Regulation of ratio aldehyde of normal structure: aldehyde of iso-structure in process of hydroformylation with mixed ligand by regulation of synthesis-gas partial pressure

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

 

The technical field to which the invention relates

This invention relates to methods of hydroformylation. In one aspect, the invention relates to the regulation of relations of the isomer with a straight chain isomer with a branched chain in the process of hydroformylation, which is used as the transition metal catalyst, for example rhodium, while in another aspect the invention relates to such a method in which metal is dissolved with the use of a mixture of two fofanah ligands. In another aspect of the invention is to regulate the relations of the isomer with a straight chain isomer with a branched chain aldehyde product without destruction of ligands by regulating the partial pressure of the synthesis gas method.

The prior art inventions

In the process of hydroformylation with variable ratio of normal isomer (i.e., the isomer with a straight chain) to ISO-isomer (i.e. the isomer branched chain) (VNI), a mixture of two fofanah ligands to achieve adjustable selectivity in respect of isomers mixture of products of normal aldehyde/soldered. In particular, the use of three-way catalytic system, which contains a transition metal, typically rhodium (Ru), organophilicity ligand, usually organobentonites ligang� (obpl) and organophosphites ligand (ompl) and in which the mole ratio organophosphites ligand to rhodium (ompl:Rh) usually support more than five to 1 (> 5:1) and the molar ratio organobentonites ligand to rhodium (obpl:Rh) is usually adjusted between 0 and 1:1, for regulating the relations N:I in the range that can be obtained based only on the molar ratio of ompl:Rh (usually between 1 and 5), the relationship obtained for a molar ratio of obpl:Rh (usually between 20 and 40 for propylene). The usual way of regulation N:I is an attitude adjustment organobentonites ligand to rhodium. In particular, the method of reducing the relationship N:I is a reduction of the concentration organobentonites ligand through normal decomposition of ligand by oxidation and hydrolysis. The difficulty of this method, however, is that it is slow, i.e. it takes time for normal decomposition organobentonites ligand. Increase the speed of decomposition organobentonites ligand is known, but this method increases the cost method. Interesting is a way of managing N:I without decomposition organobentonites ligand.

A brief summary of the invention

In one embodiment, the implementation of the proposed method of regulation of the process of hydroformylation (such as the method described in WO 2008/115740 A1) to obtain the normal (N) and ISO(I) aldehydes at a certain ratio N: (I, the method comprises contacting an unsaturated olefinic compounds with the synthesis of a-ha�ohms (also known as SYN-gas, i.e. carbon monoxide and hydrogen) and a catalyst comprising a transition metal, preferably rhodium, and organophosphites, preferably organobentonites, and organophosphites ligand, the contacting conducted under conditions of hydroformylation, which includes the partial pressure of carbon monoxide, and the method includes increasing the partial pressure of the synthesis gas to reduce the relationship N:I or reducing the partial pressure of the synthesis gas to improve the relationship N:I.

In one of the embodiments of the present invention provides an improved method of regulation in the process of hydroformylation to obtain the normal (N) and ISO(I)aldehydes at a certain ratio N: (I, the method comprises contacting an unsaturated olefinic compound with synthesis gas and a catalyst comprising a transition metal, preferably rhodium, and organophosphites, preferably organobentonites, and organophosphites ligand, the contacting conducted in a reaction zone and under conditions of hydroformylation, wherein the improvement comprises feeding the synthesis gas to the reaction zone at a constant speed. In modern methods of hydroformylation synthesis gas is supplied at a controlled rate, i.e., the synthesis gas fed into the reaction zone in response to fluctuations in partial�rated pressure of the synthesis gas in the reaction zone.

Detailed description of preferred embodiments

All references to the periodic table of elements are the Periodic table of the elements, published and copied, CRC Press, Inc., 2003. In addition, any references to a group or groups shall be to the group or groups reflected in this Periodic table of elements using the IUPAC system for numbering groups. If you do not indicate the opposite, unconditional from the context, or customary in this field, all parts and percentages are based on weight and all test methods are modern, as well as the filing date of this patent specification. For the purposes of patent practices of the United States of the contents of any referenced patent, patent application or publication of the patent incorporated by reference in its entirety (or its equivalent version of the United States is also included as a reference), especially in relation to the discovery of synthetic methods, definitions (to the limit, incompatible with any definition, especially as represented in the opening) and General knowledge in this field.

All percentages, preferred amounts or measurements, ranges and endpoints are including border, i.e. the expression “up to 10” includes 10. “At least” is equivalent to “greater than or equal to”, � “at most” so equivalent to the expression “less than or equal to”. The numbers are approximate, unless specifically indicated otherwise. All bands from the parameter described as “at least”, “greater than”, “greater than or equal” or similar, to the parameter described as “at most” “up to”, “less than”, “less than or equal” or similar, are the preferred ranges, regardless of the relative degree of preference specified for each parameter. Thus, the range that has a suitable lower limit, combined with the most preferred upper limit is preferred for practice of this invention. The term “suitable” is used to describe the degree of preference, more than required, but less than is denoted by the term “preferred”. Numeric ranges are in the open among other things for the relative amount of reactants and the conditions of the method.

Method of hydroformylation, reagents, conditions and equipment are well known and described in, among other references, patents 4169861, 5741945, 6153800 and 7615645 USA, EP 0590613 A2 and WO 2008/115740 A1. Unsaturated olefin compound, such as propylene, usually sent from synthesis gas, i.e. carbon monoxide (CO) and hydrogen (H2together with techcompany�entirely the catalyst, containing a transition metal, preferably rhodium, and organophosphites, preferably organobentonites, and organophosphites ligand, the contacting conducted under conditions of hydroformylation in the system from many reactors connected in series, i.e., the flow outlet of the first reaction zone is sent in the payload in subsequent reaction zone. The processing methods can match any of the known methods of processing used in the conventional methods of hydroformylation. For example, the methods can be carried out either in liquid or gaseous state and continuous, semi-continuous or intermittent manner, and, if required, they include the operation of recirculation of the liquid and/or gas recirculation, or a combination of such systems. Furthermore, the method or order of addition of ingredients for the reaction, catalyst and solvent are also not critical and can be accomplished in any conventional manner.

