C6+ olefin hydroformylation catalyst, method for preparation thereof, and a process for production of aldehydes c7+

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to synthesis of C7+-aldehydes from C6+-olefins, carbon monoxide, and hydrogen via hydroformylation reaction and to preparation of catalyst used in this reaction. Olefin hydroformylation catalyst contains complex compound of rhodium with polymeric nitrogen-containing ligand including phosphorus-containing fragments. Each of these fragments contains organic radicals, at least one of which is linked to nitrogen atom of polymeric nitrogen-containing ligand and phosphorus atom is in the form of Ph(III). Catalyst preparation consists in that nitrogen-containing polymer is subjected to reaction in organic solvent with Ph(III) compound including organic radicals, of which at least one radical includes group -C(O)OH. Thus obtained product is then subjected to reaction with rhodium compound and organic solvent is removed.

EFFECT: increased and preserved specific activity and regioselectivity of recycled catalyst and reduced pressure in aldehyde production process.

11 cl, 1 tbl, 8 ex

 

The technical field to which the invention relates.

The invention relates to the main organic thin organic and petrochemical synthesis and relates to a catalyst for the synthesis of aldehydes With7+of olefins With6+, carbon monoxide and hydrogen by the method of hydroformylation, method of producing the specified catalyst and method of producing aldehydes With7+using a specified catalyst.

The level of technology

Synthesis of high molecular weight (7+) aliphatic aldehydes mainly through hydroformylating olefins (C6+) using cobalt catalysts. The choice of cobalt catalysts due to their thermal stability, which allows to separate the products of hydroformylation simple distillation. The disadvantages of this catalyst are: substantial hydrogenation of olefins to paraffins (3-10%), low regioselectivity and relative products of linear structure (<75%), as well as the need to use "hard" conditions hydroformylation (P≥20 MPa, T≥150°C).

Application in industrial scale rhodium-phosphine catalysts hydroformylating olefins (C6+), which differs from the cobalt more active and regiospecificity in respect of products of linear structure, as well as more "soft is mi" conditions hydroformylation (P≈ 2 MPa, T≈100°C), is difficult, because the rhodium-phosphine catalysts are much less stable, making distillation methods are unsuitable for separation of the reaction products (aldehydes and alcohols With7+) from the catalyst.

To separate the products of hydroformylation from rhodium-phosphine catalysts hydroformylation, in addition to distillation, apply the so-called "bi-phase system (a system consisting of two or more liquid phases or become such, under certain conditions, allowing to separate the products of hydroformylation by decantation.

Known water-soluble recycled catalyst (U.S. Pat. USA. No. 4248802)consisting of compounds of rhodium and salts of sulfonated phosphine ligand, allowing the synthesis of aldehydes in the two-phase system and separated by decantation podwodny solution of the catalyst from the reaction products. However, this catalyst is hardly applicable for hydroformylating olefins With6+due to their low solubility in the aqueous phase.

Known catalyst hydroformylating olefins With6+(Patent RF № 2059598 - prototype). The catalyst consists of a compound of rhodium and water-soluble macroligand - copolymer dimethyldiallylammonium and dimethylallylpyrophosphate and additional modifier Na3PO4or Na2 SO4. This catalytic system allows two-phase synthesis of aldehydes with subsequent recycling of the catalyst by simple decantation. The disadvantage of this recycled catalyst is a significant drop in activity when conducting recyclo catalyst, as well as the need to maintain high pressure (not less than 5 MPa).

A known method of producing catalyst hydroformylating olefins With6+(Patent RF № 2059598 - prototype). This method consists in the interaction of compounds with nitrogen-containing rhodium compound is a copolymer of dimethyldiallylammonium and dimethyldiallylammonium in the presence of n-xylene and water.

This method does not allow to obtain a catalyst having the desired activity and recircularisation in the reactions of hydroformylation.

A known method of producing aldehydes With7+(Patent RF № 2059598 - prototype), namely, that hydroformylating olefins With6+carbon monoxide and hydrogen is carried out at a temperature of 90°C and a pressure of 6 MPa in the presence of a rhodium catalyst containing polymer water-soluble nitrogen-containing ligand in the form of a copolymer of dimethyldiallylammonium and dimethyldiallylammonium and dimethylcarbamodithioato. However, this method has a low rate g is reformirovania, requires high pressure and does not allow to achieve the desired activity, regioselectivity and recirculatory catalyst.

