The preparation method of catalyst for mild hydrocracking of crude oil

 

(57) Abstract:

The invention relates to a method of preparation of the catalyst for the process of oil refining in the mild hydrocracking. The method consists of introducing in the alumina carrier of the active hydrogenating component compounds of molybdenum and Nickel or cobalt, photobrush promoters and a pore-forming components, molding, drying and calcining, while razobratsya promoters, which are used separately or in combination solutions of ammonia, phosphoric, nitric, hydrochloric acid, nitrate of rare earth elements, nitrate aluminium, powder - Al2O3boric acid, contribute at pH of 2.2-5.0 to active hydrogenating component and a pore-forming components, which are used polyvinyl alcohol and/or ethoxylated polyester glycol, applied after the active hydrogenating components. Active hydrogenating components contribute salts of molybdenum and Nickel or cobalt or of the complex obtained by incorporating in an aqueous solution of proximaldistal [P2Mo5O23-x(O2)x](NH4)6where x = 1 or 2, nitrate of cobalt or Nickel in a molar ratio of Ni (the ha of crude oil, with increased activity in the conversion of FR. 360C+. 3 C.p. f-crystals, 2 tab.

The present invention relates to the field of oil refining, in particular to a method of preparation of the catalyst for the process of oil refining in the mild hydrocracking conditions: temperature 360-430oC, a pressure of 3.5 to 9.2 MPa, the volumetric feed rate of 0.4-1.5 h-1[Baral W. J., Huffman H. C. Advances in Hydrocracking of Distilates. Proceedind of the 8th Worid Petroleum Congress, Moscow, 1971, U. 4.Louden, Applied Scicnce Publishers, Ltd., 1972, p. 119-127].

There is a method of preparation of the catalyst for mild hydrocracking [SU authorship 488610, Creatnine, B 01 J 23/882; 03.02.76]. The catalyst was prepared by depositing the active hydrogenating components, which use oxides of molybdenum and cobalt in porous media, which is used as the aluminum oxide simultaneously with the oxide of cesium as gazoobraznogo promoter.

The disadvantage of this method is the low activity of the catalyst: the output of diesel fuel by hydrocracking of vacuum gas oil is only about 40 wt.%

There is a method of preparation of the catalyst for mild hydrocracking by making active hydrogenating components in the porous wear, 5.07.86].

The disadvantage of this method of preparation of the catalyst is its low activity in the process of hydrocracking of vacuum gazala, wikipaedia within 300-500oC and containing FR. 360oC+ is not less than 80 wt.%

The closest in technical essence and the achieved effect to the proposed technical solution is the method of preparation of the catalyst described in U.S. patent N 5229347, Jntevep, SA., Venezuela, B 01 J 21/06, 20.07.93.

The catalyst according to a known method is prepared by introducing alumina carrier-aluminum hydroxide pore-forming component (salt Titania) with subsequent simultaneous application of the active hydrogenating component compounds of Mo, W, Co, Ni fazoobrazovanie promoters (Re. Rh, Pd), molding, drying and calcining. Before use, the catalyst was activated by solifidianism in carbon disulfide (CS2).

The disadvantages of this method of preparation of the catalyst are:

- low activity of the catalyst in the conversion of FR. 360oC+ in the process for mild hydrocracking of vacuum gas oil 300-500oC content of FR. 360oC+ 80 wt.%;

- high cost due to the use of one of the constituent elements of awho 30 wt.%);

- environmentally unacceptable way to transfer catalyst from the oxide form to sulfide by sulfatirovnie in carbon disulfide, which is a low-boiling poisonous liquid, hazardous to health and life of people.

The objective of the proposed technical solution is to develop a method of preparation of the catalyst for mild hydrocracking of vacuum gas oil for increased activity in the conversion of FR. 360oC + vacuum gasoil, wikipaedia within 300-500oC, in combination with reasonable price and environmentally friendly way of transfer of the catalyst from the oxide form to sulfide.

The solution of this problem is achieved by the present method of preparation of the catalyst for mild hydrocracking of crude oil, including the introduction of active hydrogenating component compounds of molybdenum and Nickel or cobalt, photobrush promoters and a pore-forming components, molding, drying, calcination, while razobratsya promoters bring in the media to the active components, and a pore-forming components contribute after making active components. The inclusion of active ingredients in the carrier is carried out in the form of ammonium salts of molibdenovom is apostate [P2Vo5O23(O2)x] (NH4)6where x=1 or 2, nitrate of cobalt or Nickel in a molar ratio of Ni(Co) Mo : P= (0,8-1,8) : (1,1-2,5) : 1.

As photobrush promoters used individually or in combination of aqueous solutions of ammonia, phosphoric, nitric, hydrochloric acid, aluminum nitrate, powder - Al2O3boric acid, and depositing is carried out at a pH of 2.2 to 5.0.

As a pore-forming components used polyvinyl alcohol (PVA) and/or ethoxylated polyester glycol (surfactant OP-10).

