The catalyst for hydrodesulphurization unit desalted crude oil and its production method

 

(57) Abstract:

Use: catalyst for hydrodesulphurization unit desalted crude oil and the manufacturing method. The inventive catalyst contains oxides and/or sulfides of tungsten and/or molybdenum in the amount of 12 to 18 wt.%, the oxides and/or sulfides of cobalt and/or Nickel in amounts of 1 to 8 wt.% on a porous solid acid carrier. The carrier is molded in the form of shaped discrete particles with a length of 4.8 - 6.5 mm long, has a cross-sectional shape revolucio hexagonal star with a radius of circumcircle of 2.0 to 3.5 mm, the Rays of the stars are rounded with a radius of 0.2 - 0.5 mm, the Catalyst is prepared sequentially impregnated at pH 3 - 4 pre-molded carrier with solutions of ammonium salt of molybdenum or tungsten with intermediate and final drying and the final calcination of the catalyst precursor. 2 S. p. f-crystals, 1 table.

The invention relates to catalysts for the refining and petrochemicals used in the process for hydrogenation refining of crude desalted oil and method of its preparation.

Hydrogenation purification (TH) desalted crude oil is a promising process of refining; one of the Tr is Satarov, allowing effective removal of heteroatoms (mainly sulfur atoms and nitrogen) of desalted crude oil under mild conditions: when the hydrogen pressure of 3-5 MPa, a temperature of 340-400aboutC, flow rate of feed 2-4 l/h, the ratio of the circulation of the hydrogen-containing gas 300-400 m3H2/m3of raw materials. The simplest and most reliable in the engineering design process is the filing of a downdraft mixture heated reactants (feedstock and a hydrogen-containing gas (hydrogen-rich) in the reactor, containing a catalyst loading, made of molded particles bifunctional catalysts containing hydrogenating components on a solid acid carrier.

In this process the catalysts are especially stringent requirements due to a) kinetic energy b) hydrodynamic and) obshheehkonomicheskoe factors:

a) the process of Hydrotreating a heavy oil feedstock flows interdiffuse in the field, this effectively works the catalyst surface to a depth of about 0.25 mm; this fact suggests the desirability of using a catalyst molded in the form of particles or such smaller diameter (about 0.5 mm) for paulatsaconas weight;

b) the hydrodynamic resistance of the catalyst loading symbate dependence grows with decreasing diameter of the catalyst particles; this growth makes impossible the use of small catalyst particles;

in the process of Hydrotreating a heavy oil feedstock takes place in three phases (solid catalyst phase, Neispravna in the process of the raw material liquid phase and gas-vapor phase hydrogen gas (hydrogen-rich) + evaporated part of the raw materials), and obshheehkonomicheskoe the efficiency of the process (approximation of the reactor to the model of ideal displacement) depends essentially only on the load of the reactor in the liquid; the maximum efficiency of the reactor downstream of the liquid-vapor flow through the load solid molded catalyst is achieved when the load on the fluid in the number 9500-20000 kg liquid/m2cross-section of the reactor h; the presence of this factor necessitates the use of reactors with high (compared to the Hydrotreating of light material) ratio of the height of the reactor to its internal diameter, which increases the influence of this factor. This factor also causes increased demands on the mechanical strength of the catalyst particles, in particular cases the mechanical strength thereof.

The aggregate consideration of these three factors leads to the necessity of performing particle catalysts figure in order to combine a high ratio of geometric surface and volume of catalyst loading with a high proportion of the free volume of catalyst loading.

Closest to the claimed is the catalyst for hydrofining desalted crude oil [4] the Catalyst is made in the form of elongated particles of extrudates with a diameter of 1 mm Particles are molded of a three-section, formed by the circles, each of which is removed from the other at a distance from 3/8 up to 15/16 of the diameter of these circles. The catalyst contains oxides and/or sulfides of metals VIV group (preferably Mo or W) in the amount of 6-24 wt. metals and/or oxides and/or sulfides of group VIII (preferably Co or Ni) in an amount of 3-12 wt. on acidic oxide carrier. Examples of suitable carriers are γ-aluminum oxide as such or in a mixture with amorphous phase silicate or aluminosilicate or crystalline aluminosilicate, you can use phosphate-containing media on the basis or media that represent natural or synthetic is EcoObraz to use a two-layer catalyst loading: the first (top) layer of the catalyst carrier contains up to 10 wt. phosphates, the second (lower) layer is almost free from phosphates.

