The method of producing dimers and oligomers of olefins

 

(57) Abstract:

Usage: petrochemistry. Essence: carry out the dimerization and oligomerization of olefins in a hydrocarbon solvent in the presence of a catalyst consisting of compounds of Nickel deposited on a polymer base, swelling in hydrocarbon solvent. As the polymer base catalyst used chain rubber mesh structure with swelling properties in hydrocarbon solvent of 0.1 to 4.5 ml/g of catalyst at a molar ratio of aluminum to Nickel 1-5 and the Nickel content in the catalyst is from 0.2 to 2.2 wt.%, and as olefin using the olefin WITH2-C9including registereda refinery fractions. The technical result - the simplification of technology and increase productivity. table 1.

The present invention relates to the field of petrochemicals, in particular, to the production of dimers and oligomers of olefins, is widely used as monomers, components of motor fuels and raw materials in the production of surface-active substances, additives to oils, plasticizers, flotation agents, and synthetic oils.

Known methods for producing dimers and oligomers of olefins using the 00 (C. W. Feldblum. Dimerization and disproportionation of olefins. M.: Chemistry, 1978, S. 44).

A significant drawback of these methods is the volatility used in these catalytic systems, which leads to their rapid deactivation. This causes:

significant costs of the components of the catalytic system, especially alkylhalogenide;

- the need for a special process steps for neutralization and separation of compounds of Nickel and aluminum from the reaction products;

- low output oligomers of olefins used for the production of surface-active substances.

A method of obtaining olefinic hydrocarbons dimerization or codimerization olefins in the presence of a catalyst comprising a polymer containing atoms of Nickel complex associated with electron-donor groups of the polymer, and socializaton - alyuminiiorganicheskikh compounds, and polymer catalyst is a swelling in the solvent grafted copolymer polymer selected from the group consisting of natural rubber, ethylenepropylene polymers, polymers of diene and copolymers with other monomers and silicone polymers containing wine of the Sabbath.

In contrast to the homogeneous analogues such catalysts have a long stationary catalytic action, easily and completely separated from the reaction products, as are separate from the solvent gel phase.

The disadvantages of the method are:

- not enough high productivity of the process per unit mass of catalyst;

- multistage get used in the process of catalyst, including vaccination 4-vinylpyridine) - derivatives for polymer - rubber in the presence of a radical initiator (dinitrile azabicycloalkanes acid) and vulcanization;

- low yield in this method, tri - and tetramers of propylene and other olefins.

There are also known methods for producing dimers of ethylene (SU 681036, 25.08.1979, SU 1356384 A1, 15.11.92), propylene dimers (SU 1356383 A1, 15.11.1992), dimers of ethylene and propylene (SU 1387345 A1, 15.11.92, SU 1586382 A1, 15.11.92), trimers and tetramers of propylene (SU 1356382 A1, 15.11.1992, SU 1609065 A1, 15.11.1992) in a hydrocarbon solvent at a temperature of 0-100oAnd pressure 0-100 ATM, using a catalyst containing 0.5-2 wt. % Nickel and 3-15 wt.% aluminum in the form of Nickel - and alyuminiiorganicheskikh compounds immobilized on the polymer carrier on onondago of diene and binary macroligand.

The closest of them to the technical nature of the present method of producing dimers and oligomers of olefins is a method for olefin hydrocarbons (SU 1586113 A1, 15.11.1992) dimerization of olefins in the environment of the hydrocarbon solvent in the presence of a catalyst containing 0.6 to 2.0 wt. % Nickel and 3.0-15 wt.% aluminum in the form of Nickel - and alumnimagazine compounds immobilized on the polymer-based media crosslinked graft copolymer synthetic rubber - ternary copolymer of ethylene, propylene and a non-conjugate diene and 10-40 wt.% binary macroligand is a polymer of poly-2-methyl-5-vinylpyridine) - derivatives with a molecular mass of 20-200 thousand with polymethacrylic acid, when the mass ratio of the binary macroligand equal to (0,9-1,4):1 respectively.

The method allows to increase the productivity of the process up to 200 g of oligomers per 1 g of catalyst per hour. In the reaction products contained up to 29 wt.% tri - and tetramers of olefins.

