Method of oxidation of hydrocarbons

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of oxidation of hydrocarbons using oxygen in trifluoroacetic acid and can be used particularly for oxidation of alkanes, cycloalkanes, alkylaromatic hydrocarbons, alkenes, cycloalkenes. The method involves saturation of trifluoroacetic acid with oxygen, after which, the initial hydrocarbon is added to the obtained reaction medium and is kept until depletion of bound oxygen with obtaining the corresponding oxygen containing compound.

EFFECT: invention allows carrying out a process of selective partial catalytic oxidation of hydrocarbons with obtaining different oxygen containing organic compounds without use of high temperature and traditional catalyst systems based on transition metals.

1 tbl, 5 ex

 

The invention relates to the field of catalytic oxidation of hydrocarbons and can be used in particular for the oxidation of alkanes, cycloalkanes, alkylaromatic hydrocarbons, alkenes, cycloalkenes to the corresponding oxygen-containing organic compounds using oxygen or oxygen-containing gas.

Research in the field of partial oxidation of organic compounds, including hydrocarbons, are held for several decades, largely devoted to the oxidation of cycloaliphatic hydrocarbons, in particular cyclohexane, respectively to alcohols, ketones, mono - and/or dicarboxylic acids, for example adipic acid, and/or ε-caprolactam (examples of such developments are "ways"that are protected by patents US: 2223493, 2617835, 2828337, 3231608, 4032569, 415873, 4263453, 4902827, 5321157; GB: 415172, 942415, 1086951, 1250192; FR: 2722783, 2746671; EP: 0694333, 0870751.

In these patents describes how the partial oxidation of organic compounds by molecular oxygen or oxygen-containing gas is carried out in a liquid medium, a solvent inert to pick up an ongoing process (most often recommended as a solvent acetic acid)in the presence of certain amounts of catalysts (homogeneous or heterogeneous), which is a salt of transition metals and the organic acids, at elevated temperatures, up to 200°C.

It is possible to introduce into the reaction environment initiators, such as peroxides, in a number of patents in this use as aldehydes and ketones.

Great interest in these developments caused by the possibility of direct oxidation of hydrocarbons to the desired degree of oxidation higher selectivity and, consequently, obtaining the desired products with high output.

However, these methods have such serious flaws, as the need for process in the presence of costly catalysts based on transition metals and the target, in particular, initiating the oxidation process, the additives, the use of high temperatures, the complexity of the selection of the catalyst and intermediate oxidation products from the reaction medium, difficult and expensive recovery operations not only of the catalyst, and solvent. It should also be noted lack of selectivity used catalytic systems.

Improving the selectivity of the oxidation reaction carried out in a liquid medium using molecular oxygen in the presence of a catalyst, is achieved in the following patents.

In the patent RU 2274633 as one of the components of a liquid medium, in which are the oxidation process, it is recommended to use about the organic (aromatic) acid compound, including perfluorinated, in combination with other compounds (see extensive list), along with the known catalysts referred to as catalyst and manganese compounds.

According to the description of this patent presents it the way partial oxidation of hydrocarbons makes it possible not only to increase productivity and/or selectivity of the oxidation reaction, but also to highlight the resulting target products and to carry out recycling of the catalyst by simple operations.

In the patent RU 2208605 improve the selectivity of the oxidation reaction due to the fact that the use as a catalyst soluble in the reaction medium of a catalytic system consisting of at least one soluble compound of manganese (organic or inorganic) and at least one soluble chromium compound (organic or inorganic), it is also reasonable to use in this way various peroxy compounds, and ketones or aldehydes, initiating the oxidation reaction, provided that the reaction is carried out at temperatures below 120°C. it Should be noted that the solvent along with solvents, which have different nature (as proton and aprotic) and not significantly oxidized under the reaction conditions, the oxidation process PR is delahaut conduct, for example, in the presence of perfluoroine carbonic acid, for example triperoxonane.

However, these methods have such disadvantages as the process in the presence of costly catalysts based on transition metals and special additives, the use of high temperatures, the complexity of the selection of the catalyst and intermediate oxidation products of the proposed organic solvents, complex and expensive recovery operations not only of the catalyst, and solvent.

