Hydrotreatment using mixtures of zsm-48 catalysts

FIELD: chemistry.

SUBSTANCE: invention relates to hydrotreatment processes. Described is a method of removing paraffin from hydrocarbon material, involving reacting the material with a mixture of ZSM-48 catalysts under catalytic paraffin removal conditions for producing material from which paraffin has been removed, where the mixture of ZSM catalysts contains: a) first type ZSM-48 crystals, having molar ratio of silicon dioxide to aluminium oxide equal to 70-110 and containing inoculating crystals different from ZSM-48, and b) second type ZSM-48 crystals which differ from first type ZSM-48 crystals on one or more properties selected from presence of inoculating crystals different from ZSM-48, crystal morphology, higher kenyaite percentage and higher molar ratio of SiO2 to Al2O3.

EFFECT: high efficiency of removing paraffin from hydrocarbon material owing to use of a a highly active catalyst.

16 cl, 1 tbl, 6 dwg, 15 ex

 

The present invention relates to processes, including mixtures of catalysts ZSM-48.

The LEVEL of TECHNOLOGY

The demand for primary raw materials of high quality for the production of engine oils and other lubricants increases due to the increasing importance of environmental issues. The main raw materials affected by the requirements that must meet the requirements of Group II and Group III. So the pressure for the production of basic raw materials must meet the requirements of viscosity index (VI), the parameters of viscosity, temperature fluidity and/or volatility are subject to government regulations and requirements of the real manufacturers. The increasing demands for high quality basic raw material is restrained only cost-effective cleaning solvent. Even when using additives developed oils require the use of basic raw material of high quality in order to meet the requirements of modern engines. In addition, the sources of crude oil, rich in paraffins, limited.

Catalytic dewaxing is designed as an alternative to methods based on solvent, to produce high-quality basic raw material. The effect of dewaxing catalysts based on two mechanisms:

some catalysts Deiss who are mostly on isomerization, other when carrying out hydrocracking. There are few catalysts for dewaxing, if any such exist, with the ability to work exclusively with one of these mechanisms, excluding the other. Dewaxing through the hydrocracking may be carried out using the raw materials of relatively low quality. However, these raw materials generally requires more stringent reaction conditions to achieve the required quality of the final product, and this leads to a lower yield of the final product and the additional operations of the production process to reduce unwanted particles produced during the hydrocracking.

The dewaxing catalysts, which operate mainly through isomerization, turn paraffin molecules in molecules with branched chain. Molecules with branched-chain can have properties that are desirable for YVES and temperature fluidity. ZSM-48 is an example of such a catalyst dewaxing. As noted in U.S. patent No. 5075269, ZSM-48 are made using dichloride ammonium compounds as directing agents. And guide the agent and the ratio of silica:alumina may affect the morphology of the crystal, although the choice of the sending agent is the stronger influence. When using diamino and terminologia upravlyayuschego agent obtained plochodrazni or needle crystals. At high relationship silica:alumina and when using the smart agent-based dicatating ammonium, resulting ZSM-48 has a lamellar morphology. If the ratio of silica:alumina is reduced using the techniques described in U.S. patent No. 5075269 or in U.S. patent No. 6923949, the purity of the crystals is becoming more of a problem, so how do I get a competitive form of crystals other than ZSM-48 or ZSM-48 contains a heterogeneous grain zeolite.

It is known that the morphology of the crystals can affect the behavior of the catalyst, especially on its activity and stability. Usually it is desirable to have small crystals because the crystals of smaller size provides greater activity and stability due to the greater surface area for a given amount of catalyst.

It would be a great advantage to have crystals of ZSM-48, which could be produced with high purity and which would have a high activity for use as a catalyst for the manifestation of a suitable morphology.

A BRIEF summary of the INVENTION

In one of the embodiments of the invention, a method of dewaxing a hydrocarbon feedstock. The method includes the interaction of materials with a mixture of catalysts ZSM-48 under conditions of catalytic dewaxing for the CSOs, to make deparaffinization raw materials, the mixture of catalysts ZSM-48 includes:

(a) crystals of ZSM-48 of the first type, having a molar ratio of silica:alumina from 70 to 110 and does not contain non-ZSM-48 seed crystals, and

b) crystals of ZSM-48 of the second type, and the crystals of ZSM-48 of the first type are different from crystals of ZSM-48 of the second type.

Description of the DRAWINGS

Figure 1. Micrograph of crystals of ZSM made with respect to template:silicon dioxide, equal 0,023 illustrating the presence of a certain amount of needle-shaped crystals.

Figure 2. Micrograph showing the absence of needle-shaped crystals in crystals of ZSM-48, obtained from the reaction mixture with respect to template:silicon dioxide, equal 0,018.

Figure 3. Micrograph showing the presence of needle-shaped crystals in crystals of ZSM-48, obtained from the reaction mixture with respect to template:silicon dioxide, equal 0,029.

Figure 4. Micrograph showing the absence of needle-shaped crystals in crystals of ZSM-48, obtained from the reaction mixture with respect to template:silicon dioxide, equal 0,019.

Figure 5. The dependence of the yield of ISO-C10 conversion of n-C10.

6. The dependence of the temperature in the reactor temperature required to match the temperature fluidity 370°With+.

DETAILED description of the INVENTION

The variety of the EIT embodiments of the invention relate to methods of hydrobromide with catalysts, includes mixtures of two or more types of crystals of ZSM-48. In particular, the invention relates to mixtures of catalyst ZSM-48, where at least part of the ZSM-48 is a new type of high purity ZSM-48 having a ratio of SiO2:Al2O3less than 110 and does not contain non-ZSM-48 seed crystals. This new type crystals of ZSM-48 has a higher activity compared with crystals of ZSM-48 other types.

A mixture of crystals of ZSM-48 two or more types with different activity to help you tailor the processes to provide the desired activity at the required temperature. This adjustment activity can be achieved without the occurrence of undesirable side reactions, which otherwise can be enhanced with the introduction of another type of catalyst, such as zeolite catalyst of another type.

Synthesis of high purity ZSM-48 with respect to SiO2: Al2About3less than 110

In various embodiments of this invention is a mixture of crystals (or catalysts) ZSM-48 different types. In such embodiments, at least a portion of the mixture includes a catalyst consisting of high-purity, specific morphology of crystals of ZSM-48 having a ratio of SiO2:Al2O3equal to 110 or less, and these high-purity crystals of ZSM-48 does not contain non-ZSM-48 seed crystals. Preferably, in somocista crystals of ZSM-48 is not also contain crystals of ZSM-50. As described below, high-purity crystals of ZSM-48 with respect to SiO2:Al2O3110 or less have higher activity than the crystals of ZSM-48 another type.

In the following embodiment of the invention, the crystals of ZSM-48 describes variously as "crystals synthesized in the form", i.e. crystals that contain more organic template; "calcined crystals", i.e. such as Na-form crystals of ZSM-48; or calcined and subjected to ion exchange crystals", i.e. such as N-form crystals of ZSM-48.

The term does not include non-ZSM-48 seed crystals" means that the reaction mixture used for the formation of crystals of ZSM-48, does not contain differing from ZSM-48 seed crystals. Instead, the crystals of ZSM-48 synthesized in accordance with the invention, synthesized or without the use of seed crystals, or by using seed crystals of ZSM-48 for the formation of nuclei of crystallization. The term "does not contain keraita and ZSM-50" means that Kinijit and ZSM-50, if present, in amounts undetectable by x-ray diffraction analysis. Similarly, high-purity crystals of ZSM-48 according to the invention also does not contain non-ZSM-48 crystals in the sense that they are not detected by x-ray diffraction analysis. This assessment of what was done with the help of the apparatus Bruker D4 Endeavor production Bruker AXS, equipped with high-speed detector Vantec-1. The device worked when using standard silicon powder (Nist V), which is the material without internal stresses. The full-width half-maximum (fwhm) for the standard peak when 28,44 degrees 2 Θ is 0,132. The step value is 0,01794 degrees and the ratio of the time step equal to 2 C. For 2 Θ scan used si target at 35 kV and 45 mA. The terms not containing fibrous crystals" and "does not contain needle-shaped crystals" means that the fibrous and/or needle crystals, if present, cannot be detected using scanning electron microscopy (SEM). Micrograph obtained SEM can be used to identify crystals of different morphology. For microphotographs shown in the figures used scale of resolution (1 μm).

On the x-ray crystal ZSM-48, corresponding to the invention, identified ZSM-48, i.e. the D-spacing and relative intensities are consistent with those that have a place for pure ZSM-48. Although x-ray diffraction analysis (RDA) is used to establish the presence of zeolite, it is not possible to set specific morphology of the crystals. For example, acicular and tabular form for a given zeolite will give the same diffraction pattern. In order to determine different mo is Pologi, you must use an analytical tool with a higher resolution. Such tool is a scanning electron microscope (SEM). Micrograph obtained with its use, can be used for identification of crystals of different morphology.

