Method for continuous hydroformylation of olefins c2-c8

FIELD: chemistry.

SUBSTANCE: invention relates to continuous hydroformylation of olefins C2-C8. Proposed method comprises feeding in reactor raw material, synthesis gas and recycled catalyst solution containing rhodium complexes, organophosphorus ligands and heavy by-products, carrying out chemical reaction hydroformylation, isolated from reactor outlet liquid phase, evaporation of liquid phase separation on product aldehydes, followed by purification and fractionation of catalyst solution, from which part of heavy by-products are separated from catalyst by membrane nano filtration and removed, and remaining after this catalyst solution is returned to system. At that, after evaporation separation aldehydes on nano filtration only part of recycled catalyst solution that is preliminarily diluted with solvent, and remaining part of recycled catalyst solution is fed directly into reactor bypassing stage of nano filtration. At that, fed on nano filtration stream is kept in mass amount determined by empirical formula: P·Nt·Kt/StISP, where P is efficiency at aldehydes, Nt is normal formation of heavy products per unit mass of produced aldehydes, StISP is concentration of heavy products in catalyst solution at output of evaporator, Kt is empirical coefficient selected in range of 2…5, wherein concentration of heavy products in solution equal to StISP, is maintained within range of 0.8…0.95 wt, and as solvent for dilution of catalyst solution to be directed for nano filtration, product aldehydes are used added in filtered flow in weight ratio of 1:1…1:5, before dilution aldehydes via catalyst solution inert gas or hydrogen is passed for 3-10 minutes with volume ratio of gas and catalyst solution not less than 10:1, after nano filtration retentate is directed to evaporation stage separation of aldehydes from catalyst solution for regeneration of diluent and retained by return catalyst and diluent of permeate is removed at rectification of main flow of product aldehydes.

EFFECT: proposed method allows to reduce losses of catalytically active largest complex and organophosphorus ligand with removal of heavy by-products of condensation of aldehydes, as well as reducing speed and normal formation above heavy products.

1 cl, 3 dwg, 1 tbl, 18 ex

 



 

Same patents:

FIELD: chemistry.

SUBSTANCE: installation comprises: sources of synthesis-gas and olefins, connected to reactor via purification devices, successively connected by means of pipelines with reactor input gas-liquid separator and evaporator, collector of bottom residue of which is connected with reverse pipeline of liquid recycle, with output of aldehydes from evaporator being collected with rectification column via collector-separator, as well as unit for discharge of waste catalyst and heavy reaction products. Installation is provided with sensor of liquid level, installed in collector of bottom residue; device for preparation of fresh catalyst solution, connected with reverse pipeline of liquid recycle and made in form of mixer with dosing device of catalyst components, with unit for discharge of waste catalyst and heavy reaction products being made in from of successively connected pump with device of its switching on and off, meter of liquid flow, device for distilling aldehydes from waste catalyst solution and connected with meter of liquid flow and dosing device of catalyst components of actuator, with output for aldehydes from device for their distillation from waste catalyst solution being connected with mixer of device for preparation of fresh catalyst solution, and sensor of liquid level is located with device of pump switching on and off.

EFFECT: realisation of hydroformylation on claimed installation makes it possible to provide constant optimal quantity of heavy reaction products, optimal composition and quantity of catalyst solution.

1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of regulating hydroformylation process for obtaining aldehydes of normal structure (N) and iso-structure (I) with ratio N:I. Claimed method includes contact of unsaturated olefin compound with synthesis-gas and catalyst, which contains transition metal and organopolyphosphite and organomonophosphite ligand, with contact being carried out in conditions of hydroformylation, including partial pressure of synthesis-gas, where method includes increase of partial pressure of synthesis-gas to reduce ratio N:I or reduction of partial pressure of synthesis-gas to increase ratio N:I.

EFFECT: obtaining aldehydes of normal structure (N) and iso-structure (I) with ratio N to I.

10 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of hydroformylation and can be used in chemical industry. Claimed is method of hydroformylation for obtaining aldehyde product, including interaction in mode of continuous reaction in liquid phase for hydroformylation of unsaturated olefin compounds, carbon monoxide and hydrogen in presence of mixture of triphenylphosphine and organo-bisphosphite ligand of formula , where R1 and R2 represent monovalent aryl radical, containing from 6 to 40 carbon atoms, R28 represents C1-20-alkyl or cycloalkyl radical or alkoxyradical; and R29 can represent hydrogen atom, C1-20-alkyl or cycloalkyl radical or alkoxyradical. One of said ligands binds with rhodium with formation of hydroformylation catalyst, with molar ratio of triphenyl to metal and organo-bisphosphite ligand to metal constituting at least 4.

