Synthesis of aliphatic 1,3-dioles using reduced concentration of ligands and water extraction

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to improved method for preparing 1,3-dioles comprising (i) bringing into contact oxirane, carbon monoxide, and hydrogen at 30 to 150°C and pressure 3 to 25 MPa in essentially water-immiscible solvent in presence of effective amount of homogenous bimetallic hydroformylation cobalt carbonyl-containing catalyst and cocatalyst based on metal selected from ruthenium group and which is bound to phosphine ligand optionally in presence of promoter, wherein molar ratio of ligand to this cocatalyst metal atom is within a range of 0.2:1.0 to 0.4:1.0, under reaction conditions effective to obtain reaction products mixture containing aliphatic 1,3-diol; (ii) adding aqueous solution to reaction product mixture obtained and extracting major part of aliphatic 1,3-diol into said aqueous solution at temperature below 100°C to form aqueous phase containing aliphatic 1,3-diol in higher concentration that that of aliphatic 1,3-diol in reaction product mixture and organic phase containing at least part of bimetallic hydroformylation catalyst; (iii) separating aqueous phase from processing phase; and (iv) optionally recycling at least part of catalyst-containing organic phase to stage (i). Invention also relates to catalyst composition for hydroformylation of ethylene oxide into aliphatic 1,3-propanediol, which composition is obtained via a method comprising (i) preparation of complex A by bringing cocatalyst ruthenium-group metal compound into contact with phosphine ligand at ligand-to-cocatalyst metal atom from 0.2:1.0 to 0.4:1.0; (ii) preparation of complex B by subjecting complex A to redox reaction with cobalt carbonyl.

EFFECT: enabled less costly single-step hydroformylation process.

8 cl, 2 dwg, 4 tbl, 52 ex

 

The scope of the invention

The present invention relates to the synthesis of aliphatic 1,3-diol, in particular 1,3-propane diol, by hydroformylation and hydrogenation of oxirane, in particular of ethylene oxide (hereinafter EO), and synthetic gas for one stage, using a system of catalysts comprising cobalt carbonyl and ligand.

Background of the invention

Aliphatic 1,3-diols, in particular 1,3-propandiol have many uses, as a monomer unit for complex polyester and polyurethane, and as starting materials for the synthesis of cyclic compounds. For example, polytrimethylene terephthalate CORTERRA is a complex polyester, characterized by outstanding properties, which is obtained from 1,3-propane diol (hereinafter PDO) and terephthalic acid. In this area there is great interest in finding new methods for the synthesis of PDO that are effective, economical and demonstrate the advantages of the method (CORTERRA is a trade name).

U.S. patent No. 5304691 issued to Shell Oil Company, describes a method of hydroformylation of ethylene oxide to 3-hydroxypropane and 1,3-propane diol in one stage using an improved system of catalysts containing cobalt complex-ligand-based tertiary phosphine in combination with the ruthenium catalyst. In the specified enter the patent, using phosphine ligand, it is associated with cobalt carbonyl.

Are simultaneously pending application for U.S. patent, serial numbers 09/808,974 and 09/963,068, describe, among other things, the composition of bimetallic catalysts associated with ligand-phosphine, suitable for one-step synthesis of PDO, and method for one-step synthesis of PDO. In these links phosphine ligands associated with the connection of ruthenium, and not with the connection of cobalt.

The CARBONYLS of ruthenium, modified phosphine ligands are quite effective as complexes catalysts for one-step synthesis of PDO. However, the phosphine ligands are relatively expensive, and in some cases, the recycling of the catalyst may be terminated much earlier than the optimal time. At the same time when multiple recycling selectivity for the product may be insufficient. These observations made so far, are rather negative in regard to the use of phosphine ligands in catalysts hydroformylation for industrial applications. It would be very desirable, if significantly smaller ligands were effective in complex bimetallic catalyst for one-step synthesis of PDO and if other modifications, such as extraction with water, helped and to use low ratio and contributed to effective recycling.

Brief description of the invention

In accordance with the above, the present invention is a method of hydroformylation and hydrogenation of oxiranes, in particular of ethylene oxide, carbon monoxide and hydrogen to obtain aliphatic 1,3-diols, in particular PDO, at one stage, where the extraction is carried out by extraction with an aqueous solution, preferably water, enriched diola phase of the volume of the reaction liquid. The preferred method includes the steps:

(a) Bringing into contact at a temperature in the range from 30 to 150°C and a pressure in the range from 3 to 25 MPa of oxirane, in particular of ethylene oxide, carbon monoxide and hydrogen, in essence is not miscible with water solvent, in the presence of an effective amount of a homogeneous bimetallic catalyst hydroformylation containing compound of cobalt carbonyl, preferably, essentially not associated with ligands compounds of cobalt carbonyl and metal socializaton, which are selected from ruthenium, copper, platinum and palladium and is linked to a ligand selected from a phosphine ligand, bidentate or multidentate N-heterocyclic ligand, porporino ligand and phosphoenolpyruvate ligand, optionally in the presence of a promoter, preferably lipophilic ol the motor, where the molar ratio of the ligand to the metal atom of socializaton is in the range of 0.2:1.0 to 0.6 to 1.0 second, preferably from 0.20:1.0 to 0,40:1,0, at reaction conditions effective to obtain a mixture of reaction products containing aliphatic 1,3-diol, such as PDO;

(b) Adding to the said mixture of reaction products of an aqueous solution and extracting specified in aqueous solution greater part of the 1,3-diol (PDO), at a temperature of less than 100°C to obtain the aqueous phase containing 1,3-diol (PDO) at a concentration greater than the concentration of 1,3-diol (PDO) in the mixture of reaction products, and the organic phase containing at least a portion of the bimetallic catalyst hydroformylation and, preferably, any promoter;

(c) Separating the aqueous phase from the organic phase and

(d) an Optional, but preferred return at least part of the organic phase containing the catalyst in stage (a).

The present invention relates to modifications to the specified one-step method for the synthesis of aliphatic 1,3-diols, in particular PDO, which include: a) use 4-5 times fewer ligand at lower relations ligand/metal socializaton than was considered previously effective; and (b) the use of water extraction to extract the product and recirculatory catalyst. the tee modifications provide significant economic advantage, because the use of the lowered amount of the ligand allows for a significant reduction in the use and value of the ligand, while the extraction of water makes possible the recycling of a greater part of the catalyst together with the phase of the solvent under reduced thermal decomposition.

Brief description of drawings

Figure 1 is a schematic illustration of the method according to the present invention.

Figure 2 is a graph depicting zavisimosti the degree of conversion of the HPA to PDO, the ratio of ligand/EN.

