Method of preparing catalyst for hydrocracking of petroleum feedstock
FIELD: petroleum processing.
SUBSTANCE: petroleum feedstock hydrocracking catalyst is prepared by compounding zeolite Y with aluminonickel(cobalt)-molybdenum(tungsten) oxide system. Specifically, low-alkalinity zeolite Y having silicate modulus 5.5-7.0 and crystallinity at least 70% is mixed with aluminum hydroxide having pseudoboehmite structure in proportion (1-9):1. Thus obtained mix is molded, dried, and calcined under water steam atmosphere to give molded thermally treated zeolite. The latter is impregnated with aqueous Ni(Co) and Mo(W) salt solutions or ground and compounded with aluminonickel(cobalt)-molybdenum(tungsten) oxide system by mixing with aluminum hydroxide and Ni(Co) and Mo(W) salts, after which follow molding and impregnation with aqueous Ni(Co) and Mo(W) salt solutions.
EFFECT: expanded catalyst preparation possibilities.
2 cl, 5 tbl, 4 ex
The invention relates to the refining, in particular to the processes of deep oil processing.
The process of hydrocracking is one of the leading positions in terms of production of motor fuels. The direction of the reactions, the quality of the products of hydrocracking and their output are determined mainly used catalysts.
Catalysts for hydrocracking of crude oil are bifunctional: to provide fission reactions (cracking) of hydrocarbon molecules and subsequent saturation (hydrogenation) products. For fission reactions in the catalyst hydrocracking enter the components with the acid properties of zeolites, alumophosphate and others), for reactions of saturated enter the oxides of Nickel (cobalt) and molybdenum(tungsten).
The number of publications on the composition and methods of preparation of hydrocracking catalysts is very high.
Known review, in which the analysis of the scientific and patent publications hydrocracking catalysts for the period up to 1979 [Editatzeko, Viagrapill. Mevlana. Zeolite-containing catalysts in hydrocracking of crude oil, M: Tsniiteneftekhim, 1981, 86 S.].
Further publications are reflected in the book [Effciency, Vahakn. Deep oil processing: technological and environmental aspects, Meters: Machinery, 2001, s], which noted that if the centre of the development process of hydrocracking in the world practice of refining contributed to the use of zeolite catalysts. The zeolite component use zeolites of type X, Y, L, mordenite and other
The greatest significance of the zeolite type, as the broad porous from the group of high zeolites [Liigutav. High zeolites and their applications in petrochemistry and refining, M.: Chemistry, 1974, 101]. Progress in the production of zeolite type Y expressed, in particular, the methods of obtaining high-modulus type zeolite Y direct synthesis of [U.S. Pat. Of the Russian Federation No. 2090502 from 08.02.06 Pat. Of the Russian Federation No. 2151739 from 03.06.08]. For use as a component of a catalyst for catalytic cracking of type zeolite Y with a molar ratio of SiO2/Al2O3=3,5-7,0 transferred to ultrastable (with respect to the [U.S. Pat. U.S. No. 3449070, 1969, U.S. Pat No. 3402996, 1968] with high silicate modulus and low content of sodium oxide.
The hydrocracking catalysts include zeolite Y in ultrastable (with respect to the form in the amount of 10-20 wt.% with a molar ratio of SiO2/Al2O3from 10 to 25, the active components of the oxides of Nickel, cobalt, molybdenum, tungsten, binder - oxides of aluminum and/or silicon, titanium, zirconium.
The original zeolite Y powder with silicate module 3.5 to 7.0 and the content of sodium oxide 12,0-14,0 wt.% subjected to treatment in an aqueous medium containing ammonium salts, metal cations, acid in a wide range of concentrations, the duration of the of arazi, temperature sequence. Mandatory element of the preparation of zeolite ultrastable (with respect to Y is its treatment in the atmosphere of water vapor at a temperature of 600-850°C.
Termoparnaya processing low zeolite Y (after deep decationization, i.e. removal of cations of sodium and substitution of protons) increases silicate module, i.e. to decrease the content of aluminum in the crystal lattice, and is accompanied by an increase of the stability of the zeolite, i.e. the duration of his work in the composition of the catalyst before reduction activity. However, stabilization of zeolite by reducing the aluminum content in the crystal lattice inevitably accompanied by partial destruction of the lattice, i.e. the reduction in the degree of crystallinity, therefore increasing silicate module over 22-25 becomes impractical.
To conduct thermoprotei processing powdered zeolite necessary high-temperature furnace with a special design. The absence of a furnace for carrying out thermoprotei processing powdered zeolite is one of the obstacles to the production of highly efficient catalyst for the hydrocracking known technologies.
In the production of ball zeolite-containing cracking catalysts, this disadvantage is overcome by the formation of zeolite Y in the source on which ravoi form of aluminosilicate matrix with the subsequent operations of ion exchange and thermoprotei processing zeolite balls the size of 3-6 mm in diameter [U.S. Pat. RF№№ 2229932, 2229498, 2233309].
