to the solution, but the vanadium precipitate were almost dissolved. Full return of palladium in solution in the process of obtaining IEC did not happen, because part of it was deposited in various is Oseni palladium, in no relation to the CCP1with n4. The low stability of this catalyst proved to be its greatest disadvantage.

Over the past 30 years there have been many attempts to stabilize the palladium in the catalyst (Pd+GPK1), but they are all, for various reasons, proved unacceptable to 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) [Application 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. To maintain the stability of palladium in the catalyst had continuously add hydrochloric acid and simultaneously from the reaction products to remove and neutralize chlorine compounds. Therefore mallorey catalyst (PdCl2+GPK1also has not found industrial application.

The use of palladium in the form of complexes with pyridylcarbonyl acids (-pikolinos or dipicolinate) increases its stability [A. S. USSR USSR 1584200, B 01 J 23/44, 1994; A. S. USSR 1669109, B 01 J 23/44, 1995]. However, it is because the Pd complex derivative of pyridine is too strong and he overly stabilizes the palladium in higher oxidation degree (Pd2+). Therefore, this method turned out to be-low-tech.

In the invention [U.S. Pat. Japan 07-149685, 1995] catalysts (Pd+GPK1used in mixed solvents containing less than 50% water. As such used dioxane, ethanol, tetrahydrofuran,-butyrolactone or sulfolan. Reaction (8) underwent single-stage: dissolved-butene at 80C and a pressure of About29 kg/cm2oxidized in the IEC. The stability of the palladium ensured by the fact that reaction (9a) and (10A) proceeded simultaneously in one reactor). However, the conversion of-butene in the IEC was small: 21% per hour in aqueous dioxane and 14% in aqueous ethanol. In other solvents, it was even less. This method of ethnological and unsafe. The idea of using non-aqueous solvents for the reaction (8) was unpromising, since this reaction proceeds through the stages (9a) and (10A), in which water is acetalization reaction (8), and the decrease of its content dramatically reduces the reaction rate.

The same reason poses the solid media [Stobbe-Kreemers A. W., van der Zon M., Makkee M., Scholten, J. J. F. // J. Molec. Cat.,; Stobbe-Kreemers A. W., Makkee M., Scholten, J. J. F. Appl. Catal]. When using such catalysts were used not liquid water, and water vapor, which could let water condense in the pores of the support. Therefore, stage (9a), consisting of steps (9a’) and (9a), heterogeneous variant of the reaction (8) was very slow.

A prototype of the proposed method and catalyst to obtain the IEC is the way [A. S. USSR 1584200, B 01 J 23/44, 1994], in which the catalyst using an aqueous solution of palladium salt, a derivative of pyridine and acid salts molybdovanadophosphoric heteroalicyclic (GCA1). The oxidation reaction is carried out by interaction of the catalyst with n-butylene, at temperatures of 50-70From and after the separation of methyl ethyl ketone oxidize the recovered form of the catalyst with oxygen or air at temperatures 130-160(Two-stage version). In this way the reaction (8) is in non-stationary conditions of catalysis. The depth and speed of changes of the chemical composition, oxidation and other physico-chemical properties of the catalyst depends on its performance and sustainability at each studiotechnik both stages (9a) and (10A) were fast, deep and reversible. However, due to the precipitation stage (9a) the requirement of reciprocity is violated for both palladium and molecules GPK1patterns of Keggin. The deposition of palladium butylene reactor with incomplete return it to the solution in the air reactor instability (palladium) is the lack of a catalytic system Pd+GPK1). Even more serious disadvantage is the instability of the molecules of the CCP1caused by loss of part of vanadium, falling into the sediment at the stage of (9a) and not returned in the solution at the stage (10A).

The invention solves the problem of increasing the efficiency of the process by increasing the stability of the catalyst components (Pd+CCP) that will significantly improve the performance of the catalyst and its activity in both reactions.

The problem is solved by catalyst obtain ethyl ketone by oxidation of n-butenes by oxygen and/or oxygen-containing gas, which consists of an aqueous solution of HPC-z - molybdovanadophosphoric heteroalicyclic (z is the number of vanadium atoms in the molecule GPK-z), and/or a mixture of heteropolyacids and/or their acidic salts and palladium with a concentration of 510-4- 1phosphoric GPK-z composition: HaPxMOyVzObwhere 1x3; 820; 2z12; 40b99; a=2b-6U-5(x+z). The concentration of vanadium in aqueous solution GPK-z or a salt thereof is 0.4-2.2 gram-atom per liter.

