Catalyst, method of preparing thereof and method of single-stage manufacturing of components for jet and diesel fuels with improved low-temperature properties from oil and fat raw material

FIELD: chemistry.

SUBSTANCE: described is catalyst for single-stage manufacturing of components for jet and Diesel fuels from oil and fat raw material, containing platinum or palladium, fixed on the surface of porous carrier, represented by borate-containing aluminium oxide, with the following component ratio, wt %: Pt or Pd 0,10-0.50; B2O3 5-25; Al2O3 - the remaining part. Catalyst can be prepared by granulation of mixture of aluminium oxide hydrate of pseudoboehmite structure with orthoboric acid with the following drying of granules at 120°C and annealing at 550-700°C for 16 h. Granules are soaked with solutions of hexachloroplatinic acid or palladium chloride, subjected to drying at 120°C and annealing at 500°C. Method of single-stage manufacturing of components for jet and Diesel fuels with improved low-temperature properties from oil and fat raw material in presence of claimed catalyst includes passing mixture of hydrogen and oil and fat raw material through immobile layer of catalyst at temperature 380°C, pressure 4.0 MPa, mass rate of raw material supply 1 h-1 and with volume ratio hydrogen:raw material, equal 1300.

EFFECT: increased efficiency of single-stage manufacturing of components for jet and Diesel fuels with improved low-temperature properties from oil and fat raw material due to simplification of catalyst composition, method of its preparation and reduction of catalyst cost.

3 cl, 4 tbl, 4 ex

 

Group of inventions relates to the field of biofuels, and in particular to catalysts and processes for producing components of jet and diesel fuels from oil and fat raw materials, including improved low-temperature properties.

The continuous increase in the consumption of hydrocarbon fuels with the growth in oil prices leads to the search for alternative motor fuels. Among fuels, alternative oil, on a global level today in the spotlight of so-called "biofuels", which in addition to its high environmental friendliness, are such an important advantage, as the use in their production of renewable, plant-based, sources of raw materials. On the relevance of biofuels is reflected in the huge flow of both the patent and scientific publications, see for example, reviews [G. W. Huber, S. Iborra, A. Corma / Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering // Chem. Rev. 2006. V. 106. P. 4044-4098; S. D. Varfolomeev, E. H. Efremenko, L. P. Krylova / Biofuels // Uspekhi khimii. 2010. T. 79. No. 6. S. 544-564; V. A. Yakovlev, S. A. Khromova, V. I. Bukhtiyarov / Heterogeneous catalysts for processes of transformation of triglitseridov fatty acids and their derivatives in hydrocarbon fuel setting // Uspekhi khimii. 2011. T. 80. No. 10. S. 955-970; T. V. Choudhary, NE. Phillips / Renewable fuels via catalytic hydrodeoxygenation // Appl. Catal. A: General. 2011. V. 397. P. 1-12].

On an industrial scale produce two major t�and biofuels of the first generation [R. Cascone / Biofuels: what else, besides ethanol and biodiesel // Oil and gas technology. 2008. No. 1. P. 84-92]: bioethanol, which is used as a component of gasoline and is produced from agricultural products containing starch or sugar; methyl esters of fatty acids ("biodiesel"), which is produced from vegetable oils by transesterification with methanol.

In many countries in recent years intensively developed technologies for processing of raw oil and fat (vegetable oil, animal fats) to produce hydrocarbon biofuels, the composition of which is close to the composition of conventional oil. The most effective technology for the production of renewable jet and diesel fuel is considered to be the catalytic hydroperiod vegetable oils [J. K. Satyarthi, T. Chiranjeevi, D. T. Gokak, P. S. Viswanathan / An overview of catalytic conversion of vegetable oils/fats into middle distillates // Catal. Sci. Technol. 2013. V. 3. P. 70-80]. In the General case, catalytic conversion of fat-and-oil feedstock in the presence of hydrogen include [G. W. Huber, R. O'connor, A. Corma / Processing biomass in conventional oil refineries: Production of high quality diesel by hydrotreating vegetable oils in heavy vacuum oil mixtures // Appl. Catal. A: General. 2007. V. 329. P. 120-129]: hydrogenation of triglycerides, their hydrocracking with the propane education and free fatty acids, as well as the last transition in n-alkanes (C15-C18due to the decarboxylation reactions, decarbonylation and "restore�tion" (hydrogenation/dehydration). Recovery of carboxylic acids represented as a multistage process, including education in the first stage spirits, then their dehydration and saturation of intermediate alkenes to alkanes. Oxygen under conditions of hydroperiod of raw oil and fat is removed in the form of mono - and dioxide, and water. This option hydroperiod fat-and-oil feedstock is called hydrodeoxygenation and allows the output of 70-80 wt.% be obtained, for example, from vegetable oils, vysokotochnoye (80 p.) diesel fuel has a low density, low content of aromatic hydrocarbons and the practical absence of sulfur compounds.

To improve the low temperature properties of the components of diesel fuel (low temperature cloud point and pour point), resulting in hydrodeoxygenation fat-and-oil feedstock, is further carried to a stage of hydroisomerization in which n-alkanes are moving in isoalkane. Leaders in the development and commercialization of methods for producing components of jet and diesel fuels with improved low temperature properties of oil and fat raw materials based on the consistent application of the process steps of hydrodeoxygenation and hydroisomerization are companies Neste Oil (Finland) and UOP (USA).

Neste Oil developed process NxBTL [M. Snore, P. mäki-Arvela, I. L. Simakova, J. Myllyoja, D. Y. Murzin / Overview of catalytic methods for the production of biodiesel from natural oils and fats // Supercritical fluids: theory and practice. 2009. Vol. 4. No. 1. P. 3-17], which uses Co, Ni, Mo sulfide catalysts of Albemarle company, and as raw materials of various vegetable oils and animal fat. Formed during hydrodeoxygenation in the NExBTL process of n-alkanes can be subjected to hydroisomerization using as catalysts systems Pt/SAPO-11/Al2O3, Pt/ZSM-22/Al2O3, Pt/ZSM-23/Al2O3or Pt/SAPO-11/SiO2. Get a diesel fuel characterized by a cetane number 85-99 p.

