Single-step method for preparing 1,3-propanediol by hydroformylation and hydrogenation

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

 

The invention relates to the synthesis of aliphatic 1,3-diol, in particular 1,3-propane diol, ethylene oxide (hereinafter EO) and synthetic gas in a single stage.

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

In U.S. patent No. 3463819 and 3456017 describes a method for 1,3-propane diol and 3-hydroxypropyl (3-HPA) by hydroformylation of ethylene oxide using the catalyst based on cobalt carbonyl modified tertiary phosphine. In U.S. patent No. 3687981 disclosed a method for the synthesis of PDO. In this way the separation of the phases of the intermediate product hydroxyethylpyrrolidine occurs at room temperature or in the refrigerator before the specified material will be transferred to hydrogenation to obtain a product. U.S. patents№№ 5256827; 5344993; 5459299; 563144; 5463145; 5463146; 5545765; 5545766; 5545767; 5563302 and 5689016, all owned by Shell, describe catalyzed by cobalt hydroformylation of ethylene oxide.

U.S. patent No. 5304691 owned by Shell, discloses a method of hydroformylation of ethylene oxide to 3-hydroxypropane and 1,3-propane diol by close contact of ethylene oxide (EO) - based catalyst of cobalt carbonyl modified diretional phosphine, promoter and a catalyst based on ruthenium and synthetic gas (carbon monoxide and hydrogen) in an inert reaction solvent under the reaction conditions of hydroformylation. It assumes that the lowering of the temperature of the mixture of reaction products will lead to separation of the phases. However, as found, this does not always occur in reality, and in some desirable working conditions under the action of merely lowering the temperature of phase separation does not occur. In this case, for the separation of substances requiring costly methods of extraction liquid-liquid or distillation.

The authors of the present invention discovered another advantage in this area, which is a one-step method of hydroformylation and hydrogenation for the synthesis of PDO, which may be carried out in one phase, the conditions under which phase separation can not coil lowering the temperature used without the I of the present invention. The PDO product can be isolated from the reaction solvent without the use of expensive methods of extraction or distillation, thus making possible the recycling of valuable catalyst hydroformylation, without degradation or impact on what is happening next processes. In addition, this method is extremely effective and allows for greater transformation in the process as the rest of EO in the crude product PDO can be converted using the product as the reaction solvent and the heavy fraction (unwanted by-products that are heavier than PDO) can be displaced from the surface of the catalyst from the system with minimal impact on the catalyst.

The present invention is the one way to obtain 1,3-propane diol by hydroformylation and hydrogenation, which includes:

(a) contacting in a reaction vessel a mixture of ethylene oxide, carbon monoxide, hydrogen, is not miscible with water, the reaction solvent and the composition of the catalyst hydroformylation;

(b) heating the specified reaction mixture to a temperature in the range from 30 to 150°C and a pressure in the range of 0.7 to 27.6 MPa (100-4000 psi), in a period of time effective to obtain a single-phase mixture of the reaction product, terasawa 1,3-propandiol; and

(c) inducing phase separation by using at least one method selected from the group consisting of:

(i) lowering the temperature in combination with the addition to the mixture of the agent inducing the separation of the phases, in a quantity sufficient to induce phase separation, (ii) lowering the temperature in combination with the addition of first co-solvent, increasing the Miscibility, to maintain the mixture of reaction products in one phase, and then remove the co-solvent, increasing the Miscibility, (iii) adding a first co-solvent, increasing the Miscibility, to maintain the mixture of reaction products in one phase, and then remove the co-solvent, increasing the Miscibility, and (iv) adding the agent inducing the separation of the phases, to the mixture of reaction products in an amount sufficient to induce phase separation;

where phase separation leads to a first phase containing the main part of the reaction solvent, at least 50 wt%. composition of catalyst plus unreacted ethylene oxide, and the second phase, which contains the main part of 1,3-propane diol.

The method can be carried out when the second phase also contains the catalyst, reaction solvent and by-products with high molecular weight. The present method may also include the physical and the mental separation of two-phase mixture after induction of phase separation. The method may additionally include the recycling of the first phase directly to the step (a) further interactions with previously unreacted raw materials. The method may further include removing the residual catalyst from the second phase, recycling the specified catalyst in stage (a) and passing the remainder of the second phase containing 1,3-propandiol, in an installation for extraction. Installation for the extraction of 1,3-propane diol can be a distillation column, where the product is 1,3-propane diol is separated from side products with high molecular weight. The method may also include the selection of light solvents from 1,3-propane diol and distillation for separation of individual light solvents and optional recycling of individual light solvent back to the step (a).

Presents a schematic drawing of the method according to the present invention, including several optional features of the process.

In the present invention made some unexpected discoveries, included in the new one-step method of hydroformylation and hydrogenation for the synthesis of PDO, which demonstrates a number of advantages in comparison with all that is available at present in this area. In the present invention, the recycling of the reaction solvent and the cat who lyst if so desired, can be achieved without inhibiting the formation of mixed products. In addition, the remainder of the EO and the catalyst, which is distributed in the selected product may react in such a way that EO is converted to a product.

These advantages are achieved in the present invention, and further improvements can be achieved:

1. Solvent of moderate polarity as the reaction solvent.

2. Increase output by recirculatory EO, so that mass % EO is maintained in the range between 0.2 and 20%, to maintain a high reaction rate and to minimize the commercial cost of the reactor, removing the main part of the EO leaving the reactor, for recirculatory back to the reaction section.

3. Using one or more liquid-phase separation/extraction to facilitate recirculatory EO, and, most importantly, to enrich one of the liquid phases of the PDO in relation to the catalyst. Diagram of the method according to the present invention makes possible a more efficient allocation of PDO by thermal extraction with less impact on the catalyst. In addition, it enables recirculatory significant portion of the catalyst phase of the reaction solvent, depleted PDO, fully PP is I thermal effects. Moreover, this makes it possible to select displaced from the catalyst stream from the bottom of the enriched PDO thread after heat extraction. Decomposed catalyst, as expected, is accumulated in this polar phase, so that it becomes possible selective removal of decomposed catalyst together with heavy byproducts of the reactor in relation to the total amount of the catalyst, thus minimizing the use of very expensive very catalyst hydroformylation.

4. Continuation of hydroformylating the fraction of EO, which goes together with phase enriched PDO, compared with the phase of the reaction solvent, depleted PDO, which may be provided with means to improve the output EO, while requiring thermal recirculatory/distillation EO. Thermal recycling/distillation EO can be dangerous. Thus, phase separation liquid-liquid can be used to recirculatory the main part of the EO in the continuing hydroformylating the fraction that goes along with phase enriched PDO.

5. Re-extraction phase, enriched PDO, in the atmosphere of synthetic gas (using fresh reaction solvent of moderate polarity) to further improve recirculatory catalyst and EO.

the present invention, thus, it provides a significantly simplifiedthe method of pre-separation PDO from recycled catalyst and reaction solvent, concentrating, thus, the desired product PDO before the final stages of purification. This method uses a rather direct selection of the product than the possible introduction of liquid extractant, which subsequently must be removed due to the presence of additional capacity for distillation. This, more direct way, thereby consumes less energy and results in lower capex requirements. The catalyst separated from the PDO and recycled thus the phase separation, is not subject to the influence associated with extraction by thermal evaporation or distillation, or by means of solvent extraction.

