The system is layered catalysts and method of denitrification hydrocarbons
(57) Abstract:The invention relates to a system of layered catalysts for hydrogencitrate hydrocarbons, such as vacuum gas oil used for hydrocracking to produce different fuels. The system is layered catalysts according to the invention contains a first layer of catalyst based on Nickel-molybdenum-phosphorus/alumina or a catalyst based on cobalt-molybdenum-phosphorus/alumina and the catalyst of the second layer, representing a catalyst based on Nickel-tungsten/silica-alumina-zeolite or a catalyst based on Nickel-molybdenum/silica-alumina-zeolite. The preferred characteristics of the combination disclosed here layered catalysts are catalyst of the first layer based on aluminum has a molybdenum content of more than about 14 wt.%; the catalyst of the first layer on the aluminum oxide has a relatively large pore size, for example, at least about 60 ; the second catalyst layer contains at least about 2% zeolite component. The system is layered catalysts according to this invention and the corresponding method to provide enhanced denitrification source MSA catalytic systems and methods of Hydrotreating hydrocarbons by contacting the hydrocarbon with hydrogen in the presence of an appropriate catalyst. Sign Hydrotreating, which is of particular interest in this invention is denitration in communication with the hydrocracking.Denitrification of hydrocarbon streams to clean oil and oil products is particularly important in the process of hydrocracking to reduce the nitrogen content in the flow of raw materials to an acceptable level before the flow of the feedstock hydrocarbon is subjected to hydrocracking. In General, it is desirable to reduce the content of nitrogen in the flow of raw materials to the level of less than 10 hours /million by weight, preferably less than 2 hours/million and in many cases to achieve high durability of the catalyst, it is important to reduce the nitrogen content to a level less than 0.5 hours/millionThe catalysts which are used for hydrometrical, have various shortcomings, including their susceptibility to poisoning coke or other impurities at excessive speed, resulting in reduced service life of the catalyst is greater than required. When the catalyst is poisoned or deactivated, it is necessary to increase the temperature of the denitrification process to maintain its activity. At the maximum temperature allowed by the constraints n the market with different composition for Hydrotreating. For example, nucleopolyhedrosis catalysts and such catalysts are disclosed in U.S. patent N 4210521; 4363719; 4534852 and in the application of the U.S. N 2073770 that are listed for reference. However, none of these known technical solutions aimed at solving problems activity and increase the service life of the catalysts in the way that is acceptable for the present invention.The aim of the invention is to design catalysts for nitrification, which have an increased service life and activity and, therefore, they are more economical for Hydrotreating processes. Increased service life of the catalysts for denitrification is achieved by reducing its tendency to zakochani, improve the stability of the catalysts to poisons, as well as by improving the diffusion of hydrocarbons in the catalyst. Other objectives of this invention will become clear from the description.Summary of invention.According to one characteristic of this invention, the resulting system of layered catalysts for Hydrotreating of hydrocarbons containing the first layer of the catalyst is a catalyst based on Nickel-molybdenum-phosphorus/alumina or a catalyst based on cobalt-molybdenum-fo is long at least about 60 and a second layer of catalyst, which catalyst is based on Nickel-molybdenum/silica alumina zeolite or a catalyst based on Nickel tungsten/silica alumina - zeolite, and the zeolite component is at least about 2% by weight of the catalyst of the second layer.It was found that if the layered catalyst used in the processes of hydrometrical, this combination of layers of catalysts provides, among the various advantages of this invention, an improved denitration, increased service life and, therefore, improved economic benefits from denitrification. Also it was found that the coated catalyst according to the present invention is less exothermic, and it can operate at a more uniform temperature. Thus, the operation and control are simplified in comparison with the known catalysts. Therefore, an additional advantage is that in comparison with other catalysts are not formed hot spots in layered catalyst according to the present invention. The absence of hot spots provides a performance advantage, since eliminated to mean the layer of catalyst. Lower levels and/or the rate of coking of the catalyst contribute to increasing the service life of the layered catalyst according to the present invention.It was found that in the first layer of the catalyst, i.e. the catalyst based on