However, this leads to the fact that the volume of the equipment and the volume of technological solutions to increase considerably in comparison with required to process the zeolite. Accordingly increases the consumption of reagents, electricity, demineralized water, the volume of water etc.
The closest in technical essence and the achieved effect to the proposed technical solution is the method of preparation of catalyst for hydrocracking [application U.S. No. 20060073963, April, 2006], which is that low ammonium form of the zeolite powder Y module SiO2/Al2O3from 5.4 to 6.5 processed in the atmosphere 90-100%steam in a rotary kiln at a temperature of from 600 to 650°C for 45 minutes, then the zeolite powder treated with an aqueous solution of hydrochloric acid in an amount of from 0.03 to 0.2 g of HCl per 1 g of the zeolite, the zeolite powder is mixed in the mixer with a solution of salts of Nickel and tungsten, and then add the aluminum oxide in an amount to provide the content of Al2O3up to 80 wt.% (dry); with stirring, add water to obtain the mass, characterized by loss on ignition (SPT), equal to 50 wt.%, nitric acid (2 wt.% dry mass) for peptization of the alumina and the flocculant in an amount of about 1 wt.% (to dry). A mixture of extras is dirout, the extrudates are dried from 10 minutes to 3 hours and calcined at temperatures from 300 to 850°from 30 minutes to 4 hours. The catalyst according to example 2 had a composition (wt.%):
|Nickel oxide (Nickel)||3,3 (2,6),|
The disadvantages of this method are:
first, the relatively low silicate module (10),
secondly, the necessity of application of rotary kiln for calcination of the zeolite powder, which is technically severely limits the applicability of the method,
thirdly, the use as a binder of aluminum oxide, which causes the need of introducing a lot of nitric acid in the amount of 2 wt.% from dried, followed by calcination of the extrudates leads to large emissions of nitrogen oxides, which is unacceptable from an environmental point of view,
fourth, the resulting catalyst has a low mechanical strength, which limits its applicability in processes at high pressure.
In addition, the introduction of active hydrogenating components of the solution at the stage of preparation of the moldable mass with subsequent high temperature processing's inevitable is accompanied their losses on the formation of active phases in the interaction with the alumina, which affects hydrogenating function Katalizator.
The aim of the invention is to develop a method of producing catalyst for hydrocracking of crude oil with high activity and mechanical strength when using the methods of obtaining ultrastable (with respect zeolite and zeolite-containing catalyst without exclusive equipment, reducing the volume of harmful emissions into the atmosphere.
This goal is achieved by the proposed method to obtain catalyst for hydrocracking of crude oil by compounding zeolite Y with Ecumenical(cobalt) molybdenum(tungsten)oxide system, characterized in that the low zeolite Y with sodium silicate modulus of 5.5-7.0 and a crystallinity of at least 70% is mixed with aluminum hydroxide pseudoboehmite patterns in the ratio (1÷9):1, molded, dried, calcined in an atmosphere of water vapor with obtaining a molded heat-treated zeolite impregnated with aqueous solutions of salts of Ni (Co) Mo (W), or obtained molded and heat-treated zeolite and grind compounding with Ecumenical(cobalt)molybdenum(tungsten)oxide system by mixing with aluminum hydroxide and salts of Ni(Co) Mo(W) followed by molding or by mixing with aluminum hydroxide, forming and subsequent impregnation with aqueous solutions of salts of Ni(Co) IMO(W). While the calcination of the zeolite in the atmosphere of water vapor repeat 1-2 times with intermediate processing inorganic acid.
The hallmark of the proposed invention is that low zeolite Y with sodium silicate modulus of 5.5-7.0 and crystallinity not less than 70% is mixed with aluminum hydroxide pseudoboehmite patterns in the ratio (1÷9):1, molded, dried, calcined in an atmosphere of water vapor with obtaining a molded heat-treated zeolite impregnated with aqueous solutions of salts of Ni (Co) Mo (W), or obtained molded and heat-treated zeolite grind and compounding with Ecumenical(cobalt)molybdenum(wills-FRAM)oxide system by mixing with aluminum hydroxide and salts of Ni (Co) and Mo (W) followed by molding or by mixing with aluminum hydroxide, forming and subsequent impregnation with aqueous solutions of salts of Ni (Co) Mo (W). While the calcination of the zeolite in the atmosphere of water vapor repeat 1-2 times with intermediate processing inorganic acid.
The proposed method of producing the catalyst for hydrocracking of crude oil is as follows.
Zeolite type Y in the form of a powder with silicate module 5,5-7,0 obtained by direct synthesis, treated with ammonium salts to reduce the content of sodium oxide <0.8 wt.% preserving the crystallinity is not m is it 70%. These characteristics allow to obtain the zeolite after hydrothermal processing module 8÷20 and a crystallinity of 40÷60%, the stock of crystallinity of zeolite required for the preparation of mechanically stable catalyst with high activity.