Company UOP in collaboration with the Italian company Eni S. p.A. developed the Ecofining technology designed for two-stage (hydrodeoxygenation-hydroisomerization) hydroperiod vegetable oils in vysokotsenovoj diesel fuel, enriched isoalkane [P. Nair, A. Bozzano, T. Kaines / Production of renewable diesel and jet fuels based on biological raw materials // Oil and gas technology. 2011. No. 8. P. 72-75]. A similar technology developed by Nippon Oil Corp. and Toyota Motor Corp.[H. Ono, H. Iki, A. Koyama, Y. Iguchi / Production of BHD (Bio Hydro fined Diesel with Improved Cold Flow Properties // 19th Annual Saudi-Japan Symposium, Dhahran, Saudi Arabia, November 8-9, 2009] and the company Syntroleum [US 7846323, 2010].

<> The main drawback of the above described methods for producing components of jet and diesel fuels with improved low temperature properties of oil-and-fat feedstock is dvukhstadiinoi that requires consistent application of the two catalysts of different nature, with different conditions of operation. Furthermore, catalysts based on zeolite ZSM or silicoaluminate type SAPO applied at the stage of hydroisomerization, expensive and difficult in industrial production, and cause a decrease in the yield of liquid hydrocarbon products by side reactions of cracking and the formation of light gases (C1-C4.

More attractive are the processes of hydroperiod vegetable oils, allowing a single stage to get the fuel components of jet and diesel fuels required fractional composition and with the desired temperature cloud point and pour point. For the one-step organization to get waxy components of jet and diesel fuels from oil and fat raw materials obviously necessary polyfunctional catalyst, which, along with the activation of molecular hydrogen and oxygen atoms that are part of triglycerides and derived products must have the acid properties required for the reactions of isomerization.

As catalysts one-step transformation of vegetable oils were also examined on the basis of zeolites ZSM or silicoaluminate type SAPO modified with noble metals (Pt or Pd). The metals in the composition of such catalysts in a finely dispersed state, provide the activation of molecular hydrogen and oxygen-containing compounds and zeolite and silicoaluminate components define the course of the isomerization reactions.

However, the unsaturation of vegetable oils even at high pressures of hydrogen leads to a rapid resinification and to loss of activity of catalysts of the type Pt/ZSM-22 and Pt/SAPO-11 [P. Wang, Z. Tian, L. Wang, R. Xu, Q. Liu, W. Qu, H. Ma, B. Wang / One-Step Hydrotreatment of Vegetable Oil to Produce High Quality Diesel-Range Alkanes // ChemSusChem. 2012. V. 5. P. 1974-1983].

The possibility of single-stage hydroperiod sunflower oil with getting vysokochetkogo diesel fuel, enriched isoalkane, on the catalyst type Pd/SAPO-31 was shown by the authors []. RF 2376062, 2008], but data on the stability of the catalyst were limited to a period of 4 h. the Main drawback of this invention is very complex, multistage and costly way of making the original silicoaluminate type SAPO-31. According to this patent crystal silicoaluminate with zeolite like structure type SAPO-31 �Holocaust by preparing an aqueous reaction mixture, containing a source of aluminum, phosphoric acid, a source of silicon as well as organic structure-forming compound. As the source of aluminum can be used various hydrous oxides of aluminum, aluminum alkoxides. As the source of silicon can be used various forms of amorphous silica or organic salts of silicon. The role of organic structure-forming compounds may act di-n-butylamine or a mixture of di-n-butylamine and di-n-Propylamine. For acceleration of crystallization in the reaction mixture can enter the seed material in the form of preformed crystals of SAPO-31. Prepared reaction mixture was placed in an autoclave and heated under hydrothermal conditions. After crystallization a solid product was filtered, washed with water, dried and calcined. Then the material SAPO-31 is molded with pseudoboehmite, and the obtained granules are dried again and calcined.

The closest the technical result of the proposed invention is "Catalyst, method of its preparation and method for producing diesel fuel from raw materials of natural origin" [Pat. RF 2429909, 2010, prototype]. The present invention also describes a catalyst based on crystalline silicoaluminate with zeolite like structure type SAPO-31, modified m�the thalli of the VIII group of the Periodic system. Preliminary obtain crystalline silicoaluminate with zeolite like structure type SAPO-31 and its composition with aluminum oxide is carried out according to the method described in the invention [Pat. RF 2376062, 2008]. For preparing the catalyst composition of silicoaluminate type SAPO-31 with aluminum oxide impregnated with a solution of compounds of platinum and/or palladium at the rate of not more than 10.0 wt.% metal in the composition of the final product with the subsequent drying and oxidizing treatment at a temperature not exceeding 500°C at a speed of temperature rise above 20°C/min. the Process of transformation of sunflower oil with the use of this catalyst is carried out under flow conditions at a temperature of 340°C, a pressure of 4.0 MPa, the mass feed rate of 1.2 h-1and with a volumetric ratio of hydrogen:raw materials, is $ 1200. The result shows that the catalyst is stable ratio isoalkane/n-alkanes in the liquid products formed in the range of 15-27% of the variation in hours of work to 84-102 h. the Main disadvantages of the prototype are very complex, multistage and costly way of making the original silicoaluminate type SAPO-31 and a high content (at least 1 wt.%) also expensive precious metals (Pt and/or Pd). In addition, for the method of obtaining diesel fuel available in the prototype is not specified are necessary for realization of method performance: the yield of liquid hydrocarbon products, their group and component composition, the water outlet.

The invention solves the problem of the development of catalyst for one-step produce components of jet and diesel fuels with improved low temperature properties of oil and fat raw materials, a different more simple composition, simplicity and adaptability to obtain, at low cost, including by reducing the content of precious metals (Pt, Pd) 2-4 times, while maintaining the isomerization ability of the properties of the catalyst at a stable level for at least 100 h.