Nickel-molybdenum-phosphorus/alumina or catalyst based on cobalt-molybdenum-phosphorus/alumina is advisable to apply a relatively large pore size. I believe that more pore size contributes to the improvement of the resistance to poisons and improved resistance to coking. The preferred catalyst for the first layer is a catalyst based on Nickel-molybdenum-phosphorus/alumina.An important feature of the system of layered catalyst according to the present invention is that the second layer contains zeolite component. The second layer of catalyst may contain a Nickel-tungsten or Nickel-molybdenum, and preferably, the second catalyst layer contains silicon dioxide-titanium oxide-aluminum oxide matrix together with the zeolite component.Unique features and advantages of the layered catalyst according to this invention, partly a result of the fact that first yuusha activity. On the other hand, the catalyst of the second layer is more acidic and has a higher craterous activity, which resulted in efficient conversion of refractory nitrogen compounds not converted in the catalyst of the first layer. Thus the resulting combination of the two layers of the catalyst according to the present invention provides surprisingly improved and superior results in comparison with known systems catalysts for hydrogencitrate.According to another characteristic of the invention, a method of Hydrotreating of hydrocarbons, which consists in contacting of the hydrocarbon with hydrogen in the presence of a system of layered catalysts containing the first layer of the catalyst is a catalyst based on Nickel-molybdenum-phosphorus/alumina or of a catalyst based on cobalt-molybdenum-phosphorus/alumina, having a molybdenum content of more than about 14% by weight of the catalyst of the first layer and the average pore size of at least 60 , and a second layer of catalyst, which includes a Nickel-tungsten/silica alumina zeolite or Nickel-molybdenum/silica alumina zeolite, and the zeolite component stapedial favorable working conditions, which include lower operating temperatures for extended periods of time. This was possible partly due to the improved stability of the system catalysts to poisoning and coking, which allows the method at lower temperatures for extended service life of the catalyst.Description of the invention.This invention relates to a layered catalyst, in particular compositions that provide improved performance and enhanced service life of the catalyst for hydrogencitrate hydrocarbons, having a boiling point of about 650oF 1000oF (343oC 538oC), for example, vacuum gas oils. However, other raw materials or flows of hydrocarbons can be processed using the system of the layered catalyst under appropriate conditions to provide the desired Hydrotreating or hydrogencitrate this feedstock or threads. Unexpectedly it was found that the system is layered catalysts according to this invention provides many advantages which mainly consist in increasing the service life of the catalyst and its activity.Partially invention is based nasacor or cobalt-molybdenum-phosphorus/alumina catalyst, having at least about 14% by weight of molybdenum and a relatively large average pore size or diameter. The pore size must be equal to at least about 60 , preferably 70 , and preferably at least 75 . The preferred interval of the average pore size is from about 75 to 120 . The term "pore size" as used here, mean pore size is usually in the catalyst containing alumina. Measurement and determination of the size of the pores in the catalyst based on metal and aluminum oxide are well known in the art, as shown in the publication by S. J. Greg and K. S. W. Sing ("Adsorption, surface area and porosity" (Academic press, 1982)). The alumina is preferably gamma-alumina. Catalysts that can be used in this first layer, are commercially available catalysts that are relatively inexpensive. Discovered that the surface of aluminum oxide with low acidity is the surface, which reduces the poisoning of catalyst coking. A large average pore size makes the catalyst less sensitive to poisoning of catalyst coking. Reduced coking and lower case is RA, demonstrated system of the catalysts according to this invention.In the first layer system catalysts preferably Ni and/or Co in the range of about 2-7 wt. more preferably about 3% Mo content in the range of about 14-18 wt. and better about 15-17% and the content of P in the range of about 1-5 wt. better approximately 3% These percentages, which are used here represent the percentage by weight of the metal content in the oxide form of the catalyst (although metals are indeed present in the form of oxides), and the percentage by weight based on weight of catalyst prior to sulfatirovnie.The catalyst in the second layer system of the catalysts according to this invention is a catalyst based on Nickel-tungsten/silica alumina zeolite-based or Nickel-molybdenum/silica alumina zeolite, which may be preferred catalyst of the type silica oxide, titanium aluminum oxide