RU2199516C2 - Method for production of olefin oligomers - Google Patents

Abstract

FIELD: petrochemical processes. SUBSTANCE: method consists in cationic oligomerization of olefinic raw stock, in particular mixture of cis- and trans-isomers of 2-, 3-, 4-, and/or 5-decenes ("internal" decenes), separation of exhausted catalyst from oligomerization products, and hydrogenation of fractions isolated from oligomerization mixture. EFFECT: increased selectivity of process and improved quality of product. 11 cl, 6 tbl, 78 ex

Description

 The invention relates to a method for producing olefin oligomers by cationic oligomerization of olefin feedstocks and can be used in the petrochemical industry.

 Obtained by this method, the products can be used as the basis for synthetic oligoolefin oils for various purposes: motor (automotive, aviation, helicopter, tractor, tank); transmission, gear, vacuum, compressor, refrigeration, transformer, cable, spindle, medical, as well as plasticizers for plastics, rubbers, solid rocket fuels; raw materials for additives, emulsifiers, flotation agents, foaming agents, components of cutting lubricants and hydraulic fluids; high-octane fuel additives, etc.

Known methods for producing olefin oligomers, including oligomerization of olefin feedstock, separation of spent catalyst by water-alkaline and subsequent water washing, separation of the purified oligomerizate into fractions and hydrogenation of the selected target fractions (1. US 3780128, 12/18/1973; 2. US 3997621, 14.12. 1976; 3. US 4032591, 06/28/1977; 4. US 4376222, 03/08/1983; 5. US 4225739, 09/30/1980; 6. US 4263465, 04/21/1981; 7. US 4409415, 10/11/1983; 8. US 4956512, 09/11/1990; 9. US 4436947, 03/13/1984; 10. US 4451689, 05/29/1984; 11. US 4454366, 06/12/1984; 12. US 4587368, 05/06/1986; 13. US 5254784, 12/20/1991 ; 14. US 5191140, 03/02/1993; 15. US 5420373, 05/30/1995; 16. US 5550307, 08/27/1996; 17. US 3725498, 04/03/1973; 18. US 3952071, 04/20/1976; 19. US 3997622, 12/14/1976; 20. US 3997623, 12/14/1976; 21. US 4006199, 02/01/1977; 22. US 4031158, 06/21/1977; 23. US 4031159, 06/21/1977; 24 US 4066715, 01/03/1978; 25. US 4113790, 09/12/1978; 26. US 4219691, 08/26/1980; 27. US 5196635, 03/23/1993; 28. US 5489721, 02/06/1996; 29. US 4214112, 07.22.1980; 30. US 3168588, 03/12/1975; 31. US 3884988, 05.20.1975; FR 2221467, 1974; 32. US 4,384,089; 33. US 4,510342, 04/09/1985; 34. US 4579991, 04/01/1986; 35. US 4855526, 08/08/1989; 36. GB 1,430,497; GB 1522129; 37. SU 1073279; 38. JP 52-11350, 1977; 39. US 4952739, 08/28/1990; 40. US 4041098, 08/09/1977; 41. GB 1535324, 1535325, 1978; 42. DE 2526615, 06/13/1975; DE 2304314, 1980; 43. SU 1723101, 04.20.1989). In accordance with these methods, the oligomerization of olefin feeds is carried out under the action of cationic and multifunctional catalytic systems, including Lewis acids (the basis of cationic catalysts is BF ₃ , AlX ₃ , R _n AlX _3-n , where X is Cl, Br, I; n = 1 , 0; 1.5; 2.0; R - CH ₃ , C ₂ H ₅ , C ₃ H ₇ , i-C ₄ H ₉ ) and various cocatalysts - water, alcohols, carboxylic acids, ketones, polyols, simple and esters, haloalkyls, TiCl ₄ , ZrCl ₄ at temperatures selected from the range of 20-250 ^o C. As the olefin feed, linear alpha olefins (LAO) are used. Most often, decene-1 is used as the olefin feedstock in the preparation of olefin oligomers. This is because the decene-1 trimers isolated from decene-1 oligomers after hydrogenation are characterized by a unique set of physical properties (kinematic viscosity at 100 ^° C is 3.9 cSt, viscosity index = 130, pour point = minus 60 ^° C, flash point = 215-220 ^o C). They are used as the basis for widely consumed synthetic and semi-synthetic motor (automobile, aviation, helicopter, tractor, tank) and other oils. From olefins with a different number of carbon atoms in the molecule, olefin oils with the above characteristics are not obtained.

 All methods of this type have two significant drawbacks.

1. The main common drawback of the known methods for producing decene oligomers is their relatively low selectivity, due to the fact that as a result of the cationic oligomerization of decene-1 under the influence of the mentioned catalytic systems, decene-1 dimers with an almost linear chain structure are formed. The pour point of such decene-1 dimers after their hydrogenation exceeds minus 20 ^° C. This sharply limits the possibilities for the qualified use of decene-1 dimers, which leads to an increase in the cost of the target products.

 2. Another common drawback of the above methods is that they use only decen-1 or mixtures thereof with some other LAO as feedstock. Decen-1 belongs to the category of scarce and expensive (approximately $ 1,200 per ton) chemical raw materials. It is obtained only in the processes of ethylene oligomerization under the action of aluminum triethyl or complex metals (Ti, Zr, Ni, Fe, Pd) of organic catalysts. The high cost of decene-1 is due to the fact that its content in ethylene oligomerization products does not exceed 15 wt.% Based on ethylene converted to LAO.

