High activity zsm-48 and paraffin removal methods

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

 

This invention relates to ZSM-48 high activity. More specifically, receiving highly active ZSM-48 specific purity, and ZSM-48 does not contain non-ZSM-48 seed crystals.

The requirements for the basic raw materials of high quality for the preparation of compounds of machine oils and other lubricants are tougher due to the increasing importance of environmental issues. The main raw materials reinforced by the demand for basic raw materials, which must meet the requirements of Group II and Group III. So, the main raw material must meet the requirements of viscosity index (VI), viscosity, temperature fluidity and/or volatility imposed by government regulations and original equipment manufacturers. The increased requirements to the quality of the basic raw materials are limited by the capabilities of the cleaning solvent from the economic point of view. Even when using additives, compounded 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 was developed as an alternative to methods based on solvent, to produce high-quality basic raw material. The action of catalysts, DEPA is finitely based on two different mechanisms: some catalysts operate mainly due to isomerization, others, mainly due to hydrocracking. There are a few catalysts for dewaxing, if any such exist, with the ability to work exclusively with one of these mechanisms, excluding other mechanism. The dewaxing by hydrocracking can be carried out if the use of 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 stages of the production process to reduce the number of unwanted substances produced during the hydrocracking.

The dewaxing catalysts, which operate mainly through isomerization, turn paraffin molecules in molecules with branched chains. Molecules with branched chains may be required properties regarding YVES and temperature fluidity. ZSM-48 is an example of such a catalyst dewaxing. As noted in U.S. patent No. 5075269, ZSM-48 is produced using mixtures dicatating ammonium compounds as directing agents. As a directing agent, and the ratio of silica:alumina may affect the morphology of the crystal, although the choice of the direction of the Manager agent is a more significant factor. When using diamino and terminologia directing agent get sterjnevye or needle crystals. At high ratios of silica:alumina and when using dicatating ammonium directing agent resulting ZSM-48 has a lamellar morphology. If the ratio of silica:alumina decrease technology, using the preparation described in U.S. patent No. 5075269 or in U.S. patent No. 6923949, the purity of the crystals is becoming an increasing problem, so how do I get a competitive form of crystals other than ZSM-48 or ZSM-48 heterostructure contains the germ of the zeolite.

It is known that the morphology of the crystals can affect the behavior of the catalyst, especially on its activity and stability. Also, it is often desirable to have a small crystallite size, 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 can be done with high purity and which would have a high activity when used as a catalyst, and at the same time, favorable morphology.

In one aspect the invention relates to the composition of ZSM-48 high purity, containing particularly the full-time crystals other than ZSM-48 and ZSM-50. In various embodiments, the crystals of ZSM-48 can be crystals synthesized in the form H-form or Na-form. The composition may contain Kinijit or preferably not contain Kinijit. In another embodiment the composition of ZSM-48 does not contain crystals other than ZSM-48. In another embodiment the composition of ZSM-48 does not contain crystals having a fibrous morphology. In another embodiment the composition of ZSM-48 can contain acicular crystals. Preferably the composition of ZSM-48 does not contain acicular crystals.

In another aspect the invention provides a method of making crystals of ZSM-48 in synthesized form, containing hexamethonium guide the structure of the agent, where the crystals of ZSM-48 synthesized in the form does not contain ZSM-50 and the seed crystals other than ZSM-48. The method involves 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. The mixture has the following molar ratios: silica:alumina - from 70 to 110, base:silicon dioxide is from 0.1 to 0.3 and hexamethonium Sol:silicon dioxide - from 0.14 to 0.18. The preferred ratio hexamethonium Sol: silicon dioxide ranges from 0.15 to 0.25. The mixture is heated with stirring in a period of time and so is the temperature, sufficient for the formation of crystals.

In another aspect provides a method of dewaxing a hydrocarbon feedstock. The method includes bringing the feedstock into contact with a catalyst of the ZSM-48 of the present invention under conditions of catalytic dewaxing to obtain deparaffinizing product. The catalyst includes crystals of ZSM-48 having a molar ratio of silica:alumina from 70 to 110, and does not contain seed crystals other than ZSM-48 and ZSM-50.

Description of the drawings

Figure 1. Micrograph of crystals of ZSM-48, produced when the ratio of template:silicon dioxide, equal 0,023 showing 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 having a ratio of 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 having a ratio of 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 having a ratio of template:silicon dioxide, equal 0,019.