zeolite. Zeolite component of the catalyst should contain at least about 2 wt. the catalyst of the second layer, preferably at least about 3 wt. and preferably in the range of about 3% to 20% by weight. The most preferred katalysatoren. The weight percent of zeolite in the catalyst of the second layer, as it is expressed here, based on the weight of the catalyst of the second layer to sulfatirovnie. Preferably, the catalyst in this second layer had a content of Nickel in the range of about 2-10 wt. more preferably 7 wt. the content of tungsten in the range of about 15-25 wt. and preferably about 20 wt. molybdenum in the range of about 12-18 wt. better about 15-17 wt. and the titanium content in the range of about 2-10 wt. preferably about 4 wt.Zeolite component in the catalyst of the second layer is a zeolite of type Y, for example, Na-USY, USY or LZ-20. These zeolites are well known in the art and described D. U. by Breck "Zeolite molecular SITA, structure, chemical composition and application" (John Willy & sons, new York, 1984).The catalyst based on silica alumina zeolite for the second catalytic layer system according to this invention is prepared by conventional methods for catalysts, which contain as component amorphous silica alumina and a crystalline zeolite component. Although to obtain a catalyst based on silica alumina zeolite for the second layer, the preferred method is ICI aluminum in the catalyst.The first layer system catalysts will be approximately up to about 70. preferably about 20-70 about. and preferably about 40-60. on the basis of the total mass of the two layers of catalysts according to this invention.Therefore, the second layer will be at least about 30 about. preferably 30-80 about. and preferably about 40-60. the whole system of layered catalysts.System layered catalysts according to this invention receives by placing the first layer of the catalyst based on Nickel-molybdenum-phosphorus/alumina or catalyst based on cobalt-molybdenum-phosphorus/alumina in the first upper area of the catalyst layer in the vessel and placing the second catalyst layer containing a zeolite component, the second, the lower zone or layer downstream in the vessel. Thus this method is suitable for contacting a hydrocarbon feedstock with a first catalyst bed and then with a second layer of catalyst sequentially and in the presence of hydrogen. With this arrangement, the liquid and gas are in contact with the catalyst, passing down the reactor.When loading the catalyst into the reactor all metals are usually present in the form of BR>W WO3< / BR>Ti TiO2< / BR>Al Al2ABOUT3< / BR>Si SiO2< / BR>The system of the catalysts according to this invention sulfiderich, using known methods sulfatirovnie, after loading into the reactor.Raw materials that can be processed by the method and system of the catalysts according to the invention may contain up to 6000 hours/million of nitrogen, but preferably the nitrogen content in the feedstock will be in the range of about 500-3000 hours/million of nitrogen. The method according to this invention, in which using catalysts in accordance with the invention is usually carried out with an hourly volumetric velocity of the fluid in the range of about 0.4 to 4, and preferably 0.7 to 2. Typically, the method is carried out in the temperature range of about 650oF 800oF (343oC 427oC), preferably 700oF - 800oF (371oC
427oC), and preferably in the range of about 720oF 760oF (382oC 404oC). Pressure for efficient operation of the method according to the invention should be in the range of about 1000-3000 pounds per square inch, preferably about 1200-2500 pound/square inch and preferably in the range of about 1500-2200 pounds/square inch. The rate of hydrogen at the inlet relative velocity b.ft/bbl (standard cubic foot of supplied hydrogen per barrel of supplied oil). It was found that applying these conditions and specified raw materials, the system catalysts and method according to this invention will produce gazoochistnoe product that will have a nitrogen content of less than about 10 hours/million more typically less than about 2 hours/million and will typically be less than about 0.5 hours/millionWhen defining the required characteristics of the catalyst to hydrogencitrate important characteristic is the rate at which the catalyst was poisoned, or, conversely, the rate at which the reduced activity of the catalyst. Reduced activity of the catalyst operating temperature of the process must increase to maintain the conversion, which is required in the process. The temperature can be increased until, until you have achieved the operating limits, which may be the operating limits established by the system itself catalysts given feedstock and the desired products of the conversion of raw materials, or temperature limitations of the equipment. Thus, one important criterion for evaluating the performance of the system catalysts is the degree of loss in activity. Obviously, the lower the degree of loss in the activity