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The method of producing cyclopentanone

The method of producing cyclopentanone
IPC classes for russian patent The method of producing cyclopentanone (RU 2227135):
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(57) Abstract:

The invention relates to a process for the preparation of Cyclopentanone. The method is based on the reaction of liquid-phase oxidation of cyclopentene in Cyclopentanone nitrogen oxide in the presence of an inert gas diluent, at a temperature of 100-300And pressure of nitrous oxide 1.5 to 100 ATM. The process provides a high selectivity for the target products, the explosion of work and is promising for industrial use. 1 S. and 4 C.p. f-crystals, 4 PL.

The invention relates to a method of producing Cyclopentanone, more specifically the way it is received by the liquid-phase oxidation of cyclopentene nitrous oxide (N2O).

Cyclopentanone is a valuable intermediate product in the synthesis of various organic compounds. For example, it is used for synthesis-valerolactone, glutaric acid, and sabatinovka acid, which is used to produce nylon-6, 10. It is also used as a solvent.

There are several known methods for producing Cyclopentanone. For example, according to the patent [US Pat. No. 2223494, 1940, J. Loder] Cyclopentanone obtained by ocil the th, MT, Si, CE. The disadvantage of this method is the formation along with a ketone, a significant number of cyclic alcohol and a sharp decrease in selectivity with increasing conversion.

Cyclopentanone can also be obtained by catalytic dehydrogenation of Cyclopentanol in the gas phase at 250-375°C over Cu-Zn catalyst [US Pat. No. 2377412, 1945, F. E. Frey] or at 160-250°C over Ni catalyst [US Pat. No. 2371794, 1945, J. H. Boyd]. Practical application of this method is hampered by the lack of cheap sources of Cyclopentanol.

A known method of producing Cyclopentanone from adipic acid [US Pat. No. 5856581, 1999, Alas, et al.] or its esters [US Pat. No. 4745228, 1988, Decker, et al.] in the presence of oxide catalysts. In addition to the high cost of raw materials, the disadvantage of the first method is the need for a process in aggressive acidic environment at high temperature (200-300°C). In the case of esters requires an additional stage of their receipt, which complicates the technological scheme.

According to the patent [US Pat. No. 4806692, 1989; Yamada et al.] Cyclopentanone can also be obtained by oxidation of cyclopentene in the liquid phase oxygen using a homogeneous catalyst PdCl2-CuCl2

In the patent GB Pat. 649, 680 (1951) claimed method oxidation of olefins to carbonyl compounds nitrous oxide. According to this method, in particular, it is possible to obtain Cyclopentanone by oxidation of cyclopentene.

The main disadvantage of this method is the possibility of formation of flammable mixtures “cyclopenten nitrous oxide” during the process. To eliminate the risk, the authors of patent offer to additionally enter into the reaction mixture of saturated hydrocarbons. However, as shown by more recent studies, a mixture of saturated hydrocarbons with N2O almost as explosive as a mixture of olefins. Thus, the maximum concentrations of propylene in N2O is 1.8-26.8 per cent, and the maximum concentrations of propane 2,1-24,8% [G. Panetier, A. Sicard, V Symposium on Combustion, 620 (1955); B. B. Brandt, L. A. Matov, A. I. Raslowsky, C. S. Khailov, Chem. prom., 1960, No. 5, S. 67-73]. Therefore, saturated hydrocarbons, in spite of their lower reactivity, can not serve as a means to avoid the explosion.

This patent discloses a method of producing Cyclopentanone by oxidation of cyclopentene (C5H8) nitrous oxide (N2O, in the presence of inert gas, which does not have these llimg4/rupat5/2004/04/02/2227135-1t.gif" ALIGN="ABSMIDDLE">

According to this method, the reaction is carried out in the presence of an inert gas under conditions when cyclopenten is present in the form of a liquid phase in which the oxidation reaction proceeds with high selectivity. Excessive increase in the temperature and/or pressure N2O is undesirable because it may result in a loss of selectivity due to the contribution of gas-phase oxidation.

Intrinsically safe working conditions for the proposed method are provided by adding to the reaction mixture an inert gas reacts with N2O, for example nitrogen, argon, helium, carbon dioxide, etc. or their mixture. The role of the inert gas can play the off-gases reaction or recirculating gases. At different stages of the process, depending on the ratio of cycloalken:nitrous oxide, the proportion of inert gas required to provide proof of work can be different and be created by a separate feeder. From the point of view of simplicity and maximum process safety it is advisable to have this dilution nitrous oxide inert gas to the reaction mixture was explosive by any content of cycloalkene. This condition is satisfied if the content of N2About in a mixture in which all stages of the process.

