Single-stage 1,3-diol production process

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.

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The scope of the invention

The present invention relates to a single-stage method for producing a 1,3-diol and, in particular, 1,3-propane diol.

Background of the invention

1,3-diols are many uses, especially for the synthesis of polymers. For example, the polymer "CORTERRA" (trade mark) is a complex polyester derived from 1,3-propane diol (hereinafter 'PDO') and terephthalic acid, and has outstanding performance. Other 1,3-diols can find a similar application. Therefore, highly desirable commercial method of obtaining such 1,3-diols.

Patent application US-5304691 and opened it, the prior art relate to a method for PDO and NRA (3-hydroxypropyl, 3-hydroxyaldehyde). In the patent application U.S. And 5304691, PDO and NDA receive as a result of the interactions of oxirane (ethylene oxide, hereinafter 'SW'), modified diretional phosphine catalyst based on cobalt carbonyl, ruthenium promoter catalyst and synthesis gas (carbon monoxide and hydrogen) in an inert reaction solvent under the reaction conditions of hydroformylation. It is reported that the output PDO is up to 86-87 mol % when using a catalyst comprising cobalt, legirovannye 1,2-bis(9-phosphabicyclononanes)ethane as a bidentate ligand, and either tirutani(O)dodecanoyl, or bis[Rute is ethicalpolitical] as socializaton.

As mentioned, this method usually results in a mixture of NDA and PDO. However, it would be much more attractive to get PDO in one stage or with a higher yield, certainly without formed simultaneously impurities that interfere with the use PDO for polymers, etc. in order For this method was particularly successful, it is necessary to recycle (return process) catalyst without any noticeable degradation. Unexpectedly, was found this way and is suitable for use in this method the catalyst.

Summary of invention

In accordance with the present invention, a method for obtaining an improved catalyst hydroformylation of oxirane, an improved catalyst hydroformylation of oxirane, and one way to obtain 1,3-diol in the presence of such a catalyst, in which the selection of the product preferably completes phase split phase with a high content of diol and the rest mass of the reaction solution.

In accordance with the present invention, a method for preparation of the catalyst of hydroformylation, which includes:

a) obtaining a complex of (a) contacting the compound of ruthenium(0) diretional phosphine ligand;

b) obtaining a complex of (C) as a result of implementation acyclical the-reduction reactions of the complex (A) with a carbonyl compound of cobalt(0).

In accordance with the present invention proposed a catalyst hydroformylation obtained by the method, which includes:

a) obtaining a complex of (a) contacting the compound of ruthenium(0) diretional phosphine ligand; and

b) obtaining complex (C) in the implementation of the redox reaction of complex (A) with a carbonyl compound of cobalt(0). In the infrared absorption spectrum of the specified catalyst hydroformylation there is an absorption band of the carbonyl anion cobalt in 1890 or 1894 cm-1.

The new catalyst hydroformylation of oxirane includes a set of (In), which, as suggested, is a complex of ruthenium(+1)-bidentate of phosphine: cobalt(-1). The distinctive feature of the new catalyst is that legirovannym metal is ruthenium, not cobalt, as disclosed in the aforementioned patent application U.S. And 5304691. Indeed, in the analysis of both systems in their IR spectra observed significant differences. In the IR spectrum of the catalyst obtained in accordance with the present invention, there are absorption bands corresponding to pastorutti on 2107, 2053 and 2040 cm-1not in the IR spectrum of the catalyst obtained in accordance with the invention of the patent application U.S. And 5304691.

In addition, the present invention also proposed odnostadiinyi way of hydroformylation to obtain 1,3-diol, comprising the reaction of oxirane with sintezator in terms of hydroformylation in an inert solvent in the presence of a catalyst of hydroformylation obtained by the method, which includes:

a) obtaining a complex of (A) contacting the compound of ruthenium(0) diretional phosphine ligand; and

b) obtaining complex (C) in the implementation of the redox reaction of complex (A) with a carbonyl compound of cobalt(0).

Further in accordance with the present invention proposed a one-step method of hydroformylation to obtain 1,3-diol, comprising the reaction of oxirane with sintezator in an inert solvent in the presence of a catalyst of hydroformylation, which is a complex of ruthenium(+1)-bidentate of phosphine: cobalt (-1), where legirovannym metal is ruthenium, under conditions that preferably after completion of the reaction, oxiran/synthesis gas to cause phase separation of the reaction mixture in the upper phase of the solvent, with a high content of catalyst, and the lower phase with a high content of 1,3-diol, the management of the upper phase with a high content of catalyst directly into the reaction hydroformylation for further reaction with previously unreacted raw materials, and the selection 1,3-diol from the lower phase with a high content of 1,3-diol.

In choosing the accordance with the present invention a catalyst hydroformylation, which is a complex of ruthenium(+1)-bidentate of phosphine:cobalt(-1), where legirovannym metal is ruthenium.

Brief description of drawings

Hereinafter the present invention will be disclosed with the help of examples with reference to the accompanying drawings, on which:

FIGURE 1 represents a comparison of in situ IR absorption spectrum of the catalyst of the present invention (as received) with in situ IR absorption spectrum of the comparative catalyst (as received);

FIGURE 2 represents the comparison of in situ IR absorption spectrum NDA at 1728 cm-1in the reaction using the catalyst of the present invention compared with the comparative catalyst; and

FIGURE 3 presents plots of the IR absorption spectrum of the catalyst for the selected solid product of example 5.

Detailed description of the invention

Oxirane containing up to 10 carbon atoms, preferably up to 6 carbon atoms, and ethylene oxide, in particular, can be transformed into the corresponding 1,3-diols in the reaction of hydroformylation with sintezator in the presence of the complex (C) as a catalyst.

1,3-diols get, loading into the reactor under pressure oxiran, the catalyst, the optional socialization and/or promoter of the catalyst and reaction solvent, with input syngas (a mixture of hydrogen and carbon monoxide, prefer the LNO in molar ratio from 1:1 to 8:1, preferably from 2:1 to 6:1) under the reaction conditions of hydroformylation.

The method of the present invention includes processes with batch loading, continuous processes and their various options. For best results, the process is carried out under conditions of elevated temperatures and pressures. The temperature of the reaction are in the range from room temperature to 150°C, preferably from 50 to 125°S, and most preferably from 60 to 110°C. it is Desirable that the pressure of the reaction (total pressure or partial pressure, if used as a diluent inert gas) was value in the range from 5 to 15 MPa, preferably from 8 to 10 MPa. When using with batch loading reaction usually completes in 1.5-5 hours. The reaction solvent is preferably inert, which means that it is not consumed in the reaction. Ideal solvents for the method of the invention solubilizing raw materials and products in the reaction, but provide phase separation at low temperatures. Suitable solvents are disclosed in patent application U.S. And 5304691. For example, good results can be achieved when using ethers, including cyclic and acyclic ethers, optionally in combination with alcohol or aromatic hydrocarbon. Beautiful cut ltati reach with methyl tert-butyl ether (MTBE) and a mixture of toluene with chlorobenzene.