of cat is camping fewer changes in the catalyst and/or regeneration cycles.Having described the catalytic Converter system and method according to this invention, it is possible to illustrate the invention the following examples, which are merely specific examples of implementation of the present invention. The following examples and concrete performance are not to limit the scope of the present invention, which is defined in the attached claims.Examples. In the following examples, one of the catalysts of the first layer, for example the catalyst a which was used was a commercially available catalyst based on Nickel-molybdenum-phosphorus with a substrate of aluminum oxide (catalyst brand shell 411" company shell oil company, Houston, Texas), which had the following General specifications.The catalyst A.3.3 wt. oxide of Nickel
of 22.4 wt. oxide of molybdenum
6.6 wt. oxide of phosphorus
67,7 wt. aluminum oxide
165 m2/g surface area
of 0.43 cm3/g pore volume
104 average pore volume
Another catalyst used for the first layer, this catalyst having the following General specifications.The catalyst Century4.7 wt. oxide of Nickel
of 19.8 wt. oxide of molybdenum
5.0 wt. oxide of phosphorus
the diameter of pores
The catalyst is prepared as follows:
1. 400 g of aluminum Oxide Kaiser Versal 250 and 600 g of alumina Catapol loaded into the mixer.2. 20 g of 70% Nitric acid is added to the alumina with sufficient water to increase levels of volatile substances in the resulting mass to 55%
3. The mixture is stirred for 30 min, then ekstragiruyut through the die plate size of 0.07" (1.9 mm).4. These noodles are dried at a temperature of 250oF (121oC) for 2 hours at 400oF (204oC) within 2 hours.5. Then the obtained extrudates calcined at a temperature of 1400oF (760oC) within 4 hours.6. The solution of Nickel phosphorus molybdenum acid was prepared as follows:
a solution prepared from 39/5 g of phosphorus molybdenum acid, 6.4 g of 85% H3PO4and enough water to obtain a 30 cm3;
10.6 g NiCO3added to this solution;
add 5 drops of 30% hydrogen peroxide; and
add water to obtain a final volume of 65 cm3.7. The solution from step 6 spray on 100 g of the extrudates from step 5.8. The wet extrudates are dried at a temperature of 200oF (93oAnother catalyst used for the first layer, was "the Catalyst", a commercially available catalyst (Ketjen KF 843" from AKZO, Chemicals, Inc. Pasadena, Texas), which had the following technical parameters.Catalyst C.4.2 wt. oxide of Nickel
25,1 wt. oxide of molybdenum
7.1 wt. oxide of phosphorus
63,6 wt. aluminum oxide
162 m2/g surface area
0,37 cm3/g pore volume
91 average pore diameter of
The catalyst used for the second layer Catalyst D was jointly zatverdevanyy a catalyst based on Nickel tungsten/silicon dioxide aluminum oxide titanium dioxide zeolite, prepared according to the methods of U.S. patent N 3536605. General technical parameters of catalyst D of the second layer following:
Catalyst D.9.1 wt. oxide of Nickel
24.4 wt. oxide of tungsten
7.7 wt. oxide titanium
25,9 wt. silicon dioxide
of 28.9 wt. aluminum oxide
4.0 wt. zeolite Na USY
270 m2/g surface area
0,39 cm3/g pore volume
58 the average diameter of pores.The raw material used in these tests was a mixture of 70% vacuum gas oil North Slope and 30% vacuum gas oil is in each test, in total 130 cm3, catalyst loaded in the reactor having an inner diameter of 2.54 cm and thus the total length of the catalyst layer was equal to 30,48 see the following examples of these catalysts contained the following amount of each catalyst:
nonlamellar 130 cm3a single catalyst
45%/55% 58.5 cm3the first layer, 71.5 cm3the second layer
75%/25% 97,5 cm3the first layer, 32.5 cm3the second layer
After loading the catalyst into the reactor, the catalysts were sliderule as follows, using dimethyl disulfide (S): 1,0 volumetric hourly rate of a solution containing 2.0 wt. S in heptane normal structure With 8.0 STD. cubic ft./including hydrogen at a temperature between 450-600oF (323oC 316oC) for 9 hours
The catalyst that is5.9 wt. oxide of Nickel
for 27.6 wt. oxide of tungsten
of 38.4 wt. aluminum oxide
28,1 wt. oxide silicon
Pore volume 0,356 cm3/g
The average pore diameter of 4.0 nm (40 )
The surface area of 357 m2/g
Example 1. Working conditions: 2275 pounds/square inch, 5500 cubic feet per barrel of hydrogen without recirculation, 1,5 hour volume velocity of the fluid and the level temperature to achieve 5,0 hours/million of nitrogen in the product. P, is utilizator D, provided the required level of nitrogen at a temperature significantly below the temperature of only one of any catalyst.Example 2. Working conditions: 1600 lb/square inch, 5500 cubic feet per barrel of hydrogen without recirculation, 1,5 hour volume velocity of the fluid and the temperature level to achieve a 5.0 hours/million of nitrogen in the product. The results were as follows (see tab.3)