A method for producing olefin oligomers has been developed, according to which, to increase selectivity and improve technical and economic indicators, non-hydrogenated decene-1 dimers are recycled for their co-oligomerization with decene-1 to widely consumed decene tri- and tetramers (44, US 4263467, 2.04.1981 ) The co-oligomerization of decene-1 dimers (43.8 wt.% In the charge) with decene-1 (40 wt.% Decene-1 and 15.4 wt.% Decane in the charge) is carried out under the action of the BF ₃ / SiO _{2 system} ( D = 0.8-2.0 mm) + H ₂ 0 (65 ppm in the charge) at temperatures of 15-30 ^o C, a pressure of 0.1-0.69 MPa with a charge consumption of 2.5 l per hour per 1 liter of catalyst. The content of decene-1 dimers at the outlet of the reactor decreases to 20.7 wt.%, And the content of decene-1 trimers increases to 41.8 wt. % This solution allows qualified use of non-consumable (solidifying at high temperatures) dimers. The disadvantage of this solution is a sharp decrease in process performance.

A known method for producing olefin oligomers is according to which olefins of dehydrogenation of C ₁₀ -C ₁₃ paraffins with an ISOSIV process with a random (random) arrangement of double CH = CH bonds inside the molecule (hereinafter “internal” olefins) are used as the starting olefin feed (45, US 4167534, 09/11/1979).

The oligomerization of the indicated olefin feed is carried out under the influence of aluminum trichloride (1-3 wt.% Based on olefins) in the temperature range from 80 to 150 ^o C. The products formed in this process (including dimers) are characterized by high branching. Due to this, their pour point does not exceed minus 50 ^o C. The disadvantage of this process is its low productivity, a very complex multi-stage technological design and, as a result, low technical and economic indicators.

An improved method for producing olefin oligomers has been developed, according to which a mixture of decenes containing 50-90 wt.% Decene-1 and 10-50 wt.% "Internal" decenes is used as feedstock (46, US Pat. No. 4,910,355, 20.03. 1990). The specified olefin mixture is obtained by partial isomerization of decene-1 under the action of Lewis acids. The oligomerization of a mixture of decene-1 and "internal" decenes is carried out under the action of the BF ₃ -n-С ₄ Н ₉ ОН system in the temperature range from 10 to 80 ^o С. Partial isomerization of decene-1 into "internal" decenes leads to a decrease in the pour point of oligomers from -54 - -57 to -66 - -69 ^o C [46].

После гидрирования углеводороды (1-3) превращаются в 9-метилнанодекан:

При температурах ниже минус 20^oС этот углеводород образует коллоидно-дисперсные кристаллиты (наблюдаемые визуально в виде тонкой белой взвеси), которые забивают трубопроводы, фильтры и затрудняют эксплуатацию техники.The disadvantage of this solution is that in the process of oligomerization of partially isomerized decene-1 in parallel with highly branched di-, tri- and higher molecular weight oligodecenes from decene-1 a small amount of almost linear decene dimers is formed:

After hydrogenation, hydrocarbons (1-3) are converted to 9-methylnanodecane:

At temperatures below minus 20 ^o With this hydrocarbon forms colloidal dispersed crystallites (observed visually in the form of a thin white suspension), which clog pipelines, filters and complicate the operation of the equipment.

 The method [48] according to the technical nature and the achieved results is the closest analogue of the method developed according to the present invention. Therefore, we consider it as a prototype.

 The objective of the present invention was to develop a method for producing olefin oligomers (in particular, di-, tri- and tetramers of decenes), the implementation of which would increase its selectivity for the yield of target products, improve their quality and expand the available raw material base for their production.

 The problem is solved in that a method for producing olefin oligomers has been developed, including cationic oligomerization of olefin feedstock, separation of spent catalyst from oligomerizate, separation of oligomerizate into fractions and hydrogenation of fractions extracted from oligomerizate, in accordance with which, as an olefin feedstock for cationic oligomerization, and decenes-2, -3, -4 and / or -5 trans isomers.

In accordance with the claimed method, a mixture of cis and trans isomers of decen-2, -3, -4 and -5 is obtained by isomerization of decene-1. Isomerization of decene-1 into a mixture of cis and trans isomers of decen-2, -3, -4 and -5 is carried out in a tubular reactor for continuous displacement in the environment of the starting and resulting decenes under the action of a catalytic system comprising an olerosoluble compound of nickel (NiY ₂ ) and alkyl aluminum halide (R _n A1X _3-n ) at temperatures of 20 (mainly) - 150 ^o C, pressures of 0.1-0.5 MPa, concentrations of nickel compounds 0.0005-0.004 mol / l, concentrations of aluminum alkyl halide 0.01-0 , 08 mol / l (mainly 0.04-0.08 mol / l), with molar ratios Al / Ni = 5-50 (mainly 20), bp The reaction time is 1-60 minutes (mainly 3-5 minutes). In this case, nickel acetylacetonate or anhydrous nickel salts of saturated, unsaturated and aromatic carboxylic acids (from butyric, isobutyric, methacrylic and benzoic to stearic and oleic inclusive) are taken as an olea soluble nickel compound, and ₃ R _n A is taken as an alkylaluminum halide, where R is CH ₃ , C ₂ H ₅ , C ₃ H ₇ , iC ₄ H ₉ ; X-C1 (mainly), Br or I; n = 1.0 and 1.5 (mainly) or 2.0.

