The method of decomposition of the hydroperoxide

 

(57) Abstract:

The invention relates to an improved method of decomposition of the hydroperoxide with the formation of a mixture containing the corresponding alcohol and ketone, comprising the stage of: a) adding water in the amount of 0.5-20% in the mixture containing the hydroperoxide; (b) the deletion of specified volume of water in such a way that together with water removes water-soluble impurities; C) removing the remaining water in such a way that the reaction mixture is not more than 2% of water; and (d) decomposition of the specified hydroperoxide by contacting the reaction mixture with a catalytic amount of a heterogeneous catalyst containing gold, supported on a carrier. The technical result is an increase in the degree of conversion and the ratio of K/A. 18 C.p. f-crystals, 6 PL.

The scope of the invention

The present invention generally relates to an improved catalytic method for the decomposition of aliphatic or aromatic hydroperoxides with formation of a mixture containing the corresponding alcohol and ketone. In particular, the invention relates to the decomposition of hydroperoxide by washing raw stream with water to remove acidic impurities, remove most of the water P CLASS="ptx2">The level of technology

Industrial methods for producing mixtures of cyclohexanol and cyclohexanone from cyclohexane currently have commercial value and are well described in the patent literature. In accordance with normal industry practice, the cyclohexane is oxidized with the formation of the reaction mixture containing the hydroperoxide of cyclohexyl (GPCG). Formed GPCG either decompose or hydronaut, optionally in the presence of a catalyst, with formation of a reaction mixture containing cyclohexanol and cyclohexanone. In industry this mixture is known as a mixture To/ketone/alcohol), and it can be easily oxidized with obtaining adipic acid or caprolactam, which are important reagents in the ways of getting some condensation polymers, especially polyamides. The high ratio in the reaction mixture is usually preferred. Due to the large amounts of adipic acid consumption in these and other processes, to improve ways of producing adipic acid and its precursors can be used to provide benefits best cost.

Druliner and other (WO 98/34894) used a heterogeneous gold kata is roxide, to obtain a mixture containing the corresponding alcohol and ketone.

Two common problems in ways GPCG, especially in processes using heterogeneous catalysts, are the presence of water and acid by-products in the reaction mixture containing GPCG. Both these impurities can deactivate the catalyst, which reduces the degree of conversion and/or low ratios of K/A. One of the ways to remove acidic by-products is the addition of a neutralizing agent, such as described in U.S. patent No. 4238415. However, this leads to the formation of undesirable salts that must be removed from the final product. In both processes, hydrogenation and decomposition, is used by dehydration of the reaction mixture in situ removal of water (U.S. patent No. 5550301 and 3927108), but in these methods, together with water are not removed acidic by-products.

Applicants have discovered that it is possible to achieve a high degree of conversion and a high correlation To the/And by adding a certain quantity of water in the reaction mixture, followed by removal of water to the stage heterogeneous decomposition, remove acidic impurities.

For further universe what their level of technology. Other objectives and advantages of the present invention will become apparent to a person skilled in the art after reading the detailed description set forth herein.

The invention

Offers an improved way in which the hydroperoxide is decomposed with formation of a mixture containing the corresponding alcohol and ketone. This improvement involves the following stages: a) adding water in the amount of 0.5-20% in the mixture containing the hydroperoxide; (b) the deletion of specified volume of water in such a way that together with the water removed, and water-soluble impurities; C) removing the remaining water in such a way that the reaction mixture is not more than 2% of water; and (d) decomposition of the specified hydroperoxide by contacting the reaction mixture with a catalytic amount of a heterogeneous catalyst. Heterogeneous catalyst preferably contains gold (Au). The method according to the invention optionally can be carried out with the use of gold in the presence of other metals, preferably palladium (Pd). In addition, the catalysts can be optionally deposited on a suitable support material (media), such as silicon dioxide, aluminum oxide, carbon dioxide qi is peroxid of cyclohexyl, and the reaction mixture decomposition is preferably formed in the oxidation reaction of cyclohexane.

The preferred method for removal of water at the stage b) is decantation, and the preferred method for removal of water at the stage (C) is the instantaneous evaporation.

A detailed description of the preferred embodiment variants of the invention

The present invention provides an improved method of implementation stage of decomposition of the hydroperoxide in the industrial process in which aliphatic or aromatic compound are oxidized with the formation of a mixture of the corresponding alcohol and ketone. In particular, cyclohexane can be oxidized with the formation of a mixture containing cyclohexanol and cyclohexanone (K). Industrial process includes two stages: the first - cyclohexane is oxidized with the formation of the reaction mixture containing the hydroperoxide of cyclohexyl (GPCG); the second GPCG decomposes to form a mixture containing cyclohexanone and cyclohexanol. As noted earlier, the oxidation of cyclohexane is well known in the literature and are available to the person skilled in the technical field.