Disclosure of inventions

The objective of the invention is to provide a highly efficient and technologically simple recycling of the catalyst hydroformylating olefins With6+, method of its production and method of producing aldehydes With7+using a specified catalyst.

The technical result consists in increasing and maintaining the specific activity and regioselectivity catalyst during recirculation, the possibility of using simple technology of its separation from the reaction products by recycling, as well as the catalyst enables the use of lower pressure upon receipt of aldehydes With7+.

The technical result is achieved in that the catalyst hydroformylating olefins With6+contains complex compounds of rhodium with a polymeric nitrogen-containing ligand comprising phosphorus-containing fragments, with each specified fragment contains organic radicals, at least one of which is connected to the nitrogen atom of the polymeric nitrogen-containing ligand, and the phosphorus atom is in oxidation state (III).

An aqueous solution of the catalyst provides a stable phase - water emulsion, RA is livaudais with the organic phase of the substrate and/or product that allows the separation of the reaction product after completion of the catalyst by decantation and increase recirculatory catalyst (to keep it specific activity when conducting recyclo catalyst). The presence of the emulsion phase, which is the catalytic complex, results in high values of the velocity of hydroformylation due to the interface of the catalyst and substrate, which eliminates the limitations associated with the transport of the substrate to the catalytically active center of the metal.

The introduction of the catalyst specified phosphorus-containing fragment in which the phosphorus atom is in oxidation state (III), allows to increase the activity and regioselectivity, as well as significantly reduce the pressure required to obtain aldehydes With7+(1.5-3.5 MPa). Phosphorus-containing fragment can have the General formula:

where a, b, C - organic radicals, at least one of which is connected to the nitrogen atom of the polymeric nitrogen-containing ligand.

As complex compounds of rhodium can be used acetylacetonate of dicarbonyl rhodium (I) (Rh(acac)(CO)2).

The technical result is also achieved by the implementation of the method of producing catalyst hydroformylating olefins With6+being , coastsiders polymer is subjected to interaction in an organic solvent with a compound of phosphorus in oxidation state (III), including organic radicals, at least one of which has a group-C(O)IT, then the resulting product is subjected to interaction with the compound of rhodium and remove the organic solvent.

When implementing this method is a chemical binding of the nitrogen-containing polymer with a phosphorus-containing compound in which the phosphorus has an oxidation state (III), including organic radicals, at least one of which has a group-C(O)IT, which gives a catalyst with high specific activity and selectivity, technological simplicity of its separation from the reaction products by recycling, and also enables use of a lower pressure upon receipt of aldehydes With7+.

As the nitrogen-containing polymer can be used polyethylenimine (PAYS) a branched structure with a molecular weight of 10000 g/mol.

Fosforsoderzhashchie compound may have the General formula:

where a, b, C - organic radicals, at least one of which has a group-C(O)HE.

In particular, if the mass ratio of the PAYS/fosforsoderzhashchie connection is 20/1-10/1 or the mass ratio of nitrogen/phosphorus=142/1-70/1.

As compounds of rhodium can be used acetylacetonate of decarb the Nile rhodium (I), the rhodium nitrate, rhodium chloride, rhodium iodide, rhodium sulfate.

In the particular case of a molar ratio of P/Rh is 5/1-15/1 (preferably 10/1).

The technical result is also achieved by the implementation of the method of producing aldehydes With7+including hydroformylating olefins With6+carbon monoxide and hydrogen at elevated temperature and pressure in the presence of an aqueous solution of the catalyst containing the complex compound of rhodium with nitrogen-containing polymer, comprising the phosphorus-containing ligand fragments, with each specified fragment contains organic radicals, at least one of which is connected to the nitrogen atom of the indicated ligand, and the phosphorus atom is in oxidation state (III).

An aqueous solution of rhodium catalyst can be used in a mass ratio of water to catalyst in the range of 200:1-100:1

The volume ratio of aqueous phase (aqueous solution of catalyst) and the organic phase can be 2/1-4/1, while the organic phase are a mixture of olefins With6+, aldehydes7+and an organic solvent. In this range of ratios is formed optimum emulsion, which allows to achieve a high-speed process.