Detailed description of the invention

The present invention will now be described using examples with reference to the accompanying drawings, in which presents several modifications of the method, which can, especially in combination, can be advantageous in relation to product recovery, recirculatory catalyst and overall efficiency single-stage method hydroformylation and hydrogenation to obtain the aliphatic 1,3-diols, especially PDO, using catalyst hydroformylation cobalt:metal socializaton:the ligand. It was found that the extraction of the product water and the use of cobalt catalysts:metal socializaton:ligand having a lower concentration of ligand than previously considered effective, it is the best when one-step synthesis of aliphatic 1,3-diols. The catalyst with a reduced content of the ligand can reduce the cost of the method by minimizing the number of ligand exposed to the conditions of the method and preferred by transferring the ligand in perhaps a more stable configuration, i.e. in the form associated with metal socializaton, which preferably is a ruthenium. The extraction of water optimizes recycling of the catalyst and increases the stability of the catalyst. The extraction liquid does not create thermal stresses for expensive catalyst components and, therefore, is a primary way to recirculatory catalyst during the industrial production of products with high boiling points, such as 1,3-propandiol.

In the method according to the present invention oxirane containing up to 10 carbon atoms, preferably up to 6 carbon atoms, and, in particular, ethylene oxide (EO)can be transformed into the corresponding 1,3-diols by reaction of hydroformylation with synthesis gas in the presence of a complex catalyst of hydroformylation with low against the metal socializaton:ligand, as will be described below.

1,3-diols are obtained by loading oxirane, catalyst and/or promoter of the catalyst and the reaction RA is the solvent in the reactor high pressure together with the introduction of synthesis gas (mixture of hydrogen and carbon monoxide, better in molar ratio from 1:1 to 8:1, preferably from 2:1 to 6:1) in terms of hydroformylation.

The method according to the present invention may be implemented as a periodic way, continuous or mixed forms, however, the features of the present invention would give the opportunity for continuous one-step method worked more reliably and efficiently than previously possible. The method according to the present invention can be carried out in continuous mode in a homogeneous reaction mixture. Reaction conditions that allow for this mode of operation include the use of a solvent or mixture of solvents of moderate polarity (described below) and the concentration of oxirane in the reaction mixture, equal to at least 0.1 wt.%. Response 2-4 reactors with distributed time adding oxirane (EO) is preferred for continuous operation.

One way reaction involves the conversion of oxirane EO in PDO via the intermediate compound 3-hydroxypropyl, which is formed and hereroense to PDO in situ. Under "in situ" in this context means that the conversion of ethylene oxide in PDO is carried out without isolating the intermediate compound 3-hydroxypropane and in the presence of the same systems as catalysts for hydroformylation, and for whom gidrirovaniya. The reaction is carried out under conditions effective to obtain a mixture of reaction products containing PDO, with relatively small amounts of 3-hydroxypropane (3-HPA), acetaldehyde and heavy fractions (materials, which are less volatile than the desired product). The following description of the method will be specifically relate to the PDO, but the description of the method, as implied, is aimed at the description of how to obtain and also other aliphatic 1,3-diols.

For best results, the method is carried out under conditions of elevated temperatures and pressures. The reaction temperature is from ambient temperature, preferably from 30°C to 150°C, preferably from 50 to 125°C and most preferably from 60 to 110°C. the Pressure of the reaction (total pressure or partial pressure, if used inert gaseous diluents) preferably is in the range from 3 to 25 MPa, preferably from 5 to 15 MPa, most preferably from 7 to 12 MPa. In continuous mode, the reaction is usually completed within 1.5-5 hours.

One way to obtain 1,3-propandiol according to the present invention is conveniently described with reference to figure 1. Separate or combined streams of ethylene oxide to 1 of carbon monoxide and hydrogen 2 load capacity 3 hydroformylation, which can PR is dostavljati a reaction chamber of a high pressure, such as a bubble column or a mix tank, operating in batch or continuous mode. Input streams come into contact in the presence of diluted bimetallic catalyst with ligand of the present invention.

After the reaction of hydroformylation mixture of 4 reaction products of hydroformylation containing PDO and HPA, the reaction solvent, the bimetallic catalyst and small amounts of other reaction products, passes into the extraction tank 5 in which through 6 to add an aqueous solution, typically water, and optional miscible solvent for the extraction and concentration of PDO. The extraction liquid may be carried out using any suitable tools, such as mixers-precipitators, extraction columns with a nozzle or disc extraction column, or a rotating disk contactors. Extraction, if desired, may be carried out in many stages. Water-containing mixture of the reaction products of hydroformylation can be carried out in a precipitation tank (not shown) for separation of aqueous and organic phase.

The amount of water added to the mixture of reaction products of hydroformylation, in General, be such as to provide a ratio of water:the mixture being in the range from 1:1 to 1:20, predpochtitel is from about 1:1 to 1:10, most preferably, equal to 1:5. Add water at this stage of the reaction may have the additional advantage consisting in the suppression of undesirable heavy fractions. Extraction using a relatively small amount of water gives an aqueous phase, which contains more than 10% of bulk PDO, preferably more than 20% of bulk PDO.

The water extraction is preferably carried out at a temperature in the range of 5 to 90°C, most preferably from 25 to 55°C, thus avoiding higher temperatures to minimize condensation products (heavy fraction) and the decomposition of the catalyst. For maximizing the extraction of the catalyst is the preferred extraction with water at a pressure of carbon monoxide, equal, at least, from 0.3 to 5 MPa, preferably from 0.3 to 1.2 MPa, at a temperature of from 25°C to 55°C. the carbon Monoxide can be present as part (with the specified partial pressure) of the total gas mixture containing other components, such as mixtures with hydrogen, as the latter is used for this stage of the reaction.

The organic phase containing the reaction solvent and a major portion of the bimetallic catalyst can be recycled from the extraction vessel into the reaction hydroformylation through line 7. Water is an extract 8 optional passes through one or more layers 9 acidic ion-exchange resin to remove any presence of a catalyst. Can be made optional step after the hydrogenation to complete a full refund of the intermediate aldehyde in diol, if so desired.

Water-extractant 10 may be removed by distillation in the column 11 and recycled 12 in the process of extraction of the water by additional distillation (not shown) for separation and blowing light fractions. Containing PDO thread 13 can be carried out in one or more distillation columns 14 to retrieve PDO 15 of the heavy fractions 16.

Single-stage reaction of hydroformylation and hydrogenation is carried out in a liquid solvent, inert to the reagents. By "inert" is meant that the solvent is not consumed during the reaction. Typically, the ideal solvents will dissolve the carbon monoxide will not substantially miscible with water and will demonstrate the polarity from low to moderate, so that the PDO will be dissolved to the desired concentration of 5% mass in terms of hydroformylation, while a significant amount of solvent will remain as a separate phase at the extraction of water. By "essentially not miscible with water" is meant that the solvent has a solubility in water at 25°C less than 25% of the mass so as to form a separate phase, obocaman the Yu hydrocarbons, the extraction of PDO water from the reaction mixture of hydroformylation. Preferably the solubility is less than 10% of the mass, most preferably less than 5% mass. The solubility of carbon monoxide in the selected solvent will typically greater than 0,15.about. (1 atmosphere, 25°C), preferably greater than 0.25.about., being expressed in the form of coefficients of Ostwald.