After completion of the isomerization, the mixture of cis and trans isomers of decen-2, -3, -4, and -5 together with the NiY ₂ -R _n A1X _3-n catalytic isomerization system is sent to the oligomerization reactor, where R'X (R ' - tert-butyl, allyl, benzyl, acetyl, benzoyl) or TiCl ₄ to convert it into a soluble catalytic system of cationic oligomerization of cis and trans isomers of 2-, 3-, 4- and 5-decenes into di-, tri-, tetramers and other oligomers and co-oligomers of said decenes.

To simplify the technological design of this method, the isomerization of decene-1 into a mixture of cis and trans isomers of decen-2, -3, -4 and -5 under the action of NiY ₂ -R _n A1X _3-n (1) catalytic systems and (co) oligomerization of all decenes isomers under the action of NiY ₂ -R _n A1X _3-n - R'X or TiCl ₄ systems (2) are carried out simultaneously by synchronous feeding of decene-1 and all system components (2) into the reactor.

Isomerization of decene-1 under the action of the NiY ₂ -R _n A1X _{3-n system} under these conditions proceeds thermally neutral, selectively and at a very high rate (table 1).

From table 1 it can be seen that under laboratory conditions, under the influence of catalytic systems, nickel stearate (StH) - (C ₂ H ₅ ) _1,5 AlCl _1,5 (EACC) and StN - C ₂ H ₅ A1C1 ₂ (EADC) at EACC concentrations and EADC = 40 mmol / L (the optimal concentration of EACC and EADC in the catalytic systems of cationic oligomerization of olefins) and molar ratios Al / Ni = 20 at temperatures of 20-80 ^o With one hundred percent isomerization of decene-1 in the "internal" decenes is achieved in less than five minutes. A similar result under the above conditions was obtained at 100 ^o C (example 20). However, an increase in temperature to 150 ^o With all other conditions unchanged leads to a decrease in the conversion of decene-1 to "internal" decenes to 38.2% in 120 minutes. Moreover, at 150 ^{° C.} 3.9 wt.% Dimers and 1.2 wt.% Tri-decenes are formed from decenes (Example 21).

Other conditions being the same, the rate of isomerization and the conversion of decene-1 to “internal” decenes decreases with decreasing NiY ₂ concentration and Al / Ni molar ratio (Table 1).

 The high activity in the isomerization of decene-1 in the "internal" decenes was also shown by the nickel acetylacetonate (AAN) - EACC catalytic system (Example 17). In contrast, a system including ferric acetylacetonate and EACC, in optimal conditions for the above-mentioned nickel-containing catalytic systems, turned out to be inactive as a catalyst for the decene-1 isomerization (Example 18).

From the examples given in Tables 1, 2, it follows that the isomerization of decene-1 into a mixture of cis and trans isomers of decen-2, -3, -4, and -5 is accompanied by (co) oligomerization of decen and that an increase in temperature and an increase in the reaction time increase conversion of decenes to di- and trimers of decenes. At low temperatures (up to 70 ^° C) and short reaction times (for example, 6 minutes), diene trimerization under the action of NiY ₂ -R _n A1X _3-n isomerization catalytic systems does not take place.

The indicated features of the decene-1 isomerization under the action of NiY ₂ - (С ₂ Н ₅ ) _n А1С1 _3-n catalytic systems provide the possibility of carrying out this reaction in a small-sized tubular displacement reactor at ambient temperature with residence times of 3-5 minutes. Similar results were obtained when isomerization of decene-1 into a mixture of "internal" decenes (as well as when carrying out the combined process of isomerization-oligomerization) and in metal reactors with a reaction volume of 0.2 liters (examples 19-21, 27, 28) and 5.0 liters (examples 22, 23, 26, 29-31), as well as in a pilot plant of continuous operation with a tubular displacement reactor (examples 24, 25, 32, 33).

In examples 1-18, the isomerization of decene-1 into "internal" decenes in laboratory conditions was carried out as follows:
Example 1. In a glass thermostatted through a jacket reactor with a volume of 60 ml, while stirring with an electromagnetic stirrer in an inert atmosphere, 0.0375 g (0.06 mmol) of nickel stearate (MM = 624.7 g / mol), 30 ml of decene-1 were loaded and 1.2 mmol (0.1485 g) EAC. Isomerization was carried out under isothermal conditions for 60 minutes. During the process, using a syringe for 5, 10, 15, 30, 45 and 60 minutes, 5 ml of the reaction mixture were taken for analysis. Immediately after sampling the tubes where they were poured, 2 ml of ethanol was added with stirring to deactivate the isomerization catalyst with stirring. The conversion of decene-1 to “internal” decenes was determined by IR spectroscopy on Specord M 80, M 82 and Nicolet instruments in the bands of 910 and 968 cm ^-1 (CH ₂ = CH and trans-CH = CH groups, respectively), and also by PMR on a Varian HA-100 instrument in accordance with the Dorman method (DEDorman et al. // J. Organic Chem. 1971. V. 36. N 19. P.2757-2766). The stereoconfiguration (cis, trans) and position (2, 3, 4, 5) of double bonds in isomerized decene molecules were determined by ¹³ C-NMR from the integrated intensity of the analytical bands in the spectra of samples taken from the reactor for different durations of the process.

