A method of producing a catalyst for a process of hydroformylating

 

(57) Abstract:

The catalyst for the process of hydroformylating olefins produced by interaction of aqueous solutions of cobalt salts of organic acids WITH1-3with higher organic acids contained in the second distillation products hydroformylation formed after regeneration of cobalt acetic acid and having a boiling point above 160oWith 50-200 mm RT.article The solution is pre-treated with air or oxygen-containing gas at 80-140oC for 3-6 hours is Achieved the beneficial use of bottoms stage hydroformylation with simplified technology.

The invention relates to a method for producing oil-soluble cobalt salts of organic acids for the process of oxosynthesis - hydroformylating olefins.

In the present method hydroformylating olefins is almost only used in industry for large-scale production of aldehydes and alcohols widest range on purpose.

One option for the industrial implementation of the said reaction is the process of obtaining aldehydes using cobalto the IU original cobalt in the form, for example, cobalt acetate by interacting with naphthenic or 2-ethylhexanoic acid in the presence of solvent (corresponding cobalt containing distillation products) at the exchange reaction is transferred to the naphthenate or 2-ethylhexanoate, cobalt, soluble in circulating VAT product. The obtained concentrated solution of cobalt (2-4 wt.%. the cobalt) is used as an additive to the circulating solution to compensate for losses of cobalt.

Circulating the solution enters the reactor-carbonylethyl, where at a temperature of 170-175oC, the pressure of the synthesis gas 20,0-30,0 MPa is the conversion of a salt of cobalt in hydrocarbonyl, which is in the process of synthesis of aldehydes.

The reaction products of hydroformylation - oil aldehydes in the form of a solution circulating kovovymi products and dissolved catalyst (hydrocarbonyl cobalt) is subjected to oxidative demobilization by treating the reaction mixture with air and additives naphthenic acids. Hydrocarbonyl cobalt salt is decomposed in oil-soluble salt of cobalt naphthenate.

Received demobilizovannyy product is dispersed into factions: the target aldehydes to obtain 2-ethylhexanoic derivatives - 2-ethylhexanoic acid and alcohols C8; and distillation wastes containing dissolved cobalt naphthenate, which circulate in the process. Some of these distillation products accumulating taken for recycling. With the help of acetic acid from them washed cobalt, and the organic portion is burned in a furnace thermal treatment. The presence of emulsified water phase containing impurities acetic acid, makes this product highly corrosive to conventional steels, made of pipes, tanks and fuel system that eliminates any useful use of these wastes, such as boiler fuel.

"Dimeric" fraction is used to produce concentrate 2-ethylhexanoic acid. However, its oxidation "dimeric" faction did not exceed 32% of theory.

Advanced technology for acid C8from the "dimeric" faction includes a step of selective hydrogenation of this fraction on a palladium catalyst.

Finding ways useful life distillation waste stage of hydroformylation is an important task.

A method of obtaining oil-soluble cobalt salts of organicchemical is that aqueous solutions of acetate or propionate cobalt is heated with 2-ethylhexanoic acid or naphthenic acids 100-300oC in the presence of liquid hydrocarbons, and the resulting cobalt salts soluble in these liquids ("study of the process of preparation of the catalyst (cobalt salts of organic acids") - Alekseev, K. A., Wysocki M. P. and others, in Proc. of "Getting aldehydes and butyl alcohol oxosynthesis, 1 o'clock, L., 1977, PP 119-126).

According to this method, use solutions of cobalt salts, which is obtained by extraction of the cobalt containing reaction product of hydroformylation water or aqueous solutions of aliphatic carboxylic acids with the number of carbon atoms from 1 to 4. As higher carboxylic acids are used as saturated and unsaturated aliphatic carboxylic acids with the number of carbon atoms from 8 to 18, preferably 2-ethylhexanol, 1-ethyl-4-methylpentanol, lauric, 2-ethylhexanoyl, 2-ethyl-4-methylpentanol, 2-propyl-3-isobutylamino, oleic acid or mixtures thereof. For implementing the method are suitable and naphthenic acid.

However, this method is applicable only when used as the source prodeltaic salts required temperature not lower than 100oC.

In addition, in the case of hydroformylation low molecular weight olefins (C3-C5) almost impossible to return to the process liquid hydrocarbons, as their subsequent separation from the reaction products is difficult because of the formation of hard splittable multicomponent mixtures.

Also known is a method of obtaining cobalt catalyst of the process of hydroformylation, according to which demobilizovannyy a secondary product of the distillation product of oxosynthesis ("dimeric" fraction) oxidizes oxygen-containing gas in the presence of an aqueous alkali solution followed by treatment of the resulting mixture of the cobalt salt of an inorganic acid in the presence of an organic solvent (Alekseev, K. A. and others A. S. USSR N 349290 from 16.07.71. "Preparation method of catalyst for the process of oxosynthesis").

