Catalyst and method for oligomerisation of alpha-olefins

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for oligomerisation of alpha-olefins and a method for oligomerisation of alpha-olefins. The catalyst for oligomerisation of alpha-olefins is a two-component system containing aluminium-containing compounds and a chlorine-containing co-catalyst. The aluminium -containing compounds are selected from a group comprising triisobutylaluminium, diisobutylaluminium hydride or products of transalkylation thereof with decene-1 tridecylaluminium or decyldiisobutylaluminium, and are used in amount of 0.62-4.08 mmol per mole of alpha-olefin. The co-catalyst is selected from a group comprising hydrogen chloride or an organic monochloride, e.g., tributyl chloride. The ratio Cl:Al is equal to 2.5:16.2 mol/mol respectively. The method for oligomerisation of alpha-olefins involves preparation of olefin material, a step for oligomerisation, washing and extraction of spent catalyst from the oligomerisation product, followed by separation of the oligomerisation product into fractions and hydrogenation thereof.

EFFECT: controllability of the oligomerisation process by regulating its rate and increase in output of the desirable low-molecular weight fractions of oligomers, avoiding the step for dechlorination and depolymerisation of high-molecular weight products extracted from the oligomerisation product in form of still residues.

3 cl, 4 tbl

 

The invention relates to a method for producing polyolefins (PJSC), used as bases of synthetic oils for various purposes (motor, aircraft, gear, transformer and so on), by catalytic oligomerization of alpha-olefin feedstock and can be used in the petrochemical industry.

Known methods for producing polyolefin bases of synthetic oils differ in the compositions used in these cationic catalysts, such as proton acids (acids Branstad); aprotic acids (Lewis acids); alkylamine (or boron halides; salts of stable carbocations R+A-; 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 (J.kennedy. Cationic polymerization of olefins. Critical review. Ed. Corr. Corr. USSR Nauta. M.: Mir, 1978. 430 C.).

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 (C1-C10-, aryl-, alkene who and other groups; M is Al or B; X Is Cl, Br, I), typically use a catalytic system comprising a Lewis acid or alkylhalogenide (J.P.Kennedy, E.Marechal. Carbocationic Polymerization. N.-Y., 1982. 510 p.)

Cationic active centers ([H+(MXn+1)-] and H+in catalytic systems MXn- HX formed in accordance with the following simplified scheme:

The efficiency of complex catalysts of the type HX-MeXnin electrophilic processes is determined by the stability of the counterion to the elimination of ligands for interaction with ions Carbonia. For acid type HBF4or HAlCl4reaction constraints polymer chain on a fragment of a counterion (anion F-and Cl-) are not typical, however it is possible for (CH3)2AlCl, during cationic polymerization of olefins assumes the formation of chlorinated by-products.

Major General lack of methods with the use of catalysts of this type is that their use results in mainly high molecular weight and high viscosity, containing up to 1 wt.% chlorine products.

There are also known ways of carrying out cationic polymerization, oligomerization and alkylation using two-soluble monofunctional catalytic systems, including the actual operation of alkylaminocarbonyl R nAlX3-nand kaleidoscopically connection R X when the molar ratio R X/RnAlX3-n=1.0-5.0 (where R is CH3With2H5With3H7or ISO-C4H9; X is chlorine, bromine or iodine; n=1.0; 1.5 or 2.0; R'-N (US 4952739, CL SS 2/18, 28.08.1990), primary, secondary or tertiary alkyl, allyl or benzyl (US 4041098, CL SS 3/10, 09.08.1977); (GB 1535324, 1535325 class. SS 3/21, 1978); (DE. Application 2526615, CL SS 3/21, 13.06.1975) (DE 2304314, CL C08F 110/20, 1980); (avts USSR 1723101, CL SM 107/10, 20.04.1989). In the catalytic systems of this type, RnAlX3-nis the basis of the catalyst, a R X acetalization.

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% conversion of the initial olefin in oligomeric products at temperatures of 20-200°C is achieved within six to one minute, respectively.

The main drawback of the methods of obtaining oligoolefinic bases of synthetic oils by oligomerization of olefins under the action of catalytic systems RnAlX3-n- R X oligomerization of alpha-olefins (in particular - mission-1)is the formation predominantly of 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), and the formation of products containing up to 1.0 wt.% chlorine in the form of monochlorophenol.

