Reductive isomerisation catalyst, method of mineral oil dewaxing, method of producing base oil and method of producing lubrication base oil

FIELD: process engineering.

SUBSTANCE: this invention relates to reductive isomerisation catalyst, dewaxing of mineral oil, method of producing base oil and lubrication base oil. Invention covers reductive isomerisation catalyst. Reductive isomerisation comprises molecular sieve treated by ionic exchange or its calcinated material produced by ionic exchange of molecular sieve containing cationic fragments and using water as the primary solvent, and at least one metal selected from the group consisting of metals belonging to group VIII-X of periodic system, molybdenum and tungsten applied onto molecular sieve treated by ionic exchange, or onto its calcinated material. Dewaxing comprises converting portion of or all normal paraffins into isoparaffins whereat mineral oil containing normal paraffins is brought in contact with abode described reductive isomerisation catalyst in the presence of hydrogen. Invention covers also method of producing lubricant base oil and/or fuel base oil implemented by bringing base oil containing normal paraffins in contact isomerisation catalyst in the presence of hydrogen. Invention covers also method of producing lubricant base oil containing normal paraffins, including 10 or more carbon atoms by bringing it in contact with above describe reductive isomerisation catalyst in the presence of hydrogen in conversion of normal paraffins making in fact 100%.

EFFECT: catalyst with high isomerisation activity and sufficiently low cracking activity at high yield.

22 cl, 8 tbl, 4 ex, 11 dwg

 

The technical field to which the invention relates

The invention relates to a catalyst hydroisomerization, method of dewaxing mineral oils, the method of obtaining a base oil and a method for producing a basic component of the lubricating oil.

The level of technology

For a given lubricating oil, gasoil and jet fuel important property is the fluidity at low temperatures. For this reason, it is preferable that the base oil used for data products, such as paraffin component, which causes deterioration of fluidity at low temperatures, such as normal paraffins and slightly branched ISO, fully or partially extracted or transformed into components other than the paraffin component. Recently hydrocarbons obtained by using the method of Fischer-Tropsch synthesis (hereinafter simply called as a method of synthesis CFT) and does not contain such a polluting material, such as sulfur compounds, have attracted attention as a source of oil for production of lubricating oil or fuel. However, the hydrocarbon also contains a large amount of paraffin component.

As a method of dewaxing to remove the paraffin component of mineral oil known method of extracting the PA is atenololo component solvent, such as liquefied propane or IEC. However, the method is fraught with problems associated with high production costs, the method is applicable for limited types of raw oils, and industrial output is limited, depending on the types of the original oil.

On the other hand, as a method of transformation of the paraffin component in mineral oil in separately component method catalytic dewaxing by isomerization of normal paraffin mineral oil ISO by contacting the mineral oil with the so-called bifunctional catalyst that is capable of hydrogenation-dehydrogenization and isomerization ability in the presence of hydrogen. In addition, as a bifunctional catalyst used method for catalytic dewaxing, a catalyst containing a solid acid, especially molecular sieve consisting of such zeolite and metals belonging to groups 8-10 and group 6 of the Periodic Table of Elements, particularly the catalyst, where the above-mentioned metal supported on a carrier of the molecular sieve.

Although the method is catalytic dewaxing can be effectively used as a method of improving the fluidity at low temperature mineral oil, conversion of normal paraffins is necessary to improve the shape sufficiently to obtain a fraction that is appropriate for the base lubricating oil or base oil fuel. However, since the catalyst used for the method for catalytic dewaxing, has kekirawa ability in relation to hydrocarbons, and isomerizing the ability, when mineral oil is subjected to catalytic dewaxing, the formation of lighter hydrocarbons with increasing conversion of the normal paraffins. Therefore, it is difficult to obtain the desired fraction with a good yield. In particular, in the case of obtaining a base oil for high-quality lubricants that require a high viscosity index and low temperature fluidity loss, very difficult to obtain the desired fraction with a good economic efficiency, using the catalytic dewaxing of mineral oil. For this reason, this area is widely used synthetic base oil such as poly-alpha-olefin.

Due to these circumstances, in the production of base oils lubricants and base oil fuels, there is a need in the technology of catalytic dewaxing capable of getting the desired isoparaffin fraction with a good yield of mineral oils containing paraffin component.

Up to the present time is being developed under the od to improve the selectivity isomerization the activity of the catalyst, used for catalytic dewaxing. For example, the following Patent Document 1, a method for production of lubricating oil, which deparaffinization by contacting a hydrocarbon feedstock containing linear chain or slightly branched chain of 10 or more carbon atoms, with a catalyst comprising a molecular sieve having a unidirectional pore structure of the average size and the size of the crystals is less than about 0.5 μm, as ZSM-22, ZSM-23 and ZSM-48 containing a metal of group VIII, etc.

It turned out that the molecular sieve is included in the composition of the catalyst used for catalytic dewaxing, usually obtained by hydrothermal synthesis in the presence of organic matrix containing such an amino group and an ammonium group, which allows to obtain a pre-determined pore structure. Next, the synthesized molecular sieve is calcined at a temperature of approximately 550°C. or higher in an environment containing molecular oxygen, for removal of contained organic matrix, as disclosed in the last paragraph 2.1. Materials the following non-Patent Document 1, page 453. Next, the calcined molecular sieve is typically subjected to a process of ion exchange of ammonium type in an aqueous solution containing ammonium ions, as disclosed in the last Parag is AFE section 2.3. Catalytic experiments the following non-Patent Document 1, page 453. Next, after ion exchange, molecular sieve impose such metal elements as metals belonging to groups 8-10 of the Periodic Table of Elements. Then the molecular sieve with the introduced metal component is subjected to the drying process and the molding process (if necessary), and then loaded into the reactor and calcined usually at a temperature of approximately 400°C in a medium containing molecular oxygen. Then it is subjected to restoration processing at approximately the same temperature with hydrogen or the like, so that it creates the catalytic activity of a bifunctional catalyst.

Patent Document [1] U.S. patent No. 5282958

[Non-patent Document 1] J.A.Martens et al., J. Catal. 239 (2006)451

The invention

However, in the production process, proposed in Patent Document 1, isomerization selectivity of the catalyst is insufficient, and kekirawa ability insufficiently suppressed. Therefore, it is difficult to obtain a high yield of the desired isoparaffin fraction, suitable for base lubricating oil or base oil fuel, mineral oils comprising paraffinic component.

The present invention is made considering the above circumstances, and its tasks include the development of catalyst hydroisomerization, having a sufficiently high isomerization ability and sufficiently suppressed craterous ability, which can provide a mineral oil base oils lubricants and mineral oil to base oil, fuel, mineral oil containing normal paraffins, high yield, develop a method of dewaxing mineral oils, to develop a method of production of base oils and to develop a method for the production of base oils for lubricants.

The author of the present invention conducted extensive studies in view of the problems of the traditional method, to find that the catalyst, which is obtained by deposition of the metal on a molecular sieve, obtained by ion exchange of hydrothermal synthesized molecular sieve under specific conditions, in a state where the molecular sieve contains organic matrix, and calcining the molecular sieve coated with metal, is able to significantly increase the number C10 isomers in the reaction product during the reaction of isomerization of normal decane, that is, to have a higher isomerization ability, and lower craterous ability, compared with the conventional catalyst. In addition, the author of the present invention have conducted studies based on the above established facts and found that mozhnopoluchit isoparaffin fraction, suitable base oils lubricants or base oil fuel, especially isoparaffin fraction suitable for base oil of high quality lubricants having high viscosity index and low pour point, contacting the mineral oil containing paraffin component, and a catalyst, which is obtained by deposition of the metal on the carrier containing the above-mentioned processed by the method of ion exchange, molecular sieve, and roasting processed by the method of ion exchange, molecular sieve coated with a metal in the presence of hydrogen. As a result, created the present invention.

Namely, the present invention relates to a catalyst hydroisomerization, which is obtained by calcination of a catalyst composition comprising processed by the method of ion exchange, molecular sieve or the calcined material, which is obtained ion-exchanged molecular sieve containing an organic matrix, the solution containing the cationic fragments and uses water as the main solvent, and at least one metal selected from the group comprising metals belonging to groups 8-10 of the Periodic Table of the Elements, molybdenum and tungsten deposited on the treated by the method of ion exchange, molecular sieve or the calcined material. The period of the economic table of Elements refers to the periodic table, approved by the International Union of Pure and Applied Chemistry (IUPAC).

The catalyst hydroisomerization according to the present invention having the above structure, can act as a catalyst having a sufficiently high isomerization activity when hydroisomerization normal paraffins and sufficiently suppressed craterous ability. In addition, according to the catalyst hydroisomerization of the present invention, even when a mineral oil containing normal paraffins, subject to hydroisomerization in the presence of hydrogen under conditions when the conversion of normal paraffins is large enough, you can get the ISO with the required number or more carbon atoms, with a significantly higher yield compared with the conventional catalyst. Therefore, when the catalyst hydroisomerization according to the present invention is used for catalytic dewaxing of mineral oil containing normal paraffins, it is possible to obtain a mineral oil suitable for base oil of lubricating oil and/or mineral oil, suitable for base oil fuel with a high enough output. In addition, with regard to mineral oils suitable for base oil fuel, it is possible to obtain a mineral oil, a very p is hodne, in particular, base oil, gas oil, with a high yield. With regard to mineral oils suitable for base oil of lubricating oil, it is possible to obtain mineral oil, suitable, in particular, to a base oil of lubricating oils having high viscosity index and low pour point, high output.

In addition, according to the catalyst hydroisomerization of the present invention, when normal paraffins are hydroisomerization, it is possible to obtain a large number of isomers having two or more chain branches per molecule (multiresolution isomers). It is known that multiresolution isomers have the ability to reduce the pour point of base oil compared to dorazvedannye isomers. Therefore, the selectivity relative to multiresolutional isomer catalyst hydroisomerization according to the present invention can be very effective to impart low temperature fluidity base oil of lubricating oil or the base oil fuel produced using the method of catalytic dewaxing.

Incidentally, it is known that molecules isoparaffins, which are obtained by catalytic dewaxing of mineral oils containing paraffin component, the structure where the branched chains are in the inner position of the main chain, different from its end position, contributes to a further reduction of the temperature fluidity loss of base oil of lubricating oil or base oil fuel. And, as the operational factor of the catalyst used for catalytic dewaxing, the proposed index, reflecting the selectivity of the position of the branching circuit for forming molecules isoparaffin. For example, in the document (J. A. Martens et al., ZEOLITE, 6(1986) 451) proposed a constraint index CIothat is defined as follows.

Constraint index CIo: molar ratio of 2-methylnonane to 5-methylnonane that occurs when the output from the Dean 5% wt. in isomerization reactions using normal decane as a model of the source material. The smaller the constraint index CIothe better the selectivity of the position of the branching circuit for forming molecules isoparaffin. Therefore, the catalyst used for catalytic dewaxing, preferably used for obtaining a base oil of lubricating oil or base oil fuel.

On the other hand, in the catalyst hydroisomerization according to the present invention, as processed by the method of ion exchange, molecular sieve, is included in the composition of the catalyst obtained above in a particular way, you may get the ü small constraint index CI ocompared with a conventional catalyst, obtained using the same type of synthetic molecular sieves. Therefore, the selectivity of the provisions of branched chains in the catalyst hydroisomerization according to the present invention can provide high efficiency to obtain low temperature fluidity loss of base oil of lubricating oil or base oil fuel produced using the method of catalytic dewaxing.

In addition, the dewaxing catalyst according to the present invention, from the viewpoint of imparting high isomerization activity and low kekirawa ability, it is preferable that the molecular sieve containing an organic matrix, represented zeolite having a pore structure characterized by a 10-membered ring or 8-membered ring.

Further, from the viewpoint of more effective implementation of the selective conversion of normal paraffins, preferably, the zeolite had the unidirectional structure of pores having 10-membered ring.

In addition, from the viewpoint of ease of regulation of activity of solid acid catalyst, preferably zeolite was represented by at least one crystalline aluminosilicate selected from the group comprising ZSM-22, ZSM-23 and ZSM-48.

Further, when zeoli represent the above crystalline aluminosilicate, preferably, the molar ratio of [Si]/[Al] of silicon atoms to aluminum atoms in the crystalline aluminosilicate was lying in the range from 10 to 400. By using this crystalline aluminosilicate, it is possible to obtain a high catalytic activity and high selectivity for isomerization of normal paraffins as compared with the case when using a molar ratio deviating from the above range of values.

In addition, the present invention relates to a catalyst hydroisomerization, in which a molecular sieve containing an organic matrix, is ZSM-22, and a constraint index, defined as follows, lies in the interval from 7 to 12.

Constraint index CIo: molar ratio of 2-methylnonane to 5-methylnonane that occurs when the output of isodecanol is 5% wt. in reaction contact between the normal of the Dean with the catalyst hydroisomerization with the conversion of the first ISO-deans in the presence of hydrogen.

In addition, the present invention relates to a catalyst hydroisomerization, in which a molecular sieve containing an organic matrix, is ZSM-23, and a constraint index, defined as above, lies in the range from 3.0 to 4.0.

In addition, the present invention relates to a catalyst hydroisomerization, in which the molecular with the fact, containing organic matrix, is ZSM-48, and a constraint index, defined as above, lies in the range from 1.1 to 5.1.

In the catalyst hydroisomerization according to the present invention, from the viewpoint of reducing the influence on the properties of synthetic raw materials for molecular sieve, which is usually synthesized in alkaline medium, it is preferable that the organic matrix was derived amine.

In addition, it is preferable that the organic matrix was represented by a matrix selected from the group comprising alkylamino, alkylamino, alkilany, alliteration, pyrrolidine, piperazine, aminopiperidin, alkylbetaine, alkylguanine and their derivatives.

In addition, the catalyst hydroisomerization according to the present invention, from the viewpoint of simplicity of the process of preparation of the catalyst, preferably treated by the method of ion exchange, molecular sieve was obtained ion-exchanged molecular sieve containing an organic matrix, in the presence of ammonium ion or proton.

In addition, the catalyst hydroisomerization according to the present invention should preferably be treated by the method of ion exchange, molecular sieve was obtained ion-exchanged molecular sieve containing an organic matrix, replacing the solution fresh Rast is a PR one, two or more times. In this case you can increase the efficiency of ion exchange as compared with the case where the ion exchange is carried out without changing the solution.

In addition, the catalyst hydroisomerization according to the present invention, from the viewpoint of the ease of obtaining the required functions of the dehydrogenation and hydrogenation of the catalyst, it is preferable that the composition of the catalyst contains platinum and/or palladium, deposited on the treated by the method of ion exchange, molecular sieve or the calcined material.

In addition, the catalyst hydroisomerization according to the present invention it is preferable that the catalyst was obtained by annealing the composition of the catalyst in a medium containing molecular oxygen, with subsequent recovery in an environment containing molecular hydrogen.

In the catalyst hydroisomerization according to the present invention, from the viewpoint of the ease of obtaining the desired isomerization activity and the required ability to molding and the mechanical strength of the catalyst composition, it is preferable that the composition of the catalyst contained 1 part by weight to 90 parts by weight processed by the method of ion exchange, molecular sieve or the calcined material and from 99 parts by weight to 10 parts by mass of porous oxide that PR is dstanley a, at least one selected from the group comprising aluminum oxide, silicon dioxide, titanium oxide, boron oxide, magnesium oxide and zirconium oxide.

