Catalyst composition and single-stage process for production of 1,3-butanediol from ethylene oxide and synthetic gas using cobalt and iron-based catalyst composition

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.

EFFECT: achieved single-stage production of 1,3-butanediol with minimum amounts of impurities and by-products, and increased stability of catalyst.

10 cl, 4 dwg, 4 tbl, 20 ex

 

The scope of the invention

The present invention relates to the synthesis of aliphatic 1,3-diol, in particular 1,3-propane diol of ethylene oxide and synthetic gas in a single stage. More specifically, the present invention relates to an alternative bimetallic catalyst low cost, which provides moderate values of yield under mild conditions, when one-step synthesis of 1,3-propane diol (1,3-PDO). The catalyst according to the present invention contains a catalyst based on cobalt-iron in the presence of a ligand selected from N-heterocyclic, phosphine or porfiryevich ligands, and optionally, solubilizing in the ether solvent.

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, CORTERRA polymer (trade mark) is a complex polyester, characterized by excellent properties, which is obtained from 1,3-propane diol (hereinafter referred to 1,3-PDO) and terephthalic acid. In this area there is great interest in finding new methods for the synthesis of 1,3-PDO, which are effective, economical and demonstrate the advantages of the method.

US-A-3463819 and 3456017 describe HYDROFORM the regulation of ethylene oxide with obtaining 1,3-propane diol and 3-hydroxypropyl (hereinafter, 3-HPA), using a modified tertiary phosphine catalyst based on cobalt carbonyl.

US-A-5304691 describes how hydroformylation of ethylene oxide to 3-hydroxypropane and 1,3-propane diol at a single stage, using an improved catalyst system containing cobalt-ligand tertiary phosphine in combination with a catalyst based on ruthenium. In U.S. patent US-A-5304691, 1,3-PDO and 3-HPA is obtained by bringing into close contact oxirane, in particular of ethylene oxide (hereinafter referred to as EO), modified diretional phosphine catalyst based on cobalt carbonyl, a promoter and a catalyst based on ruthenium and synthetic gas (carbon monoxide and hydrogen), in an inert reaction solvent, the reaction conditions of hydroformylation. Reach the exit PDO to 86-87 molar % with the use of a catalyst containing cobalt, legirovannye 1,2-bis(9-phosphabicyclononanes)ethane as a bidentate ligand, and either triruthenium(0)dodecacarbonyl, or bis[ruthenium, tricarbonyl dichloride] as a co-acting catalyst.

US-A-4650911 describes a catalyst containing a cobalt component, an iron component, a ruthenium component and a component of iodine. US-A-4408069 describes a catalyst which is a compound in the form of a cluster of iron-cobalt carbonyl. WO-A-96/10552 describes p is torching 1,3-propane diol and 3-hydroxypropane in the presence of a catalyst based on cobalt. Obtaining 1,3-PDO in one stage, with a minimum of impurities and by-products, includes recycling and requires catalytic system with good stability both during the synthesis of 1,3-PDO, and during the recovery and recycling of the product. It would also be desirable if there were a combination of catalysts low cost for one-step synthesis of 1,3-PDO.

Brief description of the invention

In accordance with all of the above, the present invention provides an alternative to the use of the known compositions of the catalysts hydroformylation in one-step synthesis of 1,3-PDO. The present invention provides a catalyst composition containing:

a) component is cobalt; and

b) component is iron, legirovannye ligand selected from the group consisting of fragments of the N-heterocycle, phosphine and perforin.

More specifically, the present invention is a homogeneous catalytic system containing:

a) a cobalt component containing one or more, preferably religioun compounds of cobalt; and

b) component is iron, very ligand selected from the fragments of the N-heterocycle, phosphine or perforin.

Unexpectedly found that the bimetallic catalyst based on cobalt-iron is effective at one-phase si is thesis of 1,3-PDO and for this reason gives the advantage of alternative lower cost. For example, dicobalt octacarbonyl in combination with PENTACARBONYL iron, with N,N-dimethyldodecylamine as a promoter, solubilizing 1,3-dioxolane, as shown, shows moderate values of output with minimal formation of a precipitate, when hydroformylating (in conditions of high pressure synthetic gas).

The new catalyst hydroformylation of oxirane of the present invention includes a complex, which is thought, is a complex of cobalt:iron in combination with a ligand selected from a monodentate, bidentate or multidentate N-heterocycle, phosphine or perforin. In this new bimetallic catalyst ligand, as expected, rather mainly attached to the iron than the cobalt, as in the case of US-A-5304691.

The present invention also provides one way to obtain 1,3-diol, which includes the interaction of oxirane with synthetic gas, under conditions of hydroformylation, in an inert solvent, in the presence of a catalytic complex according to the present invention.

