Complex hydrotreatment with high-efficiency catalysts

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing base oil, involving: providing a first catalyst containing at least one group VIII metal deposited on a M41S catalyst support, such as MCM-41, and having density of 600 kg/m³ or less; providing a second catalyst containing at least one group VIII metal, having dewaxing efficiency which is sufficient to facilitate treatment of a stream of light neutral (150 N) hydrocarbons from a medium-pressure hydrocracking apparatus, having kinematic viscosity at 100°C of less than 5 and end boiling point lower than 550°C, at 320°C and liquid hourly space velocity (LHSV) of 1 h^-1, to obtain base oil having chilling temperature lower than 15°C; bringing the material into contact with the first catalyst at adequate conditions for treating the material, wherein said adequate conditions are adequate for one of the processes selected from hydrotreatment, hydrofining or hydrogenation of aromatic compounds, and bringing the treated material into contact with the second catalyst at conditions adequate for dewaxing the treated material. The invention also relates to another method of producing base oil.

EFFECT: enabling flexible treatment of material with different paraffinicity.

13 cl, 12 dwg, 3 tbl, 19 ex

The technical field

This invention relates to a method of catalytic hydroperiod raw materials.

The level of technology

Catalytic hydroperiod distillation products or raw materials, with the interval boiling point distillation products or lubricants, typically involves the use of a catalyst containing supported on a carrier metals of group VIII and/or group VI. In many cases supported on a carrier metals constitute a significant portion of the cost of the catalyst. As for loading in a typical reactor hydroperiod requires a large amount of catalyst, for any processing are popular catalysts with lower cost.

In U.S. patent No. 5951848 a method of processing hydrocarbon material by the initial impact of raw materials highly active catalyst hydrobromide, to reduce the concentration of, for example, nitrogen, sulphur and aromatic compounds. Then carry out the dewaxing hydroblasting raw materials, using a dewaxing catalyst such as ZSM-23, ZSM-35 or ZSM-48.

There is a need for an improved method of hydroperiod of hydrocarbons, which has reduced the cost of operations.

The invention

In one of the embodiments of the invention provides a method of obtaining a base oil. The way in which incorporates both the provision of the first catalyst, comprising at least one metal of group VIII supported on a carrier of M41S catalyst, such as MCM-41, and having a density of 600 kg/m³or less. Provide a second catalyst that includes at least one metal of group VIII. The second catalyst is chosen so that it has the performance when dewaxing sufficient to perform under consideration as a control processing flow of light neutral (150N) hydrocarbons obtained from hydrocracking medium pressure, and the flow of light neutral hydrocarbon and has a kinematic viscosity at 100°C. of less than 5 and a boiling point of less than 550. The second catalyst has sufficient activity at 320°C and hour space velocity of fluid (COSI)1 h^-1to obtain a base oil having a pour point less than -15°C. the Raw material is brought into contact with the first catalyst under effective conditions for the processing of raw materials, and these effective conditions are effective for one process selected from hydrobromide, Hydrotreating or hydrogenation of aromatic compounds. Then the processed raw material is brought into contact with a second catalyst under conditions effective for dewaxing the processed raw materials.

In another embodiment the invention provides the method according to the teachings of the base oil. The method comprises bringing the substrate in contact with the first catalyst and said first catalyst comprises at least one metal of group VIII deposited on a catalyst carrier, and has a density of 600 kg/m³or less, at effective conditions for the processing of raw materials, and these effective conditions are effective for one process selected from hydrobromide, Hydrotreating or hydrogenation of aromatic compounds. Processed raw material is then brought into contact with a catalyst comprising ZSM-48 with a ratio of SiO₂:Al₂O₃comprising from about 70 to about 110, and a metal hydrogenation component under conditions effective for dewaxing the processed raw materials.

In yet another embodiment the invention provides a method of producing bases for lubricating oils. The method includes providing a process line, comprising the first catalyst is a catalyst hydrobromide, Hydrotreating or hydrogenation of aromatic compounds, and a second catalyst that is a dewaxing catalyst. The first raw material having first paraffinicity process on the production line at the first temperature, to obtain a base having a pour point less than - 15°C, and the first temperature pillar is t 365°C. or less. The second raw material having a second paraffinicity handle on the same process line at a temperature in the range of 30°C. from the first temperature and the second paraffinicity at least 30% more first paraffinicity to get a second base having a pour point less than -15°C.

Brief description of drawings

Figure 1 is a micrograph of crystals of ZSM prepared at a ratio of template : silicon dioxide, equal 0,023, and showing the presence of a certain amount of needle-shaped crystals.

Figure 2 is a micrograph showing the absence of needle-shaped crystals, the crystals of ZSM-48 prepared from a reaction mixture having a ratio of template : silicon dioxide 0,018.

Figure 3 is a micrograph showing the presence of needle-shaped crystals, the crystals of ZSM-48 prepared from a reaction mixture having a ratio of template : silicon dioxide 0,029.

Figure 4 is a micrograph showing the absence of needle-shaped crystals, the crystals of ZSM-48 prepared from a reaction mixture having a ratio of template : silicon dioxide 0,019.

Figure 5 is a graph showing dependence of the yield of ISO-C₁₀the degree of conversion of h₁₀.

6 is a graph showing the dependence of the temperature of reaction is ora to the temperature required to meet the requirements of the freezing temperature of 370°With+.

7 is another graph of the reactor temperature from the desired temperature to meet the requirements of the freezing temperature of 370°With+.

Fig is a graph showing the dependence of the freezing temperature on the viscosity index for raw materials, gidromeliorativno in the presence of ZSM-48 with a low ratio and high ratio.

Figures 9 and 10 are graphs of the dependence of the freezing temperature on the viscosity index for raw materials, successively treated with different catalysts hydroperiod.

11 and 12 show the difference in the hydrogenation of aromatic compounds for the processing of different raw materials as catalysts for the hydrogenation of aromatic compounds.

Detailed description of embodiments of the invention

The invention provides a method of hydroperiod hydrocarbons, which provides increased flexibility and/or reduced operating costs. The method involves the use of catalysts hydroperiod high performance and/or low density, such as catalysts hydrobromide, Hydrotreating or hydrodewaxing, for hydroperiod hydrocarbons. The method according to the invention reduces the cost of operations in three different ways.

First, the use of high-performance catalysts with whom according to the invention leads to reduced costs. The catalyst with higher performance can achieve the same effect as a catalyst with lower productivity, with reduced amount of catalyst. Reduced the amount of catalyst required means that at every boot of the reactor requires a smaller amount of the catalyst, which leads to cost savings. Alternatively, the catalyst with higher performance can be used for carrying out the process at lower temperatures. Due to degradation of the catalyst temperature in many reactors hydroperiod it is necessary to increase during operation to maintain the required level of activity. When the catalyst degrades sufficiently, so that the required temperature exceeds the specified threshold, the catalyst is replaced. The implementation of the reaction at lower temperatures can prolong the service life of the catalyst between the operations of replacing two separate ways. Operation at a lower temperature usually reduces the degree of degradation of the catalyst. Additionally, as the catalyst starts to degrade, lower initial operating temperature means that a greater range of temperatures available to counteract the degradation of the catalyst while minimizing other side effects. So what Braz, operation at lower temperatures reduces the frequency stops the reaction of the installation, which also leads to cost reduction.

Secondly, the use of low density catalysts according to the invention ensures cost reduction through reduction of the amount of metal introduced into the catalyst. The metal content in the catalyst is usually characterized in terms of the amount of metal on the weight of the catalyst. When using the catalyst of low-density, requires less metal to achieve the desired amount of metal on the weight of the catalyst. Thus, the catalysts of low density reduces the total amount of metal present in the catalyst bed, resulting in reduced costs.

Finally, the catalysts of high performance, low density, used according to the invention allows sequential processing of raw materials in the reaction setup. Usually to handle specific materials used production line. Change the type of raw materials intended for processing, require modification of the production line. When using the catalysts according to the invention various types of raw materials can be processed in the reaction installing or without changes in operating conditions, or when changing only the temperature of the process line. Taco is the type of "processing" raw materials allows a great flexibility in the operation of the processing line, as the raw material is introduced into the process line, can be changed without modification to equipment or other loss of a significant amount of time on simple.