Closest to the present invention are catalyst system for the oligomerization of olefins, the method of its preparation and method of oligomerization (EN 2212936, CL B01J 27/06, publ. 27.09.2003) and method for producing polyolefin bases of synthetic oils (EN 2287552, CL C10G 50/00, publ. 20.11.2006), which protects the catalytic system Al(0)-HCl-(CH3)3CCl (TBH) and the way the cationic oligomerization of olefinic materials, including preparation of olefinic raw materials, preparation and dispensing into the reactor solutions and suspensions components of the catalytic system, the 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 guide the investments selected fractions under the action of the Pd catalyst (0.2 wt.%)/Al 2O3+NaOH, and the additional step of dechlorination present in oligomerizate chlorinated oligoelement metallic aluminum, triethylaluminum, alcohol solutions of KOH or thermal dehydrochlorination of chlorinated polyolefins in the absence or in the presence of KOH.

The reaction of Al(0) HCl and (CH3)3CCl starts only at temperatures higher than 110°C.

Reaction of aluminum with tertbutylamine proceeds according to the following simplified scheme:

The primary cationic active centers in this catalytic system formed according to the scheme:

The disadvantages of oligomerization of olefins under the action of the system Al(0)-HCl-(CH3)3CCl are almost uncontrollable high speed and the conversion of olefins in oligomeric products (degree of conversion above 95 mol.%) and the need of the reaction at temperatures from 110 to 180°C. during the process of oligomerization is a partial isomerization of alpha-olefins in a mixture of positional and geometric isomers of olefins with internal double bonds, which cooligomerization with the original alpha-olefin, which leads to increased branching of the molecules of the products and to decrease the viscosity index of the final commodity is about the product.

In the case of oligomerization of mission-1 using system Al(0)-HCl-(CH3)3CCl is really happening reducing the proportion of high-molecular oligodecene60+from 50 to 8 wt.%, however, this leads to deterioration of the physico-chemical properties of the final product produced by the action of this system Oligocene contain from 4300 to 9970 ppm chlorine, which in turn requires the inclusion in the technological scheme of the process stage dechlorination.

An important disadvantage of the prototype is the complexity of the catalytic system and the associated high complexity of the preparation and its use in the synthesis as well as the multistage process of obtaining polyolefin oils (POM).

It can reasonably be argued that due to the presence of HCl, and subsequently [(CH3)3C]1.5AlCl1.5in kataliticheskih systems prototypes in the process of oligomerization takes place the reactions (1) and (2) with all the disadvantages inherent in these catalytic systems, which ultimately can't manage the process both in terms of the formation of the catalytic complex, and during the process of oligomerization of alpha-olefins.

The technical result of the present invention consists of:

- in improving the yield of the desired low molecular weight FR the capabilities of oligomers (for example, dimers and trimers of mission-1);

- providing process control by speed regulation of oligomerization;

- elimination of by-products formation or flow isomerization processes;

- in providing the required physical and mechanical properties and viscosity index of the resulting polyolefins;

- exclusion stage dechlorination and depolymerization inherent prototypes.

To achieve the claimed technical result of the proposed catalyst-oligomeric alpha-olefins, which represents a two-component system containing alyuminiiorganicheskikh compounds and chlorinated socialization in which alyuminiiorganicheskikh compounds selected from the group comprising triisobutylaluminum, diisobutylaluminum or products of their parallelomania a mission-1 tridecylamine or dellverticalline used in the amount of 0.62-4,08 mmol per mole of alpha-olefin, and socialization selected from the group consisting of hydrogen chloride, or organic monochloride, such as tribouillard ratio Cl:Al is 2.5:16.2 mol/mol, respectively.

From literature data it is known that the catalytic activity of the systems when used as coinitiator TBH decreases in the series: AlEt2Cl/TBH>AlMe3/TBH>AlEt3/TBH>AliBu3/TBH (Kenna and j. Cationic polymerization of olefins. Critical review. Ed. Corr. Corr. USSR Nauta. M: Peace. 1978. P.137). Therefore as the basis of the proposed two-component catalytic system was selected triisobutylaluminum (CHIBA) TU 38.103154-79 amended. 8. Triisobutylaluminum technical (solution in toluene).

