Bead catalyst for hydrofining heavy fractions and method for preparation thereof
SUBSTANCE: invention relates to hydrofining catalysts. Described is a bead catalyst for hydrofining oil fractions, which consists of an aluminium oxide support, active components - molybdenum, nickel or cobalt compounds in form of oxides and/or sulphides and, optionally, additional zeolite Y in hydrogen form, which is in form of spherical or elliptical granules, characterised by that the catalyst granules have packed density of 0.4-0.5 g/ml and pore volume of not less than 1.2 ml/g. Described is a method of preparing said catalyst, involving peptisation of the starting powder - an aluminium oxide source with aqueous solution of an organic acid to obtain a pseudo-sol, moulding the obtained pseudo-sol in ammonia solution, drying and calcination of the support with subsequent embedding of active components therein, with optional embedding of zeolite Y in hydrogen form, drying and calcination of the catalyst in an air current, wherein the starting powder - aluminium oxide source used is weakly crystalline pseudo-boehmite; peptisation thereof is carried out using aqueous solution of an organic acid with concentration of 1-15 wt % and granulation (moulding) is carried out by drip moulding with the solid to liquid ratio in the pseudo-sol of not less than 1:2 and pH of the ammonia solution of not less than 11.0.
EFFECT: high activity, selectivity and stability of the catalyst.
3 cl, 1 tbl, 4 ex
The invention relates to the refining industry and is intended for use in the manufacture of catalysts for the process hydrofining (Hydrotreating) various petroleum fractions, mainly petrol and diesel, but also kerosene, vacuum gas oil, fuel oil, in order to remove sulfur, nitrogen and oxygen, mostly organic compounds, and metals.
The problem of increasing the efficiency of the Hydrotreating process, in particular by reducing the residual content of sulfur compounds at specific values of the pressure and feed rate of raw materials and involvement in the processing of heavier fractions, solved in different ways, but almost any process enhancements to increase the efficiency of the catalysts. Among the set of problems of improvement of the catalysts are as follows:
increasing the volume of the pores of the support, allowing one-stage simple way to enter into the contact required (maximum) number of active metals,
- change in the shape and porous structure that provides adequate duration of contact with the turning joints and full use of the physical surface of the catalyst,
- modification of the catalysts through the use of effective promoters and who sing the new original methods of synthesis,
- promotion of the catalyst by adding zeolites to increase acidity, which, in particular, allows you to convert in addition to light gasoline and diesel fractions, heavy fraction is vacuum gas oil and even oil.
To increase the area of contact of the catalyst and raw materials, as a rule, have resorted to reducing the size of the granules and apply granules complex forms - the so-called shamrocks, "vertebrae", four extrudates and the like, While the predominant industrial method for the granulation of such catalysts (media) remains screw extrusion. Technology such extruded catalysts are described, for example, in U.S. patent No. 6955752, 6984312 and 7005059. Such catalysts have insufficient effectiveness: in terms of testing their activity is 275-290°C, the selectivity of more than 2 ppm, stability is in the range of 12.5-14°C.
Because apart from the outer surface important and the inner surface, i.e. the distribution of pore size and pore shape, often in patents provides some regulation characteristics of the porous structure, as described, for example, in U.S. patent No. 5827421 and 4120826. The catalysts produced using the above-mentioned methods have a high efficiency, but the lack of activity from 275 to 282°C, stability about 13-13 .5°C and selectivity - 1,9-2,5 ppm.
To improve the selectivity and stability of catalysts use of different promoters and modifiers, including the most commonly used supplements of phosphorus, iron, titanium and tungsten. In U.S. patent No. 5968348 and 5246569 provided by the supplementation of phosphorus in the catalyst pellets including spherical shape, in U.S. patent No. 4960506 and 5010049 - iron supplements, and in U.S. patent No. 6162350 and 4839326 part of the molybdenum is replaced promoting compound of tungsten. When this pellet catalysts can have a cylindrical shape (extrudates)and spherical (rolls). Catalysts prepared with these promoters have acceptable activity - 250-270°C, but an insufficient level of selectivity and stability, respectively, more than 1.9 ppm and 12.5 to 13.5°C.
To increase the acidity of the catalyst that allows the treatment of the heavy fraction (gasoil, fuel oil), the catalyst is injected additive zeolite, usually broad porous zeolites of type X or Y. the Composition of such catalysts and methods for their preparation are known and described, for example, in U.S. patent No. 5827421, 5968348. Technology such catalysts does not provide for forming granules of spherical shape; their efficiency is not high enough: activity - within 277-292°C, the selectivity is more than 1.9 ppm, stability is on UB is 12-15°C.
To reduce the cost of catalyst while maintaining its effectiveness often strive as much as possible to lower the content of the active metal is molybdenum and Nickel or cobalt.
In addition, to obtain an effective catalyst is required to provide a particular state of the hydrogenating metals in the catalyst, their optimal location in the matrix composition and the specific interaction of oxides (sulfides) of metals with each other and with the substrate. For this purpose, in particular, use complex compounds of molybdenum and Nickel or cobalt (U.S. patent 5872073, 6156695, 4046714). Such methods, however, do not lead to an increase of the main characteristics: activity, selectivity and stability.