In the examples with 100% conversion of decene-1 to “internal” decenes, the ratio of cis / trans isomers is usually = 1: 5, the ratio of CH ₂ / CH ₃ = 5.0-5.1, and the ratio between the positional isomers of decene-2: decen- 3: decen-4: decen-5 = 1: 1: 1.1: 0.9, i.e. corresponded to the thermodynamically equilibrium ratio of these isomers.

 In examples 5, 6, 11, 12, 14-17, all the above ratios varied within wide limits, which was determined by the kinetics of the movement of the double bond from the end to the center of the decene molecules. In particular, the ratio of cisisomers to decenes transisomers ranged from 1: 2.9 to 1: 5.8.

In accordance with the present invention, the products of decene-1 isomerization together with the NiY ₂ -R _n A1X _3-n isomerization catalytic system enter the oligomerization step, where R'X (R 'is tert-butyl, allyl, benzyl, acetyl, isomerized , benzoyl) or TiCl ₄ to convert (invert) it into a soluble cationic catalytic system for oligomerization of cis and trans isomers -2, -3, -4 and decen-5 into di-, tri-, tetra- and other oligomers and co-oligomers of the above-mentioned decenes . R'X or TiCl _{4 is} fed into the reactor undiluted by an independent stream. In this process variant, isomerization and oligomerization are separated in time and space: they are carried out sequentially in two separate reactors.

Taking into account the kinetic data considered, to simplify the technological design of the method for producing olefin oligomers in accordance with the present invention, the decene-1 isomerization into a mixture of cis and decen-2, -3, -4, and -5 transisomers under the action of NiY ₂ - R _n A1X _3-n (1) (co) oligomerization of all decenes isomers under the action of bifunctional catalyst systems NiY ₂ -R _n A1X _3-n - R'X or TiCl ₄ (2) is carried out simultaneously by simultaneous supply of decene-1 and all components of systems (2) into the reactor (examples 27-33).

From table 2 it is seen that in the case of the method at temperatures of 20-70 ^o With unconverted decen, even with a residence time of 6 minutes is fully isomerized into a mixture of "internal" decen. Examples 29-33 indicate that the decene-1 isomerization rate under the action of system (1) is so high that it significantly exceeds the high (co) oligomerization rate of all decenes isomers. When changing the conditions for the implementation of the method, the conversion of all decenes isomers to oligomers varies from 67.0 to 98.7 wt.% Based on the initial decen-1 (examples 27-33). From examples 27 and 28 it follows that an increase in temperature to 100-150 ^o With, apparently, leads to a rapid deactivation of active centers of isomerization, which is manifested in a sharp decrease in the degree of isomerization of unconverted decenes (up to 17.8-22.7 wt.%, Respectively) .

 Decenes with an “internal arrangement” of double bonds in the form of mixtures of cis and decenes-5 transisomers in accordance with the present method are obtained by metathesis (disproportionation) of hexene-1.

The metathesis (disproportionation) of hexene-1 to a mixture of cis and trans decenesene-5 isomers is carried out in a mixture of the initial hexene-1 and the resulting mixture of cis and trans decenes-5 at temperatures of 20-90 ^o C and pressures of 0.1-0.3 MPa under the action of a pre-mechanically or plasma-treated suspended in the reaction medium and additionally activated in the reactor (in the liquid phase) using A1R ₃ catalyst (50-100 g / l) selected from the group comprising MoO ₃ / A1 ₂ O ₃ , MoO ₃ / SiO ₂ , Re ₂ O ₇ / A1 ₂ O ₃ , Re ₂ O ₇ / SiO ₂ (where R is CH ₃ (mainly), C ₂ H ₅ , C ₃ H ₇ or iC ₄ H ₉ ).

Catalysts MoO ₃ / A1 ₂ O ₃ or MoO ₃ / SiO ₂ and Re ₂ O ₇ / Al ₂ O ₃ or Re ₂ O ₇ / SiO ₂ were prepared by impregnating the supports with aqueous solutions of ammonium molybdenum acid (NH ₄ ) ₆ Mo ₇ O ₂₄ • 4H ₂ О (GOST 3765-78) and rhenium-ammonium NH ₄ ReО ₄ (TU 6-09-04-133-75), respectively, and then dried with stirring and (to convert ammonium salts to Mo and Re oxides) were calcined at 550 ^o C for ten hours.

Al ₂ O ₃ (fraction 0.1-0.5 mm) with a specific surface area of 210-350 m ² / g and SiO ₂ silica gel _of grades C-3, KSK, ShSK or Davison 955 (fraction 10-100 μm) were used as carriers with a specific surface area of 210-312 m ² / g and a pore volume of 1.6-1.9 cm ³ / g).

Experiments on the disproportionation of hexene-1 in the liquid and vapor-gas phase under the action of inactivated and plasma-activated supported metal oxide catalysts MoO ₃ / Al ₂ O ₃ or MoO ₃ / SiO ₂ and Re ₂ O ₇ / Al ₂ O ₃ or Re ₂ O ₇ / SiO ₂ was carried out in a continuous-flow tubular quartz electric heated reactor with an internal diameter of 1.4 cm and a length of 35 cm. A quartz grating (such as a Schott filter type) with a pore diameter of about 0.1 mm was mounted in the lower part of the tubular reactor. From 3.5 to 30 ml of one of the mentioned catalysts was loaded into the reactor in bulk or in a fiberglass bag. Hexene-1 (manufactured by NKNKh, TU 2411-05766801-96) was continuously fed through a microdosing pump to the top of a vertically installed tubular reactor. The resulting reaction products (ethylene and decen-5) were continuously withdrawn from the bottom of the reactor. The feed rate of hexene-1 into the reactor ranged from 1.0 to 100 h ^-1 .

