Method of catalytic hydrogenation processing the light fraction pyrolysis tar

 

(57) Abstract:

Usage: petrochemistry. Hydrogenation processing the light fraction tar pyrolysis is carried out in the presence of the aluminum-palladium catalyst, which is at the stage of preparation after reduction in hydrogen-containing atmosphere is further processed liquid stream containing monocyclic aromatic hydrocarbons at a temperature of 20-100C and the pressure of the hydrogenation treatment. Effect: reduction of colabrative. 2 C.p. f-crystals, 1 table.

The invention relates to the petrochemical industry, particularly to a method of liquid-phase hydrogenation of unsaturated hydrocarbons in the part of the light fraction of pyrolysis tar.

For obtaining aromatic hydrocarbons from liquid products of catalytic reforming or pyrolysis necessary preliminary cleaning these products from olefin hydrocarbons. One method of cleaning is catalytic hydrogenation in the vapor stream at elevated temperature and pressure.

Known processes for the hydrogenation of olefinic hydrocarbons on aluminium oxide-platinum catalysts, providing selective hydrogenation of olefins at a temperature of 160-the x ways hydrogenation is the need to use elevated temperatures, reducing the activity of the catalyst during operation, in particular, due to the increased colabrative.

According to the method of purification of products of catalytic reforming from olefinic hydrocarbons (RF patent No. 2118981, IPC With 10 G 45/10, 1998) purification is carried out on platypodinae catalyst in the presence of hydrogen at a temperature of C, a pressure of 1.5 MPa and circulation of hydrogen containing gas 1200 nm31 m3of raw materials. To maintain a high activity catalyst for mezhregionalnogo period and before regeneration, the catalyst is treated with hydrogen-containing gas at a temperature of 250 to 400C and a pressure of 0.1-2.0 MPa. The main disadvantage of this method is the high consumption of hydrogen containing gas (up to 15000 nm3/h at 1 m3) catalyst and high temperature processing (up to 400C).

In the method of cleaning catalytic reforming products from olefin hydrocarbons (RF patent No. 2117029, IPC With 10 G 45/10, publ. 08.10.1998) products reformer containing unsaturated compound hydronaut on platypodinae catalyst in the presence of hydrogen at elevated temperature and pressure. To maintain a high activity of the catalyst in the process exploita hydrocarbons, which are used or monocyclic aromatic hydrocarbons, or a mixture thereof, or the reforming catalysate, or hydrotreated gasoline fraction. The amount of liquid hydrocarbons is 2-10 m31 m3catalyst at a temperature of 20 to 180C and pressures of 0.1 to 3.0 MPa.

A common disadvantage of these methods of Hydrotreating is a significant resin formation, leading to deactivation of the catalyst, resulting to maintain the activity of the catalyst must be periodically medregenerativa2 processing.

That one of the reasons for the deactivation of the catalyst is a resin formation, indicates the recovery of the catalyst in the processing of liquid aromatic hydrocarbons, the step which consists in washing the resin with catalyst.

Closest to the claimed technical solution set of features is way catalytic hydrogenation processing the light fraction of the pyrolysis of the resin in the presence of the aluminum-palladium catalyst (Berent A. D. and other Processing of liquid pyrolysis products", M.: Chemistry, 1985, S. 78-88). The hydrogenation is carried out at a temperature of 45-160S and the pressure of 4.7 MPa. To regulate temperaturecontrol method is the high degree of recycling the hydrogenated feed is cut.

The aim of the present invention is to reduce colabrative in the process of hydrogenation of olefinic hydrocarbons, which will increase mainegenealogy mileage catalyst while maintaining a sufficiently high degree of conversion of unsaturated compounds.

The solution of this problem is achieved by applying the process of hydrogenation of olefinic hydrocarbons plagiarising catalyst, while at the stage of preparation (enable) catalyst after reduction in hydrogen-containing atmosphere is further processed liquid stream containing monocyclic aromatic hydrocarbons at a temperature of 20-100C and operating pressure of the process. As a liquid stream containing monocyclic aromatic hydrocarbons, may be used or individual hydrocarbons - benzene, toluene, ethylbenzene, isopropylbenzene, or mixtures thereof, or a hydrogenation product of processing the light fraction pyrolysis tar.

Activation of the catalyst is as follows: aluminum-palladium catalyst is dried in air for at least 0.5 hour at a temperature of 120-140 C, then subjected to heat treatment at 250-400C in the nitrogen-to thermally treated in an atmosphere of hydrogen or hydrogen-containing gas at a temperature of 220 -280 for at least 0.5 hours, further liquid stream containing monocyclic aromatic hydrocarbons at a temperature of 20-100C and operating pressure of the hydrogenation process for at least 0.5 hour. Further, the hydrocarbon mixture used during activation of the catalyst, continuous feed is replaced with raw materials containing unsaturated hydrocarbons.