There are several patents involving the preparation of Hydrotreating catalysts in ball form. Thus, in U.S. patent No. 4315838 this purpose is used as a binder of silicon dioxide, but this reduces the selectivity of the catalyst (about 2.2-2.8 ppm). In U.S. patent No. 3957627 describes the preparation of Hydrotreating catalyst in the form of spheres, hollow inside and with holes in the shell for the accessibility of the internal surface. In addition to the extreme complexity of such a technology catalyst it has low strength and poor stability (>14°C).
The closest essentially of the composition kompoziziii the proposed technology is U.S. patent No. 4009125, where protected the Hydrotreating catalyst in the form of granules of spherical shape and the method of its manufacture. Media or catalytic composition granularit method of seaming, which limits the ability to obtain pellets of relatively low size: size balls of the described catalyst is about 2 mm. in Addition, this provides a contact with a bulk density exceeding that of the extruded modifications, i.e. 0,65-0,90 g/ml (0.7 to 0.8 g/ml), respectively, with a pore volume of more than 0.6 ml/homema other things, this reduces the effectiveness of the catalyst activity and selectivity are 280-295°C and more than 2.2 ppm, respectively), and, moreover, does not significantly restrict the content of hydrogenating metals (the content of molybdenum oxide in the catalyst is not less than 14%, Nickel oxide is not less than 4%), and increases the supply of catalysts.
The problem to which the invention is directed, is to improve the activity, selectivity and stability, as well as reducing the cost of delivery of the Hydrotreating catalyst intended for processing as a relatively light oil fractions petrol and diesel and distillates content of heavy components (vacuum gasoil, fuel oil and so on) up to 50%. The proposed catalyst is in the form of granules of spherical shape or ellip oidy with high pore volume and having an extremely low bulk density - the order of 0.45-0.50 g/ml This allows you to enter in its composition a sufficiently large number of active metals (Moo3- 17,5-18,5%; NiO or COO - 4,0-5,0%) to provide high activity, and the use of media with extremely high pore volume (more than 1.2 ml/g) allows to form on the surface about monocline or more than monocline coating the surface of the carrier oxide of molybdenum, followed by the application on top of it the connection of the second metal (nicely or cobalt), and the quantity of metal per unit weight of the finished catalyst is significantly lower than traditional brands catalysts, and thus significantly lower the cost of delivery of the catalyst for download in industrial fixed reactor volume. The above is achieved due to the original technology of the synthesis of the carrier by drip moulding. As a variant, the catalyst is introduced zeolite Y in the hydrogen form, it can be used for Hydrotreating the heavy raw materials.
The problem is solved as follows.
The preparation of the catalyst process for Hydrotreating petroleum fractions includes the steps of cooking the sour pseudosasa, drip moulding, aging balls, then heat treatment of the medium and application of active ingredients, compounds of molybdenum, then compounds of Nickel and / or to the viola with a subsequent heat treatment of the catalyst, in which all components are in the oxide state. As the source material will be used powders of pseudoboehmite brand V-250 and/or brand V-200 series ("Versailles", "Eurosport), which has low crystallinity, low bulk density and providing a "delicate" porous media. A significant distinguishing feature of the proposed method is that the original powder of aluminum hydroxide before pelleting treated with an aqueous solution of an organic acid with a concentration of 1-15% with a ratio of solid: liquid not less than 1: 2, and then the sour psevdosily granularit drip method in solution of ammonia at high pH in excess of 11.0. Optionally, the catalyst composition is introduced additionally zeolite Y in the hydrogen form, which contribute to acid psevdosily aluminum hydroxide.
The acid can be used the following organic acids: acetic, oxalic, citric and formic and/or adipic.
Obtained sour psevdosily dropwise using a special dispenser through an orifice is introduced into a tank filled with a strong solution of ammonia (concentration not lower than 6%) and incubated for 3-15 minutes, after which the hardened balls are separated from the ammonia separator and prom is provide water from the residual ammonia and the resulting ammonium salt (usually acetate or ammonium citrate). Then the granules are dried in air at a temperature of 120-150°C and calcined in a flow of air at 700°C for 3-4 hours. Get the media in the form of beads with an adjustable diameter in the range from 1.2 to 2.0 mm and a bulk density of from 0.31 to 0.38 g/ml
On the prepared media known adsorption from aqueous solutions are applied molybdenum, then the intermediate is dried similarly to the media and calcined at a temperature of about 480°C, after which it put a solution of salts of Nickel or cobalt (usually nitrate), and finally calcined at a temperature of about 480°C and obtain a catalyst with a bulk density of 0.4-0.5 g/ml and a pore volume of not less than 1.2 ml/g ready to use.
The problem solved by the invention is achieved by cooking medium by processing the original sour pseudosasa received by patsatsia powder weakly cristallizing of pseudoboehmite a solution of an organic acid with a certain concentration (1-15%), aqueous solution of ammonia with respect to the ratio of solid:liquid = at least 1:2 and with provision at the stage of forming a specific pH value not below 11,0 implemented within the freshly formed ball pellets. Zeolite Y in the hydrogen form contribute in the prepared acidic Hydrosol before surgery drip moulding (granulation).