In the catalyst hydroisomerization according to the present invention, from the viewpoint of the ease of obtaining the desired isomerization skills and abilities required for the formation and mechanical strength of the composition of the catalyst, it is preferable that the catalyst composition contains a carrier obtained by annealing the composition of media containing 1 part by weight to 90 parts by weight processed by the method of ion exchange, molecular sieve and 99 parts by mass to 10 parts by weight of porous oxide, which represents at least one selected from the group comprising aluminum oxide, silicon dioxide, titanium oxide, boron oxide, magnesium oxide and zirconium oxide; and a metal supported on a carrier.

In addition, the present invention relates to a method of dewaxing mineral oils, including the process of converting part or all of the normal paraffins into ISO-contacting mineral oil containing normal paraffins, and catalyst hydroisomerization according to the present invention in the presence of hydrogen.

According to the method of dewaxing of the present invention when mineral oil p will gorhaut catalytic dewaxing using a catalyst of hydroisomerization according to the present invention, although the conversion of normal paraffins increases, but it is possible to considerably suppress the relief of isoparaffin fraction. Therefore, according to the method of dewaxing mineral oils according to the present invention, it is possible to obtain mineral oil, suitable for base oil of lubricating oil and/or mineral oil, suitable for base oil fuel with a high yield from a mineral oil containing normal paraffins. In addition, with regard to mineral oils suitable for base oil fuel, it is possible to obtain mineral oil, suitable, in particular, for the base oil, gas oil, with a high yield. As for mineral oil, suitable for a base oil of lubricating oil, it is possible to obtain mineral oil, suitable, in particular, to a base oil of lubricating oils having high viscosity index and low pour point, high output.

In addition, according to the method of dewaxing mineral oils according to the present invention using the catalyst of hydroisomerization according to the present invention, it is possible to increase the content multiresolution isomers in mineral oil after dewaxing. Therefore, according to the method of dewaxing mineral oils according to the present invention, it is possible to obtain a base oil of lubricating Mac is a and/or base oil fuel having good low-temperature properties with good economic efficiency.

In addition, according to the method of dewaxing mineral oils according to the present invention using the catalyst of hydroisomerization of the present invention, it is possible to increase the content isoparaffins, having a structure, when the branched chain located in the inner position of the main circuit different from its end position, in mineral oil after dewaxing. Therefore, according to the method of dewaxing mineral oils according to the present invention it is possible to obtain a base oil of lubricating oil and/or base oil fuel having good low-temperature properties with good economic efficiency.

In the method of dewaxing mineral oils according to the present invention, from the viewpoint of obtaining a base oil of lubricating oils having high viscosity index and good fluidity at low temperatures, and/or base oil fuel having good fluidity at low temperatures, with high yield, it is preferable that the mineral oil was represented by at least one selected from the group comprising paraffin GAC, fat-free wax, paraffin wax on the base, microcrystalline wax, petrolatum and waxes obtained by the method of Fischer-Tropsch.

Chrome is also the present invention relates to a method for producing base oils in the production of base oils for lubricants and/or base oil fuel, which is carried out by the contact interaction of mineral oil containing normal paraffins with a catalyst hydroisomerization according to the present invention in the presence of hydrogen.

According to the method of obtaining a base oil of the present invention, even when the conversion of normal paraffins increases during hydroisomerization mineral oil, it is possible to largely suppress the relief of isoparaffin fractions through the use of catalyst hydroisomerization according to the present invention. Therefore, according to the method of obtaining a base oil of the present invention, it is possible to obtain a base oil of lubricating oil and/or base oil fuel from mineral oil containing normal paraffins, with a high yield. Additionally, regarding the base oil of lubricating oil, it is possible to obtain a base oil of high quality lubricating oils having high viscosity index and low pour point, high yield. As for the base oil fuel, you can get a basic oil gas oil having good low-temperature properties with good output.

In addition, according to the on method for producing a base oil of the present invention, using the catalyst hydroisomerization according to the present invention, it is possible to increase the content multiresolution isomers obtained in the base oil. Therefore, according to the method of obtaining a base oil of the present invention, it is possible to obtain a base oil of lubricating oil and/or base oil fuel having good low-temperature properties with good economic efficiency.

In addition, according to the method of obtaining a base oil of the present invention using the catalyst of hydroisomerization of the present invention, it is possible to increase the content isoparaffins, having a structure in which the branched chain located in the inner position of the main circuit different from their end positions, the obtained base oil. Therefore, according to the method of obtaining a base oil of the present invention, it is possible to obtain a base oil of lubricating oil and/or base oil fuel having good low-temperature properties with good economic efficiency.

In the method of obtaining a base oil according to the present invention, from the viewpoint of obtaining a base oil of lubricating oils having high viscosity index and good properties at low temperature, and base oil fuel having good fluidity at low temperatures, with high o the house, preferably, the mineral oil was represented by at least one selected from the group comprising paraffin GAC, fat-free wax, paraffin wax on the base, microcrystalline wax, petrolatum and waxes obtained by the method of Fischer-Tropsch.

In addition, the present invention relates to a method for producing a base oil of lubricating oil by contacting the mineral oil containing normal paraffins having 10 or more carbon atoms, with a catalyst hydroisomerization according to the present invention in the presence of hydrogen under conditions when the conversion of normal paraffins defined by the following equation 1 is essentially 100 wt.%.

Conversion of normal paraffins (%wt.)=[1-(total weight of Cn or more normal paraffins contained in the mineral oil after contact interaction)/(Total mass of Cn or more normal paraffins contained in the mineral oil to the contact interaction)]×100 (I).

In equation I, Cn denotes the minimum number of carbon atoms in the normal paraffins containing 10 or more carbon atoms included in mineral oil to the contact interaction.

Here, "conversion of essentially 100 wt.%" means that the content of normal paraffins in mineral oil after contact interaction is the major rate of 0.1% wt. or less.

In particular, according to the method of obtaining a base oil of lubricating oil of the present invention can effectively get this base oil of high quality lubricating oil as indicated by the group III+, in accordance with the classification of the quality of lubricating oil American Petroleum Institute.

According to the present invention can be obtained a catalyst hydroisomerization capable of obtaining mineral oil suitable for a base oil of lubricating oil, and mineral oil suitable for base oil, fuel, mineral oil containing normal paraffins, with high yield and with high enough isomerization activity and sufficiently suppressed kekirawa ability, and to carry out the method of dewaxing mineral oils, the method of obtaining a base oil and a method of obtaining a base oil of lubricating oil capable of obtaining a base oil of lubricating oil and/or base oil fuel having good fluidity at low temperatures, with high yield.

Brief description of drawings

Figure 1 presents a diagram illustrating the composition of the cracking products.

In Fig. 2 is a diagram illustrating the composition of the cracking products.

In Fig. 3 shows the spectra is R XPS in the field of 2P orbitals of an atom of aluminum in the crystalline silicate.

In Fig. 4 shows XPS spectrum in the region of the 2P orbitals of an atom of aluminum in the crystalline silicate.

In Fig. 5 shows XPS spectrum in the region of the 2P orbitals of an atom of aluminum in the crystalline silicate.

In Fig. 6 shows an NMR spectrum with rotation under magic angle27Al crystalline aluminosilicate.

In Fig. 7 shows XPS spectrum in the region of the 2P orbitals of an atom of aluminum in the crystalline silicate.

In Fig. 8 shows XPS spectrum in the region of the 2P orbitals of an atom of aluminum in the crystalline silicate.

In Fig. 9 presents a graph of mass of the crystalline aluminosilicate.

In Fig. 10 presents a graph of mass of the crystalline aluminosilicate.

In Fig. 11 presents a graph showing the relationship between the conversion of normal paraffins and outputs isomers.

The best way of carrying out the invention

The catalyst hydroisomerization

The catalyst hydroisomerization according to the present invention is produced by calcination of a catalyst composition comprising processed by the method of ion exchange, molecular sieve or the calcined material, which is obtained by using ion-exchange molecular sieve containing an organic matrix, the solution containing the cationic fragments, and using water as the primary solvent and less is th least one metal selected from the group comprising metals belonging to groups 8-10 of the Periodic Table of the Elements, molybdenum and tungsten deposited on the treated by the method of ion exchange, molecular sieve or the calcined material.

In addition, the catalyst hydroisomerization according to the present invention in the case where the composition of the calcined catalyst contains material processed by the method of ion exchange, molecular sieve and a metal deposited on the calcined material, the calcined material is treated by the method of ion exchange, molecular sieve may be contained in the composition of the catalyst as a carrier obtained by annealing the composition of media containing processed by the method of ion exchange, molecular sieve, and the metal deposited on the calcined material may be contained in the composition of the catalyst in the form to be applied to the above media.

Molecular sieve containing an organic matrix, used as a starting material treated by the method of ion exchange, molecular sieve, is not specifically limited, as synthesized hydrothermally in the presence of organic matrix (sometimes called a synthetic molecular sieve). In the present invention the synthetic molecular sieve is predpochtite the flax zeolite.

The zeolite used in the present invention preferably has a porous structure containing a 10-membered ring or 8-membered ring, from the viewpoint of high isomerization activity and suppressed craterous steps in the reaction of isomerization of normal paraffins. In particular, as a zeolite having a pore structure that contains 10-membered ring, can be used AEL, EUO, FER, HEU, MEL, MFI, NES, TON, MTT, WEI and ZSM-48, and as a zeolite having a pore structure that contains 8-membered ring, can be used ANA, CHA, ERI, GIS, KFI, LTA, NAT, PAU, YUG and DDR. Here, a combination of three letters indicate the codes skeletal structure for structures classified zeolite-based molecular sieves, which are indicated by the Commission on the Structure of the International Association for the Zeolites of The Structure Commission of The International Zeolite Association). Zeolites which have the same topology, collectively relate to the code.

From the point of view of high isomerization activity and low kekirawa ability of the above preferred zeolites are zeolites having a TON structure with unidirectional pore structure containing a 10-membered ring zeolites having the MTT structure, and crystalline aluminosilicate ZSM-48. As the zeolite having a TON structure is preferred crystalline aluminosilicate ZSM-22, and as eolic, having MTT structure, the preferred crystalline aluminosilicate ZSM-23.

In the case when the synthetic molecular sieve is used crystalline aluminosilicate ZSM-22, ZSM-23 or ZSM-48, the molar ratio of [Si]/[Al] (hereinafter called the ratio of Si/Al) of silicon atoms to aluminum atoms in the crystalline aluminosilicate is preferably in the range from 10 to 400, more preferably in the range from 20 to 300. If the ratio Si/Al is less than the lower limit, the conversion of normal paraffins is high, but the selectivity of isomerization into ISO deteriorating. In addition, the cracking reaction, the accompanying increase in the reaction temperature increases. Therefore, the case when the ratio Si/Al is less than the lower limit is not preferable. If the ratio Si/Al is greater than the upper limit, it is difficult to obtain a catalyst is required for the conversion of normal paraffins. Therefore, the case when the ratio Si/Al is greater than the upper limit is not preferable.

Organic matrix used for the hydrothermal synthesis of the molecular sieve is selected in accordance with the structure of the synthesized molecular sieve. However, since the molecular sieve is typically synthesized in alkaline environment, predpochtitel the output is derived amine from the point of view of reducing the influence on the properties of synthetic raw materials.

In addition, the organic matrix is preferably selected from the group including alkylamino, alkylamino, alkilany, alliteration, pyrrolidine, piperazine, aminopiperidin, alkylbetaine, alkylguanine and their derivatives.

In General, after the hydrothermal synthesis of the molecular sieve, comprising the usual catalyst for catalytic dewaxing, calcined at a temperature of approximately 550º or above in a medium containing molecular oxygen to remove organic matrix contained in it. The temperature is chosen so as to remove the organic matrix of combustion. After annealing the conventional catalyst receive, through ion exchange, causing the metal component and activating annealing. On the other hand, the catalyst hydroisomerization of the present invention receives, through the above process of ion exchange in a solution containing the cationic fragments and water as the main solvent, and using the received processed by the method of ion exchange, molecular sieve.

Molecular sieve containing an organic matrix, according to the present invention may provide a molecular sieve, in which all organic matrix substantially removed during annealing. Namely, before the destruction of the organic matrix ion about the Yong calcination of synthetic molecular sieves can not hold, or even when the annealing is performed in the annealing may be conditions when all organic matrix essentially burn and removed, especially in high temperature conditions. When the annealing synthetic molecular sieve is carried out in a medium containing molecular oxygen, the preferred temperature annealing at approximately 500º or below, 450º or below is preferable, and 400ºC or below is more preferable, so that all the organic matrix is essentially not removed by annealing. In the present invention most preferably before removal of the organic matrix of the ion exchange calcination of synthetic molecular sieves did not spend at all.

If the annealing synthetic molecular sieve is carried out in conditions when all organic matrix essentially burn and removed before removal of the organic matrix of the ion exchange properties of the catalyst according to the present invention, such as sufficiently high isomerization activity, repressed kekirawa activity, high selectivity to multiresolution the isomer or a lower coefficient CIoin the reaction of isomerization of normal paraffins in the presence of hydrogen can be achieved. It is also considered why the WMD, one reason is that the temperature of the synthetic molecular sieve is much higher than the ambient temperature due to heat generated during combustion of the organic matrix, so that the structure of the molecular sieves can be changed under the action of high temperature flow generated by the combustion of the organic matrix.

Past treatment ion exchange, molecular sieve according to the present invention obtained by using ion-exchange synthetic molecular sieve containing an organic matrix, the solution containing the cationic fragments and involving the use of water as a main solvent.

Here the use of water as a main solvent" means that the water content is 50% by weight. or more relative to the total amount of the solvent in the solution. In the present invention, the water content is preferably 70% by weight. or more and more preferably 100 wt.%.

In addition, when the solution contains an organic solvent, its content is less than 50% wt. relative to the total amount of the solvent in the solution, more preferably 30 wt.%. or less. If the content of organic solvent is 50% by weight. or more, when the connection is used, providing a cationic ion fragments for about the MENA, the solubility of the compound in the solvent may deteriorate. Therefore, it is most preferable that the organic solvent contained in the solution.

The inventors have accidentally discovered that in U.S. patent No. 5143879 disclosed a method of performing ion exchange, molecular sieve containing an organic matrix synthesized in the state in the solution containing the specific polar non-aqueous solvent containing the cation to remove and recover the organic matrix of the molecular sieve without burning expensive organic matrix.

However, when the primary solvent in the solution used to make ion exchange is not water, and an organic solvent, the catalyst hydroisomerization, consisting of the obtained processed by the method of ion exchange, molecular sieve, it is difficult acquires the properties of the obtained catalyst according to the present invention, that is high enough isomerization activity, suppressed sufficiently craterous ability and selectivity to the highly branched isomer in the reaction of isomerization of normal paraffins in the presence of hydrogen. Although the reasons for this are not fully understood, but, as described in the following example, the process of ion exchange in a solution containing organizes the second solvent as a main solvent, it is believed that a suitable amount of organic matrix contained in the molecular sieve having a pore structure and containing 10-membered ring or 8-membered ring, not so easy to remove, and/or that a sufficient number of ions of an alkali metal, i.e., the counterions, usually contained in the molecular sieve synthesized using hydrothermal synthesis, not easily removed.

In molecular sieve hydrothermal synthesis of cations of alkali metal or alkaline earth cations of the metal exist as counterions. In the above ion exchange data counterions enter into ion exchange and organic matrix is simultaneously removed in a suitable manner.

Cationic fragments contained in the solution using water as a main solvent is not limited specifically to one type, but can be used in a variety of cationic fragments. In the catalyst according to the present invention, from the point of view of education important centres acid Bronsted, preferred is ammonium ion or proton. In the case when the cationic fragment is used proton typically use an inorganic acid such as hydrochloric acid, sulfuric acid, and acetic acid. In addition, molecular sieve ammonium type, obtained Jonny the exchange in the presence of ammonium ions, the ammonia during the annealing of the catalytic composite. As a result, protivoatomnom becomes a proton, and so formed the centres acid Branstad. Connection to ensure the delivery of ammonium ions in the solution is ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium acetate or other inorganic and organic ammonium salts. In the most preferred embodiment of the present invention the cationic fragment ion is ammonium. The content of cationic fragments in solution, preferably selected in the range from 10 to 1000 equivalents in the calculation of the sum of the quantities of organic matrix and counterion contained in the used molecular sieve.