The choice of catalysts for high performance and low density

The high performance catalysts are catalysts which have a relatively high reaction rate per unit volume for the desired reaction, such as hydrobromide, hydrodeparafinisation, Hydrotreating or hydrogenation of aromatic compounds. The low density catalysts are catalysts which have relatively low total mass per unit volume.

In various embodiments of the invention use high-performance catalysts hydrobromide. These catalysts hydrobromide can be characterized by the activity of k hydrobromide, which represents the reaction rate constant of removal of sulfur or nitrogen from raw materials with a certain content of sulfur and nitrogen. This reaction rate constant determined on the basis of volume, to allow comparison of catalysts.

In other embodiments of the invention use a high-performance catalysts for Hydrotreating and/or hydrogenation of aromatic compounds. For catalysts for Hydrotreating or hydrogenation of aromatic compounds performance monoproduct in temperature processing, required to achieve the desired degree of removal of aromatic compounds for certain raw materials at a certain ratio of the feed rate of raw material to the amount of the catalyst.

The dewaxing catalysts represent a different type of catalysts that can be characterized on the basis of performance. The dewaxing catalysts often affect several characteristics of raw materials at the same time. Thus, the characteristics of the catalyst dewaxing as "high performance" requires simultaneous consideration of several variables. In this invention to determine the performance of the catalyst dewaxing made the following test.

High-performance catalyst dewaxing is defined as a catalyst which gives the following result when processing light neutral (150N) raw materials obtained from hydrocracking medium pressure, having a kinematic viscosity at 100°C. of less than 5, and the final boiling point of less than 550°F. Raw materials are treated at 320°C and CHOSE 1 hour^-1in the presence of catalyst hydroperiod obtaining deparaffinizing basis with the following properties:

Pour point: less than -15°C

The degree of conversion of at least 20 wt.%

In other embodiments of the invention use the form catalysts of hydroperiod low density. In this invention under the density of the catalyst is to understand the density of the set of catalyst particles in the vessel. This value differs from the density of the individual particles of the catalyst. The density of the catalyst particles in the vessel below the density of the individual particles of the catalyst due to the voids between adjacent catalyst particles. In one embodiment the density of the catalyst is less than 600 kg/m³(0.6 g/cm³), or less than 590 kg/m³or less than 580 kg/m³or less than 570 kg/m³or less than 550 kg/m³or less than 525 kg/m³or less than 500 kg/m³or less than 475 kg/m³.

The catalysts hydroperiod (General)

In one of the embodiments of the one or more catalysts hydroperiod can be a catalyst suitable for hydrobromide, Hydrotreating and/or hydrogenation of aromatic compounds raw materials. In this embodiment the catalyst may consist of one or more metals of group VIII and/or group VI on the media. Suitable metal oxides as carriers include oxides of low acidity, such as silicon dioxide, aluminum oxide, silicates or titanium dioxide. Deposited metals may include Co, Ni, Fe, Mo, W, Pt, Pd, Rh, Ir or a combination thereof. Preferably the applied metal is Pt, Pd or a combination thereof. A number of metals, individually or in the mixtures, is from about 0.1 to 35 wt.%, based on the weight of the catalyst. In one of the embodiments of number of metals, individually or in mixtures, is at least 0.1 wt.%, or at least 0.25 wt.%, or at least 0.5 wt.%, or at least 0.6 wt.%, or at least 0.75 wt.%, or at least 1 wt.%. In another embodiment, the number of metals, individually or in mixtures, is 35 wt.% or less, or 20 wt.% or less, or 15 wt.% or less, or 10 wt.% or less, or 5 wt.% or less. In preferred embodiments, where the deposited metal is a noble metal, the amount of metals is typically less than 1 wt.%. In such embodiments, the number of metals may be 0.9 wt.% or less, or 0.75 wt.% or less, or 0.6 wt.% or less. The number of metals can be determined by methods established by ASTM for individual metals, including atomic absorption spectroscopy or atomic emission spectroscopy with inductively coupled plasma.

In the preferred embodiment of the catalyst of hydrobromide, Hydrotreating or hydrogenation of aromatic compounds is a metal of group VIII and/or group VI printed on the associated bearer of the M41S family, such as a linked MSM-41. The family of M41S catalyst is a mesoporous material having a high content is silicon dioxide, the receipt of which is described in J. Amer. Chem. Soc., 1992, 114, 10834. Examples include MCM-41, MCM-48 and MCM-50. Mesoporous called the catalysts having a pore size of from 15 to 100 Å. The preferred member of this class is MCM-41, the receipt of which is described in U.S. patent No. 5098684. MCM-41 is an inorganic, porous, nonlamellar phase having a hexagonal configuration and uniform pore size. The physical structure of MCM-41-like a bundle of straws, where the size of the hole straws (cell diameter of the pores) is from 15 to 100 Å. MCM-48 has a cubic symmetry and is described, for example, in U.S. patent No. 5198203, whereas MSM-50 has a scaly structure. MCM-41 can be made with different size openings of pores in the mesoporous range. Suitable binders for MSM-41 may include Al, Si, or any other binder or combination of binders, which provides high performance and/or low density catalyst. An example of a high-performance catalyst for the hydrogenation of aromatic compounds, which is also a catalyst with a low density, is platinum on mesoporous MCM-41, associated with aluminum oxide. MSM-41 associated with aluminum oxide, it is possible to synthesize with the density of the catalyst is less than 600 kg/m³(0.6 g/cm³), or less than 590 kg/m³or less than 580 kg/m³that is if less than 560 kg/m ³or less than 550 kg/m³or less than 540 kg/m³or less than 525 kg/m³or less than 500 kg/m³or less than 475 kg/m³. This catalyst can be impregnated with a metal hydrogenation, such as Pt, Pd, another metal of group VIII, a metal of group VI, or a mixture of these metals. In one of the embodiments of the amount of metal of group VIII is at least 0.1 wt.%, based on the weight of the catalyst. Preferably the amount of metal of group VIII is at least 0.5 wt.% or at least 0.6 wt.% In such embodiments, the number of metals may be 1.0 wt.% or less, or 0.9 wt.% or less, or 0.75 wt.% or less, or 0.6 wt.% or less. In other embodiments the number of metals, individually or in mixtures, is at least 0.1 wt.%, or at least 0.25 wt.%, or at least 0.5 wt.%, or at least 0.6 wt.%, or at least 0.75 wt.%, or at least 1 wt.%. In other embodiments the number of metals, individually or in mixtures, is 35 wt.% or less, or 20 wt.% or less, or 15 wt.% or less, or 10 wt.% or less, or 5 wt.% or less.

The dewaxing catalyst is ZSM-48

One example of a dewaxing catalyst, suitable for use in the claimed invention is ZSM-48 with a ratio of SiO₂:Al₂O₃less than 110, preferably from about 70 to use the but 110. In the preferred embodiment of ZSM-48 with a ratio of SiO₂:Al₂About₃less than 110 does not contain the seed crystals other than ZSM-48. Preferably crystals of ZSM-48 high purity also do not contain ZSM-50.

In the following embodiments, the crystals of ZSM-48 describe the different ways in terms of the crystals synthesized in the form of"that still contain organic template annealed crystals, such as Na-form ZSM-48 crystals, or annealed and subjected to ion exchange crystals, such as H-form ZSM-48 crystals.

The phrase "not containing the seed crystals other than ZSM-48" understand that the reaction mixture used for the formation of ZSM-48 crystals, does not contain the seed crystals other than ZSM-48. Instead, ZSM-48 crystals synthesized according to the invention, or synthesized without the use of seed crystals or seed crystals of ZSM-48 as a seed. The phrase "does not contain keraita and ZSM-50" understand that Kinijit and ZSM-50, if present, are present in amounts that are not detected by x-ray diffraction. Preferably ZSM-48 used in the invention, also contains no other crystals other than ZSM-48 to the extent that such other crystals also not detected by inthenews the second diffraction. It is "not detected" determination can be made on the instrument Bruker D4 Endeavor, manufactured by Bruker AXS and equipped with high-speed detector Vantec-1. The device is operated using a standard silicon powder (Nist 640B), which is the material without internal stresses. Width at half maximum (fwhm) for the standard peak when 28,44 degrees 2θ is 0,132. Step is 0,01794 degrees and the time step is 2.0 seconds. When scanning 2θ used a si target at 35 kV and 45 mA. Under the expression "does not contain whiskers" and "does not contain needle-shaped crystals," you see that thread and/or needle crystals, if present, are present in amounts that are not detectable by scanning electron microscopy (SEM). Micrograph SEM can be used to identify crystals of different morphology. Scale resolution (1 micrometer) are shown in the micrographs presented in the drawings.