The process of hydrogenation is carried out at a pressure of 2-4 MPa, a temperature of 20-200C, volume rate of flow of the liquid raw material 1-5 h-1.

Example 1. 0.1 DM3plagiarising catalyst containing 0.3 wt.% palladium, dried in air at a temperature of 130C for 1 hour, then heat-treated in attackalert mixture with the oxygen content of 1% by volume at a temperature of 380S for 4 hours, then heat-treated in an atmosphere of hydrogen at 0.1 MPa and S for 2 hours, after which the pressure was raised to 3.0 MPa in the reactor serves a light fraction of pyrolysis tar, wikipeida within 60-110S. Light fraction pyrolysis tar contains 62,7 wt.% benzene, 12.7 wt.% toluene and unsaturated hydrocarbons, the total number of which is characterized by iodine number 111.

The process of hydrogenation is carried out at a temperature of 50C, the those determined by gas chromatography, the total content of unsaturated compounds in raw materials and catalyzate characterize the iodine number.

As the metric is proportional to the tar, use the optical density of the liquid phase. The value As determined on the photocolorimeter ck-2 in the visible region of the spectrum with the optical filter 400 nm. Solution comparison - water; cuvette thickness of 0.5 cm For raw materials (light fraction pyrolysis tar) the optical density is 0.01.

Data on iodine number, composition and optical density catalyzate shown in the table.

Example 2. The process is conducted as in example 1, operating temperature up to 100C.

Data on iodine number, composition and optical density catalyzate shown in the table.

Example 3. The catalyst prepared according to example 1, but after lifting pressures up to 3.0 MPa in the reactor for 1 hour serves a mixture of benzene-heptane containing benzene 50 wt.% when flow rate of 3.5 h-1. Later in the reactor serves a mixture of benzene-heptane - light fraction pyrolysis of the resin with the iodine number of the mixture 12, after 1 hour, the content of the light fraction of the pyrolysis of the resin in the mixture to increase the iodine number 35, after 1 hour, the content of the light fraction of the pyrolysis of the resin in the mixture led the replacement of the liquid phase on the light fraction of pyrolysis tar, containing 62,7 wt.% benzene, 12.7 wt.% toluene and unsaturated hydrocarbons, the total number of which is characterized by iodine number 111.

The process of hydrogenation is carried out at a temperature of 50 ° C, a pressure of 3.0 MPa and space velocity of the raw material for 3.5 h-1.

Data on iodine number, composition and optical density catalyzate shown in the table.

Example 4. The process is conducted according to example 3, by changing the operating temperature up to 100C.

Data on iodine number, composition and optical density catalyzate shown in the table.

Example 5. The catalyst prepared according to example 1, but after lifting pressures up to 3.0 MPa in the reactor for 3 hours serves a mixture of benzene - heptane containing ethylbenzene 50 wt.% when flow rate of 3.5 h-1. After 3 hours, raise the temperature to 50C and continuous supply are replacing the liquid phase on the light fraction of the pyrolysis resin containing 62,7 wt.% benzene, 12.7 wt.% toluene and unsaturated hydrocarbons, the total number of which is characterized by iodine number 111.

Data on iodine number, composition and optical density catalyzate shown in the table.

Example 6. The catalyst prepared according to example 1, but after lifting davlantes.% when flow rate of 3.5 h-1. After 3 hours, raise the temperature to 50C and continuous supply are replacing the liquid phase on the light fraction of the pyrolysis resin containing 62,7 wt.% benzene, 12.7 wt.% toluene and unsaturated hydrocarbons, the total number of which is characterized by iodine number 111.

Data on iodine number, composition and optical density catalyzate shown in the table.

Example 7. The catalyst prepared according to example 1, but after lifting pressures up to 3.0 MPa in the reactor for 1 hour serves a hydrogenation product of processing the light fraction of the pyrolysis resin containing benzene 62,7 wt.%, toluene 12.7 wt.% and iodine number 25, whereupon the temperature rises to 50C and the hydrogenation product of processing the light fraction of the pyrolysis of the resin in the continuous feed is replaced by a light fraction of the pyrolysis of the resin with the iodine number 111.

Data on iodine number, composition and optical density catalyzate shown in the table.

Example 8. The process is conducted according to example 7, by changing the operating temperature up to 100C.

Data on iodine number, composition and optical density catalyzate shown in the table.

The proposed method can be used in an industrial set is Renga.

1. Method of catalytic hydrogenation processing the light fraction of the pyrolysis of the resin at an elevated pressure in the presence of the aluminum-palladium catalyst, characterized in that the use of the aluminum-palladium catalyst, which is at the stage of preparation after reduction in hydrogen-containing atmosphere is further processed liquid stream containing monocyclic aromatic hydrocarbons at a temperature C and operating pressure for hydrogenation treatment.

