Method of production of the polyolefin bases of the synthetic oils

FIELD: petrochemical industry; methods of production of the polyolefin bases of the synthetic oils.

SUBSTANCE: the invention is pertaining to the method of production of the polyolefin bases of the synthetic oils by cationic oligomerization of the olefinic raw and may be used in petrochemical industry. The developed method contains: the stages of preparation of the olefinic raw, preparation and batching in the reactor of the solutions and suspensions of the components of the catalytic system Al(0)-HCl-(CH3)3CCl (TBX), isomerization of alpha-olefins and oligomerizations of the highest olefins and their mixtures under action of the catalytic system Al (0)-HCl-TBX, extractions of the dead catalyst, separation of the oligomerizate for fractions and hydrogenation of the extracted fractions under action of the catalytic agent Pd (0.2 mass %)/Al2O3+NaOH. The invention ensures improvement of the stages of the developed method. For prevention of the corrosion activity of the products the method additionally contains the stage of dechlorination of the present in the oligomerizate chlorine-containing oligoolefins by the metallic aluminum, triethylaluminum, the alcoholic solutions of KOH or using the thermal dehydrochlorination of the chlorine-containing polyolefins at the presence or absence of KOH. For improvement of the technical-and-economic indexes of the method at the expense of the increase of the output of the target fractions of polyolefins with the kinematic viscosity of 2-8 centistoke at 100°C the method additionally contains the stage of the thermal depolymerization of the restrictedly consumable high-molecular polyolefins with the kinematic viscosity of 10-20 centistoke at 100°C into the target polyolefins with the kinematic viscosity of 2-8 centistoke at 100°C.

EFFECT: the invention ensures improvement of all the stages of the developed method.

1 cl, 15 tbl

 

The invention relates to a method for producing polyolefin bases of synthetic oils by cationic oligomerization of olefinic feedstock and can be used in the petrochemical industry.

Received from patenting the way products can be used as the basis of synthetic polyolefin (oligoolefinic) oils for various purposes: motor (automotive, aviation, helicopter, tractor, tank); transmission, gearbox, vacuum, compressor, refrigeration, transformer, cable, spun, medical, various lubricants, and as plasticizers for plastics, rubbers, solid rocket fuels, and raw materials for the production of additives, emulsifiers, flotation agents, foaming agents, components of lubricating and cooling and hydraulic fluids; high-octane additives for fuels, etc.

Known methods for producing polyolefin bases of synthetic oils by cationic oligomerization of higher olefins containing stage of preparation of olefinic feedstock and diluent components of the catalytic system, the stage of oligomerization of olefinic raw materials, the extraction of oligomerizate spent catalyst by the method of water-alkaline and subsequent water washing, the phase separation of a purified oligomerizate into fractions and stud is Yu hydrogenation of selected target fractions.

The most substantially known methods for producing polyolefin bases of synthetic oils differ in the compositions used in these cationic catalysts.

In accordance with known methods cationic oligomerization of olefins With3-C14(i.e. olefins containing from 3 to 14 carbon atoms) initiate (catalyze) using: proton acids (acids Branstad); aprotic acids (Lewis acids); alkylamine (or boron halides; salts of stable carbocations R+And-; natural and synthetic aluminosilicates, zeolites or heteropolyacids in the protonated form; various two - and three-component systems, including monomer; polyfunctional catalysts of the Ziegler-Natta; metallocene catalysts; physical methods of stimulating chemical reactions [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.]. The most wide industrial application as catalysts for the cationic oligomerization of olefins and other monomers found the catalytic system comprising the Lewis acid (BF3, AlCl3, AlBr3, TiCl4, ZrCl4and others), alkylamino (or boron halides RnMX3-n(where R is alkyl, Cl-C10-, aryl-, alkenyl and other groups; M Is Al or B; X Is Cl, Br, I) and natural or synthetically the aluminosilicates, zeolites and heteroalicyclic in the protonated form. Upon receipt motorized POM on the basis of the linear alpha-olefins (LAO)6-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 ways to obtain polyolefin bases of synthetic oils, according to which as catalysts for oligomerization LAO6-C14use the system comprising 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; 260-683 .15; 5. Pat. USA 4 032591 from 28.06.1977; Ál. C 07 C 5/24, 5/18; NCP. 585-643; 260-683 .65; 6. Pat. USA 4376222 from 08.03.1983. Ál. 07 With 2/74; 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 4409415 from 11.10.1983. Ál. C 07 C 3/02; NCP. 585/525; 11. Pat. USA 4956512 from 11.09.1990. Ál. 07 With 2/024; NCP. 585/521; 12. Pat. USA 4436947 from 13.03.1984. Ál. C 07 C 3/18; NCP. 585/525; 13. Pat. USA 4451689 from 29.05.1984. Ál. 07 With 3/0; NCP. 585/525; 14. Pat. USA 4454366 from 12.06.1984. Ál. C 07 C 7/12; NCP. 585/525; 15. Pat. USA 4587368 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. P is so USA 5254784 from 20.12.1991. Ál. C 07 C 2/22; NCP. 585/525; 18. Pat. USA 5191140 from 02.03.1993. Ál. 07 With 2/02; NCP. 585/525; 19. Pat. USA 5420373 from 30.05.1995. Ál. 07 With 2/08; NCP. 858/525; 20. Pat. USA 5550307 from 27.08.1996. Ál. C 07 C 2/14; NCP. 585/525.]. Polyolefin bases of synthetic oils in accordance with these methods are obtained by oligomerization of olefins With6-C14under the action mentioned bartering catalysts at temperatures 20-90°With 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, there 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 70 wt.%.

The main drawback of all methods of obtaining polyolefin bases of synthetic oils of this type is that they are based on the use of catalysts, including scarce, volatile, poisonous, corrosive boron TRIFLUORIDE. In addition, due to the relatively low activity of the catalysts of this type in the oligomerization LAO process occurs in 2-5 hours. When the industrial implementation of these methods are expensive, large and metal reactors mixing in the anti-Christ. orationem execution.

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 3997622 from 14.12.1976. Ál. C 07 C 3/18; NCP. 585-532; 24. Pat. USA 3997623 from 14.12.1976; Ál. C 07 C 3/18; NCP. 585-532; 25. Pat. USA 4006199 from 01.02.1977. Ál. C 07 C 3/18; NCP. 585-532; 26. Pat. USA 4031158 from 21.06.1977. Ál. C 07 C 3/18; NCP. 585-532; 27. Pat. USA 4031159 from 21.06.1977. Ál. C 07 C 3/18; NCP. 585-532; 28. Pat. USA 4066715 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] also a large number of ways to obtain polyolefin bases of synthetic oils, in accordance with which the oligomerization of olefins is carried out under the action of cationic catalysts include halides of aluminium and proton donor - water, alcohols, carboxylic acids, simple or complex esters, ketones (for example, dimethyl ether of ethylene glycol, etilenglikolevye), haloalkyl [28, 32] [28. Pat. USA 4066715 from 03.01.1978. 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]. In some ways these catalysts are used in combination with compounds of Nickel [33. Pat. USA 5489721 from 06.02.1996. Ál. C 07 C 2/20; NCP. 585-532]. Additives of Nickel compounds used in accordance with these methods, the catalysts provide regulation of the structure and fra the traditional composition of the obtained oligoelement.

Obtaining polyolefin bases of synthetic oils by the oligomerization of alpha-(C4-C14or internal Cl10-Cl15olefins (obtained by dehydrogenation of paraffins) method [29. Pat. USA 4113790 from 12.09.1978. Ál. C 07 C 3/10; NCP. 585-532] carried out under the action of catalysts AlX3+protonating at temperatures of 100-140°C for 3-5 hours. The concentration of AlX3range 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.%.

Methods of this type are characterized by the following common disadvantages:

- a complex procedure for preparation of the catalysts, including many operations - sublimation and grinding AlCl3the preparation of the complex.

- obtained by these methods, the catalysts are viscous, sticky substances poorly soluble in the olefin, due to the high adhesion to the walls of the cooled reactors bad they are unloaded from the reactor after completion of the oligomerization;

- low activity of the used catalyst in the oligomerization process that requires the use of large metal reactors mixing;

high expense ratios for AlX3in the calculation of the derived products.

Major General n is a wealth of methods of this type is that using it results in mainly high molecular weight and high viscosity containing up to 1 wt.% chlorine products.

Developed several ways to obtain polyolefin bases of synthetic oils based on the use of bifunctional complex catalysts comprising transition metal compounds (TiCl4, ZrCl4and alkylhalogenide RnAlX3-n(see, for example, [34-46]. [34. Patscha 4214112 from 22.07.1980. Ál. C 07 C 3/18; NCP. 585-532; 35. J.Skupmska. 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. HDN; 43. A.S. USSR 1073279. Ál. 07 With 2/32; NCP. The SUME 3/12; 44. Japanese Pat-11350. 1977 (Rehim. 1978. 2 27 0 P). Ál. From 08 F 10/14; 45. A.S. USSR 1075500. 17.03.1982. Ál. C 07 C 2/22. NCP. 01 J 31/14; 46. A.S. USSR 1192346. 12.08.1983. Ál. C 07 C 2/22. NCP. With 10 M 107/02]). As used in accordance with these methods bifunctional catalytic systems of the type TiCl4- RnAlX3-nformed two types of active centers - cation and anion-coord is discriminatory. Because of this, the oligomerization of olefins With3-C14under the action of cationic active centers in almost all cases accompanied by the polymerization of olefins With3-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 the methods of this type.

In accordance with some methods in the cationic polymerization, oligomerization and alkylation also widely used two-soluble monofunctional catalyst system comprising alkylaminocarbonyl RnAlX3-nand kaleidoscopically connection R X when the molar ratio R X/RnAlX3-n=1.0-5.0 (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 or tertiary alkyl, allyl or benzyl [48-51] [48. Pat. USA 4041098. 09.08.1977. Ál. C 07 C 3/10; NCP. 585-524; 49. Pat. The UK 1535324, 1535325. 1978. Ál. C 07 C 3/21; NCP. 1 E, 5 E; 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.S. USSR 1723101. 20.04.1989. Ál. 07 With 2/30. NCP. With 10 M 107/10]). In the catalytic systems of this type, RnAlX3-nis the basis of the catalyst, a R X acetalization.