As alyuminiiorganicheskikh compounds, two-component catalytic system was used:

- triisobutylaluminum technical (solution in toluene with a concentration of 42 wt. -%), dilute 1-mission in the ratio 1:2;

- diisobutylaluminium (DIBAH) in mission-1, which was obtained from a toluene solution triisobutylaluminum with a concentration of 42 wt%. by downloading it into a container, followed by distillation of toluene and parts of isobutylene at atmospheric pressure and a temperature of 110-120°C. then, the thus obtained catalyst was cooled to room temperature and was diluted with mission-1 in a ratio of 1:20. Getting DEBUG can be represented by the following reaction scheme:

- tridecylamine 1-mission, which was obtained from a toluene solution triisobutylaluminum with a concentration of 42 wt%. by downloading it into the vessel and subsequent dilution 1 mission at a ratio of 1:2, after which the contents of the vessel were stirred and at atmospheric pressure drove pritemperature 110-120°C at first, the mixture of isobutylene and toluene, and then toluene and 1-mission. In the process of distillation from molecules triisobutylaluminum consistently hatshepsuts all three isobutylene of alkyl, and the resulting dialkylaminomethyl attaches consistently three molecules of 1-mission, forming, thus, tridecylamine. The distillation was continued as long as the volume of distilled liquid becomes equal to 65% of the volume loaded toluene solution CHIBA. Parallelomania CHIBA is possible to present the following reaction scheme:

- dellverticalline 1-mission, which was received as tridecylamine (full parallelomania), but the distillation of a mixture of toluene-isobutylene was conducted at reduced pressure and temperature in the tank is not higher than 50°C., so that was the removal of only one isobutylene of alkyl and join only one molecule of 1-mission, respectively (not full parallelomania), which is provided by the distillation of liquids ~ 55% of the volume of the loaded solution CHIBA. Thus obtained product has a higher reactivity than tridecylamine. Incomplete parallelomania CHIBA is possible to present the following reaction scheme:

As socializaton (coinitiator) used hydrogen chloride (HCl) and tertiary butyl chloride (TBH).

HCl was obtained by the action of sulphuric acid on sodium chloride and directly introduced into the polymerization reactor in the respective reactions of its receipt equimolecular quantities.

Tertiary butyl chloride (2-methyl-2-chloropropane) was used as a domestic (TU 6-09-07-1338-83), and imported and introduced into the polymerization reactor in the desired proportions syringe or through Slinko depending on the reactor in the form of a solution in mission-1 or directly without dilution.

To ensure manageability of the process of obtaining basics of polyolefin oils by regulating the rate of oligomerization and eliminate the formation of by-products or leakage isomerization processes and provide the required physical and mechanical properties and viscosity index of the resulting polyolefin is proposed a method of oligomerization of alpha-olefins, including the preparation of olefinic raw materials, stage of oligomerization, washing and selection from oligomerizate spent catalyst with subsequent separation of oligomerizate into fractions and their hydrogenation, in which the two-component catalyst system containing alyuminiiorganicheskikh compounds and chlorinated socialization, dissolved in toluene, o-xylene, mission-1 or low viscosity polyolefin-based synthetic oil as in the individual the spine, and in the composition of their mixtures, solvents used as molecular weight regulators, mixing alpha-olefins and catalyst is carried out in a dry nitrogen atmosphere with continuous stirring, followed by neutralization, washing and distillation is obtained oligomerizate in three modes and the residual pressure of 10.0, 1.0 and 0.7 mm Hg, while Dean dezenove fraction drain and return together with the feedstock in the process of oligomerization and chlorine coming into the process with socialization, after the stage of oligomerization, shading and highlighting spent catalyst is removed from oligomerizate aqueous-alkaline washing.

