Catalyst system for the oligomerization of olefins, the method of its preparation and method of oligomerization

 

The invention relates to cationic catalytic systems oligomerization of individual or mixtures of olefins With3-C14in fundamentals of synthetic polyalphaolefin oils (POM). Described catalytic system for the cationic oligomerization of individual or mixtures of olefins With3-C14in fundamentals of synthetic POM containing the active aluminum or its alloys, for example with magnesium or titanium, in the form of materials(bodies) with a developed surface, socialization halodurans connection RX, in which R is a primary, secondary or tertiary alkyl, allyl, benzyl, acetyl or benzoyl, and X is chlorine, bromine or iodine, with each g-atom of aluminum it contains 1 to 50 moles haloidoargentum connection. Describes how to obtain this composition, and the described method of oligomerization of individual or mixtures of olefins With3-C14in fundamentals of synthetic POM. Technical result: the catalytic system has a high activity, performance, and allows you to adjust the speed of oligomerization. 3 S. and 7 C.p. f-crystals, 7 PL.

The invention relates to chemistry, particularly to cationic catalytic systems (catalysts) oligomerization individual who inovah) oils (POM).

The invention can find application in the chemical and petrochemical industries, factories for the production of basic POM and other products with the use of cationic catalysts.

The products of the oligomerization of olefins With3-C14used as the basis for the preparation of waxy multigrade engine (automotive, aviation, helicopter, tractor, tank etc), gear, gear, vacuum, compressor, refrigeration, transformer, electrical, spun, and other types of oils, as well as heat-transfer agents; plasticizers for plastics, rubbers, solid rocket fuels, and raw materials for the production of additives, emulsifiers, flotation agents, foaming agents, components, Metalworking and hydraulic liquids, etc. it is Known [1. J. Kennedy. Cationic polymerization of olefins. M.: Mir, 1978. 430 S.; 2. J. P. Kennedy, E. Marechal. Carbocationic Polymerization. N.-Y., 1982. 510 P.] that the cationic oligomerization of olefins With3-C14you can initiate (catalyze) with catalysts based on proton acids (acids Branstad); aprotic acids (Lewis acids); alkylamine (or boron halides; salts of stable carbocations R+A-; Ponente complexes, including the monomer; polyfunctional catalysts of the Ziegler-Natta; metallocene catalysts; physical methods of promoting chemical reactions. The most wide industrial application as catalysts for the cationic oligomerization of olefins and other monomers found the catalytic system comprising the Lewis acid (F3, ll3, lr3, TiCl4, ZrCl4and others), alkylamino (or boron halides RnMX3-n(where R is alkyl (C1-C10-, aryl-, alkenyl and other groups; M Is Al or B; X Is CL, Br, I) and natural or synthetic silicates, zeolites and heteroalicyclic in the protonated form. Upon receipt motorized POM on the basis of the linear alpha-olefins (LAO)3-C14(mainly on the basis of mission-1) usually use a catalytic system comprising a Lewis acid or alkylhalogenide.