The implementation of the invention

The method of producing catalyst hydroformylating olefins With6+includes posledovatel the efficiency of operations:

chemical binding of the nitrogen-containing polymer with a phosphorus-containing compound having the General formula

where a, b, C - organic radicals, at least one of which has a group-C(O)HE;

An example of such a binding is the interaction of the PAYS (polyethylenimine) n-diphenylstilbene acid, with the formation of polymeric nitrogen-containing ligand comprising phosphorus-containing fragments is carried out at a molar ratio of nitrogen/phosphorus=142/1-70/1 (preferably 70/1), preferably in an atmosphere of inert gas;

- chemical interaction of the obtained polymeric nitrogen-containing ligand comprising phosphorus-containing fragments, with the compound of rhodium in the medium of organic solvent, which may be carried out at a molar ratio of P/Rh=5/1-15/1 (preferably 10/1);

- remove the organic solvent at a temperature of 30-50°obtaining a catalyst in the form of VAT residue;

- dissolution of the obtained catalyst in water to obtain a catalyst in the form of an aqueous solution, for example, when the mass ratio of N2O/PAYS=200:1-100:1 (preferably 150:1).

How hydroformylating olefins With6+using the above catalyst includes the sequence of operations:

sequential or joint put the e in the reactor water of the catalyst solution, individual or mixture of olefins With6+and an organic solvent; however, the volume ratio of aqueous phase/organic phase can be 2/1-4/1 (preferably 2/1), where the organic phase can serve a mixture of substrate, product, and an aromatic solvent;

the mixture in the atmosphere of carbon monoxide and hydrogen at elevated temperature and pressure;

the decantation of the organic phase containing the product from the aqueous emulsion containing the catalyst.

Proposed catalytic system is used in hydroformylating olefins With6+which is conducted at the reaction temperature 70-130°With (preferably 80° (C), the pressure of the synthesis gas of 1.5 to 3.5 MPa, and the ratio of N2/CO=1/1.

The process may leak and at higher pressures, for example, 6 MPa.

The method of producing catalyst

PAYS dissolved in a minimum amount of methylene chloride, n-DFBC (n-diphenylphosphinomethyl acid) was also dissolved in methylene chloride, and then was slowly added to the solution PAYS under stirring until complete dissolution. Then to the resulting solution was slowly added a solution of Rh(CO)2(acac) in methylene chloride. Thereafter, methylene chloride was evaporated by rotary evaporator and the resulting dry residue was dissolved in water.

The way to receive the deposits of aldehydes With 7+in the two-phase system

An aqueous solution of catalyst and olefin poured into the reactor. After loading the catalyst solution and olefin autoclave is purged three times with nitrogen to remove oxygen. Next carried out heating the reaction mixture under stirring and the excess nitrogen pressure of 0.5 MPa. After heating to a temperature of 80°filed synthesis gas to achieve in a given reactor pressure. This moment was the beginning of the reaction. In the experiment, the recorded pressure drop synthesis gas.. On completion of the reaction was judged on the cessation of pressure drop. After completion of the reaction, the reaction mixture was analyzed by GC.

The method of implementation of the recycling catalyst

For the implementation of recycling catalytic reaction products (organic phase) was separated from the aqueous emulsion, mainly containing the catalyst, by means of decantation. It was further added to the catalyst solution a fresh portion of the olefin and was in the process of hydroformylation.

The implementation of the present invention illustrate the following examples, which do not limit the scope of the claims presented in the claims.

Example 1

PAYS (0,023 g) was dissolved in minimum amount of methylene chloride. n-DFBC - (0,061 g) was dissolved in methylene chloride, then slowly, dropwise, d is bavili to the solution PAYS under stirring, before the formation of a completely homogeneous solution. Next, to the resulting solution was slowly when pomeshivanii added a solution of Rh(CO)2(acac) (0.005 g) in methylene chloride. The solution was evaporated on a rotary evaporator until dry. The dry residue was dissolved in 10 ml of water.

