The method of purification of products of catalytic reforming from olefinic hydrocarbons

 

(57) Abstract:

The invention relates to the refining and can be used in the process of cleaning catalytic reforming products from olefin hydrocarbons. The products of the reforming hydronaut on platypodinae mono-, bi - or polymetallic catalyst in the presence of hydrogen at elevated temperature and pressure. When this catalyst is periodically during mezhregionalnogo period and before the regeneration process the hydrogen-containing gas with a bulk velocity of 2.0 to 15.0 thousand nm3/m3catalyst for 6 to 48 hours at a temperature of 250 - 400oC, a pressure of 0.1 - 2.0 MPa. The method provides for the maintenance of the initial activity platypodinae catalyst mainegenealogy period and the reduction of its activity during regeneration by 4% compared to 15%, thus increasing the life of the catalysts. table 2.

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

The prior art consists in the following:

For obtaining aromatic hydrocarbons of high quality method katalia reforming from olefinic hydrocarbons. One of the methods of cleaning products reformer from olefinic hydrocarbons is their selective hydrogenation in the gas-vapor stream on Latinoamerica catalysts at a temperature of 150-250oC and high pressure.

Known methods of cleaning products reformer from olefinic hydrocarbons and their hydrogenation on aluminium oxide-platinum monometallic catalyst with a platinum content of 0.10 to 0.15 wt.% (A. C. the USSR 200096, class C 10 G 45/10, 1961, publ. 29.07.67) and combined loading aluminium oxide-platinum monometallic catalysts (A. C. the USSR 1513014, class C 10 G 45/10, 1987, publ. 7.10.89), providing selective hydrogenation of olefins at a temperature of 160-220oC and high pressure.

The disadvantages of these methods are reducing the degree of hydrogenation of olefins from 98% for the fresh catalyst to 80% after 12 months of operation, and reducing the degree of hydrogenation of the olefins to 75% after regeneration.

Closest to the proposed method is a method of cleaning products reformer from olefinic hydrocarbons with a more stable polymetallic catalyst, one of the metal which is platinum (A. C. the USSR 1691410, class C 10 G 49/06, 1987, publ. 15.11.91), providing selectional the following disadvantages: the decrease of the degree of hydrogenation of olefins from 97.5% of fresh catalyst to 87% after 10 months of operation; reducing the degree of hydrogenation of the olefins to 82% after regeneration, after the second and subsequent regeneration does not provide the required degree of hydrogenation of olefins, which leads to a forced reduction in the stiffness of the reforming process with a corresponding decrease in production of aromatic hydrocarbons and eventually requires replacement of the catalyst.

The invention is directed to solution of the problem - maintaining high activity and selectivity in mainegenealogy period, the increase in life Latinoamerica catalysts cleaning products reformer from olefinic hydrocarbons.

Problem solving mediated new technical result consists in the periodic processing of the catalyst, the hydrogen-containing gas, which maintains the initial activity of the catalyst in mainegenealogy period and reducing the loss of its activity during regeneration.

Cleaning products reformer from olefinic hydrocarbons is carried out by selective hydrogenation of the latter in the presence of hydrogen at elevated pressure and temperature on platypodinae catalyst.

The hydrogenation is carried out in the presence of Jonny period and before the regeneration process the hydrogen-containing gas with a volumetric feed rate of 2.0 - 15,0 thousand nm3/m3catalyst for onset 6 to 48 hours at a temperature of 250-400oC and a pressure of 0.1 - 2.0 MPa.

The proposed method is illustrated by the following examples.

Example 1. When the catalytic reforming of hydrotreated gasoline fraction, wikipeida within 68-105oC, get produce the following composition, wt.%:

unsaturated hydrocarbon - 1,2 (bromine number 2.50 g Br/100 g)

aromatic hydrocarbons, including - 42,5

benzene - 16,6

toluene - 22,5

ethylbenzene and xylenes - 3,4

saturated hydrocarbons - 56,3

Extracted from the reactor industrial installations after 10 months of operation in the process of cleaning products reformer from olefinic hydrocarbons polymetallic catalyst G-01 content in wt.%: platinum - 0,10, rhenium - 0,025, cadmium - 0,10, antimony - 0,005 on active aluminum oxide, THE 38.101998-84, loaded into the reactor pilot plant in the amount of 50 cm3.

Spend processing of the catalyst with hydrogen-containing feed gas (hydrogen-rich) with a bulk velocity of 10.0 thousand nm3/m3catalyst at a temperature of 250oC; pressure of 1.0 MPa for 48 hours

Cleaning products reformer from olefinic hydrocarbons is carried out at temperature 1.2 thousand nm3/m3of raw materials.

The resulting hydrogenation product contains of 42.3 wt.% aromatic hydrocarbons and has a bromine number of 0.06 (table. 1).

Example 2-4. Polymetallic catalyst G-01, specified in example 1 is loaded into the reactor pilot plant in the amount of 50 cm3.

Spend processing catalyst feed everything to the conditions specified in the table. 1.

Cleaning products reformer, whose composition is given in example 1 is carried out in the conditions of example 1. Indicators of the quality of the received section of hydrogenated feed are given in table. 1.

Example 5 (the prototype). Polymetallic catalyst G-01, specified in example 1 is loaded into the reactor pilot plant in the amount of 50 cm3.

Cleaning products reformer, whose composition is given in example 1 is carried out in the conditions of example 1 without pre-treatment of the catalyst.

The resulting hydrogenation product contains 42,4 wt.% aromatic hydrocarbons and has a bromine number of 0.33 (table. 1).

Thus cleaning products reforming the prototype leads to a significant reduction in catalyst activity during mezhregionalnogo cycle.