The improved method can also be used for the CID cyclododecyl hydroperoxide and cumene hydroperoxide.

Advantages of the method using a heterogeneous catalyst according to the present invention compared with methods that use homogeneous metal catalysts such as metal salts or a mixture of metal/ligand are increased service life of the catalyst, higher outputs of other useful products and in the absence of soluble metal compounds. However, the use of heterogeneous catalysts exposes the way to the pollution of water and organic impurities from the oxidation reaction, particularly acidic impurities.

Applicants have developed a multi-stage method, which overcome these drawbacks:

a) adding water in an amount of about 0.5 to 20% in the mixture containing the hydroperoxide;

b) remove the specified volume of water using any of the methods, so that together with the water removed water-soluble impurities;

c) removing the remaining water using any method, so that the reaction mixture is not more than about 2% water; and

d) decomposition of the specified hydroperoxide by contacting the reaction mixture with a catalytic amount of a heterogeneous Katav water to the mixture, containing a hydroperoxide, with the subsequent removal of water volume in any way that will remove impurities from the reaction mixture together with water, especially acidic by-products of the oxidation process, such as an organic one - and dibasic acid. The amount of added water is 0.5-20 wt.% mixtures containing hydroperoxide. The preferred amount is about 4%.

Removal of such impurities prevents poisoning of the catalyst, which decreases the ratio K/A. Typically preferred is the high ratio of K/A. Methods of removing water from the reaction mixture together with water will be deleted also, impurities, include but are not limited to, decantation and extraction. The preferred method is to decantation. Preferably the water is removed to less than about 5%.

Preferably the hydroperoxide hydroperoxide is of cyclohexyl, and the mixture containing a hydroperoxide, preferably is a result of the oxidation of cyclohexane. You can use any method of oxidation, however, one typical method used in industry, is the method described Druliner and others, in U.S. patent No. 4326084.

The method can be either continuous or periodic.

Then, after removing the remaining water, dried reaction mixture decomposition containing a hydroperoxide, is subjected to contact with a catalytic amount of a heterogeneous catalyst. This method of decomposition can be implemented in a wide range of conditions using a wide range of solvents, including source aliphatic hydrocarbons which are oxidized to the hydroperoxide. Because the industry hydroperoxide of cyclohexyl usually obtained in the form of a solution in cyclohexane after catalytic oxidation of cyclohexane, a convenient and preferred solvent in the decomposition method of the present invention is cyclohexane. This mixture can be used as it is obtained in the first stage of the oxidation of cyclohexane, or after removal of some of its components with known Spash">The preferred concentration of cumene cyclohexyl in the reaction mixture GPCG can vary from about 0.5 wt.% to about 100 wt.% (i.e., undiluted). Used in industry preferred embodiment, the interval is from about 0.5 to about 3 wt.%.

A suitable reaction temperature for the method according to the invention varies in the range of from about 80 to about 170°C. is Usually preferred temperature is from about 110 to about 160°C. the Pressure of the reaction may preferably vary in the range from about 69 kPa to about 2760 kPa (10-400 pounds/square inch), and more preferred pressure in the range of from about 276 kPa to about 1380 kPa (40-200 lbs/square inch). The reaction time varies inversely with the reaction temperature, and is typically in the range of from about 1 to about 30 minutes.

As noted earlier, the heterogeneous catalysts of the invention contain gold and its compounds, preferably deposited on a suitable solid carriers. The method according to the invention can also be implemented using gold in the presence of other metals, preferably palladium. The percentage of metal can ismenias and the currently favored carriers include silicon dioxide (SiO2), aluminum oxide (Al2O3), carbon (C), titanium dioxide (TiO2), magnesium oxide (MgO) or zirconium dioxide (ZrO2). Zirconium dioxide is a particularly preferred carrier, and particularly preferred catalyst of this invention is the gold deposited on the aluminum oxide. The preferred catalyst is 0.1 to 10% Au/0.05 To 2% Pd-on-alumina, more preferably 1% Au/0,l% Pd-on-alumina.

Some of the heterogeneous catalysts of the invention can be obtained from the manufacturer or they can be obtained from the appropriate starting materials using methods known from the prior art. The catalysts coated with gold can be obtained by any known standard method, which provides good dispersion of gold, such as Sol-gel methods, evaporation or coating of colloidal dispersions.

In particular, preferred are particles of gold ultra-thin size. Such small particles of gold (often less than 10 nm) can be obtained according to publications M. Haruta "Size - and Support-Dependency in the Catalysis of Gold", Catalysis Today, 36 (1997) 153-166 and Tsubota and others, Preparation of Catalysts V, S. 695-704 (1991). Thus obtained gold is to obtain highly dispersed gold catalysts when they are applied on a suitable support material. Typically, the diameter of such highly dispersed gold particles ranges from about 3 nm to about 15 nm.