The solution of the catalyst in water-HEXEN-1 (10 ml) was placed in a reactor-autoclave 0,075 l, made of Hastalloy, equipped with a mixing device. Next, the reactor three times purged with nitrogen, was heated under stirring and the excess nitrogen pressure of 0.5 MPa to a temperature of 80°then handed synthesis gas (1SD:1H2) until reaching a pressure of 3.5 MPa. This moment was the beginning of the reaction. In the course of the experience recorded a drop in pressure synthesis gas. When the pressure drop of 0.5-1.0 MPa reactor was filled with the synthesis gas to the initial value. On the obtained dependency was determined by the initial value of the absorption rate of the synthesis gas and the total pressure drop of the synthesis gas during the reaction. On completion of the reaction was judged on the cessation of pressure drop. After completion of the reaction the contents of the reactor were cooled, dropped the pressure of the synthesis gas and got the reaction mixture which consists of two stratifying the liquid phase: water phase of the emulsion, which is a catalytic complex, and the organic phase product. The last analyzed n the content of products of hydroformylation and unreacted olefin with GC.

For the implementation of the recycling catalyst solution was separated from the reaction products by means of decantation. It was further added to the catalyst solution a fresh portion of hexene-1 and again was in the process of hydroformylation.

Example 2

The synthesis of the catalyst, the process hydroformylation and recycling of the catalyst was carried out according to example 1, at the first stage downloaded PAYS (0,064 g).

Example 3

The synthesis of the catalyst, the process gidrofobizirovan and recycling of the catalyst was carried out according to example 1, at the first stage downloaded PAYS (0,148 g).

Example 4

The synthesis of the catalyst, the process hydroformylation and recycling of the catalyst was carried out according to example 1, at the first stage downloaded PAYS (0,221 g).

Example 5

The synthesis of the catalyst, the process hydroformylation and recycling of the catalyst was carried out according to example 1, at the first stage downloaded PAYS (0.64 g) and n-DFBC (0,031 g).

Example 6

The synthesis of the catalyst, the process hydroformylation and recycling of the catalyst was carried out according to example 1, at the first stage downloaded PAYS (0.64 g) and n-DFBC (0,0613 g).

Example 7

The synthesis of the catalyst, the process hydroformylation and recycling of the catalyst was carried out according to example 1, at the first stage downloaded PAYS (0.64 g) and n-DFBC (0.104 g g).

For all experiments shown in the example, four of the recycling of the catalyst (Table 1).

Example 8

Synthesis of catalyst and recycling the catalysate is RA was carried out according to example 1, in the first stage have downloaded PAYS (0.64 g) and n-DFBC (0,0613 g), the process hydroformylation was carried out at 1.5 MPa.

Table 1.

The process indicators of hydroformylation hexene-1, obtained in examples 1-8.
# exampleTOF, h-1(SR, %)
1 cycle2 cycle3rd cycle4 cycle5 cycle
1388 (77)641 (74)416 (73)No dataNo data
2457 (72)706 (74)1318 (69)848 (68)413 (68)
3498 (69)580 (72)1407 (68)1278 (63)1143 (61)
4462 (70)660 (71)1159 (64)987 (60)614 (56)
5465 (73)525 (72)496 (66)no dataNo data
6457 (72)706 (74)1318 (69)848 (68)413 (68)
7414 (72)552 (74)759 (37)603 (67)518 (67)
212 (72)320 (74)No dataNo dataNo data
TOF - specific activity of the catalyst, the mol aldehyde/mol Rh*4);

SR- regioselectivity relatively grocery aldehyde linear structure, mol n-heptanes/(mol n-heptanes+mol from heptanes).

The table below shows the results show that the proposed method of preparation of the catalyst allows to achieve activity TOF up to 1000 h-1what distinguishes this catalytic system from the best known to be used in aqueous biphasic catalytic hydroformylating olefins With6+characterized by TOF<700 h-1.

The proposed recycled catalyst leads to the formation of the corresponding aldehydes with selectivity close to 100%, and regiospecificity normal isomer 68%. The proposed catalyst can be reused in reciclar without significant loss of activity and selectivity after decanting, the organic layer of the reaction products.

Industrial applicability

The invention is intended for use mainly organic and petrochemical synthesis of oxygen-containing products by the method of hydroformylating olefins With6+in particular, when conducted and syntheses of aldehydes With 7+.