Powder low zeolite is mixed with aluminum hydroxide pseudoboehmite nature with obtaining mass, characterized SPT=50÷60% with a ratio of zeolite: aluminum oxide is from 1:1 to 9:1 on absolutely dry, molded by extrusion through a die plate with holes with a diameter of granules 3÷8 mm extrudates-1 is dried and calcined in a furnace in a stationary layer, through which pass the water vapor concentration 60-100% at a temperature of 650÷850°C for 3÷10 hours. Steamed extrudates handle -1 4÷5%aqueous solution of inorganic acids (nitric, hydrochloric and other) and washed chemically demineralized water (CPW) to pH 6÷7. This operation frees the pores of the zeolite from so the extra-lattice aluminum oxide, resulting from dealumination when thermoprotei processing. Zeolite has a silica module ≥, 8.0 and crystallinity of 65%. Re-heat treatment, treatment with an acid solution and rinsing Hove results zeolite with silica module ≥12 and crystallinity ≥55%. If necessary, depending on the requirements of the asset the spine of the catalyst, repeat thermoprobe processing with intermediate treatment with an acid and washing Hove.
Further operations associated with the compounding of the zeolite with Ecumenical(cobalt)molybdenum(tungsten)oxide system:
any heat-treated, as described above, the molded zeolite (catalyst a-1) is impregnated with an aqueous solution of salts of Nickel (cobalt) and molybdenum (tungsten) at the rate of 1.5 to 5.5 wt.% oxides of Nickel (cobalt) and 8-16 wt.% molybdenum (tungsten),
any molded and heat-treated zeolite (catalyst-1) grind until you get a powder with a particle size of less than or equal to 50 microns, at least 80 wt.%, the powder is mixed with aluminum hydroxide with addition of nitric acid in an amount of 0.01-0.02 mol/mol Al2O3the ratio of zeolite: aluminum oxide is from 1:1 to 9:1 with the molding mass SPT=50-60% of the mass, formed by extrusion, dried, calcined and impregnated with an aqueous solution of salts of Nickel(cobalt) and molybdenum(tungsten) is based oxide content as above
any mix grinding (powder) molded termopreobrazovateli zeolite (catalyst 1) with aluminum hydroxide in the ratio as specified above, and salts of Nickel(cobalt) and molybdenum(tungsten) is based oxide content, as described above, molded, dried and calcined.
The above-described methods allow you to get the active and mechanically strong catalyst for hydrocracking of crude oil, containing ≥10 wt.% ultrastable (with respect zeolite Y with silicate module 8-20 without the use of exclusive prokalochnoj equipment while reducing the volume of harmful emissions into the atmosphere.
In known methods for producing catalyst for hydrocracking of crude oil the use of a combination of the described methods is unknown.
Thus, the proposed solution meets the criteria of "novelty" and "significant difference".
The following are specific examples of implementation of the proposed method, which he illustrated by, but not limited to.
The mechanical strength of the catalyst appreciate the value of factor K, defined as the ratio of the value of the breaking load P on a knife with a blade width of 0.8 mm diameter pellets d:K=P/d kg/mm
Silicate modulus and crystallinity of the zeolite was determined by x-ray phase analysis (XRD).
The catalytic activity is determined in the process of hydrocracking of vacuum gas oil in the pilot unit.
The catalyst was pulverized to a size of 0.5-1.0 mm catalyst Loading in the reactor is 70 cm3.
The catalyst test was carried out in an environment of hydrogen under the following technological parameters:
a hydrogen pressure of 100 kgf/cm2,
temperature at the inlet of the reactor - 380°C
- volumetric feed rate-1.2 h -1,
- the ratio of everything: raw materials - 500 nm3/m3.
The raw material used vacuum gas oil, the characteristics of which are given in table 1.
|The kinematic viscosity at 100°S, mm/s2:||8,1|
|Cocking behavior, %||0,08|
|Fractional composition, °:|
Measure the activity of the catalyst which is output fractions NK-360° C.
Example 1 - obtain extrudates-1.
High modulus zeolite with a silica modulus of 5.8, the content of Na2O to 12.1 wt.% and a crystallinity of 90 wt.%, obtained by direct synthesis, treated with aqueous solutions of ammonium salts by a known method to the content of Na2O 0.4 wt.%. Received low powdered zeolite in an amount of 0.5 kg for A.S. (absolutely dry) were loaded into the mixer, added 2.5 kg wet pellet of aluminum hydroxide pseudoboehmite nature with the SPT650°=80 wt.%, mixed until smooth with the addition of 4.5%nitric acid in a quantity of 50 ml (molar ratio of HNO3:Al2O3=0,008), to the SPT650°=52 wt.%, Mature missed mass through the die plate with holes with a diameter of 5.0 mm, the extrudates-1 was dried in air, and then loaded into the reactor furnace, the bottom of which is a grid with holes of 1.5-2.0 mm, a layer of extrudates-1 thickness of about 8 cm
When heated at 50°/h heated furnace to a temperature of 120°the middle layer extrudates-1 and kept at this temperature for 2 hours, then heated to a temperature of 750°starting to miss 100%of pairs with temperature 550°through the holes in the bottom of the reactor and kept at a temperature of 750°5 hours.