When using the method according to the present invention, the decomposition of the catalyst is maintained at a minimum level, because thermal effect is not applied, as in the case of distillation, and not all the amount of the catalyst is subjected to the extraction step. Displacement of the catalyst heavy fractions or by-products from the system can now be achieved with minimum impact on the catalyst. The reaction rate can be increased, as there are more than you the high concentration of EO in accordance with the concept of "final response" to the crude product PDO.

The drawing is a block diagram of the present method. A single, merged or cascading streams of ethylene oxide to 1, synthetic gas (CO/H2) 2 and catalyst 3 load capacity (capacity) 4 for the reaction of hydroformylation, which may represent a reaction chamber of a high pressure, such as a bubble column or autoclave with stirrer working in the boot or in a continuous mode. The reaction takes place with obtaining the target concentration PDO, the distribution of the reaction mixture can be induced by lowering the temperature in the range from about 0 to 90°C. In one of the embodiments of the reaction mixture of 4 at a temperature of approximately 80°C, passes through line 5 to the cooler 6, which preferably is a heat exchanger, is cooled to about 45°C, and then passes through ringrevenue capacity clarifier or separator 8, which may be a tank with overflow, mixer-settler, the coagulator with filter layer or similar capacity. Distribution and sedimentation can be carried out at a pressure within the reaction between pressure and ambient pressure, preferably at reaction pressure and will require time within about 30 minutes. After distribution and ottavianni mixture phase, mainly containing the reaction solvent, unreacted ethylene oxide and most of the catalyst (shown as the upper phase), is recycled to the reactor through line 18. Phase enriched PDO (shown as the lower phase)containing a small amount of the reaction solvent and small amounts of by-products and heavy fractions (with respect to the product), is sent via line 9 into the separation column 10, where light solvents are in the form of the head of the faction for optional recirculatory in the reaction. Sedimentary fraction 13 of the separating column 10 containing PDO and the remainder of the catalyst is sent to the column 18 for the Department of PDO product 19 in the form of a head fraction from by-products with a higher molecular weight, which is brought out through 20. Alternatively, the sedimentary fraction 13 of the separating column 10 may be directed to an optional extractor catalyst 14.

The drawing also depicts several optional features of the present method. For systems with a higher amount of the catalyst variant of the present invention is the inclusion of the extractor catalyst 14, which allows the extraction of the small quantity of catalyst which is present in the phase-enriched product. In this diagram, fresh or recycled rubber is th reaction solvent 27 15 flows countercurrent to the crude product PDO 13 in the tank 14 of the extractor, promoting close contact liquid-liquid, using plates, nozzles or forced stirring, so that the reaction solvent to extract the active catalyst from the crude product PDO. The extracted catalyst is then directed back into the main reactor 4 through line 16 in the flow of the reaction solvent. Also before the separator 8, in addition to the heat exchanger (cooler) 6, an optional evaporator presents the number 23. Optional flow for introduction of an agent inducing the separation of the phases, presents at number 24. Ways to induce and maintain separation of the phases begin with the heat exchanger (cooler) 6, which further lowers the temperature of the product stream of hydroformylation, so in some conditions is the separation of the phases. Optional evaporator 23 can be used to remove co-solvent, increasing the Miscibility, which must be added to induce separation of the phases. The co-solvent, increasing the Miscibility may include, for example, alcohols, short-chain. In an additional thread 24 optional added a small amount of reagent, inducing separation of the phases, to induce separation of the phases after hydroformylation. Agent, inducing separation of the phases, should p is establet a substance, which changes the polarity of the mixture and may include, for example, water or linear alkanes, such as hexane, heptane or dodecane. Stream 25 is an optional recycling additives that induce separation of the phases, the thread 27 is the separation and recycling of MTBE, and the thread 28 is the separation and recycling additional light solvents.

For any combination of schemes stratification of the phases are phase-enriched product PDO, and a phase enriched recycled reaction solvent from the unit 8 for separation of the phases. As mentioned above, the reaction solvent containing the largest portion of unreacted EO and the main part of the catalyst, conveniently be recycled to the reaction hydroformylation through line 16. Data showing a preferred recycling EO and catalyst are presented in table 2. Phase enriched PDO (shown as the heavier phase), from 8 goes in the section of heat extraction, including the column 10 of the separation column 18 of the product and the column 12 of the reaction solvent. In column 18 of the PDO product separates in the form of a head fraction 19, and the heavy fraction plus some remainder of the catalyst is shown in 20 together with ostatecznie fractions from distillation or evaporator 18. The data shown in the columns"% of total" in tables 2 and 4 show, that only a portion of the catalyst is distributed in phase, enriched PDO. This makes possible the removal of heavy fractions through displaced from the catalyst stream 26 losing significantly less catalyst than would be possible using any other scheme. Thus, the loss of expensive single-stage catalyst is significantly reduced. Moreover, it is expected that the active catalyst will preferably be recirculated together with the phase enriched in the reaction solvent, while the catalyst displayed together with ostatecznie factions after the distillation phase, enriched PDO will be enriched by the decomposed catalyst, which preferably should be removed from the system.

The disadvantage of option 23, including a preliminary evaporation before separation of the phases, is that it reduces the number of EO, which is convenient to recycle, and before distillation by evaporation it is necessary to lower the pressure. Other options make it possible to maintain a high pressure within stages of phase disengagement and recirculatory that minimizes the need for the injection pump. Adding a small quantity of the agent inducing the separation of phases after hydroformylation presented at number 24, may help. Agent, inducing separation of the phases would be the output of the sterile, first of all, together with phase enriched PDO will be removed in the distillation section and may, for this reason, it is not necessarily be recirculated again to initiate the separation of the phases.

As indicated, the addition of co-solvent, increasing the Miscibility, with subsequent removal is one of the variants of the control method of phase disengagement. Suitable alcohols and agents that increase the Miscibility include, for example, alcohols, short-chain, such as methanol, ethanol and isopropanol. For example, one of the co-solvents, ethanol, can be added together with an appropriate amount of solvent, if necessary, to bring the PDO product to the desired concentration at the reaction temperature. The co-solvent is used in such an amount which induces solubility, generally in amounts of from 1 to 50 wt%. of the total amount of the mixture of reaction products, preferably 2-20 wt. -%, most preferably 5-20% of the mass.

In the method according to the present invention, shown in the drawing, oxirane containing up to 10 carbon atoms, preferably up to 6 carbon atoms, and ethylene oxide (EO), in particular, can be converted to their corresponding 1,3-diols by reaction of hydroformylation with synthesis gas in the presence of a specified group of complexes catalysts hydroformylation the Oia, as will be described below.

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

The method according to the present invention can operate as a way boot type as continuous or as they are mixed, however, the features of the present invention allow continuous one-step method to work more effectively and efficiently than was possible previously. The method according to the present invention can be carried out in a continuous mode by maintaining homogeneity in the reaction mixture until then, until it reaches the maximum concentration of PDO. Reaction conditions that allow for this include the EO concentration in the reaction mixture, equal to at least about 0.5 wt. -%, and the exception formation of by-products, such as light alcohols and acetaldehyde, or use stage of evaporation to remove these by-products. Response 2-4 reactors with distributed time adding EO is preferred for continuous operation.

R the promotional process involves the conversion of EO in PDO via the intermediate product 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 product 3-hydroxypropane and in the presence of the same systems as catalysts for hydroformylation and hydrogenation. The reaction is carried out under conditions effective to obtain a mixture of the reaction products containing the desired range of maximum concentrations of PDO with relatively small amounts of 3-hydroxypropane (HPA), acetaldehyde and heavy fractions.