Example 6 (comparison). Fresh polymetallic is produktov reforming, the composition of which is given in example 1 is carried out in the conditions of example 1.

The resulting hydrogenation product contains 42,2 wt.% aromatic hydrocarbons and has a bromine number of 0.06 (table. 1).

Thus, treatment of the catalyst in accordance with examples 1-4 restores its initial activity while maintaining high selectivity.

Example 7. Polymetallic catalyst G-01, specified in example 1 is loaded into the reactor pilot plant in the amount of 50 cm3and carry out the processing of the hydrogen-containing gas at the conditions of example 4.

The catalyst is subjected to regeneration by the filing of a nitrogen-air mixture with the oxygen concentration of 2 wt.% at a temperature of 300oC and a pressure of 1.0 MPa, which corresponds to conditions regeneration in an industrial setting. Regeneration of the catalyst is carried out to achieve the concentration of CO2at the exit of the reactor is less than 0.1 wt.%.

Regenerate the catalyst by feeding a hydrogen-containing gas at a temperature of 170oC and a pressure of 1.5 MPa for 8 hours

Cleaning products reformer specified in example 1 is carried out in the conditions of example 1. You get a hydrogenation product containing 42,3 wt.% aromatic hydrocarbons and which leads to a decrease in its activity by 4%.

Example 8 (the prototype). Polymetallic catalyst G-01, specified in example 1 is loaded into the reactor pilot plant in the amount of 50 cm3.

The catalyst without pre-treatment is subjected to regeneration and subsequent recovery in the conditions of example 7.

Cleaning products reformer specified in example 1 is carried out in the conditions of example 1. You get a hydrogenation product containing 42,4 wt.% aromatic hydrocarbons and having a bromine number of 0.44 (table. 1).

Thus, when cleaning products reformer prototype is a decrease in the activity of the catalyst during regeneration by 15%.

Example 9. Extracted from the reactor industrial plants after 12 months of operation in the process of cleaning products reformer from olefinic hydrocarbons aluminium oxide-platinum catalyst AP-15 content of 0.15 wt.% platinum on active aluminum oxide, THE 38.101283-80, is loaded into the reactor pilot plant in the amount of 50 cm3.

Spend processing catalyst feed everything with a bulk velocity of 10.0 thousand nm3/m3catalyst at a temperature of 350oC and a pressure of 1.5 MPa within 24 hours

Cleaning products reformer, the decree is of such hydrocarbons and having a bromine number of 0.05 (table. 1).

Example 10 (similar). Aluminium oxide-platinum catalyst specified in example 9, is loaded into the reactor pilot plant in the amount of 50 cm3.

Cleaning products of the reforming process specified in example 1 is carried out in the conditions of example 1 without pre-treatment of the catalyst.

The resulting hydrogenation product contains 42,4 wt.% aromatic hydrocarbons and has a bromine number of 0.50 (table. 2).

Thus, cleaning products reformer by a known method leads to a significant reduction in catalyst activity during mezhregionalnogo period.

Example 11 (for comparison). Fresh aluminium oxide-platinum catalyst AP-15 is loaded into the reactor pilot plant in the amount of 50 cm3.

Cleaning products reformer specified in example 1 is carried out in the conditions of example 1.

You get a hydrogenation product containing 42,2 wt.% aromatic hydrocarbons and having a bromine number of 0.05 (table. 2).

Thus treatment of the catalyst under the conditions of example 9 restores its initial activity.

Example 12. Aluminium oxide-platinum catalyst specified in example 9, is loaded into the reactor pilot plant in the amount of 50 cm3nalivajut in the conditions of example 7.

Cleaning products reformer specified in example 1 is carried out in the conditions of example 1.

The resulting hydrogenation product contains of 42.3 wt.% aromatic hydrocarbons and has a bromine number of 0.15.

Thus, during regeneration of the treated aluminium oxide-platinum catalyst AP-15 is reducing its activity by 4%.

Example 13 (similar). Aluminium oxide-platinum catalyst specified in example 9, is loaded into the reactor pilot plant in the amount of 50 cm3.

Spend the regeneration and recovery of the catalyst under the conditions of example 7 without pre-treatment.

Cleaning products reformer specified in example 1 is carried out in the conditions of example 1.

The resulting hydrogenation product contains 42,4 wt.% aromatic hydrocarbons and has a bromine number to 0.63 (table. 2).

Thus, cleaning products reformer in accordance with the analog results in decreased activity of the catalyst during regeneration by 23%.

Cleaning products reformer from olefinic hydrocarbons by the proposed method maintains the initial activity Latinoamerica catalysts in mainegenealogy period and decrease their activity during p is mperature and space velocity SIV reduces the processing time of the catalyst, necessary to restore its initial activity, and their limit values 400oC and 15.0 thousand nm3/m3the catalyst is limited by the technical parameters of industrial reforming units. Treatment of the catalyst at a temperature below 250oC and flow rate of less than 2 thousand m3/m3catalyst requires a long processing time, which is not advisable. The increase in pressure requires a large processing time of the catalyst to achieve its initial activity and, therefore, is limited to 2.0 MPa.

The method of cleaning products reformer from olefinic hydrocarbons by selective hydrogenation of the latter at elevated temperature and pressure in the presence of hydrogen at platypodinae catalyst, wherein the hydrogenation is carried out in the presence of mono-, bi - or polymetallic platypodinae catalyst and the catalyst is periodically during mezhregionalnogo period and before the regeneration process the hydrogen-containing gas with a bulk velocity of 2.0 to 15.0 thousand nm3/m3catalyst for 6 to 48 hours at a temperature of 250 - 400oC, a pressure of 0.1 - 2.0 MPa.

 

Same patents:

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!