EFFECT: presence of organomonophosphite in said system of catalysts based on Rh/organopolyphosphite complex results in catalysts stabilisation without loss of reaction rate.

10 cl, 5 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to regioselective obtaining of n-pentanal, which is used for obtaining plasticisers, additives to motor oils, synthetic lubricating materials. The method is realised in a medium of an aldehyde-containing solvent by the interaction of synthesis-gas with an industrial butane-butene fraction in the presence of a catalytic system, containing rhodium and a diphosphite ligand, with the reaction being carried out with the content of the aldehyde in the solvent not less than 10 wt %, at temperatures 80-110°C, total pressure 0.7-3 MPa, synthesis-gas pressure 0.5-2.5 MPa, with a molar ratio of hydrogen to carbon oxide being in the range 5.0-0.5, molar ratio diphosphite/Rh being in the range 3-15, and rhodium concentration constituting 30-300 ppm, and the addition into a reaction mixture of antioxidants, selected from bisphenols of general formulas: the content of which constitutes 10-40 mol per 1 g-at. rhodium, where R stands for hydrocarbon univalent radicals or hydrogen.

EFFECT: elaboration of a method of regioselective obtaining of n-pentanal.

1 tbl, 26 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a novel acyclic aldehyde having 16 carbon atoms, containing at least three branches and selected from a group consisting of: 3-ethyl-7,11-dimethyldodecanal, 2,3,7,11-tetramethyl-dodecanal, 7,11,-dimethyl-3-vinyldodeca-6,10-dienal and 4,8,12-dimethyltrideca-4,7,11-trienal, to a composition of substances suitable for use as starting material for producing surfactants and containing at least one of the disclosed acyclic aldehydes, to a composition of detergent alcohols, suitable for producing a composition of surfactants and containing at least one acyclic alcohol converted from the disclosed acyclic aldehyde, and to a surfactant composition suitable for use in a detergent or cleaning composition and containing one or more surfactant derivatives of isomers of the acyclic detergent alcohol converted from the disclosed acyclic aldehyde. The invention also relates to versions of a cleaning composition and to versions of a method of producing an alcohol mixture for a composition of detergent alcohols.

EFFECT: improved properties of compounds.

19 cl, 10 tbl, 24 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing aldehydes via hydroformylation of terminal or internal olefins in the presence of a catalyst system containing rhodium and a mono- or polyphosphite ligand. An antioxidant is added to the reaction mixture, the antioxidant being phenols or thioureas of general formulae: where R denotes identical or different aliphatic or aromatic univalent radicals or hydrogen, and hydroformylation is carried out in liquid phase in a solvent medium in form of aldehyde, with rhodium concentration of 0.1-2 mmol/l, at temperature of 20-150°C and pressure of 0.2-5 MPa, wherein the amount of the antioxidant is 1-30 mol/mol phosphite ligand.

EFFECT: invention enables to obtain end products using an efficient method at low raw material costs.

2 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of processing a hydroformylation reaction liquid product which contains an aldehyde, high-boiling hydroformylation reaction by-products, a homogeneously dissolved rhodium complex catalyst, an unreacted olefinically unsaturated compound, synthesis gas and volatile by-products, in which a) the liquid stream after hydroformylation is throttled in an expansion tank, wherein there is separation into a liquid phase and a gas phase, b) the liquid phase obtained in the expansion tank is fed into a separation device in which there is separation into a liquid phase, which mainly contains high-boiling hydroformylation reaction by-products, a homogeneously dissolved rhodium complex catalyst and a small amount of aldehyde, and a gas phase which contains the bulk of the aldehyde, and c) a liquid rhodium-containing stream is collected from the separation device. A portion of the liquid rhodium-containing output stream collected from the separation device is removed from the process and the other portion is passed through a filter, and the separated solid substances are removed from the process while the obtained filtrate is returned to the hydroformylation reaction.

EFFECT: method enables to prevent breakdown and/or deactivation of the hydroformylation catalyst.