Diffraction x-ray (WGR) of crystals of ZSM-48, suitable for use in the invention is such that characteristic of ZSM-48, i.e. the interplanar distances and relative intensities correspond to the values for pure ZSM-48. Although DRG can be used to establish the identity of this zeolite, its not used the ü to recognize specific morphology. For example, acicular and tabular form of the zeolite will show the same diffraction of x-rays. In order to distinguish different morphology, it is necessary to apply an analytical tool with high resolution. An example of such a tool is scanning electron microscopy (SEM). Micrograph SEM can be used for identification of crystals of different morphology.

Crystals of ZSM-48 after removal of the guide structure of the agent have a special morphology and molecular composition according to the General formula:

(n)SiO₂:Al₂O₃,

where n ranges from 70 to 110, preferably from 80 to 100, more preferably from 85 to 95. In another embodiment n is at least 70 or at least 80, or at least 85. In another embodiment n is 110 or less, or 100 or less, or 95 or less. In other embodiments Si can be replaced by Ge, a Al you can replace Ga, In, Fe, Ti, V and Zr.

The synthesized form of crystals of ZSM-48 prepared from a mixture containing silicon dioxide, aluminum oxide, basis and hexamethonium salt as the directing agent. In one embodiments the molar ratio of structural directing agent : silicon dioxide in the mixture is less than 0.05, or less than 0.025 or less of 0.022. In another embodiment the molar ratio of structural directing agent silicon dioxide in the mixture is at least 0,01, or at least 0,015, or at least 0,016. In yet another embodiment the molar ratio of structural directing agent : silicon dioxide in the mixture is between 0.015 to 0.025, preferably, from 0,016 up to 0.022. In one of the embodiments of the crystals of ZSM-48 synthesized in the form have a molar ratio of silica : alumina from 70 to 110. In another embodiment, the crystals of ZSM-48 synthesized in the form have a molar ratio of silica : alumina of at least 70 or at least 80, or at least 85. In another embodiment, the crystals of ZSM-48 synthesized in the form have a molar ratio of silica : alumina 110 or less, or 100 or less, or 95 or less. For any given method of producing crystals of ZSM-48 synthesized in the form of molar composition contains silicon dioxide, aluminum oxide and smart agent. It should be noted that the crystals of ZSM-48 in synthesized form may have a molar ratio that is slightly different from the molar relationship of the reactants of the reaction mixture used to produce the synthesized form. This may be due to incomplete engagement 100% of the reactants of the reaction mixture formed in (from the reaction mixture) crystals.

Zeolite ZSM-48 or in the annealed form, or in synthetic form usually forms agglomerates of small Krista is fishing, which may have dimensions of from about 0.01 to about 1 micrometer. These small crystals are desirable because they tend to be more active. Smaller crystals mean more surface area, which leads to a greater number of active catalytic centers on the quantity of catalyst. Preferably crystals of ZSM-48 or in the annealed form, or in synthetic form have a morphology that does not contain whiskers. Under filiform understand crystals, which have a ratio L/D>10/1, where L and D are length and diameter of the crystal. In another embodiment, the crystals of ZSM-48 or in the annealed form, or in synthetic form have a small amount or do not contain needle-shaped crystals. Under needle understand crystals, which have a ratio L/D<10/1, preferably less than 5/1, more preferably from 3/1 to 5/1. SAM shows that the crystals obtained according to the methods considered here, do not contain detectable crystals with filamentous or needle-like morphology. This morphology by itself or in combination with low relationship silica : alumina leads to catalysts having a high activity, as well as the required environmental performance.

The composition of ZSM-48 receive from the aqueous reaction mixture comprising di is xed silicon or salt of silicic acid, the aluminum oxide or soluble aluminum salt of the acid, the base and the guide agent. In order to achieve the desired crystal morphology, the reagents in the reaction mixture has the following molar ratios:

SiO₂:Al₂About₃=from 70 to 100

H₂O:SiO₂=from 1 to 500

HE^-:SiO₂=from 0.1 to 0.3

HE^-:SiO₂(preferred)=from 0.14 to 0.18

template : SiO₂=0,01-0,05

template : SiO₂(preferred)=between 0.015 to 0.025

In the above ratios given two interval values for the ratios of base : silicon dioxide and guide structure agent : silicon dioxide. Over wide ranges of values of these ratios include mixtures which lead to the formation of crystals of ZSM-48 with a number of keraita and/or crystals acicular morphology. When Kinijit and/or crystals acicular morphology junk, you should use the preferred range of values, as further illustrated below in the examples.

The source of silicon dioxide is preferably precipitated silica, industrial manufactured by Degussa. Other sources of silicon oxide include powder of silicon dioxide, including precipitated silica, such as Zeosil® and silica gels, silicic acid, colloidal dioxide, PU glue, which I such as Ludox® or dissolved silica. In the presence of a base, these other sources of silicon dioxide can form silicates. The aluminum oxide may be in the form of soluble salts, preferably salts of sodium, and it is industrially produced US Aluminate. Other suitable sources of aluminum include other aluminum salts such as the chloride, the alcoholate alumina or hydrated alumina, such as gamma-alumina, pseudoboehmite and colloidal alumina. The basis used for dissolving the metal oxide may be any alkali metal hydroxide, preferably sodium hydroxide or potassium hydroxide, ammonium hydroxide, dicerorhinus hydroxide and the like compounds. The smart agent is hexamethonium salt, such as dichloride hexammine or hydroxide hexamidine. Anion (non-chloride) may be another anion, such as hydroxide, nitrate, sulfate, other halide and similar anions. Dichloride hexammine represents dichloride, N,N,N,N',N',N'-HEXAMETHYL-1,6-hexanediamine.

In the synthesis of crystals of ZSM-48 reagents comprising a silicate salt, aluminate salt, base and guide the agent, is mixed with water in the installed above ratios and heated with stirring from 100 to 250°C. the Crystals can be formed from Reagan is s or alternatively, the seed crystals of ZSM-48 can be added to the reaction mixture. Seed crystals of ZSM-48 can be added to increase the rate of formation of the crystals, but they have no impact otherwise on the morphology of the crystal. Cooking is not involved other types of seed crystals other than ZSM-48, such as zeolite beta. Crystals of ZSM-48 is cleaned, usually by filtration, and washed with deionized water.

In one of the embodiments of the crystals obtained by synthesis according to the invention have a composition that does not contain the seed crystals other than ZSM-48, and does not contain ZSM-50. Preferably crystals of ZSM-48 containing a small amount keraita. In one of the embodiments, the number keraita may be 5% or less, or 2% or less, or 1% or less. In another embodiment, the crystals of ZSM-48 can not contain keraita.

In one of the embodiments of the crystals obtained by synthesis according to the invention, have a morphology that does not include filamentous morphology. Filamentous morphology undesirable, since the morphology of crystals inhibits the catalytic activity of ZSM-48 during dewaxing. In another embodiment of the crystals obtained by synthesis according to the invention, have a morphology that includes a small percentage of needle morphology. The number of needle crystals is morphology, present in the crystals of ZSM-48 can be 10% or less, or 5% or less, or 1% or less. In an alternative embodiment, the crystals of ZSM-48 can not contain crystals are needle-like morphology. A small amount of needle-shaped crystals is preferred for some applications, as I believe that needle crystals reduce the activity ZSM-48 in some types of reactions. To obtain the desired morphology of high purity should be used the ratio of silica : alumina, base : silicon dioxide and the guide agent : silicon dioxide in the reaction mixture according to the embodiments of the invention. Additionally, if you want composition not containing Kinijit and/or crystals are needle-like morphology, use your preferred intervals.

According to U.S. patent No. 6923949 heterostructure seed crystals other than ZSM-48, used to prepare crystals of ZSM-48 having a ratio of silica : alumina less than 150:1. According to U.S. patent No. 6923949 preparation of pure ZSM-48 with a ratio of silica: alumina up to 50:1 or less depends on the application of heterostructure seed crystals, such as seed crystals of zeolite beta.