The method of the present invention as applied to a preferred method of synthesis of PDO can be represented as follows. Separate, merged or phased flows SW, syngas and catalyst loaded into the reactor, which may be a reactor under pressure, such as a column with a bubbling or autoclave with stirring, which operate in batch mode boot or in a continuous manner.

Components of raw streams are contacted in a suitable reaction solvent in the presence of a catalyst of the present invention. The EO concentration preferably should be maintained throughout the reaction is not less than 0.2 wt.%, usually in the range of from 0.2 to 20 wt.%, preferably from 1 to 10 wt.%, calculated on the total weight of the reaction mixture. The method of the present invention can be carried out in a continuous manner, while maintaining the specified concentration of EO, for example, the periodic addition of EO.

After the reaction of hydroformylation the mixture of products produce by conventional means, such as selective extraction, fractional distillation, phase separation, decanting and selective crystallization. Unreacted starting materials and the catalyst and the reaction solvent can be retalitate for further use, which is preferable and Khujand who are.

In a preferred embodiment of the method of the present invention the reaction conditions such as concentration of oxirane, the concentration of the catalyst, the solvent, the product concentration and the reaction temperature, is chosen so as to obtain a homogeneous reaction mixture at elevated temperatures and cause separation of the reaction mixture in the upper phase of the solvent with a high content of catalyst and the lower phase of the solvent, containing most of 1,3-propane diol, after cooling of the mixture. This separation facilitates the separation and isolation of the product, the management of a catalyst and removing heavy residues from the system solvent. This method is called the method of recyclization catalyst after phase separation/extraction of product.

In this way the contents of the reactor provide an opportunity to settle or transfer into a suitable reaction vessel at a pressure reaction or close to it, and due to minor or major cooling may be formed substantially different phase containing a significant amount of product or catalyst and solvent. Phase containing large amounts of catalyst and solvent, directly recyclist for further reaction with the raw materials. The product is separated from the phase containing a large amount of product in the usual way.

It is important that the reaction are such that the resulting diol retains the levels of concentration in the reaction mixture such that provide phase separation. For example, the concentration of 1,3-propane diol may be the size from less than 1 to more than 50 wt.%, preferably from 1 to 50 wt.%, usually from 8 to 32 wt.%, and preferably from 16 to 20 wt.%. Temperature during not vozmuschaemogo phase separation may be in the range of from the freezing point of the reaction mixture to 150°and above, usually from 27 to 97°S, and preferably from 37 to 47°C. the Concentration of SW support this, in order to avoid the formation of light alcohols and aldehydes, which are agents that promote dissolution. The concentration of oxirane should preferably be maintained at not less than 0.2 wt.%, usually in the range of from 0.2 to 20 wt.%, preferably from 1 to 10 wt.%, calculated on the total weight of the reaction mixture. The reaction can be conducted in a two-phase system. However, the yields and selectivity are the maximum, if high concentrations of the product are present in a single-phase reaction, and the subsequent separation of the phases takes place after cooling.

Separation of the reaction mixture can promote by adding the agent that causes the separation of the phases. Suitable agents include glycols such as ethylene glycol, and line al is Ana, such as dodecane. Such agents are added to the reaction mixture in an amount in the range of values from 2 to 10 wt.%, preferably 4 to 8 wt.% calculated on the total weight of the reaction mixture. Alternative methods include adding to the reaction mixture of 1,3-propane diol to bring the concentration of the product to the desired proportions. In addition, contributing to the dissolution of alcohols and agents with the same polarity, such as ethanol, propanol and isopropanol, can be added first, then remove to phase separation, and consequently to induce this phase separation.

It is significant that in the above-described method as the catalyst use complex (). Consider that the complex (C) includes a new class of modified ruthenium catalysts. The distinctive feature of this new class of catalysts is the fact that it includes oxidized metal ruthenium, which Legerova tertiary diphosphine ligand, with a mix of cobalt as counterion, which may be, but preferably not Legerova phosphorus ligand.

One connection of such complex includes the phosphorus ligand. As mentioned, this ligand is determinism phosphine of General formula:

where each R and R' independently or together represents a hydrocarbon fragment, with the holding up to 30 carbon atoms, and Q is an organic bridging group ranging in length from 2 to 4 atoms. Preferably, the groups R and R'being a monovalent, each independently represent alkyl, cycloalkyl, bicycloalkyl or aryl group. Each group R and R1preferably independently contains up to 20 carbon atoms, more preferably up to 12 carbon atoms. Alkyl and/or cycloalkyl group is preferable. Group Q preferably includes carbon atoms, which may form part of a ring system such as benzene ring or cyclohexane ring. More preferably, when Q is alkylenes group containing 2, 3 or 4 carbon atoms in length, more preferably 2 carbon atoms. 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. These groups R and R' can be substituted for uglevodorodnye groups. Both groups R and/or both groups R' may also be parts of the divalent group forming a ring (rings) with the atom (atoms) of phosphorus, such as phosphacyclohexane containing from 5 to 8 carbon atoms. Examples of the 5-ring systems (ligands on the basis of phospholanes) include 1,2-bis(phospholane)ethane, 1,2-bis(2,5-dimethylphosphino)benzene, optically pure (R,R), (R,S), (S,S) 1,2-bis(2,5-dimethylphosphino)atany or their racemic mixture. The rings can be an integral part multiring system. Examples of such ring systems can be found in the aforementioned patent applications U.S. And 5304691 and in WO-A-98/42717. In the first disclosed group, phosphabicyclononanes, as disclosed in the last group such adamantyl and, in particular, groups of phosphotriesterase. Preferred diphosphine, in which both groups R and R' form a ring with the phosphorus atom. The most preferred ligands are 1,2-P,P'-bis(9-phosphabicyclo[3.3.1] and/or [4.2.1]nonyl)atany (hereinafter B9PBN-2), 1,2-P,P'-propane and/or 1,3-P,P'-propane equivalents (hereinafter B9PBN-3).

Titration phosphine ligands are commercially available. Derived catalysts known in the art, and methods for their preparation are described in detail in patent applications U.S. And 3401204 and 3527818. Phosphine ligands may also be partially oxidized to phosphine oxides by the method disclosed in the patent application U.S. And 5304691./p>

The ratio of 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 is about 1:1. It is assumed that this leads to tricarbonyl connection tertiary diphosphonate, but it can also be a bis(tertiary diphosphinite)PENTACARBONYL connection. It is believed that the carbonyl religiouznogo ruthenium is inactive connection, and therefore the process of preparation of the catalyst is intended to ligitamate every atom of ruthenium.