In particular, the present invention provides a method of obtaining 1,3-propane diol, comprising the stage of:

(a) contacting in a reaction mixture of ethylene oxide, carbon monoxide, hydrogen, and the molar ratio of odor is Yes to carbon monoxide is in the range from 2:1 to 6:1, directionspanel solvent and a catalyst composition containing:

(i) component of cobalt; and

(ii) component is iron, legirovannye ligand selected from the group consisting of fragments of the N-heterocycle, phosphine and porporino, and;

(b) heating this mixture to a temperature of from 30 to 150°C and pressures of from 1500 to 2500 psi (10340 to 17240 kPa), with a two-phase mixture of reaction products containing upper phase, containing more than 50% of the solvent, at least 50% of the bulk composition of the catalyst plus unreacted ethylene oxide and the lower phase, which contains more than 50% 1,3-propane diol.

Brief description of drawings

The present invention will now be described by example with reference to the accompanying drawings.

Figure 1 represents a three-dimensional graph of the IR spectra showing the formation of a catalyst based on cobalt-iron-perforin as a function of time.

Figure 2 is an IR spectrum of the catalyst based on cobalt-iron-perforin after the preliminary formation of 1,3-dioxolane.

Figure 3 is a three-dimensional graph of the IR spectra depicting the catalyst based on cobalt-iron-perforin during the one-step conversion of ethylene oxide and synthesis gas (syngas) in 1,3-propandiol and

Figure 4 illustrates the IR spectrum is utilizator based on cobalt-iron-perforin during the one-step formation of 1,3-PDO.

Detailed description of the invention

Demonstrates selective hydroformylation/ hydrogenation of ethylene oxide to 1,3-PDO, at one stage, which is represented as:

using homogeneous bimetallic catalytic systems on the basis of cobalt-iron, in combination with soluble ligands N-heterocycle, phosphine or perforin, and optional, solubilizing in a solvent on the basis of simple ether.

One-step method for the synthesis of 1,3-PDO, in General, includes close contacting of ethylene oxide, carbon monoxide and hydrogen (synthesis gas), and bimetallic catalyst in liquid-phase solution in an inert reaction solvent, at a temperature of from 30 to 150°C and at high pressure.

Important aspects of the one-stage method according to the present invention include the use of enriched hydrogen, synthetic gas and work at a pressure slightly higher than that used in U.S. patent US-A-5304691, where the preferred operating pressure is close to 1500 psi (10340 kPa). In the present invention, the preferred pressure for one-step synthesis is preferably 2000±250 psig (13790±1725 kPa).

Other important factors in the development of this chemical mechanism on the require-effective extraction PDO from solutions of crude exonerating product and recycling of the active catalyst based on Co-Fe or Co-Fe-ligand.

In the present invention 1,3-diols are obtained by loading oxirane, bimetallic catalyst, very and, optionally, solubilizing in directionspanel the reaction solvent and the reaction solvent in the reactor high pressure, with the introduction of synthesis gas (mixture of hydrogen and carbon monoxide at a molar ratio of from 2:1 to 6:1), under conditions of hydroformylation. In the framework of the present invention is also the use of the promoter and/or co-acting catalyst.

The method according to the present invention may be implemented as a way of periodic type, as a continuous method or a combination thereof.

When working the present invention are combined, separate or spaced in time flows EO, synthetic gas and catalyst are loaded into a reaction chamber, which may represent a reaction chamber of a high pressure, such as a bubble column or autoclave with agitator running in batch or in continuous mode.

Oxirane containing up to 10 carbon atoms, preferably up to 6 carbon atoms, and ethylene oxide, in particular, may be converted to the corresponding 1,3-diols by reaction of hydroformylation with synthetic gas, in the presence of a catalytic complex according to the present image is the shadow.

The main part of the present invention is the use of a complex of Co-Fe-ligand. The combination of the present invention is assumed to contain a new class of modified bimetallic catalysts. A characteristic feature of this new class includes oxidized metallic iron, which legasuite ligand selected from a ligand is monodentate, bidentate, or multidentate N-heterocycle, phosphine or perforin and connection cobalt as counterion.

Suitable for use of iron compounds include, but are not limited to, the CARBONYLS of iron and iron salts, which are easily reduced to the condition of zero valence using a heat treatment in an atmosphere of hydrogen and carbon monoxide. Examples of such salts of iron include iron carboxylates, such as acetates, octanoate and stearates, and iron salts and mineral acids, such as phosphates, chlorides, fluorides, sulfates and sulfonates. Can also be used mixtures of these iron salts. An additional possibility is the use of ORGANOMETALLIC compounds of iron, where the iron is associated with one or more organic fragments such as cyclopentadiene, pentamethylcyclopentadiene or cyclooctatetraene cyclic p is ctory. Usable examples include bis(cyclopentadienyl)iron, commonly known as ferrocene and its derivatives. The recovery of these salts or ORGANOMETALLIC compounds can be carried out before using them as catalysts, or it may be carried out simultaneously with the process of hydroformylation. The examples demonstrate the special usefulness of iron CARBONYLS, including PENTACARBONYL iron, Fe(CO)5noncarbonyl digesta Fe2(CO)9and dodecanoyl tridelta Fe3(CO)12.