For prepara is possible catalyst of the proposed method is suitable modifications poorly cristallizing pseudoboehmite hydroxide, obtained by deposition of an aluminum salt with hydrochloric acid, mainly pseudonimity family "Versailles", produced by the company "Eurosport (USA-Holland).
The characteristics of the original powders pseudoboehmite are shown in table 1.
|The characteristics of the ORIGINAL POWDERS PSEUDOBOEHMITE ALUMINUM HYDROXIDE|
|1.1.||The crystallite size (OCR), Å||25-30||20-25|
|1.2.||The position of the line , °2θ (uKα)||14,6-15,2||~of 14.8 to 15.4|
|1.3.||Raw materials||Salts of Al, hydrochloric + acid||Salts of Al, hydrochloric acid|
|1.4.||The shape of the particles||The primary particles of irregular shape, more or less rounded||The primary particles of irregular shape, not rounded|
|2||Particle size, microns||The prevailing diameter of 20-40||The prevailing diameter of 15-30|
|3||Internal porosity||Mainly meso - and macropores||From micropores to macropores|
|4||Specific surface area, m2/g||200-270||220-290|
|5||Bulk density, g/ml: - free|
|6||The total pore volume, ml/g||1,0||1.2|
|7||SPT at 850°C, %||24-27||25-28|
|8||The data of thermal analysis, DTA||2 entopic the||2 indopia|
|peaks at 110 and 420°C||peaks at 100 and 410°C|
|9||The content of impurities, wt.%:|
|- sodium oxide (Na2O)||<0,015||<0,015|
|- iron oxide (Fe2O3)||0.03||0.03|
|- of silicon dioxide (SiO2)||0,01-0,03||0,01-0,03|
|titanium dioxide (TiO2)||UTS.||UTS.|
|- chlorine(CL)||of 0.07 to 0.3||of 0.07 to 0.3|
The method of preparation of the catalyst includes the following study is:
- peptidase powder pseudoboehmite aluminum hydroxide by treatment with water, and then a solution of an organic acid under continuous mechanical stirring, or treatment with acid solution with obtaining sour pseudosasa with pH ~1,0;
- possible introduction to the received psevdosily powder of zeolite Y in the hydrogen form;
- granulation received pseudosasa method drip molding with the introduction of droplets in strong aqueous ammonia to pH>11 and holding it to maturity within 3-15 minutes;
- heat treatment of the freshly-formed balls: drying and calcination in dried air at a temperature of about 700°C;
- coating the surface of the carrier molybdenum from aqueous solution of ammonium molybdate adsorption method with drain excess waste solution;
- drying and intermediate annealing at 480°C in a dehumidified air;
- drawing on molybdenum-containing intermediate second metal (Nickel or cobalt) from aqueous nitrate solution of the second metal;
- heat treatment of the catalyst, drying and calcination in a stream of air at 480°C.
Catalytic test is carried out in a flow-circulation installed in the hydrodesulphurization unit diesel oil fraction, wikipeida within 180-360°C. the Total concentration of sulphur compounds in the raw material is 1.1 wt.%, including the Isla of teofanov - 0.11 wt.%.
For the pilot testing of zeolite catalysts in addition to the diesel fraction in raw materials add up to 50% vacuum gas oil with end boiling point of 560°C. or up to 50% of fuel oil (the so-called weighted raw).
Test conditions: catalyst loading of 50 ml, a pressure of 35 atmospheres, the rate of circulation of the hydrogen-containing gas (hydrogen-rich) - 350 nl/l of raw material per hour, the concentration of hydrogen in SIV - 95%.
For each sample, conduct the test in a normal (soft) mode for determining activity and selectivity and in hard - to determine stability.
In soft mode in addition to the above parameters, support volumetric feed rate 6 h-1. For this activity, take the temperature of the experience, which guarantees the residual content of total sulfur in catalyzate 30 ppm (m-1). The selectivity is assumed residual content of thiophenol in the reaction products.
For testing in hard mode volumetric feed rate is increased to 20 h-1the pressure is reduced to 15 ATM, and the multiplicity of circulation - up to 150 nl/L. Quantitatively the stability is expressed as the reduction in the activity tests in hard mode between 20 and 100 hours of experience (i.e. the temperature difference for the specified time points).
Before the test the catalyst sarnaut hydrogen sulfide at a temperature of 250°C, pressure is 1.5 MPa in flow-through mode until the breakthrough of hydrogen sulfide (about 3 hours).
Take 106,71 g powder pseudoboehmite brand V-250, is characterized by loss on ignition at 850°C (SPT), is equal to 27.4 per cent of that in terms of Al2About3responsible 77,5,
To the powder add 77,5 cm3water and gradually in small portions with constant stirring add 31 cm3solution glacial acetic acid (concentration ~5 M). The ratio of solid: liquid in the finished pseudocode is more than 1. The total mixing time 30 minutes Get psevdosily (suspension) with pH<1 (~0.6m). Psevdosily dropwise through the feeder and metering device is introduced into a column filled with ammonia solution with a high concentration of not more than 25%but not less than 6%. The pH value of the aqueous solution filling the pores freshly formed balls exceeds this 11,0. The resulting beads incubated in the column for about 5 minutes, sephirot from ammonia and quickly washed with plenty of water, and then dried on a belt dryer in the current of heated air at a temperature of 110-130°C for about 1 hour. The dried pellet pellet carrier is subjected to annealing at 700°C in a stream of dry air, which is continuously served with a bulk velocity of 1000 h-1i.e. through the layer of balls received media pass 150 liters of hot air per hour.