In accordance with these methods, the catalytic system RnAlX3-n-R X are used to initiate cationic oligomerization of individual or mixtures of linear alpha-olefins from propylene to tetradecene inclusive in polyalpha-olefin bases of synthetic oils in the environment, the source of olefins or their mixtures with products of oligomerization and paraffin, aromatic or galoidsodyerzhascikh hydrocarbons at temperatures up to 250°C.

Cationic active centers ([R'+(RnAlX4-n)] and R'+in catalytic systems RnAlX3-n-R X are formed in accordance with the following simplified scheme:

The formation of cationic active centers in this catalytic system is a very high speed. Due to this, immediately after mixing the solutions of the components in question catalytic systems achieved the highest concentration of cationic active centers and oligomerization proceeds without induction period with a very high initial speed. While 95-98%the percentage conversion and the output of the olefins in the oligomeric products at temperatures of 20-200° Can 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 forced isothermal conditions in the reactor displacement of the tubular type at the time of stay from 1 to 10 minutes [51. A.S. USSR 1723101. 20.04.1989. Ál. 07 With 2/30. NCP. With 10 M 107/10; U.S. Pat. RF 2201799. 29.09.2000. Ál. 7 01 J 8/06, 08 F 110/10; bull. Fig. 2003. No. 10].

Upon receipt oligo-olefins bases of synthetic oils in accordance with these methods in the course of the oligomerization LAO in the mass or in the environment of paraffin hydrocarbons under the action of catalytic systems RnAlX3-n-R X form highly branched harden at low temperatures oligomers containing one di-, tri - or tetraalkylammonium double bond and up to 0.2 wt.% monochlorophenol, and by 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.S. USSR 1723101. 20.04.1989. Ál. 07 With 2/30. NCP. With 10 M 107/10; U.S. Pat. RF 2199516 from 18.04.2001, MKN 7 07 With 2/22. Bull. Fig. No. 6 dated 27.02.2003,].

The main drawback of the ways to obtain oligo-olefins bases of synthetic oils by oligomerization of Olaf is new under the action of catalytic systems R nAlX3-n-R X is the fact that their use in oligomerization LAO (in particular - mission-1) leads to the formation of predominantly high molecular weight products with a wide molecular weight distribution and low (less than 20 wt.%) the content of the target low-molecular-weight fractions (dimers and trimers of mission-1).

Another drawback of methods based on the use of catalytic systems of this type, is that obtained by these methods dimers of mission-1 are linear and after hydrogenation have a pour point in excess of minus 20°C.

To eliminate this drawback, i.e. for improving the selectivity and improve technical and economic performance of the method, a method was developed to obtain oligo-olefins bases of synthetic oils, according to which not hydrogenated dimers of mission-1 is sent to recycling on cooligomerization them with mission-1 in widely consumed three - and tetramer of mission [46. Pat. USA 4263467. 02.04.1981]. Cooligomerization dimers of mission-1 (43.8 wt.% in the charge) with mission-1 (40 wt.% the mission-1 and 15.4 wt.% Dean in charge) this method is carried out under the action of the system BF3/SiO2(D=0.8-2.0 mm)+H2(65 ppm in the charge) at temperatures of 15-30°C, a pressure of 1-6 .9 at the expense of the charge 2.5 l per hour per 1 l of catalyst. Dimers of mission-1 at the outlet of the reactor is reduced is moved from 43.8 to 20.7 wt.%, and the content of the trimer of mission-1 increased to 41.8 wt.%. This solution allows qualified use is not consumed (harden at high temperatures) linear dimers of mission-1. The disadvantage of this solution is a sharp decline in the performance of the process, which is based on this method.

A third common drawback of all methods based on the use of catalytic systems RnAlX3-n-R/X, is the fact that the applied catalytic systems include fuel, samovosplameneniya in the air, dangerous in the production, transportation, and using alyuminiiorganicheskikh connection RnAlX3-n.

And finally, the fourth common drawback of all methods based on the use of catalytic systems RnAlX3-nR/X, is the fact that under the action of these catalytic systems formed products containing up to 1.0 wt.% chlorine in the form of monochlorophenol.

There are also known ways of cationic polymerization, oligomerization of olefins and alkylation of aromatic hydrocarbons with olefins under the action of catalytic systems containing metallic 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 the coziness in combination with socialization. So, for example, known methods of polymerization, oligomerization and telomerization olefins and alkylation of aromatic hydrocarbons with olefins, including aluminum metal and kaleidoscopically connection [53-58] [53. AC 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.S. USSR 430581. Ál. C 07 C 3/10. 1974; 57. A.S. USSR 732229. Ál. C 07 C 15/02. 1975; 58. EN 2212935 from 27.09.03; IPC B 01 J 27/06].

The closest in technical essence and the achieved result is developed in accordance with the present invention a method for producing polyolefin bases of synthetic oils is a method of oligomerization and polymerization of olefins under the action of a catalytic system comprising a metal aluminum and carbon tetrachloride [58. EN 2212935 from 27.09.03,; IPC B01J 27/06]. The catalyst for the oligomerization and polymerization of olefins according to this method, is produced by the interaction of metallic aluminum with carbon tetrachloride at temperatures ranging from 40 to 80°and 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 [58. EN 2212935 from 27.09.03,; IPC 01J 27/06]. In accordance with this method, first, in the absence of olefins in an inert atmosphere get a solid black product of unknown composition, which Yes, is it used as a catalyst for the oligomerization of alpha-olefins and polymerization of isobutylene. We consider this method as a prototype for our developed method of producing polyolefin bases of synthetic oils.

The disadvantage of the prototype is the use of this method of carbon tetrachloride in the composition used catalytic systems with the highest ratio of CCl4/Al(0). This leads to incorporation into the products of a large number (up to 3.0 wt.%) stubborn of them chlorine.

Another disadvantage of the prototype method [58. EN 2212935 from 27.09.03,; IPC B 01 J 27/06] is low activity, low productivity and low selectivity for the target products used in this method, the catalytic system Al(0)-CCl4.

The disadvantage of the prototype is also a multi-stage and high complexity of the preparation and use of the catalyst for the oligomerization of olefins and polymerization of isobutylene from aluminum and CCl4.

The General objective of the present technical solution is to eliminate all the above-mentioned disadvantages of the known methods.

The main specific objective of the present invention was to develop a method of obtaining a polyolefin bases of synthetic oils with improved catalytic system for the cationic oligomerization of linear alpha olefins (LAO)3-C14that is the nature of what was Savalas would be increased activity and increased performance 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. The second objective of the present invention was to simplify the method of preparation and use of catalytic systems oligomerization of olefins, comprising aluminum metal.

The formulated problem is solved in the present invention in improvements in all key stages of the method of obtaining polyolefin bases of synthetic oils.

Disclosure of the invention. Designed according to the present invention is a method of obtaining polyolefin bases of synthetic oils, as well as any other similar method comprises a stage of preparation of olefinic materials and solutions of the cationic components of the catalytic system, the phase isomerization of higher linear alpha-olefins, the stage of oligomerization of olefinic raw materials under the action of cationic aluminium-containing catalytic system, the extraction of oligomerizate spent catalyst, the stage section is ing oligomerizate into fractions and phase hydrogenation of selected fractions. In addition, it is after the stage of oligomerization and/or after the stage of allocation spent catalyst from oligomerizate, further comprises a phase dechlorination present in oligomerizate monochloracetic oligomers, and after phase separation oligomerizate on faction it contains phase depolymerization of high molecular weight products, selected from oligomerizate in the form of VAT residue at the stage of separation oligomerizate into fractions (item 1 of the claims). These stages are designed to improve technical and economic performance of the method, to solve specific chemical problems and to improve the flexibility of the developed method. In particular, the phase dechlorination formed during the oligomerization and contained in oligomerizate of monochloroacetone is designed to turn covalently linked to the carbon in monochlorohydrin so-called "organic" chlorine in innovatory with metals, so-called "ion" chlorine. Derived from chlorine-containing oligodecene "ion" chlorine together with the spent cationic catalyst, as in other ways cationic oligomerization of olefins or alkylation, further removed from oligomerizate method of water-alkaline washing.

In accordance with the present invention the polyolefin basics this is a mini-oils obtained by oligomerization of higher olefins in the mixture oligomerized higher olefin products of oligomerization or in mixtures oligomerized higher olefin products of oligomerization and aromatic hydrocarbons under the action of three safe during transportation, storage and use, stable in air, available cationic catalytic system Al(0)-HCl-(CH3)3CCl at temperatures from 110 to 180°C, the concentration of Al(0) from 0.02 to 0.08 g-atom/l, a molar ratio of HCl/Al(0), which varies from 0.002 to 0.06 and molar ratios RCl/Al(0), which varies from 1.0 to 5.0, where Al(0) - fine powdered aluminum with particle sizes varying from 1 to 100 μm, for example, Al(0) mark PA-1, PA-4, ASD-4, SDA-40, DCA-T (item 2 claims). Individual components of the system Al(0)-HCl-(CH3)3CCl catalysts for the oligomerization of higher olefins are not. Predecessors (precursory) cationic active centers themselves cationic active centers of higher oligomerization of olefins in this system are formed in the sequence of many chemical reactions between components of the system. Used in the composition under consideration catalytic metal fine aluminum consists of particles of aluminum, covered with dense, not reactive aluminiumoxide shell. Because of this, it is stable in air and at temperatures 20-110°With almost no reaction with HCl and (CH3)3The CCl. The reaction of Al(0) HCl and (CH3)3CCl starts only the temperatures, exceeding 110°C. In accordance with the method of obtaining polyolefin bases of synthetic oils in the developed catalytic system aluminum primarily reacts with hydrogen chloride. HCl, at least partially destroys aluminiumoxide film on the surface of aluminum particles and enables the reaction of aluminum with tertbutylamine. In other words, the hydrogen chloride in the system under consideration is an activator of metallic aluminum. Reaction of aluminum with tertbutylamine proceeds according to the following simplified scheme:

The resulting sesquicentennial (1), as well as HCl, reacts with aluminiumoxide shell on the surface of aluminum particles. This leads to the acceleration of the process of education (1) and to the complete dissolution of aluminum metal. Activation of aluminum provides a very small amount of hydrogen chloride which is dissolved in tertbutylamine (TBH) in the process of its receipt by the reaction of isobutylene with hydrogen chloride. The molar ratio of HCl/Al(0) in the catalytic system Al(0)-HCl-(CH3)3CCl vary in the range from 0.002 to 0.06 by varying the concentration of HCl in TBH from 0.015 to 0.5 wt.%.

