RU2536585C1 - Catalyst, method of manufacturing thereof and process of diesel fuel hydroisomerisation - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: described is catalyst of hydroisomerisation, including zeolite of ZSM-23 type, palladium and aluminium oxide, containing components in the following concentrations, wt %: zeolite of ZSM-23- 50-80, palladium - not more than 0.6; boron 1.0-3.0; Al₂O₃ - the remaining part, which has pore volume not less than 0.25 cm³/g, specific surface not less than 150 m²/g, average diameter of pores not smaller than 4 nm. Method of catalyst preparation consists in soaking zeolite ZSM-23-containing carrier with boric acid solution with the following drying and calcinations, and further soaking with water solution of palladium nitrate with the following drying and calcinations. Described is process of hydroisomerisation of Diesel fuel, which contains not more than 30 ppm of sulphur, carried out at 320-340°C, pressure 2.5-6.5 MPa, volume rate of raw material supply 2-6 h^-1, volume ratio hydrogen/raw material - 200-600 nm³/m³ in presence of catalyst with given above composition.

EFFECT: obtaining catalyst, which makes it possible to carry out process of hydroisomerisation with obtaining Diesel fuels with lower pour point, with high output and cetane number.

12 cl, 2 tbl, 4 ex

Description

The invention relates to catalysts for hydroisomerization of diesel fuel, methods for preparing catalysts and processes for producing diesel fuel with a low pour point.

In recent years, the Russian Federation has been experiencing an acute need for winter-grade diesel fuels. Currently, in Russia, the total share of diesel fuels suitable for use in cold and arctic climates is no more than 11% of the total production of diesel fuels, which is approximately 10.6 million tons / year [Rudyak, KB Modernization of technological schemes of oil refineries with changing requirements for the range and quality of products [Text]: Dis. doc tech. sciences / K.B. Rudyak. - M., 2005. - 271 p.]. Russia's total demand for winter-grade diesel fuels is currently estimated at 14.7 million tons / year [Chernysheva EA, Kapustin VM Prospects for the modernization of the Russian oil refining industry until 2020 // 9 Russian Oil and Gas Congress, June 21-24, 2011 - http://mioge.ru/download/archive/2011/Chernycheva_VNIPIneft.aspx (Date of access 07.24.12)]. In the next 10 years, an increase in demand for diesel fuels of winter grades is predicted, which can reach 40% of the existing level [V. Kapustin Modernization of the oil refining industry of the Russian Federation in connection with the introduction of regulations for motor fuels // 9 Russian Oil and Gas Congress, June 21-24, 2011 - http://mioge.ru/download/archive/2011/Shuverov_VNIPIneft.aspx (Date of treatment 07.24.12)] . The most rational method for the industrial production of winter diesel fuels is catalytic processes that ensure the conversion of high-curing n-paraffins to low-curing compounds. Currently used processes and catalysts are characterized by low yields of target products and low cetane number of diesel fuel produced. Accordingly, an extremely urgent task is the creation of new processes and catalysts, allowing to obtain low-curing diesel fuel with high yields and high cetane number.

There are various known processes for producing low-hardening mixtures of hydrocarbons and catalysts for these processes, however, a common disadvantage for them is the low yield of the target fraction.

Most often, the production of low-curing petroleum products is carried out using catalysts based on various zeolites.

So known is the method of dewaxing of oil fractions, which consists in contacting the feed with a catalyst containing a zeolite type ZSM-5 [RF No. 2343183, C10G 35/00, 03/01/2007], characterized in that the catalyst contains 2-10 wt.% Decationized form of zeolite type ZSM-5 and 90-98 wt.% natural zeolite type clinoptilolite-heiladite, subjected to preliminary double treatment with 25% solution of ammonium chloride. The catalyst can also be additionally impregnated with a solution of Nickel nitrate based on the content of Nickel in it 1.5-2.5 wt.%. Upon receipt of the product with a pour point below -40 ° C, its yield does not exceed 82% with a cetane number of 45-51. The disadvantages of this process and the catalyst are low yields of catalysis and its low cetane number.