To reduce the explosion hazard in the reaction mixture can be added flame retardants, such as trifloromethyl, diperchlorate, dibromotetrafluoroethane etc.

In accordance with this invention the oxidation cyclopentene in Cyclopentanone nitrogen oxide in the presence of inert gas can be carried out in a wide range of conditions both in static and flow-through reactor, which may be made of steel, titanium, glass or other suitable material. This can be used all known technological methods that increase the efficiency of gas-liquid reactions.

In the case of a static option in the autoclave load cyclopenten (without solvent or solvent) in such quantity that when heated to the reaction temperature, he was present as a liquid phase. Then, serves a mixture of nitrous oxide with inert gas, reducing the pressure to a predetermined value. The amount of nitrous oxide selected so that its pressure at the reaction temperature was 1.5-100 ATM. The concentration of inert gas in the mixture with nitrous oxide selected so that it does not exceed 99%. Then the reactor is heated to the reaction temperature in the region 100-30 is the process, and may vary from several minutes to several tens hours.

The oxidation reaction of cyclopentene may be carried out without a solvent or with a solvent which may be selected from a wide range of substances commonly used in the practice of organic synthesis. Reaction with high enough, high speed flows without catalyst. However, it can also be carried out with the use of a catalyst.

The proposed method of producing Cyclopentanone does not require high purity reagents. So, nitrous oxide can be used both in pure form and mixed with various gases, will have no adverse impact on rates of reaction. Cyclopenten may also contain impurities of various organic compounds, especially if they do not contain double bonds C=C.

The essence of the invention is illustrated by the following examples.

Examples 1-2

Example 1. This example is comparative. In a reactor with a volume of 100 cm3made of stainless steel and equipped with a mixer (firm Parr), pour 33 cm3cyclopentene (Aldrich, 99%). The reactor is rinsed with nitrogen and then brought her pressure up to 10 ATM. The reactor was heated to 225°C and vyd. the donkey the end of the reaction the reactor is cooled to room temperature, measure pressure and analyze the final composition of the gas and liquid phases by the methods of gas chromatography and gas chromatography / mass spectrometry. From the obtained data to calculate the conversion cyclopentene and selectivity of the reaction Cyclopentanone:

where- initial concentration of cyclopentene; CCyONthe concentration of Cyclopentanone in the reaction products;Cside- total concentration of by-products. In the case of large conversion value X can be calculated also by the difference between the initial and final concentrations of cyclopentene:

Conversion cyclopentene and selectivity of the reaction Cyclopentanone shown in the table.1.

Example 2 same as example 1 with the difference that instead of pure nitrous oxide in the reactor serves its mixture with an inert gas - nitrogen, in which the concentration of N2O 25% (table.1).

Nacha who is 37 ATM.

This example shows that the reaction of the liquid-phase oxidation of cyclopentene in Cyclopentanone proceeds with retention of conversion and high selectivity when used as an oxidizer mixtures of nitrous oxide with inert gas.

Examples 3-12

Examples 3-12 show the possibility of carrying out the reaction using mixtures of nitrous oxide with inert gases of different composition (table.2).

Example 3 same as example 2 with the difference that for the oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 70%, and the initial pressure in the reactor was set to 70 ATM. The experience carried out at 100°C for 80 hours. Pressure N2O when the reaction temperature is 100 ATM.

Example 4 same as example 2 with the difference that for the oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 1%, nitrogen - 99%. The initial pressure of the mixture in the reactor was set to 90 ATM. The experience carried out at 225°C for 10 hours. Pressure N2O when the reaction temperature is 1.5 ATM.

Example 5 same as example 2 with the difference that use oxidation mixture is the actor set to 12 ATM. The experience carried out at 197C for 5 hours. Pressure N2O when the reaction temperature is 35 ATM.

Example 6 same as example 2 with the difference that for the oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O in a mixture with nitrogen is 70%, and the initial pressure of the mixture in the reactor was set to 45 ATM. The experience carried out at 197°C for 5 hours. Pressure N2O when the reaction temperature is 80 ATM.

Example 7 same as example 6 with the difference that the concentration of N2About in the mixture is 20%. Pressure N2O when the reaction temperature is 16 ATM.

Example 8 is similar to example 7 with the difference that the initial pressure in the reactor was set to 80 ATM, and the reaction is carried out at 195°C for 12 hours. Pressure N2O when the reaction temperature is 28 ATM.

Example 9 same as example 2 with the difference that for the oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of nitrous oxide is 50% and the initial pressure of the mixture set to 30 ATM. The reaction is carried out at 225°C for 3 hours. Pressure N2O when the reaction temperature is 34 ATM.

