Method for hydroformylation
SUBSTANCE: treatment method involves flowable hydroformylation reaction product contacting with an aqueous buffer solution to neutralise at least some of the acid phosphorus compound to form a neutralised acid phosphorus compound. The hydroformylation reaction product comprises an acidic phosphorus compound, a metal complex catalyst with an organophosphorus ligand that contains a group 8, 9 or 10 metal complex forming an organophosphorus ligand complex and optionally a free organophosphorus ligand. The buffer solution contains at least one unsaturated aliphatic carboxylic acid salt. Salt concentration in the buffer solution is 0.001-0.8 M and the pH value of the buffer solution is in the range of 6-8.
EFFECT: effective buffer removal of acid by-products from phosphite ligand degradation and promotion of selective hydrolysis of diorganophosphite by-products without adverse effect on the hydroformylation process.
7 cl, 1 tbl, 2 ex
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
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
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
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
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
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
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
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
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
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.
SUBSTANCE: method involves, for example: (a) evaporation of said oxidised discharge stream, containing terephthalic acid, metallic catalyst, impurities, water and solvent, in the first zone of an evaporator to obtain a vapour stream and a concentrated suspension of the discharge stream; and (b) evaporation of the said concentrated suspension of the discharge stream in the second zone of the evaporator to obtain a stream rich in solvent and a high-concentration suspension of the discharge stream, where the said second zone of the evaporator has an evaporator operating at temperature ranging from 20°C to 70°C, where from 75 to 99 wt % of the said solvent and water is removed by evaporation from the said oxidised discharge stream at step (a) and (b); (c) the said high-concentration suspension of the discharge stream is filtered in a zone for separating solid products and liquid to form a filtered product and a mother liquid; (d) washing the said filtered product using washing substances fed into the said zone for separating solid products and liquid to form a washed filtered product and washing filtrate; and dehydration of the said filtered product in the said zone for separating solid products and liquid to form a dehydrated filtered product; where the said zone for separating solid products and liquid has at least one pressure filtration device, where the said pressure filtration device works at pressure ranging from 1 atmosphere to 50 atmospheres; (e) mixing water and optionally extractive solvent with the said mother liquid and with all of the said washing filtrate or its portion in the mixing zone to form an aqueous mixture; (f) bringing the extractive solvent into contact with the said aqueous mixture in the extraction zone to form a stream of extract and a purified stream, where the said metallic catalyst is extracted from the said purified stream.
EFFECT: improved method of extracting metallic catalyst from an oxidised discharge stream obtained during production of terephthalic acid.
36 cl, 3 dwg, 2 tbl, 2 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: invention relates to regeneration of basic anionite catalysts for process of production of alkylene glycols via hydration of corresponding alkylene oxides. Method according to invention consists in treatment of spent catalyst with aqueous solution of inorganic salts of iodine and inorganic acids or with hydroiodic acid aqueous solution.
EFFECT: achieved complete restoration of initial volume and selectivity of catalyst and thereby prolonged lifetime of expensive anionite catalyst.
1 tbl, 8 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
SUBSTANCE: catalytic system of ethylene in 1-hexene trimerisation includes a chromium (III) complex with a diphosphoric ligand of the general formula [CrCl3[(Ph2P(1,2-C6H4)P(Ph)(1,2-C6H4)(R)](THF)], where R is a hydrocarbon radical or a heteroatom-containing hydrocarbon group, which is in a phenyl substituent in the ortho-position relative to one of the phosphorus atoms. A source of chromium (III) is represented by tris(tetrahydrofuran)chromium chloride, and an activator, representing a mixture of solutions of trimethylaluminium and partially hydrolysed trimethylaluminium in toluene or methylcyclohexane. The molar ratio of the catalytic system components [Cr] : partially hydrolysed trimethylaluminium : trimethylaluminium constitutes 0.03-1.09%:6.95-31.92%:67.39-92.81%.
EFFECT: obtaining high selectivity by 1-hexene with the simultaneous reduction of the quantity of ethylene polymerisation byproducts in the process of trimerisation.
2 cl, 2 tbl, 19 ex