As a solution, ensuring achievement of the set objectives, it is proposed a catalyst for one-step produce components of jet and diesel fuels with improved low temperature properties of oil-and-fat feedstock containing platinum or palladium fixed on the surface of the porous support, characterized in that as the carrier used bortagaray aluminum oxide, with the following ratio of components in the catalyst, wt.%: Pt or Pd 0,10-0,50; B2O35-25; Al2O3- the rest.

The catalyst differs from the prototype of a simple component structure and content of noble metal (Pt or Pd) is not more than 0.5 wt.% against the minimum content of 1 wt.%, characteristic for the prototype.

Needed to odnostadiinoi components of jet and diesel fuels with improved low temperature properties of oil-and-fat feedstock polyfunctionality of the proposed catalyst is provided: dealt with dispersed particles metallic platinum or palladium, ensuring the activation of molecular hydrogen and oxygen-containing compounds, and acidic properties bortagaray of aluminum oxide, which determine the formation of alkanes isotrate.

The proposed method for the preparation of a new catalyst for one-step produce components of jet and diesel fuels with improved low temperature properties of oil-and-fat feedstock is characterized by simplicity and manufacturability of production as compared with the prior art and, consequently, lower cost. The method includes obtaining prior bortagaray of aluminum oxide by mixing the hydrate of alumina of pseudoboehmite structure of orthoboric acid, granulating the mixture, followed by drying the pellets at 120°C and calcination in flowing air at 550-700°C for 16 hours Then spend the impregnation bortagaray of aluminum oxide with an aqueous solution of hexachloroplatinic acid or of palladium chloride with further drying at 120°C, calcination at 500°C for 16 h and providing the following ratio in the catalyst, wt.%: Pt or Pd 0,10-0,50; B2O35-25; Al2O3- the rest. In addition, the lower cost of the proposed catalyst in comparison with the prototype is achieved due to the reduction nigerianisation metals (Pt, Pd) 2-4 times.

With the use of the present catalyst can be implemented in a single-stage method for producing components of jet and diesel fuels with improved low temperature properties comprising passing a mixture of hydrogen and oil and fat raw materials through the fixed catalyst bed at a temperature of 380°C, a pressure of 4.0 MPa, the mass feed rate of 1 h-1, the volumetric ratio of hydrogen:the raw material is equal to 1300, while maintaining the isomerization ability of the properties of the catalyst at a stable level for at least 100 hours.

The invention is illustrated by the following examples.

Example 1.

To prepare the catalyst pre-receive bortagaray alumina by mixing the hydrate of alumina of pseudoboehmite structure and orthoboric acid based on the weight ratio (B2O3:Al2O3equal to 0,25. The resulting mixture is granulated by known methods, the granules are dried at 120°C and then calcined at 550°C in flowing air for 16 hours Obtained in granular form bortagaray aluminum oxide is impregnated with an aqueous solution of hexachloroplatinic acid based achievements contents of Pt in the finished catalyst on a dry level of 0.10, 0.25 and 0.50 wt.%. Soaked bortagaray alumina was dried at 120°C and calcined at 500°C in flowing air� for 16 hours Samples of the finished catalyst have the composition, wt.%: Pt - 0,10, 0,25, 0,50; B2O3- 20; Al2O3- the rest.

The single-stage process for producing components of jet and diesel fuels with improved low temperature properties spend on running the installation with a fixed bed catalyst at a temperature of 380°C and a pressure of 4.0 MPa. As raw material use sunflower oil which is served with a bulk velocity of 1 h-1in mixture with hydrogen at a volumetric ratio of hydrogen:raw materials, is $ 1300. Process indicators determine 1 every 4 h for a total duration of 20 h. the main parameters to be defined include: the total yield of liquid hydrocarbon products (C5+ ) water, hydrocarbons C10-C20- target products intended for use as components of jet and diesel fuels. In addition, according to gas chromatographic analysis evaluated group composition of liquid hydrocarbon products and for the target hydrocarbons of the C10-C20determine the content of n - and isoalkanes.

The test results of samples of the finished catalyst having the composition (wt.%): Pt - 0,10, 0,25, 0,50; B2O3- 20; Al2O3- other, presented in table 1. All samples provide complete hydrodeoxygenation sunflower oil that p�derided the absence of oxygen-containing compounds in the composition of liquid hydrocarbon products according to elemental and chromato-mass-spectrometric analyses. The total yield of liquid hydrocarbon products (C5+ for all the samples no lower than 78 wt.%. The maximum value of the output of 86.3 wt.%. The highest values of yield of the target products (C10-C20observed for samples of the catalyst containing 0.10 and 0.25 wt.% Pt - 73,4-74,4 wt.%. The highest content of isoalkanes for a fraction of the target products (C10-C20is achieved on the sample of catalyst containing 0.50 wt.% Pt, and is 83,0 wt.%. The ratio isoalkane/n-alkanes within 20 hours of testing is reduced by 42%.

Example 2.

Similar to example 1, but obtained in granular form bortagaray aluminum oxide impregnated with an aqueous solution of palladium chloride at the rate of achievement of the Pd content in the finished dry the catalyst at the level of 0.10, 0.25 and 0.50 wt.%. Samples of the finished catalyst have the composition, wt.%: Pd - 0.10, 0.25, 0.50; B2O3- 20; Al2O3- the rest.

The test results of samples of the finished catalyst having the composition (wt.%): Pd - 0,10, 0,25, 0,50; B2O3- 20; Al2O3- other, presented in table 2. All samples provide complete hydrodeoxygenation sunflower oil, which is verified by the absence of oxygen-containing compounds in the composition of liquid hydrocarbon products according to elemental and chromato-mass-spectrometric analyses. The total yield of liquid coal�Ogorodnik products (C 5+) for all samples not lower than 88 wt.%. The maximum output value - at 97.6 wt.%. The highest values of yield of the target products (C10-C20observed for the sample of catalyst containing 0.25 wt.% Pd - 73,9-77,6 wt.%. On the same sample achieved the highest content of isoalkanes for a fraction of the target products (C10-C20that is to 83.2 wt.%. The ratio isoalkane/n-alkanes within 20 hours of testing is reduced by 50%.

Example 3.

