The catalyst for hydroconversion with hydroisomerization of hydrocarbons and method of processing hydroisomerization heavy petroleum hydrocarbon fractions

 

(57) Abstract:

Describes a catalyst for hydroconversion with hydroisomerization of hydrocarbons containing at least one noble metal of group VIII deposited on an amorphous carrier of aluminum oxide with homogeneous distributed by silicon dioxide. The catalyst includes a carrier with a silicon dioxide content of 5 to 70 wt.% and a specific surface area determined by BET method, 100-500 m2/g and an average pore diameter of 1 to 12 nm, the volume of pores with a diameter equal to the value between the average diameter +3 nm, more than 40% of the total pore volume, the dispersion of the noble metal 20-100%, the allocation ratio of the noble metal is higher than 0.1, when the precious metal content of 0.05 to 10 wt.%. Also described is a method of processing a hydroisomerization heavy petroleum hydrocarbon fractions. The technical result - the more simple and efficient catalyst. 2 C. and 13 C.p. f-crystals, 2 tab.

The invention relates to a catalyst used in the methods of hydroconversion hydrocarbons, which contain small amounts of metals.

The present invention also relates to a method of hydroconversion with the hydroisomerization pleadeth metals.

The catalyst is particularly preferred for processing by hydroisomerization of hydrocarbons (such as hydrocracking residues) to obtain very high-value products, such as kerosene, gas oil and base oil.

To implement the reactions hydroisomerization can be used in a variety of catalysts. For example, in U.S. patent 4929795 describe the use of a catalyst consisting of 0.5 wt.% platinum deposited on halogenated alumina, containing 7.2 wt.% fluoride, to obtain base oils of paraffin. The applicant conducted a search in the direction of obtaining suitable way isomerization simpler catalyst without halogen as thus described, the catalyst requires continuous introduction of fluorinated compounds in catalytic installation.

In U.S. patent 4428819 described containing zeolite catalyst, which is used for the implementation of the isomerization reactions of the mixture of waxes derived from petroleum, and the reaction product is admixed to the base oil obtained by catalytic dewaxing, with the aim of improving its cloud point. Finally, in U.S. patent 4547283 describes the catalyst hydroisomerization periodicheskoi system elements, and in which the carrier is preferably silicon dioxide.

The applicant conducted a search in the direction of obtain a suitable, simpler catalyst, avoiding the use of zeolite or add additional elements during the preparation of the catalyst.

Currently in hydroconversion used catalysts are bifunctional type, combining an acid function with a hydrogenating function. The acid function is caused by the media with a large surface (usually 150-800 m2/g), having a surface acidity, such as halogenated (especially chlorinated or fluorinated) aluminum oxide containing phosphorus, aluminum oxide, combinations of oxides of boron and aluminium, amorphous aluminosilicates and mixtures of alumina with silica. Hydrogenating function due to the presence of either one or several metals of group VIII of the Periodic system of elements, such as iron, cobalt, Nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or a combination of at least one group VI metal, such as chromium, molybdenum and tungsten, at least one metal of group VIII.

The balance between the two, acid and hydrogenating functions is the main parameter that determines the asset is e and malosilikatnihe catalysts with respect to isomerization, whereas a strong acid function and a weak hydrogenating function give a very active and selective catalysts in relation to cracking. The third possibility is the use of a strong acid function and a strong hydrogenating function to get very active and very selective catalyst in the ratio of isomerization. Therefore, by a reasonable selection of each of these functions, you can pick up a pair of the activity/selectivity of the catalyst.

In the search operations conducted by the applicant on numerous mixtures of silicon dioxide with aluminum oxide, it was found that the use of a catalyst containing a special blend of silicon dioxide with aluminum oxide, produces a very active and very selective catalyst in some reactions, such as isomerization of raw materials such as the following.