Solid catalyst carrier, comprising silicon dioxide, aluminum oxide, carbon, magnesium oxide, zirconium dioxide or titanium dioxide, may be amorphous or crystalline, or a mixture of amorphous and crystalline forms. The choice of the optimal average particle size for the catalyst carrier will depend on such process parameters as the residence time of the mixture in the reactor and the required flow rate in the reactor. Typically the average particle size will vary from roughly 0.005 to about 5 mm are Preferred catalysts having a surface area of more than 10 m2/g, because the increased surface area of the catalyst has a direct relationship with increased rates of decomposition in the experiments, the periodic process. In addition, you can use media that has much more surface area, but the fragility inherent in the catalyst with a large surface area, and associated problems of maintaining an acceptable distribution of particle sizes will prove practical upper th way in that we receive freely the current liquid solution, "Sol", by dissolving the appropriate preceding materials, such as colloidal solutions of alkoxides or metal salts in a solvent. Then this "Sol" dispense reagent to initiate the polymerization reaction of the precursor. A typical example is tetraethoxyorthosilicate (TEOS) dissolved in ethanol. Add water with traces of acid or base as a catalyst to initiate hydrolysis. As the progress of the polymerization and crosslinking increases the viscosity freely current "Zola", and he may eventually turn into a hard gel. This "gel" consists of stitched frame of the target material, in which the inside of the open porous structure of the encapsulated original solvent. Then the gel can be dried, usually either by simple heating in a stream of dry air with the formation of a xerogel, or trapped solvent can be removed by replacing the supercritical fluid, such as liquid carbon dioxide, in order to get the aerogel. These xerogels and aerogels can be optionally calcined at elevated temperatures (above 200°C) that bring the

In the practical implementation of this invention, the catalyst may be contacted with the hydroperoxide of cyclohexyl by mixing in the catalyst bed, which is placed in such a way as to ensure close contact between catalyst and reactants. Alternatively, the catalyst may be suspended in the reaction mixture using techniques known from the prior art. The method according to the invention is suitable for batch and continuous methods of decomposition GPCG. These methods can be implemented in a wide range of conditions.

Adding air or oxygen or a mixture of air and inert gases to the mixture of decomposition of cumene cyclohexyl provides an increased degree of conversion of the reactants of the process and To A, because a certain amount of cyclohexane is oxidized directly in K and A, in addition to K and A, which are formed by decomposition GPCG. This auxiliary process is known as "the participation of cyclohexane", and he described Druliner, etc. in U.S. patent No. 4326084, the content of which is included in the description by reference.

Adding hydrogen in the reaction mixture it is possible to obtain a modest increase in conversion, which is also prepopulate stages:

a) the removal of impurities in hydroperoxide mixture by adding 4% water;

b) remove the specified water level to less than 5% by decantation at a temperature of from about 90 to about 160°C and at a pressure of from 6 to 2070 kPa (from about 1 to about 300 pounds per square inch);

c) removing the remaining water to less than about 0.5% by flash evaporation at a temperature of from about 70 to about 250°C; and

d) the decomposition of cumene cyclohexyl, by contacting the reaction mixture with a catalytic amount of a gold catalyst containing 1% of gold and 0.1% of palladium deposited on a suitable carrier is alumina.

The method of the present invention is additionally illustrated by the following non-limiting examples. In these examples, all temperatures are given in degrees Celsius and all percentages are by weight, unless otherwise indicated.

Methods and materials

The catalysts used in the following examples were obtained as described Druliner and other (WO 98/34894), the contents of which are included in the description by reference.

The following are defined and used in the description of the following abbreviations: GPCG - gisli not specified.

All examples use 10 g of a catalyst containing 1% of gold and 0.1% of palladium deposited on alumina. The reactor is a flow reactor with a fully piston fluid flow, a length of 76 cm and a diameter of 0.64, see the Pressure on the inlet and outlet is 1030 kPa (150 psi) and is controlled by a back pressure regulator. Raw stream consists of a 1.6% GPCG in cyclohexane, about 1% of cyclohexanone (K) and 2% of cyclohexanol (A) and variable amounts of water and acid impurities. These acidic impurities that are mentioned in the examples consist of monobasic and dibasic acids which may be similar to those that are formed during the oxidation of cyclohexane, such as adipic acid, succinic acid, formic acid and gidroksicarbonata acid in approximately equal amounts. GPCG, cyclohexanone and cyclohexanol were investigated by gas chromatography. Cyclohexane, GPCG, cyclohexanone and cyclohexanol were obtained from company E. I. du Pont de Nemour and Company, Wilmington, DE. The ratio K/a, obtained after the conversion of cumene cyclohexyl over the catalyst, calculated using the equation:

To illustrate the influence of water and acid p is xila with different amounts of pure water and water containing 10% acid. As shown in examples 2, 3, 5 and 6, the presence of water in amount of more than 0.1% leads to deactivation of the catalyst, which reduces the degree of transformation GPCG and the ratio K/A. As shown in example 4, the presence of acidic impurities, regardless of the amount of water present, also leads to deactivation of the catalyst, which reduces the degree of transformation GPCG and the ratio K/A.