As noted, suitable for use ligands are selected from N-heterocycles, including monodentate, bidentate and multidentate N-heterocycles, phosphine and porfiryevich ligands.

A large number of N-heterocyclic compounds identified as suitable ligands for single-stage synthesis of PDO, using catalytic pairs based on cobalt-iron. Usable types of monodentate, 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), and-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-1,2,4,5-tetrazine, 2,2':6',2"-terpyridine, 2,3-bis(pyridyl)pyrazin and 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine; pyridine selected from pyridine, 3-hydroxypyridine and quinoline, in particular homologues with lower cost, obtained from extracts of coal-tar; and certain 2,6-pyridyl-diimine, such as 2,6-bis(N-phenyl, methylamino)pyridine (BPMIP) and 2,6-bis[N-(2,6-diisopropylphenyl)methylamino]pyridine (BDPMIP). Aliphatic diimine can also be used as ligands in the present invention. Suitable here to use the ligands on the basis of aliphatic diamino include N,N-di-tert-butyldiethanolamine (DTBDB).

Suitable for use in this complex phosphine ligands include, but are not limited to, tertiary diphosphine General formula:

RRP-Q-PR R',

where each R and R', independently or in combination, represent 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 contains up to 20 atom is in carbon, more preferably contains 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 ring system such as 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; 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(diphenylphosphino)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 and the like. These groups R and R' may themselves be substituted by non-hydrocarbonaceous groups. Both groups R and/or both groups R' may also form a ring with the atom (atoms) of phosphorus, such as phosphacyclohexane of 5-8 atoms. Examples of the 5-ring systems (ligands on the basis of phospholane groups) include 1,2-bis(phospholane)ethane, 1,2-bis(2,5-d is methylphosphono)benzene, optically pure (R,R), (R,S), (S,S) 1,2-bis(2,5-dimethylphosphino)ethane or its racemic mixture. In itself, the ring may be part of a multiring system.

Examples of such ring systems can be found in the aforementioned US-A-5304691 and WO-A-98/42717.

In the first described phosphabicyclononanes group, and in the latter, in particular, describes the group, such adamantyl, and postitionsanatomically group. Diphosphine, where both groups R and R' form a ring with the phosphorus atom, are preferred. Examples include 1,2-bis(9-phosphabicyclononanes)ethane (B9PBN), in particular, 1,2-P,P'-bis(9-phosphabicyclo[3.3.1] and/or [4.2.1]nonyl)ethane, its 1,2-P,P'-propane analogue and 1,3-P,P'-propane equivalent.

Titration phosphine ligands are commercially available. Catalysts derived from them, are known in this field, and the retrieval method is described in detail in U.S. patent US-A-3401204 and US-A-3527818. Phosphine ligands may also be partially oxidized to phosphine oxides by the method described in US-A-5304691.

Partenavia ligands, typically contain four ring balance type pyrrol placed in the form of a cyclic structure, which, optionally, may also include various alkyl and aryl substituents on the pyrrole rings, and connecting them marinovich groups. Suitable for use in practicebased invention partenavia ligands include octaethylporphyrin and tetraphenylporphine, as well as closely related phthalocyanines. Example 2 further illustrates the use of 2,3,7,8,12,13,17,18-octaethyl-21H,23H-perforin iron(III) acetate (OEPFeAc) as a source of iron for the synthesis of 1,3-PDO.

The molar ratio of N - or P-ligand to the iron atom can vary from 4:1 to 1:4, but preferably from 2:1 to 1:2, and in many cases, the most preferred is a ratio of about 1:1.

Suitable sources of cobalt include salt, which is recovered to a state of zero valency by heat treatment in an atmosphere of hydrogen and carbon monoxide. Examples of such salts include, for example, cobalt carboxylates such as acetates and octanoate, which are preferred, and cobalt salts and mineral acids, such as chlorides, fluorides, sulfates and sulfonates. Also apply a mixture of these salts of cobalt. Preferred, however, is that, when mixtures are used, at least one component of the mixture consisted of alkanoate cobalt from 6-12 carbon atoms. Recovery may occur prior to the use of catalysts, or it may occur simultaneously with the process of hydroformylation in the area of hydroformylation.