Example 10 is similar psi nitrogen is 40%, and the initial pressure of the mixture set to 40 ATM. The reaction is carried out at 195°C for 12 hours. Pressure N2O when the reaction temperature is 32 ATM.

Example 11 same as example 10 with the difference that instead of argon using carbon dioxide.

Example 12 same as example 2 with the difference that for the oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of nitrous oxide is 40%, and the initial pressure of the mixture set to 40 ATM. The reaction is carried out at 300°C for 2 hours. Pressure N2O when the reaction temperature is 37 ATM.

Example 13

This example is comparative. The experience carried out analogously to example 6 with the difference that was charged to the reactor 5 ml cyclopentene. Under such load under the reaction conditions the entire cyclopenten is in the gas phase. The experience carried out at 197°C for 5 hours using a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 70%. The initial pressure of the mixture in the reactor was set to 45 ATM. In the experience of conversion cyclopentene was about 0.5%. This shows that under these conditions the reaction in the gas phase is almost not ydstie catalyst.

Example 14 same as example 5 with the difference that the reaction is carried out in the presence of 0.15 g FeiO3/SiO2(2.8 wt.% Fe2ABOUT3). The catalyst is prepared by impregnation of SiO2solution Fl3, dried at 110°C and calcined in air at 500°C for 2 hours. For oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 95%. The initial pressure of the mixture in the reactor was set to 12 ATM. The experience carried out at 197C for 5 hours. Pressure N2O when the reaction temperature is 35 ATM.

Example 15 same as example 14 with the difference that the reaction is carried out in the presence of 0.5 g of Ag/SiO2(1 wt.% Ag). The catalyst is prepared by impregnation of SiO2a solution of AgNO3, dried at 110C and calcined in air at 500C for 2 hours.

Examples 16-18

These examples show the possibility of oxidation of cyclopentene in the presence of solvent (table.4).

Example 16 same as example 8 with the difference that in the reactor pour 10 ml of cyclopentene and 50 ml of Isobutanol. For oxidation of IP is E. the pressure of the mixture in the reactor was set to 30 ATM. The experience carried out at 195°C for 5 hours. Pressure N2O when the reaction temperature is 75 ATM.

Example 17 is similar to example 16 with the difference that in the reactor pour 10 ml of cyclopentene and 50 ml of cyclohexane.

Example 18 is similar to example 16 with the difference that in the reactor pour 10 ml of cyclopentene and 50 ml of acetonitrile, and the experience is carried out at 175°C for 10 hours. Pressure N2O when the reaction temperature is 70 ATM.

Examples 2 to 12 and 14 to 18 show that cyclopenten with high selectivity oxidized in Cyclopentanone using nitrous oxide, diluted with an inert gas. The process without the use of an inert gas diluent leads to the formation of explosive compositions cycloalken-N2Oh in the gas phase when filling the reactor with nitrogen oxide, heat or reaction conditions. For example, the process of example 1 without the addition of inert gas leads to the formation of mixtures containing from 1 to 40% vapors cycloalkene in nitrous oxide, which includes the region of compositions, the explosion of which are described in [G. Panetier, A. Sicard, V Symposium on Combustion, 620 (1955); B. B. Brandt, L. A. Matov, A. I. Raslowsky, 2O-inert gas in which the concentration of N2O 25% (example 2), allows to avoid the formation of explosive mixtures and to ensure the safety of the process.

According to the proposed method the content of nitrous oxide in a mixture with an inert gas can vary widely, including in the area of concentrations of N2O 25% or less, which excludes the possibility of hazardous situations at all stages of the process when all the compositions with cycloalkenes. As shown by examples 2, 7 and 8, the oxidation reaction in this area proceeds with high efficiency.

In the present invention proposes a new method of producing Cyclopentanone, based on the reaction of liquid-phase oxidation of cyclopentene a mixture of nitrous oxide with inert gas. The process provides high selectivity, the explosion and is promising for industrial use.

1. The method of producing Cyclopentanone, carried out by contact cyclopentene with nitrous oxide in the liquid phase, characterized in that the reaction is carried out at a temperature of 100-3000And pressure of nitrous oxide 1.5 to 100 atmospheres in the presence of an inert gas diluent.

2. The method according to p. 1, in which the concentration of the inert ha the gas filled in a manner that the content of N2O in a mixture with inert gas was not more than 25% to avoid the formation of explosive compositions at all stages of the process.

4. The method according to any of paragraphs.1-3, in which the reaction is carried out in the presence of a catalyst.

5. The method according to any of paragraphs.1-4, in which the reaction is carried out in the presence of a solvent.

 

 

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