The extrudate is cooled, unloaded and filled with 3 l of 4.5%aqueous solution of nitric acid on stirring heated to a temperature of 95° With and stand for 0.5 hours, then cooled, the solution was decanted, poured chemically demineralized water (CPW), mixed them up, the water was decanted, the extrudates were dried in air.
Thermobarometry extrudates with a diameter of 3.8-·4.0 mm was composed of zeolite Y with sodium silicate modulus of 8.8 and a crystallinity of 81%.
Characteristics of the source of zeolites, their low forms, terms thermoprotei processing and characteristics of the zeolites after it are given in table 2.
Prepared according to the conditions of table 2 extrudates-1 mixtures of zeolite with aluminum hydroxide used for compounding with Ecumenical(cobalt)molybdenum(tungsten) oxide system.
Example 2 - impregnation of extrudates-1 of example 1.
The extrudates-1 mixture of zeolite:Al2O3for example 1-1 with a diameter of 3.8-4.0 mm, the strength factor of 1.8 kg/mm of diameter, containing about 40 wt.% cristallizing zeolite module 8,8 impregnated with an aqueous solution of Nickel nitrate and ammonium molybdenum acid at pH of 2.8 calculation of 4.0 wt.% NiO and 12 wt.% Moo3was dried at a temperature of 120°With 2 hours and probalily at a temperature of 550°6 hours.
The resulting catalyst has the strength of 1.8 kg/mm of diameter and active in the process of hydrocracking of vacuum gas oil output FR. NK-360°equal to 88%.
Table 3 shows the conditions of impregnation and characteristics of the catalysts in which the variants of example 2.
To use zeolite pereobrabotan extrudates-1 for the examples of table 2 in the preparation of catalysts for other options extrudates-1 milled to produce a powder with a particle size of ≤50 μm to 80 wt.%.
Example 3 - extrudates-2 and their impregnation.
Powder grinding extrudates-1 example 1-5B (table 2) in the amount of 1.25 kg, containing 36% of zeolite Y with module M=20 loaded into the mixer, put 2.5 kg of pellets of aluminum hydroxide with SPT=80 wt.%, mixed until smooth with the addition of 4.5%nitric acid in a quantity of 50 ml under heating to SPT650°=52 wt.%, Mature missed mass on the extruder through a die plate with holes with a diameter of 8 mm, the extrudates were dried in air, loaded into an oven and dried at a temperature of 120°C for 2 hours and probalily at a temperature of 550°6 hours. The obtained extrudates-2 with a diameter of 6.0-6.5 mm with zeolite to 25.3 wt.% module M=20 had a safety factor of 1.9 kg/mm
The extrudates-2 was impregnated with an aqueous solution of Nickel nitrate and ammonium molybdate at pH 3.1 out calculation of 3.0 wt.% NiO and 10 wt.% Moo3was dried at a temperature of 120°With 2 hours and probalily at a temperature of 550°6 hours.
The resulting catalyst has the strength of 1.3 kg/mm of diameter and active in the process of hydrocracking of vacuum gas oil output FR. NK-360°From 83.1 mA is.%.
Other examples of the method for the preparation of catalysts by impregnation with aqueous solutions of salts of active ingredients extrudates-2 are given in table 4.