For best results, the method is carried out in conditions of high temperature and pressure. The reaction temperature range from ambient temperature up to 150°C, preferably from 50 to 125°C, and most preferably from 60 to 110°C. it is Desirable that the pressure of the reaction (total pressure or partial pressure, if used inert gaseous diluents) were in the range of 5 to 15 MPa, preferably from 8 to 10 MPa. In the boot the way the reaction will be completed within 1.5-5 hours.

The reaction solvent is preferably inert, in the sense that it is not consumed during the reaction. The ideal reaction solvents for the method of the present invention should solubilisate source the materials and products during the reaction, but to make possible the separation of the phases at low temperatures. The ideal reaction solvents must demonstrate polarity from low to moderate to PDO (received and converted in situ) remained in solution throughout the course of the reaction, but it was easily stratified at different phases during cooling. Suitable reaction solvents are described in U.S. patent No. 5304691 included in this description by reference in its entirety. Good results can be achieved using a simple esters, including simple cyclic and acyclic ethers, optionally, in combination with alcohol or aromatic hydrocarbon.

One group of suitable reaction solvent is an alcohol and ethers, which can be described by the formula

R2-O-R1

where R1represents hydrogen or C1-20linear, branched, cyclic or aromatic hydrocarbon radical or a mono - or polyalkylated and R2represents a C1-20linear, branched, cyclic or aromatic hydrocarbon radical, alkoxy, or mono - or polyalkylated. Preferred reaction solvents can be described by the formula

in which R1represents hydrogen or C1-8a hydrocarbon is an organic radical and R 3, R4and R5independently selected from C1-8hydrocarbon radical, alkoxy or accelerated. Such ethers include, for example, methyl tert-butyl ether, ethyl tert-butyl ether, diethyl ether, phenylisopropyl ether, ethoxyethyl ether, diphenyl ether and diisopropyl ether, especially, methyl tert-butyl ether.

Preferably, the EO must be maintained throughout the reaction at a concentration of not less than about 0.2 wt. -%, typically, in the range of 0.2 to 20 wt. -%, preferably, from 1 to 10% of the mass. from the total mass of the reaction mixture. The method according to the present invention can be performed in a continuous mode, while maintaining the specified concentration of EO, for example, distributed over time by adding EO.

Catalysts suitable for use according to the scheme of the single-stage method of the present invention include certain homogeneous bimetallic catalysts containing essentially delegirovano connection carbonyl cobalt and the second metal component of Group VIII, preferably selected from a compound of ruthenium or iron, it is not necessarily very ligand selected from a phosphine ligand, bidentate or multidentate N-heterocyclic ligand, porporino ligand or phospholinoleate ligand.

Suitable sources of cobalt t is the train include salt, being restored to a state of zero valence heat treatment in an atmosphere of hydrogen and carbon monoxide. 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. Workers are also mixtures of such salts of cobalt. However, it is preferable to use a mixture in which at least one component is alkanoate cobalt with 6-12 carbon atoms. The recovery may be carried out before use of the catalyst or it may be carried out simultaneously with hydroformylation in the area of hydroformylation.

Preferred catalysts include, essentially, religiously component of cobalt and legirovannoi connection ruthenium. Such complexes catalysts can be identified at the peaks of the absorption signatures in the infrared spectrum of the composition of the catalyst. Ruthenium can be Legerova diphosphine ligand, multidentate or bidentate N-heterocyclic ligand or class of bis(phospholane)alkanovykh ligands.

The catalysts can be prepared by a multi-stage manner or method of self-Assembly, discussed below.

When does the Andes is a N-heterocyclic compound, the main amount of N-heterocyclic compounds identified as suitable ligands for single-stage synthesis of PDO using a pair of catalysts cobalt-ruthenium. Suitable 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-pyridylketone,

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;

the pyridine, 3-hydroxypyridine and quinoline, in particular, cheaper homologues derived from extracts of coal-tar; and

certain 2,6-pyridylamine, such as

2,6-bis(N-phenyl,methylamino)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). The structure of these three N-heterocyclic compounds are trail is who:

The counterion of cobalt to obtain the best results with ruthenium, legirovannym N-heterocyclic compound, as it is assumed, represents the anion of 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.

In the case where ruthenium Legerova fastenal.com suitable fastlanedaily include phosfolan-substituted alcamovia compounds of formulas I and II below:

where as in formula I and formula II, R represents lower alkyl, trifluoromethyl, phenyl, substituted phenyl, aralkyl or aralkyl substituted in the ring; and n is an integer from 1 to 12; and for formula II represents A CCH3CH, N or P. the Preferred are the compounds of formula I and II where R represents a lower alkyl selected from C1-C6Akilov, and n is 1-3. Most preferred are such compounds of formulas I and II where R is methyl and n is 1-3.

Examples of such compounds 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;

p> 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, for example, 1,2-bis(2R,5R)-2,5-dimethylphosphino]ethane (BDMPE), 1,2-bis[(2S,5S)-2,5-dimethylphosphino]ethane, racemic mixture of these two isomers plus 1,2-bis(phospholane)ethane.

It is also assumed that the anion tetracarbonyl cobalt [Co(CO)4]-is a counterion, suitable for obtaining the best results with phospholinoleate ligand. However, this ion in the active catalyst may be a modification.

System catalysts, which is very effective and is used in examples 1-14 to demonstrate how the stratification of the phases of the present invention is a modified ruthenium catalyst, characterized oxidized metal ruthenium, which Legerova tertiary diphosphine ligand, preferably having delegirovano connection cobalt as counterion.

Containing phosphorus ligand is a tertiary diphosphine General formula

RRP-Q-PR R'

where each R and R', independently or jointly, represents a hydrocarbon residue containing up to 30 carbon atoms, and Q is the battle of the organic bridging group of 2-4 atoms in the chain. The group R or R', when monovalent, can be 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 ring system such as benzene ring or cyclohexane ring. More preferably, Q represents alkylenes group of 2, 3 or 4 carbon atoms in the chain, most preferably 2 carbon atoms in the chain. 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, etc.

These groups R and R', which may be non-substituted groups. Both groups R and/or both groups R' can also obrazovyvat the ring with the atom (atoms) phosphorus, such as phosphacyclohexane of 5-8 atoms. Examples of the 5-ring systems (ligands on the basis of phospholane) 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 a racemic mixture of its isomers, and the like. The ring itself can be a part of multiring system. Examples of such ring systems can be found in the above patent '691 and in International patent WO-A-9842717 included in this description as a reference in their entirety. In the first of them describes phosphabicyclononanes group, and in the last group, such adamantyl, and, in particular, 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 dicretion of phosphine are commercially available. Catalysts derived from them, are known in this field, and the method of their preparation are described in detail in U.S. patent No. 3401204 and 3527818, which are both incorporated herein by reference in their entirety. Phosphine ligands can also be partially oxidized to phosphine oxides way, opican the m in the patent '691.

The ratio of phosphine ligand to the ruthenium atom can vary from 2:1 to 1:2, preferably from 3:2 to 2:3, more preferably from 5:4 to 4:5 and most preferably it is about 1:1. As a hypothesis it is assumed that this results in tricarbonyl connection tertiary diphosphonate, but it can also be pentacarbonyliron compound bis(tertiary diphosphonate). Religiously carbonyl ruthenium, as expected, is an inactive particles, and receiving catalyst from him for this reason should include ligation of each atom of ruthenium.