Get about 77,5 g media - gamma-aluminium oxide what s in the form of granules of spherical shape with a diameter of 1.66 mm and a pore volume of 1.55 ml/year
Next, prepare the impregnating solution of ammonium molybdate in the amount of 180 ml, which is dissolved at 70°C in 180 ml of distilled water 46,86 g of ammonium molybdate composition (NH4)6Mo7O24·4H2O that corresponds 25,55 g of Moo3or 19.8% of molybdenum trioxide by weight of the final catalyst. The system is maintained with stirring for 1 hour and then the excess solution is drained. The obtained molybdenum-containing intermediate is dried at 120°C for 4 hours and then calcined at 480°C for 3 hours in air flow. Get the 95.5 g of the intermediate product, including 77,5 g Al2About3and 18 g of Moo3.
Then prepare a solution of Nickel nitrate: 22,61 g of salt Ni(NO3)2·6N2O (contains of 5.81 g NiO) is dissolved in 180 ml of water and then poured to the Mo-containing intermediate. Stand for 0.5 hours, after which excess water is evaporated and get the catalyst. A sample of catalyst is dried at 120°C for 3 hours and then calcined in a dehumidified air at 480°C for 4 hours.
Get the catalyst composition (in wt.% in terms of dry substance): 18,0 of Moo3; 4,5 NiO; the rest is media (alumina). Bulk density was 0.45 ml/year
The results of the standard testing regime described above: the activity of the catalyst was 255°C, the selectivity to 1.4 ppm, stability -11°is.
EXAMPLE # 2
Same as in example No. 1, but instead 106,71 g initial powder charge 104,44 g powder pseudoboehmite brand V-200 with a value of SPT at 850°C, equal to 25.8 wt.%.
Other cooking parameters similar to those in example No. 1. The ratio of T: W in pseudocode is 1.0, the pH of the ammonia solution=11,4. The volume of pores in the carrier is equal 1,72 ml/g bulk density of the final catalyst is of 0.44 ml/year number of hydrogenating metals (molybdenum and Nickel in the finished catalyst are similar to those in example No. 1.
Test results: the activity of the catalyst was 263°C selectivity -1,1 ppm, stability is 9°C.
EXAMPLE # 3
Same as in examples # 1 and # 2, but for preparation of media, take the mixture of powders V-250 V-200 in the ratio of 1:1, aluminum oxide, i.e. 53,355 g of the first and 52,22 g of the second powder, respectively. Other cooking parameters and the composition is basically identical to the parameters of the synthesis described in example No. 1. The ratio of T:W=1,75, the pH of the ammonia solution of 11.2. The volume of pores in the carrier is equal 1,64 ml/g, the bulk density of the catalyst of 0.43 ml/year
Test results: the activity of the catalyst amounted to 252°C, the selectivity to 1.0 ppm, stability is 8°C.
EXAMPLE No. 4
Analogously to example No. 1, but additionally in addition to molybdenum oxide and Nickel oxide or cobalt in the catalyst composition is injected 15.0 wt.% zeal is the HY in the form of powder.
The ratio of T: W in acidic pseudocode is1/2, the pH of the ammonia solution in the column for molding is 11,12.
Active ingredients (molybdenum and Nickel) is applied in the same way and in the same quantities as in example No. 1.
Pore volume in the media is 1.48 ml/g, the bulk density of the catalyst - 0,45 ml/year
Tests are conducted on weighted raw materials with the addition of 40% vacuum gas oil, wikipaedia to 560°C.
Test results: the activity of the catalyst amounted to 274°C, the selectivity - of 1.88 ppm, stability is 12.5°C.
1. Ball catalyst for Hydrotreating petroleum fractions, consisting of medium-alumina, active ingredients, compounds of molybdenum, Nickel or cobalt in the form of oxides and/or sulfides and possibly additional zeolite Y in the hydrogen form, which granules are spherical or elliptical shape, wherein the catalyst pellets have a bulk density of 0.4 to 0.5 g/ml and a pore volume of not less than 1.2 ml/g
2. The preparation method of catalyst for Hydrotreating petroleum fractions according to claim 1, consisting of a carrier of alumina, active ingredients, compounds of molybdenum, Nickel or cobalt, and possibly additional zeolite Y in the hydrogen form, including peptization original powder - a source of aluminum oxide with an aqueous solution of organic acid to obtain the sidosos, the molding obtained pseudosasa in the ammonia solution, drying and calcination of the carrier with the subsequent introduction of active components with the possible introduction of zeolite Y in the hydrogen form, drying and calcination of the catalyst in a stream of air, characterized in that as starting powder, a source of aluminum oxide is used slaboaglomerirovannye pseudoboehmite, peptization take him as an aqueous solution of an organic acid with a concentration of 1-15 wt.%, and granulation (molding) is performed by the method of drip molding with a ratio of solid : liquid in pseudocode not less than 1:2 and the pH of the ammonia solution is not less than 11,0.