Characteristics of the source zeolite, conditions thermoprotei processing low zeolite Y, and the characteristics of its products
|Example||The zeolite before processing||Low zeolite||Ratio||Termoparnaya processing||The zeolite after processing|
|module||the crystallinity, wt.%||the content of Na2O, wt.%||the crystallinity, wt.%||zeolite/Al2O3by A.S.||No. of cycle||Temperature, °||Duration, hours||the vapor concentration, wt.%||module||the crystallinity, wt.%|
|continuation of table 2|
Characteristics of the catalysts obtained by impregnation of extrudates-1
|Example||No. extrudates according to table 2||The content of NiO(CoO) and MoO3(WO3after impregnation||Strength, kg/mm of diameter||The catalyst activity (output FR. NK-360°)|
|2-1||1-1||3,9 NiO||11,88 MoO3||1.8||88,0|
|2-2||1-2A||2,5 CoO||8,10 MoO3||1.9||85,0|
|2-3||1-5B||1.8 NiO||of 7.90 MoO3||1.0||78,0|
|2-4||1-7b||4,1 NiO||15,80 WO3||2,0||84,1|
|2-5||1-3A||2,7 NiO||10,10 MoO3||83.6|
|The placeholder||2,3 NiO||or 10.60 WO3||1,2||79,3|
Conditions of preparation, composition and properties of the catalysts obtained by impregnation of extrudates-2
|Example||The extrudate-1 example|
|The ratio of grinding the extrudate-1/ Al2O3by A.S.||The zeolite in the catalyst composition||The content of amorphous||Strength||Content, wt.%||Activity, the release of FR. NK-360°S, wt.%|
|module||content, wt.%||ASC* phase, wt.%||kg/mm||NiO (CoO)||MoO3(WO3)|
|3-1||1-5B||5:1||20,0||26,2||39,2||1,3||2,9 NiO||9,8 MoO3||83,1|
|3-2||1-5B||1:2||20,0||11,0||17,2||2,2||4,4 NiO||12,1 MoO3||82,1|
|3-3||1-4A||3:1||15,9||34,0||22,6||1,2||2,1 NiO||11,6 WO3||78,1|
|3-4||1-2A||1:3||15,1||6,5||3,5||2,4||4,3 NiO||16,0 WO3||81,4|
|3-5||1-5A||1:3||18,4||10,4||7,8||2,1||4,8 CoO||14,2 MoO3||84,6|
|3-6||1-3A||1:2||the 13.4||15,0||5,1||2,2||5,1 NiO||the 15.6 MoO3||85,9|
|1-3||1:2||8,9||of 17.0||3,5||2,1||4,3 NiO||13,9 MoO3||80,8|
|3-7||1-1||1:1||8,8||16,9||4,0||2,0||4,1 NiO||12,6 MoO3||81,2|
|The placeholder||1,2||3,3 NiO||10,6 WO3||79,3|
|* Ask aluminosilicate|
Powder grinding extrudates-1 example 1-5B (table 2) in the amount of 1.25 kg loaded into the mixer, put 2.5 kg pellet hydroxide al the MINIA with the SPT 650°=80 wt.%, mixed to obtain a homogeneous mass, introduced sequentially 220 g of Nickel nitrate, 50 mg of nitric acid and 340 g of ammonium molybdenum acid with intermediate stirring until smooth. Ripe molding with the SPT650°=52 wt.% he sformovat on the extruder through a die plate with holes with a diameter of 3.5 mm, the extrudates were dried at a temperature of 120°With 2 hours and probalily at a temperature of 550°6 hours.
The resulting catalyst had a composition in wt.%:
|SiO2||the rest of it.|
Other examples of implementation of the proposed method to obtain the hydrocracking catalyst by mixing grinding extrudates-1 with salts of active ingredients shown in table 5.
Conditions for obtaining catalysts by mixing powders milled extrudates-1 with salts of active ingredients and their characteristics
|Example||No.||Weight||The weight of the pellet||Load, kg||Strength,||Activity|
|the extrudate-1||powder, kg||of aluminum hydroxide, kg||nitrate Nickel (cobalt)||ammonium molybdate (wolframates)||kg/mm||the output FR. NK-360°S, wt.%|
|4-1||1-5B||1,25||2.5||0,22 Ni||0,34 Mo||1,4||80,0|
|4-2||1-5B||1.25||5.0||0,30 Ni||0,40 Mo||2,0||87,2|
|4-3||1-4A||1.25||3.5||0.25 Ni||0,40 W||1,8||84,1|
|4-4||1-2A||1,25||2.5||0.23 Ni||0,40 W||1,9||84,8|
|4-5||1-3A||1.25||2.5||0,23 Co||0,40 Mo||1,7||85,0|
|4-6||1-1||1,25||2,0||0,30 Ni||0,38 Mo||1?1||76,1|
Comparative analysis of the quality of the catalysts prepared by the proposed method in terms of strength and activity in PR is the process of hydrocracking of vacuum gas oil with the catalyst of the prototype demonstrated an excess of activity and strength of the proposed catalysts; however, they were prepared without the use of exclusive prokalochnoj equipment in the reduced amount of nitrogen oxides in gases baking.
1. The method of producing catalyst for hydrocracking of crude oil by compounding zeolite Y with Ecumenical(cobalt)molybdenum(tungsten)oxide system, characterized in that the low zeolite Y with sodium silicate modulus of 5.5-7.0 and a crystallinity of at least 70% is mixed with aluminum hydroxide pseudoboehmite patterns in the ratio (1-9):1, molded, dried, calcined in an atmosphere of water vapor with obtaining a molded heat-treated zeolite impregnated with aqueous solutions of salts of Ni(Co) Mo(W) or obtained molded and heat-treated zeolite grind and compounding with Ecumenical(cobalt)molybdenum(tungsten)oxide system by mixing with aluminum hydroxide and salts of Ni(Co) Mo(W) followed by molding or by mixing with aluminum hydroxide, forming and subsequent impregnation with aqueous solutions of salts of Ni(Co) Mo(W).