Example 1

For the decomposition of a raw mixture containing 1,6% GPCG, 0.9%, 1,9% AND 0,1% water and 0.3% acid, and the remainder was accounted for cyclohexane, using 10 g of the catalyst containing 1% of gold and 0.1% of palladium. This mixture was fed over the catalyst at a rate of 8 ml/min at 150C and pressure of 1030 kPa (150 psi). The results are presented in table. 1.

Example 2

This example illustrates the effect of clean water. Increase the amount of water has only a minor impact on the degree of transformation, but greatly reduces the ratio K/A. the Catalyst and reaction conditions are the same as described in example 1. Pure water is added to raw materials in varying amounts.

The results are presented in table. 2.

Example 3

This example illustrates acetelyne impact on the degree of conversion and the ratio K/A. The catalyst and reaction conditions are the same as described in example 1. Water containing 10% acid, add in raw materials in different quantities. The percentage of acid indicates the percentage of acid added to the water, but not the percentage of acid in the whole of the raw mix. The results are presented in table. 3.

Example 4

This example illustrates the effect of water containing large amounts of acids. The presence of elevated concentrations of acid greatly enhances the effect of added water on the degree of conversion and the ratio K/A. the Catalyst and reaction conditions are the same as described in example 1. In this example, the raw material contains 1.9% of GPSG, OF 0.5%, AND 2.0% AND 0.1% of water and 1% acid, and the percentage indicates the amount of acid that is present in all raw mix. The results are presented in table. 4.

Example 5

This example illustrates the effect of temperature on the reaction of decomposition GPCG. The catalyst and reaction conditions are the same as described in example 1, except for changing the temperature. In raw materials add 0.2% water containing 10% acid. The results are presented in table. 5.

Example 6

This example illustrates the influence of dalmore 1, except for changing the pressure. In raw materials add 0.2% water containing 10% acid. The results are presented in table. 6.

1. An improved method of decomposition of the hydroperoxide with the formation of a mixture containing the corresponding alcohol and ketone, which includes stages a) adding water in the amount of 0.5-20% in the mixture containing the hydroperoxide; (b) the deletion of specified volume of water in such a way that together with water removes water-soluble impurities; C) removing the remaining water in such a way that the reaction mixture remains no more than 2% of water; and (d) decomposition of the specified hydroperoxide by contacting the reaction mixture with a catalytic amount of a heterogeneous catalyst containing gold, supported on a carrier.

2. The method according to p. 1, wherein the support substance (carrier) for catalyst selected from the group consisting of silicon dioxide, aluminum oxide, carbon, titanium dioxide, magnesium oxide and zirconium dioxide.

3. The method according to p. 1, wherein the hydroperoxide is a hydroperoxide of cyclohexyl.

4. The method according to p. 1, wherein the temperature of the decomposition reaction is from 80 to 170°C and pressure of the decomposition reaction ranges from 69 to 27">6. The method according to p. 1, wherein the reaction mixture contains from 0.5 to 100 wt.% cumene cyclohexyl.

7. The method according to p. 1, which is carried out in the presence of cyclohexane.

8. The method according to p. 1, which is carried out in the presence of added oxygen.

9. The method according to p. 2, in which the gold is applied to the Zirconia.

10. The method according to p. 9, in which the gold is from 0.1 to 10% by weight of the catalyst and carrier substances.

11. The method according to p. 1, which together with gold as well metal is present in an amount of from 0.05 to 2% by weight of the catalyst and carrier substances.

12. The method according to p. 11, wherein the metal is palladium.

13. The method according to p. 1, wherein the gold is present on the raw material in the form of well-dispersed particles having a diameter of from 3 to 15 nm.

14. The method according to p. 12, wherein the catalyst is 1 wt.% gold and 0.1 wt.% palladium deposited on alumina.

15. The method according to p. 1, wherein the gold catalyst is in the form of a Sol-gel compound.

16. The method according to p. 1, which is carried out in the presence of added hydrogen.

17. The method according to p. 1, wherein the method of removing water at the stage b) is the evaporation.

19. The method according to p. 1, wherein the mixture containing the hydroperoxide formed in the oxidation of cyclohexane.



 

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