The task is also solved by a method of producing methyl ethyl ketone-MEK by homogeneous oxidation of n-butenes by oxygen and/or oxygen-containing gas, the catalyst contains GCA-z - molybdovanadophosphoric heteroalicyclic composition: HaPxMoyVzObwhere 1x3; 820; 2z12; 40b99; a=2b-6U-5(x+z), and/or the mixture of acids and/or their acidic salts and Pd concentration 510-4- 110-2M, stable phtalocyanines ligand RS at a molar ratio of [Pd]:[MS]=0.5 to 2 at a concentration of vanadium in aqueous solution of 0.4-2.2 gram-atom per liter. The method of oxidation of n-butenes in the IEC exercise gif">And regeneration of the catalyst by reacting it with oxygen or oxygen-containing gas is carried out at a temperature of 140-190When the pressure of oxygen 1-10 ATA.

The proposed method of synthesis of the IEC as a prototype, based on the use of Mo-V-phosphoric CCP as reverse acting oxidant and palladium as socializaton.

The main difference of the proposed method of synthesis IEC catalyst (Pd+CCP) is that used new methods of stabilization of the catalyst components (different for palladium and vanadium). They found us as a result of analysis of the causes system instability (Pd+GPK1), and also on the basis of studies of the kinetics and mechanism of reactions (9a) and (10A).

To eliminate the disadvantages of the known catalysts (Pd+GPK1and create a catalyst with high performance and stability of palladium ion was stabilized by complexation with phtalocyanines ligand RS and molecules GPK1magginesu patterns are replaced by molecules GPK-z nethsingha composition. The result is a new catalyst (PdPc+GPC-z).

The proposed catalysts based on GPC-z prepare the way, epicanthoplasty and do not allow precipitation when conducting phases (9a1), (9a2) and (10A) reaction (8). The activity and performance of the catalysts in a wide range can be adjusted in four ways: a) the choice of z; (b) changes in the concentration of CPC-z; C) variations of the concentrations of the complex Pd+22RS; g) the regulation of the reaction temperature (9a).

To control the degree of recovery of the catalyst (or oxidation) first used the method of measuring the oxidation potential (E) of the contact solution. Found the value of E (relative to the normal hydrogen electrode) is compared with that obtained in advance curve E of m for the used catalyst, where m is the degree of recovery of CPC (m=[V(IV)]/[CCP]). The value of E to find the current value of m. In the tables of examples, there is a separate graph, which contains values for the oxidized solutions of catalysts. It is possible to judge how well the regenerated catalyst, as this will depend on his performance.

The difference of the proposed method is to create a solution to the high concentration of vanadium (up to 2.2 gram-atom per liter), which leads to improved performance of the catalyst ensuring stabilnosti and/or oxygen-containing gas, and to improve the performance of the method, the regeneration is carried out at higher temperatures (up to 190C) and RHO2up to 10 ATA.

Another difference is that the reaction is carried out butylene and at lower, than in the method prototype temperatures (from +15C) as the catalyst (PdPc+GPC-z) has a significantly higher activity than the catalyst of the prototype method, where palladium stabilized dipicolinic acid.

The invention is illustrated by examples.

Example 1. In the reactor-type catalytic duck for 120 ml, fixed on the rocking chair, pour 20 ml of the catalyst having the composition: [H12P3Mo17V9About87]=0.2 M, [Pd+2]=210-3M, the molar ratio of [Pd]:[RS]=4. The reactor thermostatic at 60With that blow 10-fold volume of-butylene composition, %:-C4H8- 96,3, the sum of CIS - and TRANS--C4H8to 1.4, n-butane - 2,2, heavy impurities is 0.1. Connect the reactor burette filled-butylene, and with vigorous shaking of the reactor wire is g> -butylene (m=3,92 e) selectivity 98,0%. After Stripping IEC catalyst according to reaction (10) are oxidized in an autoclave with stirrer at 190With and Rho2=4 ATA for 20 minutes. The total pressure in the autoclave to 16.4 MPa by the pressure of water vapor (12,4 MPa). With this catalyst spend the 2nd cycle. The selectivity and activity of the catalyst does not change. Precipitation in solution no.