The aluminium concentration in the reaction medium in the process of oligomerization of olefinic raw materials the variation is comfort in the range of from 0.02 to 0.08 g-atom/liter At concentrations of aluminum below 0.02 g-atom/l oligomerization does not leak due to the inhibitory effect present in the olefin impurities, and at concentrations of aluminum above 0.08 g-atom/l dramatically increases the specific consumption of catalyst components. The optimal concentration of aluminum in the reaction medium ranges from 0.03 to 0.04 g-atom/liter

The molar ratio of TBH/Al(0) range from 1.0 to 5.0, the optimal molar ratio TBH/Al(0) equals 3.5. When the molar ratio TBH/Al(0) less than 3.5 dissolves only part contained in the system Al(0)-HCl-(CH3)3CCl aluminum metal, and when the molar ratios TBH/Al(0) above 4.0 dramatically increases the chlorine content in the oligomers. The primary cationic active centers in this catalytic system formed according to the scheme:

TBH when it performs the functions of socializaton.

Oligomerization of olefins under the action of the system Al(0)-HCl-(CH3)3CCl with high speed and with high conversion of olefins in the product (above 95 mol.%) takes place at temperatures from 110 to 180°C. In the course of the oligomerization of alpha-olefins under the action of the system Al(0)-HCl-(CH3)3CCl is a partial isomerization of alpha-olefins in a mixture of positional and geometric isomers of olefins with internal double what Vasey, which cooligomerization with the original alpha-olefin. This leads to increased branching of the molecules of the products and to reduce the temperature of solidification. In the case of oligomerization of mission-1 application system Al(0)-HCl-(CH3)3CCl provides a decrease in the share of high-molecular oligodecene60+50 (prototype) to 8 wt.%. Formed under the action of this system Oligocene contain from 4300 to 9970 ppm chlorine (table 1). The use of the system Al(0)-HCl-(CH3)3CCl in the process of oligomerization provides a solution to the problem of regulation of fractional composition and structure of the products of the oligomerization of detinov. The consumption component of this catalytic system mass does not exceed the relevant indicators of the best known (including bartering) catalysts.

Practically important feature of the developed method is that the interaction of aluminum with activator (HCl) and socialization (TBH) is conducted directly in the process of oligomerization in the environment of mixtures oligomerized olefins by oligomerization products and additionally add aromatic hydrocarbons (benzene, toluene, naphthalene). This solution eliminates the need to work with concentrated highly reactive precursors and products of reactions of formation of active centers and increases the t security method.

In accordance with the present invention as oligomerized higher olefins take a mixture of linear or branched alpha-olefins to ISO-olefins and olefins with intramolecular location of the double bond (with internal olefins containing from 3 to 14 (mostly 10) carbon atoms, in the following ratio of ingredients, wt.%: alpha-olefins 0.5-99.0; ISO-olefins 0.5-5.0; internal olefins - the rest up to 100 wt.% (table 2) (paragraph 3 claims). From the table 2 data shows that under other equal conditions, the increase in the number of carbon atoms in molecules of olefins leads to the reduction of branching of the molecules of oligoelement and to improve their viscosity index.

The most common methods of obtaining polyolefin bases of synthetic oils, in which the olefinic feedstock is mission-1. This is due to the fact that allocated from oligomers of mission-1 trimers of mission-1 after hydrogenation are characterized by a unique set of physical properties (kinematic viscosity at 100°With equal 3.9 cSt, viscosity index=130, pour point=-60°s, flash point=215-220°). This combination of properties provides the possibility of using them as the basis of commonly used synthetic and semi-synthetic motor (automotive manufacturing is x, aircraft, helicopter, tractor, tank) and other oils. Therefore, the best raw material for producing polyolefin bases of synthetic oils is the mission-1. In accordance with this method, the presence in the original mission-1 impurities isoolefine (from 0.5 to 11.0 wt.%) and olefins with intramolecular location of the double bond (from 0.5 to 5.0 wt.%) virtually no effect on the physico-chemical characteristics selected from products not hydrogenated and hydrogenated fractions. In the course of the cationic oligomerization of the mission-1 before entering the oligomeric product under the action of the catalytic system Al(0)-HCl-(CH3)3CCl and the other containing aluminum compounds, catalytic systems isomerized in a mixture of positional and geometric isomers of the mission with the intramolecular arrangement of double bonds. Deceny with intramolecular arrangement of double bonds (including individual mission-5) under the action of the catalytic system Al(0)-HCl-(CH3)3CCl as easily (but more slowly) oligomerized as the mission-1. During oligomerization of datenow with intramolecular arrangement of the double bonds are formed more extensive than in the case of mission-1 (and therefore harden at lower temperatures) molecule oligodecene.

From the classic stage mechanism of the processes of cationic oligomerization is Levinov under the action of chlorine (including and alyuminiiorganicheskikh) cationic catalysts should [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 generated in these processes, the oligomers may contain "organically linked chlorine (i.e. chlorine, associated with the carbon atom molecules oligodecene as part of oligomerizate). Theoretical calculations and experimental data show that from 2 to 10% of the molecules oligodecene obtained under the action of the cationic aluminium-containing catalysts contain one chlorine atom, and 90-98% of the molecules oligodecene contain one double bond. After decontamination and removal from oligomerizate method caustic wash at a temperature of +95°spent cationic catalyst, oligomerized contains about 1000 to 10000 ppm (0.1-1.0 wt.%) chlorine associated with carbon atoms of molecules Oligocene. Chlorine in Oligocene gets in acts of true (almost irreversible) open circuit as a result of capture growing carbocation chlorine anion of the anionic fragment of cationic active center (AC). The outline of this process on the example of a simple catalyst RCl+AlCl3(R+AlCl4-) has the following form (3):

Contained in oligomerizate and target fractions chlorine is syvaet corrosion of the corresponding equipment not only at all stages of the process of obtaining oligodecene, but in the process of using oligolectic bases of synthetic oils. Because of this, chlorine must be removed not only from the main fractions of oligodecene, but from oligomerizate at the earliest stages of their receipt.

In accordance with the present invention dechlorination present in oligomerizate monochloracetic molecules oligomers (RCl) is carried out after stage oligomerization, and after phase separation from oligomerizate spent catalyst Al(0)-HCl-(CH3)3CCl (item 1 of the claims). During development of the present method of producing polyolefin bases of synthetic oils developed 5 solutions to the problems dechlorination.

In the first embodiment of the present method dechlorination RCl produce superfine powder metal aluminum - Al(0) with particle sizes varying from 1 to 100 μm (for example, marks PA-1, PA-4, ASD-4, SDA-40, DCA-T) at a molar ratio of Al(0)/RCl, which varies from 0.5 to 2.0, in the temperature range from 110 to 180°C for from 30 to 180 minutes (4 claims) (table 3). Due to the high bond energy of C-Cl, chlorine from chloroalkanes containing fragments-CH2Cl, by means of chemical reagents is removed with great difficulty. The most easily from chloroalkanes removes chlorine contained in the fragments of R3/sub> The CCl. Therefore, the test is an indicator of the speed and depth dechlorination of chloroalkanes used 1-chloro-dodecane containing fragment-CH2Cl. From table 3 it can be seen that at temperatures not exceeding 95°S, under the action of aluminum brand PA-4 dechlorination of 1-chloro-dodecane and chlorinated oligodecene does not occur. Raising the temperature to 120°and above leads to the complete dechlorination mentioned chloroalkanes. The dechlorination reaction 1 hardtechno aluminum in the environment of mission-1 leads to almost 100%of oligomerization of mission-1. This suggests that the reaction of aluminum with 1-hardtechno proceeds in the same manner as the reaction of aluminum with TBH (i.e. with intermediate formation of cationic active centers oligomerization). The reaction of the aluminum with RCl leads to the conversion of covalently bonded carbon and chlorine ion associated with the metal chloride, which is at the stage of water-alkaline cleaning is removed from oligomerizate.

In accordance with a second embodiment of dechlorination on patent-pending method present in oligomerizate monochlorobenzene Oligocene (RCl) dechlorinate after stage oligomerization by triethylaluminium (tea) at a molar ratio of tea/RCl, which varies from 0.5 to 2.0, in the temperature range from 95 to 150°C for from 30 to 180 minutes (item 5 claims).

Declare the Finance RCl-triethylaluminium the above conditions is in accordance with the following scheme (4):

From tables (3, 4) shows that the dechlorination of 1-chloro-dodecane aluminum and triethylaluminium occurs only at temperatures 130-164°as in the absence of waste cationic catalyst and in the presence of the products of its evolution during the oligomerization. It is also seen that the conversion of mission-1 in the products of the oligomerization during the dechlorination reaction RCl aluminum and triethylaluminium increases. This is consistent with circuits (3, 4), according to which the reaction RCl with aluminum and triethylaluminium proceed through the stage of formation of the cationic active center {R+[(C2H5)3AlCl]-), which triggers the oligomerization of mission-1.

The General advantage of the first and second options dechlorination RCl with Al(0) and tea, in accordance with the present invention is that the reaction RCl mentioned deklariruemomu reagents carried out directly after oligomerization in the presence of the waste, but not separated from oligomerizate, transformation products used cationic catalytic system Al(0)-HCl-TBH. Formed by dechlorination alkyl aluminum chlorides stand out from oligomerizate simultaneously with the spent catalyst at the stage of water-alkaline washing. This technology simplifies the design of this stage, but requires p is increased consumption of dispersed aluminum or the use of tea.