Preferably the ion exchange is carried out, plunging powder synthetic molecular sieve, a molded body of synthetic molecular sieves, or a molded body of a mixture of synthetic molecular sieve and a binder in a solution containing the cationic fragments and involving the use of water as a main solvent, preferably an aqueous solution, and shaking or stirring the mixture.

In addition, the shaking or mixing is preferably carried out by heating to increase the overall efficiency is ü ion exchange. According to the present invention it is preferable that the ion exchange was carried out at boiling under reflux by heating an aqueous solution containing a cationic fragments.

In addition to the aforementioned conditions, the time interval of ion exchange is preferably approximately from 1 hour to 24 hours. From the point of view of efficiency of ion exchange and economic efficiency, the amount of solution in contact with a synthetic molecular sieve is preferably a value in the range from 0.01 to 10 liters per 1 g of synthetic molecular sieves. In addition, from the viewpoint of increasing the efficiency of ion exchange in the process of ion exchange synthetic molecular sieves in solution, preferably, the solution was replaced with fresh solution once or twice, or several times. More preferably, the solution was replaced with fresh solution once or twice. When the solution is replaced once, for example, by immersing the synthetic molecular sieves in a solution containing the cationic fragments and involving the use of water as a main solvent, by heating and boiling the resulting mixture for 1 to 6 hours under reflux, the replacement of the solution with fresh solution and by heating and boiling under reflux in t the value of 6-12 hours, the effectiveness of ion exchange may be increased.

Preferably processed by the method of ion exchange, molecular sieve extracted by filtration, washed with deionized water and dried at a temperature of from about 60 to 130 º C for about 10-48 hours.

At least one metal that is selected from the group comprising metals included in groups 8-10 of the Periodic Table of the Elements, molybdenum and tungsten, is applied on the treated by the method of ion exchange, molecular sieve or the calcined material. The preferred metals belonging to groups 8-10 of the Periodic Table of Elements are iron, ruthenium, osmium, cobalt, rhodium, iridium, Nickel, palladium and platinum. Next, from metals, from the point of view of activity, selectivity and duration of action, preferred are platinum and/or palladium, and more preferred is platinum. As a single metal or a combination of two or more metals selected from the group comprising metals included in groups 8-10 of the Periodic Table of Elements, can be used molybdenum and tungsten.

In addition, when the catalyst hydroisomerization according to the present invention used to hydroisomerization mineral oils containing large amounts of sulfur-containing soy is ineni and/or nitrogen-containing compounds, from the point of view of the duration of catalytic activity should preferably be treated by the method of ion exchange, molecular sieve or the calcined material was applied a combination of metals, such as Nickel-cobalt, Nickel-molybdenum, cobalt-molybdenum-cobalt, Nickel-molybdenum and Nickel-tungsten-cobalt.

As a method of coating metal on the treated by the method of ion exchange, molecular sieve or the calcined material may be used any of well-known techniques such as impregnation method (method equilibrium absorption, the method of filling the pores or method initial wetting) and the method of ion exchange. A compound containing a metal component used in this case is the hydrochloride, sulfate, nitrate or metal complexes. In addition, a compound containing platinum, are chloride of platinum, tetraammineplatinum, dinitroaniline and tetraaminopyrimidine.

The amount of metal applied on the treated by the method of ion exchange, molecular sieve or the calcined material is preferably a value in the range of from 0.001 to 20 wt.%. in calculating the masses treated by the method of ion exchange, molecular sieve or the calcined material. If the applied amount is less than the lower limit, it is difficult to get given the Yu ability hydrogenation/dehydrogenization. If the damage amount is greater than the upper limit, it is easy to proceeds the formation of lighter hydrocarbons due to cracking in the metal, so that the yield of the desired fraction can be reduced. In addition, it may increase the cost of the catalyst.

With regard to the conditions of calcination of the catalyst composition containing processed by the method of ion exchange, molecular sieve or the calcined material and the metal deposited on the treated by the method of ion exchange, molecular sieve or the calcined material, the temperature lies in the range from 250º up to 600ºC and more preferably from 300 to 500º in an environment containing molecular oxygen. With regard to the environment containing molecular oxygen, it may be gaseous oxygen, gaseous oxygen diluted with an inert gas, such as nitrogen, and air. The time of annealing is usually a value in the range from about 0.5 to 20 hours. In the process of annealing a compound containing a metal component deposited on the treated by the method of ion exchange, molecular sieve or the calcined material is converted into elemental metal, its oxide or similar material, so that the catalyst becomes a normal activity for the isomerization of paraffins. If the temperature of annealing deviates from above the second interval, the catalyst activity and selectivity can be sufficient.

In addition, when the organic matrix remains in the molecular sieve treated by an ion exchange method, the residual organic matrix can be completely removed by annealing in the above-mentioned process of roasting. Further, in the present invention the organic matrix can be removed sufficiently by annealing at a relatively low temperature. It is believed that this is due to the fact that the metal having catalytic activity in oxidation reactions, are treated by the method of ion exchange, molecular sieve according to the present invention, so that the oxidation reaction (combustion) of organic matrix can proceed at lower temperatures due to the nature of its course.

In addition, when processed by the method of ion exchange, molecular sieve is a molecular sieve ammonium type, during the process of calcination of the ammonium counterion forms ammonia and a proton, and so formed the centres acid Branstad.

According to the present invention it is preferable that after calcination the catalyst hydroisomerization was subjected to a reducing treatment at a temperature of preferably from 250 to 500º, more preferably from 300 to 400ºC in the rede, containing molecular hydrogen, for about 0.5-5 hours. Such processes can be more reliably give high catalyst activity at the dewaxing of mineral oil.

In the catalyst hydroisomerization according to the present invention it is preferable that the catalyst composition was molded into a predefined shape. A sample form is cylindrical, the shape of the tablets, the spherical shape and form heteromorş cylinder having triplochiton/four-plane cross-section. When the catalyst composition is formed into such a shape, the catalyst obtained from this calcination, may have an increased mechanical strength. In addition, it facilitates the transport of the catalyst can be reduced, the pressure loss of the reaction liquid during the reaction. The molding compositions of the catalyst can be carried out using well known methods.

In the composition of the catalyst, the content processed by the method of ion exchange, molecular sieve or the calcined material is in the range preferably from 1 to 90 wt.%. and more preferably from 10 to 80 wt.%. in the calculation of the total amount of the composition of the catalyst.

In addition, from the viewpoint of improving the forming ability of the catalyst and the mechanical strength of the molded ka is alistore, the catalyst composition preferably includes at least one porous oxide selected from the group including aluminum oxide, silicon dioxide, titanium oxide, boron oxide, magnesium oxide and zirconium oxide. In this case, in the composition of the catalyst component, the proportion treated by the method of ion exchange, molecular sieve or the calcined material and the porous oxide is preferably from 1 to 90 parts by weight and 99 to 10 parts by weight, more preferably from 10 to 80 parts by weight and 90 to 20 parts by mass.

When the porous oxide is contained in the composition of the catalyst, the carrier comprising a carrier composition containing processed by the method of ion exchange, molecular sieve and a porous oxide, may be molded to the deposition of the metal on the treated by the method of ion exchange, molecular sieve, and alternatively, may be molded mixture treated by the method of ion exchange, molecular sieve, which is applied to the metal, and the porous oxide. In the present invention, it is preferable to the first method. Namely, it is preferable that after the synthetic molecular sieve containing an organic matrix was subjected to ion exchange in a solution containing the cationic fragments and providing water quality the ve primary solvent, was molded carrier composition, obtained by blending processed by the method of ion exchange, molecular sieve, porous oxide, and if necessary, other binder components. In addition, it is preferable that the obtained molded body was calcined at a temperature of from about 500º up to 600ºC in a medium containing molecular oxygen, in order to obtain the acidity of the solid porous oxide.

In the catalyst hydroisomerization according to the present invention of metals, non metals of groups 8-10 of the Periodic Table of the Elements, molybdenum and tungsten, may be deposited on the molecular sieve treated by an ion exchange method, or calcined material in an amount not impairing the effects of the present invention. In addition, in the case where the catalyst composition contains a porous oxide, metals, non metals of groups 8-10 of the Periodic Table of the Elements, molybdenum and tungsten, may be deposited on the treated by the method of ion exchange, molecular sieve or the calcined material and/or a porous oxide.

In the catalyst hydroisomerization according to the present invention in the case where a synthetic molecular sieve used as the starting material of the catalyst is a crystalline aluminosilicate ZSM-22, the index limit is of CIº, defined as follows, has a value of from about 7 to 12, more preferably from 7 to 11.

Code restrictions: molar ratio of 2-methylnonane to 5-methylnonane that occurs when the output of isodecanol is 5% wt. in reaction contact between the normal of the Dean, turning into sodetani in the presence of hydrogen, with a catalyst hydroisomerization.

The above constraint index CIº less than the same indicator of the conventional catalyst, which can be obtained by using synthetic molecular sieves of the same type, and the value of the constraint index CIº can be achieved above the ion exchange according to the present invention. The above-mentioned catalyst hydroisomerization is advantageous for reducing the dew point of the base oil, such as a base lubricating oil or base oil fuel, which is produced by the catalytic dewaxing of mineral oils containing paraffin component.

In addition, the catalyst hydroisomerization according to the present invention in the case where a synthetic molecular sieve used as the starting material of the catalyst is a crystalline aluminosilicate ZSM-23, videopreteen constraint index CIº is preferably in the range of values from 3.0 to 4. Constraint index CIº also less than the same indicator of the conventional catalyst, which can be obtained by using synthetic molecular sieves of the same type, and the value of the above index restrictions CIº can be achieved above the ion exchange according to the present invention. The above-mentioned catalyst hydroisomerization is advantageous for reducing the dew point of the base oil, such as a base lubricating oil or base oil fuel, which is produced by the catalytic dewaxing of mineral oils containing paraffin component.

In addition, the catalyst hydroisomerization according to the present invention in the case where a synthetic molecular sieve used as the starting material of the catalyst is a crystalline aluminosilicate ZSM-48, videopreteen constraint index CIº is preferably in the range of values from 1.1 to 5.1. Constraint index CIº also less than the same indicator of the conventional catalyst, which can be obtained by using synthetic molecular sieves of the same type, and the value of the above index restrictions CIº can be achieved above the ion exchange according to the present invention. The above-mentioned catalyst hydroisomerization is Ave the property to reduce the dew point of the base oil, such as a base lubricating oil or base oil fuel, which is produced by the catalytic dewaxing of mineral oils containing paraffin component.

The method of producing catalyst hydroisomerization

The method of producing catalyst hydroisomerization according to the present invention may include a process (a) obtaining processed by the method of ion exchange, molecular sieve implementation of ion exchange, molecular sieve containing an organic matrix, the solution containing the cationic fragments and involving the use of water as the primary solvent; (b) applying at least one metal that is selected from the group comprising metals of groups 8-10 of the Periodic Table of the Elements, molybdenum and tungsten on a carrier containing processed by the method of ion exchange, molecular sieve obtained in the process (a), and process (C) calcination of the composition the catalyst containing the medium obtained in the process (b).

In process (a) is preferably used the same molecular sieve containing an organic matrix, the same solution for ion exchange containing cationic fragments and involving the use of water as a main solvent, and the same conditions of ion exchange, as discussed in the explanation of the catalyst gidrozo is erinacei according to the present invention.

In process (b) can be used a carrier obtained by forming processed by the method of ion exchange, molecular sieve obtained in the process (a). However, in an alternative case, it is preferable that the carrier was obtained by molding a mixture processed by the method of ion exchange, molecular sieve obtained in the process (a)at least one porous oxide selected from the group including aluminum oxide, silicon dioxide, titanium oxide, boron oxide, magnesium oxide and zirconium oxide, and, if necessary, other connecting components. The molded body is preferably calcined at a temperature of from about 500º up to 600ºC in a medium containing molecular oxygen.

In process (b) is preferably used the same metal and the method of its application, as discussed in the explanation of the catalyst hydroisomerization according to the present invention.

In process (C) is preferably used the same conditions of annealing, as discussed in the explanation of the catalyst hydroisomerization according to the present invention. In addition, preferably after the process (C) to carry out the above recovery process described on catalyst hydroisomerization according to the present invention.

As described above, in General, after the hydrothermal synthesis of molecular to the fact, constituting a conventional catalyst for catalytic dewaxing, calcined at a temperature of approximately 550º or above in a medium containing molecular oxygen, to remove the contained organic matrix. After calcinations carry out ion exchange. On the other hand, in the catalyst hydroisomerization according to the present invention is processed by the method of ion exchange, molecular sieve, the obtained ion-exchanged molecular sieve containing an organic matrix, the solution containing the cationic fragments and involving the use of water as a main solvent, is used as a constituent material.

Here, when the crystalline aluminosilicate is used as a synthetic molecular sieve, may be structural differences between treated by the method of ion exchange, molecular sieve, comprising the usual catalyst obtained by removing the organic matrix by annealing and subsequent implementation of the process of ion exchange, and processed by the method of ion exchange, molecular sieve according to the present invention in the following.

(1) In the case of conventional catalyst the atomic ratio of silicon/aluminum on the surface of the crystalline aluminosilicate obtained by x-ray photoemission with whom ctroscopy (XPS), is reduced in comparison with the same parameter for synthetic molecular sieves. However, in the molecular sieve treated by an ion exchange method according to the present invention the reduction of the atomic ratio of silicon/aluminum can be suppressed.

(2) In the case of the conventional catalyst, regarding the signal of the 2P orbital of aluminum on the surface of the crystalline aluminosilicate in the XPS results, the intensity of the signals belonging to Al (V) and/or Al(VI)tends to increase. However, in the treated by the method of ion exchange, molecular sieve according to the present invention this tendency to increase can be suppressed.

(3) In the case of conventional catalyst chemical shift (upper position) spectrum analysis27Al NMR in rotating under magic angle change in the direction of lower magnetic field, and the width of the signal is reduced. However, in the molecular sieve treated by an ion exchange method according to the present invention this phenomenon can be suppressed.

In addition, (3) aluminum atoms in the crystalline aluminosilicate may exist in different T centers, and data signals can generally be treated as United and observed in the form of a single signal in the NMR spectrum. In the normal process of roasting the change in chemical shift in the upper position signals which can be regarded as reflecting the that the ratio of aluminum atoms present in the various T have changed. In addition, the narrowing of the width of the signal can be considered that the effect of shielding of resonant frequency was weak. In any case, the inventors believe that there are atoms of aluminum in the environment, different from what exists in the molecular sieve at the moment of synthesis, or there is a change in percentage of atoms of aluminum in many different environments. In the method of obtaining processed by the method of ion exchange, molecular sieve according to the present invention this change aluminum fragments can be considered depressed.

Method for the production of base oils

A method of obtaining a base oil according to the present invention includes obtaining a base oil of lubricating and/or base oil fuel-based hydrogenation process of implementation of contact interaction of mineral oil containing normal paraffins, with the above catalyst hydroisomerization according to the present invention in the presence of hydrogen. Examples of the base oil, fuel oil, kerosene and gasoline. Examples of the base oil lubricants are lubricants lubricants for use in automobiles, transportation, industrial applications, for use in f is h in aviation.