Unsaturated olefinic compounds, suitable for use in the method of this invention are compounds that are able to participate in the process of hydroformylation to obtain the corresponding aldehyde product(s) and is able to stand out from the stream of crude liquid product of a hydroformylation by means of IP�of arena. For purposes of this invention “olefin” is defined as an aliphatic organic compound containing at least carbon atoms and hydrogen and having at least one carbon-carbon double bond (C=C). The olefin preferably contains one or two carbon-carbon double bond, preferably one carbon-carbon double bond. The double bond(s) may be located in the end position of the carbon chain (alpha-olefin) or in any “internal” position circuit (internal olefin). The olefin may contain optional elements other than carbon and hydrogen, including, for example, atoms of nitrogen, oxygen and Halogens, preferably chlorine and bromine. The olefin may also be substituted with functional substituents, including, for example, substituents hydroxy, alkoxy, alkyl and cycloalkyl. Olefin, preferably used in the method of this invention, preferably contains a substituted or unsubstituted olefin having from 3 to 10 carbon atoms. Illustrative olefins suitable for the method of this invention include, without limitation, the following isomers of monoolefins: butene, pentene, hexene, Heptene, ökten, nonene and deutsen with specific non-limiting examples include 1-butene, 2-butene, 1-penten, 2-penten and 1-hexene, 2-hexene, 3-hex�n and similar isomers of Heptene, ökten, nonene and deutsen. Other non-limiting examples of suitable olefins include 2-methylpropene (isobutylene), 2-methylbutan, cyclohexene, butadiene, isoprene, 2-ethyl-1-hexene, styrene, 4-methylsterol, 4-isopropylphenol, 4-tert-butalbiral, alpha methylsterol, 3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene and alkanol, such as pentanol; alkanal, for example, was pentenal; such compounds include allyl alcohol, allylmalonate, hex-1-ene-4-ol, Oct-1-ene-4-ol, vinyl acetate, allylacetate, 3-butylacetat, finalproject, arylpropionic, methylmethacrylate, unilateraly ether, vinylmations ether, arelatively ether, 3-butanetriol, 5-hexanamide and Dicyclopentadiene. The olefin may also be a mixture of olefins, the same or different molecular weight or structure (optionally with inert compounds such as the corresponding saturated alkanes).

A stream of olefins used in the method of this invention, preferably contains isomeric mixture of C4-raffinate I or C4 raffinate II, containing butene-1, butene-2, isobutylene, butane, and optionally butadiene. A stream of C4-raffinate contains from 15 to 50 percent by weight of isobutylene and from 40 to 85 mass percent normal butenes, and the remainder to 100% consisting mainly of n-butane and isobutane. The normal butenes are usually cm�sue of butene-1 and butene-2 (CIS - and TRANS-forms). The relative proportions of the components of the flow depend on the composition of crude oil, the conditions applied in the operation of cracking or catalytic cracking flow and in subsequent stages of the method, which are C4-stream. A stream of C4-raffinate contains from 15 to 55 volume percent 1-butene, from about 5 to 15 volume percent 2-butene (5-35% by volume of TRANS-2-butene), from 0.5 to 5 volume percent of isobutylene and from 1 to 40 volume percent of butane. More preferably, the olefin stream contains propylene or mixtures of propylene and propane and other inert compounds.

For the stage of hydroformylation of this invention also requires hydrogen and carbon monoxide. These gases can be obtained from any suitable source, including products of the cracking operations and oil refining. Preferably used a mixture of synthesis gas. The mole ratio of N2:WITH gaseous hydrogen to carbon monoxide may vary preferably from 1:10 to 100:1, and more preferred mole ratio of N2:CO ratio of from 1:10 to 10:1 and even more preferably from 2:1 to 1:2. The gas content is usually quantitatively determined by their partial pressures in the reactor on the basis of their molar fractions in the gas phase (measured by gas chromatography) and total pressure with the application of the law of partial pressure�th Dalton. Used in the context of this invention the expression “partial pressure of SYN-gas” is the sum of the partial pressure of CO and the partial pressure of H2.

Suitable metals that make up the catalyst in the form of a complex of a transition metal-ligand comprise a metal of group VIII selected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), Nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixtures of two or more of these metals, with the preferred metals are rhodium, cobalt, iridium and ruthenium, more preferably rhodium, cobalt and ruthenium, and most preferably rhodium. Other permissible metals include the metals of group VIB selected from chromium (Cr), molybdenum (Mo), tungsten (W) and mixtures of two or more of these metals. In the present invention can also be used mixtures of metals from groups VIB and VIII.

“Complex” and similar terms means a coordination compound formed by combining one or more enriched with electrons of the atoms or molecules (i.e., ligand) with one or more depleted in electrons by molecules or atoms (e.g., transition metal). For example, organophosphites ligand used in practice of this invention possesses a single donor-atom of phosphorus(III) having one unpaired pair of electrons, which can form�AMB coordination covalent bond with the metal. Organophilicity ligand used in practice of this invention has two or more donor atoms of phosphorus(III), each has one unpaired pair of electrons, each of which is capable of forming a coordination covalent bond independently or possibly in concert (e.g., via chelation) with the transition metal. Carbon monoxide may also be present and form a complex with a transition metal. The ultimate composition of the complex catalyst may also contain an additional ligand, for example, hydrogen or an anion satisfying the coordination centres or nuclear charge of the metal. Illustrative additional ligands include, for example, halogen (Cl, Br, I), alkyl, aryl, substituted aryl, acyl, CF3, C2F5, CN, (R)2PO and RP(O)(OH)O (wherein R are the same or different, each is a substituted or unsubstituted hydrocarbon radical, e.g. alkyl or aryl), acetate, acetylacetonate, SO4, PF4, PF6, NO2, NO3, CH3O, CH2=CHCH2, CH3CH=CHCH2, C2H5CN, CH3CN, NH3, pyridine, (C2H5)3N, monoolefins, diolefins and triolein, tetrahydrofuran and the like.

The number of available focal points of the transition metal is well known in this area and Xavi�it from specific selected transition metal. The types of catalysts can contain a mixture of complex catalysts in their forms with one, two or more nuclei, which are preferably characterized by at least one organophosphazene molecule in the form of a complex with one molecule of metal, such as rhodium. For example, the catalytic preferred type of catalyst used in the reaction of hydroformylation, can be in the form of a complex with carbon monoxide and hydrogen in addition to or organophosphites ligand or organophosphites ligand.