3. The method according to claim 2, characterized in that for peptization use aqueous acetic, oxalic or citric acid.
SUBSTANCE: present invention relates to a hydroisomerisation catalyst, a method of producing said catalyst, a method for dewaxing hydrocarbon oil and a method of producing lubricant base oil. Described is a hydroisomerisation catalyst, obtained by calcining a catalyst composition containing an ion-exchanged molecular sieve or a calcined product thereof, wherein the ion-exchanged molecular sieve is obtained by ion-exchanging a molecular sieve in a solution which contains cationic groups, the molecular sieve includes nanocrystals having a pore structure of decahedral rings or octahedral rings and having a ratio of the pore volume to the external surface area ([pore volume]/[external surface area]) from 2.0×10-4 ml/m2 to 8.0×10-4 ml/m2, and contains an organic matrix and at least one metal selected from a group consisting of metals of Groups 8 to 10 of the Periodic Table of the elements, molybdenum and tungsten, deposited on the ion-exchanged molecular sieve or the calcined product thereof. Described is a method of producing the catalyst, involving a step (a) of hydrothermally synthesising a molecular sieve comprising nanocrystals having characteristics given above and an organic matrix; a step (b) of ion-exchanging the molecular sieve comprising an organic matrix in a solution containing a cationic groups to obtain an ion-exchanged molecular sieve; a step (c) of making the ion-exchanged molecular sieve or a calcined product thereof, carrying at least one metal selected from a group consisting of metals of Groups 8 to 10 of the Periodic Table of the elements, molybdenum and tungsten to obtain a catalyst composition; and a step (d) of calcining the catalyst composition. Described is a method of dewaxing hydrocarbon oil, involving bringing the hydrocarbon oil containing normal paraffins having 10 or more carbon atoms into contact with catalyst described above in the presence of hydrogen to convert a part of or all of the normal paraffins into isoparaffins. Described is a method of producing lubricant base oil in conditions for conversion of normal paraffins of substantially 100 wt %, the conversion being defined by the formula (1): conversion of normal paraffins (%)=[1-(total wt % of normal paraffins having Cn or more carbon atoms contained in mineral oil after contact)/(total wt % of normal paraffins having Cn or more carbon atoms contained in mineral oil before contact)]×100, where Cn denotes the minimum number of carbon atoms in normal paraffins having 10 or more carbon atoms contained in mineral oil before contact.
EFFECT: obtaining a catalyst with high isomerisation selectivity, stable and high output of hydrocarbon oils, suitable for lubricant base oils.
14 cl, 1 tbl, 8 ex, 2 dwg
FIELD: process engineering.
SUBSTANCE: this invention relates to reductive isomerisation catalyst, dewaxing of mineral oil, method of producing base oil and lubrication base oil. Invention covers reductive isomerisation catalyst. Reductive isomerisation comprises molecular sieve treated by ionic exchange or its calcinated material produced by ionic exchange of molecular sieve containing cationic fragments and using water as the primary solvent, and at least one metal selected from the group consisting of metals belonging to group VIII-X of periodic system, molybdenum and tungsten applied onto molecular sieve treated by ionic exchange, or onto its calcinated material. Dewaxing comprises converting portion of or all normal paraffins into isoparaffins whereat mineral oil containing normal paraffins is brought in contact with abode described reductive isomerisation catalyst in the presence of hydrogen. Invention covers also method of producing lubricant base oil and/or fuel base oil implemented by bringing base oil containing normal paraffins in contact isomerisation catalyst in the presence of hydrogen. Invention covers also method of producing lubricant base oil containing normal paraffins, including 10 or more carbon atoms by bringing it in contact with above describe reductive isomerisation catalyst in the presence of hydrogen in conversion of normal paraffins making in fact 100%.
EFFECT: catalyst with high isomerisation activity and sufficiently low cracking activity at high yield.
22 cl, 8 tbl, 4 ex, 11 dwg
SUBSTANCE: invention relates to hydrotreatment processes. Described is a method of removing paraffin from hydrocarbon material, involving reacting the material with a mixture of ZSM-48 catalysts under catalytic paraffin removal conditions for producing material from which paraffin has been removed, where the mixture of ZSM catalysts contains: a) first type ZSM-48 crystals, having molar ratio of silicon dioxide to aluminium oxide equal to 70-110 and containing inoculating crystals different from ZSM-48, and b) second type ZSM-48 crystals which differ from first type ZSM-48 crystals on one or more properties selected from presence of inoculating crystals different from ZSM-48, crystal morphology, higher kenyaite percentage and higher molar ratio of SiO2 to Al2O3.
EFFECT: high efficiency of removing paraffin from hydrocarbon material owing to use of a a highly active catalyst.
16 cl, 1 tbl, 6 dwg, 15 ex
SUBSTANCE: invention relates to high activity ZSM-48. Described is a catalyst composition for removing paraffin from hydrocarbon material which contains ZSM-48 crystals, having molar ratio of silicon dioxide to aluminium oxide equal to or less than 110, which does not contain inoculating crystals different from ZSM-48 and does not contain ZSM-50 crystals.The invention also describes a method of producing ZSM-48 crystals contained in the composition described above, involving: preparation of an aqueous mixture of silicon dioxide or silicate, aluminium oxide or aluminic acid, hexamethonium salts and an alkaline base, where the mixture has the following molar ratios: silicon dioxide: aluminium oxide 70-110, base: silicon dioxide 0.1-0.3 and hexamethonium salt: silicon dioxide 0.01-0.05, and heating the mixture while stirring for a period of time and temperature sufficient for formation of crystals. The invention also describes a method of removing paraffin from hydrocarbon material in the presence of the catalyst composition described above.