Closest to the claimed invention is the invention "method for the oxidation of hydrocarbons" in patent RU 2210562, according to which the original substrates are alkanes, cycloalkanes, alkylaromatic hydrocarbons, alkenes and cycloalkenes, the oxidation process is performed using oxygen or oxygen-containing gas in the liquid phase in a solvent selected from the proton polar and aprotic solvents (in a fairly wide list of possible solvents are listed and triperoxonane acid), in the presence of a catalyst soluble in the reaction medium, the catalyst contains at least one soluble compound of cobalt and at least one soluble compound chromium, in particular their relationships. The catalyst according to this patent may contain additional is entrusted, at least one soluble compound of zirconium and/or hafnium (provides a wide range of both organic and inorganic compounds of these metals). In addition, in the reaction medium is injected, the initiator of the oxidation reaction, which proposed a number of hydroperoxides and aldehydes and ketones. The temperature at which the oxidation reaction varies depending on the substrate and is usually between 50° 200°C, preferably between 80 and 120°C. the Pressure is typically between 0.1 MPa and 20 MPa, however, it is noted that the pressure is not a critical parameter of the method and may be below, equal to, or above atmospheric.

It should be emphasized that this document triperoxonane acid is called the solvent in the enumeration of other solvents, presents very broadly, without specifying any of the features of this solvent before the other.

The disadvantages of this method is the technological complexity of the oxidation process taking place for quite a long time, require the presence of a catalyst based on transition metals, initiating additives, high temperature. The complexity of the method according to this patent consists in the separation of the reaction products, the allocation of spent catalyst and p is the generation, and also in the regeneration of the solvent.

In addition, the title of the invention present a generalization of the method of oxidation of hydrocarbons", in the context of the description indicates that the hydrocarbon used as the starting substrates - alkanes, cycloalkanes, alkylaromatic hydrocarbons, alkenes and cycloalkenes, but neither the claims nor the description is not represented by any description, nor the results of the implementation process of partial oxidation of these hydrocarbons, in addition to cyclohexane.

The objective of the invention is to provide a method of selective catalytic partial oxidation of hydrocarbons such as alkanes, cycloalkanes, alkylaromatic hydrocarbons, alkenes, cycloalkenes, not requiring the use of catalytic systems based on transition metals, the introduction of additional initiators of oxidation, high temperatures, to obtain various oxygen-containing organic compounds.

The problem is solved in that in the method of oxidation of hydrocarbons with oxygen in triperoxonane acid according to the invention pre-exercise feeding of triperoxonane acid with oxygen, after which the reaction medium is injected original hydrocarbon and can stand up to the exhaustion of the bound oxygen to obtain the corresponding oxygen-containing soy is inane.

The invention consists in the following.

Partial catalytic oxidation of hydrocarbons is carried out in a liquid medium, which is triperoxonane acid (hereinafter TFA), molecular oxygen, which previously, before serving in the reaction medium substrate, saturate triperoxonane acid. In this process, TPA acts not only as the environment in which the process of oxidation, but also as a catalyst for the oxidation process.

Oxygen saturation TPA takes place at any appropriate technology temperatures and pressures, which typically are in the range accordingly(-10)-(+65)°and R≤10 ATM.

These same conditions can be used for the implementation of the process of oxidation, but usually the process is conducted at room temperature (20°C) and atmospheric pressure.

As the oxygen source can be any oxygen-containing gases such as air, gaseous oxygen, which is either pumped through the volume of TPA or TPA survive in their environment.

The time of pumping oxygen-containing gas or oxygen through the volume of TFA or TFA extracts in its atmosphere and the temperature at which saturation TPA oxygen, determine the concentration of bound oxygen, and accordingly, the concentration of oxidant.

Molar is the ratio of TFA and the associated oxygen according to the invention are in the range of TPA:O 2=1:0.2 to 1:10.

The valid presence of water in the source TPA, up to 50 wt.%, but, as a rule, use anhydrous TFA.

The original hydrocarbons are aliphatic and alkylaromatic hydrocarbons, alkenes, cycloalkanes, and cycloalkene.

Products of the oxidation reaction according to the method of the invention are alcohols, aldehydes, ketones, acids.

Moreover, the number of carbon atoms in the molecule of the obtained product may be the same as in the original hydrocarbon, or less (the oxidation of ethylene or propylene), but can be as large as, for example, in the oxidation of alkylaromatic hydrocarbons.