Primary and secondary chloralkali in normal conditions (i.e. at temperatures not exceeding 100° (C) is not hydrolyzed by water and aqueous solutions of hydroxides of sodium or potassium. In accordance with a third variant of the present method of producing polyolefin bases of synthetic oils, dechlorination formed during the oligomerization and present in oligomerizate monochloracetic oligomers (RCl) is carried out before or after the stage of allocation spent catalyst alcohol (butanolide or geksanalem - ROH) potassium hydroxide solution or sodium (mon) at a molar ratio of MOH/RCl, which varies from 1.1 to 2.0, in the temperature range from 120 to 160°C for from 30 to 240 minutes (table 5) (item 6 of the patent claims). Instead mentioned ROH as solvent KOH can be used monotropy ether of ethylene glycol. The concentration of MES in ROH range from 1 to 5 wt.%. From table 5 it is seen that under other identical conditions, the reaction rate and the conversion rate of dechlorination is significantly reduced when replacing KOH to NaOH. For this reason, KOH is preferred. The dechlorination reaction RCl alcohol solutions MES even at 120°With slow. The temperature increases from 120 to 150°leads to a sharp increase of the reaction rate. At 150°the reaction is completed within 60 minutia is the W RCl by this variant of the method proceeds according to the scheme, involving the intermediate formation of alkoxides of alkali metals, which react further with chloralkali RCl:

KOH+C4H9OH→C4H9OK+H2O

With4H9OK+RCl→KCl+C4H9OR

The chlorides of sodium and potassium in the above-mentioned alcohols in the reaction conditions dechlorination of chloroalkanes not soluble, which allows to distinguish them from the reaction mixture by precipitation and subsequent dissolution of the precipitate salt water MCl.

The most simple of the developed options dechlorination of chlorinated oligodecene is a variant, according to which dechlorination present in oligomerizate monochloracetic oligomers (RCl) is carried out after the stage of allocation spent catalyst by thermal dehydrochlorination RCl in the temperature range from 280 to 350°and the pressures of 1-2 at for from 30 to 180 minutes at Stripping evolved hydrogen chloride nitrogen, carbon dioxide, methane (natural gas) or superheated steam (table 6) (item 7 of the claims). Thermal dehydrochlorination by this variant of the method is carried out in the heater-evaporator atmospheric column under intensive stirring of oligomerizate Obvodny gas or superheated steam. This option dechlorination of chlorinated oligomers of the mission is and d is storsta and disadvantages: it provides a high degree of dehydrochlorination oligomerizate (97-98%), does not require the use of new chemicals, but adds complexity to the design of the atmospheric column.

Thermal dehydrochlorination of chlorinated compounds begins at temperatures above 250°C. the Rate of heat dehydrochlorinating significantly depends on the structure of chlorinated compounds. In the case of chlorine-containing compounds having a beta-To-N communication in relation to public relations-Cl, the most heat-resistant are the primary haloalkyl, the least thermostable are tertiary haloalkyl. Thermal dehydrochlorination R3CCl with a noticeable speed flows even at 100°C. Of the composition of the starting reagents and the step-wise mechanism of oligomerization of mission-1 follows that oligomerizate can attend all theoretically possible for each specific case types of chlorine-containing compounds (containing and not containing beta-To-N communication primary, secondary and tertiary haloalkyl). Speed, and under other equal conditions, the degree of dehydrochlorination containing beta-To-N communication primary, secondary and tertiary haloalkyl usually increase with increasing temperature.

At temperatures of 250-300°With the dehydrochlorination of chlorinated oligomerizate proceeds relatively slowly, and apparently reversible within 6-10 hours. Released in the acts of digital the generation of hydrogen chloride can immediately join the molecules oligodecene, containing double bonds. This favors a relatively high concentration of double bonds of different types of molecules oligodecene.

Other things the same static conditions, the rate and extent of dehydrocorydaline oligomerizate increase with increasing temperature from 300 to 330°C. the Depolymerization of oligodecene when it does not leak. At 330°and residence time of two hours, almost all contained in the oligomers of organically bound chlorine is removed from oligomerizate in the form of HCl. In oligomerizate after heat treatment is about 20 ppm (ppm) organically bound chlorine (i.e., about 0.002 wt.%). In terms of Stripping hydrogen chloride and gaseous components from oligomerizate nitrogen at 330°and residence time of one hour in oligomerizate only 3 ppm (ppm) of organically bound chlorine. From the data obtained it follows that the degree of removal of chlorinated hydrocarbons from oligomerizate=99,94%by weight. The content of organochlorine compounds in recyclorama the mission-decanoas fraction does not exceed 160 ppm (equivalent to 0.016 wt.%). This fraction may be mixed with fresh incoming on the installation mission, and the resulting mixture can be used as a feedstock to obtain oligodecene.

Thermal dehydrochlorination of chlorinated molecules oligodecene in temp is the temperature 300-330° And the total residence time of two hours proceeds almost quantitatively according to the following scheme:

R-(Cl0H20)x-1-Cl10H21Cl→HCl+R-(Cl10H20)x-1-Cl10H20(=)

Emitted when hydrogen chloride rap nitrogen or superheated steam, and together with water vapor and hydrocarbons is fed first to the condenser and from there is sent to the scrubber to neutralize the HCl aqueous solution of sodium hydroxide.

To avoid the selection of hydrogen chloride in the free state in the vapor-gas phase, the dehydrochlorination present in oligomerizate monochloracetic oligomers (RCl), in accordance with the present invention (paragraph 8 of the claims) is carried out in the temperature range from 300 to 330°in the presence of dry hydroxides of alkali metals (mon) at a molar ratio of MOH/RCl, which varies from 1.1 to 2.0 (table 7). To ensure the highest possible degree of dispersion of the particles are not soluble in oligomerizate dry hydroxides of alkali metals receive them in accordance with the present invention (paragraph 9 claims) directly in oligomerizate by distillation of water by heating the mixture released from the spent catalyst oligomerizate and 5-40%aqueous solution of the alkali metal hydroxide is ri temperatures, changing in the temperature range from 100 to 200°With (table 7). When the temperature increases from 100 to 200°evaporation and removing water from the reaction mass. Subsequent dehydrochlorination of chlorinated oligo-datenov carried out for one hour at temperatures of 300, 310, 320 and 330°S. Of table 7 shows that under other equal conditions the residual chlorine content in the oligomer with increasing temperature from 300 to 330°With sharply reduced and at 330°up to 8 ppm (8 ppm), the extent of dehydrocorydaline 95.56 wt.%. Hydrogen chloride in the gas phase does not work - it is completely reacts with potassium hydroxide and is found in the form of KCl in the solid precipitate, which is completely soluble in water. Flushing dehydrochlorinating oligomerizate water after unloading from the reactor and analysis of the wash water by chlorine suggest that some fraction (less than 0.5 wt.%) the resulting potassium chloride is held in suspension in dehydrochlorinating the oligomer.

Developed options dechlorination molecules of chlorine oligodecene (ie - chloroalkanes) are universal and can be used independently to solve similar problems in other chemical processes, oil refining, as well as when dechlorination of mono-, di - and polychlororganic aliphatic and Aro is oticheskih hydrocarbons, oligomers, polymers, petroleum fractions, and various liquid and solid chlorine-containing organic waste (paragraph 10 claims).

For example, table 8 presents data on the dehydrochlorination of liquid polychloroprenes containing 44 wt.% chlorine, butanolide solution of KOH. This solution is used, in particular, upon receipt of synthetic drying oils and oligomers of acetylene.

Patented a method of obtaining a polyolefin bases of synthetic oils include disposal of not finding skilled application of fractions of high molecular weight Oligocene by depolymerization. Phase depolymerization of high-molecular oligodecene is designed to adjust the molecular mass distribution and the fractional composition of oligodecene obtained at the stage of oligomerization. Depolymerization of high molecular weight products allocated in the form of VAT residue at the stage of separation oligomerizate into fractions in accordance with the developed method (paragraph 11 claims), shall be performed by heating them at temperatures from 330 to 360°and pressures from 1.0 to 10.0 mm Hg for 30 to 120 minutes with continuous removal of the products from the reactor depolymerization in the atmospheric system and the two vacuum columns for the separation of oligomerizate into fractions.

Division dezenove oligomerizate is on fractions and depolymerization selected VAT residue, containing high-molecular Oligocene produced on the vacuum unit of the French company "GECIL". Used computerized automated installation (model "minidist") includes two columns, two electrically heated cube of 10 and 22 liter glass collection, about 10 receivers to allocate fractions, vacuum post, vacuum pump, vacuum gauge and two devices for measuring temperature in the cube and in the upper part of the column. The collection was equipped with automatic speed control sampling fractions. Vacuum system this setup provides the possibility of fractionating oligomerizate under strictly specified residual pressure. The first column with a regular grid nozzle and irrigation can be operated at atmospheric or reduced pressure (up to 2.0 mm Hg). The second vacuum column (without attachments and without irrigation) can operate at a high vacuum (even when the residual pressure is 1.0-0.01 mm Hg) at temperatures up to 370°C. Consider distillation system is also equipped with automatic node determine the mass fractions. All information about the details of the separation oligomerizate enters the computer, where it is collected and processed. In particular, the computer with a special program based on the actual temperature values of the cube and ver the a columns and the residual pressure in the column defines the virtual process temperature at atmospheric pressure (T in), which coincides with the conventional temperature fractionation (Tyfound with help of nomograms T - R. the Separation of oligomerizate fraction produced in the first column with a regular nozzle (15 theoretical plates) with a cube of about 20 liters. Depolymerization of high-molecular oligodecene held on the second (vacuum) column without regular packing and without irrigation cube of about 10 litres.

In electrically heated cube the first column was loaded from 5 to 10 kg purified from the catalyst and from organically bound chlorine of oligomerizate. Division of oligomerizate into fractions produced in the regime of slow rise in temperature from 20 to 300°C. Readily boiling components, and PAO-2, PAO-4 from oligomerizate allocated to the first colon with a nozzle and with irrigation. PAO-6 and PC-8 was allocated to the second vacuum system.