Usable solvents are described in U.S. patent No. 5304691. Good results can be achieved using a simple esters, including simple cyclic and acyclic ethers, optionally in combination with alcohol or aromatic hydrocarbon. Such ethers include, for example, methyl tert-butyl ether, ethyl tert-butyl ether, diethyl ether, phenylisopropyl ether, ethoxyethyl ether, diphenyl ether and diisopropyl ether, in particular methyl tert-butyl ether.

Generally, it is preferable to adjust the water concentration in the reaction mixture of hydroformylation because of excess water reduces the selectivity to PDO below acceptable levels and can induce the formation of a second liquid phase. Acceptable levels of water will depend on the solvent used, while the more polar solvents, as a rule, are more then iruntime to higher concentrations of water. For example, the optimal water levels for hydroformylation in solvent-based methyl tert-butyl ether, assumed to be in the range from 1 to 2.5% of the mass. The concentration of water to a large extent determined by the solubility of water in the solvent, when it is introduced to the stage of extraction.

The concentration of oxirane (EO) support at a low level to minimize non-selective reactions. During the reaction it is preferable to maintain the concentration of oxirane not less than 0.2% of the mass, usually in the range from 0.2 to 20% mass, preferably from 1 to 10% of the mass relative to the total mass of the reaction. The method according to the present invention can be performed in a continuous mode, while maintaining the specified concentration of EO, for example, by stepwise addition of EO.

Catalysts suitable for use in the scheme of one-stage method according to the present invention, include certain homogeneous bimetallic catalysts containing compound of cobalt carbonyl component and metal socializaton, preferably a compound of ruthenium, copper, platinum or palladium, is associated with a ligand selected from a phosphine ligand, bidentate or multidentate N-heterocyclic ligand, porporino ligand or phospholinoleate ligand. Molar is the ratio of the ligand to the metal atom of socializaton may vary from 0.2:1.0 to 0,6:1,0, preferably from 0.20:1.0 to 0,40:1,0. Can be used higher ratio of ligand to reduce the formation of by-products of light fractions, but they increase the cost method.

Suitable sources of cobalt include salts that restore to a state of zero valence using a heat treatment in an atmosphere of hydrogen and carbon monoxide. Should be added such an amount of cobalt (0), which is sufficient for complete oxidation of all the used metal socializaton associated in the complex. Can be added to an excess of cobalt, but any specific value does not exist. Usually the molar ratio of metal socializaton to cobalt may be so small as 0.05:1,0, preferably 0.1 to 1.0 second, and typically varies from 4:1 to 1:4, preferably from 2:1 to 1:3, more preferably from 1:1 to 1:2. Examples of such salts include, for example, cobalt carboxylates such as acetates, octanoate and the like, which are preferred, and cobalt salts and mineral acids, such as chlorides, fluorides, sulfates, sulfonates and the like. The oxide or hydroxide of cobalt may be in the form of a suspension. Can work well as mixtures of these salts of cobalt. Recovery can be performed before the COI is whether the catalysts, or it may be carried out simultaneously with the process of hydroformylation in the area of hydroformylation.

The amount of cobalt present in the reaction mixture will vary depending on other reaction conditions, but generally is in the range from 0.01 to 1 wt.%, preferably from 0.05 to 0.3 wt.%, in relation to the weight of the reaction mixture.

The oxidation state of the metal atom of socializaton is not well-defined (for example, in theory of ruthenium may have a valence of 0 to 8, which may even change during the reaction of hydroformylation).

Accordingly, the molar ratio of metal socializaton to cobalt may vary within relatively wide limits. Suitable sources of the metal socializaton include, but are not limited to, CARBONYLS, oxides, carboxylates and metal. Examples include tirutani dodecacarbonyl and ruthenium(IV) oxide.

Component of cobalt can be associated with the same ligand, which is the ligand of the metal socializaton, or other ligand. Preferred catalysts include mainly (essentially), preferably completely, not associated with the ligand component of cobalt and associated with the ligand compound of the metal of socializaton. These complexes catalysts can be identified by features such as the nuclear biological chemical (NBC painting the peaks of the absorption composition of the catalyst in the infrared spectrum.

Metal socializaton may be associated with diphosphine ligand. Diphosphinic phosphorus ligand has the General formula:

RRP-Q-PR R'

where each of the groups R and R', independently or together represents a hydrocarbon residue containing up to 30 carbon atoms, and Q is an organic bridging group of 2-4 atoms in length. The group R or R', when she monovalent, can be an alkyl, cycloalkyl, bicycloalkyl or aryl, and preferably contain up to 20 carbon atoms, more preferably up to 12 carbon atoms. Alkyl and/or cycloalkyl group are preferred. Group Q preferably consists of carbon atoms that can form part of a cyclic system such as a benzene ring or cyclohexane ring. More preferably Q represents alkylenes group of 2, 3 or 4 carbon atoms in length, most preferably 2 carbon atoms in length. A non-limiting list of illustrative diphosphines this class includes

1,2-bis(dimethylphosphino)ethane; 1,2-bis(diethylphosphino)ethane;

1,2-bis(Diisobutylene)ethane (BDIBPE);

1,2-bis(dicyclohexylphosphino)ethane;

1,2-bis(2,4,4-trimethylpentane)ethane;

1,2-bis(diethylphosphino)propane; 1,3-bis(diethylphosphino)propane;

1-(diethylphosphino)-3-(dibutylamino)propane,

1,2-bis(definites is Ino)ethane; 1,2-bis(dicyclohexylphosphino)ethane; 1,2-bis(2-pyridyl, phenylphosphonic)benzene;

1,2-bis(Dicyclopentadiene)ethane;

1,3-bis(2,4,4-trimethylpentane)propane;

1,2-bis(diphenylphosphino)benzene.

These groups R and R' may themselves be non-substituted groups. Both groups R and/or both groups R' may also form a ring with the atom (atoms) phosphorus, for example phosphacyclohexane of 5-8 atoms. Examples of 5-membered ring systems (ligands on the basis of phospholanes) include 1,2-bis(phospholane)ethane, 1,2-bis(2,5-dimethylphosphino)benzene, optically pure (R,R),(R,S), (S,S) 1,2-bis(2,5-dimethylphosphino)ethane or its racemic mixture. The ring itself can be part of a polycyclic system. Examples of such ring systems can be found in the above patent '691 and in the application for international patent WO-A-9842717. In the first of them describes phosphabicyclononanes group, and the latter describes, in particular, such adamantyl group and postitionsanatomically group. Diphosphine, where both groups R and R' form a ring with the phosphorus atom, are preferred. The most preferred ligands are 1,2-P, P'-bis(9-phosphabicyclo[3.3.1] and/or [4.2.1](nonyl))ethane (hereinafter B9PBN-2), 1,2-P, P'-propane and/or 1,3-P,P'-propane analogue (hereinafter B9PBN-3).