Example 2. Carried out as in example 1, but differs in that the catalyst used [Mn2H13P3Mo18V8O90]=0.3 M, [Pd+2]=610-3M when the molar ratio of [Pd]:[RS]=2, for 23 min oxidize 270 ml-C4H8(m=3.75 e) with a selectivity of 98.3%. After Stripping IEC catalyst oxidized in an autoclave under conditions analogous to example 1. With this catalyst spend the 2nd cycle. The selectivity and activity of the catalyst does not change. It's no rain.

Example 3. Carried out as in example 1, but differs in that the catalyst used [MP2H6P3Mo18V7O84]=0.3 M, [Pd+2]=610-3M when the molar ratio of [Pd]:[RS]=2, for 20 min oxidize 244 ml-C4H8(m=3,39 e) is On the second cycle, the selectivity and activity of the catalyst does not change. It's no rain.

Example 4. Carried out as in example 1, but differs in that the catalyst used [H12P2Mo12V6About62]=0.4 M, [Pd+2]=610-3M when the molar ratio of [Pd]:[RS]=2, for 17 min oxidize 270 ml-C4H8(m=2,81 e) with a selectivity of 98.3%.

Example 5. Conducted according to example 4, but differs in that [H12P2Mo12V6O62]=0.2 M, for 20 min oxidize 213 ml-C4H8(m=of 4.44 e) selectivity is 97.9%.

Example 6. Carried out as in example 1, but differs in that the catalyst used [H17P3Mo18V8O90]=0.3 M, [Pd+2]=610-3M when the molar ratio of [Pd]:[RS]=2, 22 min oxidize 275 ml-C4H8(m=3,82 e) with a selectivity of 98.2%.

Example 7. Carried out as in example 1, but differs in that the catalyst used [H10P3Mo19V7O87]=0.2 M, [Pd+2]=510-4M when the molar ratio of [Pd]:[RS]=1, for 30 min oxidize 180 ml-C4H8(m=3.75 e) with a selectivity to 98.4%.

Example 8. Carried out as in example 1, but from/sup>]=510-4M when the molar ratio of [Pd]:[RS]=1, for 29 min oxidize 171 ml-C4H8(m=3,56 e) selectivity 98,0%. After Stripping IEC catalyst oxidized in an autoclave under conditions analogous to example 1. On the second cycle, the selectivity and activity of the catalyst is not changed.

Example 9. Carried out as in example 1, but differs in that the catalyst used [H15P3Mo19V8O92]=0.2 M, [Pd+2]=510-4M when the molar ratio of [Pd]:[Pc]=1, for 31 min oxidize 177 ml-C4H8(m=3,67 e) selectivity 98,0%.

Example 10. Carried out as in example 1, but differs in that the catalyst used [H10P3Mo18V7O84]=0.3 M, [Pd+2]=610-3M when the molar ratio of [Pd]:[RS]=2, for 17 min oxidize 276 ml-C4H8(m=3,78 e) with a selectivity of 97.5%. After Stripping the IEC, the catalyst was oxidized by the method of example 1. With this catalyst spend the 2nd cycle, which for 12 min oxidize 281 ml-C4H8. Only with this catalyst spend 10 cycles, during which vary the ohms change from 10.1 ATI to 16.4 MPa. The activity of the catalyst to 10 cycle practically unchanged: 19 min on it oxidizes 278 ml-C4H8(3,83 e). The data are shown in table 1. Precipitation in solution no.

Example 11. Conducted according to example 10, but differs in that the molar ratio [Pd]:[RS]=1, for 14 min oxidize 316 ml-C4H8(4,33 e) selectivity 98,0%. After Stripping the IEC, the catalyst was oxidized by the procedure of example 1 for 15 minutes, the Catalyst has worked for 10 cycles, and then after a week of standing the tests were continued. Only with this catalyst spend 15 cycles, which gradually reduce the load on the catalyst, and the time of his regeneration to 10 min (see table. 2). Catalyst works with high stability, selectivity it is not changed, no precipitation. The drawing shows data on the activity of the catalyst in butylene reactions in 15 cycles.

Example 12. Conducted according to example 10, but differs in that the molar ratio [RS]:[Pd]=2 or [Pd]:[MS] = 0.5), and 24 min oxidize 335 ml-C4H8(4,56 e) with a selectivity of 98.1 per cent. In this example, the catalyst tested at maximum load. After Stripping the IEC, the catalyst was oxidized by the method of example 1 in the tip is retained his activity: he was found to be stable even with a full recovery during butylene reaction (6.8). It's no rain.