Similar to example 2, but getting bortagaray of aluminum oxide by mixing the hydrate of alumina of pseudoboehmite structure and orthoboric acid are based on the values of the mass ratio B2O3:Al2O3,equal: 0,00, 0,06, 0,13, 0,19, 0,25, 0,31. Obtained in granular form bortagaray aluminum oxide impregnated with an aqueous solution of palladium chloride at the rate of achievement of the Pd content in the finished catalyst on a dry level of 0.50 wt.%. Samples of the finished catalyst have the composition, wt.%: Pd - 0,50; B2O3- 0, 5, 10, 15, 20, 25; Al2O3- the rest.

The test results of samples of the finished catalyst having the composition (wt.%): Pd - 0,50;2O3- 0, 5, 10, 15, 20, 25; Al2O3- other, presented in table 3. All samples provide complete hydrodeoxygenation sunflower oil, which substantiates the lack�amount of force oxygen-containing compounds in the composition of liquid hydrocarbon products according to elemental and chromato-mass-spectrometric analyses. The total yield of liquid hydrocarbon products (C5+ for all the samples below 77,1 wt.%. The maximum output value - at 97.6 wt.%. The highest value of the yield of the target products (C10-C20is observed for the sample of catalyst containing 5 wt.% B2O3- at 82.8 wt.%. The highest content of isoalkanes for a fraction of the target products (C10-C20is achieved on a sample of catalyst comprising 25 wt.% B2O3and amounts to 87.7 wt.%. The ratio isoalkane/n-alkanes within 20 hours of testing is reduced by 70%.

Example 4.

Similar to example 2, but after drying granules bortagaray of their alumina calcined at 550, 600, 650, 700°C in flowing air for 16 hours Obtained in granular form bortagaray aluminum oxide impregnated with an aqueous solution of palladium chloride at the rate of achievement of the Pd content in the finished dry catalyst at 0.50 wt.%. Samples of the finished catalyst have the composition, wt.%: Pd - 0,50; B2O3- 20; Al2O3- the rest.

For the sample of catalyst prepared on the basis bortagaray of aluminum oxide with a calcination temperature of 700°C, the single-stage process for producing components of jet and diesel fuels with improved low temperature properties is carried out for 100 h. the Definition of process indicators additional�but to spend 52, 76 and 100 hours of catalyst operation.

The test results of samples of the finished catalyst having the composition (wt.%): Pd - 050; B2O3- 20; Al2O3- the rest, and obtained at different calcination temperatures bortagaray of aluminum oxide are presented in table 4. All samples provide complete hydrodeoxygenation sunflower oil, which is verified by the absence of oxygen-containing compounds in the composition of liquid hydrocarbon products according to elemental and chromato-mass-spectrometric analyses. The total yield of liquid hydrocarbon products (C5+ for all the samples is not lower at 76.8 wt.%. The maximum output value - at 97.6 wt.%. The highest value of the yield of the target products (C10-C20is observed for the sample of catalyst, the carrier was calcined at 550°C - 77,6 wt.%. The highest content of isoalkanes for a fraction of the target products (C10-C20achieved on samples of catalyst carriers which were calcined at 650 and 700°C, respectively, and is 87.8-to 87.9 wt.%. For the sample of catalyst, the carrier was calcined at 700°C, the ratio isoalkane/n-alkanes after 20 hours of testing is reduced by 3%, after 52 h in 3.3%, after 76 h of 4%, and after 100 h at 4.2%.

Thus, the proposed catalyst for one-step produce components of jet and diesel� fuels with improved low temperature properties of oil and fat raw materials, containing platinum or palladium fixed on bortagaray of aluminum oxide, with the following ratio of components, wt.%: Pt or Pd 0.10-0.50; B2O35-25; Al2O3- the rest is simple component composition, simplicity and adaptability to obtain, at low cost, including by reducing the content of precious metals (Pt, Pd) in 2-4 times in comparison with the prototype, and the same as the catalyst according to the method prototype, for at least 100 hours to maintain its isomerization ability functions needed to produce high quality fuel components.

Most preferred is a catalyst of the following composition, wt.%: Pd - 0,50; B2O3- 20; Al2O3- the rest is obtained at a temperature of calcination of the carrier - bortagaray of aluminum oxide at 700°C.

The technical result from the use of the invention can consist in increasing the efficiency of single-stage produce components of jet and diesel fuels with improved low temperature properties of oil and fat raw materials by simplifying the composition of the catalyst, its preparation and decrease of costs, including by reducing the content of precious metals (Pt, Pd) 2-4 times.

Table 1
The test results of samples of the catalyst of example 1
The Pt content, wt.%Time, hThe yield of liquid products, wt.%Group composition of liquid products, wt.%The isomeric composition of the fraction of C10-C20
C5+H2OC10-C20C5-C10C10-C20C21+n-alkanesisoalkane
0.10481.78.561.216.181.72.250.949.1
884.66.874.44.193.32.6 34.1
1282.36.474.03.893.72.568.631.4
1682.59.873.63.093.23.869.630.4
2083.011.372.63.791.64.769.630.4
0.25483.46.264.314.585.20.333.966.1
885.56.067.213.8 85.60.642.857.2
1284.16.168.212.587.10.445.754.3
1684.85.873.47.891.50.749.450.6
2082.19.172.17.791.11.252.347.7
0.50478.08.034.841.058.80.217.083.0
886.36.4 56.219.380.70.018.181.9
1285.78.758.717.882.10.120.579.5
1684.59.161.315.584.30.223.676.4
2082.79.863.614.485.40.226.173.9

13.0
Table 2
The test results of samples of the catalyst of example 2
The Pd content, wt.%Time, hYou�ml of liquid products, wt.%Group composition of liquid products, wt.%)The isomeric composition of the fraction of C10-C20
C5+H2OC10-C20C5-C10C10-C20C21+n-alkanesisoalkane
0.10472.98.151.120.678.50.938.161.9
880.67.668.25.789.35.075.025.0
1288.57.577.32.691.55.987.0
0.25492.16.551.626.373.50.216.683.4
896.97.371.28.091.30.727.073.0
1293.48.076.93.794.61.753.546.5
1689.07.874.51.693.25.278.521.5
2089.38.669.81.889.5 8.788.811.2
0.50493.55.069.910.089.80.216.883.2
893.24.873.97.392.60.119.980.1
1297.65.877.65.494.50.122.977.1
1694.35.877.43.995.70.425.774.3
2092.19.275.3 4.495.20.428.771.3