Ligands based on titration phosphines are commercially available is mi. Catalysts derived from them, are known in this field, and the retrieval method is described in detail in U.S. patent No. 3401204 and 3527818. Phosphine ligands can also be partially oxidized to phosphine oxides by the method described in patent '691.

Upon binding with the ligands preferred metal socializaton, namely ruthenium, for example, with diphosphine ligand, it is assumed that the result is a connection - tertiary diphosphine-ruthenium, tricarbonyl, but it can also be a compound of bis(tertiary diphosphine ruthenium)PENTACARBONYL. Not associated with the ligands of the ruthenium carbonyl, as expected, is an inactive particles, and for this reason, upon receipt of the catalyst trying to associate with ligands each atom of ruthenium.

When the ligand is a N-heterocyclic group, a large number of N-heterocyclic compounds identified as suitable ligands for single-stage synthesis of PDO using a pair of catalysts based on cobalt-ruthenium. Usable types of bidentate and multidentate N-heterocyclic ligands include, but are not limited to: diazine, such as pyrimidine, pyrazin, pyridazin and benzodiazepine, such as hinzelin and cinoxacin; bispyridine, such as 2.2 dipyridyl (DIPY), 2,2'-bipyrimidine (BPYM), 1,10-phenanthroline (PHEN), di-2-pyridyl ketone, 4,4'-dimethyl-2,2'-dipyridyl, 5,6-dimethylphenanthrene, 4,7-dimethylphenanthrene, 2,2'-baenlin, neocuproine and 2,2'-dipyridine; multiparity, such as 2,4,6-trierer-second-triazine (TPTZ), 3,6-di-2-pyridyl-l,2,4,5-tetrazine, 2,2':6',2"-terpyridine, 2,3-bis(pyridyl)pyrazin and 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine; pyridine, 3-hydroxypyridine and quinoline, in particular, cheaper homologues derived from extracts of coal-tar; and some of 2,6-pyridylamine, such as 2,6-bis(N-phenylethylamine)pyridine and 2,6-bis[N-[2,6-diisopropylphenyl)methylamino]pyridine. Preferred heterocyclic compounds for use as ligands include 2,2'-dipyridyl (DIPY), 2,2'-bipyrimidine (BPYM) and 2,4,6-trierer-second-triazine (TPTZ).

When ruthenium is associated with ligand-fastenal.com suitable for use fastlanedaily include, but are not limited to, 1,2-bis(phospholane)ethane,

1,2-bis(2,5-dimethylphosphino)ethane,

1,2-bis[(2R,5R)-2,5-dimethylphosphino]ethane;

1,2-bis[(2S,5S)-2,5-dimethylphosphino]ethane;

1,3-bis(2,5-dimethylphosphino)propane;

Tris[(2,5-dimethylphosphino)methyl]methane;

Tris[(2,5-dimethylphosphino)ethyl]amine; or

1,1,1-Tris[(2,5-dimethylphosphino)ethyl]ethane. Especially useful are bidentate bis(phospholane)alkanes, such as 1,2-bis[(2R,5R)-2,5-dimethylocta the ANO]ethane (BDMPE), 1,2-bis[(2S,5S)-2,5-dimethylphosphino]ethane, racemic mixture of both of them plus 1,2-bis(phospholane)ethane.

Partenavia ligands, typically contain four residue types pyrrole rings combined into a cyclic structure, which may also optionally contain various alkyl and aryl substituents on the pyrrole rings, and connecting them marinovich groups. Suitable for use in the practice of the present invention partenavia ligands include octaethyl-perforin and tetraphenylporphine, as well as close, related phthalocyanines.

Generally, the preferred counterion, as expected, can be a cobalt tetracarbonyl ([Co(CO)4]-), although ion in the active catalyst can be a and its modification. The connection part of the cobalt can be modified using the (excess) tertiary diphosphine, for example, up to 75% molar, preferably up to 50% molar. However, preferably, the counterion is not associated with the ligands tetracarbonyl cobalt. The cobalt CARBONYLS can be formed by the interaction of the original source of cobalt, such as cobalt hydroxide, synthetic gas or synthesis gas, as described, for example, in J. Falbe, "Carbom Monoxide in Organic Synthesis", Springer-Verlag, NY (1970).

The catalysts can be obtained using the stepwise method, which is preferred, or manner of self-Assembly, both of which are discussed briefly below and described in more detail in U.S. patent No. 6469222. In the preferred embodiment of the present invention and, in particular, the solvent is selected in such a way as to promote the formation of particles associated with the ligands of the ruthenium, copper, platinum or palladium and not particles associated with ligands cobalt.

Formed whether they Paladino or by self-Assembly, the preferred bimetallic catalysts show a specific absorption band in the infrared region, as discussed in U.S. patent No. 6469222. The presence of particles associated with ligand metal socializaton, not particles associated with the Co ligand can be confirmed, for example, using infrared analysis.

Optimal attitude coming of oxirane to the bimetallic complex catalyst will partly depend on the specific complex. However, the molar ratio of oxirane to the cobalt complex catalyst is from 2:1 to 10,000:1 are generally satisfactory, with molar ratio of from 50:1 to 500:1 are preferred.

The reaction mixture hydroformylation, optionally, but preferably, will contain a promoter and a catalyst to increase the reaction rate. Suitable PlaysForSure promoters include the sources of one - and polyvalent metal cations of weak bases, such as salts of alkali, alkaline earth and rare earth metals and carboxylic acids. Examples of salts of alkali metals, which, as found, are suitable for use include sodium bromide, sodium iodide, potassium iodide, sodium borate, lithium acetate, potassium acetate, cesium acetate and, in particular, sodium acetate.

Also suitable for use are lipophilic promoters, such as lipophilic postname salts and lipophilic amines, which increase the speed of hydroformylation without imparting hydrophilicity (water solubility) to the active catalyst. Under "lipophilic" means that the promoter has a tendency to remain in the organic phase after extraction PDO water. Lipophilic compounds can include, but are not limited to, salts of Quaternary ammonium or phosphonium, lipophilic amines or arsine and lipophilic phosphine oxide. Such Quaternary ammonium salt include benzyltrimethylammonium acetate, designed methoxide, designed hydroxide and salts of ethoxylated Quaternary ammonium compounds, such as those available under the trade name ETHOQUAD. Such oxides include triphenylphosphine, tributylphosphine, dimethylphenylphosphine and triethylphosphine. Triphenylphosphine is the OS is especially useful. Such Arseny include triphenylarsine and triethylamine. Dimethyldodecylamine used with good results in the examples presented in table 3. The promoter will generally be present in amounts in the range of 0.01 to 0.6 moles per mole of cobalt.