If heterogeneous seed crystals are not used in the synthesis of ZSM-48 with a particularly bottom is their ratio of silica : alumina formation of ZSM-50 as an impurity increases. The ratio of the guide agent : silicon dioxide more than approximately 0.025 usually leads to agglomerates mixed phase containing needle-like crystals. Preferably the ratio of the guide agent : silicon dioxide is approximately 0,022 or less. When the ratios of the guide agent : silicon dioxide below about 0,015 begins the formation of the product containing Kinijit. Kinijit is an amorphous layered silicate and is a form of natural clay. He is inactive zeolite type. Instead, it is relatively inert under the reaction conditions usually present when the raw material is exposed to ZSM-48. Thus, although the presence keraita in the sample ZSM-48 is acceptable in some applications, the presence of keraita reduce the overall activity ZSM-48. The ratio of Oh : silicon dioxide (or other base : silicon dioxide) and the ratio of silica : alumina is also important for the morphology of the resulting crystals, and also for the purity of the resulting crystals. The ratio of silica : alumina is also important for catalytic activity. The ratio of base : silicon dioxide is a factor that affects the formation of keraita. Application hexamethonium directing agent is a factor to obtain the product, not terasawa filamentary material. The formation of needle-like morphology depends on the ratio of silica : alumina ratio guide structure agent : silicon dioxide.

Crystals of ZSM-48 synthesized in the form of at least partially dried before use or further processing. Drying can be accomplished by heating at temperatures from 100 to 400°C., preferably from 100 to 250°C. the Pressure may be atmospheric or below atmospheric. If the drying is performed under conditions of low vacuum, temperature can be lower than the temperature at atmospheric pressure.

The catalysts before use is usually associated with a binder or matrix material. Binder resistant required for application temperatures and resistant to abrasion. The binder may be catalytically active or inactive and include other zeolites, other inorganic materials such as clays and metal oxides such as aluminum oxide, silicon dioxide and aluminum silicate. Clay can be a kaolin, bentonite and montmorillonite, and their commercial release. They can be mixed with other materials, such as silicates. Other porous matrix materials in addition to the silicates include other binary materials such as magnesium silicate, silicate of thorium, zirconium silicate, silicate, beryllium silicate t is Tana, and ternary materials such as aluminium silicate, magnesium aluminium silicate of thorium and Zirconia aluminosilicate. The matrix may be in the form of jointly formed gel. Bound ZSM-48 can contain from 10 to 100 wt.% ZSM-48, based on the weight of the bound ZSM-48, and the rest is binding.

Crystals of ZSM-48 as part of the catalyst can also be used with metal gidratiruyuschimi component. Metal gidriruemyi components may include metals from 6-12 groups of the Periodic table (based on the IUPAC system and the group containing 1-18), preferably 6 and 8-10 of the group. Examples of such metals include Ni, Mo, Co, W, Mn, cu, Zn, Ru, Pt or Pd, preferably Pt or Pd. You can also apply a mixture of hydrogenation metals, such as Co/Mo, Ni/Mo, Ni/W, Pt/Pd, preferably Pt/Pd. The amount of metal or metals in the hydrogenation may be from 0.1 to 5 wt.%, based on the weight of the catalyst. In one embodiment, the amount of metal or metal hydrogenation is at least 0.1 wt.%, or at least 0.25 wt.%, or at least 0.5 wt.%, or at least 0.6 wt.%. or at least 0.75 wt.% In another embodiment, the amount of metal or metals is 5 wt.% or less, or 4 wt.% or less, or 3 wt.% or less, or 2 wt.% or less, or 1 wt.% or less. Methods of introduction of the metal in the catalyst is ZSM-48 is well known and is clucalc, for example, impregnation of the catalyst ZSM-48 metal salt hydrogenating component and the heat. The catalyst ZSM-48 containing a metal hydrogenation can also be sulphydrate before use. The catalyst can also be steam treated before use.

Crystals of ZSM-48 high purity, obtained according to the above embodiments, have a relatively low ratio of silica : alumina. This lower ratio of silica : alumina means that these catalysts are more acidic. Despite this increased acidity, they have an excellent activity and selectivity, as well as provide excellent outputs product. They also have environmental advantages from the point of view of health effects due to the shape of the crystal, and a small crystal size is also an advantage for catalytic activity.

In addition to the above-described embodiments in one embodiment of the invention relates to the composition of ZSM-48 high purity, having a molar ratio of silica : alumina from 70 to 110, and ZSM-48 does not contain seed crystals other than ZSM-48, and whiskers. Preferably crystals of ZSM-48 also have low levels or not at all contain needle-shaped crystals. Another embodiment relates to cu is the growth ZSM-48, which in synthesized form, include ZSM-48 having a molar ratio of silica : alumina from 70 to 110, and is formed from a reaction mixture containing hexamethonium guide the agent in a molar ratio of hexamethonium : silicon dioxide from 0.01 to 0.05, preferably between 0.015 to 0.025. In this embodiment, the crystals of ZSM-48 synthesized in the form do not contain seed crystals other than ZSM-48, and whiskers. Preferably crystals of ZSM-48 also has a low content of needle-shaped crystals, or do not contain needle-shaped crystals.

In yet another embodiment, the crystals of ZSM-48 synthesized in the form of burning, thus removing hexamethonium guide the structure of the agent for the formation of Na-form ZSM-48 high purity. This Na-form ZSM-48 can also be subjected to ion exchange with the formation of H-form ZSM-48. In yet another embodiment, the crystals of ZSM-48 in synthesized form or calcined ZSM-48 (Na-form or H-form) combined with at least one binder and a metal hydrogenation.

In yet another embodiment the invention relates to a method for producing crystals of ZSM-48, including the preparation of an aqueous mixture of silicon oxide or salt of silicic acid, aluminum oxide or aluminum salt of the acid, hexamethonium salt and an alkaline base, where the mixture has the following molar with the relationship : silica : alumina from 70 to 110, base : silicon dioxide from 0.1 to 0.3, preferably from 0.14 to 0.18 and hexamethonium Sol : silicon dioxide from 0.01 to 0.05, preferably between 0.015 to 0.025; heating the mixture under stirring for a time and at a temperature sufficient to form crystals. Maybe add seed crystals of ZSM-48 in the reaction mixture. The above procedure leads to the formation of crystals of ZSM-48 in synthesized form, which contain hexamethonium guide the structure of the agent.

Hydroperiod with ZSM-48 and other catalysts of high-performance and low-density

Catalysts for high performance and/or low density according to the invention are suitable for hydroperiod hydrocarbons. Preferred raw materials is the basis of lubricating oil. This raw material is paraphysomonas raw material, which boils in the temperature range of the boiling lubricating oil typically has a temperature acceleration 10% more than 343°C (650°F), measured according to ASTM D86 or ASTM D2887, and derived from a mineral or synthetic sources. Raw materials can be obtained from a number of sources such as oils derived from solvent cleaning processes, such as refined petroleum products, partially solvent dewaxed oils, neasfaltirovanyj oil, distillates, vacuu the major oils, the oil coking, crude waxes, oils, selected by perspiration paraffin and similar products and the wax is Fischer-Tropsch process. Preferred raw materials are crude paraffins and waxes Fischer-Tropsch process. Raw waxes are usually obtained from hydrocarbon feedstock using a dewaxing solvent or propane. Raw waxes contain some residual oil and usually degreased. Oil allocated when sweating paraffin, obtained from low-fat crude paraffin. The wax is Fischer-Tropsch produced by the process of the Fischer-Tropsch synthesis.

Raw materials may have a high content of nitrogen and sulfur impurities. Raw materials, containing up to 0.2 wt.% nitrogen, based on the weight of raw materials, and up to 3.0 wt.% sulfur can be processed this way. Sulfur and nitrogen can be measured by standard methods ASTM D5453 and D4629, respectively.

In the invention the raw material is subjected to several stages of hydroperiod. For example, raw materials can be subjected to hydrobromide, Hydrotreating or hydrogenation of aromatic compounds and then generating units. Alternative raw materials can be subjected to hydrodewaxing, and then analyze hydrobromide, Hydrotreating or hydrogenation of aromatic compounds. The above pattern can also be combined with the receiving sequence, for example, hydrobromid is, hydrodewaxing and Hydrotreating. The set of resources includes both hydroperiodide raw material, and the wax is Fischer-Tropsch process.