The counterion for best results, as expected, is tetracarbonyl cobalt[Co(CO)4]-), although ion in the active catalyst may be a modification. The connection part of the cobalt can be modified (excess) tertiary diphosphines, for example, up to 75 mol.%, that is up to 50 mol.% or less. However, the counterion is preferably religiously tetracarbonyl cobalt discussed above. The CARBONYLS of cobalt can be obtained by the reaction of the original source of cobalt, such as cobalt hydroxide, synthetic gas, as described in J. Falbe, "Carbon Monoxide in Organic Synthesis", Springer-Verlag, NY (1970), or otherwise.

Oxidized sostoyanieeee ruthenium is not fully qualified (in theory ruthenium may have a valence of 0 to 8), it can even be changed during the reaction of hydroformylation. Accordingly, the molar ratio of ruthenium to cobalt may vary within relatively wide limits. For complete oxidation of all used ruthenium in the form of complexes must be added a sufficient amount of cobalt (0). Can be added to an excess of cobalt, but not in any particular values. Convenient to the molar ratio was changed from 4:1 to 1:4, preferably from 2:1 to 1:3, more preferably from 1:1 to 1:2.

The reaction mixture should preferably include a promoter and a catalyst to increase the reaction rate. Suitable promoters include one - and polyvalent metal cations of weak bases, such as salts of alkali, alkaline earth and rare earth metals and carboxylic acids and tertiary amines. The promoter, as a rule, must be present in an amount in the range of about 0.01 to about 0.6 mole per mole of cobalt. Suitable metal salts include acetates, propionate and octoate sodium, potassium and cesium; calcium carbonate and lanthanum acetate. Preferred promoters, because of their availability and demonstrated ability to accelerate the conversion of ethylene oxide, are dimethyldodecylamine and triethylamine.

Homogeneous bimetallic catalysis is ora, described above, can be obtained by a multi-stage method, as described below. In the scope of the present invention is also getting complex catalyst by the method of self-Assembly, where all the components of the catalyst are administered together at the same time, but the conditions and, in particular, the solvent is chosen in such a way as to promote the formation of particles very ruthenium faster than particles very cobalt.

In multi-stage procedure, first get component very ruthenium, and then to the solution of a complex of ruthenium adds a component of cobalt carbonyl and any promoter. Ruthenium complex is formed by the interaction of ruthenium carbonyl, such as dodecacarbonyl carotene, with the stoichiometric quantity of the selected ligand. The reaction is carried out in a solvent in which any intermediate compounds of the catalyst are soluble. The solution is heated to a temperature in the range of about 90 to about 130°C, preferably from about 100 to about 110°C in an atmosphere of carbon monoxide for a time sufficient to complete the reaction of the ligand to the ruthenium, usually from about 1 to about 3 hours. Selected carbonyl cobalt and any promoter is then added to the solution very ruthenium carbonyl and a solution to support the ri elevated temperature for a time equal to from about 15 to about 60 minutes.

In the method of self-Assembly by carefully selecting the precursors of catalyst and solvent to obtain a catalyst is essential for obtaining the desired composition of the final catalyst. For ligand is a necessary interaction with the carbonyl ruthenium to obtain any carbonyl cobalt (0) recovery. Obtaining the catalyst by self-Assembly is performed by the Association in the solvent cobalt salts, such as octanoate cobalt, ruthenium carbonyl (0), such as dodecacarbonyl carotene, and ligand for ruthenium. The original ingredients are present in the ratio of Co:Ru, in the range of about 1:0.15 to about 1:2, preferably 1:2, and the ratio of Ru:ligand, in the range of about 1:0.16 to about 1:1. The solution is heated at a temperature in the range of about 110 to about 130°C in a reducing atmosphere, such as CO:H21:4, in a period of time effective to complete, essentially, ligation of ruthenium, usually from about 1 to about 3 hours.

The optimal ratio of the original oxirane and bimetallic complexcatalyst depends in part on the specific complex. However, the molar ratio of oxirane and cobalt in the complex catalyst is from 2:1 is about 10000:1, as a rule, are satisfactory, with molar ratios of from 50:1 to 500:1 are preferred.

In conclusion, in relation to the reaction of hydroformylation of the present invention, the mixture of products is preferably removed by separation of the phases, followed by several stages of distillation, to make possible the recycling of unreacted starting materials and a catalyst and a reaction solvent for further use. The present invention is industrially viable method with an effective extraction of the catalyst and with many cycles, essentially, full recirculatory catalyst in the reaction. The preferred method of extraction of the catalyst involves separating liquid two-phase mixture above the recycling of the total phase of the reaction solvent in the reactor and returning with him, at least from 60 to 90% of the mass. the original catalyst.

In the preferred implementation of the present method, the reaction conditions such as concentration of oxirane, concentration of catalyst, reaction solvent, the concentration of the products, the reaction temperature and the like, chosen so as to obtain a homogeneous reaction mixture at elevated temperatures and cause the distribution of reaction the th mixture in the phase of the reaction solvent, containing most of the catalyst, and cooling the mixture in the second phase, containing most of 1,3-propane diol. This distribution facilitates the selection and extraction of the product, the recycling of the catalyst and removal of heavy fractions from the system of reaction solvents. This method is considered as the method of separation of the phases, with recycling of the catalyst/removing product.

In this way the contents of the reactor provide an opportunity to settle or move into a suitable container under pressure, equal to the reaction pressure or close to it, where minor or major cooling may be formed of different phases that differ significantly, being significantly enriched in the product or catalyst and reaction solvent. Phase enriched catalyst and reaction solvent, directly recycle for further interaction with the input source materials. The product is extracted from the phase-enriched product in the usual way.

It is important that this reaction was carried out so that the diol product was maintained at levels of concentration in the reaction mixture, suitable for phase separation. Preferably, the concentration of 1,3-propane diol is from 1 to 50 wt%. of the total amount of the mixture of the product of the reaction. More preferably, the concentration of 1,3-propane diol is from 8 to 32% of the mass. of the total amount of the mixture of reaction products. Most preferably, the concentration of 1,3-propane diol is from 16 to 20% of the mass. of the total amount of the mixture of reaction products.

Temperature during a peaceful settling of the phases should be in the range between a temperature slightly above the freezing point of the reaction mixture, and the temperature is at least 10°C less than the temperature of the reaction. Preferably, the temperature during separation of the phases is reduced by 10-100°C, depending on the reaction temperature, and preferably from 10 to 40°C. Preferably, the temperature during separation of the phases must be from 27 to 97°C, most preferably from 37 to 47°C.

Supported the concentration of EO, which prevents the formation of light alcohols and aldehydes, which are agents that increase the Miscibility. Preferably, oxirane must be maintained throughout the reaction at a concentration of not less than approximately 0.2% of the mass. of the total amount of the mixture of reaction products, typically in the range of 0.2 to 20 wt%. of the total amount of the mixture of reaction products, preferably from 1 to 10% of the mass. of the total amount of the mixture of reaction products.

The reaction can be carried out using dwuhfazno the system. However, the yield and selectivity are communicated to the maximum, when high concentrations of the product are present in a single-phase reaction and subsequent separation of the phases is carried out by cooling.

In addition to lowering the temperature of the separation of the reaction mixture can be facilitated by adding an agent which induces separation of the phases. This agent must be added to the reaction mixture in a quantity in the range of about 2 to 20 wt. -%, preferably, from 2 to 10% of the mass. and most preferably, from 4 to 8% of the mass. in relation to the total number of the reaction mixture. Suitable agents include, but are not limited to, glycols such as ethylene glycol and linear alkanes, such as hexane and dodecane.