It was found that in the process of separation dezenove oligomerizate on a narrow fraction at temperatures higher than 330°With, there is thermal depolymerization of oligodecene. In the temperature range 300-330°at a residual pressure of less than 5 mm Hg from oligomerizate allocated remaining there trimers and tetramer of the mission. With 360°C for three hours at a residual pressure in the column is less than 3 mm Hg in Cuba is almost complete depolymerization highly molekulyarnyh oligomers of the mission. Resulting products were separated into fractions. It is established that the light fraction allocated at the temperature of 20-150°With, of the products of depolymerization of high-molecular oligodecene consists of a mixture of olefins (mainly datenow) vinyl (53.6%), transfinitely (18.1%) and vinylidene (28.3%) double bonds. Selected in the interval of temperatures 150-240 and 240-300°products are dimers and trimers of the mission, respectively. This is confirmed by gas chromatography and by coincidence the basic properties of these fractions with the properties of standard samples of dimers and trimers of detinov. As residue after the separation of the degradation products into fractions contained depolimerizovannogo high molecular weight oligomers of detinov.

Describes the composition of the products indicates that during the heat treatment of high-molecular oligodecene happens (apparently, statistical) their depolymerization. The observed effect is of great practical importance because it allows, if necessary, a simple way to process high Oligocene in di-, tri - and tetramer of detinov. The results of the separation dezenove oligomerizate into fractions in partial depolymerization of high-molecular components are shown in table 9.

Depolymerization of professional who cularly oligomers of mission (PJSC-10-PSC-20) with a kinematic viscosity at 100° C=10-20 cSt purposefully conducted at temperatures 330-360°at a residual pressure on the top of the column of depolymerization 1 mm Hg, and in Cuba columns 3-5 mm Hg

For a better understanding of the work of depolymerization here is the description of one typical experiments. Cube depolymerization was loaded with 3000 g of the oligomer of the mission with a boiling point at a residual pressure on the top of the column 1 mm Hg above 360°C. as a result of depolymerization this Oligocene at a temperature of 350°C for three hours was whisked 2258 g (75.27 wt.%) products of depolymerization. Allocated through the top of the reactor column products of depolymerization of Oligocene-1 in the total number 2258 g were re-divided into the following fractions (see table A):

Table A.
Nature

faction
The interval T

boiling fractions, °
Output fractions
gwt.%
Gator. HC20-30602.6
Liquid hydrocarbon30-1501546.8
PAO-2150-2401566.9
PAO-4240-33083036.8
PAO-6330-360105846.9

When depolymerization of oligodecene with a boiling point of more than 300°s temperature Cuba 360°C, the temperature of the walls of depolymerization 350°and the residual pressure in the condenser 1 mm Hg following results were obtained (see table B):

Table B.
Nature

faction
The interval T

boiling fractions, °
Output fractions
gwt.%
Gator. HC20-3062.82.0
Liquid hydrocarbon30-150188.46.0
PAO-2150-240376.812
PAO-4240-330471.015.0
PAO-6330-3602041.065.0
∑=3148.0100.0
Note: HC - hydrocarbons; T - temperature.

To identify the optimal operating conditions of depolymerization studied the effect of temperature on the kinetics of thermal depolymerization is Yakovchenko of Oligocene with a boiling point above 330° C.

From the obtained data it should:

1. Depolymerization out at a given fixed temperature for 10-20 minutes.

2. After depolymerization the preset temperature, thermal depolymerization of high-molecular Oligocene proceeds with constant velocity.

3. The rate of depolymerization, the yield of products of the depolymerization and conversion of high-molecular Oligocene in target products with increasing temperature from 340 to 360°With monotonically increasing.

4. The observed activation energy of depolymerization is equal to 27.5 kcal/mol, lg A=9.9073.

5. With 360°an hour is more than semitestacea conversion of high-molecular Oligocene in the products of depolymerization, which are at the same temperature and at a residual pressure in the cube not more than 3 mm Hg distills from depolymerization and sent to the column for the second split.

6. The products of depolymerization differ from the products of the oligomerization of mission-1 not only because along with molecules with internal (winninowie) and vinylidene double bonds they contain a significant amount (about 30 mol.%) molecules with vinyl double bonds, but also the physico-chemical properties (Tables 9, 10).

7. Thermal depolymerization of high molecular weight oligo-olefins is sobchenko an endothermic process. To ensure the depolymerization 1000 kg of high molecular oligodecene per hour shall be provided for the heater total power 116 kW.

Heat balance of depolymerization is as follows:

The flow of heat - 116 kW/hour.

Heat consumption:

heating of high-molecular oligodecene to 360°C - 30 kW/h;

- endothermic reaction of depolymerization with 360°C - 33 kW/h;

- evaporation products formed - 28 kW/h;

- thermal reserve - 11 kW/h;

- heat loss - 14 kW/hour.

It is important to note that the process conditions (temperature, pressure) have a significant impact on the composition of the products of depolymerization and their characteristics (table 9, 10). A particularly large impact on the composition and characteristics of products of depolymerization has speed their removal from the reactor. With increasing temperature and pressure, and decreasing the time of distillation of products from depolymerization depth depolymerization of oligodecene increases.

View chromatograms of dimers and trimers, as well as the high temperatures of their solidification, suggests that during thermal depolymerization of high-molecular oligodecene under high residual pressure (>10 mm Hg) on a column with a regular nozzle and irrigation is their waxing. These conditions thermal deprimere the purpose, when the primary products of depolymerization are not removed from the reaction zone, and repeatedly return to the cube seems to favor the flow of the chain decomposition of oligodecene. This conclusion is confirmed by the example, which was carried out on a column without regular packing and without irrigation at a residual pressure of 1.0-0.6 mm Hg In this example, as the source oligomerizate used VAT residue selected from dezenove oligomerizate after water-alkaline dehydrochlorination. It contained about 30 ppm of chlorine and had the following composition (see table):

Table C.
Time hold, minComponentContent, wt.%
10.9The trimer19.93
13.8Tetramer32.91
15.9Pentamer21.75
17.7Hexamer11.48
24.2Heptamer13.93

In the cube column-depolymerization was loaded 1484.6 g described above dehydrochlorinating macromolecular Oligocene. First in Cuba under stirring of oligomerizate powerful electromagnetic stirrer was made gradual razor is in oligomerizate to 360° C. the Depolymerization of high-molecular Oligocene started at a temperature of 330°and was carried out mainly with 360°C. the Real and the virtual temperature of the cube and the top of the column was determined by the heat loss, the heat consumption for heating oligomerizate and products of depolymerization, thermal depolymerization of oligodecene and evaporation products of depolymerization. On thermogram the course of all these endothermic processes manifested in the form of several endo-effects. The rate of depolymerization (more precisely, the rate of distillation of the products of thermal depolymerization) in time was changed in complex ways. First, the process speed as the temperature rises from 330 to 360°With monotonically increased to approximately 13 ml of product per minute. However, at 170 minutes suddenly occurred abrupt increase (almost 3 times) the speed of the distillation of the products of thermal depolymerization. Since the temperature and the residual pressure will remain unchanged, we can assume that the observed acceleration of the process is determined by its virodene-chain character.

In the depolymerization of high-molecular oligodecene the above conditions in the assembled trap condensate allocated two factions products and received VAT residue. The condensate consisted mainly (98.3 wt.%) from uglev the liquids With 4-C12. The share of hydrocarbons (paraffins and olefins) in the condensate monotonically decreased from C4to C12. This condensate may reflect the correlation between different branches in molecules oligodecene. If this assumption is true, we can conclude that the molecules oligodecene most contains Budilnik branches. The first fraction of the products of thermal depolymerization allocated in the amount of 657.7 g with virtual temperatures from 209 to 575°With, has a very complex composition (see table G):

Table,
Time hold, minComponentContent, wt.%
1.09To C120.34
3.83Cl12-Cl181.09
7.33Dimer2.39
10.81The trimer3.42
13.71Tetramer3.88
15.93Pentamer21.42
17.75Hexamer46.96
25.20Heptamer20.49

The table below shows that this fraction represents the t of a mixture of 1.43 wt.% low-molecular products of thermal depolymerization, as well as the source and the resulting depolymerization di-, tri-, Tetra - or more high molecular oligodecene. The pour point of this faction = -39°C. It is reduced to -49°after separating from her low-molecular C4-Cl18of hydrocarbons.

The second fraction of the products of thermal depolymerization of high-molecular oligodecene allocated in the amount of 295.1 g with virtual temperatures 575-534°With (at a residual pressure of 0.6 mm Hg), as well as the first fraction is a complex mixture of low molecular weight products of thermal depolymerization, as well as the source and the resulting depolymerization di-, tri-, Tetra - or more high molecular oligodecene. The pour point of this faction = -33°but after separating from her low-molecular C4-Cl18hydrocarbons is reduced to -45°C. the Content of low-molecular products of depolymerization (3.0 wt.%) the second fraction is more than twice the content of low-molecular products of depolymerization (1.43 wt.%) as part of the first fraction. This indicates the increase of depth of depolymerization. The total conversion of the original oligodecene in the products of depolymerization exceed 70 wt.%. The total yield of the second and third fractions (952.8 g)=64.18 wt.%.

VAT residue (458.8 g=30.9 wt.%) consists of a mixture of source is x and depolimerizovannogo macromolecular oligodecene (see table D):

Table D.
Time hold, minComponentContent, wt.%
16.10Pentamer0.45
17.98Hexamer2.43
25.41Heptamer+97.11

He has a pour point=-30°C.

The combination of the obtained data allows to draw the following General conclusions:

- high Oligocene by the method of thermal depolymerization at temperatures 330-360°and a residual pressure of 1.0 mm Hg can be processed with high conversion in a mixture of low molecular weight products;

- from a mixture of thermal depolymerization of high molecular weight products by vacuum distillation it is possible to allocate fractions of the products on the fractional composition and viscosity properties approaching PAO-2, PAO-4, PSC-6;

- the freezing temperature of the selected fractions exceeds the freezing temperature of PAO-2, PAO-4, PSC-6, selected from the original oligomerizate, but are significantly lower than the freezing temperature appropriate for viscous properties are not compounded fractions of mineral oils.