In one of the embodiments of the feedstock can be subjected to hydrobromide either before or after dewaxing. Conditions hydrobromide include temperatures of up to 426°C, preferably from 150 to 400°C., more preferably from 200 to 350°C.; the partial pressure of hydrogen of from 1480 to 20786 kPa (200 to 3000 psig barg), preferably, from 2859 to 13891 kPa (400 to 2000 psig barg); space velocity from 0.1 to 10 h^-1preferably from 0.1 to 5 h^-1and the ratio of hydrogen to the raw material from 89 to 1780 m³/m³(from 500 to 10000 STD. cubic feet per barrel), preferably 178 to 890 m³/m³. Preferably stage of hydrobromide performed in the same reactor, and the dewaxing, with the same gas processing and at the same temperature. Preferably between stages of hydrobromide and hydrodewaxing do not steaming. Preferably between stages of hydrobromide and hydrodewaxing does not occur heat, although heat can be removed from the reactor by a liquid or gas cooling.

Alternative raw materials can be subjected to a Hydrotreating or hydrogenation of aromatic compounds either before or after dewaxing. It is desirable to implement the guide is oocysts or hydrogenation of aromatic compounds in the product, obtained by dewaxing in order to adjust the quality of the product in accordance with the required specifications. Hydrotreating and hydrogenation of aromatic compounds represent a form of moderate hydrobromide aimed to saturate any olefins boiling range of lubricating oils and residual aromatic compounds, as well as to remove any remaining heteroatoms and coloring substances. The Hydrotreating or hydrogenation of aromatic compounds after dewaxing is performed in serial connection with the stage dewaxing. Typically, Hydrotreating or hydrogenation of aromatic compounds is performed at a temperature of from about 150°C to 350°C, preferably from 180°C to 250°C. the Total pressure typically ranges from 2859 to 20786 kPa (about 400 to 3000 psig barg). Hourly space velocity of the liquid is usually from 0.1 to 5 h^-1preferably from 0.5 to 3 h^-1and the costs of hydrogen gas for processing from 44.5 to 1780 m³/m³(from 250 to 10,000 standard cubic feet per barrel). Preferably stage Hydrotreating or hydrogenation of aromatic compounds is performed in the same reactor, and the dewaxing, with the same gas processing and at the same temperature. Preferably between stages Hydrotreating/hydrogenation of the aromatic with the of dinani and hydrodewaxing not spend steaming. Preferably between stages Hydrotreating/hydrogenation of aromatic compounds and hydrodewaxing does not occur heat, although heat can be removed from the reactor by a liquid or gas cooling.

The dewaxing conditions include temperatures of up to 426°C, preferably from 250 to 400°C., more preferably from 275 to 350°C.; a pressure of from 791 to 20786 kPa (100 to 3000 psig barg), preferably, from 1480 to 17339 kPa (200 to 2500 psig barg), hourly space velocity of the liquid is from 0.1 to 10 h^-1preferably from 0.1 to 5 h^-1and consumption of hydrogen gas for processing from 45 to 1780 m³/m³(from 250 to 10,000 standard cubic feet per barrel), preferably from 89 to 890 m³/m³(from 500 to 5000 standard cubic feet per barrel).

Sequential processing of raw materials

In yet another embodiment of the high-performance catalysts can be used for "processing" raw materials. Sequential processing of raw materials refers to the application of the technological line for processing two or more materials with different properties, without requiring modification of the catalyst or equipment in the process line. As an example, a production line containing the catalyst hydrobromide and the dewaxing catalyst can be applied to GI is repairerbots light neutral source material with the first paraffinicity, such as 15%. In the scheme of processing the same production line can be applied for processing of other raw materials such as raw materials with paraffinicity 50% or more, without modifying the operating conditions of the technological line. The consumption of raw materials (hourly space velocity of the liquid, CHOSI), the catalyst, the flow rate of the hydrogen gas to be processed, the total partial pressure of H₂at the entrance of the reactor and process line remain the same. The temperature of the processing of two different types of raw materials differ at 35°C or less, or 30°C or less, or 20°C or less, or 10°C or less, or preferably use the same temperature profile for processing two different types of raw materials. Although the economic benefits of schema processing have been previously recognized, previous attempts at processing were not successful to produce high-quality base oils. Using high-performance catalysts according to the invention, the circuit processing on the production line can be used to handle very different types of raw materials, at the same time maintaining a high quality base oils.

EXAMPLES

Example 1

Prepare a mixture of 1200 g of water, 40 g of chloride hexadecane (56% solution), 228 g of Ultrasil PM (powder precipitated silica produced egussa), 12 g of sodium aluminate solution (45%) and 40 g of 50%sodium hydroxide solution. The mixture had the following molar composition:

SiO₂/Al₂O₃=106

H₂O/SiO₂=20,15

OH^-/SiO₂=0,17

Na⁺/SiO₂=0,17

Template/SiO₂=0,023

The mixture was subjected to reaction at 160°C (320°F) in a two-liter autoclave with stirring at 250 rpm for 48 hours. Specialist in the art it is clear that factors such as the size of the autoclave and the type of mixing device, can provide the other of the stirring speed and the required time of mixing. The product was filtered, washed with deionized (DI) water and dried at 120°C (250°F). DRG material in the synthesized form showed the typical pure phase topology of ZSM-48. SAM material in the synthesized form shows that the material consists of agglomerates of crystals mixed morphology (needle crystals and crystals of irregular shape). The obtained crystals of ZSM-48 had a molar ratio of SiO₂/Al₂O₃~ 100/1. Figure 1 is a micrograph of crystals of ZSM-48. This comparative example with respect to template : silicon dioxide, comprising 0,023, shows the presence of a certain amount of needle-shaped crystals.

Example 2

Prepare a mixture of water, chloride hexadecane (56% solution), Ultrasil RM, the solution is sodium aluminate (45%) and 50%aqueous sodium hydroxide solution. The mixture had the following molar composition:

SiO₂/Al₂O₃=106

H₂O/SiO₂=20,15

OH^-/SiO₂=0,17

Na⁺/SiO₂=0,17

Template/SiO₂=0,018

The mixture was subjected to reaction at 160°C (320°F) in an autoclave with stirring at 250 rpm for 48 hours. The product was filtered, washed with deionized (DI) water and dried at 120°C (250°F). DRG material in the synthesized form showed the typical pure phase topology of ZSM-48. SAM material synthesized in the form indicates that the material is composed of agglomerates of small crystals of irregular shape (with an average crystal size of about 0.05 microns). The obtained crystals of ZSM-48 had a molar ratio of SiO₂/Al₂O₃~ 94/1. Figure 2 is a micrograph of the obtained crystals of the ZSM. Figure 2 shows that in ZSM-48 according to the invention there are no needle crystals.

Example 3

Prepare a mixture of water, chloride hexadecane (56% solution), Ultrasil Modified, sodium aluminate solution (45%), 50%sodium hydroxide solution and 5 wt.% (relative loading of silicon dioxide) seed crystals of ZSM-48. The mixture had the following molar composition:

SiO₂/Al₂O₃=103

H₂O/SiO₂=14,8

HE^-/SiO₂=0,17

Na⁺/SiO₂=0,17

Template/SiO₂=0,029

The mixture was subjected to re the options at 160°C (320°F) in an autoclave with stirring at 250 rpm for 48 hours. The product was filtered, washed with deionized (DI) water and dried at 120°C (250°F). DRG material in the synthesized form showed the typical pure phase topology of ZSM-48. SAM material in the synthesized form shows that the material consists of agglomerates of elongated needle crystals (with an average size of crystal <1 μm). The obtained crystals of ZSM-48 had a molar ratio of SiO₂/Al₂About₃~ 95/1. Figure 3 is a micrograph of the obtained crystals of the ZSM. This comparative example shows the presence of needle-shaped crystals for ZSM-48 synthesized from the reaction mixture, with respect to template : silicon dioxide, comprising 0,029.