The method of obtaining basics of polyolefin oils by catalytic oligomerization of alpha-olefins with the use of the proposed catalyst is as follows:

- oligomerization of mission-1 is carried out in temperature-controlled dried glass or metal reactors mixing in a dry nitrogen atmosphere under intensive continuous stirring of the reaction mixture using a mixing device, the mixing 65-700 rpm;

- temperature polymerization regulate cooling water through the jacket of the reactor or water bath depending on the design of the reactor and the ratio of catalyst and monomer;

- neutralization of the catalyst by provocation caustic soda 10%, then oligomerized washed three times with water in a ratio of 1:1 to remove chlorine coming into the process with socialization, and allocation of spent catalyst;

- justify oligomerizate spend on a distillation column for programs previously developed for the pickup of oligomerizate, in three modes: at a residual pressure of 10.0, 1.0 and 0.7 mm Hg, when vacuumed distinguish the following fractions: Dean-detinova10(unreacted mission containing isomers X and XX), polyolefin bases of synthetic oils (PAO-2, PAO-4) and cube;

- Dean-dezenove fraction dry, clean granular oxide Al and return together with the feedstock in the process of oligomerization;

- polyolefin bases of synthetic oils (PAO-2, PAO-4 hydronaut.

The results of the syntheses are illustrated by examples, summarized in table 1.

Example 1 prototype using the catalytic system Al(0) mark PA-4 - HCl - TBH, which, as pointed out by the authors themselves, is the best on the results of preliminary studies on the totality of characteristics.

Example 2 the prototype using the catalytic system Al(0) - EACH-TBH, which also showed satisfactory results.

Examples 3-13. By the present method using as AOC - CHIBA, and as chlorinated socializaton - TBH, with optionally the cleaning mission-1 (synthesis 9, 10, 11, 13) and in the presence of a molecular weight regulator - toluene (synthesis 13).

Examples 14-21. By the present method using as AOC - DEBUG, and as chlorinated socializaton - TBH, in the presence of a molecular weight regulator - o-xylene (synthesis 21).

Examples 22-30. By the present method using as AOC - TDA, and as chlorinated socialization - HCl (synthesis 22-24) and TBH (synthesis 25-30), in the presence of a molecular weight regulator-o-xylene (synthesis 28-30).

In table 2 and 3 presents the qualitative characteristics obtained by the proposed method polyolefin bases of synthetic oils.

Data table 1-4 allow sufficient reliability to assert that the use of the catalyst and method of oligomerization of alpha-olefins with its application allows to suppress in the process of obtaining polyolefin bases of synthetic oils (PAO-2, PAO-4) adverse reactions, including isomerization and chlorination, as monomer, and the resulting oligomer (fractions of X and XX, as well as chlorinated products slightly table 1). Therefore when implementing the process of obtaining polyolefin bases of synthetic oils on the proposed method does not require dechlorination stage, and return the monomer (mission-1) may be after separating it from oligomers is the re-used in the synthesis process (table 4).

Table 2
Physico-chemical characterization of polyolefin bases of synthetic oils and fractions cube
№ p/pNamePAO-2PAO-4fraction cube
Synthesis No. 12Synthesis No. 13Synthesis No. 12Synthesis No. 13Synthesis No. 12Synthesis No. 13
1Composition, % wt.:
Xtraces0,01tracestracesn/a * mostly pentamers, gesneri and aboven/a*in the foundations of the om pentamers, gesneri and above
the mission0,010,08tracestraces
XX0,060,050,020,03
the dimers97,4897,680,100,16
trimers1,630,97at 83.5479,38
tetramera0,390,45of 14.4618,09
pentamers 0,430,761,882,34
2Pour point, °Cminus 80minus 74,9 not frozen----
3The kinematic viscosity at 100°C, mm2/s1,801,653,903,808,508,04
4Kinematic viscosity at 40°C, mm2/s--17,4516,6953,7949,04
5The viscosity index--118119133135
6Kinetic is eticeskaja viscosity at minus 40°C, mm2/s21520029172463--

Table 3
Physico-chemical characterization of polyolefin synthetic bases
oils
№ p/pNamePAO-2PAO-4
Synthesis No. 5+6Synthesis No. 5+6
1Composition, % wt.:
X0,01traces
the mission0,12traces
XX0,080,03
the dimers92,93 0,12
trimers5,9884,99
tetramera0,4212,14
pentamers6,462,72
2Pour point, °Cminus 74,9 not frozen-
The kinematic viscosity at 100 °C, mm2/s1,673,68
Kinematic viscosity at 40 °C, mm2/s-15,67
5The viscosity index-122
6Kinematic viscosity at 40°C, mm2/s2032048