Mineral oil used as raw material, can be appropriately selected according to the use of the obtained base oil. When you must obtain a base oil of lubricating and/or base oil, gas oil, as the source of the oil is preferably used mineral oil containing normal paraffins having 10 or more carbon atoms. Normal paraffins containing 10 or more carbon atoms, degrade the low temperature fluidity of the base lubricating oil or base oil gasoil. However, the method of obtaining a base oil according to the present invention can be obtained base oil of the lubricant and/or base oil gasoil with good fluidity at low temperatures with high yield from a mineral oil containing normal paraffins having 10 or more carbon atoms. In addition, in order to effectively implement the basic lubrication oil and/or base oil, gas oil, preferably as a source of oil was used mineral oil containing a hydrocarbon having a boiling point exceeding 230º, preferably greater than 315º, and content of 50% wt. or more, preferably 70 wt.%. or more and more preferably 90 wt.%. or more.

In addition, preferably, the method of obtaining the gas oil according to the present invention, used to obtain a base oil or base oil of the lubricant and base oil, gas oil, original oil contains mineral oil having an initial boiling point greater than the initial boiling point of the desired base oil of the grease. As an example of the original oil is suitable fraction having the boiling point under normal pressure in excess of 360º, such as a gasoline fraction and a synthetic oil or paraffin. In particular, there is a heavy gas oil, vacuum gas oil, purified lubricating oil, light wrap, paraffin GAC (coarse wax), restored paravenously raw materials, non-greasy wax, paraffin wax on the base, microcrystalline wax, petrolatum, synthetic oil, synthetic wax, Fischer-Tropsch, a polyolefin with a high dew point and paraffin-based linear α-olefin. These materials can be used individually or in combination of two or more of them. In addition, the data of the original oil are preferably gidrirovanie or mildly hydrocracked. Due to data processing materials, deteriorating the activity of the catalyst hydroisomerization, such as sulfur-containing compounds and nitrogen-containing compounds, and materials that reduce viscosity index base oils and lubricants, such as aromatics is their hydrocarbons and naphthenic hydrocarbons, can be restored or deleted.

The above-mentioned relatively heavy mineral oil is used as a source of oil and are in contact with mineral oil with a catalyst hydroisomerization according to the present invention in the presence of hydrogen, so that it may be carried out isomerization of normal paraffins contained in the mineral oil, the reaction dewaxing of mineral oil with simultaneous sufficient suppression of the formation of lighter fractions. As a result, it is possible to obtain a high yield of base oil in which the content of the fraction with the boiling point at normal pressure exceeding 360º is 90% wt. or more. In addition, according to the method of obtaining a base oil of the present invention, it is possible to obtain a base oil containing a large number of isomers having a branched chain structure. In particular, in the base oil of high quality lubricating oil content of normal paraffins should be 0.1% wt. or less, and it is possible to obtain a high yield of base oil lubricants that meet AYP, according to the method of obtaining a base oil of the present invention.

In addition, according to the method of obtaining a base oil really the image the structure, as can be derived base oil containing a large number multiresolution isomers of the above-mentioned original oil you can get a base oil of lubricating oil having good fluidity at low temperatures, with good profitability.

In addition, according to the method of obtaining a base oil of the present invention, since the base oil contains a large number of isomers that have a large number of branched chains in the inner position of the main chain of the above-mentioned original oil you can get a base oil of lubricating oil having good fluidity at low temperatures, with good profitability. In particular, when the catalyst hydroisomerization obtained using at least one crystalline aluminosilicate selected from the group comprising ZSM-22, ZSM-23 and ZSM-48 as synthetic molecular sieves, you can easily achieve the above effects.

In the method of obtaining a base oil according to the present invention can be divided suitable to achieve the goal base oil by distillation of the product obtained after the process of hydroisomerization.

For example, can be obtained fraction having the boiling point under normal pressure of from 170 to 360º, in the form of a base oil gasoil. As you described the e, according to the method of obtaining a base oil of the present invention, as can be derived base oil having a large number multiresolution isomers, it is possible to obtain fractions with such good characteristics as a small quantity of the component on the basis of normal paraffins and good fluidity at low temperatures.

In addition, a method of obtaining a base oil of the present invention can be applied for the production of base oil, gas oil, the main target of the product is base oil gasoil. In this case, it is preferable to use more light mineral oil as raw material than mineral oil that is used to obtain the base lubricating oil or base oil of the lubricant and base oil gasoil. In particular, mineral oil preferably contains 50% by weight. or more, preferably 70 wt.%. or more, more preferably 90 wt.%. or more hydrocarbon having the boiling point under normal pressure of from 230 to 800º.

In the hydrogenation process of the method of obtaining a base oil according to the present invention it is preferable that the reaction temperature was usually in the range from 200 to 450º, preferably from 220 to 400ºC. If the reaction temperature is lower than the lower limit, it is difficult to implement isomer is tion of normal paraffins, contained in raw materials, mineral oil, so that the paraffin component is not sufficiently restored or deleted. On the other hand, if the reaction temperature is above the upper limit, mineral oil is commonly Criciuma, so that the yield of the target base oil is reduced.

In the process of hydrogenation pressure of the reaction is usually in the range from 0.1 to 20 MPa, preferably from 0.5 to 15 MPa. If the pressure of the reaction is lower than the lower limit, the rapid destruction of the catalyst due to the formation of coke. On the other hand, if the pressure of the reaction exceeds the upper limit, because of the increased construction cost of the equipment is difficult to achieve the desired technical and economic indicators of the process.

In the hydrogenation process the volumetric rate of liquid mineral oil to the catalyst is usually in the range from 0.01 to 100 h-1preferably from 0.1 to 50 h-1. If the volumetric rate of the liquid raw material is below the lower limit, it is easy runs excessive cracking of mineral oil, so that the profitability of the target base oil is reduced. On the other hand, if the volumetric rate of liquid raw material exceeds the upper limit, it is difficult for the process of isomerization of normal paraffins contained in the mineral oil, so that the paraffin to the ponent is not enough recovered or removed.

In the process of hydrogenation ratio at the input of hydrogen and mineral oils typically lies in the range from 100 to 1000 Nm3/m3preferably from 200 to 800 Nm3/m3. If the value on the input is below the lower limit, i.e. when the original oil contains sulfur-containing or nitrogen-containing compounds, a predetermined catalytic effect is difficult to obtain due to the fact that gaseous hydrogen sulfide or ammonia formed by the reaction of desulfuromonas or reaction denitrogenization flowing together with the reaction of isomerization, is absorbed on the active metals on the catalyst. If the value on the input exceeds the upper limit, it is difficult to achieve the necessary economic indicators of the process, because it requires the installation for the production of hydrogen, which has more power.

In the process of hydrogenation conversion of normal paraffins appropriately regulated depending on the field of use of the base oil.

In the process of production of base oils and lubricants in accordance with the present invention, the base oil of the grease get making contact with mineral oil containing normal paraffins having 10 or more carbon atoms, with a catalyst hydroisomerization in conditions, when the conversion of normal paraffins, defined by the SL is blowing equation 1, is essentially 100 wt.%.

Conversion of normal paraffins (% wt.)=[1-(Total weight of Cn or more normal paraffins contained in the mineral oil after contact interaction)/(Total mass of Cn or more normal paraffins contained in the mineral oil to the contact interaction)]×100 (1).

In equation 1 Cn denotes the minimum number of carbon atoms in the normal paraffins having 10 or more carbon atoms included in mineral oil to the contact interaction.

Here the conversion is essentially 100 wt.%" means that the content of normal paraffins in mineral oil after contact interaction is 0.1% wt. or less.

If hydroisomerization mineral oil containing normal paraffins, the conversion of normal paraffins usually rises, for example, increasing the reaction temperature, so that the content of normal paraffins in the resulting reaction product can be reduced. Accordingly, it is possible to improve the low temperature fluidity of mineral oil. However, if the reaction temperature is increased, accelerating the reaction of cracking mineral oil feedstock and product isomerization, so increasing the proportion of light fraction according to the increase in conversion of normal paraffins. As an increasing proportion of light fraction result is deterioration of the viscosity index mineral oil, it is necessary to separate a light fraction and remove by distillation or the like, to control the operational characteristics of the base oil of the lubricant in a given interval. In particular, in the case where such a high amount of base oil of the lubricant, as indicated by the group III+ in accordance with the classification of grades of lubricating oils of the American Petroleum Institute, is using catalytic dewaxing of mineral oil, the conversion of normal paraffins contained in the raw materials, mineral oil, should be essentially 100%. In the method of obtaining a base oil lubrication using conventional catalyst for catalytic dewaxing conditions when the conversion of normal paraffins is essentially 100%, the output of such a base oil of high quality lubrication is very low. However, according to the production method of the base lubricating oil of the present invention, although the process of hydrogenation is carried out in conditions where the conversion of normal paraffins is essentially 100%, the output of such a base oil of high quality lubricating oil can be maintained at a high level.

Installations for the production of base oils by the method according to the present invention is not limited to one specific type, but can be used well-known installation with regard to the reaction of the installation, it can be used any continuous, periodic, and properities actions. However, from the viewpoint of productivity and efficiency, it is preferable to install a continuous action. As the catalytic layer may be used any of such as a fixed layer, active layer and the mixed layer. However, from the point of view of the cost of installation is preferred fixed bed. As the reaction phase is preferred gas-liquid mixed phase.

In the method of obtaining a base oil of the present invention, as a preliminary stage of the hydrogenation process, mineral oil, supply of raw materials may be subjected to the hydrogenation process or process hydroprocessing. Installation, catalysts and reaction conditions well known in the related fields. In undertaking this preliminary stage, it is possible to more a long time to maintain the catalyst activity of hydroisomerization according to the present invention, and can be reduced content of such environmentally hazardous materials, such as sulfur-containing compounds and nitrogen-containing compounds contained in the recovered product.

In addition, in the method of obtaining a base oil according to the present invention the reaction product obtained during hydrogenation, additionally may be subjected, for example, Hydrotreating. Hydrotreating can be making contact hydrochidae material with a hydrogenation catalyst coated metal (for example, aluminum oxide coated with platinum) usually in the presence of hydrogen. Hydrotreating can be improved color and resistance to oxidation of the reaction products obtained in the hydrogenation process, so that you can improve the quality of the products. Hydrotreating can be done in settings other than the settings for the hydrogenation process. A catalytic layer for Hydrotreating may be located downstream from the catalytic layer of the catalyst hydroisomerization according to the present invention, which is located in the reactor for the hydrogenation process, so that the Hydrotreating is carried out after the process of hydroisomerization.

By the way, the isomerization is usually specified reaction changes the molecular structure without changing the number of carbon atoms (molecular weight), and called cracking reaction, accompanied by a decrease in the number of carbon atoms (molecular weight). In the reaction of catalytic dewaxing, based on the use of isomerization reactions, to some extent proceeds cracking source of hydrocarbons and isomerization products. However, until the number of carbon atoms (Molek is popular weight) of the products of the cracking is within a predetermined allowable range, corresponding to the desired base oil, the cracking products may be components that are included in the base oil.

Method of dewaxing mineral oil

Next, we consider a method of dewaxing mineral oils according to the present invention. Method of dewaxing mineral oils according to the present invention includes the process of converting part or all of the normal paraffins into ISO when in contact with mineral oil containing normal paraffins with a catalyst hydroisomerization according to the present invention in the presence of hydrogen.

Mineral oil, used for the method for dewaxing mineral oils according to the present invention is not limited to any particular, but they can be any mineral oil containing normal paraffins. Mineral oil may contain normal paraffins, preferably having 10 or more carbon atoms, more preferably 15 or more carbon atoms. In particular, there can be used various materials from relatively light distillate such as kerosene and jet fuel to the high-boiling of the original oil, such as all crude oil, residual oil obtained by distillation of crude oil under normal pressure, the residual oil vacuum distillation, the residual is oil distillation under reduced pressure, the re-circulating oil, synthetic crude oil (e.g., shale oil and tar), gas oil, vacuum gas oil, deparaffinization oil, fuel or paraffin fraction fraction formed from synthetic waxes, Fischer-Tropsch, and others, such as heavy oil. In addition to the normal paraffins such mineral oil may contain a wax component, derived from naphthenic hydrocarbon or aromatic hydrocarbon containing long-chain alkyl group in the side chain.

As mineral oil, which deparaffinizing method of dewaxing mineral oils according to the present invention, particularly preferred is a mineral oil consisting of a hydrocarbon having a boiling point above 180ºC or higher and containing 10 or more carbon atoms. In General, because more light mineral oil essentially does not contain a wax component, which affects the fluidity at low temperatures, there is no need to deparaffinizing mineral oil, and the positive effects of the present invention is difficult to achieve.

On the other hand, the method of dewaxing according to the present invention can be particularly effectively used for the original oil distillate containing a wax component, then eats the original oil middle distillate, including gasoil, kerosene and jet fuel, a source of oil for lubricating oils, heating oils and other distillate fraction, dew point and viscosity need to be maintained within a given interval. As for the above-mentioned mineral oil, there is a gas oil, which is subjected to the process of hydrogenation or hydrocracking of heavy gas oil, vacuum gas oil, lube oil raffinate, source oil for lubricating oil, light wrap, paraffin GAC (coarse wax), the recovered paraffin oil, low-fat wax, paraffin wax on the base, microcrystalline wax, petrolatum, synthetic oil, wax, obtained by the method of Fischer-Tropsch, a polyolefin with a high dew point, paraffin-based linear α-olefin. These materials can be used individually or in combination of two or more of them.

In the method of dewaxing mineral oils according to the present invention the reaction conditions to convert at least part of normal paraffins into ISO can be set similar to those for the above method of obtaining a base oil according to the present invention.

Examples

Below the present invention is described in more detail by examples. However, the present invention is not ogran is constrained by the examples.

Evaluation of catalyst in the model reaction using n-decane

Preparing the catalyst according to the following method, and their catalytic activity was evaluated in a model reaction using n-decane.

1. Obtaining catalyst

1-1. Obtaining crystalline aluminosilicate

1-1-1. Getting ZSM-22

7 types of crystalline aluminosilicate ZSM-22 having a ratio Si/Al from 30 to 480, obtained by the method of hydrothermal synthesis using the composition of the source materials listed in table 1, according to the method, opened in the document (ERNST, S. Et al., Appl. Catal. 1989, 48, 137). Example obtain ZSM-22 having a ratio Si/Al 45, discussed in detail below.

First, 4 types of aqueous solutions was prepared as follows.

Solution A: a solution obtained by dissolving 3.9 g of potassium hydroxide in 13.5 ml of deionized water.

Solution: solution prepared by dissolving 1.8 g of 18-hydrated aluminum sulfate in 10 ml of deionized water.

Solution: the solution obtained by dissolution of 8.4 g of 1,6-hexanediamine (organic matrix) in 65 ml of deionized water.

Solution D: solution prepared by dissolving 36 g of colloidal silica (Ludox AS-40, produced by Grace Davison Co.) in 62 ml of deionized water.

Then the solution was added to the solution, and stirring was continued up until the aluminum to the ponent did not dissolve completely. To the mixed solution was added to the solution C. Then, under vigorous stirring at room temperature the mixture of solutions a, b and C was poured into a solution of d 0.1 g powdered ZSM-22, which is synthesized separately and are not subjected to any specific treatment, was added as a "seed crystal" to accelerate crystallization.

The gel-like material obtained according to the above method, were divided roughly into two parts. Each part was placed in a stainless steel autoclave having an inner volume of 120 ml the Reaction was carried out in a thermostat at a temperature of 150 º C for 60 hours, during which the reactor itself, the autoclave was rotated with a speed of approximately 60 rpm After the reaction, the reactor was cooled and the formed solid product was filtered, washed with deionized water and dried overnight in a drying chamber at 60 º C, resulting in a received ZSM-22 having a ratio Si/Al 45.