2. The method according to p. 1, characterized in that as a liquid stream containing monocyclic aromatic hydrocarbons, using a hydrogenation product of processing the light fraction pyrolysis tar.

3. The method according to p. 1, characterized in that the hydrogenation processing the light fraction of the pyrolysis of the resin is carried out at a temperature S, a pressure of 24 MPa, the space velocity of the liquid raw material 15 h-1.

 

Same patents:
The invention relates to the field of petrochemicals, and particularly to a method of Hydrotreating a liquid hydrocarbon fractions

The invention relates to a catalyst used in the methods of hydroconversion hydrocarbons, which contain small amounts of metals

The invention relates to the refining and can be used in the process of cleaning catalytic reforming products from olefin hydrocarbons

The invention relates to the field of oil and can be used in the process of cleaning catalytic reforming products from olefin hydrocarbons
The invention relates to petrochemistry and oil refining and can be used in the processes hydrodesulphurization unit hydrocarbon fractions

FIELD: desulfurization and hydrogenation catalysts.

SUBSTANCE: invention relates to preparing hydrodesulfurization and dearomatization catalysts useful in processes of deep purification of motor fuels from sulfur-containing compounds and aromatics. A sulfur-resistant catalyst is provided including active component deposited on porous inorganic support including montmorillonite or alumina and characterized by that support is composed of zeolite H-ZSM-5 with Si/Al atomic ratio 17-45 (80-65%) and montmorillonite or alumina (20-35%), while active component is platinum or palladium, platinum and palladium in quantities, respectively, 0.2-2.0, 0.2-1,5. and 0.4-0.2% based on the total weight of catalyst. Described is also catalyst comprising platinum (0.2-2.0%) or palladium (0.2-1.5%), or platinum and palladium (0.4-2.0%) supported by Ca or Na form of montmorillonite, and also catalyst with the same active components supported by zeolite H-ZSM-5 with Si/Al atomic ratio 17-45.

EFFECT: increased sulfur-caused deactivation resistance of catalyst at moderate temperatures and under conditions efficiency in hydrodesulfurization and aromatics hydrogenation processes.

8 cl, 4 tbl, 30 ex

FIELD: oil refining industry and petrochemistry; hydrorefining of petroleum distillates.

SUBSTANCE: hydrorefining of petroleum distillates is carried out at elevated temperature and increased pressure in presence of catalyst containing carrier - highly porous cellular material on base of aluminum α-oxide modified by aluminum γ-oxide or sulfated zirconium dioxide; used as active component is palladium or palladium modified by palladium nano-particles or palladium in mixture with zinc oxide in the amount of 0.35-20.0 mass-%. The process is carried out at temperature of 150-200°C and pressure of 0.1-1.0 Mpa.

EFFECT: enhanced efficiency; facilitated procedure; possibility of hydrorefining of gasoline and diesel distillates.

2 cl, 1 tbl

FIELD: petroleum processing and catalysts.

SUBSTANCE: field of invention is production of catalysts for catalytic hydrotreatment (desulfurization) of gasoline fractions, e.g. straight-run gasoline. Herein disclosed is block-type high-porosity cellular catalyst for hydrotreatment of straight-run gasoline having porosity at least 90-93% and microporosity up to 30%, average pore size being ranging from 0.5 to 2.0 μm. Catalyst consists of α-alumina-based carrier and active catalyst portion containing sulfated zirconium dioxide and metallic palladium in concentration 0.5-0.9 wt %. Catalyst preparation method is also claimed and is as follows. Carrier is prepared from reticular polyurethane foam and impregnated with slurry containing more than 30 wt % α-alumina, after which calcined at 1300-1500°C, impregnated with water-soluble zirconium salts, dried at 100-200°C, calcined at 450-950°C, treated with 5-10% sulfuric acid, dried, calcined at 500-550°C, treated with palladium nitrate, dried, and calcined at 400-450°C, whereupon palladium oxide is reduced to metallic palladium.

EFFECT: lowered pressure and temperature of hydrotreatment process, considerably reduced process duration, lowered sulfur level in straight-run gasoline due to developed surface of catalyst, and prevented crumbling and loss of catalyst due to cellular structure and high strength.

FIELD: chemistry, organic, processing of hydrocarbons.