Example 4

Prepare a mixture of water, chloride hexadecane (56% solution), Ultrasil Modified, sodium aluminate solution (45%), 50%sodium hydroxide solution and 5 wt.% (relative loading of silicon dioxide) seed crystals of ZSM-48. The mixture had the following molar composition:

SiO₂/Al₂O₃=103

H₂O/SiO₂=14,7

OH^-/SiO₂=0,17

Na⁺/SiO₂=0,17

Template/SiO₂=0,019

The mixture was subjected to reaction at 160°C (320°F) in an autoclave with stirring at 250 rpm for 24 hours. The product was filtered, washed with deionized (DI) water and dried at 120°C (250°F). DRG material in the synthesized form showed the type is know pure phase topology of ZSM-48. SAM material synthesized in the form indicates that the material is composed of agglomerates of small crystals of irregular shape (with an average crystal size of about 0.05 microns). The obtained crystals of ZSM-48 had a molar ratio of SiO₂/Al₂O₃equal to 89. Figure 4 is a micrograph of the obtained crystals of the ZSM. This example ZSM-48 crystals according to the invention shows the absence of needle-shaped crystals.

Example 5

Prepare a mixture of water, chloride hexadecane (56% solution), Ultrasil Modified, sodium aluminate solution (45%), 50% sodium hydroxide solution and 3.5 wt.% (relative loading of silicon dioxide) seed crystals of ZSM-48. The mixture had the following molar composition:

SiO₂/Al₂O₃=103

H₂O/SiO₂=14,6

OH^-/SiO₂=0,17

Na⁺/SiO₂=0,}7

Template/SiO₂=0,015

The mixture was subjected to reaction at 160°C (320°F) in an autoclave with stirring at 250 rpm for 48 hours. The product was filtered, washed with deionized (DI) water and dried at 120°C (250°F). DRG material in the synthesized form showed a mixture of ZSM-48 and traces keraita as an impurity.

Example 6

Prepare a mixture of water, chloride hexadecane (56% solution), Ultrasil Modified, sodium aluminate solution (45%), 50% sodium hydroxide solution and 3.5 wt.% (relative to load dioxide is Rennie) seed crystals of ZSM-48. The mixture had the following molar composition:

SiO₂/Al₂O₃=102,4

H₂O/SiO₂=14,8

OH^-/SiO₂=0,20

Na⁺/SiO₂=0,20

Template/SiO₂=0,019

The mixture was subjected to reaction at 160°C (320°F) in an autoclave with stirring at 250 rpm for 48 hours. The product was filtered, washed with deionized (DI) water and dried at 120°C (250°F). DRG material in synthesized form, synthesized from the reaction mixture with the ratio of base : silicon dioxide, comprising 0,20, showed a mixture of ZSM-48 and impurities keraita.

Example 7

Prepare a mixture of water, chloride hexadecane (56% solution), Ultrasil PM, sodium aluminate solution (45%), 50% sodium hydroxide solution and 3.5 wt.% (relative loading of silicon dioxide) seed crystals of ZSM-48. The mixture had the following molar composition:

SiO₂/Al₂O₃=102,4

H₂O/SiO₂=14,8

OH^-/SiO₂=0,15

Na⁺/SiO₂=0,15

Template/SiO₂=0,019

The mixture was subjected to reaction at 160°C (320°F) in an autoclave with stirring at 250 rpm for 48 hours. The product was filtered, washed with deionized (DI) water and dried at 120°C (250°F). DRG material in the synthesized form showed the typical pure phase topology of ZSM-48.

Example 8

Prepare a mixture of water, chloride hexadecane (56% solution), Ultrasil PM of sodium aluminate solution (45%) and 50% sodium hydroxide solution. The mixture had the following molar composition:

SiO₂/Al₂O₃=90

H₂O/SiO₂=20,1

HE^-/SiO₂=0,17

Na⁺/SiO₂=0,17

Template/SiO₂=0,025

The mixture was subjected to reaction at 160°C (320°F) in an autoclave with stirring at 250 rpm for 48 hours. The product was filtered, washed with deionized (DI) water and dried at 120°C (250°F). DRG material in the synthesized form showed the typical topology of ZSM-48 and found traces of impurities ZSM-50. In the product detected a certain number of crystals acicular morphology.

Example 9

65 parts of crystals of ZSM-48 high activity (initial condition: calcined at 538°C.) (Example 4) was mixed with 35 parts of aluminum oxide in the form of pseudoboehmite (initial condition: calcined at 538°C) in the edge-runner mills Simpson. Was added sufficient water to obtain a paste extrudable in two-inch Bonnot extruder. A mixture of ZSM-48 and aluminum oxide in the form of pseudoboehmite in the form of aqueous paste was extrudible and dried in an oven electrotherapy exercising at 121°C during the night. The dried extrudate was annealed in nitrogen at a temperature of 538°C. to decompose and remove the organic template. Annealed in N₂the extrudate was moistened in a saturated moisture to the air and subjected to ion exchange with 1H. the ammonium nitrate to remove sodium (technical requirements: <500 frequent the th per million Na). After ion exchange with ammonium nitrate extrudate was washed with deionized water to remove any residual nitrate ions before drying. Subjected to ammonium ion exchanged extrudate was dried at 121°C during the night and was annealed in air at 538°C. After firing in air extrudate was treated with water vapor for 3 hours at 482°C (900°F). Treated water vapor extrudate was impregnated with nitrate tetraamine platinum (0.6 wt.% Pt)using the initial wetness. The impregnated extrudate was dried overnight at 121°C (250°F) and was annealed in air at 360°C for the conversion of the nitrate salt of tetraamine in the oxide of platinum.

Example 10

Conducted testing of the dewaxing catalyst of example 9 at hydroisomerization n-C₁₀. The temperature of the catalyst was changed from 162 to 257°C in a stream of H₂(standard 100 cm³at a pressure of 0.1 MPa (1 ATM) for regulating the degree of conversion of n₁₀from 0 to 95%+. The catalyst containing highly active ZSM-48, showed excellent outputs ISO-C₁₀with minimal cracking, depending on the degree of conversion of n₁₀and the reaction temperature. Figure 5 shows a graph of the dependence of the yield of ISO-C₁₀the degree of conversion of h₁₀for the catalyst according to the embodiment of the invention and catalyst with a ratio of silica : alumina of about 200.

the example 11

This example relates to the preparation of VA (high level) - ZSM-48 seed containing crystals of ZSM-48 of the correct form. The mixture is prepared using water, chloride hexadecane (56% solution), Ultrasil PM, the sodium aluminate solution (45%) and 50% sodium hydroxide solution. Then add about 5 wt.% (relative loading of silicon dioxide) seed crystals of ZSM-48. The mixture had the following molar composition:

SiO₂/Al₂O₃=103

H₂O/SiO₂=14,7

OH^-/SiO₂=0,17

Na⁺/SiO₂=0,17

Template/SiO₂=0,019

The mixture was subjected to reaction at 160°C (320°F) in an autoclave with stirring at 250 rpm for 24 hours. The product was filtered, washed with deionized (DI) water and dried at 120°C (250°F). DRG material in the synthesized form showed the typical topology of a pure phase ZSM-48. The crystals in the synthesized form was converted into the H-form by two ion exchange with a solution of ammonium nitrate at room temperature, after which it was carried out by drying at 120°C (250°F) and calcination at 540°C (1000°F) for 6 hours. The obtained crystals of ZSM-48 had a molar ratio of SiO₂/Al₂O₃~ 88,5/1.

Example 12

This example shows the preparation of ZSM-48 seed crystals when using 5 wt.% (relative loading of silicon dioxide) beta crystals. Heterostructure the seed using beta crystals are described in U.S. patent No. 6923949. The mixture were prepared from 1000 g of water, 25 g of chloride hexadecane (56% solution), 190 g of Ultrasil PM (powder precipitated silica manufactured by Degussa), 10 g of sodium aluminate solution (45%) and 33.3 g of 50% sodium hydroxide solution. Then added 10 g of beta seed crystals (SiO₂/Al₂O₃~ 35/1). The mixture had the following molar composition:

SiO₂/Al₂O₃=106

H₂O/SiO₂=20

OH^-/SiO₂=0,17

Na⁺/SiO₂=0,17

Template/SiO₂=0,018

The mixture was subjected to reaction at 160°C (320°F) in an autoclave with a capacity of 2 l with stirring at 250 rpm for 48 hours. The product was filtered, washed with deionized (DI) water and dried at 120°C (250°F). DRG material in the synthesized form showed a net phase topology of ZSM-48. Clearly watched the absence of beta phase on DRG synthesized product. The crystals in the synthesized form was converted into the hydrogen form by two ion exchange with a solution of ammonium nitrate at room temperature, after which it was carried out by drying at 120°C (250°F) and calcination at 540°C (1000°F) for 6 hours. The obtained crystals of ZSM-48 had a molar ratio of SiO₂/Al₂O₃~ 87,2.