The system is layered catalyst composed of the catalyst, catalyst D has provided the required level of nitrogen at a temperature significantly below the temperature of only one catalyst D, and it had a lower relative degree of loss in activity.Example 3. In this example, conditions were the following: 1600 lb/square inch, 5500 cubic feet per barrel of hydrogen without recirculation, 1,5 hour volume velocity of the fluid and the temperature level to achieve a 5.0 hours/million of nitrogen in the product. The results were as follows (see tab. 4).The use of catalyst deposited on the catalyst is not improved system performance compared to the result when the catalyst D was used independently. This example demonstrates the need for the content of molybdenum in the first layer of catalyst in the amount of more than circulation; 1,5 hour volume velocity of the fluid and the temperature level to achieve a 5.0 hours/million of nitrogen in the product.The results were as follows (see tab. 5).This example shows that if the content of the catalyst in the second layer is about 25% or less loading of the catalyst into the reactor, then a marked increase in the relative extent of losses in activity. Nonlamellar system all catalysts will have a relative velocity loss in activity 5 to 10 times higher than that of non-sliced catalyst D.Example 5. Catalyst E
5.9 wt. oxide of Nickel
for 27.6 wt. oxide of tungsten
of 38.4 wt. aluminum oxide
28,1 wt. oxide silicon
pore volume 0,356 cm3/g
the average pore diameter of 4.0 nm (40 )
the surface area of 357 m2/g
Next, the layered catalyst containing 45% of catalyst A (55% of catalyst E was tested in the conditions of example 1. The catalyst As used in example 1 of the specification).The result of the experiment proved that the temperature required to achieve a 5.0 ppm produced nitrogen after 250 hours, amounted to 746oF (397oC). Although the catalyst E was not tested by itself as the nonlamellar katalizatora layer. For the layered catalyst according to the invention, containing 45% of the catalyst And/55% of catalyst D (where the catalyst D includes titanium), the temperature required to achieve a 5.0 ppm produced nitrogen after 250 hours was 739oF (393oC). Thus, within experimental error, the comparison of the two sets of data clearly shows that when titanium is not included in the second catalyst layer (catalyst E), there shall be no significant loss of catalytic activity. 1. The system is layered catalysts for Hydrotreating of hydrocarbons containing the first layer of the catalyst is a catalyst based on nicolemarie-phosphorus-alumina and a second layer of catalyst is a catalyst based on Nickel-tungsten-silica-alumina-zeolite, characterized in that the first catalyst layer contains more than 14 wt. molybdenum and has an average pore size preferably and the second catalyst layer further comprises titanium and the content of the zeolite is at least 4 wt. in the following ratio of the layers in the system, about.The first layer 40 60
The second layer 40 60
2. The system under item 1, characterized in that the catalyst of the first R> Phosphorus 2,9 3,1
3. The system under item 2, characterized in that the first catalyst layer contains gamma-aluminum oxide and has an average pore size
4. The system under item 1, characterized in that the second catalyst layer contains the following components in the following ratio, wt.Nickel 7,1
Silicon dioxide 25,9
Oxygen the Rest
5. The system under item 1, characterized in that the catalysts previously sulfatirovanne.6. How denitrification hydrocarbons by contacting the latter with hydrogen in the presence of a system of layered catalysts containing the first layer of the catalyst is a catalyst based on Nickel-molybdenum-phosphorus-alumina and a second layer of catalyst is a catalyst based on Nickel-tungsten-silica-alumina-zeolite, characterized in that use layered catalysts in which the catalyst of the first layer contains more than 14 wt. molybdenum and has an average pore size preferably the catalyst of the second layer further comprises titanium and zeolite sostave layer 40 60
7. The method according to p. 6, characterized in that use layered catalysts in which the catalyst of the first layer contains the following components in the ratio, wt.Nickel 2,6 3,3
Molybdenum 14,3 16,7
Phosphorus 2,9 3,1
8. The method according to p. 7, characterized in that use layered catalysts in which the catalyst of the first layer contains gamma-alumina has an average pore size
9. The method according to p. 6, characterized in that use layered catalysts in which the catalyst of the second layer contains the following components in the ratio, wt.Nickel 7,1
Silicon dioxide 25,9
Oxygen the Rest
10. The method according to p. 6, characterized in that use layered catalysts, in which the last pre-sulfatirovanne.
FIELD: production of hydrorefining catalyst.
SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.
EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.
10 cl, 8 ex, 4 dwg
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: 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 processing catalysts.