1. The catalyst hydroformylating olefins With6+containing complex compounds of rhodium with a polymeric nitrogen-containing ligand comprising phosphorus-containing fragments, with each specified fragment contains organic radicals, at least one of which is connected to the nitrogen atom of the polymeric nitrogen-containing ligand, and the phosphorus atom is in oxidation state (III).

2. The catalyst according to claim 1, characterized in that the phosphorus-containing fragment has a General formula

where a, b, C - organic radicals, at least one of which is connected to the nitrogen atom of the polymeric nitrogen-containing ligand.

3. The method of producing catalyst hydroformylating olefins With6+consists in the fact that nitrogen-containing polymer is subjected to interaction in an organic solvent with a compound of phosphorus in oxidation state (III), including organic radicals, at least one of which has a group-C(O)IT, then the resulting product is subjected to interaction with the compound of rhodium and remove the organic solvent.

4. The method of preparation of the catalyst according to claim 3, characterized in that as the nitrogen-containing polymer used polyethylenimine (PAYS) a branched structure with a molecular weight of approximately 10000 g/mol.

p> 5. The method of preparation of the catalyst according to claim 3, characterized in that the connection of phosphorus in oxidation state (III) has a General formula

where a, b, C - organic radicals, at least one of which has a group-C(O)HE.

6. The method of preparation of the catalyst according to claim 4, characterized in that the mass ratio of the PAYS/connection phosphorus is 20/1-10/1.

7. The method of preparation of the catalyst according to claim 3, characterized in that compounds of rhodium used acetylacetonate of dicarbonyl rhodium (I).

8. The method of preparation of the catalyst according to claim 3, characterized in that the molar ratio of phosphorus/rhodium is 5/1-15/1.

9. A method of producing aldehydes With7+including hydroformylating olefins With6+carbon monoxide and hydrogen at elevated temperature and pressure in the presence of an aqueous solution of the catalyst containing the complex compound of rhodium with nitrogen-containing polymer, comprising the phosphorus-containing ligand fragments, with each specified fragment contains organic radicals, at least one of which is connected to the nitrogen atom of the indicated ligand, and the phosphorus atom is in oxidation state (III).

10. A method of producing aldehydes With7+according to claim 9, characterized in that an aqueous solution of rhodium catalyst mass ratio of water to which utilizator is in the range of 200:1-100:1.

11. A method of producing aldehydes With7+according to claim 9 or 10, characterized in that the volume ratio of the phases is an aqueous emulsion/mixture of olefins With6+, aldehydes7+and an organic solvent is 2/1 to 4/1.



 

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9 cl, 2 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing concentrate of butyric aldehydes by oxonation. Method is carried out by the hydroformylation reaction of propylene with synthesis-gas in two in-line connected reactors at temperature 120-150°C, under pressure 250-300 kgf/cm2 and with heat removing by circulation of cooling agent through Field's tubes installed in hydroformylation reactors followed by separation of reaction products. The hydroformylation process in the first reactor is carried out in regimen when the ratio of volume consumptions of cooling agent circulating in Field's tubes and propylene feeding into reactor is (18-28):1. Invention provides enhancing yield of end products, improving energetic indices due to effective heat transfer in the hydroformylation reactor.

EFFECT: improved preparing method.

1 tbl, 4 ex

FIELD: improved processes catalyzed by complexes of a metal- organophosphorous ligand.

SUBSTANCE: the invention presents the improved processes catalyzed by complexes of metal-organophosphorous ligand. The method of extraction includes: feeding of the indicated liquid reactionary product in the zone of separation, stirring of the indicated liquid reactionary product with production by separation of phases of a polar phase containing one or several unreacted reactants, a complex catalyst metal- organophosphorous ligand, not obligatory free organophosphorous ligand and one or several polar dissolvents; and a nonpolar phase containing one or several products of decomposition of the organophosphorous ligand, one or several by-products of the reaction and one or several products. Further the method provides for the stages of withdrawal from the zone of separation and feeding into the reaction zone and-or into the zone of separation. In the given method selectivity of the polar phase for the organophosphorous ligand concerning one or several products is expressed by a ratio of distribution coefficients Efl, which has a value more than approximately 2.5; (ii) the selectivity of the polar phase for the organophosphorous ligand concerning one or several decomposition products of the organophosphorous ligand is expressed by a ratio of distribution coefficients Ef2, which has a value more than approximately 2.5; and (iii)the selectivity of the polar phase for the organophosphorous ligand concerning one or several by-products of reaction is expressed by a ratio of distribution coefficients Ef3, which value is more, than approximately 2.5. The method allows to reduce a negative effect on the process, for example, on prevention of a decrease of efficiency of the catalyst, conversion of the initial material and selectivity by a product.