Table 4
The content of the mission-1 in the Dean-deanovich fractions isolated from oligomerization obtained with the use of AOS.
№ p/pThe conditions of the oligomerizationThe content of the mission-1 in the Dean-decanoas fraction, %
1justify No. 30/2009 of oligomerizate synthesis No. 12: the mission (V-102) - 1.0 l, TBH - 8,0 ml, AOC - 24 ml, the ratio of Cl:Al = 3.2, and the temperature of the input AOS - 80°C, color oligomerizate - yellow;2,8
2justify No. 31/2009 of oligomerizate synthesis No. 13: the mission (V-102 + Al2O3) - 1.0 liter of toluene and 1.5 ml TBH - 4.0 ml AOC - 12 ml, the ratio of Cl:Al = 3.2, and the temperature of the input AOS - 80°C, color oligomerizate - light yellow.4,0
3justify No. 32/2009 of oligomerizate with synthesis No. 5+6:
synthesis No. 5: the mission (V-102) - 0.5 l, TBH - 1.6 ml, AOC - 5.5 ml, the ratio of Cl:Al = 2.6, the temperature of the input AOS - 60 °C color oligomerizate - light-light yellow;
synthesis No. 6: the mission (V-102) - 0.5 l, TBH - 3.0 ml, AOC - 10 ml, the ratio of Cl:Al= 2.6, the temperature of the input AOS - 60°C color oligomerizate - light-light yellow
of 21.2

1. The catalyst for the oligomerization of alpha-olefins, which represents a two-component system is mu containing alyuminiiorganicheskikh compounds and chlorinated socialization, characterized in that alyuminiiorganicheskikh compounds selected from the group comprising triisobutylaluminum, diisobutylaluminum or products of their parallelomania a mission-1 tridecylamine or dellverticalline used in the amount of 0.62-4,08 mmol per mole of alpha-olefin, and socialization selected from the group consisting of hydrogen chloride, or organic monochloride, such as tribouillard ratio Cl:Al is 2.5:16.2 mol/mol, respectively.

2. The method of oligomerization of alpha-olefins, including the preparation of olefinic raw materials, stage of oligomerization, washing and selection from oligomerizate spent catalyst with subsequent separation of oligomerizate into fractions and their hydrogenation, wherein the two-component catalyst system according to claim 1 dissolved in toluene, o-xylene, mission-1 or low viscosity polyolefin-based synthetic oils alone and in the composition of their mixtures, solvents used as molecular weight regulators, mixing alpha-olefins and catalyst is carried out in a dry nitrogen atmosphere with continuous stirring, followed by rectification of the received oligomerizate in three modes when residual pressure of 10.0, 1.0 and 0.7 mm Hg, with the perfect combination-dezenove fraction drain and return together with the feedstock in the process of oligomerization, and chlorine coming into the process with socialization, after the stage of oligomerization, shading and highlighting spent catalyst is removed from oligomerizate aqueous-alkaline washing.

3. The method according to claim 2, in which during preparation for the oligomerization of olefinic feedstock drain, and the source and return of the mission-1 and the Dean dezenove faction additionally cleaned granular alumina.



 

Same patents:

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

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing dimers, characterised by that starting material containing at least one n-olefin, selected from a group consisting of C8-C30 n-olefins or a mixture of n-olefins is dimerised at temperature 25-200°C and pressure from 0.001 mbar to 50 bars in the presence of a solid acid catalyst, passing the starting material into a catalytic distillation apparatus, having either a) a combination of a distillation column and a reactor, having at least one catalyst bed, or b) a distillation column connected to one or more side reactors containing at least one catalyst bed which contains acid catalyst solid material with a mesoporous surface of area greater than 100 m2/g, containing 0.2-30 wt % aluminium, where the number of acid site of the material ranges from 50 to 500 mcmol/g, and the material is selected from a group consisting of amorphous aluminium silicates and mesoporous molecular sieves with embedded zeolite, extracting the unreacted n-olefin in the top part of the distillation column or in the top part of the combination of distillation column and reactor in form of a side stream to be merged with the starting material, as a result of which 50-95% n-olefins get into contact with the catalyst bed more than once. The invention also relates to a method of producing base oil via hydrogenation of dimers obtained using the method described above.