Crystals of ZSM-48 after removal of the sending agent has a specific morphology and the molar composition corresponding to the formula

(n) SiO2·Al2O3,

in which n ranges from 70 to 110, preferably from 80 to 100 and more preferably from 85 to 95. In another embodiment of the invention n is at least 70 or at least 80, or at least 85. In another embodiment of the invention n is 110 or less, or 100 or less, or 95 or less. In another embodiment of the invention, Si may be replaced by Ge, a Al can be replaced by Ga, In, Fe, Ti, V and Zr.

Crystals of ZSM-48 in synthesized form is prepared from a mixture of silicon dioxide, aluminum oxide, bases and salts hexadecane as the directing agent. According to the embodiment of the invention the molar ratio of structure-directing agent and silicon dioxide in the mixture is less than 0.05, or less than 0.025 or less of 0.022. According to another embodiment of the invention the molar ratio of structure-directing agent and silicon dioxide in the mixture is at mere,01; or at least 0,015; or at least 0,016. According to another embodiment of the invention the molar ratio of structure-directing agent and silicon dioxide in the mixture is between 0.015 to 0.025; preferably from 0,016 up to 0.022. According to the embodiment of the invention, the crystals of ZSM-48 synthesized in the form have a molar ratio of silica:alumina from 70 to 110. In another embodiment of the invention, 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. According to another embodiment of the invention, 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. At any given preparation of 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 of the components are slightly different than in the reaction mixture used for the preparation of these crystals. This result may be due to incomplete participation in the reaction, 100% reactive substances in the formation of crystals.

Zeolite ZSM-48, as calcined, and in synthetic form, is usually in the form of agglomerates chalk is their crystals, the size of which may be in the range of 0.01 to 1 μm. Such small crystals are desirable because they lead to greater activity. Smaller crystals provide a larger surface area, which leads to a greater number of active catalytic sites in a given quantity of catalyst. Preferably crystals of ZSM-48 as calcined and synthesized in a form that does not contain fibrous crystals. Fibrous crystals are relevant L/D>10/1, where L and D are length and diameter of the crystal. In another embodiment of the invention, the crystals of ZSM-48 as calcined and synthesized form, have a small amount of needle-shaped crystals, or do not contain them. The needle crystal is a crystal in which the ratio L/D<10/1, preferably less than 5/1, more preferably ranges from 3/1 to 5/1. According to SAM the study of crystals, made in accordance with the methods described here do not have a defined crystals of fibrous or needle-like morphology. Such morphology, by itself or in combination with low silica:alumina provides catalysts with high activity and desirable from the point of view of ecology properties.

The structure of ZSM-48 prepared from an aqueous reaction mixture comprising silicon dioxide or a salt of silicic acid,aluminium oxide or soluble aluminum salt of the acid, the base and the guide agent. To obtain crystals of the expected morphology of the reagents in the mixture has the following molar relationship:

SiO2:Al2O3=70-110

H2O:SiO2=1-500

HE-:SiO2=0,1-0,3

HE-:SiO2(preferred)=0,14-0,18

template:SiO2=0,01-0,05

template:SiO2(preferred)=0,015-0,025

In the above relations shows two ranges for a relationship base: silicon dioxide and structure-directing agent:silicon dioxide. Wider ranges for these relations include mixtures which are formed crystals of ZSM-48 with a number of keraita and/or crystals acicular morphology. If Kinijit and/or crystals acicular morphology undesirable, should be used, the preferred ranges of the relationship, as illustrated below in the examples.

The preferred source of silicon dioxide is deposited silicon dioxide and a commercial product from Degussa. Other sources of silicon dioxide can be powder of silicon dioxide, including precipitated silica, such as Zeosil®and silica gels, colloidal silica, such as Ludox®or dissolved silica. In the presence of a base, these other sources of silicon dioxide can form silicates. The aluminum oxide which may be in the form of soluble salts, preferably the sodium salt, and a commercial product from US Aluminate. Other suitable sources of aluminum include other aluminum salts such as chloride, aluminum alcoholate and 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 or the like. The directing agent can serve as salt hexadecane, such as dichloride hexammine or hydroxide hexadecane. Anion (other, not chloride) may be such as hydroxide, nitrate, sulfate, other halide and the like. Dichloride hexammine is N,N,N,N',N',N' - HEXAMETHYL-1,6-hexanediamine dichloride.

In the synthesis of crystals of ZSM-48 reagents, including salt silicic acid, aluminum salt of the acid, the base and the guide agent, is mixed with water in the proportions shown above, and heated under stirring at a temperature of from 100 to 250°C. the Crystals can be formed simply from a reagent or, alternatively, the reaction mixture can be added seed crystals of ZSM-48. Seed crystals of ZSM-48 can be added to increase the rate of formation of the crystals, but not for impact totheir morphology. In the method of obtaining not participate other seed crystals other than the seed crystals of ZSM-48, such as zeolite Beta. Crystals of ZSM-48 is cleaned, usually by filtration, and washed with deionized water.

According to the embodiment of the invention, the crystals obtained by the synthesis in accordance with the invention, do not contain non-ZSM-48 seed crystals, and do not contain ZSM-50. Preferably crystals of ZSM-48 have a small amount of keraita. According to the embodiment of the invention, the content keraita can be 5% or less; or 2% or less; or 1% or less. In alternative embodiments of the invention, the crystals of ZSM-48 can generally not contain keraita.

According to the embodiment of the invention, the crystals obtained by the synthesis in accordance with the invention, does not have a fibrous morphology. Fibrous morphology undesirable, since this crystal morphology suppresses the catalytic activity of ZSM-48 in relation to dewaxing. In another embodiment of the invention, the crystals, resulting in the synthesis in accordance with the invention, had a low proportion of acicular morphology. The number of needle morphology, occurring in crystals of ZSM-48 can be 10% or less; or 5% or less; or 1% or less. In an alternative embodiment of the invention, the crystals of ZSM-48 can not contain needle m is rologie. Low content of needle-shaped crystals, preferably for some applications, as I believe that needle crystals reduce the activity ZSM-48 in some types of reactions. To obtain the desired high purity morphology of the crystal must be used relations silica:alumina, base: silicon dioxide and the guide agent:silicon dioxide in the reaction mixture, according to embodiments of the invention. In addition, if desired composition not containing keraita and/or needle-like morphology, use the preferred ranges of these relations.

In accordance with U.S. patent No. 6923949 to obtain crystals of ZSM-48 with respect to the silica:alumina less than 150:1, use a heterogeneous persecution non-ZSM-48 seed crystals. In accordance with U.S. patent No. 6923049 obtaining pure ZSM-48 with respect to the silica: alumina up to 50:1 and less dependent on the use of heterogeneous persecution, such as seed crystals of zeolite Beta.

If in the synthesis of ZSM-48 with a significantly lower relationship silica: alumina heterogeneous seed crystals no crystals are used, inclusions of crystals of ZSM-50 becomes larger. When the relations of the sending agent to the silica more about 0,025 usually get agglomera the s of mixed phases, containing needle-like crystals. The preferred ratio of the sending agent and silicon dioxide is approximately 0,022 or less. When the relations of the sending agent to the silicon dioxide below approximately 0,015 is obtained a product containing Kinijit. Kinijit is amorphous layered silicate and is a type of natural clay. It does not show the activity of the zeolite type. On the contrary, it is relatively inert under the reaction conditions, which usually occur when the raw material is exposed to ZSM-48. Thus, although the presence keraita in samples of ZSM-48 and acceptable in some applications, it leads to a reduction in overall activity ZSM-48. Relations hydroxide:silicon dioxide (or other base: silica) and silica:alumina important for the morphology of the formed crystals, and also for their purity. The ratio of silica:alumina important for the activity of the catalyst. The ratio of base: silicon dioxide is a factor influencing the formation of keraita. Use hexamethonium directing agent is a factor affecting the production of the product, not containing fibrous material. The formation of needle-like morphology depends on the relationship silica:alumina and structure-directing agent:dioc the ID of silicon.

Crystals of ZSM-48 in synthesized form should at least partially dry before using or subjected to further processing. Drying can be accomplished by heating at a temperature of from 100 to 400°C., preferably from 100 to 250°C. the Pressure may be atmospheric or below atmospheric. If drying is carried out at a partial vacuum, the temperature may be lower than what is used at atmospheric pressure.