To increase the activity of catalysts in dewaxing, the introduction of zeolites with different morphology and size of crystals having a different ratio of SiO ₂ / Al ₂ O _{3 is} used in their composition. So, the process of dewaxing hydrocarbon raw materials is known [RF No. 2411999, B01J 29/80, 12.12.2006], carried out at a temperature of 250-426 ° C, pressure 791-20786 kPa, hourly volumetric flow rate of 0.1 to 10 h ^-1 and a fraction of the processing hydrogen gas from 89 to 1780 m ³ / m ³ in the presence of a catalyst, which is a mixture of ZSM-48 zeolite crystals of needle and lamellar morphology of various sizes and with different SiO ₂ / Al ₂ O ₃ ratios. The disadvantage of this process and the catalyst is the low yield of isomers, not exceeding 85%.

To increase the isomerizing function of the zeolite catalyst, various metals, most often noble ones, for example platinum, are introduced into its composition. So, the dewaxing process is known to produce low-curing oil products [EP No. 0225053, C10G 65/04, 07/08/1992], based on the conversion of raw materials at 2.86 MPa, 330-370 ° C, feed rate 1 h ^-1 , volume ratio hydrogen / feed 356 l / l in the presence of a catalyst containing, wt.%: Pt - 0.6; zeolite Beta - 65%, alumina - the rest. The disadvantage of this process and the catalyst is the low yield of the desired dewaxed fraction.

In order to improve the catalytic properties, zeolite-containing catalysts are subjected to ion exchange and subsequent calcination. Thus, a hydroisomerization catalyst is known, a method for its preparation and a method for dewaxing [RF No. 2465959, B01J 29/74, 02/04/2009]. The hydroisomerization process is carried out in the presence of a catalyst based on zeolites of the type ZSM-22, ZSM-23 or ZSM-48, subjected to ion exchange in a solution containing cationic groups, on which platinum or palladium is then deposited. The catalyst is calcined in air and reduced in a stream of hydrogen. In this case, the yield of the isomerized fraction does not exceed 80%.

Thus, a common disadvantage for the above catalysts, methods for their preparation and methods of hydroisomerization is that with their use it is not possible to achieve high yields of low-hardening products.

из раствора, имеющего pH 10 на предварительно прокаленный цеолит, далее катализатор промывают водой, сушат при 120°C и прокаливают при 483°C на воздухе. При получении продукта с температурой застывания ниже -30°C его выход не превышает 72%.The closest in their technical essence and the achieved effect to the claimed catalyst, preparation method and hydroisomerization process are the method and catalyst [US No. 6051129, C10G 73/38, 04/18/2000], according to which hydroisomerization is carried out at a temperature of 200-475 ° C, pressure 1-200 atm, feed rate 0.1-20 h ^-1 , hydrogen / feed ratio 50-1000 m ³ / m ³ in the presence of a catalyst containing 0.5 wt.% Pd supported on zeolite ZSM-48. The catalyst is prepared by ion exchange $${\text{Pd (NH}}_{\text{3}}{\text{)}}_{\text{four}}^{\text{2}+}{{\text{(NO}}_{\text{3}}\text{)}}_{\text{2}}$$

from a solution having a pH of 10 per pre-calcined zeolite, then the catalyst is washed with water, dried at 120 ° C and calcined at 483 ° C in air. Upon receipt of the product with a pour point below -30 ° C, its yield does not exceed 72%.

The main disadvantage of the prototype, as well as other known catalysts, methods for their preparation and hydroisomerization processes is the low yield of target products.

The invention solves the problem of creating an improved catalyst for hydroisomerization, a method for its preparation and a process for hydroisomerization of diesel fuel, characterized by:

1. The optimal chemical composition of the catalyst and its texture characteristics, providing low-setting diesel fuel with a high cetane number with high yields.

2. A cooking method that provides a catalyst with a given chemical composition, texture characteristics and improved catalytic properties.

3. The process of hydroisomerization, providing low-setting diesel fuel with high yields.

The problem is solved by the composition of the catalyst for the process of hydroisomerization of diesel fuel, which contains zeolite type ZSM-23, palladium, boron and alumina, while the components are contained in the following concentrations, wt.%: Zeolite ZSM-23 - 70; palladium - not more than 0.6; boron 1.0-3.0; Al ₂ O ₃ - the rest, and the catalyst has a pore volume of at least 0.25 cm ³ / g, a specific surface area of at least 150 m ² / g, an average pore diameter of at least 4 nm.