Table 3
The test results of samples of the catalyst of example 3
The content of B2O3wt.%Time, hThe yield of liquid products, wt.%Group composition of liquid products, wt.%The isomeric composition of the fraction10-C20
C5+H2OC10-C20C5-C10C10-C20C21+n-alkanesisoalkane
0.0487.46.880.50.496.82.896.04.0
885.46.477.50.396.33.497.42.6
1287.711.378.50.395.34.496.93.1
1686.512.775.90.394.94.896.63.4
2088.911.478.70.395.93.897.62.4
5.0491.46.782.80.296.4.4 96.13.9
890.26.780.80.296.73.197.52.5
1282.89.074.20.395.93.897.22.8
1688.412.175.60.395.14.696.83.2
10.0488.16.976.90.695.83.674.225.8
888.07.776.5 0.594.94.684.415.6
1287.47.475.20.594.45.189.910.1
1687.67.774.90.594.15.491.98.1
2084.88.274.30.593.46.192.08.0
15.0492.711.474.04.195.40.520.579.5
894.3 6.478.62.297.10.727.272.8
1293.46.079.91.597.60.934.965.1
1690.010.578.61.097.21.847.952.1
2089.18.277.90.796.52.862.937.1
20.0493.55.069.910.092.60.216.883.2
893.24.873.97.389.80.119.980.1
1297.65.877.65.494.50.122.977.1
1694.35.877.43.995.70.425.774.3
2092.19.275.34.495.20.428.771.3
25.0477.18.447.522.577.40.1 12.387.7
884.77.859.914.985.10.012.287.8
1285.88.262.614.085.90.113.986.1
1680.78.867.78.291.30.518.981.1
2081.911.176.13.595.70.831.768.3

5.8
Table 4
The test results of samples of the catalyst according to PR�measure 4
The calcination temperature, °CTime, hThe yield of liquid products, wt.%Group composition of liquid products, wt.%The isomeric composition of the fraction10-C20
C5+H2OC10-C20C5-C10With10-C20With21+n-alkanesisoalkane
550493.55.069.910.089.80.216.883.2
893.24.873.97.392.60.119.980.1
1297.677.65.494.50.122.977.1
1694.35.877.43.995.70.425.774.3
2092.19.275.34.495.20.428.771.3
600481.06.656.218.281.80.012.587.5
885.08.262.218.181.90.013.786.3
1283.97.565.215.384.70.014.685.4
1683.511.267.411.688.30.115.184.9
2081.910.469.88.291.60.218.281.8
650479.08.546.625.874.20.012.187.9
884.58.557.418.081.90.1 12.187.9
1281.56.164.013.186.90.013.486.6
1680.811.970.87.592.20.319.780.3
2082.911.276.03.296.00.835.964.1
700481.38.948.426.573.40.112.387.7
876.87.457.113.1 86.90.012.287.8
1281.86.861.614.685.30.112.687.4
1681.210.263.111.888.10.113.386.7
2080.89.965.210.489.50.115.085.0
5279.69.367.38.391.60.115.284.8
7682.37.869.5 7.192.80.115.884.2
10081.18.972.77.692.30.116.084.0

1. Catalyst for one-step produce components of jet and diesel fuels with improved low temperature properties of oil-and-fat feedstock containing platinum or palladium fixed on the surface of the porous support, characterized in that as a carrier it contains bortagaray aluminum oxide, wherein the catalyst has the following composition, wt.%:

Pt or Pd0,10-0,50
B2O35-25
Al2O3else

2. Preparation method of catalyst for one-step produce components of jet and diesel fuels with improved low temperature properties of oil-and-fat feedstock, comprising impregnation of the granules of porous media, solutions� hexachloroplatinic acid or palladium chloride, followed by drying and calcination, characterized in that the porous media is obtained by granulating the mixture of hydrate of alumina of pseudoboehmite structure of orthoboric acid, followed by drying the pellets at 120°C and calcination at 550-700°C for 16 h, the resulting catalyst has the following composition, wt.%:

Pt or Pd0,10-0,50
B2O35-25
Al2O3else

3. Single-stage method of producing components of jet and diesel fuels with improved low temperature properties comprising passing a mixture of hydrogen and oil and fat raw materials through the fixed catalyst bed, characterized in that the receiving components of jet and diesel fuels is carried out on the catalyst according to claim 1 or obtained according to claim 2, at a temperature of 380°C, a pressure of 4.0 MPa, the mass feed rate of 1 h-1and with a volumetric ratio of hydrogen:raw materials, is $ 1300.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing pyrolysis oil. A method of producing biomass-derived pyrolysis oil (38) with low metal content includes steps of: filtering a biomass-derived pyrolysis oil (12) with a high-throughput filter unit (20) having throughput of 10 l/m2/h or higher to form biomass-derived pyrolysis oil (22) with low content of solid substances; filtering the biomass-derived pyrolysis oil (22) with low content of solid substances with a fine filter (28) having a pore diameter of 50 mcm or less to form biomass-derived pyrolysis oil (30) with very low content of solid substances; and contacting the biomass-derived pyrolysis oil (30) with very low content of solid substances with an ion-exchange resin to remove metal ions and form biomass-derived pyrolysis oil (38) with low metal content. A version of the method is also disclosed.