The counterion for best results, as expected, is a Carboni is cobalt, such as anion tetracarbonyl cobalt, ([Co(CO)4]-), which have the characteristic IR band of cobalt carbonyl in the area from 1875 to 1900 cm-1in particular in the field of 1888 cm-1. However, this ion in the active catalyst may represent its modification. The connection part of the cobalt can be modified by using one of the ligands listed here, that is, N-heterocycle, phosphine or perforin, for example, in excess of 75% molar, say, up to 50% molar or less. However, the counterion is preferably religiously anion tetracarbonyl cobalt discussed above. The cobalt CARBONYLS can be formed by the interaction of the original source of cobalt, such as cobalt hydroxide with a synthetic gas, as described in J. Falbe, "Carbon Monoxide in Organic Synthesis", Springer-Verlag, NY (1970), or otherwise.

The oxidized state of the iron atom in the synthesis of 1,3-PDO can change significantly (in theory, iron can have a valence of at least from zero to four), and is oxidized state may significantly change during the reaction of hydroformylation. Accordingly, the molar ratio of iron to cobalt may vary within relatively wide limits. Should be added to the amount of cobalt (0), sufficient for complete oxidation of all the iron present in the form of comp is exow. Can be added to an excess of cobalt, but any of its specific value does not exist. Accordingly, the molar ratio of iron:cobalt varies from 4:1 to 1:4, preferably from 2:1 to 1:3, more preferably from 1:1 to 1:2.

Accordingly, the initial molar stoichiometric ratio of cobalt to iron:the ligand is within at least from 0.5 to 4 moles of cobalt from 0.1 to 2 moles of iron: 0 to 2 moles of N-ligand. The preferred range should be from 1 to 3 moles of cobalt, from 0.2 to 1.5 moles of iron and from 0 to 1 mole of ligand, for example, 3:1:1. One of the drugs (see example 2) is a cobalt:iron:ligand OEPFeAc when the molar stoichiometry of 1:0,35:0.35, respectively.

In the present invention a preferred method of preparation of the catalyst based on cobalt-iron-ligand is a one-step method when all of the components of the catalyst are combined together at the same time. Complexes of cobalt-iron-ligand can form single-stage, when they solubilization in an appropriate solvent on the basis of simple ether, in the conditions of synthesis gas. Conditions and, in particular, the solvent is selected in such a way as to promote the formation of rather legirovannykh particles of iron than legirovannykh particles of cobalt. The presence of rather Fe-Ligero is the R particles, than particles Co-ligand, can be confirmed, for example, using infrared analysis.

Also, the present invention relates to a stepwise method for producing a catalyst as follows: the first stage of the preparation of the catalyst is the synthesis of the complex Fe-ligand. This can be done by reduction of the corresponding source of iron, for example, PENTACARBONYL iron, in contact with the selected ligand. Alternatively, instead of PENTACARBONYL iron can be used other easily accessible derivatives of CARBONYLS of iron, such as noncarbonyl iron or dodecanoyl iron. Other possibilities include the use of springs, which, in the atmosphere of synthetic gas will be in situ to form particles of carbonyl iron. These are not as expensive sources of iron may include nitrate iron (III) stearate and iron (III)sulfate and iron(III). The IR band of carbonyl iron is preferably in the region from 1950 to 2050 cm-1. The iron complex with N-heterocyclic, phosphine or Portanova ligand can be obtained, for example, by interaction of PENTACARBONYL iron with the stoichiometric quantity of the selected ligand in a solvent, at a temperature ranging from 25 to 150°C, possibly from 100 to 110°C, in an atmosphere of carbon monoxide or synthesis gas, within from 1 to 24 the aces (that is, before completion). At this point, optional, specified complex iron-ligand can be isolated in the form of a material composed of distinct particles. Then in the stepwise method, the complex Fe-ligand is brought into contact with a usable connection carbonyl cobalt by means of redox reactions for the formation of the complex Fe-Co-ligand and again, with the above (non-critical) conditions. Suitable for use with a source of cobalt is octacarbonyl of dicobalt, but can also be used and other complexes, and cobalt salts. For example, the selected cobalt carbonyl, and optionally a promoter, if present, are added to a solution, which is then maintained at an elevated temperature (from 25 to 150° (C)during the time from 15 minutes to 24 hours. Again, optionally, a new complex of cobalt-iron-ligand can be isolated and characterized.

As a rule, regardless, is formed if the specified active catalyst for Co-Fe-ligand of the one or Paladino, it shows the characteristic IR bands in the region of the metal-carbonyl, in particular a strong streak of cobalt carbonyl in the area from 1875 to 1900 cm-1associated with the anion [Co(CO)4]-plus a series of bands of carbonyl iron in the region from 1950 to 2050 cm-1that, as expected, associated with Katie the different particles of carbonyl iron.

The conditions under which these compounds are given the opportunity to formation of the complex, are not critical. Temperature and pressure can vary within, below, in relation to the reaction of hydroformylation, for example from 25 to 150°C. the Synthetic gas can be used to create the gas atmosphere during the formation of the complex. It is preferable to use a solvent, preferably the solvent used in the reaction of hydroformylation. Obviously, this solvent should be capable of dissolving the active catalyst without any impact on its properties. Usable solvents include ethers, described below, for use in the process of hydroformylation, in particular simple cyclic and aliphatic ethers.