Example 13. Carried out as in example 1, but differs in that the catalyst used [H6RMO9V3O40]=0.5 M, [Pd+2]=510-4M when the molar ratio of [Pd]:[RS]=1, for 30 min oxidize 175 ml-C4H8(1,46 e) with a selectivity of 98.1 per cent. After Stripping IEC regenerate the catalyst by the method of example 1. With this catalyst spend just 3 cycles. Its selectivity and activity constant.

Example 14. Carried out as in example 1, but differs in that the catalyst used [H5PMo10V2O40]=0.2 M, [Pd+2]=510-4M when the molar ratio of [Pd]:[RS]=1, for 15 minutes oxidize 113 ml-C4H8(2,35 e) selectivity 98,0%. After Stripping IEC regenerate the catalyst by the method of example 1.

Example 15. Carried out as in example 1, but differs in that the catalyst used [H10P3Mo18V7O84]=0.3 M, [Pd+2]=610-3M when the molar ratio of [Pd]:[RS]=2, and the fact that the oxidation serves industrial butylene fraction (BF) composition, %: butene-1 - 37.5, CIS-2-butene - 34.9, TRANS-2-butene - 25,9 (sum of n-buta,e) with a selectivity of 96.5%. After Stripping the IEC and regeneration of the catalyst by the method of example 1 with him conduct the 2nd cycle, which for 13 min oxidize 201 ml of BF. Similarly to the previous spend another 3 cycles. The selectivity and activity of the catalyst does not change: 5 cycle oxidizes 205 ml BF for 17.5 minutes On this catalyst then hold cycles 6-10, which gradually raise the load on the catalyst (i.e., increase its productivity). The catalyst is stable, not changing its parameters (see tab. 4). At the 10th cycle on it oxidizes 36 min 294 ml BF (m=4,06). Precipitation in solution no.

Example 16. Conducted according to example 15, but differs in that the molar ratio [Pd]:[RS] = 1, for 37 min oxidize 282 ml BF (m=3,89 e) selectivity 97,0%. After Stripping the IEC, the catalyst was oxidized by the method of example 1. With this catalyst, a further 10 cycles (see table. 5). The selectivity and activity of its practically not changed. So, at the 11th cycle solution for 39 min oxidizes 286 ml BF (m=3,96). Precipitation in solution no.

Example 17. Carried out as in example 1, but differs in that the catalyst used acid salt [Co0,5H9P3Mo18V7O84]=0.3 M, [Pd+2]=610-3M when the molar ratio of [Pd]:[RS]=4, and that the catalyst is oxidized by the method of example 1 for 15 minutes With this catalyst spend the 2nd cycle, which is 19 min oxidize 208 ml of BF. Similarly to the previous spend another 3 cycles. The catalyst is stabilized at the activity level of the 2nd cycle: 5th cycle for 19 min on it oxidizes 207 ml BF. The selectivity of the catalyst does not change (see table. 6). As noted in the comment, on the walls of the reactor by the end of the test there were small dark patina, indicating insufficient stabilization of palladium at a molar ratio of [Pd]:[RS]=4. As can be seen from examples 15 and 16, this ratio should be less than or equal to 2.

Example 18. Carried out as in example 1, but differs in that the catalyst used [Mn2H13P3Mo16V12O94]=0.2 M, [Pd+2]=210-3M when the molar ratio of [Pd]:[RS]=4 and t=70And also the fact that oxidizes BF (see example 15), 55 min oxidize 146 ml BF (m=3,05 e) with a selectivity of 96.2%. After Stripping IEC catalyst oxidized in an autoclave at 160With and Rho2=4 ATA for 20 minutes Total pressure in the autoclave to 10.1 MPa. With this catalyst spend the 2nd cycle, which for 65 min oxidize 183 ml BF (3,78). The catalyst was recovered at 140the 3rd cycle, for 59 min oxidize 165,5 ml BF (3,40). The selectivity of the catalyst is not changed.

Example 19. Conducted according to example 18, but differs in that the use of the CCP composition Sinn3P3Mo16V12O89for 40 min oxidize 188 ml BF (m=3,95 (e) with a selectivity to 96.8%. After Stripping IEC catalyst oxidized in an autoclave at 160With and Rho2=4 ATA for 20 minutes Total pressure in the autoclave is equal to 10.1 MPa (pressure of water vapor of 6.1 MPa). With this catalyst spend the 2nd cycle, which is 41 min oxidize 153 ml BF (3,19). Similarly, the conduct of the 3rd cycle, in which for 40 min oxidize 152 ml BF (3,18). The selectivity of the catalyst is practically unchanged.