If necessary it can be recommended after the Hydra is the formation for use in a mixture with the corresponding main products as the basis of synthetic and semi-synthetic oils. The presence of phase depolymerization enables processing of all limited consumption of high-molecular oligodecene with a kinematic viscosity at 100°S, which varies from 10 to 20 cSt at widely consumed polyolefins with a kinematic viscosity at 100°S, which varies from 2 to 8 Centistokes (i.e. in PAO-2, PAO-4, PC-6 and PC-8, respectively).

Division of oligomerizate on a narrow faction in patent method, as already mentioned, is made the same as in other known methods, except that a deep vacuum in the columns of the separation provided the original vacuum steam ejector system.

Allocated to phase separation oligomerizate fraction of the products in all cases a mixture of unsaturated and chlorine-containing molecules oligodecene. The residual chlorine content in the released fractions does not exceed 10 ppm (10 ppm). To improve oxidative stability of the products obtained in all known ways hydronaut.

Hydrogenation selected from oligomerizate narrow fractions of oligoelement in accordance with the present invention is performed under the action of palladium deposited on alumina catalyst (mainly Pd (0.2 wt%)/Al2O3), modified anhydrous KOH, which take the number 30 is about 100 wt.% in the calculation of the hydrogenation catalyst, at temperatures varying in the temperature range from 150 to 250°when the hydrogen pressure of 20 at. The temperature and pressure at the stage of hydrogenation on the patented method is significantly lower than in the case of other known methods. Hydrogenation of narrow fractions of oligodecene the above conditions allows gidrirovanii not only the C=C and C-Cl bonds of oligodecene. The implementation of the hydrogenation oligolectic fractions in the presence of anhydrous KOH provides increased activity and performance of catalytic hydrogenation in the neutralization of the hydrogen chloride formed during the hydrogenation of the C-Cl ties remaining in hydronamic fractions of chlorine oligodecene. This solution also eliminates corrosion of hydrogenation reactors and auxiliary equipment and prevents accelerated decontamination hydrogen chloride palladium hydrogenation catalyst.

When developing a method of producing polyolefin bases of synthetic oils you used the following reagents: the mission-1, isolated from the products of the oligomerization of ethylene under the action of triethylaluminum at OJSC "Nizhnekamskneftekhim" (TU 2411-057-05766801-96), as well as the mission-1, isolated from the products of the oligomerization of ethylene under the action of triethylaluminum in Neratovice (Czech Republic) "Solana". Used mission-1 produced by OJSC "is CNH" group had the following composition: SN 2-=CH - 83.4 mol.%; TRANS-CH=CH - 5.44 mol.%; CH2=≪11.2 mol.%. Before the use of the mission-1 were dried over calcined at 600°molecular sieve NaX; n-heptane, mark "reference", used as a solvent to prepare solutions of the components of the catalysts were dried by distillation over sodium wire; AOC General formula RnAlCl3-n, (R-C2H5; n=1.5, 3.0) was purified by distillation under reduced pressure. Prepared olefins, solvents and AOC kept in an inert atmosphere in a sealed vessel. AOS used as diluted with n-heptane solutions.

Oligomerization of mission-1 was carried out under the action of the systems Al (0)-HCl-(CH3)3CCl (TBH) and Al(0)-(C2H5)1.5AlCl1.5(EACH)-(CH3)3CCl, in which HCl and EACH acted as activators of aluminum marks ASD-4, SDA-40, PA-1 and PA-4. When developing a patentable method is mainly used aluminum brand PA-4. The rate of oligomerization of mission-1 under the action mentioned catalytic systems is limited by the rate of dissolution of aluminum tertbutylamine. This process is preceded by the formation of active centres oligomerization of mission-1. The inclusion in the above-mentioned catalytic system activators of aluminum reduces or eliminates the induction period.

As socializaton in both mentioned with the systems used tert-butyl chloride - (CH3)3CCl, which was obtained by the reaction of isobutylene with dry HCl. TBH contained 0.5 wt.% HCl (TU 6-09-07-1338-83).

In preliminary studies it was found that under the totality of characteristics best activator aluminum is HCl, and the best socialization in the oligomerization of mission-1 is TBH. Therefore, basic research is performed with the use of a catalytic system Al(0) mark PA-4-HCl-TBH.

Oligomerization of mission-1 was performed in a thermostated dried glass or metal reactors mixing in the atmosphere of dry argon with continuous vigorous stirring of the reaction mass by means of a magnetic stirrer. Testing of catalytic systems in the process of cationic oligomerization of mission-1 and other olefins produced in the following way: in temperature-controlled to a predetermined temperature, the reactor was sequentially loaded aluminum, mission-1 or other olefin, and then a solution of HCl in TBH. Al was loaded into the reactor in the form of previously prepared in an inert atmosphere sample stored in sealed glass ampoule. After loading into the reactor all of the above reagents (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 for planned lie is neither, 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 was removed by the method of caustic and water washing.

The content of the mission-1 (or other source of olefin in the reaction mass oligomerizate) during and after oligomerization (i.e. the current and the total conversion) was determined by gas chromatography on devices LHM-8-MD, LHM-2000 and Hewlett-Packard A" (internal standard - pentadecane) and by the method of IR-spectroscopy on the device "Specord M-80". For this purpose at a given point in time from the reactor under argon was selected portion of the reaction mass, which was immediately mixed with ethanol or 5%aqueous NaOH solution under intensive stirring. The reaction mixture after termination of oligomerization was repeatedly washed with distilled water in a closed funnel.

Unreacted mission-1, and di-, tri - and tetradecene from oligomerizate allocated for the vacuum column with electrically heated to 360°cube at a residual pressure of from 1 to 10 mm Hg

Fractional composition of oligomerizate was determined on the chromatographs LHM-8-MD, LHM-2000 and Hewlett-Packard 5880A" with flame ionization detectors in programming mode temperature from 20 to 350°With the speed of the rise in temperature 8-10 deg/min When chromatographicaliy of oligodecene used column stainless steel (0.4×70-0 .4×200 cm), filled with chromatone NAWDMCS with 3.0% silicone OV-17, chromo-sorbitol W-AW with 3% Dexil - 300 or Propcom-Q. Srednetsepochechnye particle diameter mentioned media 0.200-0.250 mm feed Speed pre-purified carrier gas (helium, nitrogen) was ˜40, hydrogen ˜30, air ˜300 ml/min Sample into the chromatograph evaporator was introduced using microspace (0.2-1.0 ml) after the evaporator temperature reached 350°C. Duration analysis, 50 minutes Identification of chromatographic peaks was performed by the method of the additive reference hydrocarbons (pentadecane) and by comparison with the chromatograms of hydrocarbon mixtures of known composition. Quantitative processing of chromatograms was carried out under the integrated peak areas, which were determined using computer integrator or by the method of triangulation. Fractional composition of oligomerizate was determined by the method of fractionating it to a vacuum distillation column. The results of these quantitative analyses coincided with precision ±3 wt.%.

Unsaturated oligomers (i.e. the content in the molecules, oligomers of double bonds) was determined by the method of ozonolysis on the analyzer double bonds in the BPA-4M.

The structure is not transformed datenow products and oligo is erinacei quantitatively determined by the method of IR-spektroskopie on device "Specord M-80", and spectroscopy of the PMR and NMR13C. PMR Spectra and NMR13C was recorded at room temperature on pulsed NMR spectrometer AC-200R (200 MHz) ("Bruker". To remove the PMR spectra and NMR13With cooked 10-20%solutions products in deuterium chloroform. As standard tetramethylsilane was used.

An impurity ion of chlorine in the oligomers was determined by argentometric method Folgard by titration of an aqueous extract. Covalently-linked molecules, oligomers chlorine initially translated into ionic form by wet combustion of the sample in a quartz reactor, or by using the biphenyl sodium according to method UOP 395-66 followed by argentometric titration his Foolhardy. In some cases, the content of covalently bonded to molecules of oligomers of chlorine was determined by x-ray fluorescence method spectrometer SPECTRO XEPOS" on the calibration curve.

For a better understanding of the present invention as illustrated in tables 1-10 examples of implementing the designed according to the invention, a method of obtaining a polyolefin bases of synthetic oils. These examples illustrate but do not exhaust the possibilities of the invention.

A set of decisions on various aspects of patenting inventions allows to conclude that the new method of obtaining polyolef the new bases of synthetic oils. A method includes preparation of olefinic raw materials, preparation and dispensing into the reactor solutions and suspensions components of the catalytic system Al(0)-HCl-TBH, isomerization of alpha-olefins and higher oligomerization of olefins and mixtures thereof under the action of the catalytic system Al(0)-HCl-TBH, separation of spent catalyst, separation oligomerizate into fractions and hydrogenation of selected fractions under the action of the Pd catalyst (0.2 wt%)/Al2O3+NaOH. The invention provides the improvement of all phases of the developed method.

To eliminate corrosion product activity method additionally includes the stage of dechlorination present in oligomerizate chlorine containing oligoelement metallic aluminum, triethylaluminum, alcohol solutions of KOH or thermal dehydrochlorination chlorine-containing polyolefin in the absence or in the presence of KOH. To improve technical and economic performance of the method by increasing the yield of the target fraction of polyolefins with a kinematic viscosity of 2 to 8 cSt at 100°the method additionally includes the stage of thermal depolymerization limited consumption of high molecular weight polyolefin with a kinematic viscosity of 10-20 cSt at 100°With the target polyolefin with a kinematic viscosity of 2 to 8 cSt at 100°C.

All R the solutions of the present invention confirmed not only in the laboratory, but in pilot plants and industrial installations in the shops Nizhnekamsk plant of synthetic oils.