The optimal number of each agent, inducing separation of the phases will vary and can be determined by simple experimentation. For example, hexane induces a distribution of the reaction mixture, when present in the reaction solvent, based on methyl tert-butyl ether at a concentration of about 16% of the mass. in relation to the total amount of the reaction solvent. For this reason, the primary reaction solvent and any agent, inducing separation of the phases, will influence the behaviour of the reaction mixture at its distribution.

The distribution can be OS the employees adding PDO in the reaction mixture, bringing the product concentration to the desired proportions. Also increases the Miscibility alcohols and agents with similar polarity, such as ethanol, propanol and isopropanol can be added first (co-solvent, increasing the Miscibility), and then removed before following the induction of phase separation. For example, under normal reaction conditions in the reaction solvent, based on methyl tert-butyl ether homogeneous concentration PDO, approximately 16% of the mass. at about 70°C, will lead to the distribution of the reaction mixture in a phase enriched reaction solvent, and the temperature drops to about 43°C in phase enriched PDO. Ethanol contributes to the distribution of the mixture of reaction products at a concentration in the range of about 5 to about 8% of the mass.

The industrial mode of operation requires efficient extraction of the catalyst through many cycles, essentially, full recirculatory catalyst in the reaction. The preferred method of extraction of the catalyst involves separating liquid two-phase mixture above and recycling volume phase reaction solvent in the reactor and, at the same time, the return, at least from 60 to 90% of the mass. the original catalyst.

The following examples serve to further illustrate the present image is to be placed, disclosed in this description. The examples are intended for illustration only and should not be construed as limiting in any way the scope of the present invention. The person skilled in the art will obviously many option, which can be incorporated without deviating from the essence of the described invention.

Experimental part

Table 1 lists the categories of materials, drugs and abbreviations used in the examples.

Table 1

Materials and preparations
Source CoCoOcOctoate cobalt
DCOOctacarbonyl of dicobalt
Source ENTRCDodecacarbonyl carotene
BRCCBis(tricarbonyl ruthenium)
The ligandB9PBN-21,2-P,P'-Bis(9-phosphabicyclononanes)ethane
BDEPE1,2-Bis(diethylphosphino)ethane
BDIPE1,2-Bis(Diisobutylene)ethane
BDOPE1,2-Bis(2,4,4-trimethylpentane)ethane
BDMPER,R) 1,2-Bis(dimethylphosphino)ethane
The reaction solventMTBE T/CBMethyl tert-butyl ether

5:1 volume/volume mixture of toluene/chlorobenzene
OxiranEOThe ethylene oxide
The promoterDMDADimethyldodecylamine
NaAcSodium acetate

Example 1

The method of separation of the phases, with recycling of the catalyst and/or extraction of the product with a catalyst obtained by self-Assembly

In a 300-ml autoclave in Boxing with dried and purified inert atmosphere add 1.85 grams (5,35 mmol Co) ethylhexanoate cobalt(II), 1,392 grams (4,48 mmol) 1,2-bis(9-postalcohol)ethane, 0,509 g (2.3 mmol Ru) dodecacarbonyl carotene, 145,85 grams of methyl tert-butyl ether (MTBE) and 0.30 gram of dimethyldodecylamine. The body of the autoclave is sealed and attached to the laboratory process unit. When the pressure of synthesis gas having a ratio of H2:CO 4:1 to 1500 psig (10,3 MPa), in the upper part of the tank mixture is allowed to reach equilibrium and to provide a catalyst for 2 hours at 130°C. the reactor Temperature is reduced to 90°C. Add 16,96 grams of ethylene oxide (EO) and give him the opportunity to interact with the input synthetic gas is within the ratio of H 2:CO = 2:1, up until EO essentially, but not completely used. The contents of the reactor are transferred into the reaction conditions in the tank for phase separation, which begins the separation of the phases. From the tank allocate 12,94 gram of material of the bottom layer. The reaction mother liquor from the upper layer recycle back to the reactor. The composition of the upper and lower layer are shown in table 2. Data on the distribution of the catalyst are presented in table 3. The product, 1,3-propandiol, produced at an average speed of 20 g/l/h.

Example 2

The method of phase separation, Recycling 1

Recycled reaction liquid of example 1 are heated to 90°C. Add 14,74 grams of ethylene oxide and give him the opportunity to interact in an atmosphere of synthesis gas having a ratio of H2:CO = 2:1, in the upper part of the vessel at 1500 psi (10,3 MPa), up until EO essentially not used. The contents of the reactor are transferred under pressure synthetic gas in the tank for phase separation, which begins the separation of the phases, which leads to the selection by 8.22 grams of the material of the lower layer. The reaction liquid from the upper layer recycle back to the reactor. The composition of the upper and lower layer are shown in table 2. Data on the distribution of the catalyst are presented in tab is itzá 3. The average reaction rate for this recycling is 14 g/l/h.

Example 3

The method of phase separation, Recycling 2

Recycled reaction mother liquor from example 2 is heated to 90°C. Add 14,74 grams of ethylene oxide and give him the opportunity to interact in an atmosphere of synthesis gas having a ratio of H2:CO = 2:1, in the upper part of the vessel at 1500 psi (10,3 MPa). The contents of the reactor are transferred under pressure synthetic gas in the tank for phase separation, which begins the separation of the phases, and allot of 8.50 grams of the material of the lower layer. The reaction mother liquor from the upper layer recycle back to the reactor. The composition of the upper and lower layer are shown in table 3. Data on the distribution of the catalyst are presented in table 3. The average reaction rate for this recycling is 37 g/l/h.

Example 4

The method of phase separation, Recycling 3

Recycled reaction liquid from example 3 is heated to 90°C. Add 14,74 grams of ethylene oxide and give him the opportunity to interact in an atmosphere of synthesis gas having a ratio of H2:CO = 2:1, in the upper part of the vessel at 1500 psi (10,3 MPa). The contents of the reactor are transferred under pressure synthetic gas in the tank section is of phases, where begins the separation of the phases, and produce 19.50 grams of the material of the lower layer. The reaction mother liquor from the upper layer recycle back to the reactor. The composition of the upper and lower layer are shown in table 2. Data on the distribution of the catalyst are presented in table 3. The average reaction rate for this recycling is 49 g/l/h.

Example 5

The method of phase separation, Recycling 4

Recycled reaction liquid of example 4 is heated to 90°C. Add 14,74 grams of ethylene oxide and give him the opportunity to interact in an atmosphere of synthetic gas with the ratio of H2:CO = 2:1, in the upper part of the vessel at 1500 psi (10,3 MPa). The contents of the reactor are transferred under pressure synthetic gas in the tank for phase separation, where separation begins, and allocate 32,80 gram of material of the bottom layer. The reaction mother liquor from the upper layer recycle back to the reactor. The composition of the upper and lower layer are shown in table 2. Data on the distribution of the catalyst are presented in table 3. The average reaction rate for this recycling is 34 g/l/h.

Example 6

The method of phase separation, Recycling 5

Recycled reaction liquid of example 5 is heated to 90°C. Add 14,74 gr the MMA of ethylene oxide and give him the opportunity to interact in an atmosphere of synthetic gas, with the ratio of H2:CO = 2:1, in the upper part of the vessel at 1500 psi (10,3 MPa). The contents of the reactor are transferred under pressure synthetic gas in the tank for phase separation, which begins the separation of the phases, and produce 71,90 gram of material of the bottom layer. The reaction liquid from the upper layer recycle back to the reactor. The composition of the upper and lower layer are shown in table 2. Data on the distribution of the catalyst are presented in table 3. The average reaction rate for this recycling is 30 g/l/h.