Example 20. Conducted according to example 18, but differs in that the use of the CCP composition Compn6P2Mo18V7O84for 46 min oxidize 192 ml BF (m=3,93 e) with a selectivity of 96,4%, After Stripping IEC catalyst oxidized in an autoclave at 160With and Rho2=4 ATA for 20 minutes Total pressure in the autoclave to 10.1 MPa. With this catalyst spend the 2nd cycle, which for 50 min oxidize 148 ml BF (is 3.08 (e). Similarly, a 3-th cycle, which is a 45 min oxidize 159 ml of BF (3,30). The selectivity of the catalyst is practically not b>P3Mo18V7O84]=0.2 M, [PD+2]=610-3M when the molar ratio of [Pd]:[RS]=1 and t=18C, for 40 min oxidize 64 ml-C4H8(m=1,33 e) with a selectivity of 98.5%.

Example 22. Carried out as in example 1, but differs in that the catalyst used [H7P3Mo16V12O89]=0.2 M, [Pd+2]=210-3M when the molar ratio of [Pd]:[RS]=4, for 40 min oxidize 192 ml-C4H8(m=4,0 (e) with a selectivity of 97.8%.

Example 23. Carried out as in example 1, but differs in that the catalyst used [H7P3Mo16V10O84]=0.2 M, [Pd+2]=210-3 M at a molar ratio of [Pd]:[RS]=4, 39 min oxidize 185 ml-C4H8(m=3,85 e) selectivity 98,0%.

Example 24. Carried out as in example 1, but differs in that the catalyst used [H12P3Mo17V9O87]=0.2 M, [Pd+2]=210-3M when the molar ratio of [Pd]:[RS]=4, 37 min oxidize 180 ml-C4H8(m=3.75 e) with a selectivity of 98.1%.

Example 25 V12O99]=0.17 M, [Pd+2]=510-4M when the molar ratio of [Pd]:[RS]=1, for 30 min oxidize 166 l-C4H8(m=4,07 s) with selectivity to 98.6%.

Example 26. Carried out as in example 1, but differs in that the catalyst used [H9P3Mo18V10O91]=0.2 M, [Pd+2]=510-4M when the molar ratio of [Pd]:[RS]=1, for 32 min oxidize 150 ml-C4H8(m=3,13 e) with a selectivity of 98.5%.

Example 27. Carried out as in example 1, but differs in that the catalyst used [H12P3Mo18V9O90]=0.25 M, [Pd+2]=510-4M when the molar ratio of [Pd]:[RS]=1, for 30 min oxidize 169 ml-C4H8(m=2,82 e) selectivity is 97.9%.

Example 28. Carried out as in example 1, but differs in that the catalyst used [H9P3Mo18V8O86]=0.25 M, [Pd+2]=510-4M when the molar ratio of [Pd]:[RS]=1, for 30 min oxidize 173 ml-C4H8(m=3,05 e) selectivity 98,0%.

Example 29. Carried out as in example 1, but differs in that in kachestva>10-4M when the molar ratio of [Pd]:[RS]=1, for 32 min oxidize 179 ml-C4H8(m=3,16 e) selectivity is 97.9%.

Example 30. Carried out as in example 1, but differs in that the catalyst used [H10P3Mo20V5O85]=0.25 M, [Pd+2]=510-4M when the molar ratio of [Pd]:[RS]=1, for 30 min oxidize 174 ml a-C4H8(m=3,06 e) with a selectivity of 98.2%. After Stripping the IEC, the catalyst was oxidized by the method of example 1. With this catalyst, a further 2 cycle. The selectivity and activity of its practically not changed. Thus, at cycle 3, the solution for 29 min oxidizes 177 ml BF (m=3.12). Precipitation in solution no.

All the catalysts described in examples 1-30, prepare a well-known method [A. S. USSR 1782934, 01 25/16, 1992]. First synthesize HPC solution of a given composition and a given concentration derived from the stoichiometric amounts of the components of H3RHO4Moo3and V2O5. Then, the obtained solution is injected sample PdCl2and phthalocyanine.

Example of synthesis 250 ml GPC composition of N12P3Mo17V9About87(example 1) with a concentration of 0.20 M

The calculation of the amounts of the starting components are given by equation

3H9
O87.