In addition, by the same method synthesized 6 other types of ZSM-22 having different relations Si/Al, except that change mixed number 18-hydrated aluminum sulfate.

Table 1
Source material The ratio of Si/Al (mol/mol)
30456075100350480
Mixed amount (g)Deionized water151151151151151151151
Colloidal silica (Ludox AS-40)36,036,036,036,036,036,036,0
The potassium hydroxidea 3.9a 3.9a 3.9a 3.9a 3.9a 3.9a 3.9
1,6-hexanediamine8,48,48,48,48,4 8,48,4
18-hydrated aluminum sulfate2,71,81,31,10,80,20,2
ZSM-22 (seed crystal)0,10,10,10,10,10,10,1

1-1-2. Obtaining crystalline aluminosilicate ZSM-23

Crystalline aluminosilicate ZSM-23 having a ratio Si/Al 45, was obtained by hydrothermal method of synthesis according to the method of example 2 disclosed in U.S. patent No. 4490342.

First, the synthesized organic matrix Diguat-7 (dibromide N,N,N,N',N',N'-HEXAMETHYL-1,7-diaminoheptane) by using the method of example As described in U.S. patent No. 4490342. Namely, in a round-bottom flask was mixed with 50 g of 1,7-dibromethane and 100 ml of ethanol under stirring was added 70 g of triethylamine (33% wt. ethanol solution), the solution was heated and boiled in a flask with reflux during the night. The reaction product was cooled in an ice-water environment, and the precipitated crystals were filtered. Chris is allicance the residue was washed simple diethyl ether and dried at room temperature, resulting required Diquat-7 (dibromide).

ZSM-23 was synthesized in the following manner using the obtained Diquat-7.

First, there are 2 types of solutions were prepared as follows.

Solution E: a solution obtained by dissolving 15 g of colloidal silica (Ludox HS-40, produced by Grace Davison Co.) 31.6 ml of deionized water.

Solution F: a solution obtained by mixing 48,3 ml of deionized water, 0,218 g of sodium aluminate, 12 g of sodium hydroxide, 0.9 g of sulfuric acid and 2.7 g of salt Diquat-7.

Then the solution F was poured into a solution of E with stirring. The obtained gel-like material was transferred into a reactor autoclave of stainless steel having an internal volume of 120 ml the Reaction was carried out in a thermostat at a temperature of 160º within 72 hours, during which the reactor itself, the autoclave was rotated with a speed of approximately 60 rpm After the reaction, the reactor was cooled, and the resulting solid residue was filtered, washed with deionized water and dried overnight in a drying Cabinet at a temperature of 60 ° C in the resulting received ZSM-23 having a ratio Si/Al 45.

1-2. Ion exchange of the crystalline aluminosilicate.

Each of the synthesized ZSM-22 (ratio Si/Al=30, 45, 60, 75 100, 350, 480) and ZSM-23 (the ratio Si/Al=45) were subjected to ion exchange in a state where the contained organic matrix, and ion is bmenu after removal of the organic matrix by annealing, respectively.

1-2-1. Ion exchange in the presence of organic matrix

Each of the obtained 7 types of powdered ZSM-22 and one type ZSM-23 were loaded into the flask was added 100 ml of 0.5 M aqueous solution of ammonium chloride per 1 g of the crystalline aluminosilicate, and within 6 hours was carried out by heating and boiling in the flask with reflux condenser. The resulting product was cooled to room temperature, and the upper solution was removed. Crystalline aluminosilicate was washed with deionized water. To it was added the same amount of 0.5 M aqueous solution of ammonium chloride, and within 12 hours was carried out by heating and circulation.

Then, the crystalline aluminosilicate was filtered, washed with deionized water and dried overnight in a drying Cabinet at 60 º C, resulting in the received ion exchange ZSM-22 and ZSM-23 in NH4-form. In addition, the method thermogravimetric analysis confirmed that part of the organic matrix was removed in the ion exchange, although this represented a quantitative assessment of the influence of absorbed water.

1-2-2. Ion exchange after removal of the organic matrix by annealing

Each of the obtained 7 types of powdered ZSM-22 and one type ZSM-23 was loaded in a quartz tube, heated in a stream of nitrogen to increase the temperature up to 400ºC with what speed 5 º C/min, and maintained in this condition for 6 hours. Then the gas flow was switched to gaseous oxygen, and the temperature was raised to 550º with a speed of 5 º C/min and maintained at this temperature throughout the night. Here, in a stream of nitrogen, due to calcination at a temperature of 400ºC, the organic matrix is decomposed, mainly due to hydrogen evolution, and turned into a material with a phase of carbon. Then in a stream of oxygen during annealing at temperatures 550º carbon phase material is oxidized (burned), the result was achieved by removal of the organic matrix. In addition, the inventors believe that due to the two-stage annealing effect of vaporization of the water formed during combustion of the organic matrix, can be prevented more effectively than in the case where the annealing is conducted directly in a stream of oxygen.

Each of the calcined ZSM-22 and ZSM-23 was cooled to room temperature and transferred into a flask. It was added 0.5 M by aqueous solutions of ammonium chloride, and during the night was carried out by heating and boiling in the flask with reflux condenser, which was carried out by ion exchange. After ion exchange solid precipitate was filtered, washed with deionized water and dried in an oven overnight at 60 º C, in financial p is what Tata received the NH 4the ZSM-22 and ZSM-23. Data are crystalline aluminosilicates were those who were subjected to ion exchange in a state where the organic matrix is not contained.

The obtained ZSM-22 and ZSM-23 NH4type who underwent ion exchange in a state where the annealing was not carried out, and the organic matrix was saved, and the resulting ZSM-22 and ZSM-23 NH4type who underwent ion exchange in a state where the calcination was carried out with the removal of the organic matrix, denoted by "NH4-ZSM-22 [45] IE", "NH4-ZSM-22 [45] C-IE", respectively. Here "NH4-" means that the ion exchange was carried out with the product of NH4type; the number in [] means the ratio of Si/Al; "IE" means that the ion exchange is carried out in a state where the calcination is not performed, and the organic matrix contained; and "-IE" means that the ion exchange is effected in a state where the annealing carried out, and the organic matrix no.

1-2-3. Ion exchange using a solution with an organic solvent

According to the invention, opened in U.S. patent No. 5143879, in the experimental examples 25-34 ion exchange processes using solution with an organic solvent described in the line 61 column 38 through line 17 column 41 description of the application, the following explanatory conditions was carried out by ion exchange of ZSM-22[45]containing bodies is practical matrix.

The solution for ion exchange was prepared by the addition of 0.60 g of concentrated hydrochloric acid (37% wt. HCl) to 100 ml of a mixture of heptane and ethanol in a mass ratio of 1:1.

Powdered ZSM-22[45]synthesized in part 1-1-1 were loaded into the flask, then add to it the above solution for ion exchange in respect of 33 ml per 1 g of ZSM-22, and within one hour was carried out by heating and boiling under reflux. The resulting product was cooled and the upper layer was decanted, then re-added the same amount of the above solution for ion exchange, and heating and boiling under reflux was carried out for one hour. These operations were performed twice. After that, the obtained product was cooled to room temperature, and the solid product was collected and washed with deionized water. The obtained product was dried in a drying Cabinet at 60 º C during the night, resulting in a received ZSM-22, processed by the method of ion exchange in organic solution. ZSM-22, processed by the method of ion exchange in organic solution, called "H-ZSM-22[45] IEO (IEO denotes the ion exchange carried out in organic solution).

As for the obtained H-ZSM-22[45]IEO, the results of thermogravimetric analysis it is noted that the residual amount of organic matrix was essentially equal to the quantity which is actually ZSM-22 before the ion exchange, and destruction of the organic matrix of the ion exchange is essentially not passed.

In addition, as for the obtained H-ZSM-22[45]IEO, the above ZSM-22[45]C, in which the organic matrix was removed by calcination and ion exchange which were not, and the aforementioned NH4-ZSM-22 [45]IE, calcining, which were not, and ion exchange was carried out in aqueous solution, the number of remaining potassium ions, present as counterions in the process of hydrothermal synthesis, the number was measured by ICP (inductive plasma coupling - Inductively Coupled Plasma). The measurement results are listed in table 2. It is noted that in H-ZSM-22[45]IEO potassium ions substantially not removed as a result of ion exchange, but a relatively large amount of potassium ions remained in comparison with NH4-ZSM-22[45]IE.

Table 2
ZeoliteZSM-22[45] CNH4-ZSM-22[45] IEH-ZSM-22[45] IEO
The amount of potassium (mg/g)2,8not defined (<1)2,2

1-3. The deposition of platinum on the crystalline aluminosilicate and molding

Received NH4-ZSM-22[30]IE - H 4-ZSM-22[480]IE and NH4-ZSM-23[45]IE received NH4-ZSM-22[30]C-IE - NH4-ZSM-22[480]C-IE, NH4-ZSM-23[45]C-IE and received H-ZSM-22[45]IEO covered platinum and activated by the following method.

First, tetraammineplatinum (II) (Pt(NH3)4Cl2) was dissolved in minimum amount of deionized water. The solution was impregnable each of the above-mentioned crystalline aluminosilicates NH4type, using the method of initial wetting for the application of 0.3% wt. platinum relative to the weight of the crystalline aluminosilicate. Then, each obtained product was dried in a drying Cabinet at 60 º C during the night. After this, each of the formed products was molded into a disk shape by pressing. Then the disks roughly grinded and sieved, resulting amorphous granular body having a maximum diameter of 125 to 250 microns.

1-4. Activating catalyst

50 mg of each of the obtained silicates coated with platinum NH4-ZSM-22[30]IE - NH4-ZSM-22[480]IE, NH4-ZSM-23[45]IE, NH4-ZSM-22[30]C-IE - NH4-ZSM-22[480]C-IE, NH4-ZSM-23[45]C-IE and H-ZSM-22[45]IEO was loaded into a stainless steel microreactor (discussed below) and progulivali at 400ºC in a stream of oxygen for 1 hour. After that carried out the recovery processing in a stream of hydrogen for 1 hour to activate the catalyst.

After that, ZSM-22 and ZSM-23, which was deposited platinum and the counterion is replaced by a proton in the process of activation, expressed as "Pt/H-ZSM-22[45[IE and Pt/H-ZSM-22[45]C-IE", respectively.

2. Model reaction using n-decane

The catalytic action of activated catalysts were evaluated in a model reaction using n-decane.

Model reaction using n-decane

The reaction apparatus

The model reaction was carried out using the aforementioned micro-reactor with a fixed bed. The reaction tube was a stainless steel tube with an inner diameter of 2.1 mm and a length of 30 mm, in the lower part of which was loaded with 5 mg of catalyst. In the microreactor used gaseous oxygen and gaseous hydrogen to activate the catalyst, gaseous nitrogen for ventilation and gaseous hydrogen included the source material for the reaction, that is, pairs of n-decane was applied through a supply valve. Starting material reaction, that is, n-decane was filed together with hydrogen into the reactor, directing hydrogen gas in the device saturation vapor n-decane, which was heated to a predetermined temperature. The reaction was carried out in the gas phase. In addition, from the gaseous reaction product was sampled by the sampler, which was located downstream from the reaction is of the first tube and in which pressure was controlled. The gaseous reaction product is sent to a gas chromatograph (GC), to which was attached multicapillary column with dimethylpolysiloxane as stationary phase, and automatically analyzed.

With regard to the activation of the catalyst and the reaction of isomerization of n-decane, in the reaction apparatus was carried out by a series of operations, such as selection of gas, gas flow rate, the reaction temperature, the choice of valve, sampling of the reaction product and operations GC, according to the specified sequence of signals. The main operations carried out the process of activation of the catalyst loaded into the reaction tube at a temperature of 400ºC and venting system with gaseous nitrogen. After the temperature of the reaction tube was decreased to 150 º C, began the introduction of hydrogen gas, comprising a pair of n-decane, and started the isomerization reaction. After 1 hour from the gaseous reaction product was sampled and analyzed them. The reaction temperature was then changed to 160º and after 1 hour of stabilization of the gaseous reaction product was sampled and analyzed. Then, the reaction temperature was gradually increased with the speed of 10 º C to the reaction temperature 300OC, re-held stabilization mode and the analysis of the reaction product.

Reaction conditions

The reaction of isomerization of n-decane in prisutstvie and hydrogen was performed under the following conditions.

The source material of n-decane: reagent (purity 99% or more) was used without purification.

The pressure of the reaction: 0,45 MPa

The ratio of hydrogen/n-decane: 375 mol/mol

The reaction temperature: 150 - 300OC, increased speeds of 10.

The results of the conversion of n-decane (%), output monorities C10 isomer (%), output girsvetlana C10 isomer (%), the total yield of C10 isomer (%) and yield of cracking (C9 or less) (% wt.), obtained in the model reaction using n-decane, are presented in tables 3-5.

Table 3
The catalyst Pt/H-ZSM-22[45]IEC-IEIEC-IEIEC-IE
The reaction temperature (OC)220220250250300300
Conversion of n-decane (%)of 87.888,494,096,5of 99.199,9
Output monorities C10 isomer (% wt.)74,369,848,031,66,61,2
Output girsvetlana C10 isomer (% wt.)9,17,221,413,17,62,4
The total yield of C10 isomer (% wt.)of 83.477,068,944,714,23,6
The output products of cracking (C9 or less) (% wt.)4,411,424,651,984,996,4

As shown in table 3, it can be seen that the catalysts (IE), which are synthesized by ion exchange in a state where annealing is not performed, and the organic matrix contained, have a high output monorities isomer, high output girsvetlana isomer and a low yield of products of cracking when any fact is the temperature value of the reaction from 220 to 300 º C in comparison with the catalysts (IE), obtained by ion exchange in aqueous solution in a state where the annealing carried out, and the organic matrix is missing.

In addition, we have analyzed the composition of the products of cracking (output products of the cracking of 24.6% wt.), obtained at the reaction temperature 250º when using Pt/H-ZSM-22[45] IE as a catalyst, and the composition of the products of cracking (output products of the cracking of 21.2% wt.), obtained at the reaction temperature 230º when using Pt/H-ZSM-22[45]C-IE as a catalyst. The results are illustrated in figure 1 and 2.

Figure 1 is a given graph showing the composition of the products of cracking obtained using Pt/H-ZSM-22[45]C-IE. Figure 2 presents a graph showing the composition of the products of cracking obtained using Pt/H-ZSM-22[45]IE. In these figures the horizontal axis represents the number of carbon atoms of the product of the cracking, and the vertical axis is indicated molar number of the product cracking with each number of carbon atoms is 100 mol recerving n-decane. It is evident from Fig. 1 and 2, you can see that the ratio of isoparaffin in the product of cracking obtained using Pt/H-ZSM-22[45]IE, above, in comparison with the same parameter product of cracking obtained using Pt/H-ZSM-22[45]C-IE.

On the basis of the obtained results we can conclude that in the case of using a catalyst poluchennogo the traditional way, a relatively large amount of n-decane split, but in the case of using the catalyst according to the present invention prevails isomerisation of n-decane, so it is believed that the isomers additionally split. In addition, on the basis of the fact that the product of the cracking process contains a large amount of a hydrocarbon having a branched chain structure, it can be considered that in the case of obtaining a base oil of grease and base oil gasoil at the same time when using the catalyst according to the present invention, the low temperature fluidity of the base oil gasoil can be improved, and this base oil gasoil can be obtained with high yield.