Optimal industrial production will require effective extract diluted ligand catalyst in full, in essence, the recycling of the catalyst in the reaction hydroformylation. The method of extraction of the catalyst may include two or more stages, starting with the above-described water extraction PDO in the atmosphere of carbon monoxide from a mixture of products hydroformylation. The organic phase can be recycled to the reactor hydroformylation with optional purification from heavy fractions. That part of the catalyst, which remains together with the aqueous phase of the product can be recovered and recycled through alternative separation schemes, including thermal separation (distillation). The ligand upon receipt of the catalyst lowers the volatility of the catalyst components, making it possible recycling together with the lower (bottom) phase of operations thermal separation by extraction, such as distillation or evaporation.

The following examples will serve to illustrate the op is sledge here of the invention. The examples are intended only as a means of illustration and should not be construed as limiting the scope of the present invention in any way. Specialists in this field will notice many changes that can be made without deviating from the essence of the described invention.

EXPERIMENTAL PART

Examples 1-42

Boot one-step synthesis of 1,3-propane diol (PDO) from ethylene oxide (EO) and synthetic gas (CO, H2) is carried out in a 300-ml stirred autoclave with gas dispersion using discharge tubes with a stirrer to ensure excellent mass transfer gas-liquid. The reaction mixture prepared in not containing O2glove box using does not contain O2solvents and chemicals. The obtaining includes weighing between 0.05 and 2 grams of disablecontrolpanel, carotenodermia, ligand catalyst (for example, bidentate phosphine or amine), promoter of the reaction (e.g., sodium acetate) and solvent or solvent mixture, on demand, to bring the total mass of the reaction up to 150 grams. The mixture in the case of an autoclave of stainless steel, cover cap of Teflon and transported from the glove box in the installation of the reactor. (Teflon is a trade name).

Fixed head of the reactor rinsed with nitrogen. A separate pipeline to the nitrogen attached to the reactor vessel containing the reaction mixture is sensitive to air, so that when you remove the plugs housing and the cylinder could be connected in an atmosphere of flowing nitrogen to exclude the presence of air. Then the nitrogen pressure in a sealed installation raise and lower three times to remove any residual oxygen. Then establish an appropriate synthetic gas for the reaction by increasing the pressure in the reactor using the target number of H2with further increase of pressure using a mixture of synthetic gas (CO and H2a desirable composition. Since it is desirable "one-step" synthesis of PDO EO as synthetic gas, it is desirable mixture with the ratio of H2/CO = 2:1, to provide additional "augment" synthetic gas with the correct stoichiometric composition:

Hydroformylation: EO + H2+ CO → 3-HPA

Hydrogenation: 3-HPA + H2→ 1,3-PDO,

where "3-HPA" represents an intermediate compound 3-hydroxypropyl formed by hydroformylation EO. Thus, by adding reinforcing synthetic gas with the same respect as the gas that is consumed by the reactions what s in General, in the synthetic gas can be maintained constant with respect to H2/CO.

The reaction mixture is first heated to the desired reaction temperature (typically 60-100° (C) under pressure synthetic gas from 7 to 12 MPa for pre-forming the desired catalyst particles before introduction of the reagent EO. As a rule, the preliminary formation of loose 30 minutes. The reaction device provided with measuring glass tube high pressure filled by moving from a small cylinder (capacity 0,5 kg), fitted with a submersible tube to allow the transfer of 5-50 grams of ethylene oxide in the measuring tube to measure the dosage in the autoclave reactor. On the cylinder for EO support nitrogen pressure of 0.5 to 1.5 MPa, and the device measuring tube pre-raise the pressure of the nitrogen, at least, up to 0.3 MPa, so that EO is transferred under a protective layer of N2to exclude modes, which would make possible the explosive samorazrushenie. The EO concentration in the final reaction mixture is limited to values less than 15 percent of the masses. to exclude modes, where the reaction temperatures can be explosive decomposition.

For displacement under the pressure of EO from the observation window into the reactor to initiate the reaction, use of synthetic gas. Pridobivanje EO synthetic gas is consumed in the reactions of hydroformylation and hydrogenation, described above. Register a corresponding decrease in pressure with time by using a pressure transducer and recording devices. When the pressure is reduced from 12 to 8 MPa, the reactor manually re-fill synthetic gas. The reaction is considered complete when the pressure decrease due to absorption, is reduced to negligible proportions.

The reactor connect with immersion, which allows for sampling fluid at set intervals of time. Approximately 3-5 grams of sample are drawn through the node immersion tube for receiving the sample, a typical content mixed reactor. Samples can be collected directly in the infrared cell for analysis of catalyst particles off line. These particles, as found, are sufficiently stable to allow for analysis within 30 minutes from the time of sample selection. Alternative liquid sample carefully drossellied through the internal standard solution, cooled to zero degrees Celsius, to capture neprevyshenie EO. This sample enters the capillary gas chromatograph with programming temperature, equipped with a flame ionization detector for the analysis of unreacted EO, the intermediate 3-HPA, PDO product and by-product acetaldehyde/e is anola. Separate fluid samples analyzed by atomic spectroscopy to confirm the concentrations of cobalt, ruthenium and ligand (P, N).

The entire unit is placed under the cap to prevent contact of personnel with ethylene oxide and carbon monoxide. CO detector and sensor fire provide monitoring and protection. Cover with electric heating provides temperature control for the reactor. Automatic shutdown when overheating occurs on signals from thermocouples in the reactor vessel. Destroy the drive or compatible with EO the pressure relief valve is used to protect the reactor and host from too high pressures. Table 1 shows the final concentration of the catalyst components, are investigated in the syntheses described above. Table 2 shows the comparison of the diluted ligand for a method of self-Assembly and method sequential receipt.

MTBE = methyl tert-butyl ether

DPE = diphenyl ether

TBA = tert-butyl alcohol

90 9,75 0,87
Table 1

Periodic one-step synthesis of PDO with dilute ligand through self-Assembly
Etc.The promoter/