SUBSTANCE: invention relates to catalysts for deep processing of hydrocarbon stock and can be employed in petroleum processing and petrochemical industries. Particularly, invention provides catalyst for diesel fraction hydrodesulfurization process, which contains, as active component, oxygen-containing molybdenum and cobalt and/or nickel complex compound at Mo/(Co+Ni) atomic ratio 1.5-2.5 and is characterized by specific surface 100-190 m2/g, pore volume 0.3-0.5 cm3/g, prevailing pore radius 80-120 Å. Catalyst support is constituted by alumina or alumina supplemented with silica or montmorillonite. Described are also catalyst preparation procedure and diesel fraction hydrodesulfurization process.
EFFECT: increased catalytic activity and resistance of catalyst against deactivation in presence of diesel fuel hydrocarbon components and sulfur compound of thiophene and its derivatives series.
8 cl, 1 tbl, 7 ex
FIELD: isomerization and disproportionation catalysts.
SUBSTANCE: invention relates to crystalline α-chromium oxide, chromium-containing catalytic compositions, method for preparation thereof, and to a process of fluorine distribution in hydrocarbon and/or halogenated hydrocarbon in presence of indicated catalytic compositions. In claimed α-chromium oxide, about 0.05 to about 2 atomic % chromium in the lattice of α-chromium oxide is substituted by nickel atoms and, optionally, further chromium atoms in the lattice are substituted by trivalent cobalt atoms, the total amount of nickel and trivalent cobalt atoms in the α-chromium oxide lattice not exceeding 6 atomic %. Claimed α-chromium oxide is prepared via coprecipitation of solid substance by introducing ammonium hydroxide, this method being supplemented by introducing an excess of ammonium nitrate into precipitated mixture before dehydration step and calcination step at 375 to 1000°C in presence of oxygen. Chromium-containing catalytic compositions containing crystalline nickel-substituted α-chromium oxide as chromium-containing component optionally treated with fluorination agent are also claimed. Composition preparation procedure comprises: (a) coprecipitation of solid substance by introducing ammonium hydroxide into aqueous solution of soluble bivalent nickel salt, soluble trivalent chromium salt, and optionally soluble bi- or trivalent cobalt salt, wherein solution contains at least three moles nitrate per mole chromium and has concentration of nickel from about 0.05 to about 2 mol % based on total content of nickel, chromium, and cobalt (if present) in solution and total concentration of nickel and cobalt (if present) not higher than 6 mol % on the same basis; (b) collecting coprecipitated solid substance obtained in step (a); (c) drying collected solid substance; and (d) calcination of dried solid substance at 375 to 1000°C in presence of oxygen.
EFFECT: increased activity of catalytic composition in above-indicated processes.
15 cl, 8 dwg, 13 ex
FIELD: petroleum processing.
SUBSTANCE: invention relates to preparation of protective-layer catalysts for hydrofining of petroleum fractions in petroleum processing industry. Invention provides catalyst containing oxides of molybdenum, nickel and/or cobalt, silicon, and aluminum, which catalyst is molded in the form of hollow cylindrical granules. Starting composition for preparation of alumina-based carrier includes structuring additive, 5.0-8.5%, kaolin, 2.0-5.0%, and alumino-nickel-molybdenum and/or alumino-cobalt-molybdenum catalyst, 10-20%. Thus prepared alumina-supported contains 0.5-4.0% nickel oxide and/or cobalt oxide and 0.8-3.0% silicon oxide.
EFFECT: increased degree of hydrogenation of unsaturated hydrocarbons, prevented coking of basic catalyst, and reduced pressure gradient.
3 cl, 4 ex
SUBSTANCE: principle refers to catalyst and method of complex purification of waste gases of different production, heat and power utilities, automobile transport, which works on natural gas (methane). Described is a method of complex purification of effluent gases from nitrogen oxides, carbon oxide and hydrocarbons and it involves passing the effluent gases at temperatures 455-600°C through a layer of mechanical mixture of nickel chromium oxide industrial catalyst a copper zink nickel industrial catalyst in a volume composition of 1:1 to 20:1 respectively. To the effluent gases, methane up to a volume composition of CH4/O2 0.07-0.15 can be added before passing it through the catalyst layer. Nickel chromium oxide industrial catalyst contains NiO 38-42 %; ZnO 28-32 %; NiO 4-6 % and not less than Al2O3 17 % masses.
EFFECT: increasing of the purifying index of effluent gases.