So, there are a large number of modifications of oligomerization catalysts LAO6-C14comprising boron TRIFLUORIDE and a variety of proton-donor action socializaton - water, alcohols, carboxylic acids, anhydrides of carboxylic acids, ketones, polyols and mixtures thereof [3-20] [ 3. Pat. USA 3780128 from 18.12.1973; Ál. C 07 C 5/02; NCP. 585-12; 260-683.9; 4. Pat. USA 3997621 from 14.12.1976; Ál. C 07 C 3/18; NCP. 585/255; 7. Pat. USA 4 225739 from 30.09.1980; Ál. C 07 C 3/18; NCP. 585/525; 8. Pat. USA 4263465 from 21.04.1981; Ál. C 07 C 9/00; NCP. 585/18; 9. Pat. USA 4263467 from 21.04.1981; Ál. C 07 C 9/00; NCP. 585/18; 10. Pat. USA 4 409415 from 11.10.1983. Ál. C 07 C 3/02; NCP. 585/525; 11. Pat. USA 4 956512 from 11.09.1990. Ál. 07 With 2/024; NCP. 585/521; 12. Pat. USA 4 436947 from 13.03.1984. Ál. C 07 C 3/18; NCP. 585/525; 13. Pat. USA 4 451689 from 29.05.1984. Ál. 07 With 3/0; NCP. 585/525; 14. Pat. USA 4 454366 from 12.06.1984. Ál. C 07 C 7/12; NCP. 585/525; 15. Pat. USA 4 587368 from 06.05.1986. Ál. C 10 L 1/16; C 07 C 2/02; NCP. 585/12; 16. Pat. USA 4910355 from 20.03.1990. Ál. 07 With 2/74; NCP. 585/255; 17. Pat. USA 5 254784 from 20.12.1991. Ál. C 07 C 2/22; NCP. 585/525; 18. Pat. USA 5 191140 from 02.03.1993. Ál. 07 With 2/02; NCP. 585/525; 19. Pat. USA 5420373 from 30.05.1995. Ál. From 07 With 2/08; NCP. 858/525; 20. Pat. USA 5550307 from 27.08.1996. Ál. C 07 C 2/14; NCP. 585/525.]. The oligomerization of olefins With3-C14under the action of these catalysts is carried out at temperatures 20-90oWith the mass within 2-5 hours. The concentration of boron TRIFLUORIDE in the reaction medium ranges from 0.1 to 10 wt.%. Conversion of the initial olefin varies from 80 to 99 wt.%. As a result of oligomerization, for example, mission-1 is formed a mixture of di-, tri-, Tetra-mers or more high molecular weight oligomers. The total content of di - and trimers in the products varies from 30 to 80 wt.%.

The main drawback of all cationic ky boron TRIFLUORIDE.

Furthermore, the activity of catalysts of this type are in the process of oligomerization LAO is relatively low, because of what oligomerization occurs in 2-5 hours. When the industrial implementation of these processes are expensive, large and metal reactors mixing in corrosion performance. It is known [21-32] [21. Pat. USA 3725498 from 03.04.1973. Ál. C 07 C 3/18; NCP. 585-532; 22. Pat. USA 3952071 from 20.04.1976. Ál. C 07 C 3/18; NCP. 585-532; 23. Pat. USA 3 997622 from 14.12.1976. Ál. C 07 C 3/18; NCP. 585-532; 24. Pat. USA 3 997623 from 14.12.1976; Ál. C 07 C 3/18; NCP. 585-532; 25. Pat. USA 4 006199 from 01.02.1977. Ál. C 07 C 3/18; NCP. 585-532; 26. Pat. USA 4 031158 from 21.06.1977. Ál. C 07 C 3/18; NCP. 585-532; 27. Pat. USA 4 031159 from 21.06.1977. Ál. C 07 C 3/18; NCP. 585-532; 28. Pat. USA 4 066715 from 03.01.1978. Ál. C 07 C 3/18; NCP. 585-532; 29. Pat. USA 4113790 from 12.09.1978. Ál. C 07 C 3/10; NCP. 585-532; 30. Pat. USA 4167534 from 11.09.1979. Ál. C 07 C 5/04; NCP. 585-532; 31. Pat. USA 4219691 from 26.08.1980. Ál. C 07 C 3/18; NCP. 585-532; 32. Pat. USA 5196635 from 23.03.1993. Ál. C 07 C 2/22; NCP. 585-532] a large number of cationic catalysts for the oligomerization of olefins, comprising the halides of aluminium and proton donor - water, alcohols, carboxylic acids, simple or complex esters, ketones (for example, dimethyl ether of ethylene glycol, etilenglikolevye, diethylmalonate), haloalkyl [28, 32] [28. Pat. USA 4 066715 from 03.01.1978. the result in combination with compounds of Nickel [33. Pat. USA 5 489721 from 06.02.1996. Ál. C 07 C 2/20; NCP. 585-532]. The additive compounds of Nickel in these catalysts provide regulation of the fractional composition of the obtained oligoelement.

The oligomerization of alpha-(C4-C14or internal10-C15olefins (obtained by dehydrogenation of paraffins) [29. Pat. USA 4113790 from 12.09.1978. Ál. C 07 C 3/10; NCP. 585-532] carried out under the action of catalysts l3+ protonating at temperatures of 100-140oC for 3-5 hours. The concentration l3range from 0.1 to 10 mol.% based on the olefin, the molar ratio of protonating/Al ranges from 0.05 to 1.25. With the increase of this ratio from 0.05 to 1.25 conversion of olefins is reduced from 99 to 12 wt.%.