15.7 0.1995
Table 1.
The influence of various factors on the composition and structure of the products of the oligomerization of mission-1 under the action of the system Al(0) mark PA-4-HCl-(CH3)3CCl (TBH). The mission-1=20 ml.
No.aluminumHClTBHT °τ, minS, wt.%R/1000 CH2Chlorine inDimer,The trimer,TetramerPenta measures+,
examplegmolmol/lwt.% from TBHmolmol/lCH3Tr-CH=CHppmwt.%wt.%, wt.%wt.%
10.0360.001330.06650.50.006650.3325510060100338.9761838.4422.411.92.63
20.0360.001330.06650.50.006650.3325511012098.9451.212.137.732.1511.11.9
30.0360.001330.06650.50.006650.3325511060100451.315.238.5730.910.01.9
120100461.912.67214
40.0360.001330.06650.50.006650.332551206098.5438.618.3849641.424.76.3 1.26
50.01440.00050,0260.50.002660.13351106093.9382.828.834.1322.978.82.6
12096.3383.527.04303
60.02160.00080.040.50.0040.2511060100416.521.739.4727.998.81.98
120100419.219.76343
70.02880.00100.05330.50.00530.26551106010065415547840.628.078.321.61
80.0360.001330.06650.50.006650.3325511012098.9451.212.137.732.1511.11.9
90.0360.001330.06650.50.0039931106010053019.835.5032.5812.353.7
120100521.515.536.82At 25.3711.013.05
100.0360.001330.06650.50.005320.26641106097.8342.515.1565344.724.910.11.65
110.0360.001330.06650.50.006650.3325511012098.9451.212.137.732.1511.11.9
120.0360.001330.06650.50.006650.3325511012098.9451.212.137.732.1511.11.9
130.0360.001330.06650.170.006650.3325513060100452.613.3741134.6629.3310.52.7
140.0360.001330.06650.0150.006650.3325515060100445.720.4997037.6528.728.661.77

Table 2.
The influence of the number of carbon atoms in the molecule of the olefin on the structure and characteristics of mixtures fractionated and not of hydrogenated oligoelement with those is the temperature of boiling above 170° With R≅2 mm Hg
ExamplesOlefinsC=C, mmol/g, g/mold420, g/cm3Kinematic viscosity, cSt,The viscosity indexPour point,Flashpoint
at 40°at 100°°°
1Propylene25171.934360.83535.95.689-47130
226731.326650.853142.915.774-30160
329702.834480.83336.75.177-56120
4*-0.0454300.84226.6 4.688-53-
5Butene-111592.104570.840179.314.573-32-
612301.397110.856311 240.169-24216
715401.765920.849122.111.373-41-
8Butenova14682.73380-11.02.7587-68-
9faction10451.68610-340.923.789-26-
10-2.005000.842187.417.298-45120
11*12500.046500-204.417.491 -43124
12-2.893640.85892.59.881-40120
13**-0.02450-78.810.048-25198
1412930.8011300.857167.419.67122-33.5248
15HEXEN-1710---29011107-50180
16----29624114-36228
17Octene-14701.656000.83535.46.4130-50192
18The mission-13271.277900.84158.09.5147-50
19The mission 5 trimer3652.304350.83618.763.99113-76207
20LAO12-C142150.7211800.849120.017.0132-38.5253
21LAO Cl2-Cl42120.7311700.85095.614.8136-38.0252
* Oligomers 4 and 11, respectively, after hydrogenation; ** Oligomer 13 obtained in the environment of toluene

td align="center"> 6.5 1.8
Table 3.
The influence of various factors on the composition and structure of dechlorination products 1-Cl-dodecane and oligomers of mission-1 aluminum
# exampleThe mission-1,

mol
1-chloro-

dodecan, mol
AluminumT °τminThe chromatography. mA is.% X, R/1000 CH2
markmolthe mission-1dimerthe trimertetramerpentamerhexamer1-chloro-dodec.CH3-Tr-CH=CHCH2=CH
10.0890.0127PA-40.02550.52.0206071.54.593.400020.11221.26.976.8
756070.91.771.0800020.84240.54.936.3
956071.352.342.6600020.90229.370.3
120601.8932.47At 34.0217.65000511.54.51.4
20.0890.0127PA-10.008471.50,66956072.170.3900000243.56.374.6
120602.3940.4831.299.61000569.94.92.1
30.0890.0127PA-40.0170.751.339560At 77.070.860.4300021.44229.65.673.9
 /td> 1206076.20000019.95239.26.973.1
40.0890.0127PA-40.0170.751.33956079.860.370.360.060019.09221.76.173.3
120600.8825.3552.118.6002.27480.511.20
50.0890.0127PA-40.0170.751.33956084.990.190.160.050014.4202.07.0829.0
115602.7933.4332.3312.872.9500599.97.23.1
130602.0134.2331.8113.223.2500572.85.20
6PSC-NC0PA-40.013300956044.2811.118.412.726.631.070356.67.241.6
20 ml1306042.511.0818.7812.976.631.050376.26.537.8
Ȋ 13012043.9911.1819.1712.866.611.10361.66.539.5
7PSC-NC0PA-40.013300956044.710.5217.512.246.3900362.77.443.0
20 ml1306044.710.2116.911.755.921.080391.87.942.7
13012046.3810.7819.5613.476.8511.160363.66.937.2
80.10550.0127PA-40.02540.54956023.2520.3328.0718.559.461.800376.110.70
956120.1811.8918.0812.916.530At 16.65318.99.21.1
95603.0620.7419.1512.9812.7702.38456.82.00
130601.2820.3617.8212.2711.1500.21455.61.80
90.10550.0127PA-40.01271195 608.316.0456.9422.2913.5000283.68.00
95617.6811.6718.1713.377.282.228.2241.36.30
95606.3010.7717.9914.358.272.928.5232.95.60
1306009.6615.5010.007.4000356.712.40
In experiments 8 and 9 previously held oligomerization 20 ml of mission-1 under the action of the system EACH (00008 mol) - TBH (0.0012 mol) in 95°

Table 4.
The influence of various factors on the composition and structure of dechlorination products 1-Cl-dodecane and oligomers of mission-1 triethylaluminium (tea)
If actionThe mission-1.1-chloroAOCT °τ. minutesChromatography, wt.%X, R/1000 CH2
mol-dodecan, molnaturemolthe mission-1dimerthe trimertetramerpentamerhexamer1-chloro-dodec.CH3-TRANS-CH=CHCH2=CH
1PSC-0.0127AlEt30.02540.52.0206046.025.678.45.792.761.1818.8305.74.1 38.8
NK 20756045.836.179.66.93.520.9919.6285.43.330.5
ml956047.25.819.546.53.351.1518.3279.14.039.2
1306041.77.0711.47.894.021.170.3288.74.731.5
20.1055TBH* 0.0012each0.00081.50.67956017.011.1921.4316.1911.563.80.15333.66.26.4
0.0127AlEt30.02540.52.095603.718.8322.1015.7911.400381.44.30
30.1055TBH* 0.0012each0.00081.50.67956013.0115.9524.6720.811.6300369.58.80
0.0127AlEt30.02540.52.095602.8429.3921.2712.746.330-426.72.94.8
1301202.0830.59At 23.3613.885.90-421.31.91.9
4 0.1055TBH* 0.0012EACH0.00081.50.67956014.715.41At 24.5716.510.173.350355.98.10
0.0127AlEt30.02540.52.095617.788.9317.512.17.151.7832.5287.35.80
130602.9122.7119.3812.5510.4400.65443.80.670
50.1055TBH* 0.0012EACH0.00081.50.67956012.2622.520.7316.311.452.850339.66.12.9
0.0127AlEt30.01251.01.0956110.268.317.7714.069.912.0129.06282.04.41.7
130602.4519.9119.1912.7407.4721.41414.91.90
6PSC-0.064AlEt31.01.020146.4811.8913.529.6904.5712.0292.96.228.5
NICHOLAS 85 ml16460039.327.2614.265.5900379.31.50
70.4460.064 AlEt30.0641.01.0150180.01.080.8700015.1250.271.078.6
15060025.414.386.928.900326.600
Notes: PJSC NICHOLAS is a mixture of oligomerizate from Nizhnekamsk plant of synthetic oils with mission-1; EACH - ethylaluminum; * in these experiments initially conducted oligomerization of mission-1 under the action of the system EACH-TBH, and then was added 1-chloro-dodecane and triethylaluminium; AOC - aluminum organic compound; RCl - chloroalkane - TBH and 1-chloro-dodecane.

0.0802
Table 5.
The influence of various factors on the composition and structure of dechlorination products l-Cl-dodecane and oligomers of mission-1 solutions of KOH or NaOH in n-butyl, hexyl, and other alcohols
If actionThe mission-1, mol 1-chloro-

dodecan, mol
ROHKOH, molKOH/ RClT °τ, min

Chromatography
X, R/1000 CH2
natureMolthe mission-1dimerthe trimertetramerpentamerhexamer1-chloro-dodec.CH3-Tr-CH=CHCH2=SN
10.05270.0127n-C4H9OH0.10920.0584.51206065.1215.310.160about016.8284.9075.5
12024 hours59.011.120.0200011.8360.314.631.8
20.0527/td> 0.0127n-C4H9OH0.10920.0584.51205 m54.121.99000014.0452.616.256.0
1202 hours70.518.70.270007.9181.71.934.8
1204 h69.621.80.330004.3270.66.8107.2
1207 h67.326.70.680004.2214.35.633.7
12027 h63.728.61.600004.8253.80121.5
30.05270.0127C6H13OH0.08020.0584.52010 m79.642.39000011.91351.57.480.6
1302 hours46.820.60.360000.986293.0069.3
1304 h46.1119.6300000
40.05270.0127C6H13OHNaOH201045.688.450.3000012.0202.54.341.9
0.086.313012064.4114.421.2600011.9179.60.8439.99
13012066.2617.61.1600010.92250.66.355.2
AFTER 24 HOURS13018032.228.571.590002.52306.77.9956.8
50.5270.127n-C4H9OH0.8020.5774.520 6062.591.370.5500019.94348.412.935.9
1506052.7628.370.710000.47398.218.442.3

255
Table 6.
The results of thermal dehydrochlorination dezenove oligomerizate containing 735 ppm monochloroacetic compounds (0.0735 wt.% chlorine).
Download oligomer, gThe original content of Cl, gReaction time, hoursThe residue in the flask, gThe chlorine content in the residueBlow-off, gThe chlorine content in the StrippingFound chlorine,

wt.%
T sastojati

that °
# exampleppmgppmg
10.18742189230.004366<-60
22550.18743192200.00386313330.084096.10<-60
32760.20328211240.005165<-60
42940.21617222420.00937213030.093894.70<-60
52760.20291204110.0022720.0621-64
63090.2271221740.00099216250.149590.12-54
72760.202922020074 14800.109592.13-
82470.1815118730.00066015990.095997.94-60
Notes: thermal dehydrochlorination of chlorinated oligodecene in examples 3 and 4 was carried out at 300°in example 2 330°With that in example 1 at 340°in static conditions without Stripping HCl nitrogen; thermal dehydrochlorination of chlorinated oligodecene in examples 5-8 was performed at 330°in terms of Stripping HCl and other chlorinated components nitrogen (nitrogen flow of 3 liters per hour).