EFFECT: total metal content is reduced to concentration of 100 ppm or less.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: method includes producing synthesis gas, converting the synthesis gas into methanol, producing a concentrate of aromatic hydrocarbons and water from the methanol in the presence of a catalyst, separating the water, blowing off hydrocarbon residues from the water, separating the formed concentrate of aromatic hydrocarbons and a hydrogen-containing gas, which is at least partially used when producing synthesis gas, to change the ratio H2:CO=1.8-2.3:1 therein. The production of aromatic hydrocarbons from methanol in the presence of a catalyst is carried out in two series-connected aromatic hydrocarbon synthesis reactors - a first low-temperature isothermic aromatic and aliphatic hydrocarbon synthesis reactor and a second high-temperature adiabatic reactor for synthesis of aromatic and aliphatic hydrocarbons from the aliphatic hydrocarbons formed in the first reactor and subsequent stabilisation in a unit for stabilising the concentrate of aromatic hydrocarbons. At least part of the hydrogen-containing gas is fed into a synthesis gas production unit and used to obtain synthesis gas using an autothermal reforming technique with a pre-reforming or non-catalytic partial oxidation unit using oxygen or oxygen-air mixtures as the oxidising agent to change the ratio according to the relationship (m.f.H2-m.f.CO2)/(m.f.CO+m.f.CO2)≥2, where m.f. is the molar fraction of a component in synthesis gas. The invention also relates to an apparatus.

EFFECT: high efficiency of producing concentrates of aromatic hydrocarbons.

12 cl, 2 dwg, 1 ex

FIELD: oil and gas industry.

SUBSTANCE: invention relates to a method for obtaining hydrocarbon products, which involves the following stages: (a) provision of synthesis gas containing hydrogen, carbon monoxide and carbon dioxide; (b) reaction of conversion of synthesis gas to an oxygenate mixture containing methanol and dimethyl ester, in presence of one or more catalysts, which simultaneously catalyse the reaction of conversion of hydrogen and carbon monoxide to oxygenates, at pressure of at least 4 MPa; (c) extraction from stage (b) of an oxygenate mixture containing quantities of methanol, dimethyl ester, carbon dioxide and water together with non-reacted synthesis gas, introduction of the whole amount of the oxygenate mixture without any additional treatment to a stage of catalytic conversion of oxygenates (d); (d) reaction of oxygenate mixture in presence of a catalyst, which is active in conversion of oxygenates to higher hydrocarbons; (e) extraction of the outlet flow from stage (d) and separation of the outlet flow into tail gas containing carbon dioxide occurring from synthesis gas and carbon dioxide formed at stage (b), liquid hydrocarbon phase containing the higher hydrocarbons obtained at stage (d) and liquid water phase where the pressure used at stages (c)-(e) is mainly the same as that used at stage (b); besides, some part of tail gas obtained at stage (e) is recirculated to stage (d), and the rest part of tail gas is discharged.

EFFECT: this method is a method in which there is no recirculation of non-reacted synthesis gas to a synthesis stage of oxygenates and without any cooling of a conversion reaction of dimethyl ester to higher hydrocarbons.

6 cl, 2 ex, 1 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: claimed invention relates to liquid fuel compositions. Invention deals with liquid fuel composition, containing, at least, one fuel component and from 0.1%(vil.) to 99.5% (vol.) of fraction of distillation of component, which contains, at least, one C4+ compound, derived from water-soluble oxygenated hydrocarbon. Method includes supply of water and water-soluble oxygenated hydrocarbon, including C1+O1+ hydrocarbon, in water liquid phase and/or vapour phase; supply of H2; carrying out catalytic reaction in liquid and/or vapour phase between oxygenated hydrocarbon and H2 in presence of deoxygenation catalyst at temperature of deoxygenation and pressure of deoxygenation to obtain oxygenate, which contains C1+O1-3 hydrocarbon in reaction flow; and carrying put catalytic reaction in liquid and/or vapour phase for oxygenate in presence of condensation catalyst at temperature of condensation and pressure of condensation to obtain C4+ compound, where C4+ compound includes representative, selected from the group, consisting of C4+ alcohol, C4+ ketone, C4+ alkane, C4+ alkene, C5+ cycloalkane, C5+ cycloalkene, aryl, condensed aryl and their mixture. Invention also relates to petrol composition, Diesel fuel composition, kerosene composition and methods of obtaining thereof.

EFFECT: improved characteristics of fuel composition, containing component, obtained from biomass.

9 cl, 19 dwg, 14 tbl, 59 ex

FIELD: chemistry.

SUBSTANCE: method includes stage of contact of pyrolysis oil, produced from biomass, with first catalyst of oxygen removal in presence of hydrogen under first, preliminarily set conditions of hydropurification with formation of first effluent stream of pyrolysis oil with low oxygen content. First catalyst of oxygen removal contains neutral catalytic carrier, nickel, cobalt and molybdenum. First catalyst of oxygen removal contains nickel in quantity from 0.1 to 1.5 wt % in terms of oxide. Version of method is also claimed.

EFFECT: extension of assortment of oxygen removal methods.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: method consists in successive application on carrier - amorphous aluminium oxide - by method of soaking with following drying and annealing of: water solution of thermally unstable salt of element, selected from the first group, including titanium, tin, zirconium, then water solution of thermally unstable salt of element, selected from the second group, including molybdenum, tungsten, and after that water solution of thermally unstable salt of element, selected from the third group, including cobalt, nickel. Obtained catalyst contains, wt %: oxide of element from the first group - 4.2-15.0, oxide of element from the second group - 12.4-14.2, oxide of element from the third group - 2.1-3.8, remaining part - aluminium oxide. After that, catalyst is activated first by soaking in hydrogen medium at temperature 450-500°C, pressure 5-8 MPa for 3-4 h, then sulfidation at temperature 250-300°C, pressure 5-8 MPa for 3-4 h. And sulfidation is carried out with mixture of hydrogen sulfide and hydrogen with concentration of hydrogen sulfide 10-15 vol%.

EFFECT: method makes it possible to obtain catalyst, which has increased isomerisation ability and preserves catalytic activity with respect to reaction of isomerisation for long time, which results in obtaining Diesel fuel, which has improved low-temperature properties.

4 ex

FIELD: chemistry.

SUBSTANCE: method of biodiesel production is realised by the re-etherification in mixing natural oil, alcohol and a catalyst and following separation of the target product. The method is characterised by the fact that at the first stage of the re-etherification iron sulphate (II) is applied as the catalyst, after which iron sulphate and precipitated glycerol are separated and the mixture of alcohol, oil and ethers of fatty acids are supplied to the second stage of the re-etherification, at which as the catalyst used is an enzyme - lipase, immobilised on the surface, after which glycerol and the enzyme catalyst are separated and the mixture of alcohol and biodiesel is directed to a stage of the target product separation.

