The method of obtaining @ -aldehydes

 

(57) Abstract:

The inventive product pentanal SN, Twin. 103°With butanal SN, Shiga 75,15°C reagent 1: olefin C-C reagent 2: carbon monoxide, hydrogen reaction Conditions: anhydrous hydroformylation in an organic solvent at 70 to 120°C and a total pressure l 4219-1125 kg/cm in the presence of a catalytic system, which is solubilising complex of rhodium with a phosphorus ligand containing rhodium 25 - 600 PPT at a molar ratio of free solubilizing phosphorus ligand to rhodium (9 - 200): 1, moreover, the solubilized free phosphorus ligand is a metal salt monochlorophenol tertiary phosphine of the formula (RL P-C6H4-M-SO Jn Mn J where R together or each independently represents a phenyl or cyclohexyl. p is 1 or 2, M is the cation of an alkaline or alkaline-earth metal, and the process is carried out in the presence of, if necessary, add organic solubilizing agent selected from the group consisting of: a) alkalinising oligomer in an amount of not higher than 30 wt.% from the reaction mixture, and the specified oligomer is chosen from the group of polyethylene or polypropylenglycol them the formula R (AXIS CH ) HE. where R denotes an alkyl C-C Oh 3-IV an amount not exceeding 50 wt.% from the reaction mixture; C)polar compounds selected from the group consisting of methanol, dimethyl sulfoxide, benzonitrile or sulfolane, kolicevo not higher than 35 wt.% from the reaction mixture, or mixtures of these groups a), b), C), such as a mixture of methanol, alcohol ethoxylate, and polyethylene oxide. glycerides, or a mixture of methanol, glycol and policypractice glycerides, or mixture of alcohol ethoxylate, policypractice glycerides and N-metallireducens, or a mixture ethoxylate alcohol, polietileno of polypropylenglycol and dimethyl sulfoxide, provided that the total number of a) + b) + C), is present in this mixture does not exceed 50 wt.% from the reaction mixture. 20 table. o-s I and

 

Same patents:

FIELD: improved processes catalyzed by complexes of a metal- organophosphorous ligand.

SUBSTANCE: the invention presents the improved processes catalyzed by complexes of metal-organophosphorous ligand. The method of extraction includes: feeding of the indicated liquid reactionary product in the zone of separation, stirring of the indicated liquid reactionary product with production by separation of phases of a polar phase containing one or several unreacted reactants, a complex catalyst metal- organophosphorous ligand, not obligatory free organophosphorous ligand and one or several polar dissolvents; and a nonpolar phase containing one or several products of decomposition of the organophosphorous ligand, one or several by-products of the reaction and one or several products. Further the method provides for the stages of withdrawal from the zone of separation and feeding into the reaction zone and-or into the zone of separation. In the given method selectivity of the polar phase for the organophosphorous ligand concerning one or several products is expressed by a ratio of distribution coefficients Efl, which has a value more than approximately 2.5; (ii) the selectivity of the polar phase for the organophosphorous ligand concerning one or several decomposition products of the organophosphorous ligand is expressed by a ratio of distribution coefficients Ef2, which has a value more than approximately 2.5; and (iii)the selectivity of the polar phase for the organophosphorous ligand concerning one or several by-products of reaction is expressed by a ratio of distribution coefficients Ef3, which value is more, than approximately 2.5. The method allows to reduce a negative effect on the process, for example, on prevention of a decrease of efficiency of the catalyst, conversion of the initial material and selectivity by a product.

EFFECT: the invention ensures reduction of a negative effect on the process, on efficiency of the catalyst, on conversion of the initial material and selectivity by a product.

20 cl, 2 tbl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing concentrate of butyric aldehydes by oxonation. Method is carried out by the hydroformylation reaction of propylene with synthesis-gas in two in-line connected reactors at temperature 120-150°C, under pressure 250-300 kgf/cm2 and with heat removing by circulation of cooling agent through Field's tubes installed in hydroformylation reactors followed by separation of reaction products. The hydroformylation process in the first reactor is carried out in regimen when the ratio of volume consumptions of cooling agent circulating in Field's tubes and propylene feeding into reactor is (18-28):1. Invention provides enhancing yield of end products, improving energetic indices due to effective heat transfer in the hydroformylation reactor.

EFFECT: improved preparing method.