Organophilicity ligand in General contains many fofanah groups, each containing one trivalent phosphorus atom connected with three hydrocarbonoclasticus (substituted hydrocarbyl means a hydrocarbon radical). Hydrocarbonoclasticus that connect or link the bridging link two fosfatnye group, more correctly referred to as “divalent hydrocarbondegrading”. These linking bridging the communication diradical not limited to any specific hydrocarbon types. On the other hand, requires that each of hydrocarbonoclasticus, which are side chains at the phosphorus atom and not connected by bridging link two fosfatnye groups (i.e., terminal, namestitve radicals), consisted essentially of aryloxyalkyl. “Arilo�si” in General refers to any of the two types of aryloxyalkyl: (1) monovalent aryl radical, associated one simple ether bond, as in-O-aryl, where the aryl group contains a single aromatic ring or multiple aromatic rings that are condensed together, connected directly or indirectly connected (so that different aromatic groups are linked to a common group such as a methylene or ethylene group), or (2) divalent Allenova the radical connected with two simple ether bonds, as in-O-aralen-O - or-O-aralen-aralen-O-, where Allenova group contains a divalent hydrocarbon radical, having a single aromatic ring or multiple aromatic rings that are condensed together, connected directly or indirectly connected (so that different aromatic groups are linked to a common group such as a methylene or ethylene group). Preferred aryloxy groups contain one aromatic ring or 2-4 condensed or linked aromatic rings, having from about 5 to about 20 carbon atoms, e.g., phenoxy, naphthyloxy or bifenox and allindiaradio, such as phenyleneoxy, naphthalenedione and biphenyloxy. Any of these radicals and groups may be unsubstituted or substituted.

Preferred organophosphine ligands contain two, three or more f�svitych groups. If necessary, you can apply a mixture of such ligands. Preferred are the achiral organophilicity. Characteristic organophosphate include organophilicity of formula (I)

in which X is a substituted or unsubstituted n-valent organic bridging radical containing from 2 to 40 carbon atoms, R1are the same or different, each R1represents a divalent Allenby radical containing from 6 to 40 carbon atoms, preferably 6 to 20 carbon atoms; R2are the same or different, each R1is a substituted or unsubstituted monovalent aryl radical containing from 6 to 24 carbon atoms; a and b may be the same or different, each equal to the number from 0 to 6, with the proviso that the sum a+b is 2 to 6 and n equals a+b. When a is equal to the number of 2 or more radicals R1may be the same or different, and when b is equal to the number of 1 or more radicals R2may be the same or different.

Typical n-valent (preferably divalent) hydrocarbon bridging radicals represented by X, include both acyclic radicals and aromatic radicals, such as alkylene, alkylene-Qm-alkylene, cycloalkene, Allen�high, bizarrerie, Allen-Allenova and Allen-(CH2)y-Q-(CH2)y-Allenova radicals, where each y are the same or different, each is the number 0 or 1. Q represents a divalent bridging group selected from-C(R3)2-, -O-, -S-, -NR4-, -Si(R5)2- and-CO-, where R3are the same or different, each R3represents hydrogen, an alkyl radical having from 1 to 12 carbon atoms, phenyl, tolyl or anisyl, R4represents hydrogen or substituted or unsubstituted monovalent hydrocarbon radical, e.g. an alkyl radical having 1-4 carbon atoms; R5are the same or different, each R5represents hydrogen or an alkyl radical, preferably C1-C10alkyl radical, and m is the number 0 or 1. The more preferred acyclic radicals represented by the above X represents a divalent alkylene radicals, while the more preferred aromatic radicals represented by X are divalent allenbyi and Basilashvili radicals, such as radicals, are described more fully, for example, in U.S. patents 4769498; 4774361; 4885401; 5179055; 5113922; 5202297; 5235113; 5264616; 5364950; 5874640; 5892119; 6090987 and 6294700.

Illustrative preferred organophosphate bot�t bisphosphite, such as bisphosphite formula from (II) to (IV)

in which R1, R2and X of formulas (II) to (IV) are the same as described above for formula (I). X preferably represents a divalent hydrocarbon radical selected from alkylene, arylene, Allen-alkylen-arylene and bisarjan; the radicals R1is a divalent hydrocarbon radical selected from arylene, Allen-alkylen-arylene, each radical R2represents a monovalent aryl radical. You can find that organophosphine ligands of such formulas (II) to (IV) are described, for example, in U.S. patents 4668651; 4748261; 4769498; 4774361; 4885401; 5113022; 5179055; 5202297; 5235113; 5254741; 5264616; 5312996 and 5364950.

Representatives of more preferred classes of organobentonites are organobentonite formulas from (V) to (VII)

in which Q, R1, R2, X, m and y have the meanings given above, Ar are the same or different, each Ar is a substituted or unsubstituted divalent aryl radical. Most preferably X represents a divalent radical, aryl-(CH2)y-(Q)m-(CH2)y-aryl, where each y �delino equal to the number 0 or 1; m is the number 0 or 1, Q represents-O-, -S - or-C(R3)2where R3may be the same or different, each R3represents hydrogen or C1-10alkyl radical, preferably methyl. Each aryl radical of the above groups Ar, X, R1and R2formulas from (V) to (VII) is more preferably may contain 6-18 carbon atoms, and the radicals may be identical or different, while the preferred alkylene radicals X may contain 2-18 carbon atoms. In addition, the divalent radicals Ar and divalent aryl radicals of X of the above formula are preferably phenylene radicals in which the bridging group represented by -(CH2)y-(Q)m-(CH2)y- linked to the phenylene radicals in positions that are ortho-position to the oxygen atoms of the formulas that connect the phenylene radicals to their phosphorus atom. Any radical substituent when present on such phenylene radicals, preferably associated with a para - and/or ortho position of the phenylene radicals relative to the oxygen atom that links the substituted phenylene radical, with its phosphorus atom.

Moreover, if desired any given organoplastic the above formulas (I) to (VII) may be ion hospit�m, that is, may contain one or more parts ion selected from the group consisting of-SO3M, where M represents inorganic or organic cation, -RO3M, where M represents inorganic or organic cation, -N(R6)3X1where R6are the same or different, each R6is a hydrocarbon radical containing from 1 to 30 carbon atoms, e.g., alkyl, aryl, alkalinty, Uralkaliy and cycloalkenyl radical, X1is an inorganic or organic anion, -CO2M, where M represents inorganic or organic cation, as described, for example, in U.S. patents 5059710, 5113022, 5114473 and 5449653. Thus, if necessary, such organophosphine ligands may contain from 1 to 3 such ionic parts; however, preferably only one such ion replaced at any given aryl part, when organophilicity the ligand contains more than one such ion. Suitable cationic types M include, without limitation, hydrogen (i.e. a proton), the cations of alkali and alkaline earth metals such as lithium, sodium, potassium, cesium, rubidium, calcium, barium, magnesium and strontium, the ammonium cation and Quaternary ammonium cations, cations of phosphonium, cation arsonia and cations imine. Approach�ing anions X 1include, for example, sulfate, carbonate, phosphate, chloride, acetate, oxalate and the like.