The catalysts prior to use is usually associated with a binder or matrix material. The binder is stable up to the temperature desired for use, and in relation to friction. The binder may be catalytically active or inactive and to include other zeolites, other inorganic materials such as clays, metal oxides, such as silicon dioxide, aluminium oxide and silicates. Clays may be kaolin, bentonite and montmorillonite, which are the products available from a commercial point of view. They can be mixed with other materials, such as silicates. In addition to the silicates can be used, and other porous materials basis, including other binary materials such as silica - magnesia, silica - thorium oxide, silica - Zirconia, silica - beryllium oxide and silicon dioxide - titanium oxide, that is the same as the three-component materials, such as silica - alumina - magnesia, silica - alumina - oxide of thorium, silicon dioxide - aluminum oxide - zirconium oxide. The base may be in the form of co-gel. Bound ZSM-48 can be in the range from 10 to 100 wt.% in the calculation of the bound ZSM-48, where the balance is binding.

Crystals of ZSM-48 as part of the catalyst, can also be used with metal component for hydrogenation. The metal component for hydrogenation can be from Groups 6 to 12 of the Periodic table of the system (based on the IUPAC system, groups of 1-18, preferably from Groups 6 and 8-10. Examples of such metals include Ni, Mo, Co, W, Mn, cu, Zn, Ru, Pt or Pd, preferably Pt or Pd. Can also be used to sweep away the metals for hydrogenation, such as Co/Mo, Ni/Mo, Ni/W, Pt/Pd, preferably Pt/Pd. The amount of metal or metals for hydrogenation can be from 1 to 5 wt.% by weight of the catalyst. Methods of introduction of the metals in the catalyst is ZSM-48 are well known and include, for example, impregnation of the catalyst ZSM-48 salt of the metal component for hydrogenation and heating. The catalyst ZSM-48 containing metal for hydrogenation can be before using solifidian. The catalyst may be also subjected to the action of steam.

High-purity crystals of ZSM-48, received in accordance with the described enter the embodiment of the invention, 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 excellent activity and selectivity, as well as provide excellent outputs product. They also have environmental advantages, from the point of view of their effect on health, crystalline forms, and the small size of the crystals is also advantageous in respect of catalytic activity.

In addition to the embodiments of the invention described above, the following embodiment of the invention relates to a high-purity composition of ZSM-48 having a ratio of silica:alumina from 70 to 110, and ZSM-48 does not contain non-ZSM-48 seed crystals, and contains no fibrous crystals. Preferably crystals of ZSM-48 also has a low content of needle-shaped crystals, or not include them at all. Another embodiment of the invention relates to crystals of ZSM-48, which are synthesized in the form include ZSM-48 with a molar ratio of silica:alumina from 70 to 110 and is formed from a reaction mixture containing hexamethonium guide the agent in molar ratio hexamethonium:silicon dioxide from 0.01 to 0.05, preferably between 0.015 to 0.025. In this embodiment izopet the deposits crystals of ZSM-48 synthesized in the form does not contain non-ZSM-48 seed crystals, and also do not contain fibrous crystals. Preferably crystals of ZSM-48 also has a low content of needle-shaped crystals, or not include them at all.

In the following embodiment of the invention, the crystals of ZSM-48 in synthesized form was subjected to calcination to remove hexamethonium structure-directing agent and obtain highly pure Na-form ZSM-48. This Na-form ZSM-48 using ion exchange can also go in the H-form ZSM-48. In yet another embodiment of the invention, the crystals of ZSM-48 in synthesized form or annealed crystals of ZSM-48 (Na-form or H-form) combined with at least one binder and a metal hydrogenation.

Another embodiment of the invention relates to a method for producing crystals of ZSM-48, which includes the preparation of an aqueous mixture of silicon dioxide and a salt of silicic acid, alumina and aluminum salts of the acids, salts of hexadecane and alkaline bases, where the following molar relationship: silica:alumina from 70 to 110, base:silicon dioxide from 0.1 to 0.3, preferably from 0.14 to 0.18, salt hexammine:silicon dioxide from 0.01 to 0.05, preferably from 0.15 to 0.25; heating the mixture under stirring for a time and at a temperature sufficient for the formation of the crystals. Perhaps adding to the reaction mixture of seed crystals of ZSM-48. Description the bedroom above procedure ensures crystal ZSM-48 in synthesized form, which contain hexamethonium structure-directing agent.

Hydrobromide with catalysts ZSM-48

Catalysts ZSM-48 are used as catalysts for dewaxing a hydrocarbon feedstock. The preferred raw material is the main raw materials for lubricating oils. This raw material contains paraffin, which boils in the temperature range for lubricating oils, usually having a temperature of the pickup 10% above 650°F (343°C), measured by ASTM D 86 or ASTM D2887. Raw materials can be obtained from a number of sources, such as oil obtained after extraction processes of purification, such as refined, partially deparaffinization solvent oil, neasfaltirovanyj oils, distillates, vacuum gas oils, oil coking, crude waxes or the like, and the wax is Fischer-Tropsch process. Preferred raw materials are crude paraffins and waxes Fischer-Tropsch process. Raw waxes usually get from hydrocarbons by dewaxing solvent or propane. Raw waxes contain some residual oil and it is usually removed. Raw waxes usually get apotheosia oil. The wax is Fischer-Tropsch get typically the synthesis by the Fischer-Tropsch process.

Raw materials may have a high content of nitrogen and sulfur impurities. In the present process can be used raw material containing d is 0.2 wt.% nitrogen and up to 3.0 wt.% sulfur, on the basis of the total mass of raw materials. The content of sulfur and nitrogen can be measured using standard ASTM methods DB5453 and D4629, respectively.

Raw materials may be subjected to dewaxing hydrobromide. For hydrobromide effective catalysts containing metals of Group 6 of the Periodic table (according to the IUPAC system, Groups 1-18), metals of Groups 8-10 and mixtures thereof. Preferred metals include Nickel, tungsten, molybdenum, cobalt and mixtures thereof. These metals or mixtures typically present in the form of oxides or sulphides in the media of refractory metal oxides. A mixture of metals may also be present in the form of bulk metal catalysts, where the amount of metal in the catalyst is 30 wt.% or more based on the catalyst. Suitable carrier materials of metal oxides include oxides such as silicon dioxide, aluminum oxide, silicates or titanium dioxide; the preferred aluminum oxide. Preferred aluminium oxides are porous alumina, such as gamma - or ETA-alumina. The amount of metal taken separately or in a mixture, is from about 0.5 to 35 wt.% per mass of catalyst. In the case of the preferred compounds of metals from Groups 9-10 and Group 6 metals Group 9-10 present in the amount of 0.5-5 wt.% per mass of catalyst, and is Mall group 6 - in an amount of 5 to 30 wt.%. The number of metals can be measured using the methods specified by ASTM for individual metals, including atomic absorption spectroscopy or atomic emission spectroscopy with inductively coupled plasma.

Conditions hydrobromide include temperature up to 426°C, but 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 psi, excess.), preferably, from 2859 to 13891 kPa (400 to 2000 psi, excess.); space velocity from 0.1 to 10 h-1preferably from 0.1 to 5 h-1and the ratio of hydrogen to the amount of supply of raw materials from 89 to 1780 m3/m3(from 500 to 10,000 standard cubic feet per barrel), preferably in the range from 178 to 890 m3/m3.

The dewaxing conditions include a temperature 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 pounds per square inch excess.), preferably from 1480 to 17339 kPa (200 to 2500 psi, excess.), the volumetric rate of fluid from 0.1 to 10 h-1preferably from 0.1 to 5 h-1and the share of manufacturing hydrogen gas from 45 to 1780 m3/m3(from 250 to 10,000 standard cubic feet per barrel), preferably from 89 to 890 m3/m3(250 to standard cubic feet per barrel).

Product dewaxing may be subjected to finishing hydrobromide. Finishing hydrobromide product obtained by dewaxing is desirable to adjust the quality of the product to the required specifications. Finishing hydrobromide is a soft hydrobromide aimed to saturate any olefins interval of machine oils and residual aromatic compounds, as well as to remove any residual heteroatoms and non-ferrous particles. Finishing hydrobromide after dewaxing is usually performed in sequence with the stage dewaxing. Usually the finish hydrobromide carried out at a temperature from about 150 to 350°C., preferably from 180 to 250°C. the Total pressure is usually from 2859 to 20786 kPa (about 400 to 3000 psig. pounds/square inch). The volumetric rate of fluid is usually from 0.1 to 5 h-1preferably from 0.5 to 3 h-1and the share of manufacturing hydrogen gas ranges from 44.5 to 1780 m3/m3(from 250 to 10,000 standard cubic feet per barrel).

