The method of producing trimers and tetramers of propylene

 

(57) Abstract:

Usage: petrochemistry. The inventive propylene will oligomerized at 50-80oC and elevated pressures in the presence of a catalyst containing 0.5-1.3 wt.% Nickel immobilized on a polymeric carrier, and activator - alyuminiiorganicheskikh connection with the separation of oligomerizate into two streams, one of which is recycled to the oligomerization, and the other is directed to the separation by rectification with the return allocated to the fraction of oligomers on oligomerization. Effect: improving technology and efficiency of the method. table 2.

The invention relates to the field of petrochemicals, in particular the production of trimers and tetramers of propylene, which are widely used as raw material in the manufacture of additives to oils, plasticizers, flotation agents and other surface-active substances, and synthetic oils.

Known methods for producing oligomers of propylene using homogeneous catalytic systems based on compounds of Nickel and alkylamidoamines when the ratio of Al/Ni 10-100 [C. W. feldblum. Dimerization and disproportionation of olefins. M. : Chemistry, 1978, S. 44]. A significant drawback of these is activate your product.

This makes

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 fractions of trimers and tetramers of olefins.

There are also known methods for producing trimers and tetramers of propylene [USSR author's certificate 1356382, class C 07 C 11/02, 2/08] using catalyst containing compounds of Nickel and aluminum, immobilized on a polymer-based media crosslinked graft copolymer synthetic rubber - ternary copolymer of ethylene, propylene and a non-conjugate diene, and binary macroligand. In contrast to the homogeneous analogues such catalysts have a long stationary catalytic activity and can be easily separated from the reaction products, as are separate from the solvent gel phase.

The closest of them to the technical nature of the present method of producing trimers and tetramers of propylene is a method of producing trimers and tetramers of propylene [USSR author's certificate 1609065, class C 07 C 11/02, 2/32] oligomerizes is 0.5 to 1.3 wt.% Nickel and 3.0-10 wt.% alyuminiiorganicheskikh connection immobilized on the polymer-based media crosslinked graft copolymer synthetic rubber - ternary copolymer of ethylene, propylene and a non-conjugate diene, and 10-32 wt.% binary macroligand is a polymer of 2-methyl-5-vinylpyridine) - derivatives with a molecular mass of 20-200 thousand with poly (methacrylic acid in their mass ratio in the binary macroligand (0,5-1,0):1, separating oligomerizate into two streams, one of which recycle to the oligomerization, and the other is directed to the separation by distillation with return of allocated at this dimers on oligomerization.

The method allows to increase the selectivity of the process for trimers and tetramers propylene: at the exit of the reactor in the reaction products is held by codimerization with propylene returned to the oligomerization fraction of hexene to 34.4 wt.%.

The disadvantages of the prototype method are:

1. The complexity and multi-stage of preparation of the catalyst, the production of which is an integral part of the technology process of oligomerization, including:

- shot to the polymer-rubber vinylpyridine;

- inoculation of methacrylic acid using both stages of a radical initiator - long media connections Nickel;

the application of polymeric media of the aluminum compounds.

2. The low output of the trimers and tetramers of propylene in the reactor exit (to 34.4 wt.%), which significantly increases the energy costs of rectification and recycling of dimers after rectification again on oligomerization.

3. Substantial consumption of aluminum compounds upon receipt of the catalyst, and also in the process of oligomerization of propylene (0.01 to 0.1 wt.% in the solution), which complicates and increases the cost of technology oligomerization due to the need for neutralization and separation of the products of neutralization.

4. Narrow focus: as raw material for oligomerization is used only propylene, which is associated with insufficient chemical resistance of the catalyst to such impurities as water, sulfur-containing and other compounds, and necessitates the allocation of propylene from its refinery fractions.

The task of the invention to create a more technologically advanced and cost-effective in comparison with the prototype of the process of obtaining trimers and tetramers of propylene with the expansion of raw materials from pure propylene to various Propylenediamine refinery fractions.

Our tasks is to prototype more simple in composition and manufacturing techniques and chemically more resistant to impurities in the raw materials; the increase in the output of trimers and tetramers of propylene in the reactor exit; reduction of the flow alyuminiiorganicheskikh compounds (AOC), as well as the use as raw material in addition to propylene Propylenediamine refinery fractions.

The inventive method of producing trimers and tetramers of propylene is carried out by its oligomerization at 50-80oC and elevated pressures in the presence of a catalyst containing 0.5-1.3 wt.% Nickel immobilized on the polymer carrier and activator EPA, division of oligomerizate into two streams, one of which is recycled to the oligomerization, and the other is directed to the separation by rectification with the return allocated to the fraction of oligomers on oligomerization. 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 0.1-4.0 mg/l of catalyst, the molar ratio of Al/Ni 1-5, is used as raw material along with propylene Propylenediamine refinery fractions, and as a return on the oligomerization fraction of oligomers along with the fraction of dimers is also the fraction of trimers of propylene.

According to the claimed method as a core is certain analogues (ACS, SBSR, SKB), polyisoprene (RCM), neoprene, best choice rubbers, EPDM, shungit (qualified electronic signature certificate, Sept), and their copolymers and combinations, for example with styrene.

The catalyst in contrast to the prototype synthesized in a single phase mixture of a rubber - base with a compound of Nickel and a special vulcanizing agent (for example, benzoyl peroxide, peroxide Dicumyl and others). Vulcanization can significantly improve 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 strong anchoring 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 well as the possibility of using as a raw material Propylenediamine refinery fractions.