According to the invention, the amount of alkali should match the amount of acid produced in the oxidation. From the mixture obtained aqueous layer was separated and treated with a cobalt salt of an inorganic acid in the presence of an organic solvent.

The disadvantage of this method is the complexity of technology and the need for utilization u is isemoa invention is a method of preparation of the catalyst for hydroformylating olefins by reacting aqueous solutions of cobalt salts of lower organic acids with a connection, containing higher organic acid, at a temperature of 120-125oC in the presence of solvent - products hydroformylation, boiling above 160oC, with simultaneous distillation of water and the resulting lower carboxylic acids prototype (Alekseev, K. A., and others, A. S. USSR N 541493 from 12.03.77, "Method of preparation of the catalyst for hydroformylating olefins", B. I. N 1, 1977).

According to the invention by the method prototype replacement net higher organic acids is achieved by the fact that compounds containing higher organic acids, use by-products of the reaction of hydroformylation containing not more than 0.4 wt%. salts of cobalt in terms of metallic cobalt, pre-treated oxygen-containing gas at 20-100oC for 0.5-3 hours.

As by-products of the reaction of hydroformylation usually apply VAT residue of distillation products hydroformylation after distillation of aldehydes and alcohols, and a fraction consisting predominantly of dimeric condensation products of the primary reaction product of hydroformylation.

The disadvantages of the prototype method include a large expense (loss) compounds, sodergard on commodity components.

The goal reached by the interaction of aqueous solutions of cobalt salts of low molecular weight aliphatic carboxylic acids with kovovymi remnants of the stage of distillation of the aldehyde product having a boiling point above 160oC at a pressure of 50-200 mm RT.art., pre-washed from cobalt salts and treated with air or oxygen-containing gas for 3-6 hours at a temperature of 80-140oC.

A distinctive feature of the proposed method is the use of high-boiling bottoms production of aldehydes having a boiling point above 160oC at a residual pressure of 50-200 mm RT.art., past regenerative washing cobalt and treated with air or oxygen-containing gas at a temperature of 80-140oC for 3-6 hours.

The obviousness of the proposed solution is that heavy VAT residue process of propylene hydroformylation, pre-laundered from cobalt, can be used as a substitute naphthenic or 2-ethylhexanoic acids, if the processing air is carried out at a temperature of 80-140oC for 3-6 hours. In more mild conditions of the prototype method to obtain a connection-replace.to. for its implementation does not require any special equipment or inaccessible and expensive raw materials.

Thus used in further processing by-products of the reaction of hydroformylation and aqueous solutions of cobalt salts of lower aliphatic carboxylic acids produced in the process, Refine the catalyst for hydroformylating olefins in a simple way and without the introduction of additional substances. By-products treated with air or oxygen-containing gas is used without pre-treatment and extraction of the solvent and the acid component.

The use of this method allows to exclude from oxosynthesis waste water to facilitate the regeneration process and preparation of the cobalt catalyst and make the process continuous.

The method is illustrated by the following examples.

Example 1

The fraction of by-products of hydroformylation after the stage of regeneration (cleaning) cobalt acetic acid with the following characteristics: boiling point 160oC at a pressure of 50 mm RT.article, an acid number 30,12 mg KOH/g, a carbonyl number 135,31 mg KOH/g, number mycert bubbling unit in the lower part of the reactor serves the air of 45 l/h for 3 hours at a temperature of 80oC.

The resulting reaction mixture having the characteristics: acid number 88,86 mg KOH/g, a carbonyl number 94,32 mg KOH/g, saponification number 229,36 mg KOH/g, an aqueous solution of cobalt acetate, taken in an amount of 400 g and recirculating cobalt containing CBM product hydroformylation taken in the amount of 350 g, is heated under stirring for 3 hours at a temperature of 180oC with simultaneous distillation of the water released acetic acid and organic products. The cobalt concentration in an aqueous solution of 2.5 wt.%, in the circulating VAT product of 0.4% wt. in terms of metal.

As a result of the synthesis is accomplished 486 g of a clear solution of salts containing a cobalt concentration of 2.35 wt.%. in terms of metal. The degree of transition of oil-soluble cobalt in the form of 100%.

The resulting solution of oil-soluble cobalt salts has been subjected to processing with the aim of obtaining CARBONYLS of cobalt in standard conditions. The degree of conversion of oil-soluble forms of cobalt carbonyl form of 98-100%.