Making the above photobrush promoters separately or in combination at a certain pH value before the introduction of the active component leads, firstly, to obtain further well-formed catalyst mass with pH from 6 to 8, which provides high strength catalyst, secondly, to obtain the composition of the catalyst promoting phases possessing acidic centers of the average force necessary for carrying out reactions mild hydrocracking of crude oil, in particular, vacuum gasoil.

The introduction of a pore-forming components such as polyvinyl alcohol and ethoxylated polyester Go for the conversion of FR. 360oC+ vacuum gasoil.

A method of producing a catalyst for mild hydrocracking of crude oil according to the proposed technical solution is as follows.

stage 1 (introduction photobrush promoters).

Part of aluminum hydroxide loaded into a kneading machine, after stirring contribute gazoobraznymi promoter, are thoroughly mixed to obtain and maturation plastic mass, add the rest of the aluminum hydroxide (up to 60-70 kg in terms of Al2O3), stirred until a homogeneous mass within 30-40 minutes

As a promoter in the first stage, apply solutions ortophosphoric acid, nitrate of rare earth elements, aluminum nitrate, nitric acid, hydrochloric acid, powder-Al2O3with a particle size of up to 63 MK, boric acid powder.

In the resulting mass make the second gazoobraznymi promoter, mix until smooth, to obtain a pulp with a pH of 2.2 to 5.0.

As the second gazoobraznogo promoter on the 1st stage apply solutions of rare earth elements, ammonia, phosphoric acid, boric acid powder.

stage 2 (make active to the ATA Nickel (or cobalt) in series with intermediate and final mixing until smooth, or make active complex obtained by introducing into the solution proximaldistal [P2Mo5O23-x(O2)x] (NH4)6where x=1 or 2, nitrate of cobalt or Nickel in a molar ratio of Ni(Co) Mo : P= (0,8-1,8) : (1,1-2,5) : 1.

3 stage (the introduction of a pore-forming component)

In the resulting 2-stage catalyst weight enter a pore-forming component and stabilize the mixer to the SPT (loss on ignition) = 50-60%. The finished catalyst weight serves on the screw-type machines, where the molded catalyst in the form of extrudates with a diameter of from 1.5 to 5 mm or in the form of a trefoil in size from 3 to 5 mm.

The extrudates are dried at a temperature of 110-130oC for 3-4 hours, calcined at a temperature of 500-550oC for 8-10 hours.

The prepared catalyst was examined for the content of the active components and promoters, determine the tensile splitting strength, determine the parameters of porous structure and are tested for activity in the process for mild hydrocracking of vacuum gas oil.

Process conditions:

Feedstock is a Vacuum gas oil AAO "Naftan" (b. Novopolotsk refinery)

Density at 15oC, g/cm3- 0,905

FR. MK-180,% - 0

FR.180-360oC,AU-1- 1,0

The catalyst activates elemental sulfur in the amount of 15 wt.% from the weight of the loaded catalyst. The volume of the reactor 100 cm3.

Below are examples of the implementation of the proposed technical solutions.

Example 1.

stage 1

In the kneading machine load 30 kg of active aluminum hydroxide with SPT= 78.5 per wt. % make a 1.1 l (1.7 kg) 87% phosphoric acid, stir the mass until smooth, add 39 kg of active aluminum hydroxide, stirred until smooth for 40 minutes In the resulting mass make dry boric acid powder, mix thoroughly until smooth for about 1 hour. The resulting mass has a pH of 4.0.

stage 2

In mass prepared by 1-th stage, contribute 3.8 kg of ammonium molybdate (ACA) and 4.8 kg of Nickel nitrate (NN) careful with intermediate stirring for 40 minutes

3 phase

In mass, prepared in stage 2, make a 0.25 kg surfactant OP-10 and mix thoroughly prior to maturity.

Ready to forming catalyst weight plastic and has a pH of 8.0.

Mass overload in the screw press machine and molded extrude color and overload in the drying-prokhladnyy apparatus, where they are dried at a temperature of 120oC for 4 hours, and then calcined at a temperature of 550oC for 8 hours.

After calcination of the extrudates are cooled and discharged. The finished catalyst analyze.

Chemical composition, wt.%:

In terms of oxides: - 14,0 MoO3; 5,4 NiO; 5,6 P2O5AND 4.9 BO3;

The rest is aluminum Oxide

The size of the extrudates From 3.0 to 3.5 mm;

The tensile splitting strength of 1.8 kg/mm of diameter;

Pore volume is 0.60 cm3/g;

Specific surface area (Hg) - 160 m2/g;

The average radius of the pore - 90A.

Characteristics of the porous structure was determined on porosimetry Carlo-Erba.

Testing of the catalyst in the process for mild hydrocracking of vacuum gas oil showed the release of FR. 180-360oC 56,7%.

Determination of sulfur content in the hydrogenation product in General, and in the diesel fraction 180-360oC has shown to 0.21 wt.% and 0.07 wt.% respectively.