Interest in this method of oxidation are alkenes and alkylaromatic hydrocarbons, in particular propylene, the selectivity of which the ethanol in this method of oxidation is close to 100%, and toluene or p-xylene oxidation which is carried out with high selectivity for products such as phenols and Cresols.

To control the oxidation process and the quality of the resulting oxidation products using conventional organic synthesis techniques, methods and equipment, such as gas-liquid chromatography, gas chromatography-mass spectroscopy, potentiometric titration.

The oxidation reaction proceeds until complete exhaustion of the oxygen associated TPA. The completion of the oxidation reaction hazoor the testing substrate is fixed, for example, to stop its flow, when using liquid substrates - no changes in the composition of the reaction medium.

Separation of the reaction products and TPA carried out, usually by distillation, vacuum and/or in the atmosphere of inert gas. You can use any traditional methods of separation of organic compounds, the choice of which will be determined on the basis of the quality of the source substrate, the degree of oxidation and, consequently, the composition of the final reaction mixture.

The following examples only illustrate the invention without limiting its scope.

Example 1.

In a glass bubbler with holes for inlet and outlet gas was loaded with 30 ml of 99.9% TFA, pre-oxygenated air to the ratio of TPA:O2=5:1. The supply of ethylene was carried out at 60 ml/min for 20 min at 20°and atmospheric pressure.

The oxidation products of ethylene ethanol (41 mol.%) and methanol (59 mol.%).

Example 2.

In a glass bubbler with holes for inlet and outlet gas was loaded with 30 ml of 99.9% TFA, pre-oxygenated air to the ratio of TPA:O2=5:1. The supply of propylene was carried out at a rate of 25 ml/min for 20 min at 20°and atmospheric pressure. Chromato-mass-spectrometric analysis of the final reaction mixture showed the presence of only ethanol and Etowah quantities of acetone. The interim analyses of the reaction mixture showed the presence of formic acid.

Example 3.

In a glass reactor, equipped with a magnetic stirrer, were placed 20 ml of 99.9% TFA and 20 ml of toluene. TPA pre-saturated with oxygen from the air to the ratio of TPA:O2=5:1. The reaction mixture with constant stirring was kept for 10 min at 20°and atmospheric pressure. Further keeping the reaction mixture during the week did not lead to qualitative and quantitative changes in the oxidation products, which is a sign of exhaustion during a specified period of time only oxygen associated TFA.

Department triperoxonane acid from the reaction products was performed using distillation in an atmosphere of inert gas and extraction of water.

The composition of the oxidation products of toluene, according to chromatographic analysis, are shown in table:

Table
Productsmol/100 mol of unreacted toluene
Cresols39,4
Phenols42,8
Xylenol16,7
Trimethylphenol1,1

Similar products in the same ratios were obtained in the oxidation of n-KS is Lola.

Example 4.

In a glass reactor, equipped with a magnetic stirrer, were placed 20 ml of 99.9% TFA and 20 ml of n-heptane. TPA pre-saturated with oxygen from the air to the ratio of TFA:O2=5:1. The reaction mixture with constant stirring was kept for 25 min at room temperature and atmospheric pressure. The conversion rate was 10%.

The products of oxidation of heptane represented 13% of heptanol and 87% of heptanone.

Test case with CH3COOH

In a glass reactor, equipped with a magnetic stirrer, were placed 20 ml of glacial acetic acid and 20 ml of toluene. CH3COOH pre-saturated with oxygen during the time required for saturation of TPA oxygen to the ratio of TPA:O2=5:1. The obtained mixture under stirring was kept at 20°and atmospheric pressure for 10 minutes Chromatographic analysis of the reaction mixture showed the absence of oxidation products. Further keeping the reaction mixture in the course of a week in these conditions did not lead to a change in its composition.

It was not observed the course of the oxidation reaction in the described conditions and when used as initial substrates of ethylene and propylene.

The method of oxidation of hydrocarbons with oxygen in triperoxonane acid, wherein the pre-Khujand who are saturation triperoxonane acid by oxygen, then the reaction medium is injected original hydrocarbon and can stand up to the exhaustion of the bound oxygen to obtain the corresponding oxygen-containing compounds.



 

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16 ex

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