Believe that for best results the best counterion 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 diphosphine, for example up to 75 mol %, for example up to 50 mol%. However, the counterion is preferably above delegiovaniem tetracarbonyl cobalt. The CARBONYLS of cobalt can be obtained by interacting the original source of cobalt with sintezator by the way, opened J. Falbe, "Carbon Monoxide in Organic Synthesis", Springer-Verlag, NY (1970), or any other.

The oxidation state of the ruthenium atom is not exactly known (theoretically, the ruthenium can have a valency of 0 to 8), and it may even change during the reaction is hydroformylation. Accordingly, the molar ratio of ruthenium to cobalt may vary in a wide interval of values. You should add a sufficient amount of cobalt(0) for complete oxidation of all used ruthenium in the form of complexes. You can add an excess of cobalt, which is not too significantly. It is desirable that 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 catalyst complex () can be obtained as follows. The first stage in the process of preparation of the catalyst is the synthesis of complex (A). This can be accomplished by the interaction of a suitable source of Ru(0), such as carotenodermia, with tertiary diphosphines. In another embodiment, carotenogenesis can be replaced with a cheaper source of ruthenium, therefore, which forms in situ EN(0), such as a hydrate of oxide of ruthenium (IV).

The conditions in which these compounds can form a complex, diverse enough. Temperature and pressure may vary in the intervals, already mentioned above for the reaction of hydroformylation. Synthesis gas can be used as a protective atmosphere. The reaction is best conducted in a solvent, preferably is used in the reaction of hydroformylation. Obviously, this solvent should dissolve the active catalyst without affecting its characteristicimpedance solvents include ethers, above, and methyl tert-butyl ether (MTBE), in particular.

Complex (A), for example, can be obtained by the interaction of carotenodermia with the stoichiometric quantity of the selected ligand in a solvent at a temperature of from 90 to 130°C, preferably from 100 to 110°C, in an atmosphere of carbon monoxide for 1-3 hours (i.e. until the end of the reaction).

Then communicate complex (A) with the appropriate compound of cobalt in the above conditions. A suitable source of cobalt is diaballickall, but you can also use other complexes of cobalt(0), except the complexes of Co0modified with phosphine. For example, selected carbonyl cobalt and possibly the promoter (if used), are added to a solution, heated 15-60 minutes. This method is called the method of sequential receipt.

Suitable sources of cobalt include salt, which is reduced to the zero valence using a heat treatment, for example in an atmosphere of hydrogen and carbon monoxide. Examples of such salts include cobalt carboxylates, such as acetates and octanoate, showing the best result, and cobalt salts with mineral acids, such as chlorides, fluorides, sulfates and sulfonates. You can also use a mixture of salts of cobalt. Preferably, the composition is Mesa included, at least one alkanoic cobalt containing from 6 to 12 carbon atoms. The recovery process can be performed before use of the catalyst or it can be performed simultaneously with the process of hydroformylation in the reaction zone of hydroformylation.

In the scope of the present invention includes obtaining a complex of (A) by way of "self-Assembly", when all the components of the catalyst to bring together at the same time, but the conditions and especially the solvent is chosen in such a way as to contribute more to the education legirovannykh compounds of ruthenium without exchange of ligands with cobalt. The presence legirovannykh compounds (i.e. complexation) EN, and not Co-phosphine compounds can be confirmed by IR spectroscopy.

In this regard, it should be emphasized that in the above patent application U.S. And 5304691 indicated that the form of ruthenium is not the determining parameter. Although it is assumed the use of phosphine complexes of ruthenium disclosed in this reference, any such use will be accompanied by formation of a complex catalyst of cobalt carbonyl with a tertiary phosphine and a decomposition of the initial complex of ruthenium.

The optimum oxiranes raw materials to the complex (C) partially depends on specifically used complex. However, the molar ratio of oxirane the cobalt complex (C) is from 2:1 to 10,000:1 are generally satisfactory, moreover, the preferred molar ratio of from 50:1 to 500:1.

You can use promoters, such as disclosed in the above patent application U.S. And 5304691. The currently favored by the promoters due to their availability and proven effectiveness in relation to the EO conversion are dimethyldodecylamine and triethylamine.

Industrial production requires efficient extraction of the catalyst and the plurality of cycles of use. The preferred method of selection of the catalyst includes the above separation of a mixture of two liquid phases and the return of solvent to the reactor, which allows you to save at least 60 to 90 wt.% the original catalyst.

Further, the present invention is illustrated by the following examples.

Table 1
Materials and structures
SourceSOOSOctanoate cobalt
DCODiaballickall
Source ENTRCCarotenogenesis
BRCCBis(ratemycameltoe)
The ligandB9PBN-21,2-P,P'-bis(9-phosphabicyclononanes)ethane
BDEPE1,-bis(diethylphosphino)ethane
BDIPE1,2-bis(Diisobutylene)ethane
BDOPE1,2-bis(2,4,4-trimethylpentane)ethane
BDMPE(R,R) 1,2-bis(dimethylphosphino)ethane
SolventMTBEMethyl tert-butyl ether
T/STA mixture of 5:1 V/V toluene/chlorobenzene
OxiranSWThe ethylene oxide
The promoterDMDADimethyldodecylamine
NaAcSodium acetate

IR analysis carried out in situ using a cylindrical reactor internal reflection of the type described W.R.Moser, J.E.Cnossen, A.W.Wang and S.A.Krouse in the Journal of Catalysis, 1985, 95, 21; sold Spectra-Tech Inc. complete with spectrometer Nicolet Magna 550. Interest spectral plot includes both lanes of the catalysts, and the intermediate aldehydes in the frequency range from 1500 to 2500 cm-1.

Example 1. Obtaining complex (In)

In a dry box in a 50 ml reactor made of stainless steel, equipped with optics for in situ monitoring of the reaction by IR analysis, download the following materials: 61 mg TRC (0,286 mmol Ru), 171 mg B9PBN-2 (0,551 mmol) and 17 ml of MTBE.

The reactor was sealed, removed from the dry box, combined with the IR spectrometer, and the pressure of carbon monoxide in reacto the e lead up to 2.2 MPa. The contents of the reactor are heated to 105°and behind the formation of the complex (A) is monitored by IR spectroscopy. After the temperature reaches 105°add hydrogen to bring the composition of the syngas to about a ratio of 3:1.