More specifically, according to the invention, the catalyst consists essentially of from 0.05 to 10 weight. % of at least one noble metal of group VIII deposited on an amorphous carrier of silicon dioxide (oxide of aluminum), which contains 5-70 wt.% silicon oxide and has a specific surface area determined by BET method, 100-500 m2/g, and catalognum diameter, above, minus 3 nm and the average diameter of the above, plus 3 nm, more than 40% of the total pore volume;

- dispersion of the noble metal 20-100%;

the distribution coefficient of the precious metal higher than 0.1.

These characteristics are listed below in more detail.

The silicon dioxide content: media used for preparation of the catalyst according to the invention, composed of silicon dioxide SiO2and aluminum oxide Al2O3. The silicon dioxide content, expressed in weight percent, is 5-70%, preferably 20-60%, and even more preferably 22-45%. This content is quite measurable by X-fluorescence. It is constant throughout the catalyst, i.e., the concentration of silicon dioxide is not higher, for example, on the surface of the catalyst; the catalyst is homogeneous with respect to the distribution of silicon dioxide.

The nature of the noble metal: for this particular type of reaction, the metal feature is made of a noble metal of group VIII of the Periodic system of elements and preferably platinum.

The content of noble metal, expressed in wt.% metal to the total weight of the catalyst is 0.05-10 and Balotelli, available reagents, relative to the total amount of metal in the catalyst can be measured, for example, by titration with H2/O2. Metal pre-restore, i.e., subjected to processing by a current of hydrogen at high temperature under such conditions that all of the available hydrogen atoms of platinum turned into a metal mold. Then in adequate conditions of work serves a current of oxygen, all atoms of the recovered platinum, available oxygen, oxidized to PtO2. By calculating the difference between the entered amount of oxygen and the output amount of oxygen getting consumed amount of oxygen; thus, the final values to determine the amount of platinum available oxygen. The variance is equal to the ratio of available oxygen platinum to the total amount of platinum in the catalyst. In the case of the catalyst according to the invention the dispersion is 20-100% and preferably 30-100%.

The distribution of the precious metal: the distribution of the noble metal means metal distribution in a catalyst pellet and the metal can be well or poorly dispersed. So, you can get badly distributed (for example, nnu, i.e., so that all atoms of platinum, located in the layer available reagents. In the catalyst according to the invention the distribution of platinum is good, i.e., the profile of platinum, measured according to the method of the Castaing microprobe, has a distribution coefficient higher than 0.1, and preferably above 0.2.

Determined by BET method surface: determined by BET method, the surface of the carrier is 100-500 m2/g and preferably 250-450 m2/g and even more preferably 310-450 m2/,

Average pore diameter: the average diameter of pores of the catalyst is measured on the basis of the profile distribution of the pore radii obtained with apparatus for determining the porosity in the application of mercury. The average diameter of pores is defined as the diameter corresponding to the cancellation of the derivative curve obtained from the curve porosity, determined by mercury. Thus, found the average pore diameter is a value between 1 nm (110-9m) and 12 nm (1210-9m) and preferably between 2.5 nm (2,510-9m) and 11 nm (1110-9m) and even more preferably between 4 nm (410-9m) and 10.5 nm (10,510-9m) and is preferably 3-9 nm.

The pore distribution: the catalyst according to the invention has such a distribution of purnim diameter, the above, plus 3 nm (or average diameter of 3 nm) is more than 40% of the total pore volume and is preferably 50-90% of the total pore volume, more preferably 50-80% of the total pore volume and most preferably 50-70% of the total pore volume. Therefore, the catalyst has a uniform pore distribution modal type, rather than bimodal type.

Total pore volume of the carrier: it is usually below 1.0 ml/g and preferably is 0.3-0.9 ml/g and even more preferably less than 0,85 ml/year in General, the carrier has a total pore volume of 0.55 ml/g and preferably at least 0.6 ml/g

Preparation and processing of mixtures of silicon dioxide with aluminum oxide carry out the usual, well-known specialist of ways. Preferably, prior to impregnating the metal carrier can be subjected to annealing, as, for example, heat treatment at 300-750oC (preferably 600oC) for 0.25 to 10 hours (preferably 2 hours) under the action of about 2-30. % water vapor (preferably of 7.5%).