Experiments on the disproportionation of hexene-1 in the liquid phase (in the medium of mixtures of hexene-1 and decen-5) under the action of non-activated physical methods and machined, additionally activated A1R ₃ , supported metal oxide catalysts MoO ₃ / Al ₂ O ₃ or MoO ₃ / SiO ₂ and Re ₂ O ₇ / Al ₂ O ₃ or Re ₂ O ₇ / SiO ₂ were also carried out in a batch mixing reactor with an electromagnetic stirrer. The reactor was equipped with a special device for supplying to the reaction zone at any time a predetermined amount of trialkylaluminum - AlR ₃ . Ethylene formed during the reaction was continuously withdrawn from the reactor through a reflux condenser into a volume-calibrated gas tank.

Before the reaction, the inactive catalyst was treated at 600.degree ^{. C.} with air for three hours, and then purged with high-purity nitrogen for one hour (to ensure deaeration and cooling). Cooled to ambient temperature, the catalyst was then loaded into the described reactors, or subjected to mechanical or plasma treatment.

Preliminary experiments found that the disproportionation of hexene-1 under the action of Re ₂ O ₇ / Al ₂ O ₃ occurs at temperatures of 20-120 ^o C under the influence of MoO ₃ / Al ₂ O ₃ at temperatures of 35-150 ^o C, and under the action of WO ₃ / Al ₂ O ₃ at temperatures of 300-400 ^o C. It was also established that the disproportionation of hexene-1 under the influence of MoO ₃ / Al ₂ O ₃ proceeds at a lower temperature than under the influence of MoO ₃ / SiO ₂ . From these data and the data on the cost of the catalysts, it follows that the available (commercially available) aluminum-molybdenum catalyst MoO ₃ / Al ₂ O ₃ is preferred.

Table 6 shows the dependence of the average disproportionation rate of hexene-1 on the content of MoO ₃ in the samples MoO ₃ / Al ₂ O ₃ , MoO ₃ / SiO ₂ . From this table it follows that the maximum value of activity is observed when the content in the catalyst of MoO ₃ / Al ₂ About ₃ 8.15 wt. % MoO ₃ (in the case of MoO ₃ / SiO ₂ 15 wt.% MoO ₃ ).

In the case of non-activated samples of the considered catalysts, an induction period was observed, the presence of which indicates the activation of transition metal oxide with hexene-1. The induction period in the case of MoO ₃ / Al ₂ O ₃ was significantly less than in the case of MoO ₃ / SiO ₂ .

The disproportionation of hexene-1 at temperatures of 20-150 ^o With is accompanied by the occurrence of side reactions of isomerization, oligomerization and polymerization and is characterized by a decrease in the activity of the aluminum-molybdenum catalyst. At elevated temperatures, along with the mentioned reactions, skeletal isomerization, dehydrogenation and cleavage of carbon-carbon bonds of hexene-1 and the resulting decenes-5 take place. The decrease in the activity of the catalysts during the disproportionation of hexene-1 may be due to the blocking of the surface of the catalyst particles by the resulting polymers and / or the deep reduction of molybdenum under the action of hexene-1. Both of these assumptions are confirmed by the fact that the maximum activity of deactivated catalysts MoO ₃ / Al ₂ O ₃ , MoO ₃ / SiO, Re ₂ O ₇ / A1 ₂ O ₃ and Re ₂ O ₇ / SiO _{2 is} restored as a result of calcination in air flow at 550 ^o C for two hours. The deactivation of the catalyst MoO ₃ / Al ₂ About ₃ during the disproportionation of hexene-1 in the liquid phase occurs more slowly than in the case of vapor-phase disproportionation. This can be explained by the fact that liquid-phase disproportionation occurs at lower temperatures (at which the polymerization of ethylene and hexene-1 does not occur or proceeds at a low rate), as well as the fact that the resulting polymers are at least partially dissolved in the liquid phase and do not block active disproportionation centers.

The machining of the above catalysts is carried out in a ball mill at ambient temperature in an atmosphere of argon or methane (natural gas). To do this, 5 g of catalyst (for example, MoO ₃ / SiO ₂ ) and 60-100 g of steel balls with a diameter of 12 mm are loaded into a 100 ml stainless steel reactor, the reactor is sealed, deaerated with a vacuum pump and filled with argon or methane from cylinders until a pressure of 0.1-0.3 MPa is reached. The machining of the catalysts is carried out by shaking the filled reactor on a mechanical vibrator with a frequency of 5-15 Hz and an amplitude of 5-20 mm for 5-60 minutes. The activated catalyst from the machining reactor is loaded into the metathesis reactor, excluding its contact with oxygen and moisture. In the process of machining, energy is supplied to the catalyst particles in acts of mechanical action. As a result of this, a stress field is created in the particles. The relaxation of the stress field occurs in several ways: crushing the catalyst particles to form a new defective highly active surface, emission of electrons when microcrystals crack, excitation and breaking of some bonds, initiation and occurrence of chemical reactions in the solid phase. All these processes can lead to the formation of potentially active centers of metathesis. Upon contact with hexene-1 in the liquid or vapor phase, these centers turn into carbene active centers of metathesis. Similar processes occur during the treatment of molybdenum and rhenium oxide catalysts with argon or methane plasma of a high-frequency (HF) discharge. The above catalysts are treated with rf discharge plasma at temperatures of 20-80 ^° C and at argon or methane pressures of 0.01-10.0 mm Hg. Art. For this, a catalyst is loaded into a quartz duck reactor (diameter 35 mm, length 150 mm, volume 0.2 l), the reactor is fixed in a mechanical rocking chair, connected to a vacuum system and with a device for dispensing argon or methane, the reactor is deaerated, a continuous flow is established argon or methane (linear gas velocity of 30 cm / s) and connected using external electrodes to the glow discharge generator UHF-66. The frequency of the discharge current is 40.68 MHz, the electric field strength is 8000 V / cm, the current density = 1.8-8.8 mA / cm ² , the concentration of electrons in the discharge is varied from 10 ¹³ to 10 ¹⁴ e / cm ³ , the power discharge vary in the range from 20 to 70 watts. Mixing is carried out using a mechanical stirrer, and the temperature in the reactor using a thermostat. The specified conditions and parameters provide continuous combustion of the RF discharge and the effective activation of the above catalysts.