Of course, any of the radicals R1, R2, X, Q and Ar such non-ionic and ionic organophosphites the above formulas (I) to (VII) can be optionally substituted by any suitable substituent optionally containing from 1 to 30 carbon atoms that does not adversely affect the desired result of the method of this invention. Substituents, which can be radicals in addition of course, corresponding hydrocarbon radicals such as alkyl, aryl, kalkilya, alkalline and pirazinokarbazolovogo cyclohexyl substituents, may include for example silyl radicals such as-Si(R7)3; aminosalicylic, such as-N(R7)2, phosphine radicals such as-aryl-P(R7)2; acyl radicals such as-C(O)R7; aryloxyalkyl, such as-OC(O)R7; emidiately, such as-CON(R7)2and-N(R7)COR7; sulfonylurea radicals such as-SO2R7; alkoxyalkyl, such as-OR7; sulfinyl radicals such as-SOR7; sulfanilimide radicals such as-SR7; postonline radicals such as-P(O)(R7)2; and halogen radicals, nitro, cyano, trifluoromethyl, hydroxy and the like, where R7are Odin�new or different, each R7individually represents a monovalent hydrocarbon radical having about 1 to about 18 carbon atoms (e.g., alkyl, aryl, kalkilya, alkalline and pirazinokarbazolovogo cyclohexyl radicals), with the condition that aminosalicylates such as-N(R7)2the substituents R7taken together can also represent a divalent bridging group that forms a heterocyclic radical with the nitrogen atom, and in aminosubstituted such as-C(O)N(R7)2and N(R7)COR7each R7associated with N, can be hydrogen. Of course, any of the groups substituted or unsubstituted hydrocarbon radicals which form this specific organoplastic, may be the same or different.

More specifically illustrative substituents include primary, secondary and tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, amyl, sec-amyl, tert-amyl, isooctyl, decyl, octadecyl and the like; aryl radicals such as phenyl and naphthyl; kalkilya radicals, such as benzyl, phenylethyl and triphenylmethyl; alkaline radicals, such as tolyl and xylyl; alicyclic radicals such as cyclopentyl, cyclohexyl, 1-methylcyclohexyl, cyclooctyl and cyclohexylethyl; alcox�radicals, such as methoxy, ethoxy, propoxy, tert-butoxy, -och2CH2Och3, -O(CH2CH2)2Och3and -(och2CH2)3Och3; aryloxyalkyl, such as phenoxy; as well as silyl radicals such as-Si(CH3)3, -Si(OCH3)3and-Si(C3H7)3; aminosalicylic, such as-NH2, -N(CH3)2, -NHCH3and-NH(C2H5); arylphosphine radicals such as-P(C6N5)2; acyl radicals such as-C(O)CH3, -C(Oh)2N5and-C(Oh)6N5; carboniteservice, such as C(O)och3; oxycarbonyl radicals such as-O(CO)6N5; emidiately, such as-CONH2, -CON(CH3)2and-NHC(O)CH3; sulfonylurea radicals such as-S(O)2C2H5; sulfinyl radicals such as-S(O)CH3; sulfanilimide radicals such as-SCH3, -SC2H5and SC6H5; postonline radicals such as-P(O)(C6N5)2, -P(O)(CH3)2, -P(O)(C2N5)2, -P(O)(C3N7)2, -P(O)(C4N9)2, -P(O)(C6N13)2, -P(O)CH3(C6N5) and-P(O)(N)(C6N5).

Specific examples of organobentonites are ligands A-S in WO 2008/115740.

Organothiophosphate that �can be used in practice of this invention, include any organic compound containing one tofinou group. You can also apply a mixture of organophosphates. Characteristic organothiophosphate include organothiophosphate of formula (VIII)

in which R8is a substituted or unsubstituted trivalent hydrocarbon radicals containing 4-40 carbon atoms or greater, such as trivalent acyclic and trivalent cyclic radicals, e.g., trivalent alkylene radicals, such as radicals, formed from 1,2,2-trimethylpropyl, or trivalent cycloalkene radicals, such as radicals, formed from 1,3,5-trihydroxychalcone. A more detailed description of such organophosphites can be found, for example, in U.S. patent 4567306.

Characteristic diorganotin include diorganotin of formula (IX)

in which R9is a substituted or unsubstituted divalent hydrocarbon radical containing 4-40 carbon atoms or greater and W represents a substituted or unsubstituted monovalent hydrocarbon radical containing 1-18 carbon atoms.

Typical substituted and unsubstituted monovalent hydrocarbon radicals represented by W in formula IX, include alkyl and aryl�nye radicals, whereas the characteristic of substituted and unsubstituted divalent hydrocarbon radicals represented by R9include divalent acyclic radicals and divalent aromatic radicals. Illustrative divalent acyclic radicals include, for example, alkylene, alkylenediamine, alkylene-NX2-alkylen, where X2represents hydrogen or substituted or unsubstituted hydrocarbon radical, alkylene-S-alkylene and cycloalkene radicals. More preferred divalent acyclic radicals are the divalent alkylene radicals, such as radicals, are described more fully, for example, in U.S. patents 3415906 and 4567302. Illustrative divalent aromatic radicals include, for example, Allen, bizarre, Allen-Allen, Allen-alkylen-Allen, Allen-hydroxy-Allen, Allen-NX2-aralen, where X2has the values specified above, Allen-S-Allen and Allen-S-alkylen. More preferably, R9represents a divalent aromatic radical such as a radical, described more fully, for example, in U.S. patents 4599206 and 4717775.

Representatives of more preferred class of georganopoulou are georganopoulos of formula (X)

in which W has the values specified above, radika�s Ar are the same or different, each represents a substituted or unsubstituted divalent aryl radical and y are the same or different, each is the number 0 or 1, Q represents a divalent bridging group selected from-C(R10)2, -O-, -S-, -NR11-, -Si(R12)2- and-CO-in which the radicals R10are the same or different, each represents hydrogen, an alkyl radical having from 1 to 12 carbon atoms, phenyl, tolyl and anisyl, R11represents hydrogen or an alkyl radical having 1-10 carbon atoms, preferably methyl, the radicals R12are the same or different, each represents hydrogen or an alkyl radical having 1-10 carbon atoms, preferably methyl, and m is the number 0 or 1. Such georganopoulos described in more detail, for example, in U.S. patents 4599306, 4717775 and 4835299.