To this mixture add a solution of 113 mg DCO and 47 mg DMDA, dissolved in 5 ml of MTBE using the excess syngas with a composition of 1:1 to establish the total pressure in the reactor to 8.6 MPa. Incubated for another 35 minutes at 105°and then the reactor is cooled.

Comparative example A. Getting very (substituted) With the catalyst according to the method of patent application U.S. And 5304691

In a dry box in a 50 ml reactor made of stainless steel, equipped with optics for in situ monitoring of the reaction by IR analysis, download the following materials: 228 mg SOOS (0.66 mmol, 74 mg BRCC (0,289 mmol Ru), 222 mg B9PBN-2 (0,715 mmol), 18 mg of sodium acetate (0.22 mmol) and 23 ml of T/ST

The reactor was sealed, removed from the dry box, combined with the infrared spectrometer and bring pressure to 9.0 MPa, using synthesis gas composition 4:1. The temperature in the reactor is brought to 130°and control the formation of the catalyst using IR spectroscopy.

Example 2. Getting complex by "self-Assembly"

In a 100 ml autoclave according to the method of the comparative example And downloads: 228 mg SOOS (0.66 mmol); 23 ml of MTBE; 62 mg TRC (0.29 mmol); 167 mg B9PBN-2 (0.50 mmol who); and 17 mg NaAc (0.21 mmol). Reaction formation control using IR spectroscopy.

Analysis of the catalyst by using IR spectroscopy

After adding B9PBN-2 TRC absorption band TRC at 2059, 2029 and 2009 cm-1disappear and there is an increase of absorption bands in 1954, 1884 1853 cm-1. After the addition of cobalt carbonyl oxidation chelated ruthenium, accompanied by an immediate shift of the IR absorption bands and the appearance of characteristic bands at 2040, 2053, and 2107 cm-1and stripes at 1890 cm-1that is characteristic for carbonyl anion (religiouznogo) cobalt.

Figure 1 is a solid line presents the obtained in situ IR absorption spectrum of the complex (B)obtained by the method of example 1. The strongest bands of catalyst (2040, 2053, and 2107 cm-1are the characteristics of compounds modified with phosphine ruthenium. The dashed line presents the obtained in situ IR spectrum of the catalyst of comparison. Obtained in situ IR spectrum of the complex (B)obtained by the method of self-Assembly, corresponds to the range of the catalyst obtained in example 1.

Example 3. Receive PDO

At a temperature of 80°in the reaction mixture of example 1 add 1.1 g EO using excessive pressure syngas composition 1:1. Gas (1:1) are added to the reaction mixture as needed, the button to maintain the pressure of the reaction in the range between 10.4 to 11.1 MPa. SW provide to react completely. After cooling the reactor open and produce a two-phase fluid. According to GC analysis, the main product obtained from the SW, in both phases is PDO. (Output is more than 50 mol %). Similarly, using the catalyst of comparative example A. However, it appeared that the two-phase fluid is allocated at the end of this experiment, which includes the lower phase, containing approximately 50/50 mixture of PDO and the NRA, and the upper phase containing PDO, HPA and other materials. (Out of more than 50 mol %).

Over the course of both reactions was monitored using IR spectroscopy by observing the intensity of the absorption band of the carbonyl intermediate 3-hydroxypropionate aldehyde (1728 cm-1). The results are presented in figure 2.

When using the catalyst according to the present invention shows that the aldehyde band only slightly increases with the beginning of the reaction, and then decreases rapidly as the NRA turns into a PDO. When using the catalyst of the comparative example And the bandwidth is constantly increasing in the reaction. This indicates a high hydrogenating ability of the catalyst of the present invention.

Comparative example

Repeat the experiment of example 3, using the catalyst of comparative example A, with the sequential addition of EO (4 with the adiya's). For about 4-6 hours receive 1,3-PDO with the release of 66 mol % and a selectivity of 80%. Then the crude liquid product is subjected to fractional distillation in vacuo (< 0.1 kPa) to highlight the PDO as a fraction of the product of distillation. The remaining recyclist with additional quantities of EO and syngas, plus the solvent for the second cycle. It was found that the yield of PDO was only 44 mol %, a selectivity of only 67%. If the residue from this operation to use again, and to carry out the catalytic reaction in the third cycle, the formation of PDO is practically not observed (2 mol %).

Example 4

Repeat the experiment of example 3, using the catalyst of example 1, but using BDEPE instead of sequential addition of EO (4 stage). Approximately 4-6 hours receive PDO with the release of 48 mol% with selectivity of 57%. Then the crude liquid product is subjected to fractional distillation in vacuo (< 0.1 kPa) to highlight the PDO as a fraction of the product of distillation. The rest recyclist with additional quantities of EO and syngas plus solvent for the second cycle. It is found that the output PDO is 40 mol % at a selectivity of 54%. If the catalyst recyclist and realize thus the catalytic reaction of 10 times, the output PDO still is 49 mol % with selectivity 59%.

Not observed appreciable loss of catalytic the activity after 12 additions SW. In addition,1H NMR spectrum of a solution of the final product indicates the absence of free BDEPE, with most of the P-ligand still attached to the ruthenium. Therefore, we can conclude that the new catalyst of the present invention has a high stability.

Example 5

Carry out experiments similar to example 3, using a catalyst obtained by self-Assembly, when the initial molar ratio of Co:Ri:ligand 2:1:2. The results of the tests are presented in the following table.

Table 2
The ligandOutput PDO (mole.%)The PDO selectivity (%)
BDEPE48-7383-87
BDIPE36-5380-86
BDOPE3169
BDMPE51-7178-95

Based on these results we can conclude that the catalysts of the present invention is certainly suitable for one-step conversion of oxiranes.

Example 6. Obtaining complex (In)

In a dry box in a 50 ml reactor made of stainless steel, equipped with optics from zinc sulfide for in situ monitoring of the reaction by IR-spectroscopy, download the following materials: 128 mg TRC (0,600 Ru), 186 mg B9PBN-2 (0,600 mmol), 9 ml of toluene and 9 ml of MTBE.