To simplify the technological design of this variant of the method, the metathesis (disproportionation) of hexene-1 into a mixture of cis and trans isomers of decene-5 is carried out in the vapor phase under the action of plasma-treated one-component catalysts MoO ₃ / SiO ₂ or Re ₂ О ₇ / Al ₂ О ₃ at temperatures of 120 -150 ^o C (table 6).

 The results obtained indicate that preliminary mechanical (grinding) and plasma treatment of the catalysts provide an increase in their activity in the process of hexene-1 metathesis in both the liquid and vapor phases (table 6).

 Processing hexene-1 into decenes-5, and decenes-5 into the bases of synthetic oils for various purposes will significantly expand the raw material base for obtaining these products and get a significant economic effect. The latter is ensured by the fact that the price of hexene-1 on world markets (600-800 US dollars / t) is significantly lower than the price of decene-1 (1200 US dollars / t) and that hexene-1 is produced in large quantities and consumed in smaller quantities than decen-1.

 Mixtures of cis and trans isomers of 2-, 3-, 4- and / or 5-decenes can be used not only in the preparation of olefin oligomers, but also in other processes (for example, in alkylation processes in the preparation of higher alkyl aromatic hydrocarbons and various surfactants based on them, in epoxidation processes, etc.). Therefore, the developed method for producing olefin oligomers additionally includes the isolation and purification of a mixture of cis and trans isomers of 2-, 3-, 4- and / or 5-decenes by appropriate known methods.

According to the present invention, olefin oligomers from individual or mixtures of cis and trans isomers of 2-, 3-, 4- and / or 5-decenes are obtained in continuous mixing or displacement reactors with residence times of 1 to 120 minutes under the action of a soluble cationic catalyst system, comprising alkylaluminium halide R _n AlX _3-n and haloalkyl R'X or TiCl ₄ in a medium of a mixture of oligomerizable olefin feed and reaction products in the absence or presence of nickel compounds at concentrations of R _n AlX _3-n 0.02-0.08 mol / L , molar ratios R'X / Al = 1-3 or TiCl ₄ / Al = 0.5-1.5 in the temperature range from 20 to 150 ^o C, at pressures of 0.1-1.0 MPa. Moreover, as R _n AlX _3-n and R'X, compounds are used in which R is CH ₃ , C ₂ H ₅ , C ₃ H ₇ , iC ₄ H ₉ ; X-C1 (predominantly), Br or I; n = 1.0 and 1.5 (mainly) or 2.0; R 'is tert-butyl (predominantly), allyl, benzyl, acetyl or benzoyl.

 The developed method allows oligomerization of olefin feeds in the presence of paraffinic or aromatic hydrocarbons (such as decane, benzene, toluene, xylene or naphthalene). The oligomerization of olefin feedstocks (including decenes) leads to the formation of "aromatized" oligomers functionalized by molecules of aromatic hydrocarbons that are highly resistant to thermal oxidative degradation.

 The yield, structure and some characteristics of the target oligodecene fractions isolated from the decene-1 conversion products (oligomerization isomerization) in accordance with the present invention are shown in Table 5.

 The testing of the catalysts and the development of the processes of isomerization of decene-1 and cationic oligomerization of other decenes in the laboratory and in the experimental setup was carried out in metal mixing and displacement reactors (respectively, capacitive and tubular type) as follows.

In the case of a thermostatically controlled cleaned and dried batch type reactor with a stirrer of 1 or 10 liters in an inert atmosphere at ambient temperature (+ 15- + 25 ^o С) in the case of decene-1 isomerization, the nickel compound was first charged. Following this, an olefin (in some cases an aromatic hydrocarbon) was charged from the measuring tanks into the reactor (the degree of filling of the reactor was 50 vol%). There, using a calibrated syringe, with stirring, solutions of an organohalogen compound R'X and an organic modifier (OM) were introduced, the reactor and its contents were heated with a thermostat to a predetermined temperature, and only then, with the help of a special dosing device, the necessary amount of aluminum-aluminum halide R _n was loaded with stirring AlX _3-n . Immediately after this, the isomerization and / or oligomerization of the olefin began. Oligomerization was usually accompanied by a marked increase in the temperature of the reaction medium (oligomerizate). The reaction was continued for the scheduled time, and then terminated by introducing into the reactor an aqueous solution of alkali (NaOH) or ethanol. The resulting products from the reactor were further discharged into an intermediate tank. Spent (deactivated) catalyst from the reaction products was isolated by the adsorption method or by the method of water-alkaline and water washing.