Characteristic trigonometric include trigonometric of formula (XI)

in which the radicals R13are the same or different, each represents a substituted or unsubstituted monovalent hydrocarbon radical, for example alkyl, cycloalkyl, aryl, alkalline or Uralkaliy radical, which may contain from 1 to 24 carbon atoms. Illustrative trigonometric VC�ucaut to, for example, trialkylphosphine, dialkylacrylamide, alkyldithiophosphate and triarylphosphite, such as triphenylphosphite, Tris-(2,6-triisopropyl)FOSFA, Tris(2,6-di-tert-butyl-4-methoxyphenyl)FOSFA, and more preferred Tris(2,4-di-tert-butylphenyl)fosfat. Monovalent hydrocarbon radical parts themselves can be functionalized, with the proviso that functional groups do not interact significantly with the transition metal or otherwise not inhibit hydroformylation. Typical functional groups include alkyl and aryl radicals, groups, ethers, NITRILES, amides, esters, -N(R11)2, -Si(R12)3, phosphate groups and the like, where R11and R12have the meanings given previously. Such trigonometric described in more detail in U.S. patents 3527809 and 5277532.

As an additional benefit, as organophosphites ligand in the present invention can apply any organophosphoric-monophosphate ligand or organophosphoric-polyphosphate ligand. For example, any of organophosphine ligands, including preferred organobentonite ligands described previously, can be subjected to oxidation, so that all the atoms of phosphorus(III) except one, turned into atoms of phosphorus(V). The resulting oxidized �hand may contain organophosphoric-polyphosphate or preferably, organophosphoric-monophosphate, which is suitably used in a molar excess 2/1 relative to the transition metal, to ensure the presence organophosphites ligand component used in practice of this invention. Used in the context of the term “organophosphites ligand” and similar terms include organomodified-monophosphate ligand and organophosphoric-polyphosphate ligand (which is appropriate for a text that used the term), unless stated specifically otherwise.

As an additional feature, any organophilicity ligand can be used as such or in combination with organophosphites ligand used in practice of this invention, and any organophilicity ligand can be used as such or in combination with organophosphites ligand used in practice of this invention. Organophosphonate ligands are known, and they are used in the same way as organophosphine ligands. Characteristic organophosphonate ligands are ligands of formula (XII-XIV).

Organophosphoric further described, for example, in U.S. patent 7615645. Used in �ontext the term “organophosphites ligand” and similar terms include organophosphonate ligands, unless stated specifically otherwise, and “organophilicity ligand” and similar terms include organopolysiloxane ligands, unless specifically indicated otherwise.

The catalyst of hydroformylation contains stable complex (1) of the transition metal in the form of carbonitride; (2) organobentonites ligand contained in the catalyst system at concentrations on a molar basis up to and including 1:1 relative to the transition metal component of the stabilized complex catalyst, and (3) monodentate fosdinovo ligand, which is present in excess molar quantity relative to the rhodium metal component of the stabilized complex catalyst.

The catalyst can be obtained in situ in the reaction zone of the hydroformylation or, alternatively, it can be obtained ex situ and then you can enter into the reaction zone with suitable reagents of hydroformylation. In one embodiment, the implementation of the catalyst prepared by mixing one mole of a suitable transition metal source with 0.1 mol organobentonites ligand and 5-100 mol organophosphites ligand. In one embodiment, the implementation of the catalyst prepared by mixing the components with respect to one mole of a suitable source of rhodium for 5-100 mol monodentate fosdinovo ligand and oleinitialize reaction of hydroformylation add bisphosphites ligand (< 1 mol).

Variety of catalysts can contain a complex mixture of catalysts in the forms of their Monomeric, dimeric or higher centers, which are preferably characterized by at least one organophosphazene molecule in complex with one molecule of the transition metal. The transition metal may be, for example, in the form of a complex with carbon monoxide and hydrogen in addition to either a monodentate toshitomo ligand or bisphosphite ligand.

The catalyst and its preparation is described more fully in U.S. patents 4169861, 5741945, 6153800 and 7615645 and WO 2008/115740.

The of hydroformylation catalysts may be in homogeneous or heterogeneous form during the reaction and/or during the product separation. The amount of complex catalyst metal-ligand present in the reaction medium, should be only such that it is minimal amount necessary for the catalysis process. If a transition metal is rhodium, the concentration in the range of 10-1000 parts per million (ppm), calculated as free rhodium in the reaction medium of the hydroformylation is sufficient for most methods, whereas usually it is preferred to use from 10 to 500 ppm rhodium, and more preferred from 25 to 350 ppm of rhodium.

Besides complex catalyst of a metal-ligand in CP�de reaction of hydroformylation can also attend the free ligand (i.e., a ligand which is complexed with the metal). Preferred free fosfatnyi or phosphoramidite ligand, mono - or polydentate, but not required is the use of the same fosdinovo or phosphoramidite ligand to complex the metal catalyst-fosfatnyi ligand or metal-phosphoramidite ligand. Method of hydroformylation of the present invention may include the use of 0.1 mol or less to 100 mol or more of free ligand per mole of metal in the reaction medium of the hydroformylation. The process of hydroformylation is preferably carried out in the presence of 1 to 50 moles of ligand, and more preferably from 1.1 to 4 moles of ligand per mole of metal present in the reaction medium; wherein the amount of ligand is the sum of both the amount of ligand that is bound (by complexation) with present metal, and the amount of free (not bound by complexation) the presence of ligand. Of course, if necessary, to the reaction medium of the process of hydroformylation can be submitted recharging or additional ligand at any time and by any suitable method, for example, to maintain a predetermined level of free ligand in the reaction medium.

As a General procedure for the catalytic system are first obtained in the environment of dioxygen�separate solvent in the reaction zone of the hydroformylation. Excess monodentate ligand can function as environment-solvent. In the first zone of the hydroformylation pressure is increased by the introduction of hydrogen and carbon monoxide, and the area is heated to the selected reaction temperature. Unsaturated olefinic feedstock is then loaded into the first zone of the hydroformylation and the reaction is carried out to achieve the desired product yield and efficiency of transformation, at this time, the product of the first reaction zone is transferred to the next reaction zone in which add fresh and/or recycled reagents. The reaction in the following reaction zone (or more subsequent reaction zones) continue to achieve the desired product yield and efficiency of transformation, at this time, the product of the last reaction zone is isolated and purified. In a continuous system, the catalyst is preferably recycled back into the first reaction zone.