Catalysts finish hydrobromide are the catalysts containing metals of Group 6 of the Periodic table (according to the IUPAC system, Groups 1-18), metals of Groups 8-10 and mixtures thereof. Preferred metals include at least audibleready metal, having strong ability to hydrogenation, especially platinum, palladium and their mixture. A mixture of metals may also be present in the form of bulk metal catalyst where the metal is 30% or more by weight of catalyst. Suitable carrier materials of metal oxides include weakly acidic oxides, such as silicon dioxide, aluminium oxide, aluminium silicate or titanium dioxide, preferred is alumina. Preferred catalysts finish hydrobromide to saturate aromatic compounds include at least one metal having a relatively strong ability to hydrogenation on a porous carrier. The usual media materials include amorphous or crystalline oxide materials, such as aluminum oxide, silicon dioxide and aluminum silicate. The content of base metals in the catalyst is often greater than about 20 wt.%. Precious metals are usually present in amounts up to about 1 wt.%. The preferred catalyst for finishing hydrobromide is a mesoporous material belonging to the class or the M41S family of catalysts. The M41S family of catalysts is a mesoporous material with a high silicon dioxide content, the preparation of which is described in J. of AMAG. Chem. Soc., 1992, 114, 10834. Examples include MCM-41, MCM-48 and M Is the M-50. The mesopores of the catalyst have a size of from 15 to 100 angstroms. A preferred representative of this class of catalysts MCM-41, the preparation of which is described in U.S. patent No. 5098684, is an inorganic porous, not layered phase having a hexagonal arrangement of pores of the same size. The physical structure of MCM-41-like beam Solomon where holes Solomon (pore diameter of the cell) have a size of from 15 to 100 angstroms. MCM-48 has a cubic symmetry and is described, for example, in U.S. patent No. 5198203, while MSM-50 has a layered structure. MCM-41 can be obtained with the openings of pores of different sizes in the mesoporous range. Mesoporous materials can carry a metal component for hydrogenation, of which at least one is a metal of Group 8, Group 9 or Group 10. Preferred noble metals, especially noble metals of Group 10, most preferred Pt, Pd or mixtures thereof.

Hydrobromide with mixtures of catalyst ZSM-48

6 reflects the activity of two different types of catalysts ZSM-48 to achieve the desired temperature fluidity of the raw material. The upper curve shows the reaction temperature required for the catalyst containing crystals of ZSM-48 with the ratio of SiO:Al2O3approximately equal to 200, so that the fraction of the raw materials involved in the process, achieved the desired fact the temperature value of the yield strength of 370°C+. The lower curve shows the same for the catalyst containing high-purity crystals of ZSM-48 with respect to SiO2:Al2O3less than 110. As can be seen from Fig.6, with the catalyst of the ZSM-48 containing crystals with a lower ratio of SiO2:Al2O3you can achieve the same temperature fluidity at the temperature about 10°C lower than for catalyst ZSM-48 containing crystals with a higher ratio of SiO2:Al2O3.

In General, high-purity crystals of ZSM-48 with respect to SiO2:Al2O3less than 110 have increased activity relative to other types of crystals of ZSM-48 at the same reaction temperature. Alternatively, the temperature required for the process from raw materials brought out a product with the desired characteristics, below for catalysts containing high-purity crystals of ZSM-48 with respect to SiO2:Al2O3110 or less, compared to catalysts with other types of crystals of ZSM-48. In various embodiments of the invention the temperature difference to achieve the desired product characteristics (such as temperature yield strength) between the catalyst containing high-purity crystals of ZSM-48 with respect to SiO2:Al2O3equal to 110 or less, and another type of catalyst is ZSM-48 can be at least 5°C, or at m is re 10°C, or at least 20°C, or at least 30°C.

According to the embodiment of the invention, the crystals of ZSM-48 and two more types that are used in a mixture of ZSM-48 in accordance with the invention, may have a different activity from the one or more properties of these types ZSM-48. One of the properties, which leads to the difference of activities, this content in ZSM-48 non-ZSM-48 seed crystals. Another property that leads to the difference of activities, it is the morphology of the crystals. For example, crystals having a fibrous morphology are considered to be of lower reactivity than other types of crystals. In some embodiments of the invention the presence of needle-like morphology may also indicate the difference in activity. Another property is the presence of impurities, such as Kinijit. And another property is the ratio of SiO2:Al2O3in crystals. The crystals with respect to SiO2:Al2O3less than approximately 110 have a higher activity than the crystals with respect to SiO2:Al2O3about 110.

The difference in the activity of different types of crystals of ZSM-48 can be used in different ways. For example, lowering the reaction temperature required to achieve the desired result, prolongs the lifetime of the catalyst hydrobromide. This can directly lead to economy the AI tools, because the action of the catalyst at lower temperatures will increase the lifetime of the catalyst (or in other words, increase the length of time between replacements of the catalyst).

Another potential advantage is the ability to adapt the activity of a mixture of ZSM-48 to the desired range of temperatures depending on the curve exit. Although the lower temperature of the process can increase the duration of use of the catalyst, some existing configuration processes require a minimum temperature in the reactor where the use of the catalyst of hydrobromide, such as ZSM-48.

For example, in some cases, the equipment for manufacture of lubricants do not provide heat between stages occurring in the dewaxing reactor and the reactor finish hydrobromide. If the temperature of the dewaxing reactor is too low and/or if the heat loss between the dewaxing reactor and the reactor finish hydrobromide too big deparaffinizing product, which is in the finishing reactor hydrobromide, will not have a temperature sufficient for effective finishing hydrobromide. The mixture of catalyst ZSM-48 can be used for the production of mixed catalytic compositions which correspond to the minimum temperature required in the reactor. This item is well positioned to optimize the process using standardized versions of catalysts or Vice versa, to synthesize a specific catalyst, suitable for the requirements of the reactor.

In another example, a mixture of catalyst ZSM-48 can be used to obtain the desired activity at a desired temperature for processes involving a cascade of reactions within a single reactor. One typical process of hydrobromide raw material is subjected to hydrodesulfurization followed by dewaxing and then perform post-processing with hydrogen. It is desirable to combine these reactions and to implement them in a single reactor. In situations where numerous operations hydrobromide are cascade, to maintain a large temperature variations can be difficult. In integrated circuits the process of hydrobromide catalysts ZSM-48 are suitable for use as catalysts for dewaxing. When using mixtures of catalysts ZSM-48 can be selected as desired combination of output and operating temperature in order to reduce or minimize the temperature difference between pre-hydrobromide, which used a mixed catalysts ZSM-48, or following behind her.

The use of mixtures of ZSM-48 for adjusting the activity of the catalytic system provides advantages over using a mixture of ZSM-48 with a catalyst of a different type, such as CE is lit another type. ZSM-48 - selective dewaxing catalyst, the main function of which is the isomerization of long chain molecules to create a branched chain. This distinguishes it from many other types of zeolite catalysts such as ZSM-5, ZSM-11, USY zeolite and mordenite, which act mainly by breaking down long-chain molecules into shorter ones. As ZSM-48 is not conducive to fission reactions, ZSM-48 can be used in the process of hydrobromide raw materials (such as deparaffinize) to reduce or minimize the loss of raw materials arising from conversion to more short-chain, lighter components. When using mixtures of ZSM-48 to control the properties of the catalyst to poojabrahmi desired curve of the output, you can avoid the use of catalysts that will increase the number of undesirable side reactions such as cleavage).

In one of the embodiments of the invention described above, the crystals of ZSM-48 having a ratio of SiO2:Al2O3less than 110, can be combined with the crystals of ZSM-48 various other types. For example, crystals of ZSM-48, described above, which have a ratio of SiO2:Al2O3less than 110, can be mixed with crystals of ZSM-48 with respect to SiO2:Al2O3more than 110, such as crystals of ZSM-48 with respect to SiO2/sub> :Al2O3more than 150 or more than 200. Alternatively, the above-described crystals of ZSM-48 with respect to SiO2:Al2O3110 or less can be mixed with ZSM-48 crystals containing seed crystals, different ZSM-48. In yet another embodiment of the invention, the crystals of ZSM-48 with respect to SiO2:Al2O3110 or less, can be mixed with ZSM-48 crystals, some of which are presented in the form of less desirable morphology. Crystals of ZSM-48, some of which are presented in the form of less desirable morphology may include crystals of ZSM-48, which are at least partly in fibrous form. Alternatively, crystals of ZSM-48 with less than desirable morphology may include ZSM-48 crystals having a higher percentage of needle morphology than high-purity crystals of ZSM-48 containing ,for example, at least 1%or at least 2%or at least 5%or at least 10% of the crystals are needle-like morphology. In another embodiment of the invention, high-purity crystals of ZSM-48 with respect to SiO2:Al2O3less than approximately 110 can be mixed with crystals of ZSM-48 containing a high percentage keraita than in high-purity crystals of ZSM-48 containing, for example ,at least 1%or at least 2%or at least 5%or at least 10%.

In one of the embodiments of the image is to be placed crystals of ZSM-48, related SiO2:Al2O3110 or less may preferably have a ratio of SiO2:Al2O3equal to 100 or less, or 90 or less, or 80 or less. Alternatively, the ratio of SiO2:Al2O3in high-purity crystals of ZSM-48 can be 70 or more, or 80 or more.