Catalysts of this type are characterized by the following common disadvantages: - complex procedure of preparation, involving many operations - sublimation and grinding ll3the preparation of the complex; complexes are viscous, sticky substances poorly soluble in the olefin, there are problems with unloading them from the reactor during oligomerization; - low activity in the oligomerization process that requires the use of large metal reactors mixing; high expenditure koena high molecular weight and high viscosity products. In the implementation of the oligomerization of olefins under the action of catalysts on the basis of Ahs difficulties with regulation of fractional composition of the oligomers. Developed many bifunctional complex catalysts comprising transition metal compounds (TiCl4, ZrCl4and alkylhalogenide Rnl3-n(see, for example, [34-46]. [34. Pat. USA 4214112 from 22.07.1980. Ál. C 07 C 3/18; NCP. 585-532; 35. J. Skupinska. Oligomerization of alpha-olefins to higher excl. reaction // Chem. Rev. 1991. V. 91. # 4. P. 613-648; 36. Pat. USA 3168588. 12.03.1975. Ál. C 07 C 2/22; NCP. 260-683.15; 37. Pat. USA 3884988. 20.05.1975. Ál. C 07 C 3/10; NCP. 584-524; Franz. Application 2221467. 1974. Ál. 08 F 1/32, 15/40; 38. Pat. USA 4384089. Ál. 07 F 4/64; NCP. 526-159; 39. Pat. USA 4510342. 09.04.1985. Ál. C 07 C 3/02; NCP. 584-524; 40. Pat. USA 4579991. 01.04.1986. Ál. C 07 C 2/22; NCP. 585-524; 41. Pat. USA 4855526. 08.08.1989. Ál. 07 With 2/02; NCP. 585-524; 42. Pat. The UK 1430497. Ál. C 07 C 2/22; U.S. Pat. The UK 1522129. Ál. C 07 C 2/22. NCP. SR; 43. A. C. the USSR 1073279. Ál. 07 With 2/32; NCP. WITH 10 M 3/12; 44. Japanese Pat. 52-11350. 1977 (Rehim. 1978. SP), Ál. 08 F 10/14; 45. A. C. the USSR 1075500.17.03.1982. Ál. C 07 C 2/22. NCP. 01 J 31/14; 46. A. C. the USSR 1192346. 12.08.1983. Ál. C 07 C 2/22. NCP. WITH 10 M 107/02]). In the catalysts of this type is formed of two types of active centers of cationic and anionic coordination. Because of this, the oligomerization of olefins With3-C14under b>3-C14under the action of anionic-active coordination centers in insoluble hard to remove from the reactor of high molecular weight polyolefins. Under the action of a bifunctional complex catalysts in all cases formed of high molecular weight high viscosity oligohaline, which cannot be used as the basis for the most commonly used motor oils. This is the main drawback of catalysts of this type. In addition, the catalytic system of this type, as well as the previously mentioned classical cationic catalysts have a relatively low activity, which requires, as already noted, the use in industrial environments large bulky inefficient reactor blending.

In the cationic polymerization, oligomerization and alkylation also widely used two-soluble monofunctional catalyst system comprising alkylaminocarbonyl Rnl3-nand kaleidoscopically connection R X (where R is CH3C2H5With3H7or ISO-C4H9; X is chlorine, bromine or iodine; n=1.0; 1.5 or 2.0; R' - N [47. Pat. USA 4952739. 28.08.1990. Ál. C 07 C 2/18; NCP. 585/18; 585/511], primary, secondary, who 35324, 1535325. 1978. Ál. C 07 C 3/21; NCP. WE, SE; 50. Avca Germany 2526615. 13.06.1975. Ál. C 07 C 3/21; U.S. Pat. Germany 2304314. 1980. Ál. 08 F 110/20; 51. A. C. the USSR 1723101. 20.04.1989. Ál. 07 WITH 2/30. NCP. With 10 M 107/10]) at a molar ratio R X/Rnl3-n, =1.0-5.0. In the catalytic systems of this type, Rnl3-nis the basis of the catalyst, a R X acetalization.