Use 122,4 g of Moo3H. H., 40,95 g V2O5H. H., to 20.88 ml 7,183-molar solution of N3RHO4and 30% H2O2OS.h. The dissolution of the reagents is carried out in four stages:

1) 122,4 g of Moo3+10,88 ml of N3RHO4+1500 ml of N2O+2,0 ml of N2O2

2) 14,00 g V2O5+700 ml of H2O+50 ml of N2O2+3,00 ml of N3RHO4

3) 14,00 g V2O5+700 ml of N2About+50 ml of N2O2+3,00 ml of N3RHO4

4) to 12.95 g V2O5+700 ml of N2O+50 ml of N2O2+4,00 ml of N3RHO4

For dissolving Moos in a conical 3-liter flask is charged with the entire sample of Moo31.5 liters of distilled water, 10,88 ml of N3RHO4and 2 ml of 30% H2O2H. H. the mixture boil (it is straw yellow in color) and gradually evaporated to ~ 0,8 liter boiling mixture consistently impose solutions obtained by dissolving V2O5in water in the presence of N2O2and H3RHO4. Each subsequent portion of the solution V2About5+H3RHO4enter after evaporation of the mixture in the flask up to ~ 1 l

For the dissolution of the 1st sample V2O5in 1-liter glass download 14 g V2About5, 0,7 l dis is e above) for 20-30 min to get dark red-brown solution. After the dissolution of V2O5to the mixture was added with stirring 3 ml of N3RHO4and expect the termination of allocation of About2formed by the decomposition of peroxide complexes of vanadium. The obtained dark brown solution was poured into the flask with boiling suspension of Moo3+H3RHO4and evaporated to ~ 1 l Similarly carry out the dissolution of the 2nd and 3rd portions of the V2O5and adding the resulting solution to a suspension of Moo3+V2O5+H3RHO4. This mixture is then boiled and evaporated to 400 ml.

After cooling the resulting solution GPK filtered through filter paper with a red stripe and the filter is washed with water. If the precipitate on the filter exceeds 2% by weight of the original V2O5it is with the filter process in the glass 15% H2O2(~ 50 ml), the resulting solution was heated until complete decomposition of H2O2and after cooling is filtered through a fresh filter paper. This filtrate is added to the combined solution of the CCP leaching with water and evaporated to 250 ml.

Catalysts for experiments containing CPC, PdCl2and phthalocyanine, usually prepared in 20 ml. for Example, to obtain a catalyst composition [H12P3Mo1sup>]=1:4 in a solution of 0.20 M CCP injected sample 0,0071 g of PdCl2and 0,0084 g of phthalocyanine. The solution is heated and boiled for 8-10 minutes until complete dissolution hanging. Then the solution is cooled and bring its volume up to 20ml

As seen from the above examples and tables, the present invention can significantly increase the stability of the catalyst and to increase the efficiency of the process.

Claims

1. The catalyst obtain ethyl ketone by catalytic oxidation of n-butenes by oxygen and/or oxygen-containing gas on the basis of palladium, stable complexing ligand, and heteroalicyclic and/or its acid salts, characterized in that as heteroalicyclic the catalyst contains GCA-z-molybdovanadophosphoric heteroalicyclic, and/or a mixture of heteropolyacids and/or their acidic salts, the composition of the CCP-z satisfies the General formula HaPxMoyVzObwhere 1x3; 8y20; 2zl2; 40b99; a=2b-6U-5(x+z), and as a complexing ligand - f the e GPK-z or a salt thereof is 0.4-2.2 gram-atom per liter.

3. The catalyst PP.1 and 2, characterized in that the palladium concentration 510-4110-2M is stable in solution phtalocyanines ligand RS at a molar ratio of [Pd]:[RS]=0,52.

4. The method of producing ethyl ketone by catalytic oxidation of n-butenes by oxygen and/or oxygen-containing gas using a catalyst based on palladium complexes of its ligand and heteroalicyclic and/or its acid salt with subsequent regeneration of the catalyst by its interaction with oxygen or oxygen-containing gas, characterized in that the use of the catalyst according to any one of paragraphs.1-3.

5. The method according to p. 4, characterized in that the oxidation reaction of n-butenes is carried out at a temperature of 1590°C.

6. The method according to PP.4 and 5, characterized in that the regeneration of the catalyst is carried out by reacting it with oxygen or oxygen-containing gas at a temperature of 140190°C.

7. The method according to PP.4-6, characterized in that at the stage of regeneration of the catalyst partial pressure of oxygen is 110 ATA.

 

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