Salt of the metal is injected in one of the usual methods used for the deposition of metal (preferably platinum) on the surface of the carrier. One of the preferred methods is by impregnation moisture capacity is imago catalyst. Before the restore operation, the catalyst can be subjected to annealing, as, for example, treatment in dry air at 300-750oC (preferably 520oC) for 0.25 to 10 hours (preferably within 2 hours).

Before use in the reaction of conversion contained in the catalyst metal to be recovered. One of the preferred methods of implementing the recovery of the metal is processed in an atmosphere of hydrogen at a temperature of 150-650oC and at a total pressure of 0.1 to 25 MPa. For example, the recovery is maintaining at a temperature of 150oC for 2 h, and then raising the temperature up to 450oC with a speed of 1oC/min, then maintaining at a temperature of 450oC for 2 h; throughout this recovery phase, the flow rate of hydrogen is 1000 l of hydrogen/l of catalyst. Also it should be noted that any suitable method of recovery coc-situ.

The catalyst according to the invention is active, for example, to hydroisomerization hydrocarbons such as described below, to obtain significant quantities of the products formed as a result of hydroisomerization present in the feedstock molecules. Particularly of interest Polubotko any appropriate substrate, as, for example, vacuum distillates, distillation residue under vacuum, the residue of distillation at atmospheric pressure or paraffin products originating from a process for the dewaxing of crude oil, and, for example, when the material is DisasterRecovery distillation residue under vacuum. This raw material contains molecules of at least about 10 carbon atoms. It may contain paraffin sections, or may entirely be a paraffin molecule, and the number of aromatic carbon atoms is at most 20 wt.% of the total number of carbon atoms of raw materials. Under suitable raw material understand the raw materials, the sulfur content is lower than 1000 weight.m.D. and preferably less than 500 weight. M. D. and even more preferably less than 300 weight.m.D., and a nitrogen content of less than 200 weight. M. D. and preferably below 100 weight.m.D. and even more preferably below 50 weight. M. D. the metal Content in raw materials, such as Nickel and vanadium, are negligible, i.e. less than 50 weight.m.D. and more preferably less than 10 weight.m.D.

Preferably processed by hydroisomerization heavy hydrocarbons, such as hydrocracking residues, i.e., which has a boiling essentially above 350o

Working conditions this reaction hydroisomerization are a temperature of 200-450oC and preferably 250-430oC and preferably above 340oC; the partial pressure of hydrogen 2-25 MPa, and preferably 3-20 MPa; the hourly volumetric velocity of 0.1-10 h-1and preferably 0.2 to 2 h-1and the number of hydrogen 100-2000 l of hydrogen per 1 liter of feedstock and preferably 150-1500 l of hydrogen per 1 liter of raw materials.

The use of this catalyst is not limited to hydroisomerization, in General, it is suitable for the conversion of hydrocarbons carried out in the required conditions.

The example below illustrates the characteristics of the invention, however, does not limit the scope of the invention.

The preparation of the catalyst.

The carrier is a mixture of silicon dioxide with aluminum oxide used in the form of an extrudate. This mixture contains 29,1% wt. silicon dioxide SiO2and 70.9 wt.% aluminium oxide Al2O3. The mixture of silicon dioxide with aluminum oxide before adding the noble metal has a surface 389 m2/g and an average pore diameter of picky noble metal carrier. Platinum salt Pt(NH3)4Cl2, is dissolved in a volume of solution corresponding to the total pore volume impregnated media. The impregnated mass is then calcined for 2 hours in an atmosphere of dry air at 520oC. the Content of platinum is 0.60 wt.%. The dispersion of platinum is 60% and its distribution uniformly in the pellet. Measured for the catalyst pore volume 0.75 ml/g determined by BET method, the surface is equal to 332 m2/g, average diameter of these pores is 6.5 nm, and the volume of pores with a diameter of 3.5 to 9.5 nm, is 0.46 ml/g or 59% of the total pore volume.