The catalytic system Rnl3-n-R X are used to iniciirovanie cationic oligomerization of individual or mixtures of linear alpha-olefins from propylene to tetradecene including the basics of synthetic polyalpha-olefin oils in the environment, the source of olefins or their mixtures with products of oligomerization and paraffinic or aromatic hydrocarbons at temperatures up to 250oC.

Cationic active centers ([R,+(Rnl4-n)-] and R,+in catalytic systems Rnl3-n-R X are formed in accordance with the following simplified scheme: Rnl3-n+R X<-->[R,+(Rnl4-n)-]<-->R,++( Rnl4-n)-The formation of cationic active centers in this catalytic system is a very high speed. Due to this, immediately after mixing of the solutions component is a process for the oligomerization proceeds without induction period with a very high initial speed. While 95-98% conversion of the initial olefin in oligomeric products at temperatures of 20-200oCan be achieved within six to one minute, respectively. This type of kinetics of oligomerization of linear alpha olefins (LAO) under the action under consideration catalytic systems provides the possibility of oligomerization in forced mode in reactors displacement of the tubular type at the time of stay from 1 to 6 minutes [51. A. C. the USSR 1723101. 20.04.1989. Ál. 07 WITH 2/30. NCP. With 10 M 107/10], but complicates the removal of the liberated heat of oligomerization.

During oligomerization LAO under the action of these catalytic systems in the mass or in the environment of paraffin hydrocarbons are formed highly branched harden at low temperatures oligomers containing one di-, tri - or tetraalkylammonium double bond, and at oligomerization in the environment or in the presence of aromatic hydrocarbons (benzene, toluene, naphthalene) are formed oligonucelotides oily products (telomeres) that do not contain double bonds [51. A. C. the USSR 1723101. 20.04.1989. Ál. 07 WITH 2/30. NCP. WITH 10 M 107/10].

The main disadvantage of catalytic systems Rnl3-n-R X is that their use in the process oligoprobes molecular weight distribution and low (less than 20 wt.%) the content of the target low-molecular-weight fractions (dimers and trimers of mission-1) (table 1).

Another disadvantage of the catalytic systems of this type is that formed under their influence dimers of mission-1 are linear and after hydrogenation have a pour point greater than -20oC.

The third disadvantage of catalytic systems Rnl3-n-R X is that they include fuel samovosplameneniya in the air, dangerous in the production, transportation, and using alyuminiiorganicheskikh connection Rnl3-n.

Closest to the designed in accordance with the present invention a catalytic systems for cationic polymerization, oligomerization, telomerization olefins and alkylation of aromatic hydrocarbons with olefins are catalytic system comprising a metal aluminum. By itself, the aluminum metal is not a catalyst of the above-mentioned processes. To ensure that the catalytic activity of the aluminum is usually used in combination with socialization.

According to [ 52. Pat. England 868607. NCP. 2/3 C. 1960] as socializaton use of dry hydrogen chloride. The catalyst for alkylation of benzene with olefins produced by the interaction of metal ADP reaction formed low in the oligomerization of olefins triple arene complexes of aluminum trichloride: Hcl(arenas)xll3.

The disadvantage of this catalytic system and method of its preparation and use is the fact that in order to avoid intensive corrosion of the equipment under the action of hydrochloric acid must be used carefully dried reagents. Another disadvantage of the considered catalytic system and method of its preparation and use is that the interaction of aluminum metal with dry hydrogen chloride proceeds slowly (2-3 hours) and only at elevated temperatures. This eliminates the possibility of preparation of cationic active centers by reaction of aluminum chloride with hydrogen directly in the oligomerization of olefins.