The reactor was sealed, removed from the dry box, combined with the IR spectrometer, and bring the pressure of carbon monoxide in the reactor to 1.7 MPa. The contents of the reactor are heated to 105°and behind the formation of the complex (A) is monitored by IR spectroscopy. After heating the absorption band TRC at 2059, 2029 and 2009 cm-1disappear and the increase of absorption bands in 1954, 1882 1861 and cm-1. After 1 hour at 105°add hydrogen to bring the composition of the gas to approximately the ratio of 3:1 syngas, 8,29 MPa, and add a solution of 105 mg DCO (0,614 mmol) in 6 ml of MTBE, bringing sintezator pressure in the reactor to 10.3 MPa. After the addition of cobalt carbonyl oxidation chelated ruthenium, accompanied by a shift of the absorption bands and the appearance of characteristic bands at 2040, 2053 and 2107 cm-1and stripes at 1890 cm-1that is the characteristic anion unsubstituted carbonyl cobalt. The contents of the reactor is maintained at 105°C for 1.5 hours without visible changes of the catalyst composition. After heating to 130°With the data of the IR spectrum indicated the absence of changes in the composition of the catalyst. The reactor is cooled to room temperature, opened and allocate 0.25 g of yellow-orange of the catalyst in the form of solids by filtration and drying is it in a vacuum. The IR spectrum of the selected solids are presented in figure 3, and the only present strip of metal carbonyl associated with legirovannym phosphine ruthenium (I) anion tetracarbonyl cobalt (-1). No other CARBONYLS of cobalt is not present. This complex is identical to the solid catalyst, selected after one-step reaction of obtaining 1,3-propane diol of the present invention.

Example 7. The use of the selected set (I) to obtain 1,3-propane diol in a single phase

In a dry box in a 50 ml reactor made of stainless steel, equipped with optics from zinc sulfide for in situ monitoring of the reaction by IR analysis, download 0.24 g of the solid catalyst of example and 23 ml of MTBE. The reactor was sealed, removed from the dry box, placed in an IR spectrometer and bring the reactor pressure up to 7.0 MPa with a mixture of 4:1 hydrogen: carbon monoxide. The contents of the reactor are heated to 90°and to the reaction mixture are added to 1.9 g of EO due to excessive pressure syngas (1:1). The gas composition of 1:1 is added to the reaction mixture, maintaining the reactor pressure in the range from 10.1 to 10.8 MPa. Within hours spent first aliquot of ethylene oxide, and injected into the reactor second of 1.9 g (only 3.8 g) of ethylene oxide. The reaction mixture is again quickly Deplete synthesis gas, which is added as necessary. The reaction is carried out to pattern the Eski full of SW flow throughout the reaction, moreover, the IR spectrum of the plot, corresponding to the catalyst remains the same as the spectrum of the original solid catalyst. After the reactor is cooled and opened, receive a two-phase mixture.

GC analysis of both phases provides access PDO over 50%, and detected only trace amounts of the NRA.

Example 8. The process of recyclization catalyst after phase separation/extraction of product with a catalyst obtained by self-Assembly

In an inert atmosphere in a 300 ml autoclave load of 1.85 g (to 5.35 mmol) of ethylhexanoate cobalt(II), 1,392 g (4,48 mmol) 1,2-bis(9-postalcohol)ethane, 0,509 g (2.3 mmol Ru)carotenodermia, 145,85 g of methyl tert-butyl ether (MTBE) and 0.30 g of dimethyldodecylamine. The autoclave is sealed and placed in an installation for synthesis laboratory scale. Under the pressure of the syngas with a ratio 4:1 N2: 10,34 MPa (gauge) (1500 psig) mixture is allowed to reach an equilibrium state, and the catalytic reaction are for 2 hours at 130°C. the Temperature in the reactor is reduced to 90°C. Add additional 16,96 g of ethylene oxide (EO) and allowed to react with sintezator at a ratio of 2:1 N2:WITH up to almost full flow SW. The reactor is transferred into a separating funnel, where it immediately starts to phase separation. Separate 12,94 g of the material of the lower layer. The top layer reacts the Onna mixture used again. The compositions of the upper and lower layers are presented in table 3. Data on the separation of the catalyst are presented in table 4. Product: 1,3-propandiol get at an average speed of 20 g/l/h.

Example 9. The process of phase separation, recycling 1

Retalitory the reaction solution from example 8 was heated to 90°C. Add 14,74 g of ethylene oxide and left to react under pressure syngas with a ratio of 2:1 H2:10,34 MPa (wt.) (1500 psig) to almost complete consumption of SW. The contents of the reactor are transferred by pressure syngas into a separating funnel, where phase separation immediately begins receiving the result by 8.22 g isolated from the lower layer of material. The upper layer of the reaction solution recyclist (return) back to the reactor. The compositions of the upper and lower layers are presented in table 3. Data on the separation of the catalyst are presented in table 4. The average reaction rate in this recycling was 14 g/l/h.

Example 10. The process of phase separation, recycling 2

Retalitory the reaction solution from example 9 was heated to 90°C. Add 14,74 g of ethylene oxide and left to react in the atmosphere syngas in the ratio 2:1 N2:When 10,34 MPa (wt.) (1500 psig). The contents of the reactor is transferred by the pressure of syngas in a phase separation vessel, where it is phase separation immediately starting the is, receiving the result of 8.50 g isolated from the lower layer of material. The upper layer of the reaction solution is recycled back to the reactor. The compositions of the upper and lower layers are presented in table 3. Data on the separation of the catalyst are presented in table 4. The average reaction rate in this recycling was 37 g/l/h.

Example 11. The process of phase separation, recycling 3

Retalitory the reaction solution from example 10 was heated to 90°C. Add 14,74 g of ethylene oxide and left to react in the atmosphere syngas in the ratio 2:1 N2:When 10,34 MPa (wt.) (1500 psig). The contents of the reactor is transferred into the atmosphere syngas in a phase separation vessel, where it is phase separation immediately begins to deliver 19,50 g isolated from the lower layer of material. The upper layer of the reaction solution is recycled back to the reactor. The compositions of the upper and lower layers are presented in table 3. Data on the separation of the catalyst are presented in table 4. The average reaction rate in this recycling was 49 g/l/h.

Example 12. The process of phase separation, recycling 4

Retalitory the reaction solution from example 11 was heated to 90°C. Add 14,74 g of ethylene oxide and left to react in the atmosphere syngas in the ratio 2:1 N2:When 10,34 MPa (wt.) (1500 psig). The contents of the reactor is transferred into the atmosphere Sintez is in a phase separation vessel, where phase separation immediately begins to deliver 32,80 g isolated from the lower layer of material. The upper layer of the reaction solution is recycled back to the reactor. The compositions of the upper and lower layers are presented in table 3. Data on the separation of the catalyst are presented in table 4. The average reaction rate in this recycling was 34 g/l/h.

Example 13. The process of phase separation, recycling 5

Retalitory the reaction solution from example 12 was heated to 90°C. Add 14,74 g of ethylene oxide and left to react in the atmosphere syngas in the ratio 2:1 H2:CO 10,34 MPa (wt.) (1500 psig). The contents of the reactor is transferred into the atmosphere syngas in a phase separation vessel, where it is phase separation immediately begins to deliver 71,90 g isolated from the lower layer of material. The upper layer of the reaction solution is recycled back to the reactor. The compositions of the upper and lower layers are presented in table 3. Data on the separation of the catalyst are presented in table 4. The average reaction rate in this recycling is 30 g/l/h.