Co
EN/CoLigand

/EN
Solventwt.% CoTemp (° (C) before the Ari-tion receiving Temp (° (C) reactionH2COThe reaction rate, g/l/hEnd % PDO+HPAThe selective behaviour-ness to PDO+HPAThe transformation of HPA to PDO
10,300,400,3930%THF/MTBE0,10808053516,020,710,98
20,300,400,3930%THF/MTBE0,10808053311,490,680,95
30,300,200,3330%THF//MTBE0,208080522to 11.520,660,90
40,700,600,2730%of TBA/MTBE0,10808052513,000,650,81
50, 700,600,2730%of TBA/MTBE0,10808055611,95NM0,82
60,70 0,600,2730%of TBA/MTBE0,1080805676,74NM0,59
70,300,300,2230%MTBE/THF0,208080216911,650,850,06
80,700,550,2830%of TBA/MTBE0,10808053414,670,820,96
90,700,550,2830%of TBA/MTBE0,1080805389,450,710,85
100,700,550,2830%of TBA/MTBE0,1080805404,600,580,12
110,700,550,28MTBE0,10808052311,400,570,94
120,700,55 0,28MTBE0,108050545the 10.400,840,83
130,700,550,28MTBE0,1080805174,850,550,78
140,700,550,28MTBE0,1080805353,610,400,47
150,300,300,28MTBE0,2090905406,910,380,78
16*
170,000,550,56MTBE0,0580805107,680,850,99
180,000,550,56 MTBE0,0580805134,570,890,92
190,700,600,27MTBE0,1070755157,980,650,91
200,700,600,27MTBE0,1070755247,010,680,77
210,700,600,27MTBE0,1070755404,630,780,29
220,700,600,25MTBE0,10808052412,410,670,95
230,700,600,25MTBE0,1080805479,030,640,54
240,330,300,28MTBE0,20904509,620,480,02
250,330,300,28MTBE0,20909042037,000,780,36
266,330,300,2830%DPE/THF0,2080135241,490,110,85
270,671,000,30MTBE0,058080521of 8.060,680,98
280,671,000,30MTBE0,0580805235,950,780,95
290,671,000,30MTBE0,0580805364,080,890,47
300,000,300,28MTBE0,1080805340,580,18
310,000,300,28MTBE0,1080805448,940,800,11
320,000,300,28MTBE0,1080805505,040,700,06
330,700,600,271PDO/3TBA/6MTBE0,1080802105,190,260,63
340,700,600,271PDO/3TBA/6MTBE0,10808024311,340,830,74
35*
360,300,300,331PDO(1:1MTBE/THF)0,20808053 1,160,620,85
370,670,600,801PD01:1MTBE/TBA0,1080805144,500,240,00
380,670,600,801PDO 1:1 MTBE/TBA0,108080546of 7.960,530,36
390,670,600,801PDO 1:1 MTBE/TBA0,1080805354,000,370,47
400,670,600,2710% PDO/MTBE0,1080805219,100,480,62
410,670,600,2710% PDO/MTBE0,1080805316,720,590,70
420,670,600,2710% PDO/MTBE0,1080805595,120,41
Promoter = Na-acetate

Ligand = B9PBN-2

THF = tetrahydrofuran

TBA - tert-butanol

MTBE = simple methyl tert-butyl ether

DPE = simple diphenyl ether

16* and 35* = abnormal

Examples 43-46

Table 2

Comparison of methods prior, self-Assembly and stepwise diluted with ligand
Etc.The ligandThe provisional receiptPromo-torwt.% CoThe atomic ratio of Ru/CoBidentate L/ENCo:EN:L:Time clock% semi-treatmentThe conversion

use

HPA to PDO
g/l/

hour
wt.% PDOwt.% HPA
43BDIBPEPaladinoNaOAc0,20,40,3852,000,800,31310,340,49is 25.505,0145,322
44B9PBN-2PaladinoNaOAc0,20,40,3852,00,80 0,3116,910,7051,134,8672,043
45BDIBPESelf-AssemblyNaOAc0,10,40,3852,000,800,31311,290, 6327,857,1384,151
46B9PBN-2Self-AssemblyNaOAc0,10,40,3852,000,800,31413,670,7825,2910,663,008
BDIBPE = 1,2-bis(di-isobutylamino)ethane

Self-Assembly = Co/Ru/P pre-get together

Paladino = getting phosphine ligand using ruthenium carbonyl, followed by the addition of disablecontrolpanel

g/l/h = reaction rate, expressed as grams of PDO + HPA produced per liter of volume of liquid per hour.

The extraction of water

The extraction of water should be carried out at a temperature that is low in relation to the stages of the reaction, the pressure of CO to suppress degradation of the catalyst based on the carbonyl of the metal. In this case, for experiments in periodic is egime this is done by cooling the reaction mixture to 45° C or below. Then the desired amount of water (typically 1/5 to 1/10 of the reaction mass for the implementation of product concentration) is added to a small cylinder connected with the upper part of the reactor, and is blown into in the reactor by applying pressure synthetic gas. The extraction carried out by stirring a mixture of water/solvent (two immiscible liquid phases) using the same autoclave agitators are used for mixing and dispersion of synthetic gas during the reaction. After stirring for 0.5 - 1.0 hour, the mixture is transported to the site of the separator containing the high pressure cylinder (500 ml) with lower sight glass such size that were visible to the lower 10 - 75 milliliters of the sample, so as to make it possible to visually detect the boundary between the phases of the solvent and water product. The node separator support at a temperature below 45°C and at a pressure of at least 3 MPa syngas 2:1 (minimum partial pressure of CO 1 MPa). Under these conditions, decomposition of the catalyst on the basis of the metal carbonyl is not observed. Thus, it is possible to separate the water phase of the product and solvent.

The device separator supply the bottom drain valve to allow the descent of all aquatic products (as the rights of the lo, 10 - 40 grams) in a container for the sample. Then the remaining solvent and catalyst can be filed under back pressure in the autoclave reactor for the implementation of the second cycle of the reaction, whereas the loss of solvent and catalyst due to the selection of the sample during the reaction. Before the total loss of solvent and catalyst will make it impossible to further research can be carried out five or more cycles. Optional you can add additional solvent to make it possible recycling at a concentration of diluted catalyst.

Examples 47-52

Conducted a series of experiments in periodic mode to demonstrate the effectiveness of recirculatory water to extract the product and recirculatory one-stage catalyst together with the phase is not miscible with water solvent.

The reaction mixture contains 133,5 grams of methyl tert-butyl ether (MTBE) and 14.8 grams of ethanol as solvent. They added 2.0 grams of cobalt 2-ethylhexanoate ("octoate cobalt ") when the content of cobalt metal 16.5 percent of 0.54 gram tirutani-dodecacarbonyl, 1.50 grams of bidentate phosphine "B9PBN-2", 0.4 gram dimethyldodecylamine promoter, 0.1 gram of triethyl-phosphine oxide (a marker for NMR identification of phosphine ligand) and 1.0 grams of toluene (the body of the static marker particles, participating in the reaction). The mixture is loaded into the H2/CO 4:1 to obtain a pressure of 1500 psi (10,3 MPa) and heated to 135°C to obtain an active catalyst.

The reaction mixture is cooled to 90°C and add to 12.0 grams of ethylene oxide (EO) to initiate the reaction. Reactions give the possibility to place up until the absorption of gas will not stop, indicating almost complete conversion of EO. Additional 10.4 grams of EO added for the second phase of the reaction. After the absorption of the gas is again reduced, the reactor is cooled to ambient temperature (< 30°C) and add 25.2 grams of deionized water for the extraction of the product under pressure synthetic gas 3 MPa. After 15 minutes, extracted the mixture is transferred into a measuring tube/separator under pressure synthetic gas) and phases provide an opportunity for separation. The resulting layer of product (29.3 grams) descend from the separator.

