Method for introduction and reclamation of cobalt during hydroformylation of propylene

FIELD: chemistry.

SUBSTANCE: invention discloses introduction of cobalt in form of a cobalt salt solution into a process for hydroformylation of propylene performed in the presence of a cobalt catalyst, where the said cobalt salt solution is specifically cobalt butyrate dissolved in a high-boiling azeotropic mixture of dimethyl acetamide (DMA) and dimethyl formamide (DMF) in butyric acid. Regeneration of a catalyst which is a mixture of cobalt butyrate and the azeotropic mixture of DMA and DMF with butyric acid is performed by treating the still residue after distillation of the end products with water, followed by stripping off the obtained aqueous extract and returning the stripped off residue to the hydroformylation step.

EFFECT: simple hydroformylation process.

2 ex

 

The invention relates to the field of organic synthesis, namely the production of isomeric aldehydes from propylene and synthesis gas by the method of oxosynthesis by the reaction of hydroformylation. With respect to propylene:

In addition to the main reaction by hydrogenation of aldehydes with appreciable yield can be obtained with the corresponding butyl alcohols, as well as the products of secondary transformation of aldehydes and alcohols: esters, acetals, dimers - condensation products of aldehydes and other side, mostly high-boiling compounds.

In most industrial installations, the propylene hydroformylation is carried out at a temperature of 120-150°C and pressures up to 30 MPa in the presence of a catalyst - hydrocarbonyl cobalt concentration in the reaction zone is 0.1 to 0.4 wt.% in terms of cobalt metal.

Techno-economic performance of the process is largely determined by how the introduction of cobalt in the process of its regeneration and return to the process.

Widespread technology the introduction of cobalt and its regeneration by acid-evaporation scheme, in which the cobalt is introduced into the process in the form of oil-soluble salts of organic acids (2-ethylhexanol, naphthenic or similar)dissolved in high-boiling organic solvent, in the example as residue, obtained by distillation from the reaction mass of target products (avts the USSR№178814, №245759, №372199, №403665, №858913).

Under carbonylation under the influence of the synthesis gas at a temperature of 130-180°C and pressures up to 30 MPa is recovering 2-ethylhexanoic acid, and cobalt in the composition of the catalytic complex HCo(CO)4- hydrocarbonyl cobalt - acquires zero valence. From the stage of carbonylative the resulting mixture of products, to which is added propylene, is fed to phase synthesis of aldehydes. Next, produce from the stage of synthesis of aldehydes into the reactor oxidative demobilization, which under the influence served in the air at a temperature not exceeding +50°C (to avoid thermal decomposition of carbonite to the deposition of metallic cobalt) is the oxidation of aldehydes (mainly n-oil) with the formation of namakani acid. Ratmalana acid, interacting with hydrocarbonyl cobalt, lead to its decay. This cobalt enters the composition of the cobalt butyrate, again acquiring valence +2. Then, in the result of exchange reactions of cobalt butyrate, 2-ethylhexanoic acid cobalt enters 2-ethylhexanal cobalt soluble in the product mixture. Since this reaction is reversible, to ensure its fulfilment in the enjoyment of the torus add excess 2-ethylhexanol acid.

However, in the product mixture remains insoluble in her butyrate cobalt precipitated. In addition to butyrate cobalt in the precipitate, called cobalt sludge, there are also other, unidentified form compounds of cobalt.

When sparging air cobalt sludge in the reactor oxidative demobilization in the state of microwaves, is taken out of the reactor, and then as a result of coagulation of particles of microwaves sludge deposits in the apparatus on the path of further movement, which particularly affects the operation of a node separation of the products of synthesis, hinders the normal operation of equipment. This causes the need for frequent stops for washing and cleaning equipment from cuttings, which reduces the production time. Paged (usually manually) from the system, the sludge is usually sent to specialized plants for regeneration of cobalt on a multistage, expensive technology.