Oligomerization of propylene or its fractions is carried out in solution. The solvent serves as oligomerized or fraction of oligomers. As AOC during activation of the catalyst used alkylhalogenide connection. The process is conducted at a temperature of 50-80oC. For uvelichenie a temperature of 70-80oBy using quality raw material papaprodromou faction. This also contributes to the increase in time of contact of the feedstock with the catalyst, increasing the conversion of olefin per pass, and feed in the reaction zone the fraction of dimers or trimers, which timeresults with propylene. The process can be carried out both periodic and continuous technological scheme in one or more reactors.

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 polybutadiene rubber SBSR, 0.6 g of Nickel acetylacetonate Ni(C5H7ABOUT2)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 120oWith 5 hours. The resulting catalyst by vulcanization of the carrier has a durable mesh structure and limited swelling in hydrocarbon solvents. The swelling properties in heptane 2.5 ml/g maple):

In a metal reactor of 200 ml was placed 0.3 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 hour. Then the reactor at 60oC and a constant pressure of 8 MPa serves propylene. Stirring implement a magnetic stirrer. After 1 hour the reaction is stopped obtained oligomerized drained and analyzed chromatographically. The results of the experiment are given in table. 1. Elemental analysis oligomerizate showed the absence of Nickel, which demonstrates its strong binding to the polymer carrier.

As can be seen from the table. 1, the inventive method in the case of oligomerization of propylene exceeds the prototype performance of the catalyst (in the prototype. C. the USSR 1609065, example 2 - performance of 45.5 g/g of catalyst per hour). While it is much easier to be used in the method prototype as composition and its manufacturing technology. In addition, significantly reduces the consumption of EPA (in the prototype, the Al/Ni (mol) = 16,7).

Example 2

In the experience of using the catalyst obtained in example 1A. Activation and testing of the catalyst is carried out according to example 1B. However, the quality of the output of the experiment is shown in table. 1.

As can be seen from the table. 1, the performance of the process in this case is lower than in experiment 1, so as propylene diluted with propane. However, the content of trimers and tetramers in the products of the oligomerization of propylene in comparison with example 1 and the prototype increases significantly (in the prototype of their content at the outlet of the reactor to 34.4 wt.%).

Examples 3-6

In experiments using the catalysts obtained in example 1-based rubber qualified electronic signature certificate-PB with different Nickel content and swelling properties. The results of their tests in various conditions of experiment is shown in table. 1.

As can be seen from the table. 1, the selectivity of the process for trimers and tetramers propylene increases with increasing temperature, duration of reaction and decreasing the pressure of propylene (PPF). The output of trimers and tetramers reaches 54,7 wt.%.

Examples 7, 8

Experiments are performed on a continuous installation. In a reactor with a capacity of 100 ml load of 2 g of the catalyst obtained according to example 1A rubber-based qualified electronic signature certificate-PB. The catalyst contains 1.9 wt.% Nickel, swelling ability in heptane of 2.8 ml/year Activation is carried sesquiterpenoids, Al/Ni = 4,5 mol.

Propylene from the cylinder enters the bottom of the reactor. Leaving regiem fraction6and target (product) fraction9-C15. Fraction WITH6is returned by the pump to the reactor for codimerization with propylene. By reducing the activity of the catalyst in the reactor periodically serves AOC (concentration in oligomerizate 0.001 to 0.01 wt.%).

The results of the experiments are presented in table. 2. Comparing the figures obtained with the same parameters of the prototype method (in the prototype under the same conditions performance to 45.5 g/g of catalyst per hour, the contents of FR. C9-C12at the exit of the reactor to 34.4 wt.%), it is seen that the inventive method and the continuous mode is superior to the prototype as output fractions WITH9WITH12for passage, and the performance of the catalyst.

Examples 9, 10

Experiments carried out on a continuous installation, as described in example 7, using as raw material papaprodromou faction. The results are shown in table. 2.

Example 11

The experience carried out in example 7. As raw materials use propylene. Fraction WITH6after rectification sent to another reactor on codimerization with propylene. Conditions and results of codimerization presented in table. 2. They show that using this technique, the content of fractions With6codimerization direct fraction WITH9(see tab. 2). As can be seen from the table. 2, in this case, the products of oligomerization increases the content of fractions WITH12.

As seen from the above examples, conducting the oligomerization of propylene using new catalysts and new technology the process can simplify the process by simplifying the stage of preparation of the catalyst and reduce costs for AOC and its neutralization, increase productivity and selectivity of the process for fractions WITH9WITH12and also to use as raw material Propylenediamine refinery fractions.

The method of producing trimers and tetramers of propylene by oligomerization with 50-80oC and elevated pressures in the presence of a catalyst containing 0.5-1.3 wt. % Nickel immobilized on a polymeric carrier, and activator - alyuminiiorganicheskikh connection with the separation of oligomerizate into two streams, one of which is recycled to the oligomerization, and the other is directed to the separation by rectification with the return allocated to the fraction of oligomers on oligomerization, characterized in that as polimernogo Al/Ni 1-5 as propylene is used along with propylene as well Propylenediamine refinery fractions, and as a fraction of oligomers returned after rectification on oligomerization, along with the fraction of dimers is also the fraction of trimers of propylene.

 

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