Also known catalytic systems for the polymerization, oligomerization and telomerization olefins and alkylation of aromatic hydrocarbons with olefins, including aluminum metal and kaleidoscopically connection [53-60] [53. A. C. the USSR 541494. NCP. 01 J 37/00. 1975; 54. Pat. USA 3303230. NCP. 260-671. 1967; 55. Pat. USA 3343911. NCP. 260-683.15. 1969; 56. A. C. the USSR 430581. Ál. C 07 C 3/10. 1974; 57. A. C. the USSR 732229. Ál. C 07 C 15/02. 1975; 58. A. C. the USSR 732003. NCP. 01 J 37/00. 1977; 59. A. C. the USSR 1031046. NCP. 01 J 37/00. 1977; 60. in accordance with the present invention the catalytic systems is a catalyst system for the oligomerization and polymerization of olefins includes metallic aluminum and carbon tetrachloride (acetalization) (prototype composition of the catalytic system) [60. A. C. the USSR 803200. NCP. 01 J 31/14. 1979].

There is a method of preparation of the catalyst for the oligomerization and polymerization of olefins by reacting aluminum metal with carbon tetrachloride at temperatures of 40-80oAnd the mass ratio of aluminum to carbon tetrachloride, equal to 1: (20-80) in the environment of carbon tetrachloride in the absence of olefins in an inert atmosphere (the prototype for the method of preparation and use of the catalyst for the oligomerization of olefins) [ 60. A. C. the USSR 803200. NCP. 01 J 31/14. 1979]. In accordance with this method, first, in the absence of olefins in an inert atmosphere (nitrogen or argon) get a solid black product of unknown composition, which is then used as a catalyst for the oligomerization of alpha-olefins and polymerization of isobutylene.

The disadvantage of the composition of the catalytic system of the prototype is using in its composition of carbon tetrachloride with the highest ratio of chlorine to aluminum. This leads to getting into the composition of the products of a large number of stubborn of them chlorine.

Another disadvantage of catalanist and low selectivity for the target fractional composition of the products.

The disadvantage of the method of preparation and use of the catalyst for the oligomerization of olefins and polymerization of isobutylene from aluminum and haloidoargentum connection (CCl4is it a multi-stage and high complexity.

The main task of the present invention was to develop an improved catalytic system for the cationic oligomerization of linear alpha olefins (LAO)3-C14characterised by increased activity and increased productivity would increase the manageability of oligomerization, in particular, would allow you to adjust the speed of oligomerization, to increase the yield of the desired low molecular weight fractions of oligomers (such as dimers and trimers of the mission is 1) to increase the branching of the chain oligomerization products and to reduce the temperature of solidification, and would increase the safety of its use in the oligomerization of olefins.

In addition, the invention was the simplification of the preparation and use of catalytic systems for the oligomerization of olefins, comprising aluminum metal.

In the present invention this involved the expansion of the available systems for the oligomerization of olefins of this type.

The problem is solved in that the catalytic system for the cationic oligomerization of individual or mixtures of linear olefins With3-C14in fundamentals of synthetic polyalpha-olefin oils contains aluminum (base catalyst) and socialization, which according to the invention (paragraph 1 of the claims) it contains halodurans connection RX, in which R is a primary, secondary or tertiary alkyl, allyl, benzyl, acetyl or benzoyl, and X is chlorine, bromine or iodine (item 1 of the claims), each g-atom of aluminum it contains from 1 to 50 (preferably from 1.5 to 5.0) moles of halogen organic compounds.

On set of technical, economic and environmental reasons are preferred such catalytic systems, which as haloidoargentum connection RX contains (item 2 claims) tertbutylamine (TBH), allylchloride (S), benzylchloride (BH), acetylchloride or benzoyl chloride. Among these compounds physico-chemical properties of the most suitable is TBH and AH. All of these organochlorine compounds (in contrast to carbon tetrachloride) contain fragments with weak high reaktionsmotor is the temperature, which leads to the formation of cationic active centers and initiating cationic oligomerization of olefins.

The catalytic system according to the present invention may contain aluminum in the form of alloys, for example, magnesium or titanium (paragraph 3). While aluminum or its alloys in the developed catalytic systems contains (item 4) in the form of materials (bodies) with a developed surface (powder, disperse spherical or flat particles (for example, aluminum ASD-4), flakes, rods, wire, mesh or plates.

Aluminum is among the highly active metals. Therefore, it is easily oxidized by oxygen in the air. While on the surface mentioned aluminum material is formed of a dense film (membrane) of aluminum oxide, which prevents complete oxidation of aluminum to aluminum oxide. This film dramatically slows and also other reactions of aluminum with highly active reagents (including the reaction of aluminum with a halogen organic socialization). It is noticed that the more developed the surface of the aluminum material (i.e. the higher the dispersion of aluminum particles), the more salient inhibitory effect aluminiumoxide film (membrane) on the reaction of aluminum with vysokokonsolidirovannoj film).