The reaction conditions of the process of hydroformylation can vary within wide limits. For example, the mole ratio of N2:WITH gaseous hydrogen to carbon monoxide is mainly can vary from 1:10 to 100:1 or more, and more preferred molar ratio of hydrogen to carbon monoxide is from 1:10 to 10:1. The process of hydroformylation mostly can be performed at the reaction temperature is higher than -25°C, more pre�respectfully, higher than 50°C. the Process of hydroformylation can be performed mainly at the reaction temperature less than 200°C, preferably less than 120°C. a Total absolute pressure of the gas containing olefinic reactant, carbon monoxide, hydrogen, and any inert light components, can vary from 1 psi (6.9 kPa) to 10,000 psi (68,9 MPa). The method preferably is carried out at a total absolute pressure of the gas containing olefinic reactant, carbon monoxide and hydrogen, less than 2000 psi (13800 kPa) and more preferably less than 500 psi (3450 kPa). Partial absolute pressure of carbon monoxide mainly varies from 1 psi (6.9 kPa) to 1000 psig (6900 kPa) and preferably from 3 psi (20.7 kPa) to 800 psig (5516 kPa) and more preferably from 15 psi (103,4 kPa) to 100 psi (589 kPa); whereas the absolute partial pressure of hydrogen varies preferably from 5 psi (34.5 kPa) to 500 psi (3450 kPa) and more preferably from 10 psi (69 kPa) to 300 psig (2070 kPa).

The flow rate of the raw synthesis gas (CO+H2) can vary in a wide range within any suitable flow rate is sufficient to carry out the desired process of hydroformylation. The flow rate of the source of the SYN-gas depends on the nodules�Noah form of the catalyst, the flow rate of the original olefin and other working conditions. Similarly, the flow rate of the outlet from ecoreactor(s) may be any suitable flow rate is sufficient to carry out the desired process of hydroformylation. The flow rate of the outlet depends on the size of the reactor and purity of the reagent and the original SYN-gas emissions. Suitable rates of flow of the original SYN-gas and the flow rate of the outlet are well known or easily calculated by a person skilled in the art. In one embodiment, the implementation of the partial pressure of H2and regulate so as to perform the reaction under conditions in which the rate of hydroformylation is the speed of positive order for partial pressures of SYN-gas (N2and for monophosphine catalyst and negative order for the partial pressure of CO for bisphosphite catalysts (as described in WO 2008/115740 A1).

The inert solvent can be used as a diluent the reaction medium of the hydroformylation. You can apply various solvents, including ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and cyclohexanone; aromatic compounds such as benzene, toluene and xylenes, halogenated aromatic compounds, including o-Dee�Lorenzo; ethers, such as tetrahydrofuran, dimethoxyethane and dioxane; halogenated paraffins including methylene chloride; paraffinic hydrocarbons such as heptane; and the like. The preferred solvent is an aldehyde product and/or oligomers of the aldehyde product, together with a reactive olefin or olefins.

In one embodiment of the process of hydroformylation is carried out in a multistage reactor such as the reactor described in U.S. patent 5763671. Such multi-stage reactors can be designed with internal, physical barriers, resulting in a more than one theoretical reaction stage or zone in the vessel. The effect is similar to a number of reactors within a single reaction vessel with continuous stirring tank. Several reaction stages in a single vessel is a cost-effective way to use the volume of the reaction vessel. This greatly reduces the number of vessels that are otherwise required to achieve the same results. It is obvious, however, that if the goal is the use of different partial pressures of reactant at different stages of the process, then apply two or more reactors or vessels. The reaction zone may be arranged in parallel or sequentially, but �the ideal are preferred sequential zones.

The process of hydroformylation of this invention is usually carried out in a continuous manner. Such methods are well known in this field and may include (a) the olefin hydroformylation original substance (substances) effects of carbon monoxide and hydrogen in a liquid homogeneous reaction mixture comprising a solvent, a metal complex-fosfatnyi ligand as a catalyst, free fosfatnyi ligand, (b) maintaining the reaction conditions of temperature and pressure favorable to the hydroformylation of an olefin of the initial substance (substances); (C) replenish the supply of quantities of olefin original substance (substances), carbon monoxide and hydrogen in the reaction medium, when these reagents are used up, and (d) the selection of the desired aldehyde product(s) hydroformylation of any desirable way. Continuous method can also be based on one passage, in which a vaporous mixture comprising unreacted olefinic original substance (substances) and vaporized aldehyde product is removed from the liquid reaction mixture, which emit from the aldehyde product, and replenish olefin original substance(a), carbon monoxide and hydrogen is served in a liquid reaction medium for the next single pass through without recycling the unreacted olefinic substance (substances). Such type� recycling procedures are well known in the field and may involve the liquid recycling of the liquid complex catalyst metal-pofit, separated from the desired aldehyde product(s) reaction, such as described in U.S. patent 4148830, or procedure gas recirculation, such as described in U.S. patent 4247486 and, if required, a combination of both liquid treatments and procedures gas recirculation. The most preferred process of hydroformylation of this invention provides a method for the continuous recirculation of the liquid catalyst. Suitable treatments recirculation liquid catalyst is described for example in U.S. patents Nos. 4668651; 4774361; 5102505 and 5110990.

In one embodiment, the implementation of increasing the partial pressure of the SYN-gas shifts the equilibrium of reaction from bisphosphite ligand to monodentate toshitomo ligand, resulting in the displacement of a quick response to a lower ratio N:I, for example, from 2 to 20 units to a minimum, based on the ratio N:I for the catalyst containing only metal-monodentate ligand. The lower partial pressure of SYN-gas shifts the equilibrium of reaction from monodentate fosdinovo ligand to bisphosphite ligand and the increasing ratio of N:I, usually from 2 to 20 units up to the maximum observed with the catalyst containing only metal-bisphosphines ligand. Increasing the partial pressure of the SYN-gas also changes the relative velocities of the reactions in the application of the complexes monodentate�CSOs and the bidentate phosphite and metal and, in the methods, which are used in many areas of the reaction, displaces a greater degree of the reaction of the first reaction zone into a second reaction zone, etc. (up to 30% of the total reaction). Thus, the total ratio N:I can be calculated via the molar average of the transformation in many reaction zones based on the amount of olefin converted into each reactor. The movement amount of the reaction mixture from one reaction zone to another modifies the average molar conversion, thereby changing the final ratio N:I the product is extracted from the last reaction zone. These calculations can be based on the kinetics of complexes of monodentate postit - and bidentate postit-metal, measured independently.