 When testing the isomerization and / or oligomerization of decenes in a continuously operating tubular reactor, two types of tubular reactors were used: a tubular reactor, which was a metal tube with an inner diameter of 10 mm and a length of one meter with a jacket (the volume of the reaction space was 78.5 ml), and a tubular-slit reactor 1.5 m long with a tubular-slit reaction space with a gap width between the coaxial tubes forming the reaction space of 4 mm. The volume of this type of reactor was 205 ml. The tube-gap reaction space was heated or cooled on both sides of the gap gap using a thermostat or network running water.

Before starting the development of these reactions in tubular reactors in a pilot plant in an inert atmosphere, 30 l of solutions of the components of the catalyst in olefin (in particular, decene-1) were separately prepared. In the first apparatus (stirred reactor), a solution of NiY ₂ and / or organohalogen compound R'X in olefin was prepared. In a second apparatus (stirred reactor), 30 L of a solution of alkylaluminium halide R _n AlX _{3-n of a} predetermined concentration (usually 0.08 mol of R _n AlX _3-n / l solution in this apparatus) was prepared. After a short (5-10 min) intensive mixing with a frame stirrer (100 rpm), the solutions of the catalyst components of a given concentration were supplied by independent (identical in flow) flows to the inlet of the mentioned tubular reactors. The temperature entering the reactor flows corresponded to the ambient temperature (15-25 ^o C). In some cases, the solutions of the catalyst components were heated to a predetermined temperature before being fed to the reactor. At the moment of mixing the streams of solutions of the catalyst components entering the reactor, active centers of isomerization and / or cationic active centers formed with a very high speed and olefin isomerization and / or oligomerization began. Isomerization proceeded at a high rate, but without heat. Oligomerization also proceeded at a high rate, but with the release of a large amount of heat (ΔН) - (ΔН = 22 [11 / P _n ] kcal / mol of the converted olefin, where P _n is the number average degree of oligomerization of the olefin). The released heat of oligomerization was removed from the reaction zone with a refrigerant (heat carrier) (usually water) through the shirts of the aforementioned tubular reactors. The use of a tubular slit reactor during the development of the decene oligomerization stage according to the invention ensured oligomerization under practically isothermal conditions.

 From the tubular reactor, the reaction mass (oligomerizate) was sent to a batch collector, to an adsorber, or to a washer.

 The collection batch was a stirred tank reactor where the isomerization and / or oligomerization of the unconverted olefin continued for another 60 minutes. Staying of the reaction mass in the collector-batch helped to increase the conversion of the initial olefin by 3-10 wt.% Compared with the case when the reaction mass was immediately sent for purification. From the collector-batch, the reaction mass was sent to the adsorber or to the washer.

 The adsorber was a thermostatically controlled column apparatus filled with activated calibrated particles of aluminum oxide or bauxite. With the passage of the reaction mass (bottom-up) through the layer of the specified adsorbent, the frontal adsorption of spent deactivated catalyst occurred and the reaction mass was purified.

The washer was used to isolate spent catalyst by the method of water-alkaline and then water washing (purification) of the reaction mixture. It functioned periodically and consisted of a thermostatically controlled (heated) reactor with a stirrer, into which from the auxiliary measuring tanks the reaction mixture, a 5% aqueous solution of NaOH or NH ₃ , and then fresh demineralized water were fed. In some cases, the reaction mass entered the washer directly from the tubular reactor. After sampling for analysis, the purified reaction mass was loaded into a cube of a vacuum column for subsequent azeotropic drying, isolation of unconverted olefins, and for separation of the oligomer into fractions.

The fractional composition of oligomerization products was determined by a standard chromatographic method using LHM-8 MD devices, Hewlett Packard Model 5710A and / or a fractionation method on a vacuum distillation column. The results of these analyzes coincided with an accuracy of ± 2 wt.%. The structure of the isolated products was quantitatively determined by ozonolysis using an ADS-4M, IKS, 1H NMR and ¹³ C-NMR instrument.

 For a better understanding of the present invention, as examples, the tables show examples of the implementation of the method of producing olefin oligomers developed according to the invention and the results of determining the composition, structure and properties of the obtained products. These examples demonstrate but do not exhaust the scope of the invention.

 From the above examples it follows that "internal" decenes, as well as decen-1, can be used to obtain oligodecene oligomers. The reactivity of “internal” decenes is lower than the reactivity of decene-1, which, ceteris paribus, oligomerization is manifested in a certain decrease in the conversion of decenes to oligodecenes. The use of "internal" decenes in the process of producing olefin oligomers according to the invention provides improved process control and allows to obtain highly branched dimers, trimers and decene oligomers with record low pour points with some change in the complex and other physical properties of the resulting products.

 The combination of physico-chemical properties of olefin oligomers synthesized in accordance with the present invention, allows you to select them in a new group of olefin oligomers.