The remaining upper layer is transferred back into the reactor and re-heated to 90°C under pressure synthetic gas is 4:1. Again enter EO to initiate the second cycle of the reaction. This process continued for 6 cycles, the results are shown in table 3:

Table 3

Research one-step reaction with recircula the cation, with the release of water: 90°C
no reactionThe dilution of the catalystReaction watchThe total reaction time, hoursThe total number of received HPA = PDO, gramsOutput PDO/EOThe reaction rate, g/l/h. Set to 0.2 wt.% CoThe transformation of HPA to PDOExtraction PDO, wt.%, ULExtraction PDO, wt.%, LL
11,003312,590,7230,420, 993,728, 9
20,876919,920,98to 24.840,993,534,4
30,7561515,001,0227,040,983,129,4
40,6362113,870,8832,370,972,526,0
50,529,530,515,300, 9733,780,983,0of 31.8
60,41 636,511,420,7359,090,962,024,5
Explanation

• reaction Rate = grams PDO obtained per liter of volume of liquid per hour

• UL = upper layer solvent

• LL = lower layer solvent

While the overall yield of PDO EO reflects both the selectivity of the reaction, and extraction efficiency for this cycle, the average molar yield was 88%. Some catalyst is lost at each extraction in the aqueous phase, but the overall rate of reaction per mole of cobalt remained approximately constant. The PDO product to a great extent distributed in the aqueous phase, while the catalyst preferably remains in the upper phase of the solvent (see table 4,below). It is important that the conversion of 3-HPA to PDO remains high for all cycles, indicating effective recycling component of the hydrogenation catalyst, necessary for the implementation of "one-step" synthesis. Table 4 shows the analysis of the catalyst components, leaching into water product, for different number of cycles:

Table 4
Cycle #PhaseCo is/million EN h/millionP h/million
0UL214516501950
1LL110016001600
3LL4150200
6LL716,465
6UL8003001000
LL = lower water layer

UL = upper layer solvent

Significant amounts of the catalyst components are lost during the first extraction with water. This is consistent with the visible poor separation ("torn" layer). However, at such a low ratio of aqueous phase to the solvent (the ratio of extraction of H2O/solvent is 1:7) this does not lead to a significant loss of catalyst. The following cycles of reaction and extraction provide a clean separation of aqueous/organic phase with an effective extraction PDO (table 3), but with low loss of catalyst components (table 4). The final top layer of solvent analyze by the end of the reaction. The analysis shows the retention of a significant part of the source of catalyst and a favorable distribution coefficient for all components (Co, Ru and P) is the aqueous phase.

Significance:

The experiments with the one-stage reaction and recycling demonstrate the ability to provide initial separation of catalyst and product by extraction with water. Most of the product is extracted into the aqueous phase, while a large part of the catalyst in the active form is retained in the upper phase of the solvent and can be recycled back into the reaction.

The extraction liquid does not cause thermal loads on expensive components of catalysts and, therefore, is a primary way to recirculatory catalyst during the industrial production of products with high boiling points, such as 1,3-propandiol.

1. The method of obtaining aliphatic 1,3-diols, which includes

(a) bringing into contact at a temperature in the range from 30 to 150°and a pressure ranging from 3 to 25 MPa of oxirane, carbon monoxide and hydrogen, in essence, is not miscible with water solvent in the presence of an effective amount of a homogeneous bimetallic catalyst hydroformylation containing compound of cobalt carbonyl, and socializaton-based metal, which is selected from the group consisting of ruthenium, and which is associated with a phosphine ligand, optionally, in the presence of promote is a, where the molar ratio of the ligand to the metal atom of socializaton is in the range of 0.2:1.0 to 0.4:1.0, with reaction conditions effective to obtain a mixture of reaction products containing aliphatic 1,3-diol;

b) adding to the said mixture of reaction products of an aqueous solution and extracting specified in aqueous solution mostly aliphatic 1,3-diol at a temperature of less than 100°With, to create an aqueous phase containing an aliphatic 1,3-diol in greater concentration than the concentration of aliphatic 1,3-diol in a mixture of reaction products, and the organic phase containing at least a portion of the bimetallic catalyst hydroformylation;

(c) separating the aqueous phase from the organic phase; and

(d) optional return at least part of the organic phase containing the catalyst in stage (a).

2. The method according to claim 1, where the connection of the cobalt carbonyl is, in essence, is not associated with the ligand compound of cobalt carbonyl.

3. The method according to claim 1 or 2, where the aliphatic 1,3-diol is a 1,3-propandiol.

4. The method according to claim 1 or 2, where the molar ratio of metal socializaton to cobalt is at least approximately 0.05:1.

5. The method according to claim 1 or 2, further comprising an extraction residue of the catalyst from the aqueous phase and in surasena specified residue of the catalyst in stage (a).

6. The method according to claim 1 or 2, where at least part of the organic phase containing the catalyst, return to the step (a).

7. The composition of the catalyst for hydroformylation of ethylene oxide to aliphatic 1,3-propane diol, obtained by using a method, which includes

a) obtaining a complex of (A) by bringing into contact of the connection metal socializaton, which are selected from the group consisting of compounds of ruthenium, with a phosphine ligand, where the molar ratio of the ligand to the metal atom of socializaton is in the range of 0.2:1.0 to 0.4:1,0;

b) obtaining a complex of (C) by the influence of the complex of (A) oxidation-recovery connection - carbonyl cobalt.

8. The composition according to claim 7 where the compound is a cobalt carbonyl is a carbonyl cobalt, essentially, is not associated with the ligands.



 

Same patents:

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention provides alternative bimetallic catalyst composition comprising a cobalt component constituted by a number of non-alloyed cobalt carbonyl compounds and a ruthenium component including ruthenium carbonyl compound alloyed with N-heterocyclic ligand selected from group of bidentate and multidentate N-heterocyclic ligands. 1,3-Butanediol production process comprises providing reaction mixture containing ethylene oxide, carbon monoxide, hydrogen, inert organic solvent, and above-defined catalyst, and heating this reaction mixture to temperature from 30 to 150°C at pressure from 100 to 4000 psig (690 to 27580 kPa) over a period of time long enough to obtain biphasic mixture of products composed of (i) upper phase including major part of solvent, at least wt 50% of catalyst composition plus unreacted ethylene oxide and (ii) lower phase containing major part of 1,3-butanediol.