The optimal ratio of oxirane introduced into the complex Co-Fe-ligand, in part, will depend on the specific complex. However, the molar ratio of oxirane to the cobalt complex Co-Fe-ligand equal to from 2:1 to 10000:1, as a rule, are satisfactory, when this molar ratio is 50:1 to 500:1, are preferred.

The reaction solvent should be inert, meaning that it is not consumed during the reaction. The ideal solvent is La method according to the present invention will be solubilisate input source substances and products during the reaction, but will give the possibility of phase separation at low temperatures. Usable solvents are described in US-A-5304691. Good results can be obtained using a simple esters, in particular simple cyclic, aliphatic esters, optionally, in combination with alcohol, such as ethanol or tert-butanol, and/or with aromatic hydrocarbons such as toluene and chlorobenzene.

Can be used promoters. Suitable promoters are described in US-A-5304691, cited previously. Examples of promoters that work well, are easily accessible and demonstrated promotion of EO conversion, are tertiary amines, such as N,N-dimethyldodecylamine and triethylamine, and alkaline salts such as sodium acetate.

For best results step hydroformylation/hydrogenation is carried out under conditions of elevated temperature and pressure. The reaction temperature is from 30 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 approximately 2000±250 psi (13,790±1725 kPa). In a periodic way reaction, as a rule, ersetze within 1-5 hours.

The components of the input streams are brought into contact in an appropriate reaction solvent in the presence of catalytic complexes of the present invention. EO preferably maintained during the reaction at a concentration 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 mixture. The method according to the present invention can be carried out in a continuous mode, with the specified concentration of EO is supported, for example, by a distributed time adding EO.

Upon completion of the reaction hydroformylation, 1,3-PDO is extracted from a mixture of products using conventional methods, such as selective extraction, fractional distillation, phase separation and selective crystallization. Unreacted starting materials and a catalyst and the reaction solvent can retsiklirovaniya, and preferably, get recycled for further use.

The distribution of the reaction mixture can be facilitated by adding a substance which causes the separation of the phases. Suitable for use substances include glycols such as ethylene glycol and linear alkanes, such as dodecane. This substance is added to the reaction mixture in a quantity in the range of 2 to 10% of the mass is, preferably, from 4 to 8% of the mass relative to the total mass of the reaction mixture. Alternative methods include adding 1,3-propane diol in the reaction mixture to bring the concentration of the product to the desired proportions. Also contributing to the compatibility of alcohols and agents with similar polarity, such as ethanol, propanol and isopropanol can be added initially, and then they are removed before following the induction of phase separation.

On an industrial scale will require effective extraction of the catalyst with many cycles essentially complete recycle of the catalyst in the reaction. The preferred method of extraction of the catalyst involves dividing the mixture into two liquid phases, mentioned earlier, and the recycling of the bulk phase solvent into the reactor, and return to him, at least from 60 to 90% of the mass of the original catalyst.

In a preferred mode of the method of reaction conditions such as concentration of oxirane, the concentration of the catalyst, the solvent, the product concentration and the reaction temperature is chosen in such a way as to obtain a homogeneous reaction mixture at elevated temperatures and cause separation of the reaction mixture in the upper phase of the solvent, containing most of the catalyst, and the lower phase containing the major part 1-propane diol, upon cooling the mixture. This distribution facilitates the selection and extraction, recycling of the catalyst and removal of heavy by-products from the system solvent. This method is mentioned as a way of recycling the catalyst/product recovery by phase separation.

In this way the contents of the reactor allow for a deposition, or it is transferred into an appropriate container at a pressure in the range from atmospheric pressure to approximately the pressure of the reaction, where the slight or significant cooling, can be formed of different phases that differ significantly, being significantly enriched in the product of 1,3-propane diol or a catalyst and a solvent. Phase enriched catalyst based on cobalt-iron and a solvent, directly recycled for further interaction with the input source materials. The product 1,3-PDO is extracted from the phase-enriched product, using conventional methods.

Drugs, containing CARBONYLS of cobalt, in combination with portalname iron and phosphines iron provide a one-step synthesis of 1,3-PDO, when they solubilization suitable for use solvents on the basis of simple ether.

The following examples will serve to illustrate the present invention, described here. This paragraph shall emery are intended only as illustrations and should not be construed as limiting the scope of the present invention in any way. To a person skilled in the art it will be clear that there are many embodiments of the invention without deviating from the claimed scope of the claims.