EFFECT: obtained ZSM-48 crystals and a composition based on said crystals exhibit high activity during removal of paraffin from hydrocarbon material.
29 cl, 1 tbl, 6 dwg, 15 ex
SUBSTANCE: invention refers to noble-metal catalyst, to method for making and application thereof. There is disclosed method for making noble-metal catalyst for hydrocarbon conversion, involving the stages as follows: a) preparation of the carrier containing zeolite, chosen from zeolites with medium and large pores and acid sites, at temperature within 423 to 1173 K and optional carrier modification; b) deposition of noble metal chosen from platinum, palladium, ruthenium, rhodium, iridium and their mixtures and combinations, by gas-phase deposition including evaporation of noble metal precursor chosen from β-diketonates and metallocenes, and interaction with the carrier, and c) heat treatment in oxidising or reducing environments. There is disclosed application of noble-metal catalyst produced by the method described above, in ring opening, isomerisation, alkylation, hydrocarbon reforming, dry reforming, hydrogenation and dehydrogenation, and preferentially, in ring opening of naphthenic molecules. Additionally, there is disclosed method for making medium diesel fuel distillate by introducing raw medium distillate into the reactor wherein it reacts at temperature 283-673 K and under pressure 10-200 bar with hydrogen with added noble-metal catalyst produced as described above until ring opening of naphthenes with two or more rings completed to produce isoparaffins, n-paraffins and mononaphthenes within medium distillate.
EFFECT: production of catalyst with improved selectivity for hydrocarbon conversion.
16 cl, 5 tbl, 20 ex
SUBSTANCE: said invention relates to method for improvement of loss of mobility temperature of hydrocarbon material obtained by Fischer-Tropsch synthesis, in particular to satisfactory-yield conversion of material with high temperature of mobility loss, at least one fraction of which has low mobility loss temperature and high viscosity index for base oil. Method implies utilisation of dewaxing catalyst, which contains at least one zeolite (molecular sieve) chosen from a group of TON type zeolites (Theta-1, ZSM-22, ISI-1, NU-10 and KZ-2), and at least one ZBM-30 zeolite, at least one inorganic porous matrix, at least one hydrogenating/dehydrogenating element, preferentially from group VIB and group VIII of periodic table.
EFFECT: improved loss of mobility temperature for hydrocarbon material obtained by Fischer-Tropsch synthesis.
14 cl, 7 ex, 1 dwg
SUBSTANCE: dewaxing procedure of raw material produced by Fischer-Tropsch method implies that processed raw materials contact with catalyst containing at least one zeolite ZBM-30, synthesised with triethylene tetramine, at least one hydrogenating- dehydrogenating element preferably selected from elements of group VIB and group VIII of periodic table, and at least one inorganic porous matrix.
EFFECT: good recovery of raw material, raised pour point.
13 cl, 5 ex, 1 dwg
FIELD: petroleum chemistry.
SUBSTANCE: invention relates to microcrystalline paraffin obtained by catalytic hydroisomerization at temperature more than 200°C from FT paraffin having from 20 to 105 carbon atoms. Microcrystalline paraffin is non-liquid at 25°C, but at least pasty with needle penetration less than 100x10-1, measured according to DIN 51579. Disclosed is method for production of microcrystalline paraffin.
EFFECT: microcrystalline paraffin free from naphthenes and aromatics.
17 cl, 1 dwg, 1 tbl, 3 ex
FIELD: production of catalysts.
SUBSTANCE: proposed method is used for production of catalyst containing zeolite and heat-resistant oxide binder at low acidity practically containing no aluminum; proposed method includes the following operations; (a) preparation of mass suitable for extrusion and containing homogeneous mixture of zeolite, water, binder of heat-resistant binder at low acidity which is present as acid sol and aminocompounds; (b) extrusion of mass obtained at stage (a) suitable for extrusion; (c) drying extrudate obtained at stage (b); and (d) calcination of dried extrudate obtained at stage (c).
EFFECT: increased strength of catalyst at high resistance to crushing.
10 cl, 1 tbl, 2 ex
FIELD: powder metallurgy; method of impregnation by a metal(of VIII group) of a molecular sieve extrudate with cementing material with the help of ion exchange with an aqueous solution of metal salt of VIII group.
SUBSTANCE: the invention presents a method of impregnation by metal of VIII group of an extrudate of a molecular sieve with cementing material, in which the cementing material represents a refractory oxidic material with a low acidity, practically free of aluminum oxide, using: a) impregnation of porous volume of an extrudate of a molecular sieve with cementing material with an aqueous solution of nitrate of the corresponding metal of VIII group with pH from 3.5 up to 7, in which the molar ratio between cations of a metal of VIII group in a solution and a number of centers of the adsorption available in the extrudate, is equal to or exceeds 1; b) drying of the produced at the stage a) extrudate of the molecular sieve with the cementing material. The technical result is good distribution of the metal and a short period of drying.