2. The method according to claim 1, characterized in that the stage of calcination of the zeolite in the atmosphere of water vapor repeat 1-2 times with intermediate processing inorganic acid.
FIELD: petrochemical processes.
SUBSTANCE: group of inventions relates to processing of hydrocarbon feedstock having dry point from 140 to 400°C and is intended for production of fuel fractions (gasoline, kerosene, and/or diesel) on solid catalysts. In first embodiment of invention, processing involves bringing feedstock into contact with regenerable catalyst at 250-500°C, pressure 0.1-4 MPa, and feedstock weight supply rate up to 10 h-1, said catalyst containing (i) crystalline silicate or ZSM-5 or ZSM-14-type zeolite having general empiric formula: (0.02-0.35)Na2O-E2O3-(27-300)SiO2-kH2O), where E represents at least one element from the series: Al, Ga, B, and Fe and k is coefficient corresponding to water capacity; or (ii) silicate or identically composed zeolite and at least one group I-VIII element and/or compound thereof in amount 0.001 to 10.0 % by weight. Reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-4 MPa. Hydrocarbon feedstock utilized comprises (i) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of isoparaffins and naphtenes in summary amount 54-58.1%, aromatic hydrocarbons in amount 8.4-12.7%, and n-paraffins in balancing amount; or (ii) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of following fractions, °C: 43-195, 151-267, 130-364, 168-345, 26-264, 144-272. In second embodiment, feedstock boiling away up to 400°C is processed in presence of hydrogen at H2/hydrocarbons molar ratio between 0.1 and 10 by bringing feedstock into contact with regenerable catalyst at 250-500°C, elevated pressure, and feedstock weight supply rate up to 10 h-1, said catalyst containing zeolite having structure ZSM-12, and/or beta, and/or omega, and/or zeolite L. and/or mordenite, and/or crystalline elemento-aluminophosphate and at least one group I-VIII element and/or compound thereof in amount 0.05 to 20.0 % by weight. Again, reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-6 MPa.
EFFECT: improved flexibility of process and enlarged assortment of raw materials and target products.
12 cl, 3 tbl, 22 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: catalyst (water-soluble silicon compound) solution is added to hydrocarbons, which are then subjected to cracking in presence of hydrogen at temperature and overpressure providing explosive transfer of catalyst solution into vapor phase. Motor fuel components are predominantly obtained. Yearly processing of 0.5 to 1.0 million ton petroleum is thus envisaged.
EFFECT: simplified process, increased yield of commercial products, and enabled creation of mediate-scale cracking plants.
5 cl, 2 tbl, 3 ex
FIELD: petroleum processing.
SUBSTANCE: at least part of heavy feed is supplied to deasphalting section in presence of hydrocarbon solvents to form two streams, of which one stream is composed of deasphalted petroleum products and the other of asphalts. The latter is mixed with hydrogenation catalyst and optionally with the rest of heavy feed not directed to deasphalting section. Resulting mixture is fed to hydrofining reactor, to which also hydrogen or H2/H2S mixture is supplied. Stream containing hydrofining reaction product and dispersed catalyst is routed to one or more distillation or evaporation stages, by means of which most volatile fractions, including hydrofining gases, are separated. At least 60 wt % of bottom residue (goudron) or liquid leaving evaporation unit containing dispersed catalyst, sulfide-rich metals obtained in feed demetallization stage, and optionally coke is recycled to deasphalting zone.
EFFECT: simplified technology.
18 cl, 2 dwg, 4 tbl, 3 ex
FIELD: petroleum processing.
SUBSTANCE: blend composed of vacuum distillate and distilled fraction of secondary destruction processes is subjected to hydrogenation processing at elevated temperature and pressure in presence of catalyst, said secondary destruction process fraction containing sulfur up to 1% and being taken in amount 2 to 25% based on total weight of feedstock, while vacuum distillate boils up to 560°C. More particularly, secondary destruction process fraction is catalytic cracking, visbreaking, or retarded coking gas oil fraction. Process is carried out at 340-415°C, pressure 4-10 MPa, and feedstock supply volume flow rate 0.5-2.0 h-1.
EFFECT: improved purification degree of residue and enabled involvement of heavy vacuum distillate.
2 cl, 3 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: to crude oil with 2-10% water content is added catalyst followed by activation of hydrogen donors and hydrogenation of crude oil. Catalyst is used in the form of water-soluble group VI and VIII element compounds, which dissolves in water contained in crude oil to form true solution. Hydrogen donors are own crude oil fractions and products obtained from own crude oil fractions.
EFFECT: simplified and deepened oil processing.