13 cl, 1 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method for direct conversion of lower C1-C4 paraffins to oxygenates such as alcohols and aldehydes, which are valuable intermediate products of organic synthesis and can be used as components of engine fuel and/or starting material for producing synthetic gasoline and other engine fuels. The method involves passing a mixture consisting of a lower paraffin or oxygen, diluted with an inert gas or air or pure oxygen, through a catalyst bed at temperature not higher than 350°C. The catalyst used is a catalyst system for heterogeneous reactions, which contains microfibre of a high-silica support and at least one active element, the active element being in form of either a MeOxHalv composite or a EwMezOxHaly composite, wherein the element Me in both composites is selected from a group which includes transition metals of groups 5-12 and periods 4 and 5, or elements of lanthanum or lanthanide groups or, preferably, ruthenium; element Hal is one of the halogens: fluorine, chlorine, bromine, iodine, but preferably chlorine; element E in the EwMezOxHaly composite is selected from a group which includes alkali, alkali-earth elements, or hydrogen, and indices w, z, x and y are weight fractions of elements in given composites and can vary in the following ranges: z - from 0.12 to 0.80, x - from 0.013 to 0.34, y - from 0.14 to 0.74, w - from 0 to 0.50.

EFFECT: method enables to achieve high degree of conversion of starting reactants and high selectivity of formation of alcohols.

4 cl, 15 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a continuous hydroformylation process for producing a mixture of aldehydes with improved control over normal/branched (N/I) isomer ratio of the product aldehydes. The method involves contacting under continuous reaction conditions in a hydroformylation reaction fluid, one or more olefin compounds, carbon monoxide and hydrogen in the presence of a mixture of an organopolyphosphite ligand and an organomonophosphite ligand, at least one of said ligands being bonded to a transition metal to form a hydroformylation catalyst containing a transition metal-ligand complex; the organopolyphosphite ligand comprising a plurality of phosphorus (III) atoms each bonded to three hydrocarbyloxy radicals, any non-bridging species of which consists essentially of an aryloxy radical (substituted or unsubstituted); the contacting is further conducted: (a) at a sub-stoichiometric molar ratio of organopolyphosphite ligand to transition metal such that said molar ratio is greater than 0 but less than 1.0/1; (b) at a super-stoichiometric molar ratio of organomonophosphite ligand to transition metal such that said molar ratio is greater than 2/1; (c) at a carbon monoxide partial pressure in a negative order region of a hydroformylation rate curve wherein rate of reaction decreases as carbon monoxide partial pressure increases, and wherein rate of reaction increases as carbon monoxide partial pressure decreases, the rate curve being measured on an identical hydroformylation process in the presence of the organopolyphosphite ligand but not the organomonophosphite ligand; and (d) with varying the molar ratio of organopolyphosphite ligand to transition metal within the aforementioned sub-stoichiometric range while maintaining the molar ratio of organomonophosphite ligand to transition metal in the aforementioned super-stoichiometric range, so as to control continuously the normal/branched isomer ratio of the aldehyde products.

EFFECT: providing a continuous production of a mixture of aldehydes with improved control over normal/branched (N/I) isomer ratio of the aldehyde products.

21 cl, 3 ex, 4 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a carbonylation method in which at least one compound olefinically unsaturated compound reacts with carbon monoxide in the presence of a complex catalyst of a metal of subgroup VIII of the periodic table of elements, containing an organophosphorus compound as a ligand, where the additional reagent used is at least hydrogen and hydroformylation is carried out. Carbonylation is carried out in the presence of at least one sterically hindered secondary amine with 2,2,6,6-tetramethylpiperidine , units. The invention also relates to a mixture for use in the disclosed carbonylation method.

EFFECT: invention enables to obtain desired products with high selectivity using a stable catalyst system.

18 cl, 4 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: installation comprises: sources of synthesis-gas and olefins, connected to reactor via purification devices, successively connected by means of pipelines with reactor input gas-liquid separator and evaporator, collector of bottom residue of which is connected with reverse pipeline of liquid recycle, with output of aldehydes from evaporator being collected with rectification column via collector-separator, as well as unit for discharge of waste catalyst and heavy reaction products. Installation is provided with sensor of liquid level, installed in collector of bottom residue; device for preparation of fresh catalyst solution, connected with reverse pipeline of liquid recycle and made in form of mixer with dosing device of catalyst components, with unit for discharge of waste catalyst and heavy reaction products being made in from of successively connected pump with device of its switching on and off, meter of liquid flow, device for distilling aldehydes from waste catalyst solution and connected with meter of liquid flow and dosing device of catalyst components of actuator, with output for aldehydes from device for their distillation from waste catalyst solution being connected with mixer of device for preparation of fresh catalyst solution, and sensor of liquid level is located with device of pump switching on and off.