The control the feed rate of SYN-gas to maintain the pressure of the reaction (as described in NSSN 60/598032) is not quite suitable for the regulation method in the conditions in which monophosphines the catalyst dominates the total reaction mixture. This is typical of the reactions at high partial pressure of CO (for example, N:I from 3:1 to 4:1 for propylene). If the reaction system is carried out if necessary anticipatory regulation of blood pressure, i.e., at constant pressure and the regulation of the outlet at higher speeds, unsaturated olefin compound, such as propylene (while maintaining a pic�permanent feed rate of raw materials), begins to replace the SYN-gas. The system slowly shifts from a higher partial pressure of SYN-gas to lower the partial pressure of SYN-gas and the difference is replenished by the olefin. This means that the relative order of reaction WITH propylene and is almost equivalent, which leads to the impossibility of maintaining a constant partial pressures. This is the result of regulation of one variable the magnitude of the two parameters.

First, since the number of SYN-gas in the reactor is significantly smaller than the number of propylene, any perturbation in the system (higher or lower reactivity), ultimately, lead to a reduction in the number of SYN-gas (and partial pressure) relative to the olefin.

Second, the system of regulation of the flow of the SYN-gas is usually the time lag, which allows the system to shift toward the steady state with lower reactivity while maintaining, however, the same feed rate of the olefin.

In the way that you want to apply the pressure are two possible scenarios. In the first scenario, a small increase in temperature leads to a higher reaction rate (approximately doubling for every 10°C). When the flow rate of the SYN-gas and the olefin increases, the pressure in the reactor falls and falls immediately reactionary ability� due to decrease in the partial pressures of the reactants. The number of SYN-gas decreases faster than the number of olefin. Replenishment of the SYN-gas then returns to the point of pressure regulation. Even a very small delay in the replenishment of the SYN-gas results in equal or lower partial pressure of SYN-gas, which filled the olefin (flow remains constant throughout the cycle, thus eliminating the delay). Over time, the decrease in the partial pressure of SYN-gas displaces the reaction from monodentate ligand to a bidentate ligand, which in itself affects the change of the reactivity and the relationship N:I.

In the second scenario, a small decrease in temperature leads to a lower reaction rate, an approximate 50% decrease in speed for every 10°C decrease in temperature. This leads to less need for SYN-gas, and therefore increases the partial pressure of olefin (constant flow) and it replaces the SYN-gas.

The problems associated with the required pressure regulation either significantly reduced or eliminated by way of the fixed feed SYN-gas, i.e., a small excess SYN-gas (which is usually lost in the purge stream, which is necessary for removal of inerts from the system). In the first scenario, the shift to a higher reaction rate (i.e., a small temperature increase) when�odit to higher consumption of reagents, approximately doubling for every 10°C. the Flow outlet is reduced, and the reaction rate slows due to depletion SYN-gas. Since the reaction rate is reduced, the temperature drops, the contents of the reactants increases again, the flow of the outlet is reduced and the partial pressure is restored on the basis of the stoichiometry of the feed of the mixture of the SYN-gas/olefin.

In the second scenario, the shift to the lower speed of the reaction is the result of a slight decrease in temperature. This causes the consumption of a smaller amount of a reagent that increases the flow orifice, and the stoichiometry of the raw material remains constant, even more blowing. The composition of the mixture in the reactor essentially remains the same until the temperature is restored to previous levels.

Specific implementation options

The attitude adjustment N:I of the product by changing the partial pressure of the synthesis gas

Ligand 1, bulk organometalic, and ligand 2, organoplastic, with different vospriimchivosti partial pressure of the synthesis gas is mixed with rhodium and evaluated as a catalytic system with varying selectivity.

The process of hydroformylation was conducted in a glass designed for a high pressure reactor operating in continuous mode. The reactor�worth of thick-walled 0,888 l (three-ounce) bottle partially submerged in an oil bath with a glass front for observation. After you purge the system with nitrogen to 20 ml of a freshly prepared solution of rhodium catalyst precursor was charged into the reactor by syringe. A solution of catalyst precursor contains 300 ppm of rhodium (introduced in the form radiokarbonmethode), ligand 1 and tetralin (dimethyl ether of tetraethyleneglycol) as the solvent. After sealing the reactor system was purged with nitrogen and the oil bath was heated until the reaction temperature of 50°C. a Solution of catalyst was activated by the supply of CO and H2when the ratio is 1:1 at a total operating pressure of 150 psi (1034 kPa) for 30-60 minutes. After the activation reaction is initiated by the introduction of olefin (propylene). If necessary, separate streams of gases regulate and, if necessary, add nitrogen to maintain the desired total working pressure of 150 psi (1035 kPa). Flows of feed gas (N2, CO, propylene, N2) is controlled separately by mass flow meters and the feed gases dispersed into the precursor solution of the catalyst by bubblers from frictioning metal. The partial pressure of N2, H2WITH propylene aldehyde products determined by gas chromatographic analysis (GC) method the stream� at the outlet and the law of partial pressures Dalton. The unreacted portion of the source gases stripped from Butyraldehyde products in the flow of nitrogen to maintain essentially constant liquid level. The gas outlet openings are periodically analyzed by GC. If desired, samples of the reaction liquid can be selected (via syringe) to analyze31P NMR to determine the speed of decomposition of the ligands as a function of time under the reaction conditions. The system requires one day to reach the stationary state conditions through the removal of traces of air from the flow of raw materials and achieve thermal equilibrium oil baths; thus, the study of the decomposition of the ligands start after reaching a steady state. This equipment also allows to determine the rate of hydroformylation and parameter N:I as a function of the reaction temperature, partial pressures of CO and H2and content of Rh for each catalytic system independently.

Reaction system to activate the catalyst rhodium/ligand 1 for the preliminary operation of a stationary mode and then the ratio of isomers regulate to the desired relationship by the slow addition of ligand 2.

Glass reaction system is loaded with a solution of a catalyst consisting of Rh(CO)2(ASAS) (300 ppm Rh), ligand 1 (10 �of equivalentof/Rh) and tetragona (20 ml). Then set out the following conditions and supports the overall absolute pressure operation 1037,5 kPa (150 psi).