The three most important result of phase separation are: 1) achieving acceptable fairly high speed receive PDO 2) recycling of the greatest parts of catalyst (upper phase) and 3) removing the concentrated product (PDO) in the lower phase.

Data on the rate of production of PDO in the examples above demonstrate that an acceptable reaction rate and that the catalyst is active after 5 recyclo (#1).

Table 3 shows that a high percentage of catalyst is recycled directly into the upper phase (#2).

Table 2 shows high recovery of PDO in the lower phase of the product and high recycling EO in the upper, recycled phase (#3).

the table 2

The primary composition in the stratification of the phases
ExampleLayerPDO

wt. -%
MTBE

wt. -%
Weight

(g)
% availability. EO
1Bottom59,7018,1312,94*--
2Bottom47,9716,60by 8.22*--
3Bottom45,9719,158,50*--
4Bottom47,3221,7319,50at 7.55
5Bottom45,1620,9932,8010,55
6Bottom47,5025,7871,9025,06
1Top4,7485,70shall be 152.3 6*--
2Top5,1587,16160,04*--
3Top17,6777, 60167,19*--
4Top27,3154,86163,4792,45
5Top14,4169.85 mm147,0489,45
6Top10,5980,3693,4674,94
* Reactions where EO purposefully communicates to acquisitions

Table 3

Data on the distribution of catalyst
ExampleLayer% of available catalyst (Co;Ru)
1Top90; 88
2Top91; 88
3Top93; 91
4Top82; 75
5Top78; 71
6Top61; 75
1Bottom10; 12
2Bottom9; 12
3Bottom7; 9
4Bottom18; 25
5Bottom21; 29
6Bottom38; 25

Example 7

Separation of phases with recycling of the catalyst and/ or extraction of the product with a catalyst obtained stepwise method.

In a 300-ml autoclave in Boxing with dried and purified inert atmosphere add 2.14 grams (6,90 mmol) 1,2-bis(9-postalcohol)ethane, 0,694 g (3.25 mmol Ru) dodecacarbonyl carotene, 119 grams of methyl tert-butyl ether (MTBE). The body of the autoclave is sealed and attached to the laboratory process unit. In the upper part of the vessel at a pressure of 1500 psi (10,3 MPa) synthetic gas having a ratio (H2:CO)equal to 4:1, the mixture was allowed to reach equilibrium for 1 hour at 105°C. In the reactor under the reaction conditions add a solution of 1.11 g (6,50 mmol Co) octacarbonyl of dicobalt and to 0.108 gram (1,32 mmol) of sodium acetate in 33.3 grams of MTBE. The catalyst provides the opportunity to work at 105°C and 1500 psi (10,3 MPa) for 1.75 hours. The reactor temperature was lowered to 90°C. Conduct two separate add in General 13.2 g of ethylene oxide (EO) and give him the opportunity to interact with the input synthetic gas having a ratio (H2:CO = 2:1, up until essentially the entire EO will not be spent. Contents Rea the Torah is transferred under pressure synthetic gas in the tank for phase separation temperature-controlled. The partial phases provide an opportunity to balanced at 43°C. the Lower phase, 36.8 grams, is separated. The upper phase recycle back to the reactor. The composition of the upper and lower phase are given in table 4. Data on the distribution of the catalyst are presented in table 5. The product, 1,3-propandiol get at an average speed of 26 g/l/h.

Example 8

The method of phase separation, Recycling 1

Recycled reaction liquid of example 7 is heated to 90°C. Add 14,74 grams of ethylene oxide and give him the opportunity to interact in an atmosphere of synthesis gas having a ratio of H2:CO = 2:1, in the upper part of the vessel at 1500 psi (10,3 MPa). The contents of the reactor are transferred under pressure synthetic gas in the tank for phase separation. After equilibration at 43°C separate 28.5 grams of the material of the lower phase. The reaction mother liquor from the upper phase recycle back to the reactor. The composition of the upper and lower phase are given in table 4. Data on the distribution of the catalyst are presented in table 5. The average reaction rate for this recycling is 24 g/l/h.

Example 9

The method of phase separation, Recycling 2

Recycled reaction liquid of example 8 was heated to 90°C. Type of 11.00 grams of ethylene oxide and give him the opportunity mutual is to act in an atmosphere of synthetic gas, 2:1, in the upper part of the vessel at 1500 psi (10,3 MPa). The contents of the reactor are transferred under pressure synthetic gas in the tank for phase separation. After equilibration at 43°C allocate 24.8 grams of the material of the lower phase. The reaction mother liquor from the upper phase recycle back to the reactor. The composition of the upper and lower phase are given in table 4. Data on the distribution of the catalyst are presented in table 5. The average reaction rate for this recycling is 35 g/l/h.

Example 10

The method of phase separation, Recycling 3

Recycled reaction mother liquor from example 9 was heated to 90°C. Type of 11.00 grams of ethylene oxide and give him the opportunity to interact in an atmosphere of synthetic gas, 2:1, in the upper part of the vessel at 1500 psi (10,3 MPa). The contents of the reactor are transferred under pressure synthetic gas in the tank for phase separation. After equilibration at 43°C allocate 19.1 per gram of material of the lower phase. The reaction mother liquor from the upper phase recycle back to the reactor. The composition of the upper and lower phase are given in table 4. Data on the distribution of the catalyst are presented in table 5. The average reaction rate for this recycling is 23 g/l/h.

Example 11

The method of phase separation, Recycling 4

Re erculiani reaction mother liquor from example 10 was heated to 90° C. Type of 11.00 grams of ethylene oxide and give him the opportunity to interact in an atmosphere of synthetic gas, 2:1, in the upper part of the vessel at 1500 psi (10,3 MPa). The contents of the reactor are transferred under pressure synthetic gas in the tank for phase separation. After equilibration at 43°C allocate for 38.9 grams of the material of the lower phase. The reaction mother liquor from the upper phase recycle back to the reactor. The composition of the upper and lower phase are given in table 4. Data on the distribution of the catalyst are presented in table 5. The average reaction rate for this recycling is 18 g/l/h.

Example 12

The method of phase separation, Recycling 5

Recycled reaction mother liquor from example 11 was heated to 90°C. Type of 11.00 grams of ethylene oxide and give him the opportunity to interact in an atmosphere of synthetic gas, 2:1, in the upper part of the vessel at 1500 psi (10,3 MPa). The contents of the reactor are transferred under pressure synthetic gas in the tank for phase separation. After equilibration at 43°C allocate for 38.9 grams of the material of the lower phase. The reaction mother liquor from the upper phase recycle back to the reactor. The composition of the upper and lower phase are given in table 4. Data on the distribution of the catalyst are presented in table 6. Average speed reaktsii during this recycling is 17 g/l/h.

Data on the rate of production of PDO in the examples above demonstrate that an acceptable reaction rate and that the catalyst is active after 5 recyclo (#1).

Table 5 shows that a high percentage of catalyst is recycled directly into the upper phase (#2).

Table 4 shows high extraction PDO in the lower phase (#3).