The three most important results of the phase separation are: 1) achieving acceptable fairly high speed receive PDO 2) management of the greater part of the catalyst (upper phase); 3) the allocation of concentrated product (PDO) at the bottom f the see.

Velocity data receive PDO in the above examples suggest that an acceptable reaction rate and that the catalyst remains active after 5 recyclo (#1).

The data of table 4 demonstrate that a high percentage of catalyst directly return to the upper phase (#2).

The data of table 3 demonstrate a high percentage of allocation PDO from the lower phase (#3).

8
Table 3
Phase separation of basic compounds
ExampleLayerPDO wt.%MTBE wt.%Weight (g)
8Bottom59,7018,1312,94
9Bottom47,9716,60by 8.22
10Bottom45,9719,158,50
11Bottom47,3221,7319,50
12Bottom45,1620,9932,80
13Bottom47,5025,7871,90
     
Top4,7485,70152,36
9Top5,1587,16160,04
10Top17,6777,60167,19
11Top27,3154,86163,47
12Top14,4169.85 mm147,04
13Top10,5980,3693,46

0,1
Table 4
record/No. of recyclingLayerEN wt.%With the weight.%R, wt.%% With catalyst
23661-187-2/R0bottom0,210,250,23 
23661-188-1/R1bottom0,210,180,2191
23661-188-4/R2bottom0,160,150,1493
23661-188-7/R3bottom0,140,130,1282
23661-188-10/R4bottom0,090,0878
23661-191-3/R5bottom0,060,090,04 
      
23661-187-3/R0top    
23661-188-2/R1top0,080,110,119
23661-188-5/R2top0,080,10,17
23661-188-8/R3top0,050,070,0618
23661-188-11/R4top0,050,080,0721
23661-191-4/R5top0,140,110,12 

Example 14. The process of recyclization catalyst after phase separation/separation of product from catalyst obtained stepwise method

In an inert atmosphere dry box in an autoclave with a capacity of 300 ml load 2.14 g (6,90 mmol) 1,2-bis(9-postalcohol)ethane, 0,694 g (3.25 mmol Ru) carotenodermia, 119 g of methyl tert-butyl ether is (MTBE). The autoclave is pressurized and transferred to the installation for synthesis laboratory scale. In the atmosphere of the syngas in the ratio of 4:1 (H2:) When 10,34 MPa (wt.) (1500 psig), the mixture is left to reach equilibrium for 1 hour at 105°C. To the reactor was added a solution of 1.11 g (6,50 mmol) disablecontrolpanel and to 0.108 g (1,32 mmol) of sodium acetate 33.3 g of MTBE in the reaction conditions. The catalytic reaction proceeds at 105°and a pressure of 1500 psig (10,34 MPa (psig) for 1.75 hours. The temperature in the reactor is reduced to 90°C. Double-add portions just 13.2 g of ethylene oxide (EO) and left to react with sintezator at a ratio of 2:1 (H2:) To almost complete consumption of SW. The contents of the reactor is transferred into the atmosphere syngas into the reactor at a controlled temperature for phase separation. Phase separation occurs before reaching equilibrium at 43°C. From the lower phase allocate 36,8, the Upper phase is recycled back to the reactor. The compositions of the upper and lower phases are presented in table 5. Data on the separation of the catalyst are presented in table 6. The product 1,3-propandiol get at an average speed of 26 g/l/h.

Example 15. The process of phase separation, recycling 1

Retalitory the reaction solution from example 14 was heated to 90°C. Add 14,74 g of ethylene oxide and left to react in the atmosphere of the synthesis gas is in the ratio 2:1 N 2:10,34 MPa (wt.) (1500 psig). The contents of the reactor is transferred into a syngas atmosphere in the vessel for phase separation. Upon reaching equilibrium at 43°allocate 28.5 g of material from the lower phase. The upper layer of the reaction solution is recycled back to the reactor. The compositions of the upper and lower phases are presented in table 5. Data on the separation of the catalyst are presented in table 6. The average reaction rate in this recycling is 24 g/l/h.

Example 16. The process of phase separation, recycling 2

Retalitory the reaction solution from example 15 is heated to 90°C. Type of 11.00 g of ethylene oxide and left to react in the atmosphere syngas in the ratio 2:1 with 10,34 MPa (wt.) (1500 psig). The contents of the reactor is transferred into a syngas atmosphere in the vessel for phase separation. Upon reaching equilibrium at 43°allocate 24.8 g of material from the lower phase. The upper phase of the reaction solution is recycled back to the reactor. The compositions of the upper and lower phases are presented in table 5. Data on the separation of the catalyst are presented in table 6. The average reaction rate in this recycling is 35 g/l/h.

Example 17. The process of phase separation, recycling 3

Retalitory the reaction solution from example 16 was heated to 90°C. Type of 11.00 g of ethylene oxide and left to react in the atmosphere syngas in the ratio 2:1 with 10,34 MPa (gage) (1500 psig). The contents of the reactor is transferred into a syngas atmosphere in the vessel for phase separation. Upon reaching equilibrium at 43°With allot of 19.1 g of the material from the lower phase. The upper layer of the reaction solution is recycled back to the reactor. The compositions of the upper and lower phases are presented in table 5. Data on the separation of the catalyst are presented in table 6. The average reaction rate in this recycling is 23 g/l/h.

Example 18. The process of phase separation, recycling And

Retalitory the reaction solution from example 17 was heated to 90°C. Type of 11.00 g of ethylene oxide and left to react in the atmosphere syngas in the ratio 2:1 with 10,34 MPa (wt.) (1500 psig). The contents of the reactor is transferred into a syngas atmosphere in the vessel for phase separation. Upon reaching equilibrium at 43°With allot of 38.9 g of the material from the lower phase. The upper layer of the reaction solution is recycled back to the reactor. The compositions of the upper and lower phases are presented in table 5. Data on the separation of the catalyst are presented in table 6. The average reaction rate in this recycling is 18 g/l/h.

Example 19 the Process of phase separation, recycling 5

Retalitory the reaction solution from example 18 was heated to 90°C. Type of 11.00 g of ethylene oxide and left to react in the atmosphere syngas in the ratio 2:1 with 10,34 MPa (wt.) (1500 psig). Content reacto is and is transferred into a syngas atmosphere in the vessel for phase separation. Upon reaching equilibrium at 43°With allot of 38.9 g of the material from the lower phase. The upper layer of the reaction solution is recycled back to the reactor. The compositions of the upper and lower phases are presented in table 5. Data on the separation of the catalyst are presented in table 6. The average reaction rate in this recycling is 17 g/l/h.