In various embodiments of the invention, the crystals of ZSM-48 different types can be mixed together in any suitable way. For example, the above-described crystals of ZSM-48 having a ratio of SiO2:Al2O3110 or less, can be mixed with crystals of ZSM-48 different type before manufacture of the catalyst of these crystals. Alternatively, the crystals of the ZSM-48 two or more types can make for some catalysts, and then made the catalysts can be mixed together.

Mixtures of catalysts ZSM-48 can include crystals of ZSM-48 two or more types. The number of crystals of ZSM-48 of each type in the mixture may be high-purity crystals of ZSM-48 with respect to SiO2:Al2O3110 or less, may be at least 10%or at least 25%or at least 50%or at least 75%or at least 90%or at least 95% of the crystals of ZSM-48 in the mixture. Alternatively, the number of crystals of high purity ZSM-48 with respect to SiO2:Al2O3110 or less, may be 99% or less, the sludge is 95% or less, or 90% or less, or 75% or less, or 50% or less of the crystals of ZSM-48 in the mixture.

In another embodiment of the invention stacked on top of other layers ZSM-48 different type can be used for dewaxing of raw materials. In many embodiments of the invention stacked on top of other layers ZSM-48 can provide characteristics similar to the characteristics of the mixtures of ZSM-48.

In another embodiment of the invention stacked on top of other layers ZSM-48 can be used for multi-stage dewaxing raw materials with high content of sulfur and/or nitrogen. Due to the higher activity of high purity ZSM-48 with respect to SiO2:Al2O3equal to 110 or less, can be used in the layer of the first catalyst to contact with the raw material. Interaction with the layer of the first catalyst of the ZSM-48 will convert some of the particles of sulfur and nitrogen in H2S and NH3that will increase the activity of the subsequent catalytic layers. In the layer of the second catalyst can be placed particles of ZSM-48 of another type. Due to different activity ZSM-48 different types, both layers can operate at the same temperature.

This invention is further illustrated by the examples.

EXAMPLE 1

A mixture prepared from 1200 g of water, 40 g of chloride hexadecane (56% solution), 228 g of Ultrasil PM (precipitated powder of silicon dioxide from Degussa), 12 g of a 45% solution of aluminate Natrii 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 a temperature of 320°F (160°C) in a 2 l autoclave with stirring at 250 rpm for 48 hours. Specialist it is known that factors such as the size of the autoclave and the type of mechanism for mixing, can determine the other of the stirring speed and the desired process. The resulting product was filtered, washed with deionized (DI) water and dried at a temperature of 250°F (120°C). Radiograph of the material in the synthesized form showed the typical picture of a pure phase ZSM-48. SAM analysis of the material synthesized in the form showed 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 these crystals of ZSM-48. This comparative sample with respect to template:silicon dioxide 0,023 shows the presence of a certain amount of needle-shaped crystals.

EXAMPLE 2

A mixture prepared from water, chloride hexadecane (56% solution), Ultrasil PM, 45% sodium aluminate solution and a 50% sodium hydroxide solution. The mixture was pursuing the 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 a temperature of 320°F (160°C) in an autoclave under stirring at 250 rpm for 48 hours. The resulting product was filtered, washed with deionized (DI) water and dried at a temperature of 250°F (120°C). Radiograph of the material in the synthesized form showed the typical picture of a pure phase ZSM-48. SAM analysis of the material synthesized in the form showed that the material was 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 have a molar ratio of SiO2/Al2O3~ 94/1. Figure 2 is a micrograph of the obtained crystals of ZSM-48. Figure 2 shows that needle-like crystals obtained in accordance with the invention, ZSM-48 are not available.

EXAMPLE 3

A mixture prepared from water, chloride hexadecane (56% solution), modified Ultrasil, a 45% sodium aluminate solution and a 50% sodium hydroxide solution and 5 wt.% (on silica) seed crystals of ZSM-48. The mixture had the following molar composition:

SiO2/Al2O3=103

H2O/SiO2=14,8

OH-/SiO2=0,17

Na+/SiO2=0,17

template/SiO2=0,029

The mixture which was advergames reaction at a temperature of 320°F (160°C) in an autoclave under stirring at 250 rpm for 48 hours. The resulting product was filtered, washed with deionized (DI) water and dried at a temperature of 250°F (120°C). Radiograph of the material in the synthesized form showed the typical picture of a pure phase ZSM-48. SAM analysis of the material synthesized in the form showed that the material consists of agglomerates of elongated needle crystals (with an average size of crystal <1 micron). The obtained crystals of ZSM-48 had a molar ratio of SiO2/Al2O3~ 95/1. Figure 3 is a micrograph of the obtained crystals of ZSM-48. This comparative example shows the presence of needle-shaped crystals in ZSM-48 synthesized from the reaction mixture, with respect to template:silicon dioxide, equal 0,029.

EXAMPLE 4

A mixture prepared from water, chloride hexadecane (56% solution), modified Ultrasil, a 45% sodium aluminate solution and a 50% sodium hydroxide solution and 5 wt.% (on silica) 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 a temperature of 320°F (160°C) in an autoclave under stirring at 250 rpm for 24 hours. The product was filtered, washed with deionized (DI) water and dried at a temperature of 250°F (120°C)Roentgenogram material in the synthesized form showed the typical picture of a pure phase ZSM-48. SAM analysis of the material synthesized in the form showed that the material consists of agglomerates melky crystals of irregular shape (with an average size of crystal <0,05 MK). The obtained crystals of ZSM-48 had a molar ratio of SiO2/Al2O3~89/1. Figure 4 is a micrograph of the obtained crystals of ZSM-48. This example crystals of ZSM-48 according to the invention shows that needle-like crystals in the material are missing.

EXAMPLE 5

A mixture prepared from water, chloride hexadecane (56% solution), modified Ultrasil, a 45% sodium aluminate solution and a 50% solution of sodium hydroxide and 3.5 wt.% (on silica) 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=0,17

template/SiO2=0,015

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

EXAMPLE 6

A mixture prepared from water, chloride hexadecane (56% solution), modified Ultrasil, a 45% sodium aluminate solution and a 50% solution of hydroxide NAT the Oia and 3.5 wt.% (on silica) 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 a temperature of 320°F (160°C) in an autoclave under stirring at 250 rpm for 48 hours. The product was filtered, washed with deionized (DI) water and dried at a temperature of 250°F (120°C). Radiograph of the material synthesized in the form synthesized from the reaction mixture with respect to the basis of:silicon dioxide, equal to 0.20, showed a mixture of ZSM-48 and impurities keraita.

EXAMPLE 7

A mixture prepared from water, chloride hexadecane (56% solution), Ultrasil PM, 45% sodium aluminate solution and a 50% solution of sodium hydroxide and 3.5 wt.% (on silica) 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 a temperature of 320°F (160°C) in an autoclave under stirring at 250 rpm for 48 hours. The product was filtered, washed with deionized (DI) water and dried at a temperature of 250°F (120°C). Radiograph of the material in the synthesized form showed the typical picture of a pure phase ZSM-48.

EXAMPLE 8

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

SiO2/Al2O3=90

H2O/SiO2=20,1

OH-/SiO2=0,17

Na+/SiO2=0,17

template/SiO2=0,025

The mixture was subjected to reaction at a temperature of 320°F (160°C) in an autoclave under stirring at 250 rpm for 48 hours. The product was filtered, washed with deionized (DI) water and dried at a temperature of 250°F (120°C). Radiograph of the material in the synthesized form showed the typical picture of a pure phase ZSM-48 and traces of impurities ZSM-50. The product contains crystals acicular morphology.

EXAMPLE 9

65 parts (base: calcination 586°C) crystals of ZSM-48 high activity (Sample No. 4) was mixed with 35 parts pseudoboehmite aluminum oxide (basis: calcination at 586°C) in the edge-runner mills type Simpson. Added an amount of water sufficient to make a paste that can be ekstradiroval on the extruder 2" (2 inches=5.08 cm) Bonnot. A mixture of ZSM-48, pseudoboehmite of aluminum oxide and water component of the paste was extruded and dried in an oven with a hot wrap (electrotherapy exercising) at 121°C during the night. The dried product was probalily in nitrogen at 538°C. to decompose and remove the organic template. Calcined in nitrogen, the product ek is cruzii was moistened in a saturated moisture to the air and was carried out by ion exchange by treatment with 1 N ammonium nitrate to remove sodium (analysis: < 500 ppm Na). After treatment with ammonium nitrate extrudate was washed with deionized water to remove any residual nitrate ions before drying. The extrudate after ammonium exchange was dried at a temperature of 121°C during the night and was progulivali in air at 538°C. After calcination in air extrudate was subjected to the action of steam for 3 hours at a temperature of 900°F (482°C). Steamed extrudate was fed nitrate terminplan (0.6 wt.% Pt), using the initial wetting. After saturation the extrudate was dried overnight at 250°F (120°C) and progulivali in air at 360°C for conversion of nitrate salts tetramine in the oxide of platinum.