In accordance with the invention offers the catalysts for hydrodesulphurization unit desalted crude oil containing oxides and/or sulfides of tungsten and/or molybdenum in the amount of 12-18 wt. the oxides and/or sulfides of cobalt and/or Nickel in the amount of 1-8 wt. on a porous solid acid carrier, molded in the form of shaped discrete particles with a length of 4.8-6.5 mm long, has a cross-sectional shape revolucio hexagonal star with a radius of circumcircle of 2.0-3.5 mm, and the rays of the stars are rounded with a radius of 0.2-0.5 mm

The catalyst in accordance with the invention can be prepared by conventional methods.

The most typical methods of preparation of the catalyst include forming a suitable media, such as silicates, active alumina, active alumina with the addition of silica, active alumina, halogenated, for example, fluorinated or chlorinated active alumina, active alumina with other additives such as zeolites, phosphates, etc., Molding can be carried out by conventional means, for example by extrusion patinirovannoy of plastes, drying these particles and their subsequent calcination. Then the granules media by the method of successive impregnation with intermediate and final drying and calcination can be applied active ingredients: connection VIB and VIII groups of the Periodic system of elements. Another alternative preparation of the catalyst according to the invention is extruded through the die plate configuration soosaipillai mass media and hydrogenating components. The claimed catalyst can be prepared by known methods.

The catalyst in accordance with the invention has in common with the prototype signs: same destination as hydro cleaning desalted crude oil, it contains oxides and/or sulfides of tungsten and/or molybdenum in the amount of 12-18 wt. the oxides and/or sulfides of cobalt and/or Nickel in the amount of 3-6 wt. on a porous solid acid carrier, molded in the form of discrete particles with shaped cross-section.

The catalyst differs from prototype [4] the fact that the length of the particles is 4.8-6.5 mm long, curly cross-section made in the form of revolucio hexagonal star with a radius of circumcircle of 2.0-3.5 mm, and the rays of the stars rounded sake.

Known method of preparing catalysts for crude oil by successively impregnating a pre-formed solid acid carrier with solutions of soluble ammonia complex compounds of a metal of group VIB of the Periodic system of elements, such as paramolybdate ammonium, and a solution of salts of Nickel or cobalt. The impregnation is conducted with intermediate heat treatment of the catalyst precursor, which includes the drying and calcination of the intermediate after impregnation with a solution of compound VIB group. After impregnation with a solution of compounds of group VIII (Nickel or cobalt) catalyst precursor is subjected to a final heat treatment drying and calcination. While thoroughly studied the influence of the conditions of impregnation on the properties of the catalyst, in particular on its gidroobesserivaniya activity, and in the circle of those studied conditions a prominent place is occupied by the pH of the treatment solutions. This parameter was studied in the range of 1-12, with the presence of high gidroobesserivaniya activity in the implementation of impregnation at pH 4-5.

However, the known method it was not possible to prepare catalysts suitable for TH desalted crude oil. In addition, t is can be considered as optimal, for each annealing requires considerable time and heat consumption. The last of the above mentioned disadvantages are eliminated in accordance with the technology of preparation of the catalyst hydrodesulphurization unit of crude oil by successively impregnating a pre-formed solid acid carrier with solutions of soluble ammonia complex compounds of a metal of group VIB of the Periodic system of elements, such as paramolybdate ammonium, and a solution of salts of Nickel or cobalt. The impregnation is conducted with intermediate heat treatment of the catalyst precursor, which includes the intermediate drying after impregnation with a solution of compound VIB group and subsequent impregnation of the dried catalyst precursor solution of the compound of group VIII (Nickel or cobalt). After impregnation, the catalyst precursor is subjected to a final heat treatment drying and annealing [5]

However, there is no information to believe that the catalysts obtained in [5] can be quite effective in the process TH desalted crude oil.