EFFECT: use of the disclosed invention significantly reduces problems and shortcomings of solutions of the preceding level of technology, allowing for achieving high selectivity of dimerisation and reducing the number of secondary reactions.

16 cl, 10 ex, 10 tbl, 4 dwg

FIELD: oil and gas production.

SUBSTANCE: invention refers to procedure for processing natural gas into liquid hydrocarbons in flow reactor with non-equilibrium electric discharge. Also, flow of natural gas with atmospheric pressure in the reactor is subjected to pulse volumetric discharge initiated with a pulse electron beam. Strength of electric field in discharge is 8-10 kV/cm, while specific power in a pulse is 1-2 J/cm3.

EFFECT: reduced consumption of energy for production of liquid hydrocarbons and increased efficiency of reactor.

2 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining a product with the boiling range corresponding to a gasoline fraction from a stream of material from a mixture of light olefins containing ethylene, propylene and butene, and a stream of liquid aromatic material containing monocyclic aromatic compounds which contain 5-60 wt % benzene, involving: (i) separation of the stream of material from the mixture of light olefins to obtain two streams of material; (ii) reaction one of the said two streams of material in liquid phase at temperature 90-250°C and excess pressure not higher than 7000 kPa, in a fixed catalyst bed for condensation of olefins, which contains MWW zeolite as the active component, to obtain a polymer product with boiling range which corresponds to a gasoline fraction, through polymerisation of olefins in the stream; (iii) extraction of olefins from the other of the two streams of material from the mixture of light olefins through counterflow contact between the stream of olefin material and a stream of aromatic material to dissolve olefins in the stream of liquid aromatic material and formation of a stream of aromatic compounds rich in propylene and butene, and an olefin output stream containing ethylene; (iv) passing the stream of aromatic compounds containing extracted propylene and butene to the liquid-phase alkylation step on which the aromatic compounds are alkylated with extracted olefins in liquid phase at temperature 90-250°C on a solid fixed bed catalyst based on molecular sieves, which contains MWW zeolite, to form a first output stream containing alkylaromatic compounds with boiling range corresponding to the gasoline fraction; (v) passing the olefin output stream containing ethylene with the output stream from the liquid-phase alkylation step to the alkylation step on which the stream of aromatic compounds is kept in the vapour phase, on an alkylation catalyst which contains ZSM-5 zeolite, at temperature 200-325°C to obtain a second output stream containing alkylaromatic compounds with boiling range corresponding to the gasoline fraction; (vi) merging the polymer product with boiling range corresponding to the gasoline fraction with the second output stream which contains alkylaromatic compounds to obtain a product with boiling range corresponding to the gasoline fraction.

EFFECT: present invention enables to use light olefins which are processing products from a catalytic cracking apparatus in a fluidised bed for use in production of petrol.

6 cl, 5 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining a product with boiling range corresponding to a gasoline fraction from a stream of material from a mixture of light olefins containing ethylene and propylene, and a stream of liquid aromatic material containing benzene, involving: extraction of light olefins from a stream of gaseous olefins, containing ethylene and propylene, through counterflow dissolving at temperature of up to 120°C and excess pressure of up to 3500 kPa, in a stream of light aromatic hydrocarbons containing 5-60 wt % benzene to obtain a stream of extract containing extracted olefins in aromatic hydrocarbons, and a stream containing non-sorbed olefins; alkylation of aromatic hydrocarbons contained in the stream of extract which is extracted with olefins dissolved in the stream of aromatic hydrocarbons on a fixed bed solid alkylation catalyst based on molecular sieves, containing MWW zeolite, through reaction in liquid phase at temperature not higher than 250°C, weight ratio of aromatic hydrocarbons: olefins between 0.5:1 and 5:1 and space velocity of olefins between 0.5 and 5.0 to form a product with boiling range corresponding to the gasoline fraction which contains alkylaromatic hydrocarbons, including alkylbenzenes, feeding the stream containing non-sorbed olefins to the vapour-phase alkylation step on which olefins contained in the stream are brought into contact with an additional stream of light aromatic hydrocarbons containing 5-60 wt % benzene for alkylation of aromatic hydrocarbons in that stream with non-sorbed olefins in a catalytic reaction in vapour phase on a fixed catalyst bed which contains a ZSM-5 zeolite catalyst at temperature 200-325°C to obtain alkylated aromatic hydrocarbons, including alkylbenzenes, and fractionation of products from the liquid-phase alkylation step and vapour-phase alkylation step in a common distillation column to obtain a product with boiling range corresponding to the gasoline fraction containing alkylaromatic compounds.