The problem is also solved by the method of preparation of the catalyst, which consists in impregnating a support containing zeolite ZSM-23 with a ratio Si / Al = 30, a solution of boric acid, followed by drying and calcination at 550 ° C, and subsequent impregnation of a boron-containing support with an aqueous solution of palladium nitrate and ammonia having a pH of 6.5-7.0 s, followed by drying and calcination at 550 ° C. Impregnation is carried out with excess solutions in a rotary evaporator for 1 hour at 60 ° C, 1 hour at 80 ° C with air supply. In this case, for the preparation of the catalyst, the ratios of the components and the concentration of the solutions are used, which provide a catalyst containing, wt.%: Zeolite ZSM-23 - 50-80, optimally - 70; palladium - not more than 0.6; boron 1.0-3.0; Al ₂ O ₃ - the rest, and having a pore volume of at least 0.25 cm ³ / g, a specific surface area of at least 150 m ² / g, an average pore diameter of at least 4 nm.

The problem is also solved by the method of hydroisomerization of diesel fuel, with a boiling point of not more than 360 ° C and containing no more than 30 ppm of sulfur, by contacting it at a temperature of 320-340 ° C, a pressure of 2.5-6.5 MPa, a volumetric feed rate - 2-6 h ^-1 , the volumetric ratio of hydrogen / feed - 200-600 nm ³ / m ³³ with a catalyst containing, wt.%: Zeolite ZSM-23 - 50-80, optimally 70; palladium not more than 0.6; boron 1.0-3.0; Al ₂ O ₃ - the rest, having a pore volume of at least 0.25 cm ³ / g, a specific surface area of at least 150 m ³ / g, an average pore diameter of at least 4 nm.

A distinctive feature of the proposed catalyst in comparison with the prototype is that the catalyst contains boron and zeolite ZSM-23 with a ratio of Si / Al = 30, containing not more than 0.05% sodium oxide and not less than 95% MTT phase, as well as palladium and oxide aluminum, while the concentration of components in the catalyst, wt.%: zeolite ZSM-23 - 50-80, optimally - 70; palladium - not more than 0.6; boron 1.0-3.0; Al ₂ O ₃ - the rest, and the catalyst has a pore volume of at least 0.25 cm ³ / g, a specific surface area of at least 150 m ² / g, an average pore diameter of at least 4 nm.

The exit content of components and texture characteristics of the catalyst for the claimed boundaries leads to a sharp deterioration in its catalytic properties. The use of a catalyst with a different palladium content is impractical for the following reasons: a decrease in the concentration of palladium worsens the catalytic properties; an increase in the concentration of palladium does not lead to a significant improvement in the catalytic properties, but causes an unjustified consumption of palladium and a rise in the cost of the catalyst.

The main distinguishing feature of the proposed method for the preparation of the catalyst in comparison with the prototype is that the result is a catalyst containing, wt.%: Zeolite ZSM-23 - 50-80, optimally 70; palladium - not more than 0.6; boron 1.0-3.0; Al ₂ O ₃ - the rest, and the catalyst has a pore volume of at least 0.25 cm ³ / g, a specific surface area of at least 150 m ² / g, an average pore diameter of at least 4 nm.

The second distinguishing feature of the proposed method for the preparation of the catalyst compared with the prototype is that for the preparation of the catalyst using zeolite type ZSM-23 with a ratio of Si / Al = 30, containing not more than 0.05% sodium oxide and not less than 95% crystalline phase MTT, in an amount providing a content in the finished catalyst of 50-80, optimally 70 wt.% zeolite.

The third distinguishing feature of the proposed method for the preparation of the catalyst is that boron is introduced into its composition so that its concentration in the finished catalyst lies in the range of 1.0-3.0 wt.%.

A distinctive feature of the claimed process of hydroisomerization of diesel fuel is that the hydroisomerization of diesel fuel, with a boiling point of not more than 360 ° C and containing not more than 30 ppm of sulfur, is carried out by contacting it at a temperature of 320-340 ° C, pressure 2.5-6, 5 MPa, a volumetric feed rate of 2-6 h ^-1 , a volumetric hydrogen / feed ratio of 200-600 nm ³ / m ³ with the inventive catalyst prepared by the inventive method.

The technical effect of the proposed catalyst for hydroisomerization, the method of its preparation and the process of hydroisomerization of diesel fuel, consists of the following components:

1. The claimed chemical composition of the catalyst determines its maximum activity and selectivity in the target hydroisomerization reactions of normal paraffins contained in diesel fuel and causing its high pour point.