EXAMPLE 10

The dewaxing catalyst of Example 9 was tested in a test 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%+. Highly active catalyst containing ZSM-48, showed excellent release from a-n-C10with minimal cracking, depending on the degree of conversion of n10and the reaction temperature. Figure 5 shows the dependence of the yield of ISO-n-C10the degree of conversion of h10for the catalyst according to the embodiment of the invention and catalyst with the ratio of silica:alumina equal to around the 200.

EXAMPLE 11

This example relates to the preparation of HA-ZSM-48 with the seed of a regular crystal ZSM-48. A mixture prepared from water, chloride hexamidine (56% solution), Ultrasil PM, 45% sodium aluminate solution and a 50% sodium hydroxide solution. Then to the mixture was added approximately 5 wt.% (on silica) seed crystals of ZSM-48. The mixture had the following molar relationship:

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 a temperature of 320°F (160°C) in an autoclave under stirring at 250 rpm for 24 hours. The product was filtered, washed with deionized (DI) water and dried at a temperature of 250°F (120°C). Radiograph of the material in the synthesized form showed the typical picture of a pure phase ZSM-48. Crystals in synthetic form by double ion exchange with a solution of ammonium nitrate at room temperature were converted to the hydrogen form, and then dried at 250°F (120°C) and calcined at 1000°F (540°C) for 6 hours 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 with persecution, by using 5 wt.% beta crystals (with respect to the contents of dioxi is and silicon). Heterogeneous persecution with the use of 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 from Degussa), 10 g of sodium aluminate solution (45%) and 33.3 g of 50% sodium hydroxide solution. Then to the mixture was added 10 g of beta-crystals (SiO2/Al2About3~ 35,5/1) as a seed. The mixture had the following molar relationship:

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 a temperature of 320°F (160°C) in an autoclave with a volume of 2 l with stirring at 250 rpm for 48 hours. The product was filtered, washed with deionized (DI) water and dried at a temperature of 250°F (120°C). Radiograph of the material in the synthesized form showed the typical picture of a pure phase ZSM-48. It is clear that the x-ray picture of the synthesized product was not detected beta phase. The synthesized crystals were converted into the hydrogen form by double ion exchange with a solution of ammonium nitrate at room temperature, then dried at 250°F (120°C) and progulivali at 1000°F (540°C) for 6 hours Obtained crystals of ZSM-48 had a molar ratio of SiO2/Al2O3~ 87,2/1.

EXAMPLE 13

This example shows prigotovleniya ZSM-48 with 10 wt.% the seed of beta-crystals (on silica). Used reagents, the amount of reagents and procedures described in Example 2, but as the directing agent used double the amount of beta crystals. Radiograph of the material in the synthesized form showed the typical picture of a pure phase ZSM-48. It is clear that the x-ray picture of the synthesized product was not detected beta phase. The synthesized crystals were converted into the hydrogen form by double ion exchange with a solution of ammonium nitrate at room temperature, then dried at 250 F (120°C) and progulivali at 1000 F (540°C) for 6 hours Obtained crystals of ZSM-48 had a molar ratio of SiO2/Al2O3~ 80/1.

EXAMPLE 14

The products obtained in Examples 11-13 were tested using the test on the adsorption of hexane. Test on the adsorption of hexane determines pore volume in any of the tested catalysts. The calcined catalysts obtained by the methods described above, was heated in a thermogravimetric analyzer (TGA) in nitrogen atmosphere at 500°C for 30 minutes the Dried catalyst was then cooled to 90°C. and subjected to the processing of n-hexane at a partial pressure of 10 kPa (75 Torr). The weight change was measured in the TGA using a microbalance. For each crystal was determined by the alpha value. The alpha value for the catalyst is a standardized measure and the activity of the catalyst relative activity of the comparative catalyst. The results of the analysis are presented in table 1.

Table 1
Samplen-hexane (mg/gAssessment % beta productThe alpha value
Example 11, HA-ZSM-48 reaction with seed crystals of ZSM-4837,7070
Example 12, HA-ZSM-48 reaction with ~5% beta-priming (on silica)42,4~5,3~125
Example 13, HA-ZSM-48 reaction with ~10% beta-priming (on silica)48,3~12~180
Bare beta crystals used in Examples 12 and 13126100690

Based on the data in table 1 shows that beta crystals are not dissolved in the crystallization, and remained in the synthesized product. This conclusion is confirmed by the increasing values of the adsorption of n-hexane in which the reamers 12 and 13. The conclusion also podtverzdaetsa by increasing the value of alpha for catalysts for the growth of crystals of the percentage of beta-form. The increase in the magnitude of adsorption of n-hexane and the alpha value of the catalyst shows that the crystals of ZSM-48 with persecution heterogeneous seed have a different reactivity than the crystals of ZSM-48 with a homogeneous persecution.

Note that the alpha value is an approximate indicator of activity in the catalytic cracking of the investigated catalyst compared to a standard catalyst and it gives a constant relative velocity (degree of conversion of normal hexane to volume of catalyst per unit time). This assessment is based on the activity of highly active cracking catalyst from aluminosilicate taken as an alpha of 1 (rate Constant=0,016-1). Alpha test is conventional and is described, for example, in U.S. patent No. 3354078; in Journal of Catalysis, v. 4, p.527 (1965); v.6, p.278 (1966) and v.61, p.395(1980).

EXAMPLE 15

This example compares the activity ZSM-48, received in accordance with the invention, with the activity of ZSM-48 with a higher ratio of silica: alumina. 600N crude paraffin was deparaffinization when 6996 kPa (1000 psi excess.), hourly volumetric velocity of the fluid 1 l/h, and fractions of a processing gas 445 m3/m3(2500 standard is s cubic feet per barrel). Figure 6 shows the dependence of the temperature in the reactor temperature required to meet temperature fluidity 370°C+. Figure 6 the difference between the top line (representing ZSM-48 with a higher ratio of silica: alumina) and bottom line (ZSM-48 of the present invention) gives an idea about the advantage in the activity.

1. The method of dewaxing a hydrocarbon feedstock, comprising the interaction of materials with a mixture of catalysts ZSM-48 under conditions of catalytic dewaxing to produce deparaffinizing raw materials, where the mixture of catalysts ZSM-48 includes:
(a) crystals of ZSM-48 of the first type, having a molar ratio of silica : alumina from 70 to 110 and does not contain non-ZSM-48 seed crystals, and
b) crystals of ZSM-48 of the second type, and the crystals of ZSM-48 of the second type differ from crystals of ZSM-48 of the first type one or more properties, chosen from the presence of non-ZSM-48 seed crystals, the crystal morphology, a higher percentage keraita, and a higher molar ratio of SiO2:Al2O3.

2. The method according to claim 1, in which crystals of ZSM-48 of the second type include crystals of ZSM-48 containing non-ZSM-48 seed crystals.

3. The method according to claim 1, in which crystals of ZSM-48 of the second type include crystals of ZSM-48 with respect to SiO2:Al2/sub> O3more than 110.

4. The method according to claim 1, in which crystals of ZSM-48 of the second type include crystals of ZSM-48 with a fibrous morphology.

5. The method according to claim 1, in which crystals of ZSM-48 of the second type include a higher percentage keraita than the crystals of ZSM-48 of the first type.

6. The method according to claim 1, in which crystals of ZSM-48 mixed by entering in the composition of the particles of the first catalyst crystals of ZSM-48 of the first type, making the crystals of the ZSM-48 of the second type particles of the second catalyst, and mixing the particles of the first and second catalysts.

7. The method according to claim 1, in which crystals of ZSM-48 are mixed with the catalyst particles, containing crystals of ZSM-48 of the first type, and the crystals of ZSM-48 of the second type.

8. The method according to claim 1, in which crystals of ZSM-48 of the first type do not contain crystals fibrous morphology.

9. The method according to claim 1, in which crystals of ZSM-48 of the first type do not contain crystals acicular morphology.

10. The method according to claim 1, in which crystals of ZSM-48 of the first type do not contain keraita.

11. The method according to claim 1, in which crystals of ZSM-48 of the first type do not contain ZSM-50.

12. The method according to claim 1, in which the raw material before interacting with a mixture of catalysts ZSM-48 is subjected to hydrobromide under conditions of hydrobromide.

13. The method according to claim 1, in which deparaffinization raw material is subjected to finish hydrobromide under conditions of finishing hydrobromide

14. The method according to claim 1, in which the conditions of catalytic dewaxing include a temperature of from 250 to 426°C, a pressure of from 791 to 20786 kPa (100-3000 excess, pounds/square inch), hourly volumetric rate of fluid from 0.1 to 10 h-1and the share of manufacturing hydrogen gas from 89 to 1780 m3/m3(500-10000 stub feet/barrel).