Table 7.
Thermal dehydrochlorination of chlorinated oligodecene in the presence of alkali (MES). The chlorine content in the source oligomerizate - 180 ppm (ppm). The duration of the reaction (60 min
WeightMonDispersant monT °The chlorine content in the product, ppm
oligomer, gnaturemass, gnatureweightȊ in the original oligomerin washed oligom.in the wash H2Oin the solid precipitatein distilled H2O
250KOH5H2O20300180145033720
250KOH5H2About20310180791135490
250KOH5H2O20320180351739050
250KOH5H2O2033018081446850
250KOH5H2O20330430535552.12%0
250NaOH5H2O2033018079751990
250KH 5With2H5HE203301806274188-
125KOH5n-C4H9OH12520018011032--

Table 8.
The dehydrochlorination of chlorinated paraffin wax (CP)containing 43 wt.% chlorine solutions of KOH in n-butanol under conditions of azeotropic distillation of water during the reaction. The initial molar ratio With4H9HE/Cl=2.7.
KOH/WITH-Cl,

mol/mol
T

reaction °C
Time

reaction watch
OutputOutputCharacteristics of dehydrochlorination (DGHP)
H2Oh, mol/mo eh CClDGHP, wt.%The Cl contentMM, g/molBr number, gC=C in the moleculeWith4H9About in the molecule
wt.%mol/molBr2/100 gwt.%mol/mol
1.251203-72.28.531.45600115.04.310.80.89
1.251073-76.013.51.952093.13.08.90.64
1.2512131.3474.912.91.8490109.03.49.80.66
1.251086-74.511.41.7533108,03.610.60.65
1.2512261.5673.36.30.9508128.64.19.30.77
1.2514071.6169.03.740.6533144.04.811.70.81
1.10 14071.4769.03.830.5505135.54.3--
1.0014071.5068.24.080.6513135.04.313.30.93
0.9814071.5070.06.250.9535125.04.212.50.92

IV 462
Table 9.
The results of the separation dezenove oligomerizate into fractions in partial depolymerization of high-molecular oligodecene and characteristics of the fractions
No.WeightThe composition of oligomerizateCharacteristics of the fractions
exampleoligomerizate in Cuba, gdeceny, gdimers (D) (PSC-2)trimers (T) (PAO-4)VAT residue (K) (PJSC-10+)C=C, mmol/gMn, g/molcinematic. viscosity, cSt
gwt.%gwt.%gwt.%
171001304155.8276538.9355050.0D: 3.792642.08-
T: 2.324304.09133
To: 1.2580012.93130
288002153804.3475554.0261029.7T: 2.414153.96129
385651705856.8432050.4335039.1T: 2.164.21136
48565120157518.4428550.0243028.4----
5860016016016.9--697081.0To: 1.506609.82124
68635908018.2--690079.9To: 1.3971610.54127
Notes: the Dimers were selected during the heating of the cube up to 300°and the top of the column up to 180°; Trimers selected when heated cube to 350°and the top of the column up to 230°at a residual pressure of 1 mm Hg

6.98
Table 10.
The yield, composition, structure and properties of the products obtained by targeted thermal depolymerization of Oligocene (with a kinematic viscosity at 100°C=10 cSt) at 360°
ΔT, °Output fractions Cube, wt.%X, R/1000 CH2Product properties
gwt.%Dimers, wt.%Trimers, wt.%Tetramera, wt.%CH3CH2=CH-Tr-CH=CH-CH2- ≪Tthe urban.that °TVSP.that °η40, FTAη100, FTAIV
20-150238.0-----53.6%18.1%28.3%-----
150-2403412.099.0----171484.831.74-
240-3004215.03.096.01.0-Before hydrogenation-3820614.543.53130
240-300 4215.03.096.01.0-After hydrogenation-3710616.393.83135
300-310761.850.789.010.3-350.4-7.92.2-7215.673.69129
310-320922.240.658.840.8-352.3-7.82.5-22016.403.84135
320-3301824.440.539.160.4-315.6-6.32.9-5218020.204.46141
330 to 340902.200.56.593.0-344.54.26.65.1-5018.104.19147
340-350286----Has 317.6-4.02.7-----
>36028632.0---32.0Before hydrogenation-62256At 44.857.72131
>36028632.0---32.0After hydrogenation-6024862.539.70127
Note: ΔT - the temperature range in which the selected corresponding fraction of the products of depolymerization

1. A method of obtaining a polyolefin bases of synthetic oils with higher oligomerization of olefins containing preparation of olefinic materials and solutions of the cationic components of the catalytic system, isomerization of higher linear alpha-olefins, oligomerization of olefinic raw materials under the action of cationic aluminum-containing catalytic systems, discharges from oligomerizate spent catalyst, separation oligomerizate into fractions and guide the financing of selected fractions, characterized in that after the stage of oligomerization and/or after the stage of allocation spent catalyst from oligomerizate conduct phase dechlorination present in oligomerizate monochloracetic oligomers, and after phase separation oligomerizate into fractions conduct phase depolymerization of high molecular weight products allocated in the form of VAT residue at the stage of separation oligomerizate into fractions.

2. The method according to claim 1, characterized in that the oligomerization of higher olefins is carried out in mixtures oligomerized higher olefin products of oligomerization or in mixtures oligomerized higher olefin products of oligomerization and aromatic hydrocarbons under the action of the catalytic system Al(0)-HCl-(CH3)3CCl at temperatures from 110 to 180°C, the concentration of Al(0) from 0.02 to 0.08 g-atom/l, a molar ratio of HCl/Al(0), which varies from 0.002 to 0.06 molar ratios RCl/Al(0), which varies from 1.0 to 5.0, where Al(0) - fine powdered aluminum with particle sizes varying from 1 to 100 μm, for example, Al(0) mark PA-1, PA-4, ASD-4, SDA-40, ASD,

3. The method according to claims 1 and 2, characterized in that the quality of higher olefins take a mixture of linear or branched alpha-olefins to ISO-olefins and olefins with intramolecular location double the communication (internal olefins), containing from 4 to 14 (mostly 10) carbon atoms, in the following ratio of ingredients, wt.%: alpha-olefins of 0.5-99,0; ISO-olefins 0,5-5,0; "internal olefins - the rest up to 100 wt.%.

4. The method according to claim 1, characterized in that the dechlorination present in oligomerizate monochloracetic oligomers (RCl) is carried out after the stage of oligomerization superfine powder metal aluminum - Al(0) with particle sizes varying from 1 to 100 μm (for example, marks PA-1, PA-4, ASD-4, SDA-40, DCA-T) at a molar ratio of Al(0)/RCl varies from 0.5 to 2.0 in the temperature range from 110 to 180°C for from 30 to 180 minutes

5. The method according to claims 1,4, characterized in that the dechlorination present in oligomerizate monochloracetic oligomers (RCl) is carried out after the stage of oligomerization by triethylaluminium (tea) at a molar ratio of tea/RCl, which varies from 0.5 to 2.0, in the temperature range from 95 to 150°C for from 30 to 180 minutes

6. The method according to claim 1, characterized in that the dechlorination present in oligomerizate monochloracetic oligomers (RCl), carried out after the stage of allocation spent catalyst alcoholic solution of potassium hydroxide or sodium (MY) at a molar ratio of MOH/RCl, changing in the range from 4.5 to 6.3, in the temperature range from 120 to 160&#HWS in the period from 30 to 240 minutes

7. The method according to claim 1, characterized in that the dechlorination present in oligomerizate monochloracetic oligomers (RCl), carried out after the stage of allocation spent catalyst by thermal dehydrochlorination them in the temperature range from 280 to 350°and pressure 1-2 bar for from 30 to 180 minutes at a Stripping evolved hydrogen chloride nitrogen, carbon dioxide, methane or superheated steam.

8. The method according to claim 1, characterized in that the dechlorination present in oligomerizate monochloracetic oligomers (RCl), is carried out in the presence of dry hydroxides of alkali metals (mon) at a molar ratio of MOH/RCl changing in the range from 4.5 to 6.3.

9. The method according to claim 8, characterized in that the dry hydroxides of alkali metals is obtained directly in oligomerizate distillation of the water by heating the mixture released from the spent catalyst oligomerizate and 5-40%aqueous solution of alkali metal hydroxide at temperatures varying in the temperature range from 100 to 200°C.

10. The method according to claim 1, characterized in that the dechlorination subjected to mono-, di-, and polychlorobenzene aliphatic and aromatic hydrocarbons, oligomers.

11. The method according to claim 1, characterized in that the depolymerization of high molecular weight products, identified as CC mod is and at the stage of separation oligomerizate into fractions produced by heating them at temperatures varying in the temperature range from 330 to 360°and pressures from 1.0 to 10.0 mm Hg for 30 to 120 min with continuous removal of the products of the depolymerization reactor.

12. The method according to claim 1, characterized in that the hydrogenation selected from oligomerizate narrow fractions of oligoelement carried out under the action of palladium deposited on alumina catalyst (mainly Pd (0.2 wt.%)/Al2O3), modified anhydrous potassium hydroxide, which are taken in an amount of from 30 to 100 wt.% in the calculation of the hydrogenation catalyst, at temperatures varying in the temperature range from 150 to 200°and a hydrogen pressure of 20 at.



 

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FIELD: petrochemical processes.

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FIELD: machine-building, automotive, and oil refining industries, rail transport, and agricultural sector.

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