SUBSTANCE: invention is related to an improved method for hydroprocessing of hydrocarbon raw stock containing sulphur- and/or nitrogen-bearing contaminants. The method comprises the first contact interaction of hydrocarbon raw stock with hydrogen in the presence of at least one first catalyst based on VIII group metals on an acidic carrier, the carrier being selected from the group of zeolites and zeolite-bearing carriers, and then the flow leaving the first catalyst directly contacts hydrogen in the presence of at least one second catalyst based on a VIII group metal on a less acidic solid carrier, said solid carrier being selected from the group of carriers based on silicon dioxide-aluminium oxide and other solid carriers that are not zeolites. Said combination of two catalyst layers allows processing of raw stock with a high content of contaminating impurities without high-level cracking that involves the use of highly acidic carriers.

EFFECT: processing of hydrocarbon raw stock with contaminating impurities without high-level cracking.

14 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of purifying lower alkanes from methanol through contact between the raw material and a catalyst which contains aluminium oxide at high temperature and pressure. The method is characterised by that the catalyst used is an aluminiuim-platinum catalyst and contact takes place at temperature of 180-400°C, pressure of 1.5-4.0 MPa, volume rate of supply of material of 0.4-4 h-1 and volume ratio of material : hydrogen equal to 1:(5-900).

EFFECT: invention increases degree of purity of lower alkanes from methanol.

3 cl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of hydrofining synthetic oil, realised by bringing synthetic oil, obtained via Fischer-Tropsch synthesis and having content of C-9-21 hydrocarbons greater than or equal to 90 wt %, into contact with a hydrofining catalyst which has a support which contains one or more solid acids selected from ultra-stable Y-(USY) zeolite, aluminosilicate, zirconia-silicate and aluminium-bromine oxide catalyst and at least one metal selected from a group comprising group VIII metals, deposited on the support, in the presence of hydrogen with regulation of the reaction temperature when the hydrofining catalyst is in contact with the synthetic oil, in order to hydrofine the synthetic oil such that content (wt %) of C8 or lower hydrocarbons in the synthetic oil after contact is 3-9 wt % higher than before contact. The invention also relates to a method of producing base fuel material.

EFFECT: obtaining base oil with excellent low-temperature rheological properties with good output of the middle fraction of the synthetic oil.

6 cl, 8 ex, 2 tbl, 1 dwg

FIELD: oil and gas industry.

SUBSTANCE: paraffin hydrotreating method involves the first stage at which paraffin with content C21 or higher of normal paraffins 70% wt or higher is used as basic material, and paraffin contacts with catalyst at reaction temperature of 270-360 °C in presence of hydrogen for hydrocracking, catalyst consisting of metal of group VIII of the Periodic Table, which is put on carrier containing amorphous solid acid; the second stage at which raw material from paraffin is replaced for some time with light paraffin with content C9-20 of paraffins 60% wt or higher, and light paraffin contacts with catalyst at reaction temperature of 120-335 °C in presence of hydrogen for hydrocracking; and the third stage at which raw material of light paraffin is replaced with paraffin and paraffin contacts with catalyst at reaction temperature of 270-360 °C in presence of hydrogen for hydrocracking. Also, invention refers to method for obtaining material of fuel system, which involves the above method.

EFFECT: use of this invention allows improving activity of hydrocracking catalyst, which deteriorates with time.

6 cl, 1 tbl, 4 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for realising a method of hydrogenating olefins and oxygen-containing compounds in synthetic liquid hydrocarbons obtained via a Fischer-Tropsch method, containing a porous support made from γ-aluminium oxide on which a catalytically active palladium component is deposited, characterised by that pores in the support have effective radius of 4.0-10.0 nm, wherein content of foreign-metal impurities in the support is not more than 1500 ppm, and content of palladium in the catalyst is equal to 0.2-2.5 wt %. The invention also relates to a hydrogenation method using said catalyst.

EFFECT: invention enables to obtain saturated hydrocarbons from liquid Fischer-Tropsch synthesis products, which are a complex mixture of paraffin hydrocarbons with 5-32 carbon atoms, with ratio of normal paraffin hydrocarbons to isoparaffin hydrocarbons ranging from 1:1 to 7:1, containing up to 50% olefins and up to 5% oxygen-containing compounds.

2 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention discloses a method for producing diesel fuel from a hydrocarbon stream, comprising: hydrotreating the main hydrocarbon stream and a co-feed hydrocarbon feedstock containing diesel fuel in the presence of a hydrogen stream and a pre-purification catalyst to produce a pre-purified effluent stream; hydrocracking a pre-purified effluent stream in the presence of a hydrocracking catalyst and hydrogen to produce an effluent hydrocracking stream; fractionating, at least, a portion of the hydrocracking effluent to produce a diesel fuel stream; and hydrotreating the diesel fuel stream in the presence of the hydrogen stream for hydrotreating and a hydrotreating catalyst to produce an effluent stream.

EFFECT: producing diesel fuel with low sulfur and ammonia content.

10 cl, 2 dwg

Up!