2. The presence of ZSM-23 zeolite with Si / Al = 30 in the catalyst composition, modified with boron blocking the centers of excess acidity, minimizes the occurrence of undesired hydrocarbon cracking reactions and thereby provides the desired products with maximum yields.

3. The presence of palladium in the catalyst composition, in addition to the high isomerizing activity, ensures the hydrogenation of the unsaturated and aromatic compounds contained in the feed, which compensates for the drop in the cetane number of diesel fuel, which occurs due to the conversion of high-cetane, but with a high pour point n- paraffins to low-curing isoparaffins, the cetane number of which is lower than that of n-paraffins with an equal number of carbon atoms.

4. The use of palladium as the active metal in the claimed concentration ensures the stability of the catalyst to the toxic effects of sulfur compounds contained in the feed.

Description of the proposed technical solution.

First, a carrier is prepared containing zeolite and alumina. To prepare the carrier and catalyst, ZSM-23 zeolite powder in the H-form can be used prepared by any of the known methods, provided that it meets the requirements given in table 1.

Table 1 The main characteristics of zeolite ZSM-23 Characteristic Norm Appearance White powder The molar ratio of Si / Al thirty Mass fraction of losses during calcination 700 ° C,% no more 10 Specific surface, cm ³ / g, not less 200 Mass fraction of sodium oxide,%, no more 0.05 Mass fraction of alumina,%, no more 1,0 The proportion of the zeolite phase of the MTT structure,%, not less 95

An aluminum hydroxide powder AlOOH having a boehmite or pseudoboehmite structure is used.

To a sample of AlOOH aluminum hydroxide powder, with continuous stirring in a mixer with Z-shaped blades, the calculated amount of ZSM-23 zeolite powder in the H-form, water and nitric acid is successively added and stirring is continued until a homogeneous mass is formed.

The finished mass is transferred from the mixer into the molding cylinder of the laboratory extruder and pressed through the hole of the die, providing extrudates of the finished carrier with a cross section in the shape of a trefoil with a size from 1.3 to 1.7 mm from the top of the trefoil to the middle of the base.

Then heat treatment is carried out, including drying and calcination. The extrudates are dried in an oven at a temperature of (120 ± 10) ° C. Calcination is carried out in a muffle furnace with compressed air supplied to the furnace. The extrudates in a porcelain cup are placed in an oven and calcined at a temperature of (550 ± 10) ° C for 4 hours. The air flow during calcination is 1 dm ³ / min. After completion of the operation, the container with the carrier is cooled to a temperature not exceeding 50 ° C and discharged from the muffle furnace.

The result is a homogeneous carrier of white color, representing granules with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of 2-20 mm.

Next, prepare an aqueous impregnating solution with a given concentration of boric acid. The resulting solution is impregnated with a zeolite-containing carrier. The impregnation is carried out with an excess of solution in a rotary evaporator for 1 hour at 60 ° C, 1 hour at 80 ° C with air supply, however, the total amount of boron introduced into the carrier should provide a boron content of 1.0-3.0 in the finished catalyst. The resulting support containing boron, zeolite and alumina is dried at 120 ° C and calcined at 550 ° C.

Next, the resulting carrier is impregnated in a rotary evaporator for 1 h at 60 ° C, 1 h at 80 ° C with air supply, an excess of an aqueous solution of palladium nitrate and ammonia having a pH of 6.5-7.0, while the concentration of palladium in the solution is to provide a finished catalyst containing 0.6 wt.% palladium. The catalyst was dried at 120 ° C and calcined at 550 ° C.

As a result, a catalyst is obtained whose characteristics fully correspond to the claimed intervals.

Next, hydroisomerization of hydrotreated diesel fuel is carried out with a sulfur content of not more than 30 ppm and a boiling point of not more than 360 ° C, having a pour point of -13 ° C.

To do this, a portion of the catalyst is placed in a stainless steel flow reactor, incubated for 2 hours at 3.5 MPa and 400 ° C in a stream of hydrogen flowing at a volume flow of 1000 h ^-1 , then hydroisomerization is carried out at a temperature of 320-340 ° C, pressure 3 , 5 MPa, a volumetric feed rate of 4.0 h ^-1 , a volumetric hydrogen / feed ratio of 500 nm ³ / m ³ .

The invention is illustrated by the following examples.