EFFECT: the invention ensures good distribution of the metal and a short period of drying.
9 cl, 1 tbl, 4 ex
SUBSTANCE: stable composition for application for catalyst carrier impregnation in order to obtain catalytically active solid substance includes: (A) water; (B) catalytically active metals, which are in form of and containing: (1) at least, one component, ensuring, at least, one metal of group VIB of Periodic system; and (2) at least, one component, ensuring, at least, one metal of group VIII of Periodic system, selected from group consisting of Fe, Co and Ni; and (i) said metal of group VIII is supplied with, in fact, insoluble in water component; (ii) molar ratio of said metal of group VIII and metal of group VIB constitutes approximately from 0.05 to approximately 0.45, on condition that amount of said metal of group VIII is sufficient for promoting catalytic impact of said metal of group VIB; (iii) concentration of said metal of group VIB, expressed as oxide, constitutes, at least, from approximately 3 to approximately 50 wt % of said composition weight; and (C) at least, one, in fact, water-soluble phosphorus-containing acid component in amount, insufficient for dissolving said metal of group VIII at room temperature, and sufficient for ensuring molar ratio of phosphorus and metal of group VIB from approximately 0.05 to less than approximately 0.25. Described is method of obtaining described above composition, including addition to suitable water amount of: (A) at least, one in fact water-insoluble component based on metal of group VIII, selected from group consisting of Fe, Co and Ni; and (B) at least, one in fact water-soluble phosphorus-containing acid component in amount insufficient for causing dissolution of said component based on metal of group VIII, with obtaining suspension, and combining suspension with: (C) at least, one component based on metal of VIB group; and (D) mixing of combinations (A), (B) and (C), and heating mixture during time and to temperature sufficient for formation of solution by (A), (B) and (C); and (E) adding supplementary amount of water, if necessary, in order to obtaining concentrations of solution of, at least, one said metal of group VIII, at least, one said metal of group VIB and phosphorus, suitable for impregnation of said carriers; group VIB and VIII refer to groups of periodic system of elements. Described is catalyst obtained by carrier impregnation with stable composition, suitable for hydrocarbon raw material processing.
EFFECT: increase of conversion degree of sulphur, microcarbon residue.
23 cl, 3 ex
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
SUBSTANCE: invention relates to promoter catalysts on a combined zeolite/aluminosilicate substrate with low content of macropores and to methods of hydrocracking/hydroconversion and hydrofining, in which said catalysts are used. The catalyst contains at least one hydrogenating-dehydrogenating element, selected from a group comprising group VIB and group VIII elements, a promoter element in a controlled amount, selected from phosphorus oxide, and a substrate based on zeolite Y, defined by constant a of the unit cell of the crystal lattice, ranging from 24.40·10-10 m to 24.15·10-10 m, and based on aluminosilicate, containing silicon dioxide (SiO2) in amount exceeding 5 wt % and less than or equal to 95 wt %. The catalyst has the following characteristics: average pore diametre, total pore volume, BET specific surface area, volume of pores of different diametre, characterised by X-ray diffraction pattern and packing degree of the catalyst.
EFFECT: catalyst provides for suitable selectivity of middle distillates, ie fractions with initial boiling point of at least 150°C and final boiling point which reaches initial boiling point of residue, for example below 340°C or 370°C.
28 cl, 4 tbl, 21 ex
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: 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
SUBSTANCE: invention relates to catalysts of hydrorefining Diesel distillates, method of obtaining catalyst and method of hydrorefining Diesel distillates in order to obtain ecologically pure Diesel fuels and can be used in oil-refining industry. Described is catalyst for the process of hydrorefining Diesel fractions, which contains as carrier composition of aluminium oxide and zeolite β, which includes, wt %: 0.25-0.85 of magnesium compounds counted per MgO, 5-15 of silicon compounds counted per SiO2, aluminium oxide - the remaining part; and as active component catalyst contains, wt %: tungsten oxide WO3 - 20-25, nickel oxide - 3.8-4.1, phosphorus oxide - 1-1.5, carrier - the remaining part, with molar ratio tungsten/nickel W/Ni - 1.9-2.1 and phosphorus/tungsten P/W - 0.09-0.1. Described is method of catalyst preparation and method of hydrorefining of Diesel fractions, containing up to 30 wt % of catalytic cracking gas oil for which hydrorefining is carried out in reactor of hydropurification, loaded in layers with catalyst described above catalyst and CoMo/Al2O3 - catalyst, the latter is located in the first layer in the direction of movement, which are taken in ratio from 1:3 to 1:1.4, at temperature 340-370°C, hydrogen pressure 3.5-7.0 MPa.
EFFECT: high efficiency of hydrorefining of Diesel fraction with higher content of polycyclic aromatic hydrocarbons, nitrogen-containing and stable sulphur-containing compounds.