10 cl, 1 dwg, 1 tbl
FIELD: petroleum processing.
SUBSTANCE: invention provides oil stock hydrotreatment catalyst containing alumina-supported hydrogenation components: cobalt, molybdenum, and tungsten in the form of oxides at weight ratio Co/Mo/W = 20:45:35 (15-25% in total), aluminum fluoride (10-30%), and promoter (2.5-16.5%): silicon oxide and/or rare-earth element oxides, in particular lanthanum oxide or lanthanum/cerium oxide mixture. Promoter may further contain up to 3% zirconium oxide. Alumina functions as binding material. Invention also covers oil stock hydrotreatment process, which is conducted in presence of claimed catalyst at 340-430°C, pressure 3-10 MPa, oil stock flow rate 0.5 to 3 h-1, and hydrogen-to-oil stock ratio 250 to 1000 nm3/m3. Catalyst is characterized by elevated hydrocracking and hydro-desulfurization activity and selectivity in oil stock hydrotreatment processes resulting in production of diesel distillates meeting European requirements (EN-590). Catalyst can be prepared on any existing catalyst preparation equipment.
EFFECT: simplified catalyst preparation technology and avoided formation of effluents.
5 cl, 3 tbl, 6 ex
FIELD: petroleum processing.
SUBSTANCE: invention, in particular, relates to petroleum fraction hydrofining process utilizing presulfided catalysts. Hydrofining process is described involving contacting petroleum fractions with presulfided catalyst containing alumina-carried cobalt, molybdenum, phosphorus, and boron, said process being conducted at 320-340°C, pressure 3.0-5.0 MPa, volumetric feed supply rate 1.0-6.0 h-1, normalized volumetric hydrogen-containing gas-to-feed ratio (500-1000):1 in presence of catalyst sulfided outside of reactor. Sulfidizing of catalyst is accomplished with hydrogen sulfide at 80-500°C and volumetric hydrogen sulfide flow rate 0.02-6.0 h-1. Chemical composition of catalyst is the following, wt %: MoS2 8.0-17.0, Co3S2 1.5-4.0, P2O3 2.5-5.0, B2O3 0.3-1.0, La2O3 1.0-5.0, and aluminum oxide - the balance.
EFFECT: simplified process.
2 cl, 1 tbl, 3 ex
FIELD: production of catalytic compositions.
SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.
EFFECT: enhanced efficiency.
29 cl, 8 ex
FIELD: petroleum processing catalysts.
SUBSTANCE: invention provides petroleum fraction hydrofining catalyst with following chemical analysis, wt %: CoO 2.5-4.0, MoO3 8.0-12.0, Na20.01-0.08, La2O3 1.5-4.0, P2O5 2.0-5.0, B2O3 0.5-3.0, Al2O3 - the balance.
EFFECT: enhanced hydrofining efficiency in cases of feedstock containing elevated amount of unsaturated hydrocarbons.
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: catalytic system of hydrocarbon feedstock hydrofining is activated by circulating hydrogen-containing gas or mixture thereof with starting feedstock through layer-by-layer loaded catalysts in presulfided or in presulfided and oxide form at elevated temperature and pressure. Hydrogen is injected into circulating hydrogen-containing gas or mixture thereof with starting feedstock portionwise, starting concentration of hydrogen in circulating hydrogen-containing gas not exceeding 50 vol %. Starting feedstock consumption is effected stepwise: from no more than 40% of the working temperature to completely moistening catalytic system and then gradually raising feedstock consumption to working value at a hourly rate of 15-20% of the working value. Simultaneously, process temperature is raised gradually from ambient value to 300-340°C. Circulating factor of hydrogen-containing gas achieves 200-600 nm3/m3. Addition of each portion of hydrogen is performed after concentration of hydrogen in circulating hydrogen-containing gas drops to level of 2-10 vol % and circulation of hydrogen-containing gas through catalysts loaded into reactor begins at ambient temperature and further temperature is stepwise raised. Starting feedstock, which is straight-run gasoline or middle distillate fractions, begins being fed onto catalytic system at 80-120°C.
EFFECT: enabled prevention and/or suppression of overheating in catalyst bed.
5 cl, 6 tbl, 12 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: catalytic system is prepared by consecutively charging into reactor alumino-cobalt and alumino-nickel-molybdenum catalysts containing 12.0-25.0% molybdenum oxide, 3,0-6.0% nickel oxide, and 3.0-6.9% cobalt oxide provided that alumino-cobalt and alumino-nickel-molybdenum catalysts are charged at ratio between 1.0:0.1 and 0.1:1.0, preparation of catalysts employs mixture of aluminum hydroxide and/or oxide powders, to which acids are added to pH 1-5. More specifically, aluminum hydroxide powder mixture utilized is a product of thermochemical activation of gibbsite and pseudoboehmite AlOOH and content of pseudoboehmite in mixture is at least 70%, and aluminum oxide powder mixture utilized comprises powders of γ-Al2O3 with particle size up to 50 μm and up to 50-200 μm taken at ratio from 5:1 to 2:5, or γ-Al2O3 powders with particle size up to 50 μm, 50-200 μm, and up to 200-400 μm taken at ratio between 1:8:1 and 3:6:1.