EFFECT: the invention ensures reduction of a negative effect on the process, on efficiency of the catalyst, on conversion of the initial material and selectivity by a product.

20 cl, 2 tbl

The invention relates to an improved method of separating one or more products from the liquid reaction product containing the catalyst in the form of complex compounds of a metal with an organophosphorus ligand, optionally free organophosphorus ligand, a non-polar solvent, the polar solvent is selected from the group comprising NITRILES, lactones, pyrrolidone, formamide and sulfoxidov, and named one or more products, the method comprises (1) mixing named liquid reaction product to obtain phase separation a nonpolar phase containing the above catalyst, optionally free organophosphorus ligand and called nonpolar solvent and a polar phase, contains named one or more products and a polar solvent, and (2) the Department called the polar phase from the named non-polar phase, and named the organophosphorus ligand has a distribution coefficient between the nonpolar solvent and the polar solvent of greater than about 5, and named one or more products is the distribution coefficient between the polar solvent and the nonpolar rastvorimo of the reaction product, containing the catalyst in the form of complex compounds with metal-phosphorus metal, optionally free organophosphorus ligand, a non-polar solvent and one or more products, the method comprises (1) mixing named liquid reaction product with a polar solvent selected from the group comprising NITRILES, lactones, pyrrolidone, formamide and sulfoxidov, to obtain phase separation a nonpolar phase containing the above-mentioned catalyst, optionally free organophosphorus ligand and called nonpolar solvent and a polar phase containing named one or more products and a polar solvent, and (2) the Department called the polar phase from the named non-polar phase, and named the organophosphorus ligand and named one or more products have the distribution coefficient between the nonpolar solvent and the polar solvent of greater than about 5, and named one or more products is the distribution coefficient between the polar solvent and the nonpolar solvent of greater than about 0.5

The invention relates to new furifosmin formula I

< / BR>
where n denotes an integer of 1 or 2; R1denotes a hydrophilic group selected from the following groups: -SO2M, -SO3M, -CO2M, -PO3M, where M represents inorganic or organic cationic residue selected from a proton, cations, alkaline or alkaline earth metals, ammonium cations -- N(R)4where R denotes hydrogen or C1-C14alkyl, and the other cations are based on metals, salts with acids: fullsleeve, fullcarbon, fullsleeve or furylphosphonous soluble in water; m denotes an integer of 1; R2denotes a hydrophilic group,- SO2M, -SO3M, -CO2M, RHO3M, where M denotes hydrogen or an alkaline metal salt with the acid fullsleeve, fullcarbon, fullsleeve or fullfactorial soluble in water, R denotes an integer from 0 to 2

The invention relates to a mixture of branched primary alcohols from C11to C36and to mix them sulfates, alkoxylated, alkoxylates and carboxylates, which have high washing ability in cold water and good biological degradability

FIELD: carbon monoxide conversion catalysts.

SUBSTANCE: invention relates to a method of preparing catalysts for middle-temperature conversion of carbon monoxide, which can be used in industry when producing nitrogen-hydrogen mix for ammonia synthesis. Preparation of catalyst for middle-temperature conversion of carbon monoxide with water steam, comprising precipitation of iron hydroxide from iron nitrate solution with ammonia-containing solvent, washing of iron hydroxide with water to remove nitrate ions, mixing with calcium and copper ions, mechanical activation of components, molding, drying, and calcination of granules, is characterized by that, in the component mixing step, lanthanum oxide is supplementary added, in which case molar ratio of components is as follows: Fe2O3/CaO/CuO/La2O3 = 1:(0.8-0.9):(0.045-0.08):(0.005-0.01).

EFFECT: increased catalytic activity and more than thrice reduced content of by-products in condensate.

1 tbl, 3 ex

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