Example 2

The fraction of by-products of hydroformylation after the stage of regeneration of cobalt in an amount of 200 g with characteristics as in example 1, cislscuolait 140oC.

The resulting reaction mixture having the characteristics: acid number 147,95 mg KOH/g, a carbonyl number 37,24 mg KOH/g, saponification number 300,81 mg KOH/g, is processed with an aqueous solution of cobalt salts and circulating kovovymi products in the conditions as described in example 1.

As a result of the synthesis is accomplished 434 g of a clear solution of salts containing a cobalt concentration of 2.6% by weight. in terms of metal. The degree of transition of oil-soluble cobalt in the form of 100%.

The resulting solution of oil-soluble cobalt salts has been subjected to processing with the aim of obtaining CARBONYLS of cobalt in standard conditions. The degree of conversion of oil-soluble forms of cobalt carbonyl form of 96-99%.

Example 3

The fraction of by-products of hydroformylation after the stage of regeneration of cobalt in an amount of 200 g with characteristics as in example 1, are oxidized by air in the installation and conditions as described in example 1, except the temperature oxidation, which is 100oC, and the process time, which is 6 hours.

The resulting reaction mixture having the characteristics: acid number 131,24 mg KOH/g, a carbonyl number Mimi kovovymi products in terms as described in example 1.

As a result of the synthesis is accomplished 408 g of a clear solution of salts containing a cobalt concentration of 2.8% by weight. in terms of metal. The degree of transition of oil-soluble cobalt in the form of 100%.

The resulting solution of oil-soluble cobalt salts has been subjected to processing with the aim of obtaining CARBONYLS of cobalt in standard conditions. The degree of conversion of oil-soluble forms of cobalt carbonyl form 98 - 100%.

Example 4

The fraction of by-products of hydroformylation after the stage of regeneration of cobalt with the following characteristics: boiling point 160oC at a pressure of 200 mm RT.art., the acid number of 17 mg KOH/g, a carbonyl number 67 mg KOH/g, saponification number 45 mg KOH/g, 200 g oxidized by air in the installation and conditions as described in example 1, except the temperature oxidation, which is 120oC.

The resulting reaction mixture having the characteristics: acid number 138,36 mg KOH/g, a carbonyl number 62,86 mg KOH/g, saponification number 336,6 mg KOH/g, is processed with an aqueous solution of cobalt salts and circulating kovovymi products in the conditions as described in example 1.

In ,7% wt. in terms of metal. The degree of transition of oil-soluble cobalt in the form of 100%.

The resulting solution of oil-soluble cobalt salts has been subjected to processing with the aim of obtaining CARBONYLS of cobalt in standard conditions. The degree of conversion of oil-soluble forms of cobalt carbonyl form of 98-99%.

Example 5

(on prototype, for comparison)

The fraction of by-products of hydroformylation after the stage of regeneration (cleaning) cobalt acetic acid with characteristics as in example 1: boiling point 160oC at a pressure of 50 mm RT. Art., acid number 30,12 mg KOH/g, a carbonyl number 135,31 mg KOH/g, saponification number 98,46 mg KOH/g, 200 g load in a heated glass reactor with a diameter of 45 mm and a height of 500 mm bubbling Through the device in the lower part of the reactor served in the air in quantities of 55 l/h for 3 hours at a temperature of 50oC.

The resulting reaction mixture having the characteristics: acid number 38,59 mg KOH/g, a carbonyl number 128,43 mg KOH/g, saponification number 129,54 mg KOH/g, an aqueous solution of cobalt acetate, taken in an amount of 400 g, and recirculating cobalt containing CBM product hydroformylation taken in number 3 is acetic acid and organic products. The cobalt concentration in an aqueous solution of 2.5 wt.%, in the circulating VAT product of 0.4% wt. in terms of metal.

As a result of the synthesis is accomplished 473 g of a solution of salts of sediment on the bottom of the flask. The content of cobalt in the reaction solution is 1.6% wt. in terms of metal.

The resulting solution soluble salt of cobalt has been subjected to processing with the aim of obtaining CARBONYLS of cobalt in standard conditions. The degree of conversion of oil-soluble forms of cobalt carbonyl form of 96-99%.

A method of producing a catalyst for a process of hydroformylating olefins by reacting aqueous solutions of cobalt salts of lower organic acids C1-C3with a compound containing higher organic acid, at elevated temperature, characterized in that compounds containing higher organic acids, use side distillation of the reaction products of hydroformylation formed after regeneration of cobalt, acetic acid, and having a boiling point above 160oWith at a residual pressure of 50 to 200 mm RT. senior pre-treated with air or oxygen-containing gas at a temperature of 80 - 140

 

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