1 tbl, 4 ex

FIELD: methods of production of 1.3 alkandiol.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to production of 1.3 alkandiol by hydrogenation of the raw material, containing 3-hydroxyaldehyde at presence of a catalyst and a source of hydrogen, where as a source of hydrogen use a synthesis gas, and the catalyst represents a heterogeneous catalyst containing copper on the carrier; and also to the method of production of 1.3-alkandiol by conversion of an oxide in the process including a hydroformylation and hydrogenation. At that it is not obligatory to realize the indicated phases simultaneously in one reaction vessel. The reached technical result consists in essential reduction of the fixed value of equipment and in bringing to a "single-phase" production of 1.3-propandiol (or a similar 3-alcandil) from ethylene oxide (or a corresponding oxide).

EFFECT: the invention ensures essential reduction of the fixed value of equipment and reduction to a "single-phase" process of the propandiol or alkandiol production.

9 cl, 2 tbl, 2 ex

FIELD: processes catalyzed by metal-phosphoro-organic ligand complexes when target product may be selectively extracted and separated from liquid product.

SUBSTANCE: Specification gives description of methods of separation of one or several products of decomposition of phosphoro-organic ligand, one or several reaction byproducts and one or several products from liquid reaction product synthesized continuously and containing one or several non-consumed reagents, catalyst in form of complex of metal-phosphoro-organic ligands, not obligatory free phosphoro-organic ligand, one or several said decomposition products of phosphoro-organic ligand, one or several said reaction byproducts, one or several said products, one or several non-polar solvents and one or several polar solvents by separation of phases where (i) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several products expressed by ratio of distribution coefficient Ef1 whose magnitudes exceeds about 2.5; (ii)is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several decomposition products expressed by ratio of distribution coefficients Ef2 whose magnitude exceeds proximately 2.5; and (iii) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several reaction byproducts expressed by ratio of distribution coefficients Ef3 whose magnitude exceeds approximately 2.5 (versions). Description is also given of continuous methods of obtaining one or several products (versions) and reaction mixture containing one or several aldehyde products.

EFFECT: increased conversion of initial materials and selectivity by product; avoidance or exclusion of deactivation of catalyst.

20 cl, 2 tbl

FIELD: chemical technology.

SUBSTANCE: invention describes a method for realization of the multiphase reaction of hydroformylation of olefins in tube reactor wherein a catalyst is in the continuum liquid phase and at least one the parent product is in the dispersed phase. The hydroformylation reaction is carried out at the loading coefficient B 0.8 or above that is calculated as a quotient from the pressure fall PD length value and the static pressure PS value wherein PD = Cw x g/2 x w2/D and PS = (M/V) x g wherein Cw means a tube reactor resistance coefficient; D means diameter of tube reactor; W means a flow rate moving; S means a density value of flowing phase; M means a weight flow of all components in reactor; V means a volume flow; g = 9.81 m/c2.

EFFECT: improved method, enhanced output of process.

11 cl, 1 dwg, 9 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the hydroformylation process of olefins with using rhodium catalyst for preparing aldehydes comprising 3-21 carbon atoms. Reaction products from the hydroformylation reactor are separated for: (a) gaseous and liquid phase; (b) liquid phase is fractionated for a head fraction containing unreacted olefins and aldehydes and a vat fraction containing by-side products and rhodium catalyst, and (c) the vat fraction is cooled to temperature lower than the hydroformylation point into reactor, preferably, to 10-120°C. Then the vat fraction is saturated with carbon monoxide-containing gas under partial pressure of carbon monoxide 0.1-300 bars. The vat fraction containing catalyst and carbon monoxide are recovered completely or partially into the hydroformylation reactor. Invention provides prolonged working life of catalyst due to prevention of its inactivation in stages for isolation of the end product.

EFFECT: improved preparing method.

11 cl, 3 tbl, 3 dwg, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to technology of production of higher aldehydes and alcohols via hydrofomylation of olefins. C6-C24-olefins are subjected to hydrofomylation on cobalt or rhodium catalyst to achieve degree of conversion 20 to 98%, whereupon catalyst is removed from the product, regenerated and returned to hydrofomylation reactor. Resulting liquid mixture is separated by distillation into low-boiling olefins- and paraffins-containing fraction and bottom fraction containing aldehydes or aldehydes/alcohols mixture. In the case of alcohols being desired product, product fraction is subjected to hydrogenation on hydrogenation catalyst including copper, nickel, chromium, zinc, molybdenum, or mixture thereof, after which hydrogenate is routed to distillation. Olefins contained in low-boiling fraction are subjected to hydrofomylation comprising above-indicated stages. Bottom fractions obtained in all process stages are processed together in common reaction product separation stage.