Table 4

The primary composition in the stratification of the phases
ExampleLayerPDO

wt. -%
MTBE

wt. -%
Weight

(g)
% availability. EO
7Bottom63,6816,1524,807,03
8Bottom49,6817,3928,50to 11.52
9Bottom68,0818,0324,8013,45
10Bottom53,3424,3119,1015,97
11Bottom33,3219,3938,9022,36
12Bottom30,0325,9129,8033,07
7Top7,2044,63165,0792,97
8Top8,8961,35152,7388,48
9Top36,6948, 66139,0986,55
10Top16.88 in54,86131,4284,03
11Top6,1486, 65104,9277,64
12Top27,3034,5788,1266,93

12
Table 5

Data on the distribution of catalyst particles
ExampleLayer% of available catalyst (Co;Ru)
7Top70; 67
8Top82; 68
9Top85; 72
10Top89; 73
11Top67; 63
Top73; 73
7Bottom30; 33
8Bottom18; 32
9Bottom15; 28
10Bottom11; 27
11Bottom33; 37
12Bottom27; 27

Example 13

Recycling is received by a multi-stage method of catalyst from the lower phase

Samples of the bottom layer of examples 7 and 8, enriched product 1,3-propane diol is distilled off at 90-110°C in vacuum conditions, 60-4 mm Hg In the upper part of the vessel selected reaction solvent based on methyl tert-butyl ether and 1,3-propane diol. Material head of the faction more than 92% is a 1,3-propandiol. The distillation is carried out so that Argonauts 75% of the mass of the initial load. A 10-Gram sample of the bottom fraction from the distillation containing recycled catalyst, a certain amount of 1,3-propane diol and small amounts of heavy fractions, loaded into a 300-ml autoclave in Boxing with dried and purified inert atmosphere. In the autoclave added 74 grams of fresh reaction solvent based tert-is etilovogo ether. The autoclave is pressurized and attached to the laboratory process unit. Uterine fluid with a catalyst heated to 90°C under stirring. When the pressure of synthesis gas having a ratio of H2:CO = 4:1, in the upper part of the vessel type of 11.00 grams of ethylene oxide and give him the opportunity to interact. The contents of the reactor are transferred under pressure synthetic gas in the tank for separation of the phases, where at 45°C begins the separation of the phases. After equilibration allocate 12.6 grams of the material of the lower phase. This lower phase contains 56,47% product 1,3-propane diol. The reaction mother liquor from the upper phase recycle back to the reactor and heated to 90°C at a pressure of synthesis gas having a ratio (H2:CO = 2:1, in the upper part of the vessel. This phase is recycled to the reaction solvent type of 11.00 grams of ethylene oxide and provide an opportunity to interact. The contents of the reactor are transferred under pressure synthetic gas in the tank for phase separation, where 43°C begins the separation of the phases. After equilibration allocate 24.5 grams of the material of the lower phase. This lower phase contains 45,14% product 1,3-propane diol. These reactions give a yield of 81%. This proves that the catalyst remains strong and is still active even after about the race of the product phases and two recirculatory through the upper phase following reactions.

Example 14

Using hexane as an agent for inducing separation of the phases

In a 300-ml autoclave in Boxing with dried and purified inert atmosphere add 1,159 g (3.73 mmol) of 1,2-bis(9-postalcohol)ethane, 0,696 grams (with 3.27 mmol Ru) dodecacarbonyl carotene, 119 grams of methyl tert-butyl ether (MTBE). The body of the autoclave is sealed and attached to the laboratory process unit. At a pressure of 1500 psi (10,3 MPa) synthetic gas having a ratio of H2:CO = 4:1, in the upper part of the tank mixture is allowed to reach equilibrium for 1.5 hours at 105°C. In the reactor under the reaction conditions add a solution of 1.13 g (6,50 mmol Co) octacarbonyl of dicobalt and to 0.108 gram (1,32 mmol) of sodium acetate in 33.3 grams of MTBE. The catalyst allows you to work at 105°C and 1500 psi (10,3 MPa) for 1.75 hours. The reactor temperature was lowered to 90°C. have one added 22 grams of ethylene oxide (EO) and give him the opportunity to interact with the input synthetic gas having a ratio (H2:CO)equal to 2:1. The contents of the reactor are transferred under pressure synthetic gas in the tank for phase separation temperature-controlled. Enable trim phase separation at 43°C. Distinguish 9,746 gram of the lower phase. The upper phase recycle the back to the reactor. By a similar method to the above examples recycled to the top layer add a further ethylene oxide and give him the opportunity to interact with the subsequent separation of the phases, induced by temperature. On the third cycle of this example, add 11,00 grams of ethylene oxide and give him the opportunity to interact at 90°C and 1500 psi (10,3 MPa). Transfer to a container for phase separation and subsequent cooling to 35°C not give visible phase separation. Two separate add aliquot on 11,00 grams of ethylene oxide with subsequent interaction within set conditions and cooling to 33°C does not give a concentration of 1,3-propane diol, which may be implemented separation of phases. Assume that this reaction leads to some side-products such as ethanol and propanol, which by their nature increase the Miscibility and which prevent separation of the phases. Add 10 grams of hexane, when the mixture is in the reactor, in specified conditions and then migrate into the separation tank and cooling induces phase separation at 77°C. It is one of the ways to change the polarity of this system, so that could be the induction stratification of the phases. It seems even possible to add, to the reaction or during it, Agay is tov, increasing Miscibility, to ensure the passage of a single-phase reaction. Then agents that increase the Miscibility can be removed, for example, by distillation or evaporation inducyruya stratification of the phases to extract the product. After equilibration to 43°C distinguish the pattern of the lower layer in 92.7 grams, containing 48% of the product 1,3-propane diol.

1. One way to obtain 1,3-propane diol by hydroformylation and hydrogenation, which includes:

(a) contacting in a reaction vessel a mixture of ethylene oxide, carbon monoxide, hydrogen, is not miscible with water, the reaction solvent and the composition of the catalyst hydroformylation;

(b) heating the specified reaction mixture to a temperature of from 30 to 150°and at a pressure of from 0.7 to 27.6 MPa (100-4000 lb/in2in a period of time effective to obtain a single-phase mixture of reaction products containing 1,3-propandiol; and

(c) inducing phase separation by using at least one method selected from the group consisting of:

(i) lowering the temperature in combination with the addition to the mixture of the agent inducing the separation of the phases, in a quantity sufficient to induce phase separation, (ii) lowering the temperature in combination with the first addition of co-solvent, increasing smeshame the ü, to maintain the mixture of reaction products in one phase and then remove co-solvent, increasing the Miscibility, (iii) first, add a co-solvent, increasing the Miscibility, to maintain the mixture of reaction products in one phase and then remove co-solvent, increasing the Miscibility, and (iv) adding the agent inducing the separation of the phases, to the mixture of reaction products in a quantity sufficient to induce phase separation;

where phase separation results in the first phase containing the main part of the reaction solvent, at least 50 wt.% composition of catalyst plus unreacted ethylene oxide, and the second phase, which contains the main part of 1,3-propane diol.

2. The method according to claim 1, where the second phase also contains the catalyst, reaction solvent and by-products with high molecular weight.

3. The method according to claim 1, additionally including the physical separation of two-phase mixture after the induction phase separation.

4. The method according to claim 3, further comprising recycling the first phase directly to the step (a) further interactions with previously unreacted raw materials.

5. The method according to claim 3 or 4, further comprising extracting the residue of the catalyst from the second phase, recycling the specified catalyst is as in stage (a) and passing the remainder of the second phase, containing 1,3-propandiol, in an installation for extraction.

6. The method according to claim 5, where the plant is to extract 1,3-propane diol is a distillation column, where the product is 1,3-propane diol is separated from by-products with high molecular weight.

7. The method according to claim 3, further comprising the separation of light solvents from 1,3-propane diol and distillation to separate the individual light solvents and optional recycling of individual light solvent back to the step (a).