Other examples of implementation of the proposed technical solutions (NN 2-9), and an example of the prototype (N 10, comparative) are given in table.1. In table.2 shows characteristics of the catalysts synthesized under the conditions of table.1.

Example 10 (comparative is Matrena data on the proposed conditions for the synthesis of catalysts for mild hydrocracking of crude oil, for example, hydrocracking of vacuum gas oil (PL.1) in comparison with the characteristics of the obtained catalysts (table.2) and in comparison with the catalyst of the prototype showed that the proposed method for obtaining permits to obtain the catalyst, giving the yield of the target fraction 180-360oC in volume 51,0-57,1 wt.% against 41,7 wt.% catalyst-prototype. While catalysts are well manifest themselves as catalysts for hydrodesulphurization unit, namely, the residual sulfur content in the hydrogenation product as a whole is reduced to 0.20 to 0.28 wt.% against 0.36 wt.% catalyst-prototype and the residual sulfur content in the target diesel fraction 180-360oC is reduced to 0.06 and 0.12 wt.% vs. 0.13 wt.% catalyst-prototype. At the same time increased the strength of the catalyst with 1.8 kg/mm diameter pellets to 2.4, and in the case of forming a trefoil - to 6.2 kg/granule.

It is also important to improve the processability of the way by improving the rheological properties of the catalyst mass before forming, increasing the plasticity and fluidity, resulting in reduced power consumption in the formation, and the granules are formed with smooth, almost defect-free surface. In the future it is manifested in the higher is talization on the proposed method of oxide forms in sulfide was carried out using elemental sulfur, not a disulphide - environmentally unacceptable liquid, hazardous to health and life of people. As you can see, this method has led to an increase in the yield of the target diesel fraction against the catalyst according to the method prototype.

1. The preparation method of catalyst for mild hydrocracking of crude oil, including the introduction in alumina porous carrier of the active hydrogenating component compounds of molybdenum and Nickel and/or cobalt, photobrush promoters and a pore-forming components, molding, drying, calcining, wherein forming the promoters bring in the media to the active components, and a pore-forming components contribute after making active components.

2. The method according to p. 1, characterized in that the active hydrogenating components contribute in the promotion of ammonium molybdate and Nickel nitrate or cobalt.

3. The method according to p. 1, characterized in that the active hydrogenating components making the complex obtained by incorporating in an aqueous solution of proximaldistal

[P2Mo5O23-x(O2)x](NH4)6,

where x = 1 or 2, nitrate of cobalt or Nickel in a molar ratio of Ni(Co) Mo : P= (0,8 - 1,8) : (1,1 - 2,5) : 1.

and combined solutions of ammonia, phosphoric, nitric, hydrochloric acid, nitrate of rare earth elements, nitrate aluminium, powder-Al2O3boric acid and depositing is carried out at a pH of 2.2 to 5.0, and as a pore-forming components using polyvinyl alcohol and/or ethoxylated polyester glycol.

 

Same patents:

The invention relates to methods for preparing catalysts for the process of ethylene oxide gas-phase oxidation of ethylene with oxygen

The invention relates to catalytic chemistry, in particular to a method for preparing a catalyst for vapor-phase synthesis of vinyl acetate from acetylene and acetic acid

The invention relates to petrochemical synthesis and can be used in the preparation of catalysts for selective hydrogenation of acetylene and diene compounds

The invention relates to the synthesis of catalysts that can be used in a variety of chemical-technological processes in the chemical, oil and gas industry and for wastewater treatment and. etc

The invention relates to the protection of the environment from toxic industrial emissions, and in particular to methods of preparation of catalysts for purification of exhaust gases from harmful substances

The invention relates to catalytic chemistry, in particular to catalysts for the synthesis of dichloroethane oxychloination ethylene

The invention relates to a process for the preparation of catalysts, and can be used to extract copper from solutions, industrial effluents and sewage

The invention relates to high-strength porous systems and concerns of the catalyst precursor or membrane, or catalytic membrane system, and method of production thereof

The invention relates to methods for preparing catalysts for reforming of gasoline fractions and can be used at the enterprises of chemical, oil-refining and petrochemical industry
The invention relates to mechanical engineering and can be used for purification of exhaust gases of internal combustion engines

The invention relates to the refining catalysts, in particular catalysts for Hydrotreating of crude oil

The invention relates to catalysts for Hydrotreating and hydrogenation of oil and coke raw material and method of its use

The invention relates to the refining of crude oil and, in particular, to the Hydrotreating of petroleum distillates

The invention relates to the refining of crude oil and, in particular, to the Hydrotreating of petroleum distillates

The invention relates to petrochemistry and oil refining, more specifically, to the manufacture of catalysts for Hydrotreating petroleum fractions
The invention relates to the refining, in particular to a method of Hydrotreating petroleum fractions
The invention relates to mechanical engineering and can be used for purification of exhaust gases of internal combustion engines

The invention relates to systems for producing high-octane gasoline low-octane reforming of gasoline fractions
Up!