Example 13

This example shows the preparation of ZSM-48 using diluted with 10 wt.% (relative loading of silicon dioxide) beta seed crystals. Ispolzovanie same reagents, the composition and order of operations as in example 2, except that the added double the amount of beta crystals as seed. DRG material in the synthesized form showed a net phase topology of ZSM-48. Clearly watched the absence of beta phase on DRG synthesized product. The crystals in the synthesized form was converted into the hydrogen form by two ion exchange with a solution of ammonium nitrate at room temperature, after which it was carried out by drying at 120°C (250°F) and calcination at 540°C (1000°F) for 6 hours. The obtained crystals of ZSM-48 had a molar ratio of SiO₂/Al₂O₃~ 80/1.

Example 14

Conducted testing of the products of examples 11-13 on the adsorption of hexane. Tests on the adsorption of hexane is a measure of pore volume for any of the considered catalyst. The calcined catalysts prepared as above, was heated in an apparatus for thermogravimetric analysis (TGA) in nitrogen atmosphere at 500°C for 30 minutes. The dried catalyst was then cooled to 90°C. and was subjected to n-hexane at a partial pressure of 10⁴PA (75 Torr). The change in mass as the absorption of n-hexane was measured on a microbalance in the instrument TGA. For each crystal were also determined by the alpha index. The alpha index for the catalyst is a standardized measure of Catalytica is some activity relative to the activity of the catalyst of comparison. The results are presented in table 1.

Based on the data presented in table 1, we can conclude that dobavlen the e beta seed crystals does not melt during crystallization and remained in the synthesized product. The conclusion is supported by data showing an increase in the adsorption of n-hexane in examples 12 and 13. The conclusion is also confirmed by the increase in alpha as the percentage of beta crystals increases. The increase in the adsorption of n-hexane and alpha index shows that the crystals of ZSM-48 with heterogeneous seed crystal has a different reactivity than the crystals of ZSM-48 with a homogeneous seed crystals.

Note that the alpha index is a rough measure of the activity of the catalyst during catalytic cracking, compared to a standard catalyst and it gives the relative rate constant of reaction (rate of conversion of normal hexane to volume of catalyst per unit time). It is based on the activity of the highly active silica-alumina cracking catalyst taken for the alpha of 1 (rate constant for the reaction = 0,016 sec^-1). Test with determination of the rate of alpha-known in the prior art and described, for example, in U.S. patent No. 3354078; in Journal of Catalysis, vol.4, p.527 (1965); vol.6, p.278 (1966) and vol.61, p.395 (1980).

Example 15

In this example, compare the additional activity ZSM-48 according to the invention compared to ZSM-48 with a higher ratio of silica : alumina. 600N crude paraffin was deparaffinization when 6996 kPa (1000 psi), CASE equal to 1.0 l/h, and gas consumption for processing 445 m³/m³(2500 standard cubic feet per barrel). Figure 6 presents a graph showing the dependence of the temperature of the reactor to the temperature required to meet the requirements of the freezing temperature of 370°C.+. Figure 6 the difference between the top line (representing ZSM-48 with a higher ratio of silica : alumina) and bottom line (representing ZSM-48 with a lower ratio of silica : alumina) is an optional activity.

Example 16

This example shows the difference between option ZSM-48 having a ratio of SiO₂:Al₂O₃less than 110, and options ZSM-48 having a ratio of SiO₂:Al₂O₃more than 110. These two options ZSM-48 can be called ZSM-48 with a low ratio and ZSM-48 with a high ratio. 7 shows the dependence of the freezing temperature from the temperature for ZSM-48 with a high ratio and low ratio. As shown in Fig.7, ZSM-48 with a low ratio has a significantly lower temperature curing at ordinary temperatures hydroperiod comprising more than 300°C. note that the temperature is plotted on the x-axis is the estimated internal temperature (OVT). The advantages of ZSM-48 with a low ratio are additionally shown in Fig, which marked a pour point of hanging the basis of the viscosity index for fractions 370°C+, obtained from the processed raw materials. On Fig for ZSM-48 with a low ratio can be achieved more favorable combinations pour point and viscosity index.

Example 17 (MCM-41 with low density and high activity followed by Pt ZSM-48 with a low density and high activity)

In figures 9 and 10 show examples of raw materials which were subjected to hydroperiod by the impact of raw materials at the beginning catalytic hydrogenation of aromatic compounds, and then dewaxing catalyst. For the hydrogenation of aromatic compounds, one or two of the used catalyst was an industrially produced a catalyst having 0.3 wt.% Pt and 0.9 wt.% Pd deposited on silicon dioxide and/or aluminum oxide. Another shows the catalyst is a variant associated with alumina, MCM-41 with a low density, impregnated with 0.3 wt.% Pt and 0.9 wt.% Pd. This linked aluminum oxide MCM-41 has a density of less than 550 kg/m³. For hydrodewaxing shows two types of catalysts Pt-ZSM-48. One type of Pt-ZSM-48 has a ratio of SiO₂:Al₂O₃more than 110. Another type is the ratio of SiO₂:Al₂O₃in the catalyst is from about 70:1 to about 110:1. ZSM-48 with a low ratio of silica : alumina obtained without the use of heterogeneous seed crystals. In figures 9 and 10 JV the property And refers to the processing of raw materials using industrial catalyst Pt/Pd on silica and/or alumina, and then Pt-ZSM-48 with a high ratio. The method relates to the processing of raw materials with the use of Pt/Pd on the associated aluminum oxide MCM-41, and then the Pt-ZSM-48 with a low ratio. The method relates to the processing of raw materials with the use of industrial catalyst Pt/Pd on silica and/or alumina, and then the Pt-ZSM-48 with a low ratio.

Figure 9 shows the performance curves for various combinations of catalysts acting on 150N raw materials, processed by hydrocracking. Figure 9 shows the combination of pour point and viscosity index, which can be achieved at different operating temperatures. For 150N raw materials associated with alumina, MCM-41, after which use the Pt-ZSM-48 with a low ratio (ratio of SiO₂:Al₂About₃less than 110), shows an average of the lowest combination of values of the pour point and viscosity index. This trend is more pronounced in Figure 10, which shows the pour point and viscosity index for processing 500N raw materials, processed by hydrocracking.

Example 18

On 11 and 12 presents additional evidence of the advantages of the catalysts with low density and high activity, such as associated with aluminum oxide or titanium dioxide MSM-41. Figure 11 shows data for different 150N raw materials derived from hydrocracking, last the dewaxing with a ratio of SiO ₂:Al₂About₃from 70 to 110 at a given temperature. On Fig shows the same data for 500N raw material, obtained from hydrocracking. As shown in 11 and 12, dewaxed raw material is additionally subjected to the hydrogenation of aromatic compounds, or the effects of Hydrotreating catalyst. Shows two types of industrial catalysts containing Pt and Pd supported on alumina. One of the catalysts is from 0.3 wt.% Pt and 0.9 wt.% Pd on a carrier of silica and/or alumina. Also includes the option of "high metal content of this catalyst, which contains approximately twice as much Pt and Pd on a substrate of silicon dioxide and/or aluminum oxide. Also shown are two types of MCM-41 catalysts, the choice of catalyst associated with alumina and catalyst associated with titanium dioxide. MCM-41 catalysts include 0.3 wt.% Pt and 0.9 wt.% Pd.

Figure 11 catalysts MCM-41 show superior results for the hydrogenation of aromatic compounds, in comparison with the catalyst of 0.3 wt.% Pt / a 0.9 wt.% Pd on aluminum oxide for all temperatures above 300°C and comparable results at temperatures below 300°C. the higher the metal content of the catalyst of 0.6 wt.% Pt / 1.8 wt.% Pd on aluminum oxide shows comparable results for catalysts MCM-41 at temperatures above 300°C. Improvements to the made in the application of MCM-41, more pronounced on Fig.