The distribution of pores in the catalyst the following:

pores with diameter

< 6 nm - pore volume = 0.6 ml/g or 21% of the total pore volume;

6-15 nm to 0.36 ml/g or 48%;

15-60 nm - 0.06 ml/g or 8%;

> 60 nm to 0.17 ml/g or 23%.

Characteristics of raw materials.

In table. 1 shows the physico-chemical characteristics of the raw materials used for the reaction of hydroisomerization. This residue hydrocracking, originating from the fraction from the distillation under vacuum.

Obtaining a base oil having a reaction.

The catalyst, the preparation of which is described, is used to produce base oil by hydro which I hourly rate is 1 h-1and the consumption of hydrogen is 1000 l of hydrogen/l of raw materials. In these working conditions is a clear conversion "faction 400-" 55 wt.% and the output of the base oil is equal to 85 wt.%. The recovered oil has a viscosity index equal to 135.

In table. 2 compares the characteristics of the base oil after hydroisomerization with the characteristics of oil extracted from the residue hydrocracking classical method of extraction solvent (methyl ethyl ketone/toluene). It should be noted that these two oils are very similar in density to viscosity. On the contrary, the viscosity index temperature expires and especially the release of oil/residue best if hydroisomerization product.

1. The catalyst for hydroconversion with hydroisomerization of hydrocarbons containing at least one noble metal of group VIII deposited on an amorphous carrier of aluminum oxide with homogeneous distributed silicon dioxide, wherein the catalyst includes a carrier with a silicon dioxide content of 5 to 70 wt.% and a specific surface area determined by BET method, of 100 - 500 m2/g and an average pore diameter of 1 to 12 nm, the volume of pores with a diameter equal to the average diameter of 3 nm, more than 40% of the total volume is Ergani noble metal of 0.05 - 10 wt.%.

2. The catalyst p. 1, characterized in that it contains media having a total pore volume of less than 1.0 ml/g

3. Catalyst under item 1 or 2, characterized in that it contains media from the total pore volume of at least 0.3 ml/g and less than 0.9 ml/g

4. The catalyst according to any one of paragraphs.1 to 3, characterized in that it contains media from the total volume of pores less of 0.85 ml/g

5. The catalyst according to any one of paragraphs.1 to 4, characterized in that it has an average pore diameter of 2.5 to 11 nm.

6. The catalyst according to any one of paragraphs.1 to 5, characterized in that it has an average pore diameter of 4 to 10.5 nm.

7. The catalyst according to any one of paragraphs.1 - 6, characterized in that the volume of pores whose diameter is the average diameter of 3 nm, 50 - 90% of the total pore volume.

8. The catalyst according to any one of paragraphs.1 to 7, characterized in that the volume of pores whose diameter is the average diameter of 3 nm, 50 - 80% of the total pore volume.

9. The catalyst according to any one of paragraphs.1 to 8, characterized in that the volume of pores whose diameter is the average diameter of 3 nm is 50 - 70% of the total pore volume.

10. The catalyst according to any one of paragraphs.1 to 9, characterized in that it contains wear is that it contains the media content 22 - 45 wt.% silicon dioxide.

12. The catalyst according to any one of paragraphs.1 - 11, characterized in that it contains a carrier having a surface defined by BET method, 250 - 450 m2/,

13. The catalyst according to any one of paragraphs.1 - 12, characterized in that it contains a carrier having a surface defined by BET method, 310 - 450 m2/,

14. The catalyst according to any one of paragraphs.1 - 13, characterized in that the noble metal is platinum.

15. Method of processing hydroisomerization heavy hydrocarbon oil fractions with boiling points essentially above 350oWith, the nitrogen content in which less than 200 weight. memorial plaques and metal content below 50 weight. M. D., wherein the process is conducted at a temperature of 200 - 450oWith under a partial hydrogen pressure of 2 to 25 MPa, with an hourly volumetric velocity of 0.1 - 10 h-1and with a volume ratio of hydrogen/feedstock 100 - 2000, using a catalyst according to any one of paragraphs.1 - 14.

 

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