By this time developed many ways of activation of aluminum. Conditionally they can be divided into chemical, physical and mechanical. In accordance with the present invention (paragraph 5) aluminum activates a chemical way. For chemical activation of the aluminum catalytic system according to the present invention (paragraph 5) further comprises a chemical activator of aluminum selected from the group of substances containing iodine, bromine, methyl ethyl, titanium tetrachloride, trichloracetic vanadium, tin tetrachloride, ethylaminoethanol, ethylaminoethanol and aluminum trichloride in an amount of from 1 to 25 wt.%, and tertbutylamine, allylchloride, benzylchloride, benzene, and toluene in an amount of from 10 to 200 wt.% in the calculation for aluminum.

The activating action of iodine, bromine, methyl ethyl, titanium tetrachloride, trichloracetic vanadium, tin tetrachloride, ethylaminoethanol, ethylaminoethanol trichloride and aluminum due to the fact that under the action of these substances there is a partial or complete destruction (dissolution) aluminiumoxide film. In the same way, at elevated temperatures the activation of aluminium and haloalkyl the combine functions and activator of aluminum, and reagent forming with aluminum base cationic active centers and socializaton. By themselves, benzene and toluene can't activate the aluminum. The activating action of these compounds is caused, apparently, by the fact that when the catalytic assistance of aluminum oxide is slow alkylation of benzene and toluene by acetalization - halodurans connection, resulting in the formation of hydrogen chloride (RCl+C6H6+Al2About3HCl+R-C6H5+Al2O3), which dissolves aluminiumoxide film and, thus, activates the aluminum.

Al2About3+6l-->2 ll3+3 H2O Subsequent reaction of aluminum with halodurans socialization has not been studied. By analogy with the reactions vyurts and Grignard we can assume that the reaction purged with Al RX initially lead to the formation of alkylaminomethylated (ASH), and then carboneau salt HASH: 3RCl+2l-->2R1.5AlCl1.5
R1.5AlCl1.5+RCl-->R+[R1.5AlCl2.5]-(I)
So produced molecules carboneau salts (I) are the active centers of the cationic oligomerization of olefins.

In accordance with the present invention (paragraph 6) atmosphere directly in the process of oligomerization in the environment oligomerized olefins or their mixtures with products of oligomerization (e.g., with dimers, trimers, and so on) and add paraffin or aromatic hydrocarbons at temperatures from 10 to 150oWith the reactor mixing capacitive type within 10-60 minutes. In reactors of periodic action activator and socialization fully restauraut aluminum. The concentration of the formed soluble aluminum compounds varies from 10 to 80 (preferably 30-40) mmol/L.

The reactor mixing capacitive type of continuous intensive mixing of the contents in their characteristics close to the ideal mixing reactor, which is characterized by the fact that at any given time at any point in the reactor the concentration of all reactants and products are equal. As applied to continuous processes for the oligomerization of olefins under the action of catalytic systems containing fine metal aluminum, an activator of aluminum and socialization, this means that some particles of aluminum will not have time to react with other components of the catalyst and will be carried from the reactor in the initial state. This will lead to reduced performance of the catalysts.

In accordance with the present invention (item 7) on the n reactor mixing. The second reactor of a mixture performs the functions of desreves, which passed from the first reactor aluminum particles into cationic active centers.

Activated aluminum and the products of reaction with the activator and socialization are among the highly reactive substances, which are easily oxidized by the oxygen in the air. Therefore, the preparation of catalysts for the oligomerization of olefins is carried out in an inert atmosphere. As the inert atmosphere in accordance with the present invention (paragraph 8 of the claims) are used not only nitrogen or argon, as in the prototype, but also carbon dioxide when the absolute partial pressure of carbon dioxide, equal to 1.0-10.0 (preferably 1.0-1.5) atmospheres. For the same reason, the oligomerization of olefins in accordance with the present invention (paragraph 9 of the claims) is conducted in an atmosphere of carbon dioxide at the absolute partial pressure of carbon dioxide, equal to 1.0-10.0 atmospheres.