3 cl, 4 ex
SUBSTANCE: claimed invention relates to catalysts of hydration, method of their production and use for hydration such as selective hydration of acetylene admixtures in non-purified olefinic and diolefiniuc flows. Described is a selective catalyst of hydration for selective hydration of acetylene admixtures in non-purified olefinic and diolefinic flows, containing only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, applied on carrier, which is alumunium oxide with the following physical characteristics: BET surface area from 30 to approximately 100 m2/g, total volume of pores on nitrogen from 0.4 to approximately 0.9 cm3/g and the average pore diameter from approximately 110 to 450 Å , where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Described are the method of catalyst production, which includes impregnation of carrier represented by aluminium oxide and having the aforesaid physical characteristics, with soluble salts of only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, from one or more solutions, obtaining impregnated carrier, where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Also described is the method of selective hydration of acetylene compounds, which includes contact of original raw material containing acetylene compounds and other unsaturated compounds, with the described above catalyst.
EFFECT: increased degree of 1,3-butadien extraction with full or nearly full conversion of C4-acetylenes.
25 cl, 1 dwg, 1 tbl, 2 ex
FIELD: technological processes.
SUBSTANCE: invention is referred to technological processes, namely to ways of realisation of chemical processes, in particular, to area of the general and specific catalysis. The method of catalytic element manufacturing, including preparation of catalytically active coating by spraying of a powder composition on the metal carrier using high-speed cold gas-dynamic method is described. The powder composition contains in wt %: aluminium 30-50, nickel 30-45, oxide of transition metals 1-6, oxides of rare-earth metals in the sum 1-6, alpha oxide of aluminium 5-25, aluminum hydroxide - the rest. Simultaneously with spraying of the same powder composition an erosive handling of the metal carrier surface is performed. At temperature not exceeding 100°C spray a powder composition on distance of 40-70 mm from the metal carrier at speed of a composition stream of 450-600 km/s with 50-200 microns coating.
EFFECT: increase of mechanical strength of a catalytic element, high activity of catalytically active coating.
1 cl, 1 ex
SUBSTANCE: description is given of a catalytic composition with general formula, in consideration of oxides: (X)b(M)c(Z)d(O)e (I), in which X represents at least one group VIII base metal, M represents at least one group VIB metal, Z represents one or more elements, chosen from aluminium, silicon, magnesium, titanium, zirconium, boron and zinc, O represents oxygen, one of b and c represents an integer 1, and d, e and one of b and c represents each a number bigger than 0, such that the molar ratio b:c ranges from 0.5:1 to 5:1, molar ratio d:c ranges from 0.1:1 to 50:1, and molar ratio e:c ranges from 3.6:1 to 108:1. The method of obtaining the composition involves heating a composition with general formula (NH4)a(X)b(M)c(Z)d(O)e (II), in which a represents a number bigger than 0, and X, M, Z, O, b, c, d and e are such that, they are bigger, at temperature ranging from 100 to 600°C, where the composition with formula II is in suspension form or is extracted from a suspension, optionally after maturing at temperature ranging from 20 to 95°C for a period of not less than 10 min. The above mentioned suspension is obtained by precipitation at temperature and within a period of time, sufficient for obtaining formula II composition, of at least one compound of a group VIII base metal at least one compound of a group VIB metal at least one refractory oxide material and alkaline compound in protonic liquid. At least one of the metal compounds is partially in solid state and partially in dissolved state. Description is given of volumetric metal oxide catalytic composition, obtained using the method given above, and a composition with general formula I, which can be obtained using a precipitation method, in which a refractory oxide material in quantity ranging from 15 to 40 wt % is precipitated at least with one compound of a group VIII base metal, and at least with one compound of a group VIB metal, as well as the method of obtaining it. Description is also given of the use of compositions, moulded or sulphided when necessary, in hydro-processing.
EFFECT: increased activity of catalytic compositions.
14 cl, 10 tbl, 24 ex
FIELD: alternate fuel production and catalysts.
SUBSTANCE: synthesis gas containing H2, CO, and CO2 is brought into contact, in first reaction zone, with bifunctional catalyst consisting of (i) metal oxide component containing 65-70% ZnO, 29-34%, Cr2O3, and up to 1% W2O5 and (ii) acid component comprised of zeolite ZSM-5 or ZSM-11, beta-type zeolite or crystalline silica-alumino-phosphate having structure SAPO-5 at silica-to-alumina molar ratio no higher than 200, whereas, in second reaction zone, multifunctional acid catalyst is used containing zeolite ZSM-5 or ZSM-11 and having silica-to-alumina molar ratio no higher than 200.