The temperature of the oil bath (°C)50
Overpressure N2(kPa/psi)241,5/35
Excess pressure (kPa/psi)241,5/35
Excess propylene pressure (kPa/psi)41,4/6
Excess nitrogen pressure (kPa/psi)balance

After several days of continuous operation using a syringe add aliquot of ligand 2 (0.5 equivalent/Rh in THF) followed by continuous addition of dilute solution of ligand 2 (2,5×10-5M in THF, 0,017 ml/min) through the pump Gilson HPLC. When installing a sustainable ratio N:I, the partial pressure of the synthesis gas change and determine the achieved changes.

During the period 1080 minutes of absolute partial pressure of each of the N2and WITH support 241,5 kPa (35 psi) and the ratio N:I as average of 9.4. Absolute partial pressure of H2and then reduce over 80 min�t to 72,45 kPa (10.5 psi) and the pressure was maintained for 350 min, during this time, the ratio N:I averaged as 17,95. Absolute partial pressure of H2and then increase again for 80 minutes before 407,1 (53 psi) and maintain this pressure for 1160 minutes, during this time average, the ratio N:I like to 8.6. Absolute partial pressure of H2and then again lower for 80 minutes again to 241,5 kPa (35 psi) and maintain this pressure for 1200 minutes, during this time, the ratio N:I averaged out how to 12.4.

The rate of addition of ligand 2 was slightly higher than the rate of decomposition, so the ratio N:I at an absolute pressure of FROM:H21:1 483,0 kPa (70 psi) to some extent has changed over time. However, this example clearly shows that for this catalytic system of rhodium/bulk organophosphoric/organoplastic the ratio of normal aldehyde to saldehyde can be varied by a simple raising or lowering the partial pressure of the synthesis gas.

In General, inherent in the ratio N:I for catalyst consisting only of rhodium and ligand 1, is approximately 1, the change in the relationship N:I is limited to the limit of plus or minus 1 in the ranges of partial pressure of SYN-gas previous example, inherent in the ratio N:I for catalyst consisting only of rhodium and ligand 2, is approx�tive 30, and changing attitudes N:I is limited to approximately plus or minus 5.

Although the invention has been described largely in detail the previous description, this detailed description is for illustration purpose and should not be construed as limiting to the following appended claims.

1. Method of controlling the process of hydroformylation to obtain aldehydes of normal structure (N) and ISO-structure (I) with respect to N:I, and this method comprises contacting an unsaturated olefinic compound with synthesis gas and a catalyst comprising a transition metal and organophilicity and organophosphites ligand, the contacting conducted under conditions of hydroformylation, including the partial pressure of the synthesis gas, where the method includes increasing the partial pressure of the synthesis gas to reduce the relationship N:I or a lower partial pressure of synthesis gas to improve the relationship N:I.

2. A method according to claim 1, wherein the unsaturated olefinic compound is an olefin having from 3 to 10 carbon atoms.

3. A method according to claim 1, wherein the unsaturated olefin compound is an isomeric mixture of C4-raffinate I or C4-raffinate II, containing butene-1, butene-2, isobutylene, butane, and optionally butadiene.

4. A method according to claim 1, wherein not�asystem olefinic compound is propylene.

5. A method according to claim 1, in which the SYN-gas contains carbon monoxide and hydrogen at a molar ratio of H2:CO from 10:1 to 1:10.

6. A method according to claim 1, wherein the catalyst comprises a stabilized complex of (1) radicalmediated; (2) bisphosphite ligand, the presence of which provide in the catalytic system at concentrations providing its molar ratio to the rhodium metal component of the stabilized catalyst complex up to and including 1:1; and (3) monodentate fosdinovo ligand, the presence of which is provided in excess molar quantity relative to the rhodium metal component of the stabilized catalyst complex.

7. A method according to claim 1, wherein the catalyst is obtained by mixing one mole of a source of rhodium with 5-100 mol monodentate fosdinovo ligand and, after initiation of the reaction of hydroformylation, the addition of from 0.1 to less than one mole bisphosphite ligand.

8. A method according to claim 6, in which monodentate fosfatnyi ligand has the formula

and bisphosphites ligand has the formula
.

9. A method according to claim 1, wherein the conditions of hydroformylation include the reaction temperature is higher than -25°C and lower than 200°C and the total pressure of the gas containing olefinic reactant, carbon monoxide, water�rod and any inert light components, from 6.8 kPa (1 psi) to 68,9 MPa (10000 psi).

10. A method according to claim 1, wherein the process of hydroformylation is carried out in continuous mode.



 

Same patents:

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: 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 relates to production of butyl aldehydes via hydroformylation of propylene in the presence of unmodified cobalt catalyst at high temperature and pressure with incomplete conversion of propylene, separation of unreacted propylene from the reaction products and recycling it into the process. The hydroformylation products are cooled to 45-50°C at pressure of 20-30 MPa. Unreacted propylene is extracted from the said products through after-cooling into volume-gravity action separator with propylene residence time of not less than 4 minutes at pressure of 0.1-0.2 MPa, with subsequent extraction of unreacted propylene from the gaseous phase of the separation products through compression, cooling and condensation.

EFFECT: method reduces propylene consumption, increases reactor output, simplifies and reduces cost of process engineering.

3 cl, 4 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 relates to novel compounds of general formula (I)

, in which X denotes a CHO, CH2OH or CH2OC(O)R group, where R denotes a straight of branched C1-C5 alkyl chain; as well as to a synthesis method, particularly synthesis of 6,8-dimethylnon-7-enal (1) through hydroformylation of 5,7-dimethylocta-1,6-diene. The invention also relates to fragrant compositions containing formula (I) compounds. Owing to their fragrant properties, these compounds are of great interest in perfumery, particularly cosmetic products and household chemicals.

EFFECT: obtaining novel fragrant compositions.

12 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of butyl aldehydes via hydroformylation of propylene in the presence of unmodified cobalt catalyst at high temperature and pressure with incomplete conversion of propylene, separation of unreacted propylene from the reaction products and recycling it into the process. The hydroformylation products are cooled to 45-50°C at pressure of 20-30 MPa. Unreacted propylene is extracted from the said products through after-cooling into volume-gravity action separator with propylene residence time of not less than 4 minutes at pressure of 0.1-0.2 MPa, with subsequent extraction of unreacted propylene from the gaseous phase of the separation products through compression, cooling and condensation.

EFFECT: method reduces propylene consumption, increases reactor output, simplifies and reduces cost of process engineering.

3 cl, 4 ex

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

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