EFFECT: increased yield of desired product due to improved technology.

19 cl, 3 dwg, 2 tbl, 6 ex

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: 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: chemistry.

SUBSTANCE: invention relates to method of hydrophormylation of unsaturated olefine compounds with number of carbon atoms from three to sixteen in presence of catalyst in form of rhodium, modified with ligands, selected from group including phosphonites, phosphites, phosphinoxides, phosphines, phosphinites, phosphinines and/or phosphinanes, and is characterized by carrying out hydrophormylation in presence of not less than 0,1-106 mol% per unsaturated olefine compound of not less than one cyclic ether of carbonic acid, selected from group, which includes ethylcarbonate, propylene carbonate, buthylene carbonate and their mixtures.

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

9 cl, 4 ex, 1 tbl, 3 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: technology for separation of hydroformylation products by naphthenate-evaporating schedule of oxo-synthesis. Separation of propylene hydroformylation products after its decolbatization is carried out by a single evaporation under atmosphere pressure with separation of distillate - fraction of butyric aldehydes from the vat residue - cobalt salts solution in high-boiling by-side products. Indicated evaporation with separation of vapor phase from liquid phase is carried out in separator device under atmosphere pressure, at temperature of liquid phase 90-115°C or 130-170°C with reinforced circulation of liquid phase through boiler at the circulation ratio = (3-30):1. Then the successive additional extraction aldehydes and alcohols from the vat residue are carried out by a single evaporation under vacuum. Method provides reducing loss of cobalt catalyst at the stage for separating products of oxidative decolbatization, and improved economic indices.

EFFECT: improved method for separating.

9 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing concentrate of butyric aldehydes by oxonation. Method is carried out by the hydroformylation reaction of propylene with synthesis-gas in two in-line connected reactors at temperature 120-150°C, under pressure 250-300 kgf/cm2 and with heat removing by circulation of cooling agent through Field's tubes installed in hydroformylation reactors followed by separation of reaction products. The hydroformylation process in the first reactor is carried out in regimen when the ratio of volume consumptions of cooling agent circulating in Field's tubes and propylene feeding into reactor is (18-28):1. Invention provides enhancing yield of end products, improving energetic indices due to effective heat transfer in the hydroformylation reactor.

EFFECT: improved preparing method.

1 tbl, 4 ex

FIELD: chemical technology.

SUBSTANCE: invention describes a method for realization of the multiphase reaction of hydroformylation of olefins in tube reactor wherein a catalyst is in the continuum liquid phase and at least one the parent product is in the dispersed phase. The hydroformylation reaction is carried out at the loading coefficient B 0.8 or above that is calculated as a quotient from the pressure fall PD length value and the static pressure PS value wherein PD = Cw x g/2 x w2/D and PS = (M/V) x g wherein Cw means a tube reactor resistance coefficient; D means diameter of tube reactor; W means a flow rate moving; S means a density value of flowing phase; M means a weight flow of all components in reactor; V means a volume flow; g = 9.81 m/c2.

EFFECT: improved method, enhanced output of process.

11 cl, 1 dwg, 9 ex

FIELD: organic chemistry, in particular production of carbonyl compounds such as aldehydes and ketones.

SUBSTANCE: claimed method includes reaction of nitrous oxide with alkenes in presence of inert gas as diluent. Reaction is carried out in gas phase at 401-700°C and under pressure of 2-300 atm. Target compounds represent value intermediates for precise and base organic synthesis.

EFFECT: method of high selectivity in relation to target products and improved explosion proofing.

5 cl, 1 tbl, 14 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the hydroformylation process of olefins with using rhodium catalyst for preparing aldehydes comprising 3-21 carbon atoms. Reaction products from the hydroformylation reactor are separated for: (a) gaseous and liquid phase; (b) liquid phase is fractionated for a head fraction containing unreacted olefins and aldehydes and a vat fraction containing by-side products and rhodium catalyst, and (c) the vat fraction is cooled to temperature lower than the hydroformylation point into reactor, preferably, to 10-120°C. Then the vat fraction is saturated with carbon monoxide-containing gas under partial pressure of carbon monoxide 0.1-300 bars. The vat fraction containing catalyst and carbon monoxide are recovered completely or partially into the hydroformylation reactor. Invention provides prolonged working life of catalyst due to prevention of its inactivation in stages for isolation of the end product.