EFFECT: realisation of hydroformylation on claimed installation makes it possible to provide constant optimal quantity of heavy reaction products, optimal composition and quantity of catalyst solution.

1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of regulating hydroformylation process for obtaining aldehydes of normal structure (N) and iso-structure (I) with ratio N:I. Claimed method includes contact of unsaturated olefin compound with synthesis-gas and catalyst, which contains transition metal and organopolyphosphite and organomonophosphite ligand, with contact being carried out in conditions of hydroformylation, including partial pressure of synthesis-gas, where method includes increase of partial pressure of synthesis-gas to reduce ratio N:I or reduction of partial pressure of synthesis-gas to increase ratio N:I.

EFFECT: obtaining aldehydes of normal structure (N) and iso-structure (I) with ratio N to I.

10 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of hydroformylation and can be used in chemical industry. Claimed is method of hydroformylation for obtaining aldehyde product, including interaction in mode of continuous reaction in liquid phase for hydroformylation of unsaturated olefin compounds, carbon monoxide and hydrogen in presence of mixture of triphenylphosphine and organo-bisphosphite ligand of formula , where R1 and R2 represent monovalent aryl radical, containing from 6 to 40 carbon atoms, R28 represents C1-20-alkyl or cycloalkyl radical or alkoxyradical; and R29 can represent hydrogen atom, C1-20-alkyl or cycloalkyl radical or alkoxyradical. One of said ligands binds with rhodium with formation of hydroformylation catalyst, with molar ratio of triphenyl to metal and organo-bisphosphite ligand to metal constituting at least 4.

EFFECT: presence of organomonophosphite in said system of catalysts based on Rh/organopolyphosphite complex results in catalysts stabilisation without loss of reaction rate.

10 cl, 5 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to regioselective obtaining of n-pentanal, which is used for obtaining plasticisers, additives to motor oils, synthetic lubricating materials. The method is realised in a medium of an aldehyde-containing solvent by the interaction of synthesis-gas with an industrial butane-butene fraction in the presence of a catalytic system, containing rhodium and a diphosphite ligand, with the reaction being carried out with the content of the aldehyde in the solvent not less than 10 wt %, at temperatures 80-110°C, total pressure 0.7-3 MPa, synthesis-gas pressure 0.5-2.5 MPa, with a molar ratio of hydrogen to carbon oxide being in the range 5.0-0.5, molar ratio diphosphite/Rh being in the range 3-15, and rhodium concentration constituting 30-300 ppm, and the addition into a reaction mixture of antioxidants, selected from bisphenols of general formulas: the content of which constitutes 10-40 mol per 1 g-at. rhodium, where R stands for hydrocarbon univalent radicals or hydrogen.

EFFECT: elaboration of a method of regioselective obtaining of n-pentanal.

1 tbl, 26 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing aldehydes via hydroformylation of terminal or internal olefins in the presence of a catalyst system containing rhodium and a mono- or polyphosphite ligand. An antioxidant is added to the reaction mixture, the antioxidant being phenols or thioureas of general formulae: where R denotes identical or different aliphatic or aromatic univalent radicals or hydrogen, and hydroformylation is carried out in liquid phase in a solvent medium in form of aldehyde, with rhodium concentration of 0.1-2 mmol/l, at temperature of 20-150°C and pressure of 0.2-5 MPa, wherein the amount of the antioxidant is 1-30 mol/mol phosphite ligand.

EFFECT: invention enables to obtain end products using an efficient method at low raw material costs.

2 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of processing a hydroformylation reaction liquid product which contains an aldehyde, high-boiling hydroformylation reaction by-products, a homogeneously dissolved rhodium complex catalyst, an unreacted olefinically unsaturated compound, synthesis gas and volatile by-products, in which a) the liquid stream after hydroformylation is throttled in an expansion tank, wherein there is separation into a liquid phase and a gas phase, b) the liquid phase obtained in the expansion tank is fed into a separation device in which there is separation into a liquid phase, which mainly contains high-boiling hydroformylation reaction by-products, a homogeneously dissolved rhodium complex catalyst and a small amount of aldehyde, and a gas phase which contains the bulk of the aldehyde, and c) a liquid rhodium-containing stream is collected from the separation device. A portion of the liquid rhodium-containing output stream collected from the separation device is removed from the process and the other portion is passed through a filter, and the separated solid substances are removed from the process while the obtained filtrate is returned to the hydroformylation reaction.