Claims (11)

 1. A method of producing olefin oligomers, including cationic oligomerization of olefin feedstock, separation of spent catalyst from oligomerizate, separation of oligomerizate into fractions and hydrogenation of fractions extracted from oligomerizate, characterized in that a mixture of cis- and trans-cene oligomerizations is taken from -2, -3, -4 and / or -5.  2. The method according to claim 1, characterized in that a mixture of cis and trans isomers of decen-2, -3, -4 and -5 is obtained by isomerization of decene-1. 3. The method according to PP. 1 and 2, characterized in that the isomerization of decene-1 into a mixture of cis and trans isomers of decen-2, -3, -4 and -5 is carried out in a tubular reactor for continuous displacement in the medium of the initial and formed decen under the action of a catalytic system, including the olerosoluble compound of nickel (NiY ₂ ) and alkyl aluminum halide (R _n AlX _3-n ) at temperatures of 20 (mainly) - 150 ^o C, pressures of 0.1-0.5 MPa, the concentration of Nickel compounds 0,0005-0,004 mol / l, concentrations of alkylaluminium halide 0.01-0.08 mol / L (mainly 0.04-0.08 mol / L), with molar ratios Al / Ni = 5-50 (mainly 20), reaction times 1-60 minutes (mainly 3-5 minutes), while nickel acetylacetonate or anhydrous nickel salts of saturated, unsaturated and aromatic carboxylic acids (from butyric, isobutyric, methacrylic and benzoic, including stearic and oleic, inclusive), and R _n AlX _3-n , where R-CH ₃ , C ₂ H ₅ , C ₃ H ₇ , iC ₄ H ₉ , is taken as the aluminum alkyl halide; X-Cl (mainly), Br or I; n = 1.0 or 1.5 (predominantly) or 2.0. 4. The method according to claims 1 to 3, characterized in that the mixture of cis and trans isomers of decen-2, -3, -4 and -5 together with the NiY ₂ -R _n AlX _3-n catalyst isomerization system is sent to the reactor oligomerization, where the isomerization catalytic system is treated with R'X (R 'tert-butyl, allyl, benzyl, acetyl, benzoyl) or TiCl ₄ to convert it into a soluble catalytic system of cationic oligomerization of cis and trans isomers 2-, 3-, 4 - and 5-decenes in di-, tri-, tetramers and other oligomers and co-oligomers of said decenes. 5. The method according to PP. 1 and 2, characterized in that the isomerization of decene-1 into a mixture of cis and trans isomers of decen-2, -3, -4 and -5 under the action of NiY ₂ -R _n AlX _3-n (1) catalytic isomerization systems and (co) oligomerization of all decenes isomers under the action of NiY ₂ -R _n AlX _3-n - R'X or TiCl ₄ systems (2) is carried out simultaneously by simultaneously supplying decene-1 and all system components (2) to the reactor.  6. The method according to p. 1, characterized in that a mixture of cis and trans isomers of decen-5 is obtained by metathesis (disproportionation) of hexene-1. 7. The method according to claims 1 and 6, characterized in that the metathesis (disproportionation) of hexene-1 to the mixture of cis and trans isomers of decene-5 is carried out in a medium of mixtures of the starting hexene-1 and the resulting decenes-5 at temperatures of 20-90 ^o With and pressures of 0.1-0.3 MPa under the action of a pre-mechanically or plasma treated suspended in the liquid phase and additionally activated in the liquid phase using AlR ₃ catalyst selected from the group comprising MoO ₃ / Al ₂ O ₃ , MoO ₃ / SiO ₂ , Re ₂ O ₇ / Al ₂ O ₃ , Re ₂ O ₇ / SiO ₂ (where R is CH ₃ (mainly), C ₂ H ₅ , C ₃ H ₇ or iC ₄ H ₉ ). 8. The method according to claim 1, characterized in that the metathesis (disproportionation) of hexene-1 to the mixture of cis and trans isomers of decene-5 is carried out in the vapor phase under the influence of plasma-activated one-component catalysts MoO ₃ / SiO ₂ or Re ₂ O ₇ / Al ₂ O ₃ at temperatures of 120-150 ^o C. 9. The method according to PP.1-3, 6-8, characterized in that it further comprises the allocation in the purification of a mixture of cis and trans isomers of decen-2, -3, -4 and / or -5 by appropriate known methods. 10. The method according to claim 1, characterized in that the oligomerization of individual or mixtures of cis and trans isomers of 2-, 3-, 4- and / or 5-decenes is carried out in continuous mixing or displacement reactors with residence times from 1 to 120 min under the action of a soluble cationic catalytic system, including alkyl aluminum halide R _n AlX _3-n and haloalkyl R'X or TiCl ₄ in a medium of a mixture of oligomerizable olefin feed and reaction products in the absence or presence of nickel compounds at concentrations of R _n AlX _3-n 0 , 02-0.08 mol / L, molar ratios R'X / Al = 1-3 or TiCl ₄ / Al = 0.5-1.5 in the temperature range from 20 to 250 ^o C, at pressures of 0.1-1.0 MPa, while using the compounds R _n AlX _3-n and R'X in which R is CH ₃ , C ₂ H ₅ , C ₃ H ₇ , iC ₄ H ₉ ; X is Cl (predominantly), Br or I; n = 1.0 and 1.5 (mainly) or 2.0; R 'is tert-butyl (predominantly), allyl, benzyl, acetyl or benzoyl.  11. The method according to PP. 1, 4, 5 and 10, characterized in that the oligomerization of the olefin feed is carried out in the presence of paraffinic or aromatic hydrocarbons (such as decane, benzene, toluene, xylene or naphthalene).  12. Olefin oligomers, which are obtained according to claims 1, 4, 5, 10 and 11.

Images