EFFECT: present method enables to use light olefins - petroleum refining products coming from a catalytic cracking apparatus in a fluidised bed, for alkylation of benzene - a petroleum refining product, to obtain products with boiling range corresponding to the gasoline fraction.

9 cl, 5 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining a product with the boiling range corresponding to a gasoline fraction from a stream of material from a mixture of light olefins containing ethylene and propylene, and a stream of aromatic material containing monocyclic aromatic compounds and containing 5-60 vol % benzene, involving: reaction of monocyclic aromatic compounds containing benzene in the stream of aromatic material with propylene from the stream of material from the mixture of olefins at the first step in vapour phase in the presence of a catalyst system containing a catalyst component which contains the MWW zeolite family in a fixed catalyst bed at temperature of 90-250°C and pressure of not higher than 7000 kPa isb; passing the stream coming from the first step to the second step, on which monocyclic aromatic compounds containing benzene in the stream of aromatic material react with ethylene from the stream of material from the mixture of olefins in vapour phase in the presence of a catalyst system containing a catalyst component which contains zeolite ZSM-5 with intermediate size pores in a fixed bed at temperature of the bed of 200-400°C and pressure of not higher than 7000 kPa isb, to form a product with boiling range corresponding to the gasoline fraction which contains alkyaromatic compounds.

EFFECT: use of present method enables recycling of light olefins into a product with boiling range corresponding to the gasoline fraction.

7 cl, 3 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining high-quality saturated base oil or a base oil component based on hydrocarbons. The method of obtaining a saturated hydrocarbon component for use as petrol, base oil, diesel components and/or solvent fractions involves oligomerisation of starting material which contains one or more components selected from a group comprising carboxylic acids having 4-38 carbon atoms, C4-C38 carboxylic acid esters and C1-C11 alcohols, C4-C38 carboxylic acid anhydrides and C4-C38 alcohols, in the presence of a cationic clay-based catalyst and deoxygenation. The starting material contains at least 50 wt % unsaturated and/or polyunsaturated compounds. The invention also relates to base oil obtained using the method given above, which is distinguished by that the base oil contains at least 90 wt % saturated hydrocarbons, 20-90 % mono-naphthenes, less than 3.0% polycyclic naphthenes, not more than 20 wt % linear parafins and at least 50 wt % saturated hydrocarbons have carbon number value interval not greater than 9 carbon atoms. The base oil is a biological product and has kinematic viscosity at 100°C ranging from 3 cS to 8 Cs.

EFFECT: obtaining saturated base oil which does not contain heteroatoms from biological starting material, which satisfies group III API requirements.

23 cl, 7 ex, 5 tbl, 2 dwg

FIELD: technological processes; chemistry.

SUBSTANCE: method involves reaction of raw material containing organic component with a catalyst composition. Processing method is selected out of alkylation, acylation, hydrotreatment, demetallisation, catalytic deparaffinisation, Fischer-Tropsch process and cracking. Catalyst composition includes mainly mesoporous silicon dioxide structure containing at least 97 vol.% of pores with size in the interval from ca. 15 Å to ca. 300 Å, and at least ca. 0.01 cm3/g of micropores. Mesoporous structure features at least one catalytically and/or chemically active heteroatom in amount of at least ca. 0.02 mass %, selected out of a group including Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Ru, Pt, W and their combinations. The catalyst composition radiograph has one 0.3° to ca. 3.5° peak at 2θ.

EFFECT: highly efficient method of organic compound processing in the presence of catalyst composition without zeolite.

20 cl, 31 ex, 17 tbl, 22 dwg

FIELD: organic chemistry.

SUBSTANCE: invention refers to technology and technique of gas hydrocarbons conversion to liquid hydrocarbons stable at normal conditions. The invention concerns method of gas hydrocarbons conversion to liquid hydrocarbons under electric discharges. Converted hydrocarbons are subject to partial discharges by dispersion in dielectric organic liquid in DC electric field. Process is carried out by means of gas hydrocarbons converter including coaxial internal and outer electrodes. Outer electrode comprises sequence elements every of which is dielectrically isolated sections one of which is under tension and another one is electrically neutral. Process is carried out section by section. In addition invention concerns device for gas hydrocarbons conversion to liquid hydrocarbons.