The disadvantages of the prototype method are:

- a multi-stage of preparation of the catalyst, the production of which is an integral part of the process of dimerization, including:

1) vaccine to the polymer-rubber vinylpyridines acid;

3) curing the resulting polymer carrier using benzoyl peroxide;

4) the application of polymeric media of Nickel compounds;

5) application of aluminum compounds (ll3);

6) activation of the catalyst alyuminiiorganicheskikh connection;

substantial consumption of aluminum compounds, which complicates the process of dimerization due to the need for neutralization and separation of the products of neutralization;

narrow focus: as raw material for the dimerization uses only purified ethylene and propylene, as well as the reaction products obtained mainly dimers;

- not a high performance catalyst that with its high cost significantly increases the cost of production;

- insufficient mechanical strength of the gel catalyst due to its high swelling that leads to its destruction during operation and storage.

The task of the invention to create a more technological in comparison with the prototype of the production of dimers and oligomers of olefins with the expansion of the resource base from C2-C3to C4-C9including registergui oil fractions, thanks to the use of the Oia flow alyuminiiorganicheskikh compounds (AOC), and also increase the performance of the process.

The task is carried out by the method of producing dimers and oligomers of olefins by dimerization and oligomerization of olefins in a hydrocarbon solvent in the presence of a catalyst consisting of compounds of Nickel deposited on a polymer base, swelling in the solvent and activator - AOC. The method differs from the prototype in that as the basis of the catalyst used carboranyl rubber mesh structure with swelling properties in a solvent of 0.1 to 4.5 ml/g of catalyst, molar ratio AL/Ni 1-5, when the Nickel content of 0.2-2.2 wt.%, when used as olefin olefins WITH2-C9including registergui refinery fractions.

According to the claimed method as a basis for preparation of the catalyst used carboranyl rubber: polybutadienes with different structures and their industrial counterparts (ACS, SBSR, SKB), polyisoprene (RCM), neoprene, butadiene-styrene rubbers, EPDM, shungit (qualified electronic signature certificate, Sept), and their copolymers and combinations, for example with styrene.

For the formation of durable mesh with swelling properties in hydrocarbon solvent of 0.1 to 4.5 ml/g katarinam vulcanizing agent (for example, the peroxide Dicumyl, peroxide benola and others ). This allows to significantly simplify the manufacturing technology of the catalyst and, consequently, the entire process, as well as to increase the mechanical strength of the catalyst. On the other hand, it was unexpectedly found that the vulcanization medium in the presence of compounds of Nickel leads to a solid fixation of Nickel in the rubber and increase the chemical stability of the synthesized deposited Nickel catalyst, resulting in a significant increase in the period of its operation and the reduction of the AOC as socializaton.

As compounds of Nickel use organic, inorganic, complex compounds such as acetylacetonate, naphthenate, carboxylates, chlorides.

As AOC when activated, it is used alkyl - and alkylhalogenide connection.

Dimerization and oligomerization of the olefin is carried out in a hydrocarbon or chlorophenothane solvent. Preferably use a straight-run gasoline, toluene or dimerized.

With the aim of expanding the range of olefins in addition to ethylene and propylene using butenes, pentene, hexene, as well as oligomers of olefins. The stability of the catalyst to impurities in cheese is yolisa oil, propane-propylene fraction (PPF), propylene-butenova (LPG), butane-butylene (BBF, beef), the fraction of n-butenes, as well as the fraction of oligomers of olefins.

The process of dimerization and oligomerization of olefins is carried out at a temperature of 20-80oC. To increase the yield of different fractions of trimers, tetramers and other oligomers up to 50% and the above process is carried out at elevated temperature 50-80oC. This also contributes to the increase in time of contact of the feedstock with the catalyst and increase the conversion of olefin per pass.

The process can be carried out both periodic and continuous technological scheme.

The process is characterized by a long service life of the catalyst (thousands of hours). In the case of reducing the activity of the catalyst regenerate his AOC.

Below are examples illustrating the present invention.

Example 1.