EFFECT: method enables to prevent breakdown and/or deactivation of the hydroformylation catalyst.

13 cl, 1 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a continuous hydroformylation process for producing a mixture of aldehydes with improved control over normal/branched (N/I) isomer ratio of the product aldehydes. The method involves contacting under continuous reaction conditions in a hydroformylation reaction fluid, one or more olefin compounds, carbon monoxide and hydrogen in the presence of a mixture of an organopolyphosphite ligand and an organomonophosphite ligand, at least one of said ligands being bonded to a transition metal to form a hydroformylation catalyst containing a transition metal-ligand complex; the organopolyphosphite ligand comprising a plurality of phosphorus (III) atoms each bonded to three hydrocarbyloxy radicals, any non-bridging species of which consists essentially of an aryloxy radical (substituted or unsubstituted); the contacting is further conducted: (a) at a sub-stoichiometric molar ratio of organopolyphosphite ligand to transition metal such that said molar ratio is greater than 0 but less than 1.0/1; (b) at a super-stoichiometric molar ratio of organomonophosphite ligand to transition metal such that said molar ratio is greater than 2/1; (c) at a carbon monoxide partial pressure in a negative order region of a hydroformylation rate curve wherein rate of reaction decreases as carbon monoxide partial pressure increases, and wherein rate of reaction increases as carbon monoxide partial pressure decreases, the rate curve being measured on an identical hydroformylation process in the presence of the organopolyphosphite ligand but not the organomonophosphite ligand; and (d) with varying the molar ratio of organopolyphosphite ligand to transition metal within the aforementioned sub-stoichiometric range while maintaining the molar ratio of organomonophosphite ligand to transition metal in the aforementioned super-stoichiometric range, so as to control continuously the normal/branched isomer ratio of the aldehyde products.

EFFECT: providing a continuous production of a mixture of aldehydes with improved control over normal/branched (N/I) isomer ratio of the aldehyde products.

21 cl, 3 ex, 4 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of processing a butanol-butyl formate fraction, relating to by-products of the propylene hydroformylation process. The method involves splitting butyl formates at temperature 220-260°C, pressure 1.5-10 atm, volume rate of feeding raw material and hydrogen of 0.2-0.5 h-1 and 360-2150 h-1, respectively, to obtain butanols and carbon monoxide as end products. The process is carried out on a catalyst having the following composition, wt %: zinc oxide - not less than 98.0, sulphur - not more than 0.3, carbon - the balance.

EFFECT: method enables to obtain end products (butanols) with high output and selectivity with high conversion of butyl formates.

11 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a carbonylation method in which at least one compound olefinically unsaturated compound reacts with carbon monoxide in the presence of a complex catalyst of a metal of subgroup VIII of the periodic table of elements, containing an organophosphorus compound as a ligand, where the additional reagent used is at least hydrogen and hydroformylation is carried out. Carbonylation is carried out in the presence of at least one sterically hindered secondary amine with 2,2,6,6-tetramethylpiperidine , units. The invention also relates to a mixture for use in the disclosed carbonylation method.

EFFECT: invention enables to obtain desired products with high selectivity using a stable catalyst system.

18 cl, 4 tbl, 2 ex

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

FIELD: chemistry.

SUBSTANCE: invention discloses a novel type of polyimide membranes with high permeability and high selectivity with respect to the separation of gases, namely, with respect to versions of separation CO2/CH4 and H2/CH4. With respect to CO2/CH4 separation polyimide membranes have passing ability by CO2, equal 50 Barrere or higher, and the selectivity of CO2/CH4 monogas, equal 15 or higher, at 50°C and 791 kPa. The polyimide membranes contain functional groups transversely cross-linked under an impact of UV rays and can be applied for the production of the polyimide membranes transversely cross-linked under an impact of UV rays, with passing ability by CO2, equal 20 Barrere or higher, and the selectivity of CO2/CH4 monogas, equal 35 or higher, at 50°C and 791 kPa with respect to CO2/CH4 separation.

EFFECT: obtaining the novel type of polyimide membranes with high permeability and high selectivity with respect to the separation of gases.

10 cl, 4 tbl, 15 ex

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