EFFECT: method makes it possible to simplify the process of the re-etherification reaction and increase the completeness of the reaction process.

6 cl, 1 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to hydraulic treatment of hydrocarbon fuel. Proposed method comprises production of hydrocarbon stock to be processed including renewable organic substance with hydrogen flow and its feed to hydraulic treatment by bringing said hydrocarbon stock in contact with at least one stationary catalyst bed. Exit flow is fed into hot separator for extraction of top fraction from hot separator and of bottom fraction from separator bottom. Top fraction is fed to water steam conversion while exit flow is directed into cold separator for extraction of gaseous top fraction from cold separator as gas flow enriched with hydrogen to be directed to circulation. Gaseous top fraction is fed to hydrogen sulphide recuperation plant to extract a gaseous flow with decreased content of hydrogen sulphide and carbon dioxide to be fed back in the process.

EFFECT: production of hydrogen to allow decreasing the fresh hydrogen demand at hydraulic treatment stage.

9 cl, 2 dwg, 3 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to methods (processes) and systems for processing triglyceride-containing oils of biological origin with obtaining base oils and fuels for vehicles. Method of obtaining base oil and Diesel fuel includes the following stages: a) processing triglyceride-containing vegetable oil with realisation of oligomerisation and deoxygenation of components on the basis of unsaturated fatty acids, contained in it, with obtaining oligomerised mixture, with said processing including hydration and further removal of water; b) isomerisation of oligomerised mixture above isomerisation catalyst with obtaining isomerised mixture, and isomerised mixture contains base oil component and Diesel fuel component, and isomerised mixture contains, at least, 10 wt % of alkanes with number of carbon atoms 30 or higher, and c) distillation of isomerised mixture with obtaining base oil and Diesel fuel, where oligomerised mixture includes oligomer component, and said oligomer component includes, at least, 50 wt % of dimeric compounds.

EFFECT: processing of oils of biological origin into wide range of products with good level of properties.

11 cl, 4 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: present invention describes a method of producing hydrocarbon raw material for synthesis of biofuel from lignin. The method involves hydrotreatment of lignin-containing raw material to obtain raw material for biofuel. The lignin-containing raw material contains lignin which is separated from black liquor from a pulping method. The lignin is separated from black liquor from a pulping method by injecting carbon dioxide (CO2) gas. The lignin-containing raw material further contains still residues from an oil refining plant.

EFFECT: as a result of hydrotreatment of lignin contained in raw material for biofuel, oxygen content and average molecular weight of the latter decreases compared to lignin.

8 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for producing synthesis gas during partial oxidation of methane, which is a microspherical support with a deposited active component based on metal oxides, wherein the microspherical support used is aluminium oxide and/or aluminosilicate particles with diameter of 50-160 mcm, and the active component used is an oxide of Co or Ni or Fe or Mn or Cu or Ce or a mixture of oxides NiO, Co3O4 and Ce2O3, with the following ratio of components, wt %: said active component 2-40, aluminium oxide and/or aluminosilicate - the balance. The invention also relates to a method of producing the catalyst and a method of producing synthesis gas in the presence of the disclosed catalyst.

EFFECT: high specific output of the product, eliminating explosion and ignition hazard, low power consumption, obtaining synthesis gas with H2/CO ratio in the range of 1,5-2,5, obtaining a by-product - technical nitrogen - with high conversion of methane-containing material.

7 cl, 3 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing a catalyst for producing a component of environmentally safe hydrocarbon-based drilling mud, having a boiling range of 188-304°C according to ASTM D 86, which includes preparing a paste from gel obtained by mixing boehmite Pural SB with a mixture of nitric acid and distilled water, triethylene glycol and zeolite HY with molar ratio SiO2/AlO3 equal to 30 or 60, the porous structure of which is a system of interconnected straight channels formed by 12-member rings with diameter of the entrance window of 7E, extrusion, holding at room temperature for 9-10 hours, drying, grinding to particle size of 2-4×2 mm and calcining. The invention also relates to a catalyst for producing a component of environmentally safe hydrocarbon-based drilling mud and a method of producing said component.

EFFECT: simple technique, low cost of production while maintaining physical and chemical properties and improved performance in a wide temperature range, cetane number of not more than 45, and complete absence of aromatic, amine- and sulphur-containing compounds.

7 cl, 6 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: method includes processing, preparation and soaking of a carrier with an intermediate coating with an active phase salt solution. The carrier is prepared from reticulated foam polyurethane by soaking with ceramic slip, which contains an inert filler - electro-fused corundum, dispersive powder of aluminium oxide with additives of magnesium and titanium oxides and a solution of polyvinyl alcohol (PVA), dried at a temperature of 100…120°C, and annealed at a temperature of 1470…1510°C. Then the obtained ceramic highly-porous block-cellular matrix is successively soaked with an alumina sol solution in a quantity to 10.0 wt % of the carrier weight, dried at a temperature of 100…120°C and annealed in air at a temperature of 550…600°C, cooled, processed with a palladium chloride solution with the content of palladium of 1.5…4.0 g/l, dried at a temperature not higher than 120°C, annealed at a temperature of 450…500°C in air, reduced in a molecular hydrogen flow until a catalytic layer in the form of metal palladium with the weight content not higher than 1.0 wt % is formed at a temperature of 60…85°C.

EFFECT: method makes it possible to obtain catalysts, which have high activity in the process of hydrogen oxidation, to reduce the temperature of their exploitation.

4 ex

FIELD: chemistry.

SUBSTANCE: group of inventions relates to catalytic materials for chemical reactors. Said catalytic materials contain hybrid inorganic/polymer carriers and preliminarily obtained molecular catalysts immobilised on them. Hybrid inorganic/polymer carrier consists of hybrid inorganic/polymer compound, in which organic polymers are chemically bound with at least one inorganic compound, selected from the group, consisting of silicic acid compound, tungstic acid compound, molybdic acid compound and stannic acid, and immobilised preliminarily obtained molecular catalyst contains at least one atom or ion of transition metal, selected from groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII of periodic system of elements, which one or several ligand(s) is(are) bound with.