In addition to providing comparable or improved reactivity of the catalysts MCM-41 used in the experiments shown in 11 and 12, have significantly reduced the metal content because of the lower density of the substrate MSM-41. The metal content in the catalyst MCM-41 is also lower compared to industrial catalyst with high metal content, as shown at 11 and 12. As a result, the catalyst MCM-41 instead of the usual associated aluminum oxide industrial catalyst allows to save costs when operations on catalyst loading.

Example 19 (scheme processing)

As described, in the present invention using the catalysts of hydroisomerization with high activity, such as ZSM-48, which have sufficient activity to ensure that the processing of raw materials with a large difference in paraffinicity in the same block. Moreover, this increased activity can be used for processing raw materials with a higher content of nitrogen in combination with higher paraffinicity. Because of the lower operating temperatures of this invention achieve lower outputs of the dry gas, which, in turn, simplifies the design of the equipment is.

In the invention using the catalyst based on the ZSM-48 zeolite from 40 to 80% and a content of metals of group VIII, individually or in combination, from 0.3 to 1.5 wt.%, and a ratio of silicon dioxide and aluminum oxide less than 110 to 1. The preferred range of the content of the zeolite is from 50 to 70% with platinum concentration from 0.3 to 0.8% and the ratio of SiO₂/Al₂O₃below is 110 to 1.

In one embodiment of the invention can be used for processing raw materials paraffinicity varying within wide limits, on the same production line, while maintaining the desired characteristics of the product. Preferably the temperature at the stage hydrodewaxing process for both types of raw materials is 365°C. or below. For example, the method according to the invention can be applied to hydroperiod first raw material with the first paraffinicity. The second raw material with the second paraffinicity can then be processed without modifying the configuration of the production line. In particular, the catalyst used in the process of hydroisomerization, is the same for both processes. In embodiments that use an additional stage of hydroperiod, preferably catalysts for additional stages of hydroperiod also remain the same.

In one embodiment the first prefinished which may differ from the second paraffinicity at least 15%, or at least 20%or at least 25%, or by at least 30%. In another embodiment the first paraffinicity may differ from the second paraffinicity 80% or less, or 75% or less, or 70% or less or 60% or less, or 50% or less. Preferably each raw material has paraffinicity at least 10%or at least 15%or at least 20%.

In one of the embodiments of both types of materials have a pour point after hydroisomerization processing -10°C or less, or -12°C or less, or -15°C or less, or -18°C or less, or -20°C or less. In another embodiment, the pour point of both types of raw materials after hydroisomerization processing is at least -50°C., or at least -40°C., or at least -30°C.

In one embodiment, the process temperature of hydroisomerization for both types of raw materials is 365°C. or less, 360°or less, 350°C or less. The temperature for processing the first raw material preferably is not more than 35°C from the temperature of the second material, or in the range of 30°C., or not more than 20°C., or not more than 10°C. Alternatively, the temperature profile for the processing of two types of raw materials is the same. In one embodiment the yield of dry gas in the process of hydroisomerization each raw material is 5% or less, or 4% or less, or 3% or less, or 2%, or men who that is

In yet another embodiment, the raw materials can be described in connection with the selected catalyst, for example, raw materials can be characterized on the basis of the temperature of the processing required to achieve the desired pour point when the process is run hydroisomerization with the use of a specific catalyst. For example, raw materials can be classified in relation to the temperature of hydroisomerization necessary to achieve the desired properties, such as pour point, when using a specific catalyst, such as Pt-ZSM-48. In one embodiment, the raw materials can be classified as requiring temperature hydroisomerization at least 285°C, but less than 315°C., or at least 315°C, but less than 340°C., or at least 340°C., but less than 365°C., to achieve a pour point of -15°C. For simplicity, each of these classifications can be classified processing with the use of ZSM-48.

In this embodiment, the raw materials from different classes can be processed on the production line, only by changing the operating temperature. For example, the source material, classified as requiring a temperature of 285°to 315°C, can be processed in a production line. The temperature on the production line can then be increased and can be recycled source material class from 315°C. to 345°C.

In the data presented is built in the following tables And In and applied the dewaxing catalyst with low density and high activity (Pt-ZSM-48 with a ratio of silicon dioxide and aluminum oxide from 70 to 110) for generating units after the initial hydrobromide with conventional catalyst hydrobromide containing Pt/Pd on aluminum oxide. The catalyst hydrobromide approximately 15% of the volume of the catalyst. In table a presents the characteristics of four different types of raw materials. In the table In detail the conditions hydroisomerization used for each type of raw material. Table shows the quality control of the product for heavy lubricating oil and light lubricating oil from the processing of raw materials under certain conditions hydroisomerization.

In the example above, by comparing the required reaction temperatures (hydroisomerization) depending on paraffinicity can be seen that for light neutral(LN) raw paraffin, and LF product of hydrocracking required raising the temperature of the reactor is approximately 0,47°C 1% increase paraffinicity raw materials. This is an improvement compared to conventional technologies, which required raising the temperature of the reactor by 0.65°C or more, to compensate for the increase in paraffinicity raw materials 1%. A smaller increase in the temperature of the reactor for the processing of raw materials with higher paraffinicity, as shown in the tables above, it means that it is possible to apply a lower operating temperature for the processing of raw materials with higher paraffinicity. In the above table also shows significantly lower gas output, partly due to the type of catalyst and partially due to a lower required temperatures. This allows to improve the yield in the processing of raw materials with high paraffinicity. Due to their improved performance processing method according to the invention, it is possible even higher paraffinicity to 100%, for example processing of natural gas into synthetic liquid fuels (GTL).

1. A method of obtaining a base oil, comprising:
providing a first catalyst comprising at least one metal of group VIII supported on a carrier of M41S catalyst, such as MCM-41, and having a density of 600 kg/m³or less;
the provision in the showing of the catalyst, comprising at least one metal of group VIII, with performance when dewaxing sufficient to ensure flow of light neutral (150N) hydrocarbons from hydrocracking medium pressure, having a kinematic viscosity at 100°C. of less than 5, and the final boiling point of less than 550°C, 320°C, and time volumetric liquid velocity (COSI)1 h^-1, obtaining a base oil having a pour point less than -15°C;
the conversion of raw materials into contact with a first catalyst under effective conditions for the processing of raw materials, and these effective conditions are effective for one process selected from hydrobromide, Hydrotreating or hydrogenation of aromatic compounds, and
bringing the processed raw materials into contact with a second catalyst under conditions effective for dewaxing the processed raw materials.

2. The method according to claim 1, wherein the dewaxing catalyst comprises ZSM-48 with a ratio of SiO₂:Al₂About₃comprising from about 70 to about 110.

3. The method according to claim 1, wherein the dewaxing catalyst has a density of 600 kg/m³or less.

4. The method according to claim 1, wherein the first catalyst has a density of 550 kg/m³or less.

5. The method according to claim 1, wherein the first catalyst has a density of 500 kg/m^{3 or less.}

^{6. The method according to claim 1, wherein the first catalyst comprises at least one metal of group VIII selected from Pt, Pd and mixtures thereof.}

^{7. The method according to claim 6, in which the first catalyst comprises at least 0.5 wt.% at least one metal of group VIII.}

^{8. The method according to claim 1, further comprising bringing deparaffinizing processed raw materials in contact with the third catalyst under conditions effective for Hydrotreating or hydrogenation of aromatic compounds, and the specified third catalyst has a density of 600 kg/m3or less.}

9. The method according to claim 8, in which the third catalyst comprises MCM-41.

10. The method according to claim 8, in which the third catalyst has a density of 550 kg/m³or less.

11. The method according to claim 8, in which the third catalyst comprises at least one metal of group VIII selected from Pt, Pd and mixtures thereof.

12. The method according to claim 8, in which the third catalyst comprises at least 0.5 wt.% at least one metal of group VIII.

13. A method of obtaining a base oil, comprising:
bringing raw materials in contact with the first catalyst and said first catalyst comprises at least one metal of group VIII supported on a carrier of M41S catalyst, such as MCM-41, and has a density of 600 kg/m³or less, at effective conditions for the processing of raw materials, and specified the haunted effective conditions are effective for one process, selected from hydrobromide, Hydrotreating or hydrogenation of aromatic compounds, and
bringing the processed raw materials into contact with a catalyst comprising ZSM-48 with a ratio of SiO₂:Al₂O₃comprising from about 70 to about 110, and a metal hydrogenation component under conditions effective for dewaxing the processed raw materials.