Table 4
The ratio Si/al in the catalyst Pt/H-ZSM-22[]IE30456075100350480
Conversion of n-decane (% wt.)92,0of 87.887,787,6at 88.135,6 8,0
Output monorities C10 isomer (% wt.)62,374,376,177,276,929,47,5
Output girsvetlana C10 isomer (% wt.)14,69,17,66,56,71,70,1
The total yield of C10 isomer (% wt.)76,3of 83.483,783,783,631,17,6
The yield of cracking (C9 or less) (% wt.)15,74,44,0a 3.94,54,50,4

As shown in table 4, in the case of a catalyst which is obtained by ion exchange in aqueous solution in a state where ZSM-22 is not calcined and contains organic matrix to nverse n-decane and the yield of the isomer, associated with ZSM-22 having a ratio Si/Al from 30 to 350 exceeds the conversion is achieved through the use of ZSM-22 having a ratio Si/Al 480.

Table 5
The catalyst Pt/H-ZSM-23[45]IEC-IEIEC-IE
The reaction temperature (OC)220210270240
N-decane (% wt.)79,490,795,198,4
Output monorities C10 isomer (% wt.)70,065,235,920,2
Output girsvetlana C10 isomer (% wt.)5,22,718,78,8
The total yield of C10 isomer (wt. %)to 75.267,954,6 29,0
The yield of cracking (C9 or less) (% wt.)4,222,840,569,4

As shown in table 5, when the catalyst obtained from ZSM-23 having a ratio Si/Al45, there is a big difference in catalytic activity between the catalyst (IE), which is obtained by ion exchange in the state, when ZSM-23 not calcined and contains organic matrix, and a catalyst (P-IE), which is obtained by ion exchange in the state, when ZSM-23 calcined and does not contain organic matrix. Namely, it can be seen that the Pt/H-ZSM-23[45]IE has a high isomerization activity, along with low craterous action compared to the Pt/H-ZSM-23[45]C-IE.

In addition, in the model reaction using n-decane constraint index CIº defined as follows, was obtained from output 2-methylnonane and exit 5-methylnonane. The results are presented in table 6.

Constraint index CIº:=molar ratio of 2-methylnonane to 5-methylnonane incurred, when the output from the Dean amounted to 5% wt.

In addition, the model reaction was carried out under conditions, when the pressure of the reaction was of 0.45 MPa, WHSV 2530 kg·s/l, the ratio of hydrogen/n-decane 375 mol/mol, and the output from the Dean changed depending on temperature changes re the options.

Table 6
CatalystCIº
Pt/H-ZSM-22[30]IE14,3
C-IE9,8
Pt/H-ZSM-22[45]IE15,0
C-IE8,3
Pt/H-ZSM-22[60]IE15,4
C-IE7,7
Pt/H-ZSM-22[75]IE12,4
C-IE8,7
Pt/H-ZSM-22[45]IE4,5
C-IE3,7

As shown in table 6, it can be seen that for any of the 4 types ZSM-22 having different relations Si/Al, and ZSM-23 catalyst (IE)obtained by ion exchange in a state where the crystalline aluminosilicate on calcined and contains organic matrix, it is no small value CIº, that is, it increases the ratio of isomers formed, where the position of the branched chain exists in the inner position of the main chain in comparison with the catalyst (P-IE), which is obtained by ion exchange in a state where the crystalline aluminosilicate calcined and does not contain organic matrix.

As for the catalyst consisting of ZSM-22[45]IEO subjected to ion exchange in solution, involving the use of an organic solvent, and a catalyst consisting of ZSM-22[45]IE subjected to ion exchange in aqueous solution, the model reaction using n-decane was carried out according to the same techniques that the above methods. The results are presented in table 7.

Table 7
The catalyst Pt/H-ZSM-23[45]IEIEOIEIEOIEIE
The reaction temperature (OC)180180190190240240
Conversion of n-decane (% wt.) 66,150,0of 87.086,198,096,7
Output C10 isomer (% wt.)62,546,681,378,138,419,5
The yield of cracking (C9 or less) (% wt.)3,63,4the 5.78,059,577,2

As shown in table 7, compared with the Pt/H-ZSM-23[45]IE, Pt/H-ZSM-23[45]IEO has a tendency to low activity at low reaction temperature and low isomerization selectivity at high temperature reactions.

3. Analysis of the structures of the crystalline aluminosilicate and catalyst

3-1. Analysis by x-ray photoemission spectroscopy (XPS) of the crystalline aluminosilicate

ZSM-22[45] (the product, not treated by an ion exchange method), NH4-ZSM-22[45]IE and NH4-ZSM-22[45]C-IE was analyzed by the XPS method. As an analytical device used spectrometer (Kratos Axis Ultra from Kratos Analytical Co. The obtained XPS spectra shown in Fig. 3-5.

In Fig. 3 pre is submitted XPS spectrum of the region of the 2P orbitals of an atom of aluminum in the ZSM-22[45] (product, not the last ion exchange). In Fig. 4 shows the XPS spectrum of the region of the 2P orbitals of an atom of aluminum in NH4-ZSM-22[45]C-IE. In Fig. 5 shows the XPS spectrum of the region of the 2P orbitals of an atom of aluminum in NH4-ZSM-22[45]IE.

The spectrum of ZSM-22[45] observed in about one signal near 74,3 eV belonging to Al(IV), and in the spectrum of NH4-ZSM-22[45]IE there is approximately the same signal. On the other hand, in the spectrum of NH4-ZSM-22[45]C-IE additionally observed the signal of 74.3 eV, and another signal is observed near 77,3 eV. The signal near 77,3 eV attributed to Al(V) or Al(VI), which exists in a region outside of the skeleton of the zeolite. About spectrum was applied to the curve corresponding to the use of the function Gauss/Lorentz composite (=7/3), and the proportion of Al(V) and/or Al(VI), which exists in areas outside of the skeleton of zeolite was evaluated based on the ratio of the squares of the two signals. As a result, the share of the above-mentioned Al(V) and/or Al(VI) was approximately 15% relative to the total number of atoms of aluminum in the zeolite.

Additionally, regarding ZSM-22[60], ZSM-22[75] and ZSM-23[45], was performed the same comparison of the XPS spectra. As a result, observed the same differences between IE and IE.

In addition, the ratio of Si/Al to the surface of the crystal was obtained from the results of XPS analysis of ZSM-22[45], NH4-ZSM-22[45]C-IE and NH4-ZSM-22[45]IE. The results are presented in table 8. In addition, in comparison with respect to the receiving Si/Al for the entire crystal of the crystalline aluminosilicate ratio Si/Al to the surface of the crystal will tend to low values (high Al content).

Table 8
Crystalline aluminosilicateZSM-22[45]NH4-ZSM-22[45]
C-IE
NH4-ZSM-22[45]IE
The ratio of Si/Al on the surface30,017,231,6
AI(IV) %10085100
AI(V+VI) %0150

As shown in table 8, the results of the analysis from the point of view of the aluminum atoms constituting the skeleton, it is obvious that the NH4-ZSM-22[45]C-IE has a different structure from the structure of the crystalline aluminosilicate as hydrothermal synthesized.

3-2.27Al NMR analysis during the rotation of the magic angle (MAS) of the crystalline aluminosilicate.

ZSM-22[45] (the product, not the last ion exchange), NH4-ZSM-22[45]IE and NH4-ZSM-22[45]C-IE was subjected to27Al NMR analysis during the rotation of the magic angle (MAS). As an analytical device used spectrometer DSX400 (Bruker). The obtained XPS spectra presented in Fig.6

In the spectrum of ZSM-22[45] the signal observed near chemical shift 54 million days, and in the spectrum of NH4-ZSM-22[45]IE there is approximately the same signal. On the other hand, in the spectrum of NH4-ZSM-22[45]C-IE the signal is observed at the position shifted by approximately 1 million on, in the direction of low magnetic field, and the width of the signal is narrowed compared with ZSM-22[45]. As discussed above, since the aluminum atoms ZSM-22 can exist in different T centers, usually this signal can be considered as combined into a single signal when removing the NMR spectrum. In NH4-ZSM-22[45]C-IE the change in chemical shift position signal can be considered as reflecting the change in the share of aluminium atoms present in the various T centers. In addition, the narrower the width of the signal can be viewed as a weakening effect shielding of resonant frequency.

Accordingly, with results from aluminum using XPS and27Al MAS NMR shows that the NH4-ZSM-22[45]IE, obtained by ion exchange in a state where the crystalline aluminosilicate is not calcined and contains organic matrix has a structure similar to the structure of ZSM-22[45]synthesized by hydrothermal and NH4-ZSM-22[45]IE, obtained by ion exchange in a state where the crystalline aluminosilicate calcined and does not contain organic matrix, has a different structure./p>

3-3. XPS analysis of the catalyst after activation

Pt/H-ZSM-22[45]C-IE and Pt/H-ZSM-22[45]IE obtained by applying platinum and activation was analyzed by the XPS method, as described above. The obtained XPS spectra shown in Fig. 7 and 8.

In Fig. 7 shows XPS spectrum region of the 2P orbitals of an atom of aluminum in Pt/H-ZSM-22[45]C-IE. In Fig. 8 shows XPS spectrum region of the 2P orbitals of an atom of aluminum in Pt/H-ZSM-22[45]IE. Between the two spectra is not observed much difference.

As you can see from the above model reactions using n-decane, the catalysts according to the present invention have excellent performance properties compared with the catalyst, obtained in the traditional way. However, the relationship between good performance characteristics of the catalyst and the structure of the last ion exchange, molecular sieve, which is included in the composition of the catalyst according to the present invention, it is still not clear. However, we can assume that in the case of the conventional catalyst, which is obtained by ion exchange after removal of the organic matrix of the crystalline aluminosilicate calcination, a part of aluminum atoms is moved from the inner part of the crystal to its surface, and the surface of the crystal is formed of Al(V) and/or Al(VI), resulting in deformation. Conversely, we can assume that in the case of the catalyst according to the of the present invention, since ion exchange is performed in a state where the crystalline aluminosilicate contains organic matrix, such changes in the structure does not occur, so that the structure of the molecular sieve in the process of ion exchange affects the performance properties of the resulting catalyst.

3-4. Analysis after re-ammonium ion exchange activated catalyst

Pt/H-ZSM-22[45]C-IE and Pt/H-ZSM-22[45]IE obtained by applying platinum and activation in 0.5 M aqueous solution of ammonium chloride, was heated and boiled under reflux overnight and subjected to ion exchange, resulting in received NH4-type Pt/H-ZSM-22[45]C-IE and Pt/NH4-ZSM-22[45]IE. Conducted thermogravimetric analysis (TG) of the obtained products. As an analytical tool used Q500 TGA production of TA Instruments Co., in which the temperature was increased with a rate of 2OC/min in a stream of nitrogen. The obtained curves weight change is shown in Fig. 9 and 10. In Fig. 9 shows a graph of weight change Pt/NH4-ZSM-22[45]C-IE, and Fig. 10 shows a graph of weight change Pt/NH4-ZSM-22[45]IE.

As shown in Fig. 9 and 10, from the results of TG analysis, you can see that in Pt/NH4-ZSM-22[45]IE exception of ammonia occurs at a higher temperature compared to Pt/NH4-ZSM-22[45]C-IE. Accordingly, we can assume that Pt/NH4-ZSM-22[45]IE is the acidic centers who you Branstad with higher acidity compared to Pt/NH 4-ZSM-22[45]C-IE.

Dewaxing wax

Example 1

Obtaining catalyst

Silica as a binder for molding was added to the NH4-ZSM-22[45]IE, which was prepared by the above method, the mass ratio ZSM-22/silica 70/30. In addition, there was added a small amount of water and suitably mixed in a mortar. The resulting mixture was loaded into an extruder for molding her into a cylindrical shape with a diameter of about 1.5 mm and a length of about 5 mm Molded body was dried in a drying unit at 120°C in a stream of air for 3 hours and then was progulivali in an electric furnace at 550°C in an atmospheric environment for 3 hours.

Then, tetraammineplatinum (II) (Pt(NH3)4Cl2) was dissolved in minimum amount of deionized water and the solution was impregnable obtained molded body by the method of initial wetting with the introduction of 0.3% wt. platinum relative to the weight of the crystalline aluminosilicate. Then the obtained product was dried in a drying unit at 60°C over night. After that, the obtained product was progulivali in an electric furnace at 550°C in the environment for 3 hours, resulting in the obtained molded catalyst precursor containing Pt/H-ZSM-22 [45]IE.

Dewaxing wax

The obtained molded predecessor cat who lyst was loaded into a tubular reactor made of stainless steel, having an inner diameter of 15 mm and a length of 380 mm, and was in the process of recovery at the average temperature of catalyst layer 350°C in a stream of hydrogen (fractional hydrogen pressure: 3 MPa) for 12 hours. After that, the wax consisting of hydrocarbon (distribution by number of carbon atoms: from C21 to S; initial boiling point of from 300 to 400°C, the point of 50% distillation from 400 to 500°C, and the end point of the distillation 500°C or higher; the mass ratio of normal paraffins to the total weight of the paraffin 94% wt.) as starting raw materials were loaded to start the isomerization reaction in the presence of hydrogen under conditions of reaction temperature of 200°C, the partial hydrogen pressure of 3 MPa, a LHSV of 2.0 HR-1and the ratio of hydrogen/oil 594 nl/L. the Reaction was carried out for 72 hours, then the reaction product was sampled and analyzed.

Then, supporting the validity of the partial hydrogen pressure, LHSV, and relationships hydrogen/oil, gradually raised the reaction temperature to approximately 350º, resulting in conversion of the original oil was increased. At each reaction temperature the reaction was carried out for 72 hours to achieve equilibrium state of the reaction product was sampled and analyzed.

Based on the results of the analyses of the reaction products of the conversion of normal paraffin laid along the horizontal about the and, and outputs isomer branched chain laid on the vertical axis. The graph shown in Fig. 11.

In the above-mentioned reaction of isomerization of paraffin conversion of normal paraffin feedstock wax at the reaction temperature of 330°C was 100%, and all components with the number of carbon atoms of 21 or above in the obtained product were ISO. In addition, by fractional distillation of the resulting reaction product was obtained base oil of lubricating oils, the appropriate SAE-10 and 70 Pale. In the properties of the base oils base oil of lubricating oil corresponding to SAE-10, had a kinetic viscosity 3,987 CST at 100°C viscosity index 142, a pour point of -25°C, and the output of the base oil of 35.6% wt. regarding oil feedstock, and the base oil of lubricating oil corresponding to 70 Pale, had a kinetic viscosity 2,71 CST at 100°C and the yield of base oil 35,0% wt. relative to the original oil.

Example 2

Obtaining catalyst

The catalyst containing Pt/H-ZSM-23[45]IE, obtained using the same method as in example 1, except that used NH4-ZSM-23[45]IE, obtained by the above method, instead of NH4-ZSM-22[45]IE.

Dewaxing wax

The reaction of isomerization of paraffin was carried out in the presence of hydrogen wax to use is using the same as in example 1, processes, except that the molded catalyst precursor containing Pt/H-ZSM-23[45]IE, used instead of the molded catalyst precursor containing Pt/H-ZSM-22[45]IE as a catalyst precursor. The conversion of the normal paraffins in the wax at the reaction temperature of 340°C was 100%, and all components with the number of carbon atoms of 21 or more in the resulting product were ISO. In addition, carrying out fractional distillation of the resulting reaction product, obtained base oil of lubricating oils, the relevant SAE-10 and 70 Pale. The base oil of lubricating oils, the appropriate SAE-10, had a kinetic viscosity 3,968 CST at 100°C viscosity index 150, pour -22,5°C, and the output of the base oil is 38.2% wt. relative to the original oil and the base oil of lubricating oil corresponding to 70 Pale, had a kinetic viscosity 2,70 CST at 100°C and the yield of base oil 37,3% wt.