Velocity data receive PDO in the above examples suggest that an acceptable reaction rate, and that the catalyst remains active after 5 recyclo (#1).

Data in table 6 indicate that a high percentage of catalyst directly return from the upper phase (#2).

The data of table 5 demonstrate a high percentage of allocation PDO from the lower phase (#3).

Table 5
Phase separation of basic compounds
ExampleLayerPDO weight %MTBE weight %Weight (g)
14bottom63,6816,1524,80
15bottom49,6817,3928,50
16bottom68,0818,0324,80
17bottom53,34 24,3119,10
18bottom33,3219,3938,90
19bottom30,0325,9129,80
     

14top7,2044,63165,07
15top8,8961,35152,73
16top36,6948,66139,09
17top16.88 in54,86131,42
18top6,1486,65104,92
19top27,3034,5788,12

Table 6
record/No. of recyclingLayerEN wt.%With the weight.%R, wt.%% With catalyst
23661-187-2/RObottom0,210,250,23 
23661-18-1/R1 bottom0,210,180,2191
23661-188-4/R2bottom0,160,150,1493
23661-188-7/R3bottom0,140,130,1282
23661-188-10/R4bottom0,090,10,0878
23661-191-3/R5bottom0,060,090,04 
      
23661-187-3/ROtop    
23661-188-2/R1top0,080,110,119
23661-188-5/R2top0,080,10,17
23661-188-8/R3top0,050,070,0618
23661-188-11/R4top0,050,080,0721
23661-191-4/R5top0,140,11/td> 0,12 

Example 20. Recycling the lower phase at Paladino obtained catalyst

Samples of the bottom layer of examples 14 and 15 with a high content of the obtained 1,3-propane diol is distilled under 90-110°With vacuum 60-4 mm RT. Art. In the upper part of the column selected solvent is methyl tert-butyl ether and 1,3-propandiol. The material of the upper shoulder strap consists of more than 92% of 1,3-propane diol. The distillation is carried out in such a way that surpass 75% of the mass of the initial download. A sample of 10 g of distillation residues containing recyclery catalyst, a certain amount of 1,3-propane diol and a small amount of heavy residue is placed in a 300 ml autoclave in an inert atmosphere dry box. In the autoclave add 74 g of fresh solvent: methyl tert-butyl ether. The autoclave is pressurized and transferred into a laboratory setting. The catalyst solution is heated to 90°under stirring. In the atmosphere at a ratio of 4:1 (H2:CO) syngas add 11,00 g of ethylene oxide and left to react. The contents of the reactor is transferred into a syngas atmosphere in the vessel for phase separation, where 45°begins With the separation of the phases. Upon reaching equilibrium allot of 12.6 g of the material of the lower phase. This lower phase contains 56,47% 1,3-propane diol. The upper phase of the reaction solution return back what about in the reactor and heated to 90° C in an atmosphere of raw syngas with a ratio of 2:1 (H2:CO). This recyclebank phase solvent type of 11.00 g of ethylene oxide and left to react. The contents of the reactor are transferred in the atmosphere gas in the tank for phase separation, where at a temperature of 43°begins With the separation of the phases. On the balance of the lower phase allocate 24.5 g of material. This lower phase contains 45,14% 1,3-propane diol. These reactions provide an 81% yield of product. This proves that the catalyst is stable and remains active after it is distilled from the product phases and double-return from the upper phase of the subsequent reactions.

Example 21. The use of hexane as the agent causing phase separation.

In an inert atmosphere dry box in an autoclave with a capacity of 300 ml download 1,159 g (3.73 mmol) of 1,2-bis(9-postalcohol)ethane, 0,696 g (of 3.27 mmol Ru) carotenodermia, 119 g of methyl tert-butyl ether (MTBE). The autoclave is pressurized and transferred to a laboratory setting for the reaction. In the atmosphere of the syngas in the ratio of 4:1 (H2:) When 10,34 MPa (1500 psig) obtained mixture is allowed to reach equilibrium for 1.5 h at 105°C. To the reactor was added a solution of 1.13 g (6,50 mmol) disablecontrolpanel and to 0.108 g (1,32 mmol) of sodium acetate 33.3 g of MTBE under the reaction conditions. The catalytic reaction proceeds at 105°10,34 MPa (wt.) (1500 psig) for 1.75 hours. The temperature in the reactor is reduced to 90°C. Perform one addition of 22 g of ethylene oxide (EO) and left to react in the atmosphere syngas with a ratio of 2:1 (H2:CO). The contents of the reactor is transferred into a syngas atmosphere in the vessel for phase separation at a controlled temperature. Phase separation occurs in equilibrium at 43°C. Distinguish 9,746 g lower phase. The upper phase is recycled back to the reactor. The same way as the above examples add additional ethylene oxide to recyclebank upper layer and left to react with subsequent phase separation induced by temperature. In the third recycle this example, add 11,00 g of ethylene oxide, and the reaction proceeds at 90°and the pressure 10,34 MPa (wt.) (1500 psig). After migration into the vessel for separation of the phases and subsequent cooling to 35°phase separation is not observed. Two separate add aliquot on 11,00 g of ethylene oxide followed by reaction under these conditions, and cooling to 33°not led to the achievement of such a concentration of 1,3-propane diol, which would have been the separation of the phases. The authors believe that in this reaction formed a number of by-products such as ethanol and propanol, which by their nature are agents that promote dissolution, and therefore prevent the individual separation of the phases. Add 10 g of hexane into the reactor under these conditions, with subsequent transfer to a separating funnel and cooling cause phase separation at 77°C. It is one way of changing the polarity of the system, which can cause phase separation. To ensure single-phase reactions can even add an agent that promotes dissolution, before or during the reaction. Such contributing to the dissolution of the agents can then be removed, e.g. by distillation, to cause phase separation to separate the product. After reaching equilibrium at 43°To emit the pattern of the lower layer of 92.7 g, which contains 48% 1,3-propane diol.

1. The method of producing catalyst hydroformylation, which includes:

a) obtaining a complex of (a) contacting the compound of ruthenium(0) diretional phosphine ligand; and

b) obtaining complex (C) in the redox reaction of complex (A) with a carbonyl compound of cobalt(0).

2. The method according to claim 1, where directiony phosphine ligand has the General formula

where each R and R' independently or together represents a hydrocarbon fragment containing up to 30 carbon atoms, and Q represents an organic bridging group ranging in length from 2 to 4 atoms.

3. The method according to claim 2, g is e groups R and R' each independently represents alkyl, cycloalkyl, bicycloalkyl or aryl group.