In accordance with the invention proposes a method of preparation of the catalyst for hydrodesulphurization unit desalted crude oil, soy in cross-sectional shape revolucio hexagonal star with a radius of circumcircle of 2.0-3.5 mm, moreover, the rays of the stars are rounded with a radius of 0.2-0.5 mm, sequentially impregnated with a solution of ammonium complex salt of molybdenum or tungsten and a solution of the compound of Nickel or cobalt with intermediate between the impregnation drying, and final heat treatment comprising drying and calcination of the catalyst precursor, and the impregnation is carried out at pH 3-4.

In common with the prototype [5] a characteristic of the invention is the technology includes sequential impregnation of a pre-formed solid acid carrier solution of ammonium complex salt of molybdenum or tungsten and a solution of the compound of Nickel or cobalt with intermediate between the impregnation drying, and final heat treatment comprising drying and calcination of the catalyst precursor. In contrast to [5] impregnate the carrier, molded in the form of discrete particles with a length of 4.8-6.5 mm long, has a cross-sectional shape revolucio hexagonal star with a radius of circumcircle of 2.0-3.5 mm, and the rays of the stars are rounded with a radius of 0.2-0.5 mm, impregnation is carried out at pH 3-4.

Prepare a number of samples of the catalyst in accordance with the invention, a number of samples of the catalysts known forms.

Nicolemarie INIA bemani phase (90%) and Zola SiO2(10%) obtained by extrusion of the wet mass, followed by drying and calcination at a temperature of 550-700aboutWith made in the form of shaped molded particles, the parameters are given in table impregnated with a solution of paramolybdate ammonium (62 ml, concentration of 280 g/l) at pH 4.0, dried at a temperature of 120aboutC for 4 h, impregnated with a solution of Nickel nitrate (58 ml Ni/NO3)2concentration of 75 g/l) is dried at a temperature of 120aboutC for 4 h, and calcined at a temperature of 400aboutC for 2 h

Cobaltmolybdenum catalysts are prepared in a similar manner. Unlike nikolkaiyevich catalysts, secondary impregnation lead nitrate cobalt (58 g With/(NO3)2/ concentration of 75 g/l).

Michelwolverine catalysts prepared as follows: 100 g of silica-alumina carrier prepared in the described manner, is impregnated with a solution of metavolume ammonium (62 ml, the concentration of 265 g/l) at pH 4.0, dried at 120aboutC for 4 h, impregnated with a solution of Nickel nitrate (58 ml Ni/(NO3)2) concentration of 75 g/l), dried at a temperature of 120aboutC for 4 h, and calcined at a temperature of 400aboutC for 2 h

In financial p is th 250-270 m2/, All samples have a specific surface 250-270 m2/g (by BET adsorption of nitrogen), the porosity of 0.5 to 0.65 ml/g, with pore radius 6-9 nm 35-40% of the pore volume, and pore radius 25-500 nm 60-65%

Samples of the catalyst in accordance with the invention and the catalyst samples prepared for comparison, experience in the Hydrotreating process (hydrodesulphurization unit) raw bussoleno oil. As such, use of sulfur Romashkinskoye oil having the following characteristics: density 8620 kg/m3; viscosity at 20aboutWith 14.2 mm2/C; pour point (-42)aboutWith flash (in close. the crucible) (-38)aboutWith; the content, wt. paraffins 2,1, sulfur 1,61, nitrogen 0,17, asphaltenes 4, coking ability of 5.3% yield fractions: up to 200 24 about. up to 350 49 about.

Test lead into the laboratory facility is equipped with a reactor with an inner diameter of 120 mm, height 1000 mm was charged To the reactor: a sample of catalyst volume of 500 cm3. All the experiments carried out by feeding a raw material with a flow rate of 2 l/h in a stream of hydrogen which is supplied by a flow of 300 m3/m3of raw materials.

The results are given in the table.