4 cl, 11 ex, 1 tbl
SUBSTANCE: invention relates to a method of producing a hydrotreatment catalyst. Described is a method of producing a hydrotreatment catalyst which involves the following steps: a) at least one step for saturating a dried and/or annealed catalyst precursor containing at least one group VIII element and/or at least one group VIB element and an amorphous support using an impregnating solution consisting of at least one phosphorus-containing compound dissolved in at least one polar solvent with relative permittivity higher than 20; b) a step for maturation of said saturated catalyst precursor obtained at step a); wherein said maturation step is carried out at atmospheric pressure, at temperature ranging from ambient temperature to 60°C for maturation period of 12 to 340 hours; c) a step for drying without a subsequent step for annealing said catalyst precursor obtained at step b), wherein the drying step c) is carried out in a drying oven at atmospheric or low pressure and at temperature 50-200°C. Described is use of the catalyst obtained using the described method to carry out hydrofining and hydroconversion of hydrocarbon material.
EFFECT: high catalyst activity.
14 cl, 8 tbl, 17 ex
FIELD: oil and gas industry.
SUBSTANCE: invention refers to crude product obtaining method involving contact of hydrocarbon raw material, where hydrocarbon raw material has viscosity at least of 500 cSt at 37.8°C, with hydrogen in presence of one or several catalysts so that total product can be obtained, which includes crude product, where crude product represents liquid mixture at 25°C and pressure of 0.101 MPa. At that, crude product has viscosity of not more than 50% of viscosity of hydrocarbon raw material at 37.8°C; and where P-factor of hydrocarbon raw material/total product mixture is at least 1.0. At that, viscosity is determined as per ASTM, method D445, and P-factor is determined as per ASTM, method D7060; where at least one catalyst includes metal (metals) of 6-10 groups in combination with carrier and has pore distribution as per sizes with average pore diameter in the range of 50 to 180 A; at that, catalyst includes at least 0.01 gram of aluminium silicate per 1 gram of catalyst; and where contact conditions are controlled at temperature of 370 to 450°C, partial hydrogen pressure of not more than 7 MPa and volume rate of liquid supply of at least 0.1 h-1. Invention also refers to catalyst for obtaining crude product.
EFFECT: crude product with residue content of not more than 90 percent of residue content in hydrocarbon raw material or reduced viscosity value which represents not more than the half in relation to residue content or viscosity value in hydrocarbon raw material.
14 cl, 27 dwg, 34 ex
FIELD: process engineering.
SUBSTANCE: invention relates to oil processing, in particular, to production of catalyst for extracting sweet oil fraction to be used in oil processing and petrochemistry. Proposed catalyst including commercial molybdenum disulphide and/or tungsten disulphide, as active components, produced by CBC-method with carrier, a nano-sized pseudo-boehmite, in 20:80 ratio or without, subjected to mechanical and chemical effects, promoter, e.g. nanopowders of 3D-metals (Ni, Co, Fe) produced by physical methods at active component-to-promoter ratio of 70:30 with particle size of smaller than 100 nm, and, additionally, gas-phase nanopowder of Ni in pyrocarbon shell with particle size of smaller than 10 nm in amount of 3 wt % of active component. Invention covers method of producing said catalyst in vertical vibration mill by mechanical and chemical activation of components at vacuum of 10-5 torr with frequency and amplitude of vibration of 16 Hz and 2 mm, respectively, and activation time of 4-12 h.
EFFECT: higher activity of catalyst, ultralow content of residual sulfur in hydrodesulfuration products.
2 cl, 2 dwg, 1 tbl, 14 ex
SUBSTANCE: invention relates to a hydrodemetallation and hydrosulphurisation catalyst, a catalyst system and a method for hydrotreatment of hydrocarbon material. Described is a catalyst containing at least one group VIB metal, at least two group VIII metals designated main promoter VIII-1 and co-promoter VIII-i, where i ranges from 2 to 5, and at least one carrier consisting of a porous refractory oxide, in which group VIII elements are present in proportions determined by atomic ratio [VIII-l/(VIII-l+…+VIII-i)], said ratio ranging from 0.5 to 0.85 and said catalyst containing a group VIB metal or metals in amount of 2-9 wt % of a group VIB metal trioxide with respect to total weight of the catalyst and total content of group VIII metals ranges from 0.3 to 2 wt % of a group VIII metal oxide with respect to total weight of the catalyst. Described is a catalyst system consisting of at least two catalysts described above, in which the first catalyst contains a group VIB metal or metals in amount of 2-9 wt % of a group VIB metal trioxide with respect to total weight of the catalyst and total content of group VIII metals ranges from 0.3 to 2 wt % of group VIII metal oxides with respect to total weight of the catalyst, and the second catalyst contains a group VIB metal or metals in an amount which is strictly more than 9 wt % and less than 17 wt % of a group VIB metal trixode with respect to total weight of the catalyst and total content of group VIII metals is strictly higher than 2 wt % and less than 5 wt % of group VIII metal oxide with respect to total weight of the catalyst, wherein said first and second catalysts have the same atomic ratio. Described is a method for hydrotreatment of heavy hydrocarbon material, involving at least one hydrodemetallation step and at least one hydrodesulphurisation step using at least one catalyst with atomic ratio which is equal at each of the hydrodemetallation and hydrodesulphurisation steps, in which said catalyst is the catalyst described above.
EFFECT: high catalyst activity and degree of conversion of hydrocarbon material.
15 cl, 8 tbl, 9 ex