15. The method according to item 12, in which the conditions of hydrobromide include a temperature of from 150 to 426°C, the partial pressure of hydrogen of from 1480 to 20786 kPa (200-3000 excess, pounds/square inch), a space velocity from 0.1 to 10 h-1and the ratio of hydrogen to boot from 89 to 1780 m3/m3(500-10000 stub feet/barrel).

16. The method according to item 13, in which the conditions finishing hydrobromide include a temperature of from 150 to 350°C., a total pressure from 2859 to 20786 kPa (400-3000 excess, pounds/square inch), hourly volumetric rate of fluid from 0.1 to 5 h-1and the share of manufacturing hydrogen gas from 44.5 to 1780 m3/m3(250-10000 stub feet/barrel).



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to high activity ZSM-48. Described is a catalyst composition for removing paraffin from hydrocarbon material which contains ZSM-48 crystals, having molar ratio of silicon dioxide to aluminium oxide equal to or less than 110, which does not contain inoculating crystals different from ZSM-48 and does not contain ZSM-50 crystals.The invention also describes a method of producing ZSM-48 crystals contained in the composition described above, involving: preparation of an aqueous mixture of silicon dioxide or silicate, aluminium oxide or aluminic acid, hexamethonium salts and an alkaline base, where the mixture has the following molar ratios: silicon dioxide: aluminium oxide 70-110, base: silicon dioxide 0.1-0.3 and hexamethonium salt: silicon dioxide 0.01-0.05, and heating the mixture while stirring for a period of time and temperature sufficient for formation of crystals. The invention also describes a method of removing paraffin from hydrocarbon material in the presence of the catalyst composition described above.

EFFECT: obtained ZSM-48 crystals and a composition based on said crystals exhibit high activity during removal of paraffin from hydrocarbon material.

29 cl, 1 tbl, 6 dwg, 15 ex

FIELD: oil and gas production.

SUBSTANCE: inventions relates to oil processing, particularly to methods of refining of gasoline fractions. Invention relates to method of selective treatment of gasoline fractions of catalytic cracking by means of its stepped hydro-refining at presence of alumo-oxide catalyst in medium of hydrogen at increased pressure and temperature with separation of product of the first stage for light and sinking fractions, with following hydro-refining of sinking fraction at second stage at temperature 280-340°C, pressure 2-3 MPa, volume velocity of raw material feeding 4-8 hour-1 and mixing of received product after the second stage of hydro-refining with light fraction of product of the first stage with receiving of cleaned product. Separation of product of the first stage or separation of initial gasoline for light and sinking fractions is implemented by temperature 70-90°C at processing of raw materials with content of sulfur higher than 0.16% wt, 90-120°C - at processing of raw materials with content of sulfur 0.005-0.16% wt.

EFFECT: declared methods provide for reduction of sulfur content up to level not more than 0,0010% wt in gasoline fraction at minimal reduction of content of olefinic hydrocarbons.

3 cl, 3 ex, 5 tbl

FIELD: oil and gas industry.

SUBSTANCE: invention refers to methods of hydrogenating processing oil stock at presence of catalytic system and hydrogen and it can be implemented in oil processing industry. The method of hydro-fining oil fractions at raised temperatures and pressure and circulation of hydrogen containing gas in two stages at presence of a package of alumina support catalyst is performed at the temperature of 330-390°C, pressure 40-50 atm, circulation of hydrogen containing gas 250-400 nm3/m3 of stock, volume rate of stock supply 0.8-1.3 n-1 at presence of catalysts package, which at the first stage includes the catalyst of a protecting layer as an upper retaining layer and ANM (alumina-nickel-molybdenum) as a lower layer at the following ratio of components, wt %: catalyst of protecting layer 3.0-10.0, alumina-nickel-molybdenum catalyst - the rest; on the second stage catalyst package includes AKM (alumina-cobalt-molybdenum catalyst or ANM as an upper layer and AKM as a lower layer at the following ratio of components, wt %: alumina-cobalt-molybdenum catalyst 20.0-30.0, alumina-nickel-molybdenum catalyst - the rest.

EFFECT: development of efficient method of hydro-fining oil fractions.

3 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: method is enabled by kerosene cut hydrotreating at higher temperature and pressure with catalyst added. Invention concerns the method implying that raw stock is pre-passed through the inert "filter" bed in ratio of inert bed and catalyst within 2-98 vol. % to 25-75 vol. %. Prepared hydrogenation product is mixed with initial raw stock in ratio 60-40 wt % to 95-5 wt %.

EFFECT: prepared hydrogenation product is characterised by practically total absence of mercaptans (~0,001 wt %) and minimal content of the other sulphide compounds.

3 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: said invention relates to method for improvement of loss of mobility temperature of hydrocarbon material obtained by Fischer-Tropsch synthesis, in particular to satisfactory-yield conversion of material with high temperature of mobility loss, at least one fraction of which has low mobility loss temperature and high viscosity index for base oil. Method implies utilisation of dewaxing catalyst, which contains at least one zeolite (molecular sieve) chosen from a group of TON type zeolites (Theta-1, ZSM-22, ISI-1, NU-10 and KZ-2), and at least one ZBM-30 zeolite, at least one inorganic porous matrix, at least one hydrogenating/dehydrogenating element, preferentially from group VIB and group VIII of periodic table.

EFFECT: improved loss of mobility temperature for hydrocarbon material obtained by Fischer-Tropsch synthesis.

14 cl, 7 ex, 1 dwg

FIELD: physics.

SUBSTANCE: dewaxing procedure of raw material produced by Fischer-Tropsch method implies that processed raw materials contact with catalyst containing at least one zeolite ZBM-30, synthesised with triethylene tetramine, at least one hydrogenating- dehydrogenating element preferably selected from elements of group VIB and group VIII of periodic table, and at least one inorganic porous matrix.

EFFECT: good recovery of raw material, raised pour point.

13 cl, 5 ex, 1 dwg

FIELD: oil and gas industry.

SUBSTANCE: here is disclosed group of inventions related to versions of two-stage method of calalytic hydro-treatment of heavy oil hydrocarbons with high content of metals, total sulphur, pyrobitumens and total nitrogen, containing less, than 80% for volume of distillates extracted at 538°C and possessing density API lower, than 32°. According to the first version at the first stage hydrocarbons hydro-metallisation and hydrogen cracking of pyrobitumens are carried out, and at the second stage hydrocarbons hydro-desulphurisation and hydro-denitrogenation are performed; at that both stages of process are performed in a reactor with an immovable layer of catalyst. The second version includes: a) passing hydrogen and hydrocarbon raw material of heavy oil with specific mass (density) less, than 32° API and contents of distillates extracted at 538°C less, than 80% of volume through to the first stage of reaction for hydro-treatment of the said raw materials; at that the said first stage of reaction is performed in the reactor with the immovable layer of catalyst, containing a catalyst of hydro-demetallization and facilitating operation under pressure from 40 to 130 kg/cm2, at temperature from 320° to 450°C, at a volume speed (LHSV) from 0.2 to 3.0 hr-1 and at ratio of hydrogen/hydrocarbon (H2/HC) from 350 to 1.200 In/I with the result of production of hydro-treated heavy hydrocarbons; b) passing hydrogen and the said hydro-treated heavy hydrocarbons through to the second stage of reaction for hydro-treatment in the reactor with the immovable layer of catalyst containing hydro desulphurisation catalyst and facilitating operation under pressure from 40 to 130 kg/cm2, at temperature from 320° to 450°C, at a volume speed (LHSV) from 0.2 to 3.0 hr-1 and at ratio of hydrogen/hydrocarbon (H2/HC) from 350 to 1.200 In/I, at that the amount of sediments formed at each the said first and second stages of reaction is less 0.65% from weight of hydro-treated hydrocarbons. Also one of the inventions of the group refers to the product produced by the method according to the second variant. Employing of the said variant of the method facilitates high degree of metals, sulphur, nitrogen and pyrobitumens extraction and also limits formation of sediments which provides receiving the product after hydro-treatment with improved characteristics.

EFFECT: facilitating high degree of metals, sulphur, nitrogen and pyrobitumens extraction and also limits formation of sediments which provides receiving product after hydro-treatment with improved characteristics.

10 cl, 26 tbl, 10 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention refers to method of base oil processing with viscosity index within 80 to 140, made of charge stock in the form of vacuum distillate or asphalt-free oil and resulted from hydrogen contact of charge stock with catalyst containing group VIB metal and group VIII base metal on amorphous carrier, followed by dewaxing cycle. Method of base oil processing with viscosity index within 80 to 140 is made of charge stock in the form of vacuum distillate or asphalt-free oil by the following stages: caused hydrogen contact of charge stock with sulphided unfluorinated hydrosulphur removal catalyst containing nickel and tungsten on carrier based on acid amorphous silicon dioxide - aluminium oxide. Then pour point for product of stage (a) is lowered, and base oil is produced. Hydrosulphur removal catalyst is produced by method implying that nickel and tungsten are applied on the carrier based on acid amorphous silicon dioxide - aluminium oxide consequently from chelator impregnation.