EFFECT: increased selectivity with regard to C5+-hydrocarbons and increased yield of C5+-hydrocarbons based on synthesis gas supplied.
7 cl, 2 tbl, 15 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 hydrocarbon conversion catalysts containing zeolite. Described is hydrocarbon conversion catalyst containing the following (of total weight of catalyst): 1-60 wt % mixture of zeolites, 5-99 wt % heat-resistant inorganic oxide and 0-70 wt % clay, where the mixture of zeolites contains the following (of the total weight of the mixture): 1-75 wt % beta-zeolite, modified with phosphorus and a transition metal M, 25-99 wt % zeolite with MFI-structure and 0-74 wt % zeolite with large pores, where the anhydrous chemical composition of the beta-zeolite modified with phosphorus and transition metal M has the following formula: (0-0.3)Na2O·(0.5-10)Al2O3·(1.3-10)P2O5·(0.7-15)MxOy·(64-97) SiO2 (weight percentages of oxides are indicated in the brackets), where the transition metal M is one or more metals selected from a group comprising Fe, Co, Ni, Cu, Mn, Zn and Sn; x is the number of atoms of the transition metal M, and y is the number for which valence, which corresponds to oxidation state of transition metal M, is provided.
EFFECT: high conversion capacity of petroleum hydrocarbons and higher output of light olefins, especially propylene.
12 cl, 30 ex, 5 tbl
FIELD: oil and gas production.
SUBSTANCE: invention refers to procedure for catalytic conversion of hydrocarbons. The procedure consists in contacting source hydrocarbons with catalyst of hydrocarbon conversion to ensure reaction of catalytic cracking in a reactor. Further, products of reaction are withdrawn from the reactor and are divided into fractions to produce light olefines, gasoline, diesel fuel, heavy diesel fuel and other saturated low-molecule hydrocarbons. Also, catalyst of hydrocarbons conversion contains (of total weight of catalyst): 1-60 % wt of mixture of zeolite, 5-99 % wt of heat-resistant non-organic oxide and 0-70 % wt of clay. Mixture of zeolite contains (from total weight of mixture): 1-75 % wt of beta-zeolite modified with phosphorus and transition metal M, 25-99 % wt of zeolite with MF-structure and 0-74 % wt of zeolite of large pores. Waterless chemical composition of beta-zeolite modified with phosphorus and transition metal M is of the following kind: (0-0.3)Na2O·(0.5-10)Al2O3·(1.3-10)P2O5·(0.7-15)MxOy·(64-97)SiO2 (in brackets there are indicated wt percents of oxides) where transition metal M is one or several metals chosen from a group consisting of Fe, Co, Ni, Cu, Mn, Zn and Sn; x is number of atoms of transition metal M, and y is number ensuring valence corresponding to a degree of transition metal M oxidation.
EFFECT: increased conversion of hydrocarbons of oil and higher output of light olefines, particularly, propylene.
17 cl, 43 ex, 8 tbl
SUBSTANCE: invention relates to a method of producing acrolein by dehydrating glycerol. The method is carried out in the presence of solid-phase catalysts containing tungsten compounds with Hammett pH Ho less than +2, which contain palladium as a promoter. The catalyst is periodically regenerated separately in time from the glycerol conversion reaction and continuously regenerated separated in space from the glycerol conversion reaction, and for regeneration thereof, the catalysts are subjected to an oxidative or reducing atmosphere.
EFFECT: method of regenerating a catalyst which is suitable for dehydration of glycerol, which exhibits low susceptibility to coking with possibility of easy regeneration thereof.
18 cl, 5 ex
FIELD: oil and gas industry.
SUBSTANCE: zeolite-containing catalyst is proposed based on high-silica zeolite, which includes hydrogenating components and additives with the following components ratios, wt %: zeolite 50.0-70.0; MoO3 4.0-5.0; ZnO 1.0-3.0; P2O5 1.0-2.0; B2O3 1.0-3.0; γAl2O3 - the other are up to 100. At that, zeolite of ZSM-5 structural type is used as a base, having: crystallinity degree 95-100%; crystallite size 5-30 mcm; static capacity by heptane 0.18-0.21 cm3/g; silica module 30.0-55.0.
EFFECT: increased output of target product, reduction of its chilling point, carrying out dewaxing process at lower temperatures.
3 tbl, 3 ex