Known method of recovery of cobalt from cobalt containing slurry obtained in the process of hydroformylating olefins. Unloaded from the apparatus, the sludge is processed to separate the installation by dissolving it in 2-ethylhexanoic acid (RF patent for application No. 2007120357/04, the decision to grant a patent dated 04.02.2009). The sludge treatment is carried out in the apparatus with m is szalkai and heating elements under stirring at a temperature of not lower than 190°C for at least 4 hours. When this sludge is decomposed with formation of a solution of 2-ethylhexanate cobalt 2-ethylhexanoic acid. The resulting solution recycle in the process.

However, this method of regeneration of cobalt does not eliminate the need for regular stops production for time-consuming cleaning equipment from deposits of sludge. In addition, the process is complicated by the introduction of a scheme of site recovery of cobalt from slag.

The known method of introducing cobalt in the process of hydroformylation in the form of oil-soluble salts of 2-ethylhexanoic acid as residue obtained after the distillation of the desired products from the products of hydroformylation. VAT residue treated with an aqueous solution of acetic acid. The resulting exchange reactions cobalt acetate dissolved in water is sent to the column reactor, which also serves a 2-ethylhexanoyl acid and high boiling solvent. Water and released from the exchange reactions of acetic acid is withdrawn from the reactor in the form of distilled water, and 2-ethylhexanal cobalt in high-boiling solvent is directed through carbonylative (Vasyukov, Allicin and other "Technology oxosynthesis and related processes involving carbon monoxide". Ed. CJSC "SIBUR-Khimprom", Perm, 2004, p.32, 37-44).

The disadvantages of this method of introduction and is egenerali cobalt in the process are:

a) the complexity of the technology as a result of repeated transformations cobalt schemes: 2-ethylhexanal cobalt → hydrocarbonyl cobalt → 2-ethylhexanal cobalt (via intermediate formation of cobalt butyrate) → cobalt acetate → 2-ethylhexanal cobalt;

b) loss of expensive cobalt and 2-ethylhexanoic acid due to the incompleteness of equilibrium reactions of transformation of hydrocarbonyl cobalt 2-ethylhexanoyl acid and 2-ethylhexanate cobalt as cobalt acetate.

To simplify technology and cheaper process of propylene hydroformylation proposed cobalt to enter into the process in the form of butyrate cobalt in solution azeotropic mixture of dimethyl amides of lower acids, namely N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMAA) with n-butyric acid. In addition, we found that butyric acid and the above-mentioned amides form azeotropic mixtures with a negative deviation from the law of Raul, i.e. with a high boiling point and is completely miscible with water. Thus, the solvent azeotropic mixture of butyric acid (boiling point 163,5°C) and DMF (boiling point 153,0°C) pressure range 755-765 mm Hg has a boiling 174,8 covers 175.6 With and contains in its composition of 35.6% vol. DMF and 64.4% vol. butyric acid.

The solvent azeotropic mixture of butyric acid and DMAA boiling point 165,5°C) pressure range 755-765 mm Hg - has a boiling 183,4-184,2°C and contains 51,8% vol. DMAA and 48.2% vol. butyric acid.

The presence in the reaction zone of the proposed solvents in quantities that ensure the dissolution of catalytic doses of cobalt, does not degrade the performance of the process as being carbonylative, and at the stage of hydroformylation. When the temperature of 170°C, corresponding to the temperature of boiling VAT residue in the allocation of aldehyde-alcohol fraction from the product mixture after stage oxidative demobilization and processing time 10-20 minutes, cobalt sludge at a ratio of solvent : sludge, corresponding to the material balance, completely soluble in both solvents, and, as a result of decomposition of the sludge, cobalt in its structure, is transformed into the cobalt butyrate. Thus, directing in an apparatus for distillation of aldehyde-alcohol fraction products of oxidative demobilization, which will be one of our solvents, as residue from the distillation get a homogeneous mixture consisting of high-boiling by-products of synthesis, solvent and cobalt butyrate. High-boiling by-products of synthesis is practically insoluble in water, so the solvent as cobalt butyrate, easily stands out from the VAT residue when e is straccia water. In the subsequent Parke aqueous extract warded off water is applied again, and dehydrated solution of cobalt butyrate in the used solvent is recycled to the stage of carbonylative.