Example 1

In a 100 ml Parr autoclave with a stirrer, equipped with the necessary means of control of temperature and pressure, load 23 ml of dry, flushed with nitrogen 1,3-dioxolane, 113 mg octacarbonyl cobalt(II) (0.66 mmol Co), 152 mg 2,3,7,8,12,13,17,18-octaethyl-21H,23H-perforin iron(III) acetate (0.23 mmol) and 90 mg of promoter-based N,N-dimethyldodecylamine. The autoclave is pressurized and increase the pressure therein up to 1300 psi (8960 kPa) using a synthetic gas of 1:4 (CO:H2) and heated to 90°C for three hours under stirring at 1500 psi (10340 kPa). At this point, the reactor and contents are cooled to 5°C, and gases are pumped. After this pre-treatment system reactor add the ethylene oxide (EO, 3.5 g, 80 mmol), and upon further increase of pressure up to 1800 psi (12410 kPa) using synthetic gasthe reactor is heated to 90°C at 2000 psi (13790 kPa) synthetic gas(CO:H2within 2 hours. If necessary, introduce additional syngas. After cooling again to 5°C and pumping extract of 29.1 g of a dark red liquid product without any doubt is any signs of precipitation. Analyses by GC and GC-MS/IR confirmed the presence of 1,3-PDO. The concentration of 1,3-PDO in the obtained crude product is 1.1%, the obtained yield of 1,3-PDO is 5.1% molar with respect to the downloaded EO.

Example 2

Following the procedures of example 1, a reactor with a capacity of 50 ml, coupled in situ with infrared (IR) device, fill in 23 ml of 1,3-dioxolane, 116 mg dicobalt of octacarbonyl (of 0.68 mmol Co), 149 mg 2,3,7,8,12,13,17,18-octaethyl-21H,23H-perforin iron(III) acetate (0.22 mmol) and 89 mg of N,N-dimethyldodecylamine. Then a solution of cobalt-iron-perforin pre-treated using a synthetic gas (1000 psi; 6900 kPa; 1/4(CO:H2) at 90°C. After adding EO (2.0 g), hydroformylation carried out at 90°C, at a pressure synthetic gas 1/4CO/H21500 psi (10340 kPa).

Typical IR spectra of a solution of cobalt-iron-perforin during and after completion of the preliminary processing stage, showing the characteristic bands in the region of carbonyl metal particle-bound carbonyl cobalt (1886 cm-1and with the CARBONYLS of iron (1955 and 2010 cm-1), are illustrated in figures 1 and 2. Spectra of the reaction solutions after addition of EO are illustrated in figures 3 and 4. The solution of the final product is transparent, without any signs of sludge.

Example 3

In example 3, which in General should PR is the procedures of example 1, bimetallic catalyst contains dicobalt octacarbonyl and 2,3,7,8,12,13,17,18-octaethyl-21H,23H-perforin iron(III) acetate (atomic ratio Co:Fe is 1:0,3), but the solvent is a mixture of chlorobenzene and toluene (1:1 by volume). The catalyst was pretreated at 90°C, at a pressure of synthesis gas (1:4, CO/H2)equal to 1500 psi (10340 kPa)for 3 hours. After cooling, pressure reduction and adding EO reaction hydroformylation carried out at a gas pressure of(CO/H2)equal to 2000 psi (13790 kPa). Time absorption EO is 1hour. Phase product weighs 23,7, the Presence of 1,3-PDO is confirmed, and the resulting yield of 1,3-PDO is defined as equal to 4.4% molar.

Examples 4-20

In the examples 4-20 follow the procedures described in example 1, using various combinations of compounds of cobalt and iron, forming complexes with many ligands, selected from N-heterocyclic, phosphine and porfiryevich ligands. For example, in the downloads 5-7, shown in table 1, the composition of bimetallic catalyst comprising 2,3,7,8,12,13,17,18-octaethyl-21H,23H-perforin iron(III) acetate, is investigated by using different initial relations Co:Fe. The presence of 1,3-PDO in the product is confirmed.

Table 1
ExampleCatalystSolventTemperature, °The time of absorption of SW (h)The many phases of product (g)Conc. (%)Performance PDO (mmol)Output PDO (molar.%)
PDOHPA
4With-

1/2 OEPFeAc
1,3-Dioxolane90and3P20,8The CONCENTRATION is

The CONCENTRATION is
3,1

0,8
The CONCENTRATION is

The CONCENTRATION is

<0,1
<0,1
5With-

OEPFeAc
"90a>2,5P19,20,01

The CONCENTRATION is
0,2

The CONCENTRATION is
H.O.

The CONCENTRATION is

<0,1
<0,1
6With-

1/3 OEPFeAc
"90a3,25P20,30.04

The CONCENTRATION is
2,7

0,8
0,1

The CONCENTRATION is

0,1
0,2
a) the Experience carried out in 50 cm3the Parr reactor, at a pressure of 2000 psig (13790 KP is) 1/4(WITH/N 2gas.