EFFECT: claimed catalytic material acts as heterogenic catalyst with selectivity, comparable with selectivity, observed in homogenous phase, with said catalyst being insoluble in reaction solvent and easily removable from reaction mixture.

27 cl, 3 tbl, 7 ex

FIELD: oil and gas industry.

SUBSTANCE: invention is related to suppression methods of harmful effects of metals on catalytic cracking of hydrocarbon stock. This target is reached by use of metal-catching particle, which contains spray-dried mixture of kaolin, magnesium hydrate or oxide and calcium carbonate, at that the spray-dried mixture was ignited at temperature within the range from 816°C up to almost 899°C. The invention is also related to a metal passivation method, which includes: contact of hydrocarbon flow containing metal in the fluid-catalytic cracking plant with mixture of suspended cracking catalyst and granulate metal trap; at that the metal trap contains spray-dried mixture of kaolin, magnesium hydrate or oxide, and calcium carbonate, at that the spray-dried mixture subjected to ignition at temperature within the range from 816°C up to almost 899°C and the ignited metal trap contains magnesium oxide in quantity of at least 10 wt %.

EFFECT: invention is related to suppression methods of harmful effects of metals on catalytic cracking of hydrocarbon stock.

20 cl, 1 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: method of obtaining platinum-containing catalysts on nanocarbon carriers includes processing of nanocarbon component with chloroplatinic acid with the following reduction of the latter with ethyleneglycol in alkaline medium, with carbon nanoparticles being preliminarily subjected to functionalisation by boiling in concentrated nitric acid, washed after that with distillated water to neutral pH, dried in vacuum at temperature 40°C; after which carbon nanoparticels are placed in flask, which contains distillated water and chloroplatinic acid, ethyleneglycol and twice-normal solution of NaOH are added to pH ≈ 12-14, mixture is mixed in ultrasonic bath, then heated to 140-150°C with continuous mixing of said mixture in argon flow. After that, polyetheneglycol with molecular weight MM ~ 40000 is added, after that, mixture is cooled to room temperature, placed in centrifuge and washed with distillated water to neutral pH with the following drying in vacuum at 40°C to constant weight.

EFFECT: obtaining catalyst with more monodispersive and regulated distribution of platinum nanoparticels by size, which leads to economy of electric power and work labour saving and to reduction of price of obtained catalysts.

3 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: catalyst is obtained by impregnation of glass fibre carrier (structured in form of material, woven from threads with 1 mm diameter) with film-generating solution, maturation of which is realised at temperature 20-22°C for 4-5 days, and its further step-by-step thermal processing - at 60°C for 30-40 minutes and at 700°C for 1 hour, with the following ratio of initial solution components, wt %: titanium tetra-n-butoxide from 4.09 to 4.13, tetraethoxysilane from 0 to 1.49, cobalt(II) chloride tetrahydrate from 2.15 to 3.41, hydrochloric acid 0.27, distilled water from 0.56 to 1.04, n-butyl alcohol - the remaining part.

EFFECT: increased level of purification.

1 tbl, 2 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: stage of nickel and molybdenum evaporation from combined solution, containing nickel nitrate and ammonium molybdate, is carried out, after which stage of thermochemical processing of sediment in hydrogen flow and its passivation are performed. Catalyst activation is performed by processing suspension of 10 wt % of nitride powder in ethanol by ultrasound with power to 1 kW.

EFFECT: method makes it possible to increase catalytic activity, selectivity and mechanical strength of obtained catalyst.

1 ex

FIELD: chemistry.

SUBSTANCE: method consists in electrolytic sedimentation of zinc on foam-nickel and thermal processing in inert medium at temperature from 650 to 750°C for not more than 2 h.

EFFECT: method makes it possible to simplify preparation of skeletal catalyst, reduce time of thermal processing and create foam-nickel with developed porous surface.

3 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: method consists in successive application on carrier - amorphous aluminium oxide - by method of soaking with following drying and annealing of: water solution of thermally unstable salt of element, selected from the first group, including titanium, tin, zirconium, then water solution of thermally unstable salt of element, selected from the second group, including molybdenum, tungsten, and after that water solution of thermally unstable salt of element, selected from the third group, including cobalt, nickel. Obtained catalyst contains, wt %: oxide of element from the first group - 4.2-15.0, oxide of element from the second group - 12.4-14.2, oxide of element from the third group - 2.1-3.8, remaining part - aluminium oxide. After that, catalyst is activated first by soaking in hydrogen medium at temperature 450-500°C, pressure 5-8 MPa for 3-4 h, then sulfidation at temperature 250-300°C, pressure 5-8 MPa for 3-4 h. And sulfidation is carried out with mixture of hydrogen sulfide and hydrogen with concentration of hydrogen sulfide 10-15 vol%.

EFFECT: method makes it possible to obtain catalyst, which has increased isomerisation ability and preserves catalytic activity with respect to reaction of isomerisation for long time, which results in obtaining Diesel fuel, which has improved low-temperature properties.

4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for producing synthesis gas during partial oxidation of methane, which is a microspherical support with a deposited active component based on metal oxides, wherein the microspherical support used is aluminium oxide and/or aluminosilicate particles with diameter of 50-160 mcm, and the active component used is an oxide of Co or Ni or Fe or Mn or Cu or Ce or a mixture of oxides NiO, Co3O4 and Ce2O3, with the following ratio of components, wt %: said active component 2-40, aluminium oxide and/or aluminosilicate - the balance. The invention also relates to a method of producing the catalyst and a method of producing synthesis gas in the presence of the disclosed catalyst.

EFFECT: high specific output of the product, eliminating explosion and ignition hazard, low power consumption, obtaining synthesis gas with H2/CO ratio in the range of 1,5-2,5, obtaining a by-product - technical nitrogen - with high conversion of methane-containing material.

7 cl, 3 tbl, 13 ex

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