Comparative example 1

Obtaining catalyst

Molded precursor of the catalyst comprising Pt/H-ZSM-22[45]C-IE, was prepared by the same methods as the methods of preparation of the catalyst of example 1, except that used NH4-ZSM-22[45]C-IE, obtained by the above method, instead of NH4-ZSM-22[45]IE.

Dewaxing wax

The reaction of isomerization of paraffin was carried out in the presence of hydrogen paraffin using the same as in example 1, methods, except that the molded catalyst precursor containing Pt/H-ZSM-22[45]C-IE, used instead of the molded catalyst precursor containing Pt/H-ZSM-22[45]IE, as a catalyst precursor. The reaction product was analyzed as in example 1 and the results obtained are shown in Fig. 11. The conversion of the normal paraffins in the wax at the reaction temperature of 340°C was 100%, and all components with the number of carbon atoms of 21 or more in the resulting product were ISO. In addition, carrying out fractional distillation of the resulting reaction product, obtained base oil of lubricating oils, the appropriate SAE-10 and Pale 70. In the properties of the base oils base oil of lubricating oils, the appropriate SAE-10, had a kinetic viscosity 3,974 CST at 100°C viscosity index 142, pour -22,5°C and the yield of base oil 20.0% by wt. relative to the original oil and the base oil of lubricating oil corresponding to 70 Pale, had a kinetic viscosity 2,70 CST at 100°C and the yield of base oil 16,0% wt.

Comparative example 2

Obtaining catalyst

Molded precursor of the catalyst comprising Pt/H-ZSM-23[45]is-IE, received using the same as in example 1, methods, except that used NH4-ZSM-23 [45]C-IE, produced by the above method, instead of NH4-ZSM-22[45]IE.

Dewaxing wax

The reaction of isomerization of paraffin was carried out in the presence of hydrogen paraffin using the same as in example 1, methods, except that the molded catalyst precursor containing Pt/H-ZSM-23[45]C-IE, used instead of the molded catalyst precursor containing Pt/H-ZSM-22[45]IE, as a catalyst precursor. The conversion of the normal paraffins in the wax at the reaction temperature of 340°C was 100%, and all components with the number of carbon atoms of 21 or more in the resulting product were ISO. In addition, carrying out fractional distillation of the resulting reaction product, obtained base oil of lubricating oils, the appropriate SAE-10 and 70 Pale. The base oil of lubricating oil corresponding to SAE-10, had a kinetic viscosity 3,920 CST at 100°C viscosity index 146, pour -22,5°C and the yield of base oil 26,0% wt. relative to the original oil and the base oil of lubricating oil corresponding to 70 Pale, had a kinetic viscosity 2.68 CST at 100°C and the yield of base oil 16,0% wt.

From the obtained results it is clear, Thu is the catalyst hydroisomerization according to the present invention can increase the yield of the isomer compared with the conventional catalyst of the catalytic dewaxing, although mineral oil deparaffinized in conditions, when the conversion of normal paraffin increased. You can see that, according to the catalyst hydroisomerization of the present invention, it is possible to obtain the isomers with high yield even in the case where the conversion of normal paraffin is 100%, and significantly suppress the formation of a lighter product of the reaction. Therefore, according to the method of obtaining a base oil of the present invention using the catalyst of hydroisomerization of the present invention, it is possible to obtain a base oil of high quality lubricating oils with a high output.

In addition, according to the catalyst hydroisomerization of the present invention, it is possible to sufficiently increase the number of compositions isoparaffins in the reaction product having 15 or more carbon atoms obtained by the dewaxing of wax. The product of the cracking can be used as a base oil, gas oil, having a good fluidity at low temperatures. Therefore, according to the method of obtaining a base oil of the present invention using the catalyst of hydroisomerization of the present invention, it is possible to obtain a base oil, gas oil, having a good fluidity at low temperatures, with high output

According to the present invention, it is possible to obtain a catalyst hydroisomerization having a high activity of hydroisomerization, as well as small craterous activity, compared with conventional catalysts, and, in particular, to obtain the catalyst hydroisomerization having these properties in the case where the conversion of normal paraffin high. In addition, according to the present invention, it is possible to obtain a catalyst hydroisomerization capable of providing a large number of branches and isomers having side chains in the lower position of the main circuit. The isomers can more effectively improve the low temperature fluidity of the base lubricating oil or base oil gasoil. In addition, according to the present invention, it is possible to provide a method of dewaxing mineral oils and method for producing base oil capable of obtaining a base oil of lubricating and/or base oil fuel having good fluidity at low temperatures, using a catalyst hydroisomerization.

Industrial applicability

According to the present invention, it is possible to obtain a catalyst hydroisomerization, allowing to receive mineral oil, suitable for base oil of lubricating oil, and the mineral is deficient in oil, suitable for the base fuel oil containing normal paraffins with high output, which has a sufficiently high isomerization ability and low enough craterous activity. In addition, according to the present invention, it is possible to provide a method of dewaxing mineral oils, the method of obtaining a base oil and a method of obtaining a base oil of lubricating oil, allowing to obtain a base oil of lubricating oil and/or base oil fuel having good fluidity at low temperatures, with high output.

1. The catalyst hydroisomerization, which is obtained by calcination of a catalyst composition comprising processed by the method of ion exchange, molecular sieve or the calcined material, which is obtained by using ion-exchange molecular sieve containing an organic matrix, the solution containing the cationic fragments and involving the use of water as the primary solvent, and at least one metal selected from the group comprising metals belonging to groups 8-10 of the Periodic Table of the Elements, molybdenum and tungsten deposited on the treated by the method of ion exchange, molecular sieve or the calcined material.

2. The catalyst hydroisomerization according to claim 1 where the molecular sieve containing an organic matrix is, is a zeolite having a porous structure containing a 10-membered ring or 8-membered ring.

3. The catalyst hydroisomerization according to claim 2, where the zeolite has a unidirectional porous structure having 10-membered ring.

4. The catalyst hydroisomerization according to claim 3, where the zeolite is at least one crystalline aluminosilicate selected from the group comprising ZSM-22, ZSM-23 and ZSM-48.

5. The catalyst hydroisomerization according to claim 4, where the molar ratio of [Si]/[Al] of silicon atoms to aluminum atoms in the crystalline aluminosilicate is in the range from 10 to 400.

6. The catalyst hydroisomerization according to claim 1 where the molecular sieve containing an organic matrix, is ZSM-22, and where the constraint index, defined as follows, lies in the interval from 7 to 12:
constraint index = molar ratio of 2-methylnonane to 5-methylnonane that occurs when the output from the Dean is 5%, in the reaction contact between the normal of the Dean with the catalyst hydroisomerization with the conversion to ISO-deans in the presence of hydrogen.

7. The catalyst hydroisomerization according to claim 1 where the molecular sieve containing an organic matrix, is ZSM-23, and where the constraint index, defined as follows, lies in the range from 3.0 to 4.0:
constraint index = molar ratio of 2-methylnonane to 5-methylnonane that occur when the and output from the Dean 5% in the reaction contact between the normal of the Dean with the catalyst hydroisomerization with the conversion to ISO-deans in the presence of hydrogen.

8. The catalyst hydroisomerization according to claim 1 where the molecular sieve containing an organic matrix, is ZSM-48, and where the constraint index, defined as follows, lies in the range from 1.1 to 5.1:
constraint index = molar ratio of 2-methylnonane to 5-methylnonane that occurs when the output from the Dean 5% in the reaction contact between the normal of the Dean with the catalyst hydroisomerization with the conversion to ISO-deans in the presence of hydrogen.

9. The catalyst hydroisomerization according to any one of claims 1 to 8, wherein the organic matrix is derived amine.

10. The catalyst hydroisomerization according to any one of claims 1 to 8, wherein the organic matrix is selected from the group comprising alkylamino, alkylamino, alkilany, alliteration, pyrrolidine, piperazine, aminopiperidin, alkylbetaine, alkylguanine and their derivatives.

11. The catalyst hydroisomerization according to any one of claims 1 to 8, where treated by the method of ion exchange, molecular sieve obtained ion-exchanged molecular sieve containing an organic matrix, in the presence of ammonium ions or protons.

12. The catalyst hydroisomerization according to any one of claims 1 to 8, where treated by the method of ion exchange, molecular sieve obtained ion-exchanged molecular sieve containing an organic matrix, replacing the solution with fresh solution one, two Il is several times.

13. The catalyst hydroisomerization according to any one of claims 1 to 8, where the composition of the catalyst contains platinum and/or palladium, deposited on the treated by the method of ion exchange, molecular sieve or the calcined material.

14. The catalyst hydroisomerization according to any one of claims 1 to 8, wherein the catalyst is obtained by calcination of the catalyst composition in a medium containing molecular oxygen, and then recovery in the medium containing molecular hydrogen.

15. The catalyst hydroisomerization according to any one of claims 1 to 8, wherein the catalyst composition contains 1 part by weight to 90 parts by weight processed by the method of ion exchange, molecular sieve or the calcined material and from 99 parts by weight to 10 parts by mass of porous oxide, which is at least one selected from the group comprising aluminum oxide, silicon dioxide, titanium oxide, boron oxide, magnesium oxide and zirconium oxide.

16. The catalyst hydroisomerization according to any one of claims 1 to 8, wherein the catalyst composition contains a carrier obtained by annealing the composition of media containing 1 part by weight to 90 parts by weight processed by the method of ion exchange, molecular sieve and 99 parts by mass to 10 parts by weight of porous oxide, which is at least one selected from the group comprising aluminium oxide, dioxi the silicon, the titanium oxide, boron oxide, magnesium oxide and zirconium oxide, and a metal supported on a carrier.

17. Method of dewaxing mineral oils, including the process of converting part or all of the normal paraffins into ISO, where contact mineral oil containing normal paraffins with a catalyst hydroisomerization according to any one of claims 1 to 16 in the presence of hydrogen.

18. Method of dewaxing mineral oils at 17, where the mineral oil is at least one selected from the group comprising paraffin GAC, fat-free wax, paraffin wax on the base, microcrystalline wax, petrolatum and waxes obtained by the method of Fischer-Tropsch.

19. A method of obtaining a base oil to obtain a base oil of lubricating and/or base oil fuel, which is carried out by the contact interaction of mineral oil containing normal paraffins, and catalyst hydroisomerization according to any one of claims 1 to 16, in the presence of hydrogen.

20. A method of obtaining a base oil according to claim 19, where the mineral oil is at least one selected from the group comprising paraffin GAC, fat-free wax, paraffin wax on the base, microcrystalline wax, petrolatum and waxes obtained by the method of Fischer-Tropsch.

21. A method of obtaining a base oil of the lubricant to obtain a base oil smask is, by the contact interaction of mineral oil containing normal paraffins having 10 or more carbon atoms, and a catalyst hydroisomerization according to any one of claims 1 to 16 in the presence of hydrogen under conditions when the conversion of normal paraffins defined by the following equation I, is essentially 100 wt.%:
The equation I
Conversion of normal paraffins (%)=[1-(total mass JV normal paraffins contained in the mineral oil after contact interaction)/(Total mass JV normal paraffins contained in the mineral oil to the contact interaction)]×100 (I),
where Cn denotes the minimum number of carbon atoms in the normal paraffins containing 10 or more carbon atoms included in mineral oil to the contact interaction.

22. A method of obtaining a base oil of grease on item 21, where the mineral oil is one selected from the group comprising paraffin GAC, fat-free wax, paraffin wax on the base, microcrystalline wax, petrolatum and waxes obtained by the method of Fischer-Tropsch.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to hydrotreatment processes. Described is a method of removing paraffin from hydrocarbon material, involving reacting the material with a mixture of ZSM-48 catalysts under catalytic paraffin removal conditions for producing material from which paraffin has been removed, where the mixture of ZSM catalysts contains: a) first type ZSM-48 crystals, having molar ratio of silicon dioxide to aluminium oxide equal to 70-110 and containing inoculating crystals different from ZSM-48, and b) second type ZSM-48 crystals which differ from first type ZSM-48 crystals on one or more properties selected from presence of inoculating crystals different from ZSM-48, crystal morphology, higher kenyaite percentage and higher molar ratio of SiO2 to Al2O3.

EFFECT: high efficiency of removing paraffin from hydrocarbon material owing to use of a a highly active catalyst.

16 cl, 1 tbl, 6 dwg, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to high activity ZSM-48. Described is a catalyst composition for removing paraffin from hydrocarbon material which contains ZSM-48 crystals, having molar ratio of silicon dioxide to aluminium oxide equal to or less than 110, which does not contain inoculating crystals different from ZSM-48 and does not contain ZSM-50 crystals.The invention also describes a method of producing ZSM-48 crystals contained in the composition described above, involving: preparation of an aqueous mixture of silicon dioxide or silicate, aluminium oxide or aluminic acid, hexamethonium salts and an alkaline base, where the mixture has the following molar ratios: silicon dioxide: aluminium oxide 70-110, base: silicon dioxide 0.1-0.3 and hexamethonium salt: silicon dioxide 0.01-0.05, and heating the mixture while stirring for a period of time and temperature sufficient for formation of crystals. The invention also describes a method of removing paraffin from hydrocarbon material in the presence of the catalyst composition described above.

EFFECT: obtained ZSM-48 crystals and a composition based on said crystals exhibit high activity during removal of paraffin from hydrocarbon material.

29 cl, 1 tbl, 6 dwg, 15 ex

FIELD: chemistry.

SUBSTANCE: invention refers to noble-metal catalyst, to method for making and application thereof. There is disclosed method for making noble-metal catalyst for hydrocarbon conversion, involving the stages as follows: a) preparation of the carrier containing zeolite, chosen from zeolites with medium and large pores and acid sites, at temperature within 423 to 1173 K and optional carrier modification; b) deposition of noble metal chosen from platinum, palladium, ruthenium, rhodium, iridium and their mixtures and combinations, by gas-phase deposition including evaporation of noble metal precursor chosen from β-diketonates and metallocenes, and interaction with the carrier, and c) heat treatment in oxidising or reducing environments. There is disclosed application of noble-metal catalyst produced by the method described above, in ring opening, isomerisation, alkylation, hydrocarbon reforming, dry reforming, hydrogenation and dehydrogenation, and preferentially, in ring opening of naphthenic molecules. Additionally, there is disclosed method for making medium diesel fuel distillate by introducing raw medium distillate into the reactor wherein it reacts at temperature 283-673 K and under pressure 10-200 bar with hydrogen with added noble-metal catalyst produced as described above until ring opening of naphthenes with two or more rings completed to produce isoparaffins, n-paraffins and mononaphthenes within medium distillate.

EFFECT: production of catalyst with improved selectivity for hydrocarbon conversion.

16 cl, 5 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: said invention relates to method for improvement of loss of mobility temperature of hydrocarbon material obtained by Fischer-Tropsch synthesis, in particular to satisfactory-yield conversion of material with high temperature of mobility loss, at least one fraction of which has low mobility loss temperature and high viscosity index for base oil. Method implies utilisation of dewaxing catalyst, which contains at least one zeolite (molecular sieve) chosen from a group of TON type zeolites (Theta-1, ZSM-22, ISI-1, NU-10 and KZ-2), and at least one ZBM-30 zeolite, at least one inorganic porous matrix, at least one hydrogenating/dehydrogenating element, preferentially from group VIB and group VIII of periodic table.

EFFECT: improved loss of mobility temperature for hydrocarbon material obtained by Fischer-Tropsch synthesis.

14 cl, 7 ex, 1 dwg

FIELD: physics.

SUBSTANCE: dewaxing procedure of raw material produced by Fischer-Tropsch method implies that processed raw materials contact with catalyst containing at least one zeolite ZBM-30, synthesised with triethylene tetramine, at least one hydrogenating- dehydrogenating element preferably selected from elements of group VIB and group VIII of periodic table, and at least one inorganic porous matrix.