When using the proposed method of introduction and regeneration of cobalt

- greatly simplified the process of hydroformylation, since the turnover of cobalt is carried out according to the scheme: butyrate cobalt ⇒ hydrocarbonyl cobalt ⇒ cobalt butyrate;

- eliminated the use of expensive 2-ethylhexanoic acid and acetic acid and, accordingly, their losses;

- excluded from the process time-consuming operation of cleaning equipment from cobalt sludge and stop production on its implementation;

- reduced loss of cobalt.

Significant difference between the proposed method and the introduction of cobalt in the process of propylene hydroformylation and its regeneration is the introduction of cobalt in the form of butyrate dissolved in a mixed solvent, which represents a high-boiling azeotropic mixture of dimethyl amides of lower acids, namely N,N-dimethylformamide or N,N-dimethylacetamide, oil acid, and the regeneration of cobalt from the products obtained after conducting hydroformylation carried out by aqueous extraction of VAT residue after the distillation of the target product is mswb followed by parcoy the obtained extract and return the process to the stage of hydroformylation residue from parki, containing butyrate, cobalt solvent.

Industrial applicability of the proposed method is confirmed by the following examples.

Example 1.

In thermally-controlled autoclave load 23.1 g of a solution containing 5.7 g of cobalt butyrate and 15.6 g of azeotropic mixtures DMAA with butyric acid. The solution is heated to a temperature of 170°C, after which the autoclave is introduced synthesis gas. The process of carbonylative performed at a pressure of 25-30 MPa, after which the temperature was lowered to 125-145°C and injected into the autoclave 420 g of propylene, continuing the supply of synthesis gas to equalize the pressure in the system and in the autoclave. The solvent of propylene are purged of hydroformylation. The reactor is cooled to a temperature of 50°C, relieve pressure and poured into a distillation flask equipped with a bubbler. Through the bubbler within 20-30 minutes of breathable, regulating the flow control of the temperature in the flask, which should not exceed 50°C. When the reaction products are virtually absent CARBONYLS of cobalt, and the walls of the flask there is a plaque sludge pink-purple color. After that, the content of the flask is distilled, the distillate to a temperature in the liquid 170°C. the result 661 g of distillate (aldehyde-alcohol fraction), and 80.3 g VAT residue and sludge on the walls of the flask are missing. Cooled to t is mperature 40-50°C VAT residue poured into a separating funnel and add water in an amount of 80.3, After intensive mixing and subsequent sedimentation of the separating funnel unload of 58.6 g of an oil layer containing no solvent (less than 0.01%) and cobalt (less than 1 mg/l), and 102 g of the water layer.

After parki water layer received an 80.5 g of an aqueous distillate containing 0.2 g of butyric acid, and balance - almost the entire original solution of cobalt butyrate for later use.

Example 2.

In the autoclave load of 4.8 g of cobalt butyrate and 13 g of azeotropic mixture of DMF with butyric acid. The process of carbonylation and propylene hydroformylation is carried out in the conditions of example 1. The reaction came in 350 g of propylene in a mixture of 54 g of high-boiling by-products of synthesis used for dissolving popeline. Chilled products hydroformylation poured into a distillation flask.

In the distillation flask as in example 1 operate oxidative demobilization products hydroformylation and distillation of aldehyde-alcohol fraction.

As a result, 552 g of distillate and 105 g of the cubic residue. From VAT residue is separated 54 g for further use in the process of hydroformylation, and the remaining 51 poured into a separating funnel.

In a separating funnel, add 51 g of water and after intensive mixing and subsequent Ottawa the Oia get to 38.4 g of an oil layer high-boiling products of synthesis, containing no cobalt and solvent, and 64.4 g of the water layer.

As a result, parki get water layer with 46.6 g of an aqueous distillate containing 0.14 g of butyric acid, and balance - solution of cobalt butyrate in the azeotropic mixture of DMF and butyric acid in the amount of 17.8 g, which is used for re-use.