Example 1

First, a zeolite-containing carrier is prepared, for which 60.0 g of ZSM-23 zeolite with a Si / Al ratio of 30 in the H-form and 30.6 g of aluminum hydroxide with pseudoboehmite structure are weighed and loaded into the trough of the mixer with Z-shaped blades and mixed for 30 minutes. Then, 50 ml of water and 20 ml of nitric acid having a density of 1.4 g / cm ^{3 are} added to a mixture of powders with stirring. The paste is mixed until a plastic molding material is obtained.

The finished mass is transferred from the mixer into the molding cylinder of the laboratory extruder and pressed through the hole of the die, providing extrudates of the finished carrier with a cross section in the shape of a trefoil with a size from 1.3 to 1.7 mm from the top of the trefoil to the middle of the base.

Then heat treatment is carried out, including drying and calcination. The extrudates are dried in an oven at a temperature of (120 ± 10) ° C. Calcination is carried out in a muffle furnace with compressed air supplied to the furnace. The extrudates in a porcelain cup are placed in an oven and calcined at a temperature of (550 ± 10) ° C for 4 hours. The air flow during calcination is 1 dm ³ / min. After completion of the operation, the container with the carrier is cooled to a temperature not exceeding 50 ° C and discharged from the muffle furnace. The yield of zeolite-containing carrier is 64 g.

Then, 0.5635 g of boric acid is dissolved at 60 ° C in 15 ml of distilled water. A portion of a zeolite-containing carrier is placed in a flask of a rotary evaporator, a solution of boric acid is added, and the mixture is kept under rotation at 4-6 rpm for 1 h at 60 ° C, then 1 h at 80 ° C with an air supply of 100 ml / min. Then the carrier is dried for 4 hours at 120 ° C and calcined for 4 hours at 550 ° C.

Next, a solution of palladium nitrate is prepared, for which 0.25 g of a commercial solution of palladium nitrate having a palladium concentration of 27.15% is dissolved in 10 ml of water to which aqueous ammonia is added so that the pH of the solution is 6.5 and its volume is 15 ml

The previously obtained boron-containing support and a solution of palladium and ammonia nitrate are placed in a flask of a rotary evaporator, the mixture is kept at 4-6 rpm for 1 hour at 60 ° C, then 1 hour at 80 ° with an air supply of 100 ml / min. The catalyst is then dried for 4 hours at 120 ° C and calcined for 4 hours at 550 ° C. The finished catalyst contains, wt.%: Zeolite ZSM-23 - 70; palladium - 0.6; boron 1.0; Al ₂ O ₃ - the rest has a pore volume of 0.45 cm ³ / g, a specific surface area of 190 m ² / g, an average pore diameter of 4.8 nm.

A portion of the catalyst 2 g (in the form of a fraction of 0.5-0.25 mm) is placed in a stainless steel flow reactor, incubated for 2 hours at 3.5 MPa and 400 ° C in a stream of hydrogen flowing at a volumetric flow rate of 1000 h ^-1 , then hydroisomerization of diesel fuel containing 30 ppm sulfur, having a boiling point of 360 ° C and a pour point of -13 ° C at a temperature of 320-340 ° C, a pressure of 3.5 MPa, a volumetric feed rate of 4.0 h ^-1 , volumetric the ratio of hydrogen / raw materials is 500 nm ³ / m ³ .

The results of hydroisomerization are shown in table 2.

Example 2

The zeolite-containing support from Example 1 was used, as well as the similar catalyst preparation steps as in Example 1, with the difference that 0.845 g of boric acid was used and the palladium-ammonia solution had a pH of 7. The conditions for intermediate and final drying and calcination were similar to those in Example 1 The finished catalyst contains, wt.%: Zeolite ZSM-23 - 70; palladium - 0.6; boron 1.5; Al ₂ O ₃ - the rest has a pore volume of 0.43 cm ³ / g, a specific surface area of 185 m ² / g, an average pore diameter of 4.7 nm.

The results of hydroisomerization are shown in table 2.

Example 3

The catalyst is prepared analogously to example 2, with the difference that the weight of boric acid is 1.125 g. The finished catalyst contains, wt.%: Zeolite ZSM-23 - 70; palladium - 0.6; boron 2.05; Al ₂ O ₃ - the rest has a pore volume of 0.41 cm ³ / g, a specific surface area of 180 m ³ / g, an average pore diameter of 4.6 nm.

The results of hydroisomerization are shown in table 2.