8. The method according to claim 1, where the temperature during the phase separation ranges from 27 to 97°C.

9. The method of claim 8, where the temperature during the separation of the phases is from 37 to 47°C.

10. The method according to claim 1, where the temperature during the phase separation ranges from 27 to 97°C, the concentration of 1,3-propane diol is from 1 to 50% of the total amount of the mixture of reaction products and the concentration of oxirane is more than 0.2% of the total amount of the mixture of reaction products.

11. The method according to claim 10, where the temperature during the separation of the phases is from 37 to 47°C, the concentration of 1,3-propane diol is from 8 to 32% of the total amount of the mixture of reaction products and the concentration of oxirane is from 0.2 to 20% of the total amount of the mixture of reaction products.



 

Same patents:

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to production of alkylene glycols used as components of low-freezing, anti-icing, hydraulic fluids, and braking fluids and also used in production of solvents, plasticizers, and materials employed to obtain materials used in areas of plastics, pesticides, varnishes, and paints. Process resides in hydration of alkylene oxides at elevated temperatures and pressure in reactor or a series of reactors in presence of catalytic system based of anion-exchange resins in salt form. Process is conducted while periodically redistributing stream with maximum alkylene oxide concentration across reactor or reactors of reactor series. Typically, hydration process is conducted in a series of displacement-type reactors interconnected in consecutive-parallel chain with fractional (distributed) alkylene oxide supply to reactors of reactor series. Typically, redistribution of the stream with maximum alkylene oxide concentration through reactors of reactor series is accomplished by periodically switching supply of the stream with maximum alkylene oxide concentration from one reactor to another. Generally, hydration process is conducted in presence of inorganic and/or organic acids, and/or their salts, and/or carbon dioxide.

EFFECT: reduced catalyst swelling rate.

5 cl, 4 dwg, 2 tbl, 29 ex

FIELD: organic chemistry, in particular improved method for production of alkylene glycol useful in antifreeze compositions, as solvent and starting material for production of polyalkylene terephthalate.

SUBSTANCE: starting mixture containing corresponding alkylene oxide and water is fed into reactor through at least one inlet, wherein reactor contains fixed bed of solid catalyst based on anion exchange resin. Mixture of reaction products containing alkylene glycol and non-reacted starting material is discharged through at least one outlet and at least one mixture part is recycled into at least one inlet or the same reactor.

EFFECT: decreased catalyst swelling and increased durability thereof.

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.

2 cl, 1 ex

Glycol purification // 2264377

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.

EFFECT: reduced content of aldehydes and improved transmission characteristics in UV region.

5 cl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for chemical reutilization of depleted polyethylene terephthalate, especially to non-classified crumbs of utilized polyethylene terephthalate articles resulting to preparing terephthalic acid and ethylene glycol. Method involves hydrolysis of utility waste polyethylene terephthalate with aim for its depolymerization and involves the following steps: (a) separation of polyethylene terephthalate component in the parent raw by its transfer to fragile form by using crystallization, grinding and the following screening processes; (b) continuous two-step hydrolysis of polyethylene terephthalate carried out at the first step by injection of steam into polymer melt followed by carrying out the hydrolysis reaction of products from the first step with ammonium hydroxide and by the following (c) precipitation of terephthalic acid from aqueous solution of hydrolysis products from the second step with inorganic acid and separation of terephthalic acid by filtration method and by the following (d) extraction of ethylene glycol by rectifying from solution of the second step hydrolysis products after separation of terephthalic acid. This technologically simple and effective method provides possibility for treatment of very contaminated the parent raw and providing high purity of end products.

EFFECT: improved treatment method.

5 cl, 1 ex

FIELD: methods of production of 1.3 alkandiol.

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

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

9 cl, 2 tbl, 2 ex

FIELD: 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

The invention relates to a method distillative get monoethylene glycol of high purity of the product of hydrolysis of ethylene oxide using a bog of water under pressure, vacuum Stripping of water and subsequent distillative purification, characterized in that at least the first Stripping column under pressure in the cascade equipped with a distillation unit having at least one degree of separation, and part of the flow of the top of the column (columns) bog water under pressure, equipped with(local) unit of distillate, derived from the process, the temperature in the zone below the point of input power in the first column of the cascade is more than 80With, and the pressure in the distillation unit is at least 1 bar

The invention relates to an improved method of cleaning and selection of water-glycol solution from used antifreeze to cooking fluids and antifreeze fluids comprising adding a coagulant to the exhaust antifreeze, followed by filtration through a sand filter, then clean the adsorbent is activated carbon, and after adding coagulant addition carry out stage centrifuge separator, and as a coagulant products of oxidation and corrosion of waste antifreeze using a hydroxide of an alkali metal, 75% phosphoric acid, carbonate of alkaline metal and sodium sulfate, in the following ratio, wt.%: sodium hydroxide (caustic soda) or potassium 0,01-1,0; phosphoric acid 75% 0,02-1,6; sodium carbonate or potassium (potash) of 0.05-0.5; sodium sulfate 0,01-0,07; glycols of 40.0 to 90.0; water products of oxidation and corrosion rest

The invention relates to a new method of joint receipt of 1,1,3-trialkyl-1,5-pentandiol formula (1) and 1,1,4-trialkyl-1,5-pentandiol formula (2)

where the values of R, R1and R2in formulas (1) and (2) are the same and are selected from R=n-C4H9n-C6H13, R1=CH3WITH2H5, R2=C2H5the h4H9consists in the fact that it is held in the atmosphere of inert gas interaction-olefin of General formulawhere R=n-C4H9the h6H13with triethylaluminium in the presence of a catalyst - zirconatetitanate Cp2ZrCl2in a molar ratio:AlEt3:Cp2ZrCl2=10:(10-14):(0,3-0,7) at room temperature, and then cooling the reaction mixture, adding a catalyst - odnoklasniki copper and ketone of formula R1C(O)R2where R1=CH3WITH2H5, R2=C2H5n-C4H9in a molar ratio of CuCl:R1C(O)R2=(0,8-1,2):(10-14), and stirring at room temperature, with the latter the

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

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

The invention relates to a method for producing a mixture of C9-alcohols for plasticizers of olefins, comprising the dimerization in the presence of a solid catalyst based on phosphoric acid olefinic feedstock containing butene and possibly, propene, and having a molar ratio of butene from the overall content of olefins of at least 50%, and the content of isobutene in the butene is not more than 55%, while the temperature of the reactor output maintained within the range of from 200 to 235oC, spatial speed is not more than 4.1 DM3/h/kg-catalyst ozonirovanie olefinic dimer and the hydrogenation product oksanalove

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

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, 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: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of alcohol comprising synthesis of olefins by the Fischer-Tropsch process followed by the hydroformylation reaction and isolation of mixture of alcohols. Hydrocarbon fraction with the content of linear olefins 10-45 wt-% is separated from products reaction synthesized by the Fischer-Tropsch process with using cobalt catalyst by distillation followed by its hydroformylation with carbon monoxide and hydrogen taken in the molar ratio hydrogen to carbon monoxide = 1.0-5.0. The reaction of synthesis is carried out in the presence of cobalt-base catalyst and a substituted or unsubstituted monophosphocycloalkane ligand followed by steps of hydrogenation and distillation. Invention provides preparing a composition with the content of linear (C7-C12)-alcohols 60 wt.-%, not less, high rate of reaction and high selectivity of the process.

EFFECT: improved method of synthesis.

8 cl, 3 tbl, 4 ex

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