Additional experiments carried out using as ligands N,N-di-tert-butyldiethanolamine (DTBDB), 2,6-bis(N-phenyl, methylamino)pyridine (BPMIP), 1,2-bis(9-phosphabicyclononanes)ethane (B9PBN) and 1,2-bis(diethylphosphino)ethane (BDEPE); the experimental data are shown in table 2. The presence of 1,3-PDO is confirmed in each example.

Table 2
ExampleCatalystSolventTemperature, °The time of absorption of SW (h)The many phases of product (g)Conc. (%)Performance PDO (mmol)Output PDO (molar.%)
PDOHPA
7Co2(CO)8-Fe(CO)5< / br>
DTBDB
1,3-Dioxolane90and1,75P26,00,1

The CONCENTRATION is
0,5

The CONCENTRATION is
0,3

The CONCENTRATION is

0,3
0,3
8Co2(CO)8-Fe(CO)5< / br>
BPMIP
"90a2P27,7The CONCENTRATION is
The CONCENTRATION is
The CONCENTRATION is

The CONCENTRATION is
H.O.

The CONCENTRATION is

The CONCENTRATION is
<0,1
9Co2(CO)8-Fe(CO)5< / br>
B9PBNb
"90a<1P27,50,1

The CONCENTRATION is
1,3

The CONCENTRATION is
0,4

The CONCENTRATION is

0,3
0,5
a) the Experience carried out at a pressure of 2000 psi (13790 kPa) gas 1/4(WITH/N2).

b) Co-Fe ligand pre-treated at 130°C.

N-heterocyclic ligand, 2,2'-dipyridyl (DIPY) used in the examples 10, 11, 14, 16, 17, 18, and 20; Diemen, 2,6-bis(N-phenyl, methylamino)pyridine (BPMIP), in examples 12 and 13, and 2,4,6-trierer-second-triazine (TPTZ) used in example 15, as noted in tables 3 and 4. Phthalocyanine iron(II) is a source of iron in example 19. The presence of 1,3-PDO confirmed.

The combination of the CARBONYLS of cobalt-ruthenium-iron with 2,2'-dipyridil, solvent-based 1,3-dioxolane, used as catalysts in examples 17 and 18. The output values of 1,3-PDO in each of these two examples represent approximately 55% molar with respect to the loading EO.

Table 3
ExampleCatalyst SolventTemperature, °The time of absorption of SW (h)The many phases of product (g)Conc. (%)Performance PDO (mmol)Output PDO (molar.%)
PDOHPA
10Co2(CO)8-Fe(CO)5< / br>
DIPYb
"120and3P28,40,2

The CONCENTRATION is
0,3

The CONCENTRATION is
0,6

The CONCENTRATION is

0,6
0,6
11Co2(CO)8-Fe(NO3)3< / br>
DIPYa
"90a3P26,8The CONCENTRATION is

The CONCENTRATION is
The CONCENTRATION is

The CONCENTRATION is
H.O.

The CONCENTRATION is

<0,1
<0,1
12Co2(CO)8-Fe(CO)5< / br>
BPMIPa
ClC6H5/

C7H8
90a3P24,90.02

0,3
0,2

1,5
0,2

0,3

0,5
0,6
13Co2(CO)8-Fe(CO)5-

BPMIPa
1,3-dioxolane 90a1P25,90,4

The CONCENTRATION is
3,8

0,9
1,3

The CONCENTRATION is

1,3
1,6
a) the Experience carried out at a pressure of 2000 psi (13790 kPa) gas 1/4(WITH/N2)

b) Co-Fe ligand pre-treated at 130°C.

"
Table 4
ExampleCatalystSolventTemperature, °The time of absorption of SW (h)The many phases of product (g)Conc. (%)Performance PDO (mmol)The PDO selectivity (%)Output PDO (molar.%)
PDOHPA
14Co2(CO)8-Fe(CO)5< / br>
DIPY
1,3-dioxolane90and2,25P26,8The CONCENTRATION is

The CONCENTRATION is
0,6

The CONCENTRATION is
The CONCENTRATION is

The CONCENTRATION is

<0,1


The CONCENTRATION is


<0,1
15Co2(CO)8-Fe(CO)5< / br>
TPTZand
90and2,25P27,60.02

The CONCENTRATION is
0,5

The CONCENTRATION is
<0,1

H.O.