Example 4

The catalyst is prepared analogously to example 1, with the difference that a portion of boric acid is 1.7 g. The finished catalyst contains, wt.%: Zeolite ZSM-23 - 70; palladium - 0.6; boron 3.0; Al ₂ O ₃ - the rest, has a pore volume of 0.40 cm ³ / g, specific surface area of 170 m ² / g, average pore diameter of 4.4 nm.

The results of hydroisomerization are shown in table 2.

table 2 Residual sulfur content in products after hydrotreatment of hydrocarbons Example No. Hydroisomerization Temperature Diesel yield 140-360 ° C Cetane number The pour point of diesel fuel, ° C one 320 89.0 52.1 -42 2 330 90.6 52.6 -40 3 330 89.5 52,2 -40 four 340 89.1 52.3 -41

Thus, as can be seen from the above examples, the proposed catalyst due to its chemical composition and texture, due to the presence of boron, palladium and zeolite ZSM-23 in the catalyst, prepared by the present method, allows the hydroisomerization process to produce a low-curing high-cetane diesel fuel with a yield significantly exceeding those achieved with known catalysts.

Claims (12)

1. The catalyst for the hydroisomerization of diesel fuel, comprising palladium and zeolite, characterized in that it contains zeolite type ZSM-23, palladium, boron and aluminum oxide, while the components are contained in the following concentrations, wt.%: Zeolite ZSM-23 - 50-80; palladium - not more than 0.6; boron 1.0-3.0; Al ₂ O ₃ - the rest. 2. The catalyst according to claim 1, characterized in that it has a pore volume of at least 0.25 cm ³ / g, a specific surface area of at least 150 m ² / g, an average pore diameter of at least 4 nm. 3. The catalyst according to claim 1, characterized in that the zeolite type ZSM-23 included in the catalyst has a Si / Al ratio of 30, contains not more than 0.05% sodium oxide and not less than 95% of the crystalline phase. 4. A method of preparing a hydroisomerization catalyst by applying the active component to a carrier, followed by drying and calcining, characterized in that the carrier containing a zeolite type ZSM-23 and alumina is impregnated with an aqueous solution of boric acid H ₃ BO ₃ , dried, calcined and then impregnated with a nitrate solution palladium (II) Pd (NO ₃ ) ₂ , dried, calcined and receive a catalyst containing components in the following concentrations, wt.%: zeolite ZSM-23 - 50-80; palladium - not more than 0.6; boron - 1.0-3.0; Al ₂ O ₃ - the rest. 5. The method according to claim 4, characterized in that the resulting catalyst has a pore volume of at least 0.25 cm ³ / g, a specific surface area of at least 150 m ² / g, an average pore diameter of at least 4 nm. 6. The method according to claim 4, characterized in that the ZSM-23 type zeolite included in the catalyst has a Si / Al ratio of 30, contains not more than 0.05% sodium oxide and not less than 95% crystalline phase. 7. The method according to claim 4, characterized in that for the application using solutions of boric acid and palladium nitrate (II) with concentrations that provide a catalyst containing components in the following concentrations, wt.%: Zeolite ZSM-23 - 50-80; palladium - not higher than 0.6; boron 1.0-3.0; Al ₂ O ₃ - the rest. 8. The method according to claim 4, characterized in that the carrier is impregnated with an excess of an aqueous solution of boric acid in a rotary evaporator with air supply. 9. The method according to claim 4, characterized in that the carrier containing boron is impregnated with a solution of palladium (II) nitrate, to which an aqueous solution of ammonia is added in quantities that provide a solution with a pH of 6.5-7.0. 10. The process of hydroisomerization of diesel fuel, characterized in that the hydroisomerization is carried out by contacting the feed in a stream of hydrogen with a catalyst containing components in the following concentrations, wt.%: Zeolite ZSM-23 - 50-80; palladium - not more than 0.6; boron 1.0-3.0; Al ₂ O ₃ - the rest. 11. The process according to claim 10, characterized in that the hydrotreated diesel fraction with a boiling end of not more than 360 ° C, containing not more than 30 ppm of sulfur, is used as raw material. 12. The process according to claim 10, characterized in that the hydroisomerization is carried out at a temperature of 320-340 ° C, a pressure of 2.5-6.5 MPa, a volumetric feed rate of 2-6 h ^-1 , a volumetric ratio of hydrogen / raw material 200- 600 nm ³ / m ³ .