EFFECT: good recovery of raw material, raised pour point.

13 cl, 5 ex, 1 dwg

FIELD: petroleum chemistry.

SUBSTANCE: invention relates to microcrystalline paraffin obtained by catalytic hydroisomerization at temperature more than 200°C from FT paraffin having from 20 to 105 carbon atoms. Microcrystalline paraffin is non-liquid at 25°C, but at least pasty with needle penetration less than 100x10-1, measured according to DIN 51579. Disclosed is method for production of microcrystalline paraffin.

EFFECT: microcrystalline paraffin free from naphthenes and aromatics.

17 cl, 1 dwg, 1 tbl, 3 ex

FIELD: production of catalysts.

SUBSTANCE: proposed method is used for production of catalyst containing zeolite and heat-resistant oxide binder at low acidity practically containing no aluminum; proposed method includes the following operations; (a) preparation of mass suitable for extrusion and containing homogeneous mixture of zeolite, water, binder of heat-resistant binder at low acidity which is present as acid sol and aminocompounds; (b) extrusion of mass obtained at stage (a) suitable for extrusion; (c) drying extrudate obtained at stage (b); and (d) calcination of dried extrudate obtained at stage (c).

EFFECT: increased strength of catalyst at high resistance to crushing.

10 cl, 1 tbl, 2 ex

FIELD: powder metallurgy; method of impregnation by a metal(of VIII group) of a molecular sieve extrudate with cementing material with the help of ion exchange with an aqueous solution of metal salt of VIII group.

SUBSTANCE: the invention presents a method of impregnation by metal of VIII group of an extrudate of a molecular sieve with cementing material, in which the cementing material represents a refractory oxidic material with a low acidity, practically free of aluminum oxide, using: a) impregnation of porous volume of an extrudate of a molecular sieve with cementing material with an aqueous solution of nitrate of the corresponding metal of VIII group with pH from 3.5 up to 7, in which the molar ratio between cations of a metal of VIII group in a solution and a number of centers of the adsorption available in the extrudate, is equal to or exceeds 1; b) drying of the produced at the stage a) extrudate of the molecular sieve with the cementing material. The technical result is good distribution of the metal and a short period of drying.

EFFECT: the invention ensures good distribution of the metal and a short period of drying.

9 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: described is a catalyst for producing high-octane gasoline with low content of benzene via combined treatment of low-octane hydrocarbon fractions with initial boiling point - 205°C and aliphatic alcohols and/or dimethyl ether, which contains a mechanical mixture of pentasil type zeolite with silica modulus SiO2/Al2O3=18-25 which is first treated with aqueous solution of an alkali, modified with rare-earth metal or lanthanum oxide in amount of 0.5-2.0 wt % and a pentasil type zeolite with silica modulus SiO2/Al2O3=70-90, modified with magnesium oxide in amount of 0.5-3.0 wt %, taken in ratio from 1/1 to 1/5, as well as binder in amount of 20 to 25% of the weight of the catalyst. Described also is a method of producing high-octane gasoline with low content of benzene via combined treatment of low-octane hydrocarbon fractions with initial boiling point - 205°C and aliphatic alcohols and/or dimethyl ether, in which the catalyst described above is heated in an isothermic reactor with heat pipes to temperature 280-350°C, the process of contacting the raw material with the catalyst, which is heated in the isothermic reactor with heat pipes, takes place at pressure 0.1-1 MPa while feeding into the reactor in two streams a mixture of methanol as oxygen-containing raw material and low-octane hydrocarbon fractions with volume rate of feeding the liquid raw material equal to 0.5-5 h-1 after evaporation of the raw material in a pre-heater.

EFFECT: catalyst enables to obtain high-octane gasoline with low content of benzene.

7 cl, 3 tbl, 17 ex

FIELD: oil and gas production.

SUBSTANCE: here is disclosed procedure for processing gas condensate consisting in its preliminary heating in corresponding process vessels, in contacting in adiabatic reactor at temperature 320-480°C and pressure 0.1-4 MPa with zeolite containing catalyst, in cooling and in separation of reaction products into gaseous and liquid fractions by separation and rectification, and in successive oxidising regeneration of catalyst. Also, prior to process of regeneration heavy resins collected on catalyst are removed by vacuumising of adiabatic reactor during 0.5-6.0 hours. Catalyst is regenerated in a regenerator at temperature 350-620°C and pressure 0.1-0.2 MPa with air with contents of oxygen 21 vol. %. Upon heating an upper or lower layer of catalyst air is supplied from a side opposite to a heated layer.

EFFECT: reduced time for processing gas condensate due to reduced process of regeneration of coked catalyst and reduced expenditures for regeneration process.

3 cl, 1 tbl, 4 ex

FIELD: oil and gas industry.

SUBSTANCE: invention refers to method for obtaining high-octane benzene and/or aromatic hydrocarbons with low benzene content from hydrocarbon raw material, namely aliphatic hydrocarbons C5-C12 or aliphatic oxygen-containing compounds C1-C12, including in composition of basic products and by-products in oil, gas, chemical industry; phase of raw material contact in the first reaction zone is conducted at temperature of 400-600°C, pressure of 0.1-4.0 MPa and mass raw material supply rate of 1 -200 h-1 with aromatisation catalyst on the basis of modified zeolite of MFI structural type which is characterised with value of molar ratio SiO2/Al2O3 20-133, residual content of sodium ions of less than 0.1 %, which is treated in addition with 0.01-2.0 "н" solution of ammonium fluoride. Obtained reaction flow is subject to contact in the second reaction zone at temperature of 300-400°C, pressure of 0.1-4.0 MPa and mass raw material supply rate of 1-40 h-1 with catalyst of alkylation and/or transalkylation; at that, flow temperature at the inlet to the second reaction zone is not less than by 70°C lower than flow temperature at the inlet to the first reaction zone.

EFFECT: higher capacity of the process and output of gasoline.

7 cl, 24 ex, 3 tbl

FIELD: oil and gas production.

SUBSTANCE: invention refers to procedure of production of high-octane benzine or aromatic hydrocarbons out of hydrocarbon containing stock by contacting stock with catalyst at increased temperature and pressure of stock flow. Also, contact of stock with catalyst is carried out successively in two reaction zones of one reactor or in each of the reaction zones of two reactors. Temperature of reaction flow is changed in each successive zone. Further, products of contact are separated and rectified in each successive zone and a benzine fraction, or aromatic hydrocarbon fraction, hydrogen containing gas and propane-butane and benzyl-containing fraction are extracted. As hydrocarbon containing stock there are used aliphatic hydrocarbons C2-C22 and/or aliphatic oxygen containing compounds C1-C12 including those in composition of main and side products of oil, gas, and chemical industries. Stage of contact of stock with catalyst facilitating formation of aromatic hydrocarbons and olefines is performed in the first and second reaction zones. Catalyst contains zeolite of structural type MFI. Zeolite is modified with at least one of elements of I-VIII groups at 320-620°C, pressure 0.1-4.0 MPa, and mass rate of stock supply 1-200 h-1. Produced reaction flow is subjected to additional contact with catalyst of alkylation and/or trans-alkylation in the third reaction zone of an additional reactor. This catalyst contains zeolite of a structural type MFI, BEA, FAU, MOR. Also, zeolite is modified with at least one element out of I-VIII groups at 200-450°C, pressure 0.1-4.0 MPa and mass rate of flow 1-40 h-1. Temperature of flow at input into the third reaction zone is not less than 60°C below temperature of flow of the preceding reaction zone. Extracted benzyl containing fraction is directed to recycle into any of the first, second or third reaction zones of the reactors.

EFFECT: processing wide range of hydrocarbon containing stock into high octane benzine; increased efficiency of process.

6 cl, 19 ex, 7 tbl, 2 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to method of producing aromatic hydrocarbon compounds from light hydrocarbons by catalytic reaction of ring formation and to catalyst to this end. Zeolite-containing compacted catalyst, to be used in method of producing aromatic hydrocarbon compounds from light hydrocarbons by catalytic reaction of ring formation, wherein zeolite contained in zeolite-containing compacted catalyst meets the following requirements: (a) zeolite represents that with average diametre of pores varying from 5 to 6.5 Å; (b) zeolite features diametre of primary particle varying from 0.02 to 0.25 mcm; and (c) zeolite comprises at least one metal element selected from the group consisting of metals from IB-group of periodic system in the form of appropriate cations, and wherein zeolite-containing compacted catalyst comprises at least one element selected from the group made up of elements that belong in IB, IIB, IIIB, VIII groups of periodic system.

EFFECT: lower carburisation and reactivation of catalyst.

6 cl, 4 ex, 6 tbl, 5 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to oil refining and petrochemical industries and is aimed at preparing catalysts used in processing petroleum cuts and gas condensates into engine fuel. The zeolite-containing catalyst for preparing engine fuel from petroleum cuts and gas condensates contains a pentasil ZSM-5 zeolite with silica module SiO2/Al2O3=20-80 mol/mol and residual content of sodium oxide 0.02-0.05 wt %, bismuth oxide as a structure element of the zeolite component with the following content of components (wt %): zeolite 70.00-85.00; Bi2O3 1.0-6.00; Na2O 0.02-0.05; binding component - the rest. The method of preparing the zeolite-containing catalyst involves hydrothermal synthesis of Na-forms of zeolite with subsequent salt ion exchange and obtaining an ammonium form of zeolite, after which a catalyst mass is prepared which is then granulated, dried and annealed at temperature 550-650°C. The method of preparing engine fuel from petroleum cuts and gas condensates involves passing vapour of petroleum cuts and gas condensates through a fixed bed of zeolite catalyst heated to temperature 300-440°C, with catalyst material loading of 2 h-1.

EFFECT: reduced number of components and stages for synthesis of zeolite-containing catalyst, increased degree of converting raw material, quality and output of end products on the proposed catalyst, reduced number of stages for processing hydrocarbon material into the end product.

3 cl, 6 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts and methods of producing high-octane petrol or aromatic hydrocarbons. A catalyst is described for converting aliphatic C2-C12 hydrocarbons and/or aliphatic oxygen-containing C1-C12 compounds to high-octane petrol or aromatic hydrocarbons, containing pentasil type zeolite, zinc aromatisation promoter, and binder, where the said zeolite is characterised by molar ratio SiO2/A2O3 ranging from 20 to 100, residual content of sodium ions less than 0.1%, aromatisation promoter is introduced using any known method with the following ratio of components: zeolite - 30.0 to 90.0 wt %; zinc - 0.5 to 8.0 wt %; binder - the rest. The catalyst is further treated with ammonium fluoride solution after introduction of zinc. A method is also described for producing this catalyst, involving introduction of pentasil type zeolite and zinc aromatisation promoter into the catalyst, moulding with the binder, subsequent drying and thermal treatment of the catalyst mass, where the zeolite used is pentasil with molar ratio SiO2/AlO3 ranging from 20 to 100 and residual content of sodium ions less than 0.1%. The aromatisation promoter is introduced using any known method in amount ranging from 0.5 to 8.0 wt %, and the obtained zinc-containing catalyst is further treated with aqueous solution of ammonium fluoride. Also described is a method of producing high-octane petrol or aromatic hydrocarbons by converting hydrocarbon material, involving supply of the material and bringing it into contact with heated zeolite-containing catalyst at high pressure with subsequent extraction of reaction products. The hydrocarbon material used is aliphatic C2-C12 hydrocarbons and/or aliphatic oxygen-containing C1-C12 compounds, including as part of main- and by-products of oil, gas and chemical industry, as the catalyst used is the one described above.

EFFECT: design of highly-active and stable catalyst, which provides for processing a wide range of hydrocarbon material.

16 cl, 4 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention concerns method of catalytic reforming of gasoline fractions preceded with dehydrogenation of contained naphthene hydrocarbons enabled in series rector system at higher temperature and pressure with industrial platinoerionite-containing reforming catalyst SG-3P, containing erionite 10-15 wt % where in the first downstream reactors there is used industrial low-erionite (4-8 wt %) catalyst SG-3P-M type A. Reforming process is ensured with two catalysts added: at first catalyst SG-3P-M type A, and with catalyst SG-3P.

EFFECT: higher end product yield, improved circulated hydrogenous gas features.

2 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention refers to noble-metal catalyst, to method for making and application thereof. There is disclosed method for making noble-metal catalyst for hydrocarbon conversion, involving the stages as follows: a) preparation of the carrier containing zeolite, chosen from zeolites with medium and large pores and acid sites, at temperature within 423 to 1173 K and optional carrier modification; b) deposition of noble metal chosen from platinum, palladium, ruthenium, rhodium, iridium and their mixtures and combinations, by gas-phase deposition including evaporation of noble metal precursor chosen from β-diketonates and metallocenes, and interaction with the carrier, and c) heat treatment in oxidising or reducing environments. There is disclosed application of noble-metal catalyst produced by the method described above, in ring opening, isomerisation, alkylation, hydrocarbon reforming, dry reforming, hydrogenation and dehydrogenation, and preferentially, in ring opening of naphthenic molecules. Additionally, there is disclosed method for making medium diesel fuel distillate by introducing raw medium distillate into the reactor wherein it reacts at temperature 283-673 K and under pressure 10-200 bar with hydrogen with added noble-metal catalyst produced as described above until ring opening of naphthenes with two or more rings completed to produce isoparaffins, n-paraffins and mononaphthenes within medium distillate.

EFFECT: production of catalyst with improved selectivity for hydrocarbon conversion.

16 cl, 5 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: described is method of obtaining zeolite-containing catalyst for processing low-octane benzene fractions based on ZSM-5, in which to natural zeolite clinoptilolite-heulandite, double-processed with NH4Cl water solution, 2.5-10 wt % of highly siliceous zeolite ZSM-5 with molar ratio SiO2/Al2O3=60 and content of Na2O not more than 0.02 wt % is added, and additionally 0.5 wt % of ultra-dispersive zinc powder is added. Also described is method of processing low-octane benzene fractions in presence of obtained zeolite-containing catalyst, process being carried out by passing raw material vapours through stationary catalyst layer at temperature 300-400°C, atmospheric pressure, volumetric rate of raw material supply 2 hour-1.

EFFECT: increase of iso-structure alkanes content in obtained marketable benzenes and reduction of aromatic hydrocarbons content.

2 cl, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing vinyl acetate, involving bringing starting material containing ethylene, acetic acid and an oxygen-containing gas into contact with a palladium- or gold-containing catalyst obtained on a calcined and modified carrier material to form vinyl acetate and at least one by-product, where the carrier material is modified with 1) niobium, magnesium, tantalum, yttrium, lanthanum, praseodymium or combinations thereof; or 2) titanium, zirconium or combinations thereof, where the carrier material is selected from zirconium dioxide, titanosilicate or zirconosilicate, and where the modified carrier material is calcined before adding catalyst components. The invention also relates to a method of producing a catalyst which is suitable for producing vinyl acetate, as well as a catalytic composition for catalysis of production of alkenylalkanoates, including carrier material with at least one modifier, palladium and gold, which react to form a catalyst, where the modified carrier material undergoes calcinations in a non-reducing atmosphere, and the modifier includes 1) niobium, magnesium, tantalum, yttrium, lanthanum, praseodymium or combinations thereof; or 2) titanium, zirconium or combination thereof, where the carrier material is selected from zirconium dioxide, titanosilicate or zirconosilicate.

EFFECT: obtaining catalysts which can be used to produce alkenylalkanoates in general and vinyl acetate in particular, and which are suitable for use in obtaining low ratio of EA/VA while maintaining or improving selectivity of producing CO2.

34 cl

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