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8 cl, 5 dwg, 19 tbl, 98 ex

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention provides alternative bimetallic catalyst composition comprising a cobalt component and a iron component alloyed with ligand selected from group consisting of T-heterocycle residue, phosphine, and porphyrin. 1,3-Butanediol production process comprises providing reaction mixture containing ethylene oxide, carbon monoxide, hydrogen (H2/CO molar ratio being between 2:1 and 6:1), inert solvent, and above-defined catalyst composition, and heating this reaction mixture to temperature from 30 to 150°C at pressure from 1500 to 2500 psig (1034 to 17420 kPa) to form biphasic mixture of reaction products composed of (i) upper phase including at least wt 50% of solvent, at least 50 wt % of catalyst composition plus unreacted ethylene oxide and (ii) lower phase containing more than 50% of 1,3-butanediol.

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10 cl, 4 dwg, 4 tbl, 20 ex

FIELD: organic chemistry.

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20 cl, 2 ex

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11 cl, 3 tbl, 1 dwg, 14 ex

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5 cl, 4 dwg, 2 tbl, 29 ex

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10 cl, 1 tbl, 5 ex

Treatment of glycol // 2265584

FIELD: chemical technology.

SUBSTANCE: invention relates to removing impurities, such as aldehydes, from ethylene glycol aqueous solutions by treatment with bisulfite-treated strong-base anion-exchange resin. Invention describes a method for reducing the content of aldehydes in ethylene glycol aqueous solution containing about from 0.2 wt.-% to 20 wt.-% of ethylene glycol containing about from 80 wt.-% to 99.7 wt.-% of water and about from 100 mln-1 (mas.) to 0.1 wt.-% of aldehydes. Method involves contacting indicated solution with bisulfite-treated solid strong-base anion-exchange resin that before treatment with bisulfite comprises quaternary ammonium functional groups in hydroxide form. Invention provides the improvement in removing impurities, such as aldehydes, from flows of ethylene glycol aqueous solutions.

EFFECT: improved method for treatment.

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FIELD: organic compound technology.

SUBSTANCE: invention relates to improved method of reducing content of aldehydes in ethylene glycol containing up to 2000 ppm aldehydes comprising bringing glycol in liquid phase into contact with solid high-acidic cation-exchange resin.

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8 cl, 5 dwg, 19 tbl, 98 ex

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10 cl, 4 dwg, 4 tbl, 20 ex

FIELD: industrial organic synthesis.

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19 cl, 3 dwg, 2 tbl, 6 ex

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EFFECT: improved method of synthesis.

8 cl, 3 tbl, 4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to technology for synthesis of 1,3-propanediol by the hydroformylation reaction of ethylene oxide with the simultaneous hydrogenation step. Method involves the following steps: (a) contacting a mixture consisting of ethylene oxide, carbon monoxide, hydrogen, water-nonmixing reaction solvent and the hydroformylation catalyst composition; (b) heating this reaction mixture to obtain a monophase mixture of the reaction products comprising 1,3-propanediol wherein separation of phases can be induced by decreasing the temperature; (c) inducing for separation of phases by at least one method chosen from the group comprising: (1) decreasing temperature with combination of addition agent inducing separating into layers to the mixture; (2) reducing temperature in combination with the first addition of co-solvent at first increasing capacity for mixing followed by removal of co-solvent increasing capacity for mixing; (3) the following addition of co-solvent at first increasing capacity for mixing followed by removal of co-solvent increasing capacity for mixing, and (4) addition agent inducing separating phases to the products mixture wherein separating phases results to arising the first phase containing the main part of reaction solvent, at least, 50 wt.-% of the catalyst composition plus unreacted ethylene oxide, and the second phase that comprises the main part of 1,3-propanediol. Extraction of the catalyst residue is carried out preferably from the second phase and its recirculation to the step (a). The end product is isolated by distillation with recycle of unreacted compounds. Invention provides carrying out the process for a single step and simplifying technology for separating reactions products.

EFFECT: improved method for synthesis.

11 cl, 3 tbl, 1 dwg, 14 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides a method for preparing improved oxirane hydroformylation catalyst, improved oxirane hydroformylation catalyst, and single-stage process for production of 1,3-diol in presence of such catalyst. Preparation of catalyst comprises preparing complex A by contacting ruthenium(0) compound with di-tertiary phosphine ligand and preparing complex B via redox reaction of complex A with cobalt(0) carbonyl compound. Single-stage 1,3-diol production process involves reaction of oxirane with synthesis gas under hydroformylation conditions in inert solvent in presence of aforesaid catalyst, where recovery of product is preferably accomplished through separation of product-rich phase.

EFFECT: reduced number of stages to a single one or increased yield of 1,3-diol without by-products and preserved catalytic activity after catalyst regeneration operation.

10 cl, 3 dwg, 6 tbl, 21 ex

FIELD: organic chemistry, in particular production of high oxoalcohols.

SUBSTANCE: invention relates to method for production of high oxoalcohol from isomeric olefin mixture containing from 5 to 24 of carbon atoms. Claimed method includes hydroformylation in presence of catalyst at elevated temperature and elevated pressure. Hydroformylation in carried out in one step, and ones-through olefin conversion is limited in range of 40-90 %. Obtained reaction mixture after catalyst separation is preferably transferred to selective hydration carrying out at 120-220°C and pressure of 5-30 bar in presence of supported catalyst containing copper, nickel and chromium as active ingredients. Hydration product mixture is separated by distillation, and olefin fraction is recycled into hydroformylation step. As starting materials for hydroformylation mixtures of C8-, C9-, C12- or C16-olefins are used.

EFFECT: high olefin conversion ratio, selectivity, and capability.

15 cl, 1 dwg, 1 tbl, 2 ex

The invention relates to the production of 1,3-propane diol by hydroformylation of ethylene oxide through the intermediate solution of 3-hydroxypropane from which to remove residual carbon dioxide and insoluble catalytic compounds of cobalt or rhodium
The invention relates to a method for producing alcohols from 7-18 carbon atoms by hydroformylation corresponding olefins with synthesis gas in the presence containing cobalt catalyst of the organic phase with 50 - 220oC and a pressure of 100 to 400 bar, with subsequent hydrogenation of the thus obtained aldehyde

The invention relates to the separation of a mixture of alcohols derived from CO and H2(synthesis gas) can be used as additives with high octane fuel mixtures

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides a method for preparing improved oxirane hydroformylation catalyst, improved oxirane hydroformylation catalyst, and single-stage process for production of 1,3-diol in presence of such catalyst. Preparation of catalyst comprises preparing complex A by contacting ruthenium(0) compound with di-tertiary phosphine ligand and preparing complex B via redox reaction of complex A with cobalt(0) carbonyl compound. Single-stage 1,3-diol production process involves reaction of oxirane with synthesis gas under hydroformylation conditions in inert solvent in presence of aforesaid catalyst, where recovery of product is preferably accomplished through separation of product-rich phase.

EFFECT: reduced number of stages to a single one or increased yield of 1,3-diol without by-products and preserved catalytic activity after catalyst regeneration operation.

10 cl, 3 dwg, 6 tbl, 21 ex

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