<0,1


NO


<0,1
16Co2(CO)8-Fe(NO3)3< / br>
DIPYb
"90a3P26,70,08

The CONCENTRATION is
0,9

The CONCENTRATION is
<0,1

The CONCENTRATION is

<0,1


The CONCENTRATION is


<0,1
17Co2(CO)8-EN3(CO)12-

Fe(CO)5-

DIPYa,c
"90a6,25P29,113,3

1,1
1,3

The CONCENTRATION is
43,8

0,9

44,7


71


55
18Co2(CO)8-EN3(CO)12-

Fe(CO)5-

DIPYa,d
"90a5,50P28,58,0

0,3
1,9

The CONCENTRATION is
28,8

0,2

29,0


64


36
19Co2(CO)8-

Fe(phthalo-cyanin)
"90and 1,25P27,5The CONCENTRATION is

The CONCENTRATION is
0,5

The CONCENTRATION is
The CONCENTRATION is

The CONCENTRATION is

<0,1


The CONCENTRATION is


<0,1
20Co2(CO)8-

Fe(CO)9-

DIPYa
"90and1,25P27,10.04

The CONCENTRATION is
0,6

The CONCENTRATION is
<0,1

The CONCENTRATION is

<0,1


The CONCENTRATION is


<0,1
a) the Experience carried out at a pressure of 2000 psi (13790 kPa) gas 1/4(WITH/N2)

b) Co-Fe-ligand pre-treated at 130°

c) the Initial ratio of Co:Ru:Fe 3:2:1

d) the Initial ratio of Co:Ru:Fe 2:1:1

1. The composition of the catalyst for one-step method of producing 1,3-propane diol, containing

a) component is cobalt; and

b) component is iron, legirovannye ligand selected from the group consisting of residues N-heterocycle, phosphine and perforin.

2. The composition according to claim 1, where component cobalt is selected from salts of cobalt, which is restored to the condition of zero valency by heat treatment in the presence of synthesis gas.

3. The composition according to claim 1 or 2, where component iron represents a carbonyl is ELISA or ORGANOMETALLIC compound of iron.

4. The composition according to claim 1, 2 or 3, where the ligand is selected from the group consisting of monodentate, bidentate and multidentate N-heterocyclic ligands.

5. The composition according to claim 1, 2 or 3, where the ligand is a ligand of the tertiary diphosphine General formula

RRP-Q-PR R'

where each R and R', independently or in combination, is a hydrocarbon residue containing up to 30 carbon atoms, and Q is an organic bridging group of 2-4 atoms in length.

6. The composition according to claim 1, 2 or 3, where the ligand is perforin, which includes four pieces of type pyrrole, in the cyclic structure.

7. Composition according to any one of the preceding paragraphs, where the molar ratio of ligand to the iron atom is from 4:1 to 1:4.

8. The method of obtaining 1,3-propane diol, which includes stages

(a) contacting, in a reaction mixture, ethylene oxide, carbon monoxide, hydrogen, and the molar ratio of hydrogen to carbon monoxide is in the range from 2:1 to 6:1, directionspanel solvent and a catalyst composition containing

(i) component of cobalt; and

(ii) component is iron, legirovannye ligand selected from the group consisting of N-heterocyclic, phosphine and porfiryevich fragments; and

(b) heating this mixture to a temperature of from 30 to 15° C and a pressure of 1500 to 2500 psi (10340 to 17240 kPa), with a two-phase mixture of reaction products containing upper phase, containing more than 50% of the solvent, at least 50 wt.% the composition of the catalyst, plus unreacted ethylene oxide, and the lower phase, which contains more than 50% 1,3-propane diol.

9. The method of claim 8, where the catalyst was prepared using the one-stage method, where all the components are brought together at the same time, in the presence of synthesis gas.

10. The method of claim 8, where the catalyst was prepared Paladino, where iron component interacts with the ligand in the presence of synthesis gas, at temperatures ranging from 25 to 150°and then undergoes a redox reaction with a cobalt component, at a temperature ranging from 25 to 150°C.



 

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11 cl, 3 tbl, 1 dwg, 14 ex

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9 cl, 2 tbl, 2 ex

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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.

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EFFECT: improved method for synthesis.

11 cl, 3 tbl, 1 dwg, 14 ex

FIELD: industrial organic synthesis.

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10 cl, 3 dwg, 6 tbl, 21 ex

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

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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

The invention relates to processes for the oxidized products, namely the processes of obtaining the oxidized products enriched in olefins feedstock

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FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to a nickel-containing catalyst and to a method for the oligomerization reaction of ethylene to a mixture of olefin products with high degree of linearity. Invention describes a composition of catalyst comprising product prepared by interaction of the following components in a polar organic solvent in the presence of ethylene: (a) bivalent nickel simple salt with solubility at least 0.001 mole per liter in indicated polar organic solvent; (b) boron hydride-base reducing agent; (c) water-soluble base; (d) ligand chosen from o-dihydrocarbylphosphinobenzoic acids and their alkaline metal salts; (e) trivalent phosphite wherein the molar ratio of ligand to phosphite is in limits from about 50:1 to about 1000:1. Also, invention describes a method for preparing the catalyst composition and a method for synthesis of a mixture of olefin products showing the high degree of linearity. Invention provides preparing the economically effective catalyst useful in synthesis of olefin substances showing the high degree of linearity.

EFFECT: improved and valuable properties of catalyst.

10 cl, 2 tbl, 3 ex

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