The test of catalytic systems in the process of cationic oligomerization of mission-1 and other olefins produced as follows.

In thermally cleaned and dried reactor capacitive type of periodic action with a stirrer under inert at what was aeronavali using a vacuum pump to a residual pressure of not less than 0.01 mm RT. Art. from the volumetric containers were loaded olefin (in some cases, and aromatics) (degree of filling of the reactor50 vol.%), there with a calibrated syringe with stirring was injected solutions are soluble in organic solvents activator aluminum and haloidoargentum connection R X, calibrated spray reactor filed carbon dioxide to achieve the absolute pressure of 1.5 atmospheres; with thermostat warmed up the reactor and its contents to the desired temperature. After that (usually immediately) started oligomerization of olefin, which was accompanied by a noticeable increase in the temperature of the reaction medium (oligomerizate). The reaction was continued during the scheduled time, and then broke off by introducing into the reactor an aqueous solution of alkali (NaOH) or ethanol. The resulting oligomerized from the reactor was unloaded later in the intermediate tank. Exhaust (deactivated) catalyst from oligomerizate allocated adsorption method or the method of caustic and water washing.

The temperature of the incoming flows into the reactor corresponded to the ambient temperature (15-25oC). In some cases, the solutions of the catalyst components is R solutions of the components of the catalysts with metallic aluminum with a very high speed is formed of cationic active centers and began oligomerization of the olefin. Oligomerization proceeded with high speed and emitting a large amount of heat (N) (N= 22[1-1/Pn] kcal/mol of the transformed olefin, where Rn- Brednikova degree of oligomerization of the olefin). Heat oligomerization was removed from the reaction zone coolant (usually water) through shirts mentioned reactors.

Collection-gotravel was a capacitive reactor with a stirrer, where the oligomerization neprevyshenie of olefin continued for another 60 minutes. Stay oligomerizate in the collection-doznavatel contributed to the increase of conversion of the initial olefin 3-10 wt.% compared with the case where oligomerized immediately went to clean it. From the collection-doserates oligomerized went in the washer or in the adsorber.

The washer was used for separation of spent catalyst by the method of water-alkaline, and then water washing (cleaning) oligomerizate. He functioned intermittently and was a cooled (heated) reactor with a stirrer, in which one of the auxiliary tanks-tanks has been oligomerized, 5% aqueous solution of NaOH or NH3and then fresh demineralization is.

The adsorber was a thermostatted column apparatus, filled with activated calibrated particles of alumina or bauxite. With the passage of oligomerizate (bottom-up) through the specified layer of the adsorbent was frontal adsorption allocation spent the deactivated catalyst and purification of oligomerizate.

After sampling for analyses of purified oligomerized loaded into the cube vacuum columns for subsequent azeotropic dehydration, separation neprivrednih olefins and for the separation of the oligomer fraction.

Fractional composition of the products of oligomerization was determined by standard chromatographic methods (using devices LHM 8-MD, Hewlet Packard Model 5710 (A) and/or method of fractionation by vacuum distillation column. The results of these analyses coincided with precision of2 wt.%. The structure of the selected products were quantitatively determined methods of ozonolysis on the device DT-2, X, PMR and13C-NMR.

For a better understanding of the present invention as illustrated in tables 1-7 are examples of structures designed according to the invention catalytic systems for cationic oligomerization of olefins; OPI is s test them in the oligomerization of mission-1 and other olefins, and output, structure and properties of selected products from the oligomerization of olefins target fractions oligoelement. These examples illustrate but do not exhaust the possibilities of the invention.