EFFECT: improved preparing method.

11 cl, 3 tbl, 3 dwg, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to improved process for production of 2-ethylhexanal, which is raw material for production 2-ethylhexanoic acid and/or 2-ethylhexanol. Starting material of invention is bottom residue from rectification of butyl alcohols produced in oxo synthesis, from which bottom residue a fraction mainly containing saturated and unsaturated C8-alcohols with 5-15% of C12-acetals is isolated on two columns operated at column top residual pressure 50-90 mm Hg. This fraction is subjected to vapor-phase processing at atmospheric pressure on copper-containing catalyst at 200-300°C followed by rectification of catalysate on two columns to isolate, as first-column top distillate, fraction obtained at 20-50 mm Hg and containing light components and 2-ethylhexanal, which fraction is fed into second column operated at column top residual pressure 60-100 mm Hg to isolate distilled fraction containing light components and 30-60% of 2-ethylhexanal, whereas desired 2-ethylhexanal is recovered as bottom product or as product tapped from the side of bottom column section.

EFFECT: improved quality and yield of desired product.

2 cl, 14 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for oxidizing liquid hydrocarbons in barrier discharge carried out in the bubble reactor with mixtures of oxygen with helium, argon or nitrogen. Method involves using helium, argon and nitrogen taken in the amount 20-80%. The oxidation process is carried out in the presence of solid additives wherein aluminum, nickel, molybdenum, copper oxides or zeolite catalyst ZSM-5 comprising 1.2% of Fe is used. Method provides reducing energy consumptions for oxidation of the parent hydrocarbon in the barrier discharge.

EFFECT: improved oxidizing method.

3 cl, 2 tbl, 10 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for isolating n-butyric aldehyde from the aldehyde distillate of a propylene hydroformylation product containing, n-butyric aldehyde, isobutyric aldehyde and water, butyl alcohols, methanol, butylformate, acids, hydrocarbons, saturated and unsaturated butyl esters, propylketones, butylbutyrates, C8-aldehydes, C12-acetals and unidentified oxygen-containing components as impurities. Method is carried out into two fractionating devices wherein isobutyric aldehyde, water and some amount of n-butyric aldehyde and other impurities are isolated by upper part of the first device, and the end n-butyric aldehyde is isolated by upper part of the second device from vat product of the first device. Isolation of n-butyric aldehyde is carried out in heat-mass-exchange devices equipped by heat-mass-exchange packages made of metallic sheet or net and prepared as Z-shaped crimps, and special equipments for uniform distribution of phlegm by device section and wherein the specific surface of these packages is 100-800 m2/m3 and with corresponding height of crimps and their slope by vertical providing the pressure drop value between upper part and bottom of the first device in the range 0.01-0.10 atm., and that of the second device in the range 0.01-0.07 atm. Isolation of head fraction in the first device is carried out with consumption wherein amount of n-butyric aldehyde in its is 2-2 wt.-% of potential content in rectification raw. Separation in the second device is carried out at the spraying temperature on upper package of the device in the range 20-30oC. Method provides simplifying of technology in isolation of n-butyric aldehyde, enhancing potential removal of n-butyric aldehyde and decreasing consumption of heating steam per 1 t of the end product.

EFFECT: improved isolating method.

11 ex

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 refers to method of aldehydes C3-C21production, consisting that olefins are hydroformylated with the catalyst system added as containing rhodium, polyphosphide ligand of general formula: where k+m≥2, and optionally k=0 or m=0; X is hydrocarbon radical including 1 to 50 carbon atoms; Z is hydrocarbon radicals identical or different in fragments m including 2 to 30 carbon atoms; Y is hydrocarbon radicals identical or different including 1 to 30 carbon atoms, and phosphoprous-containing promoting ligand chosen of monodentate organophosphine, bidentate organodiphosphine and organophosphite. Then product aldehydes are separated from the dissolved catalyst by distillation. The mole ratio of promoting ligand/Rh is 1-50. The disclosed method allows for radioselective production of linear aldehydes C3-C21.

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

8 cl, 8 tbl, 25 ex

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