(Synthesis catalyst)

In a flask of 200 ml load 10 g industrial rubber BCC BSR, 0.5 g of Nickel acetylacetonate Ni(C5H7O2)2, 0.5 g of benzoyl peroxide and 50 ml of chloroform. The mixture was incubated at room temperature the day. The solvent is then evacuated, and the remaining mixture is heated at 120o5 o'clock P. the swell in hydrocarbon solvents. The swelling properties in heptane to 2.7 ml/g of catalyst. The content in the catalyst, wt.%: Nickel 1,1; rubber - rest.

B (dimerization of ethylene)

In a metal reactor of 200 ml was placed 0.4 g of the catalyst obtained in paragraph a, and 0.6 ml (0.5 mol/l) heptane solution of Al(C2H5)1,5Cl1,5and 5 ml of heptane. Activation of the catalyst is carried out at 50o0.5 h Then the solution AOC is drained, add in the reactor 5 ml of heptane and 40oC and a constant pressure of 15 ATM serves ethylene. Stirring implement a magnetic stirrer. After 1 h the reaction is stopped obtained dimerized drained and analyzed chromatographically. The results of the experiment are shown in table. Elemental analysis of dimezzato showed the absence of Nickel, which demonstrates its strong binding to the polymer carrier.

As can be seen from the table, the inventive method in the case of dimerization of ethylene is considerably larger than the prototype performance of the catalyst (in the prototype.with. The USSR 1586113, example 5 - performance 200 g/g catalyst h). The latter is much easier to be used in the method prototype as composition and its manufacturing technology. In addition, significantly reduces the consumption of CAPT-IB.

The swelling properties in heptane to 2.1 ml/g of catalyst.

Activation of the catalyst and the dimerization of propylene is carried out according to the method of example 1B, varying the conditions of experience. The results are shown in the table.

As the table shows, the performance of the dimerization of propylene reaches 65,5 g/g of catalyst (experience 3/3) against 47,3 g/g of catalyst in the prototype (example 7, and.with. 1586113). The output of oligomers WITH9C12increases with increasing temperature and decreasing pressure of propylene.

Examples 3-9.

The catalyst prepared according to example 1A using NiCl26H2O. the Catalyst contains, wt%: Nickel-1,1; rubber - 98,9.

By a similar method to prepare catalysts with different Nickel content.

Activation of the catalysts and the test is carried out according to example 1B, varying conditions. Characteristics of the catalysts and the results of their tests in the dimerization of olefins and registergui refinery fractions given in the table.

Examples 10-12.

In experiments using catalysts synthesized on the basis of industrial rubber chemicals: 1,2-polybutadiene (10), SKEPT-SKI (11) and "Neoprene" (12) according to example 1A. The results of dimerization on either the congestion, obtained in example 2, 0.5 g of Al(i-C4H9)1,5Cl1,5and 20 ml of oligomerizate obtained in example 2/4. The catalyst was activated at 50oWith 1 h and Then into the reactor serves propylene. The dimerization is carried out at 50oC and a pressure of 4 ATM of propylene, continuously merging dimerized in the receiver. After 48 h the analysis of dimezzato shows the lack of AOS. After 120 h the process speed is gradually reduced. Adding a fresh portion of the AOC (Al/Ni=3) leads to a complete regeneration of the catalyst. In this mode, with periodic replenishment of the AOC process spend 2000 hours, and the catalyst remains active. The performance of the process 21,4 g/g catalyst including Average composition of the flow of dimezzato at the exit of the reactor, wt.%: WITH3OF-2.1; (C6-69,7; C9-24,6; C12+-5,8.

As seen from the above examples, the conduct of processes of dimerization and oligomerization of olefins using a new catalyst enables to simplify the technology of the processes by simplifying the stage of preparation of the catalyst and reduce costs for AOC and its neutralization, to improve the performance of processes, and ispolzovat as raw material olefins WITH2- C9including registereda refinery of fractale olefins in a hydrocarbon solvent in the presence of a catalyst, consisting of compounds of Nickel deposited on a polymer base, swelling in the solvent and activator - alyuminiiorganicheskikh connection, characterized in that as the polymer base catalyst used chain rubber mesh structure with swelling properties in hydrocarbon solvent of 0.1 to 4.5 ml/g of catalyst, molar ratio Al/Ni 1-5 and the Nickel content in the catalyst is from 0.2 to 2.2 wt. %, and olefin using the olefin WITH2-C9including registereda refinery fractions.

 

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