EFFECT: developed method of gas hydrocarbons conversion to liquid hydrocarbons under electric discharges.

3 cl, 2 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing poly-alpha-olefin compound. Method involves combined oligomerization of a mixture containing about from 60 to 90 weight% of 1-dodecene and about from 10 to 40 weight% of 1-decene in the presence of BF3 as a catalyst and alcoholic promoter at temperature in the range about from 20°C to 60°C followed by distilling the mixture and hydrogenation to yield poly-alpha-olefin. Product has kinematic viscosity in the range about from 4 to 6 centistokes at 100°C, loss by Noak mass in the range about from 4% to 9%, viscosity index in the range about from 130 to 145 and fluidity loss temperature in the range about from -60°C to -50°C.

EFFECT: improved method of synthesis.

11 cl, 9 tbl, 14 ex

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

FIELD: petrochemical processes.

SUBSTANCE: invention relates to catalytic oligomerization of ethylene into C8-olefins, widely used as polyethylene and polypropylene modifiers, as raw materials in production of surfactants and motor fuel additives, and in organic synthesis. Oligomerization is conducted in catalytic system, which is namely nickel(0) complex Ni(PPh3)4 in combination with boron fluoride etherate (BF3·OEt2), styrene, and methyl methacrylate at molar ratios Ni(PPh3)4/BF3·OEt2/styrene between 1:5:0.5 and 2:0.5:2.

EFFECT: increased yield of desired product.

1 tbl, 4 ex

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 cationic catalytic systems (catalysts) oligomerization of individual or mixtures of olefins WITH3-C14in fundamentals of synthetic automotive, aircraft, gear, and other types polyalpha-olefin oils (POM)

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

The invention relates to the field of petrochemical synthesis, in particular to a method for simultaneous obtaining of tree-5,6-disubstituted hept-1-ENES, tree-5,6-disubstituted DECA-1,9-dienes of General formula

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These compounds may find application in thin organic synthesis and in the synthesis of biologically active preparations containing substituents exclusively threo-configuration, special polymers

FIELD: chemistry.

SUBSTANCE: invention relates to use of heteropoly acid catalysts for converting oxygenates to alkenes. Described is a method of producing an alkene (alkenes) from an oxygenate starting material through dehydration in a reactor in the presence of a heteropoly acid catalyst deposited on a support, characterised by that the specific pore volume thereof satisfies the following relationship: OP>0.6-0.3 [amount of heteropoly acid catalyst/surface area of dried catalyst], where OP denotes the specific pore volume of the dried heteropoly acid catalyst deposited on the support (given in ml/g catalyst); the amount of the heteropoly acid catalyst is the amount of heteropoly acid contained in the dried heteropoly acid catalyst deposited on the support (given in micromole/g); the surface area of the dried catalyst is the specific surface area of the dried heteropoly acid catalyst deposited on the support (given in m2/g). Described is a method of converting a hydrocarbon to an alkene (alkenes), involving the following successive steps: a) converting hydrocarbon starting material in a synthetic gas reactor into a mixture of carbon oxide (oxides) and hydrogen, b) converting said mixture of carbon oxide (oxides) and hydrogen from step a) in the presence of a powdered catalyst in a reactor at temperature ranging from 200 to 400°C and at pressure ranging from 50 to 200 bars into starting material containing at least one monoatomic aliphatic paraffin alcohol and/or the corresponding ether containing 2-5 carbon atoms, and c) continuing to realise the method as described above to obtain alkenes, owing to which the oxygenate starting material contains at least a portion of alcohol (alcohols) and/or ethers obtained at step b). Described is use of the heteropoly acid catalyst deposited on a support in the method of producing alkene (alkenes) from oxygenate starting material for increasing alkene selectivity and output while simultaneously preventing formation of alkanes, in the presence of the catalyst described above.

EFFECT: high efficiency of producing alkenes and low amount of alkanes formed.

20 cl, 7 tbl, 1 dwg, 19 ex

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