EFFECT: developed processing method of base oil with viscosity index.

16 cl, 7 dwg, 3 tbl, 6 ex

FIELD: petrochemical processes.

SUBSTANCE: major amount of hydrocarbon stock is brought into countercurrent contact with hydrogen in first reaction zone under hydrogenation reaction conditions in presence of hydrogenation catalyst in at least first catalyst bed wherein liquid leaving stream comes out of the bottom of the first reaction zone and hydrogen-containing gas stream comes out of the top of the first reaction zone. After that, insignificant part of hydrocarbon-containing stock comes into contact with above-mentioned hydrogen-containing gas stream in the second reaction zone accommodating catalyst bed disposed in such a way as to receive hydrogen-containing stream from the first reaction zone.

EFFECT: enabled production of product with ultralow content of sulfur using simple processing flowsheet.

19 cl, 7 dwg

FIELD: production of super-low-sulfur diesel fuel; oil and gas producing industry.

SUBSTANCE: proposed method consists in stage-by-stage catalytic hydraulic cleaning of diesel fraction in presence of hydrogen-containing gas at elevated temperature and increased pressure. At the first stage of process, starting material - diesel fuel fraction at temperature of 180-260C is subjected to hydraulic cleaning. At hot separation of hydrogenation product obtained at the first stage, vapor phase and liquid phase - fractions boiling-off at temperature above 330C are obtained; liquid phase of hydrogenation product of the first stage is subjected to hydraulic cleaning at the second stage, thus obtaining the hydrogenation product of the second stage; then, both products are combined with vapor phase of the first stage hydrogenation product.

EFFECT: improved quality of product; low cost of process; increased life of catalyst.

1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to high activity ZSM-48. Described is a catalyst composition for removing paraffin from hydrocarbon material which contains ZSM-48 crystals, having molar ratio of silicon dioxide to aluminium oxide equal to or less than 110, which does not contain inoculating crystals different from ZSM-48 and does not contain ZSM-50 crystals.The invention also describes a method of producing ZSM-48 crystals contained in the composition described above, involving: preparation of an aqueous mixture of silicon dioxide or silicate, aluminium oxide or aluminic acid, hexamethonium salts and an alkaline base, where the mixture has the following molar ratios: silicon dioxide: aluminium oxide 70-110, base: silicon dioxide 0.1-0.3 and hexamethonium salt: silicon dioxide 0.01-0.05, and heating the mixture while stirring for a period of time and temperature sufficient for formation of crystals. The invention also describes a method of removing paraffin from hydrocarbon material in the presence of the catalyst composition described above.

EFFECT: obtained ZSM-48 crystals and a composition based on said crystals exhibit high activity during removal of paraffin from hydrocarbon material.

29 cl, 1 tbl, 6 dwg, 15 ex

FIELD: chemistry.

SUBSTANCE: invention refers to noble-metal catalyst, to method for making and application thereof. There is disclosed method for making noble-metal catalyst for hydrocarbon conversion, involving the stages as follows: a) preparation of the carrier containing zeolite, chosen from zeolites with medium and large pores and acid sites, at temperature within 423 to 1173 K and optional carrier modification; b) deposition of noble metal chosen from platinum, palladium, ruthenium, rhodium, iridium and their mixtures and combinations, by gas-phase deposition including evaporation of noble metal precursor chosen from β-diketonates and metallocenes, and interaction with the carrier, and c) heat treatment in oxidising or reducing environments. There is disclosed application of noble-metal catalyst produced by the method described above, in ring opening, isomerisation, alkylation, hydrocarbon reforming, dry reforming, hydrogenation and dehydrogenation, and preferentially, in ring opening of naphthenic molecules. Additionally, there is disclosed method for making medium diesel fuel distillate by introducing raw medium distillate into the reactor wherein it reacts at temperature 283-673 K and under pressure 10-200 bar with hydrogen with added noble-metal catalyst produced as described above until ring opening of naphthenes with two or more rings completed to produce isoparaffins, n-paraffins and mononaphthenes within medium distillate.

EFFECT: production of catalyst with improved selectivity for hydrocarbon conversion.

16 cl, 5 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: said invention relates to method for improvement of loss of mobility temperature of hydrocarbon material obtained by Fischer-Tropsch synthesis, in particular to satisfactory-yield conversion of material with high temperature of mobility loss, at least one fraction of which has low mobility loss temperature and high viscosity index for base oil. Method implies utilisation of dewaxing catalyst, which contains at least one zeolite (molecular sieve) chosen from a group of TON type zeolites (Theta-1, ZSM-22, ISI-1, NU-10 and KZ-2), and at least one ZBM-30 zeolite, at least one inorganic porous matrix, at least one hydrogenating/dehydrogenating element, preferentially from group VIB and group VIII of periodic table.

EFFECT: improved loss of mobility temperature for hydrocarbon material obtained by Fischer-Tropsch synthesis.

14 cl, 7 ex, 1 dwg

FIELD: physics.

SUBSTANCE: dewaxing procedure of raw material produced by Fischer-Tropsch method implies that processed raw materials contact with catalyst containing at least one zeolite ZBM-30, synthesised with triethylene tetramine, at least one hydrogenating- dehydrogenating element preferably selected from elements of group VIB and group VIII of periodic table, and at least one inorganic porous matrix.

EFFECT: good recovery of raw material, raised pour point.

13 cl, 5 ex, 1 dwg

FIELD: petroleum chemistry.

SUBSTANCE: invention relates to microcrystalline paraffin obtained by catalytic hydroisomerization at temperature more than 200°C from FT paraffin having from 20 to 105 carbon atoms. Microcrystalline paraffin is non-liquid at 25°C, but at least pasty with needle penetration less than 100x10-1, measured according to DIN 51579. Disclosed is method for production of microcrystalline paraffin.

EFFECT: microcrystalline paraffin free from naphthenes and aromatics.

17 cl, 1 dwg, 1 tbl, 3 ex

FIELD: production of catalysts.

SUBSTANCE: proposed method is used for production of catalyst containing zeolite and heat-resistant oxide binder at low acidity practically containing no aluminum; proposed method includes the following operations; (a) preparation of mass suitable for extrusion and containing homogeneous mixture of zeolite, water, binder of heat-resistant binder at low acidity which is present as acid sol and aminocompounds; (b) extrusion of mass obtained at stage (a) suitable for extrusion; (c) drying extrudate obtained at stage (b); and (d) calcination of dried extrudate obtained at stage (c).

EFFECT: increased strength of catalyst at high resistance to crushing.

10 cl, 1 tbl, 2 ex

FIELD: powder metallurgy; method of impregnation by a metal(of VIII group) of a molecular sieve extrudate with cementing material with the help of ion exchange with an aqueous solution of metal salt of VIII group.

SUBSTANCE: the invention presents a method of impregnation by metal of VIII group of an extrudate of a molecular sieve with cementing material, in which the cementing material represents a refractory oxidic material with a low acidity, practically free of aluminum oxide, using: a) impregnation of porous volume of an extrudate of a molecular sieve with cementing material with an aqueous solution of nitrate of the corresponding metal of VIII group with pH from 3.5 up to 7, in which the molar ratio between cations of a metal of VIII group in a solution and a number of centers of the adsorption available in the extrudate, is equal to or exceeds 1; b) drying of the produced at the stage a) extrudate of the molecular sieve with the cementing material. The technical result is good distribution of the metal and a short period of drying.

EFFECT: the invention ensures good distribution of the metal and a short period of drying.

9 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to high activity ZSM-48. Described is a catalyst composition for removing paraffin from hydrocarbon material which contains ZSM-48 crystals, having molar ratio of silicon dioxide to aluminium oxide equal to or less than 110, which does not contain inoculating crystals different from ZSM-48 and does not contain ZSM-50 crystals.The invention also describes a method of producing ZSM-48 crystals contained in the composition described above, involving: preparation of an aqueous mixture of silicon dioxide or silicate, aluminium oxide or aluminic acid, hexamethonium salts and an alkaline base, where the mixture has the following molar ratios: silicon dioxide: aluminium oxide 70-110, base: silicon dioxide 0.1-0.3 and hexamethonium salt: silicon dioxide 0.01-0.05, and heating the mixture while stirring for a period of time and temperature sufficient for formation of crystals. The invention also describes a method of removing paraffin from hydrocarbon material in the presence of the catalyst composition described above.

EFFECT: obtained ZSM-48 crystals and a composition based on said crystals exhibit high activity during removal of paraffin from hydrocarbon material.

29 cl, 1 tbl, 6 dwg, 15 ex

Up!