Known catalysts made in the form of elongated discrete particles, cross-secatary intended for promotion of various gas-phase reactions (oxidation of SO2in SO3[1] synthesis of vinyl acetate [2] They have acceptable mechanical properties. Investigated the same hydrodynamic characteristics of such catalysts show no advantage of one form over the other shaped-shaped catalysts: three to five beam stars, crosses, concave channels, etc. in Addition, the catalysts described in [1 and 2] because they are intended for promotion of gas-phase reactions are characterized by a significantly large linear dimensions (length, diameter of the circumcircle) than the claimed catalysts for Hydrotreating.

In [3] describes catalysts for Hydrotreating distillate and residual oil raw material, made in the form of elongated particles, the cross section of which is made in the form of three - and five-way stars rounded rays. This source of information valuable for the present description it is the fact that it shows the trials in the Hydrotreating process, conducted in a three phase system with downward movement of the reactants catalysts of different configurations, in particular tested catalysts with a cross-section shaped particles in the form of three - and five-way stars with the three-pointed star before in other forms: routine cylindrical extrudates and five-way star. In this connection, it should be concluded that demonstrated the advantages of the catalysts in accordance with the invention not only does not follow from the prior art, but are in clear contradiction with the prevailing prejudice of experts on the equivalence of ways of development of the external surface of the catalyst particles [1] [2], or of the benefits in the near essentially the process of Hydrotreating gas oil oblong shaped particles three-beam cross-section.

The catalyst for hydrodesulphurization unit raw bussoleno oil containing oxides and/or sulfides of tungsten and/or molybdenum in the amount of 12 to 18 wt.%, the oxides and/or sulfides of cobalt and/or Nickel in amounts of 1 to 8 wt.% on a porous solid acid carrier, molded in the form of shaped discrete particles, wherein the catalyst is molded in the form of discrete particles with a length of 4.8 - 6.5 mm long, has a cross-sectional formulalocal hexagonal star with a radius of circumcircle of 2.0 - 3.5 mm, and the rays of the stars are rounded with a radius of 0.2 - 0.5 mm

2. A method of producing a catalyst, comprising the sequential impregnation of a pre-formed solid acid carrier solution of ammonium complex salt molybdenum, including drying and calcination of the catalyst precursor, wherein the permeate carrier, molded in the form of discrete particles with a length of 4.8 - 6.5 mm long, has a cross-sectional shape revolucio hexagonal star with a radius of circumcircle of 2.0 - 3.5 mm, and the rays of the stars are rounded with a radius of 0.2 - 0.5 mm, and carry out impregnation at pH 3 to 4.

 

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FIELD: petroleum processing.

SUBSTANCE: catalyst contains 15-30% hydrogenation components including groups VU and VIII metals, 20-40% acid component, and 1-4% promoter, the rest being binder: alumina, aluminosilicate, clay, or their mixture. Catalyst is distinguished by having three-component system composed by nickel, molybdenum, and tungsten in the form of their oxides at weight ratio Ni/Mo/W equal to 25:35:40. Above-mentioned acid component contains aluminum fluoride and promoter contains boron oxide and/or zirconium oxide. Preparation technology is simple and completely suppresses production of waste water. Invention describes hydrocracking process in presence of the claimed catalyst, which is carried out at 380-430оС, pressure 3 to 10 MPa, and volume flow rate 1 -3 h-1 at H2/feedstock ratio 250 to 1000. Process is especially appropriate for diesel fuel production.

EFFECT: enabled preparation of high-activity and high-selectivity catalyst at any catalyst production plant without additional equipment.

2 cl, 3 tbl, 7 ex

FIELD: petrochemical processes.

SUBSTANCE: 1,3-butadiene is obtained via catalytic dehydrogenation of n-butylenes at 580-640°C and essentially atmospheric pressure while diluting butylenes with water steam at molar ratio 1:(10-12) and supplying butylenes at space velocity 500-750 h-1. Catalyst is composed of, wt %: K2O 10-20, rare-earth elements (on conversion to CeO2) 2-6, CaO and/or MgO 5-10. MoO3 0.5-5, Co2O3 0.01-0.1, V2O5 0.01-0.1, and F2O3 the balance. Once steady condition is attained, dehydrogenation is carried out continuously during all service period of catalyst.

EFFECT: increased yield of 1,3-butadiene and process efficiency.

2 ex

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