4. The method according to claim 2 or 3, where Q includes the carbon atoms.

5. The method according to claim 4, where Q is alkylenes group of length 2, 3 or 4 carbon atoms.

6. The method according to any one of claims 1 to 5, where directiony phosphine ligand selected from one or more of 1,2-bis-(dicyclohexylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane, 1,2-bis(diethylphosphino)ethane,

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

1,2-bis(diphenylphosphino)benzene,

1,2-bis-(dimethylphosphino)ethane,

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

1,2-bis(Diisobutylene)ethane,

1,2-P,P'-bis(9-phosphabicyclo[3.3.1] and/or [4.2.1]nonyl)ethane, 1,2-P,P'-propane or 1,3-P,P'-propane counterparts.

7. The catalyst hydroformylation obtained by the method, which includes:

a) obtaining a complex of (a) the contacting of ruthenium(0) diretional phosphine ligand; and

b) obtaining complex (C) in the redox reaction of complex (A) with a carbonyl compound of cobalt(0).

8. One way of hydroformylation to obtain 1,3-diol, comprising the reaction of oxirane with synthetic gas in terms of hydroformylation in an inert solvent in the presence of a catalyst, hydroformylation is, obtained by a method that includes:

a) obtaining a complex of (a) the contacting of ruthenium(0) diretional phosphine ligand; and

b) obtaining complex (C) in the redox reaction of complex (A) with a carbonyl compound of cobalt (0).

9. One way of hydroformylation to obtain 1,3-diol, comprising the reaction of oxirane with synthetic gas in terms of hydroformylation in an inert solvent in the presence of a catalyst of hydroformylation, which represents a bidentate complex of ruthenium (+1)-phosphine: cobalt (-1), where legirovannym metal is ruthenium, under conditions that preferably after completion of the reaction, oxiran/syngas cause phase separation of the reaction mixture in the upper phase of the solvent with a high content of catalyst and the lower phase of a solvent with a high content of 1,3-diol, the management of the upper phase with a high content of catalyst directly into the reaction hydroformylation for further reaction with previously unreacted raw materials, and the selection 1,3-diol from the lower phase with a high content of 1,3-diol.

10. The catalyst hydroformylation, which represents a bidentate complex of ruthenium(+1)-phosphine:cobalt(-1), where legirovannym metal t is aetsa ruthenium.



 

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

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15 cl, 1 dwg, 1 tbl, 2 ex

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FIELD: organic synthesis catalysts.

SUBSTANCE: invention, in particular, concerns preparation of catalyst soluble in reaction medium, which is efficient in reactions of epoxidation of olefins by organic hydroperoxides. Preparation of catalyst comprises providing water-ammonia solution of ammonium molybdate, bringing it into reaction with C2-C8-alkanediol, and distilling away aqueous ammonia and excess diol followed by modifying resulting catalyst with nitrogen-containing organic compound, which is introduced into catalyst in aliphatic C3-C4-alcohol solution at molar ratio of nitrogen-containing organic compound to molybdenum compound (1-10):1. Nitrogen-containing organic compound is selected from diamines of general formula R1NHR2NHR3, where R1 is phenyl, C6-cycloalkyl, naphthyl, or diphenylamine, R2 is C1-C2-alkylene, C6-C8-arylene, or -C(=NH)-, and R3 is isopropyl, phenyl, naphthyl or diphenylamine; aminophenols of general formula R4R5R6N, where R4 is hydroxynaphthyl or 4-hydroxy-3,5-di-tert-butylbenzyl, R5 is hydrogen, C1-C2-alkyl, or phenyl, and R6 is methyl or 4-hydroxy-3,5-di-tert-butylbenzyl; and stable nitroxyl radical 2,2,6,6-tetramethylpyperidine-1-oxyl. Method allows: preparation of molybdenum-containing catalyst showing high activity and selectivity in reaction of hydroperoxide epoxidation of olefins, including low-reactive ones, e.g. propylene; simplification of technology due to use of commercially available organic nitrogen-containing compounds, so that additional synthesis stages can be avoided; and use of ammonium molybdate obtained during regeneration of molybdenum-containing epoxidation catalyst.

EFFECT: increased catalyst preparation efficiency and increased activity and selectivity of catalyst.

2 cl, 2 tbl, 18 ex

FIELD: polymerization catalysts.

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EFFECT: increased activity and stereoselectivity of catalyst.

10 cl, 1 tbl, 20 ex

FIELD: catalyst manufacture technology.

SUBSTANCE: invention relates to carbon monoxide-water steam conversion to form nitrogen-hydrogen mixture that can be used in ammonia synthesis. Preparation of catalyst comprises precipitation of iron hydroxide from iron nitrate solution with ammonia-containing precipitator, washing of iron hydroxide to remove nitrate ions, mixing with copper compound, granulation, and drying and calcination of granules. Invention is characterized by that iron hydroxide is mixed with copper and calcium oxides at molar ratio Fe2O3/CuO/CaO = 1:(0.03-0.2):(1.0-2.0), after which mechanical activation is performed. Resulting catalyst is 1.8-2.0-fold stronger and by 11.0-15.4% more active than prototype catalyst.

EFFECT: increased strength and catalytic activity.

1 tbl, 3 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention disclose a method for preparing catalyst based on DMC (4,4'-dichloro-α-methylbenzhydrol) appropriate to be used in polymerization of alkylene oxides into polyol-polyethers comprising following stages: (i) combining aqueous solution of metal salt with metal cyanide aqueous solution and allowing these solutions to interact, while at least one part of this reaction proceeds in presence of organic complexing agent to form dispersion of solid DMC-based complex in aqueous medium; (ii) combining dispersion obtained in stage (i) with essentially water-insoluble liquid capable of extracting solid DMC-based complex and thereby forming biphasic system consisting of first aqueous layer and a layer containing DMC-based complex and liquid added; (iii) removing first aqueous layer; and (iv) removing DMC-based complex from layer containing DMC-based catalyst.

EFFECT: lack of negative effect on DMC-based catalyst activity.

16 cl, 1 tbl, 3 ex

FIELD: catalytic chemistry.

SUBSTANCE: the invention is dealt with the fields of catalytic chemistry. The invention offers a predecessor of the cobaltic catalyst, which contains a catalyst carrier impregnated with cobalt. All the restorable cobalt is present in the carrying agent in the form of a sustained cobalt oxide in accordance with a block formula CoOaHb, in which a ≥ 1.7 and b ≥ 0. The invention also offers alternatives of the method of preparation of the predecessor of the cobaltic catalyst. The technical result is production of a cobaltic catalyst with a higher activity.

EFFECT: the invention ensures production of a cobaltic catalyst with a higher activity.

20 cl, 10 ex, 12 tbl, 10 dwg

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