EFFECT: method of preparing catalytic systems for large-scale high-sulfur hydrocarbon feedstock hydrofining processes is provided allowing production of products with desired levels of residual sulfur and polycyclic aromatic hydrocarbons.
4 tbl, 3 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention provides catalyst for hydrofining of petroleum fractions, which catalyst shows elevated strength and stability upon regeneration. This is achieved supplementing alumina-based carrier with texturing additives selected from alumina and gibbsite thermochemical activation product in amount 5 to 30 wt %. Alumina additive is used with particle size not larger than 15 μm and gibbsite thermochemical activation product with that not larger than 45 μm. As binding agent in catalyst, nitric acid is used at molar ratio to alumina (0.01-0.03):1 and/or aluminum nitrate/ aluminum metal reaction product in amounts 1 to 5% based on alumina. Prior to be impregnated, catalyst is steamed at elevated temperature and impregnation is carried out from aqueous solution of nickel-cobalt-molybdenum-containing complex at pH 1-3.
EFFECT: improved performance characteristics of catalyst.
2 cl, 3 tbl, 10 ex
FIELD: petroleum refining industry.
SUBSTANCE: the invention is pertaining to the field of petroleum refining industry, in particular, to the methods of production of an ecologically pure diesel fuel. Substance: carry out hydraulic purification of a mixture of a virgin diesel fraction and distillate of carbonization and a catalytic cracking. The layers of the catalysts are located in the following way. The first on a course of traffic of a gas-raw material stream protective layer of wide-porous low-percentageNi-Co-Mo/Al2O3 catalyst is made in the form of the hollow cylinders. The second layer - the catalyst with a diameter of granules of 4.5-5.0 mm. The third - the basic catalyst made in the form of granules with a diameter of 2.0-2.8 mm. The basic catalyst has a surface of 250-290 m2 /g, a pore volume - 0.45-0.6 cm3 / g, in which - no less than 80 % of poremetric volume is formed by the through internal pores predominary of a cylindrical shape with a diameter of 4.0-14.0 nanometers. The last layer on a course of raw material traffic layer is organized analogously to the second layer. Loading of 2-4 layers is performed by a method of a tight packing. The technical result - production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm from the mixture of the virgin run fraction and distillates of a carbonization and a catalytic cracking containing up to 1.3 % mass of sulfur, at a low hardness of the process and a long time interrecovery cycle.
EFFECT: the invention ensures production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm.
7 cl, 2 tbl, 2 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: preparation of catalyst comprises two-step impregnation of preliminarily calcined carrier with first ammonium heptamolybdate solution and then, after intermediate heat treatment at 100-200°C, with cobalt and/or nickel nitrate solution followed by final heat treatment including drying at 100-200°C and calcination at 400-650°C. Catalyst contains 3.0-25.0% MoO3, 1.0-8.0% CoO and/or NiO on carrier: alumina, silica, or titanium oxide.
EFFECT: enhanced hydrodesulfurization and hydrogenation activities allowing involvement of feedstock with high contents of sulfur and unsaturated hydrocarbons, in particular in production of environmentally acceptable motor fuels.
3 cl, 4 tbl, 13 ex
FIELD: petroleum processing catalysts.
SUBSTANCE: invention related to hydrofining of hydrocarbon mixtures with boiling range 35 to 250оС and containing no sulfur impurities provides catalytic composition containing β-zeolite, group VIII metal, group VI metal, and possibly one or more oxides as carrier. Catalyst is prepared either by impregnation of β-zeolite, simultaneously or consecutively, with groups VIII and VI metal salt solutions, or by mixing, or by using sol-gel technology.
EFFECT: increased isomerization activity of catalytic system at high degree of hydrocarbon conversion performed in a single stage.
40 cl, 2 tbl, 19 ex
FIELD: hydrogenation and dehydrogenation catalysts.
SUBSTANCE: catalyst according to invention is composed of, wt %: potassium and/or lithium, and/or rubidium, and/or cesium compound 5-30, magnesium oxide 0.5-10, cerium(IV) oxide 5-20, calcium carbonate 1-10, molybdenum oxide 0.5-5, ferric oxide - the balance. Catalyst is characterized by loose density at least 1.0 g/cc but not higher than 2.00 g/cc and apparent density at least 2.0 g/cc but not higher than 3.5 g/cc. Starting ferric oxide has loose density 1.0-1.5 g/cc.
EFFECT: increased selectivity and strength of catalyst.
1 tbl, 13 ex