The method of introduction and regeneration of cobalt in the process of propylene hydroformylation in the form of a solution of cobalt salt of organic acid in a high boiling solvent, its regeneration by distillation (rectification) of the target product from the reaction products and subsequent processing of VAT residue to move the compounds of cobalt in its original form, characterized in that the cobalt is introduced into the process hydroformylation in the form of cobalt butyrate dissolved in high-boiling azeotropic mixture of N,N-dimethyl-formamide or N,N-dimethyl-ndimethylacetamide oil acid and regeneration of cobalt together with the solvent is carried out VAT residue obtained after the distillation of the target products hydroformylation by extraction of the residue with water, followed by parcoy the obtained extract and return the product after parki containing cobalt butyrate and solvent, on the stage of hydroformylation.



 

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FIELD: chemistry.

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26 cl, 2 tbl, 20 dwg, 7 ex

FIELD: chemistry.

SUBSTANCE: invention refers to the field of organic synthesis, namely to the preparation of butyraldehyde from synthesis gas and propylene by the method of oxo process (called also propylene hydroformylation process), particularly to the cobalt regeneration of cobalt sludge. The described method involves the regeneration of the cobalt from cobalt-containing sludge forming in oxo process with usage of cobalt dicarbonyl as catalyst by the way of sludge treatment by the high-boiling organic acid with stirring at elevated temperatures, preferably 190-220°C at the ratio acid: sludge equal 10-20 during no less than 4 hrs.

EFFECT: simplifying of the technology of cobalt sludge regeneration and implementation of the regeneration stage directly on the hydroformylation plant.

3 cl, 3 tbl, 1 ex

FIELD: chemistry.

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EFFECT: reduced initial charge of polyphosphite ligand with lowered deactivation.

8 cl, 8 tbl, 25 ex

FIELD: chemistry.

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6 cl, 6 ex, 2 tbl

FIELD: chemistry.

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EFFECT: increasing catalyst stability and output on more preferable terminal aldehydes.

9 cl, 4 ex, 1 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: hydrophormylation is carried out in presence of cyclic ether of carbonic acid, selected from group, which includes ethylene carbonate, propylene carbonate or butylene carbonate or their mixtures, content of carbonic acid ether constituting from 1 wt % to 98 wt % from reaction mixture.

EFFECT: simplicity of catalyst regeneration and low degree of catalyst deactivation.

9 cl, 3 ex, 3 tbl, 2 dwg

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to synthesis of C7+-aldehydes from C6+-olefins, carbon monoxide, and hydrogen via hydroformylation reaction and to preparation of catalyst used in this reaction. Olefin hydroformylation catalyst contains complex compound of rhodium with polymeric nitrogen-containing ligand including phosphorus-containing fragments. Each of these fragments contains organic radicals, at least one of which is linked to nitrogen atom of polymeric nitrogen-containing ligand and phosphorus atom is in the form of Ph(III). Catalyst preparation consists in that nitrogen-containing polymer is subjected to reaction in organic solvent with Ph(III) compound including organic radicals, of which at least one radical includes group -C(O)OH. Thus obtained product is then subjected to reaction with rhodium compound and organic solvent is removed.

EFFECT: increased and preserved specific activity and regioselectivity of recycled catalyst and reduced pressure in aldehyde production process.

11 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to regeneration of spent metal-containing catalysts for organic synthesis. Described is a method of regenerating metal oxide industrial catalysts for organic synthesis, comprising a support with oxides of Cu and Bi or Cu, Ni and Cr, the method involving treatment of the spent catalyst with salicylalaniline solution in dimethyl formamide with concentration between 0.1 and 0.5 mol, filtration of the solution of the complex compound, which is adsorbed directly on the cleaned support which is silica gel or zeolite obtained after filtration, and the obtained adsorbent undergoes thermal decomposition on the surface of the support at temperature 150-200°C.

EFFECT: described catalyst regeneration method enables multiple regenerations, lowers power consumption of the regeneration process while simplifying the process and without aggressive and toxic media.

2 ex

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