Comparison of test results designed according to the invention catalytic systems A1 - activator - RX (tables 2-7) test results known catalytic systems Rnl3-n-R X (table 1) and l3OM (organic modifier) (analogues) in the oligomerization of mission-1 allows to draw the following General conclusions:
1. Developed in accordance with the present invention the catalytic system Al - activator - RX operate most effectively at temperatures 20-125oWith, the concentrations of Al=0.02-0.08 mol/l, molar ratios RC1/A1=1.0-5.0 when specified in the description and in the examples, the flow rate of activators and provide 80-99-percent conversion of olefins (including mission-1) in the oligomers within 10-60 minutes;
2. Additional inclusion in the catalytic system Al-RX are listed in the description and claims of the present invention activators aluminum provides increased manageability process: eliminates the induction period, it simplifies the removal of heat oligomerization, IP the measures LAO) and provides a more uniform composition of the oligomers. On the other hand, activity and performance designed according to the invention catalytic systems Al-activator - RX is significantly higher than the activity and performance of the catalytic system Al-CCL4(the prototype). The design according to the present invention catalytic systems Al - activator - RX in the oligomerization of mission-1 reduces the reaction time from 2-3 hours in case of system Al-CCL4to 10-60 minutes - if developed according to the invention catalytic systems Al - activator - RX.

3. The application is developed according to the invention catalytic systems for the oligomerization of mission-1 helped to increase the partial yield of the desired low molecular weight fractions oligodecene (dimers and trimers of the mission) to 40-50 wt.% in the calculation of the original mission-1 (up to 60 wt.% based on the mission-1, converted into oligomers) and reduced to 10-20 wt.% content oligomerizate macromolecular oligodecene.

4. Structure and physico-chemical properties of di-, tri - and other oligomeric fractions oligodecene allows you to use them as the basis of synthetic poly-alpha-olefin oils (POM-2, PAM-4, PAM-6, POM-10, POM-14 and so on).

5. Developed sagmore of carbon dioxide help to improve technical and economic performance technology POM.

Advantages designed according to the invention catalytic systems Al - activator - RX, including many options available components, before known catalytic systems are that they combine high activity, high specific capacity, high selectivity for the target products, versatility with respect to the olefinic feedstock and provide targeted products with lower freezing temperatures.


Claims

1. Catalytic system for the cationic oligomerization of individual or mixtures of olefins With3-C14in fundamentals of synthetic polyalpha-olefin oils containing active aluminum and socialization, characterized in that as socializaton it contains halodurans connection RX, in which R is a primary, secondary or tertiary alkyl, allyl, benzyl, acetyl or benzoyl, and X is chlorine, bromine or iodine, with each g-atom of aluminum it contains 1-50 moles haloidoargentum connection.

2. The catalytic system under item 1, characterized in that as haloidoargentum connection RX it contains tertbutylamine, allylchloride, benzylchloride, ACET uminia it contains 1.5 to 5.0 moles haloidoargentum connection.

4. Catalytic system for PP. 1-3, characterized in that it contains aluminum in the form of alloys, for example, magnesium or titanium.

5. Catalytic system for PP. 1-4, characterized in that the aluminum or its alloys it contains in the form of materials with a developed surface, which is selected from a powder, disperse spherical or flat particles, wires, meshes or plates.

6. Catalytic system for PP. 1-5, characterized in that it further contains an activator of aluminum selected from the group of substances containing iodine, bromine, methyl ethyl, titanium tetrachloride, trichloracetic vanadium, tin tetrachloride, ethylaminoethanol, ethylaminoethanol and aluminum trichloride in an amount of 1-25 wt. % and tertbutylamine, allylchloride, benzylchloride, benzene and toluene in amount of 10-200 wt. % (based on aluminum.

7. The method of preparation of the catalytic system on the PP. 1-6 by the reaction of aluminum with activator and socialization in the environment of the solvent in an inert atmosphere, wherein the interaction of aluminum with activator and socialization RX carried out directly in the process of oligomerization in the environment oligomerized olefins or their mixtures with products of oligomerization and paraf who I am, the preparation of the catalytic system is performed in the atmosphere of carbon dioxide at the absolute partial pressure of carbon dioxide, equal to 1.0 to 10.0 atmospheres.

9. The method of oligomerization of individual or mixtures of olefins With3-C14in fundamentals of synthetic polyalpha-olefin oils under the action of a cationic catalyst systems for PP. 1-6 in continuous mode, characterized in that the oligomerization of olefins is carried out in a cascade of at least two serially connected reactors mixing.

10. The method according to p. 9, characterized in that the oligomerization of olefins is carried out in an atmosphere of carbon dioxide at the absolute partial pressure of carbon dioxide, equal to 1.0 to 10.0 atmospheres.

 

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