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

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

The invention relates to crystals of ZSM-48 high purity, with a specific morphology that does not contain the seed crystals other than ZSM-48 and ZSM-50, and method of manufacturing the composition of ZSM-48. Crystals of ZSM-48 can be crystals in synthetic form, which still include organic template, or annealed, such as crystals of ZSM-48 in the Na-form, or the crystals can be annealed and subjected to ion exchange, such as crystals of ZSM-48 in H-form. The term "not containing the seed crystals other than ZSM-48" means that the reaction mixture used to obtain ZSM-48, does not contain the seed crystals other than ZSM-48. In contrast, crystals of ZSM-48 synthesized in accordance with the invention, are either synthesized without the use of seed crystals or using seed crystals of ZSM-48. The term "does not contain Kinijit and ZSM-50" means that Kinijit and ZSM-50, if present, are contained in an amount which is not registered by x-ray diffraction analysis. Similarly, ZSM-48 high purity according to the present invention also does not contain crystals other than ZSM-48, to the extent that such other crystals also not re astronauts using x-ray diffraction analysis. This analysis was performed on the instrument Bruker D4 Endeavor Bruker AXS, equipped with high-speed detector Vantec-1. The device worked when using standard silicon powder (Nist 640), which is the material without internal stresses. The full-width half-maximum (PMPs) for the standard peak when 28,44 degrees 2θ equal 0,132. The step size is 0,01794 degrees and the magnitude of the time step is 2 sec. At the scan angle 2θ used copper target at 35 kV and 45 mA. The terms not containing fibrous crystals" and "does not contain acicular crystals" means that the fibrous and/or needle crystals, if present, are not detected scanning electron microscopy (SEM). Micrograph can be used to identify crystals of different morphology. For microphotographs shown in the drawings used scale of resolution 1 micron.

The x-ray crystal ZSM-48, obtained by x-ray diffraction analysis (RDA), according to the present invention is similar to the x-ray ZSM-48, i.e. the D-spacing and relative intensities are consistent with those that find pure ZSM-48. While RDA can be used to identify the zeolite, it cannot be used to identify specific morphology. For example, igol is striated and flat shapes for a given zeolite will give the same diffraction image. In order to recognize different morphology, it is necessary to use an analytical tool with high resolution. Such tool is a scanning electron microscope (SEM). Micrograph obtained with its use, can be used to identify crystals of different morphology.

Crystals of ZSM-48 after removal of the guide structure of the agent have 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, 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 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, grounds and hexamethonium salt as the directing agent. In one embodiments the molar ratio of the guide structure of the agent and the 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 the guide structure of the agent and the silicon dioxide in the mixture is at least 001; or at least 0,015; or at least 0,016. In another embodiment the molar ratio of the guide structure of the agent and the 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 yet 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. At any given preparation of crystals of ZSM-48 in synthesized form, the composition includes 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 slightly different than the molar ratio of the reagents of the reaction mixture used to prepare the synthetic form. This result can occur because of incomplete interaction 100% reagent mixture with the formation of crystals.

Zeolite ZSM-48, or annealed, or in synthetic form, which usually forms agglomerates of small crystals, which can have a size of from 0.01 to 1 μm. Oba is desirable but such small crystals, because they lead to greater activity. Crystals of small size provides a large surface area, which leads to a greater number of active catalytic centers in a given quantity of catalyst. Preferably, when the crystals of ZSM-48 in the annealed or synthesized form have morphology without fibrous crystals. Fibrous crystals are having a ratio L/D>10/1, where L and D are length and diameter of the crystal. In other embodiments, the crystals of ZSM-48 or in the annealed or synthesized form have a small amount of needle-shaped crystals, or do not contain them. The needle crystal is a crystal with a ratio of L/D<10/1, preferably less than 5/1, more preferably from 3/1 to 5/1. Analysis using the SEM shows that the crystals produced in accordance with the methods described herein are not registered crystals fibrous or needle-like morphology. Such morphology, separately or in combination with a low ratio of silica:alumina provides catalysts with high activity, and along with it, harmless to the environment.

The composition of ZSM-48 prepared from an aqueous reaction mixture comprising silicon dioxide or salt of silicic acid, aluminium oxide or soluble aluminum salt of the acid, the basis of which the W and smart agent. To obtain the desired crystal morphology reagents in the mixture has the following molar ratios:

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 ratios of base:silicon dioxide and guide structure agent:silicon dioxide. Wider ranges for these ratios include mixtures which are formed crystals of ZSM-48 with a number morphology keraita and/or needle-like morphology. If morphology keraita and/or needle-like morphology is objectionable should be used, the preferred ranges of proportions, as illustrated below in the examples.

The preferred source of silica is a precipitated silica manufactured by Degussa. Other sources of silicon oxide include 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 may be in the form dissolve the ima salt, preferably the sodium salt, and it supplies 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 dicatating ammonium or similar connection. The directing agent may serve hexamethonium salt, such as hexamethonium dichloride or hexamethonium hydroxide. Anion (non-chloride) may be, for example, hydroxide, nitrate, sulfate, other halide compound and similar compounds. Hexamethonium dichloride represents 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 specified above, and heated under stirring at a temperature of from 100 to 250°C. the Crystals can be formed directly from the 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 speed the formation of crystals, but not to influence their morphology. Do not include other seed crystals such as beta zeolite. 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 do not contain seed crystals other than ZSM-48 and ZSM-50. Preferably crystals of ZSM-48 should have a small amount keraita. In one embodiment, the content keraita may be 5% or less; or 2% or less; or 1% or less. In alternative embodiments, the crystals of ZSM-48 can generally not contain Kinijit.

The crystals obtained by synthesis according to the invention do not contain fibrous morphology. Fibrous morphology undesirable, because the morphology of crystals inhibits the catalytic activity of ZSM-48 during dewaxing. In another embodiment of the crystals obtained by the synthesis in accordance with the invention, have a morphology with a low percentage of needle morphology. The content of needle-like morphology in 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 needle-like morphology. Low content of needle-shaped crystals, preferably for some applications, as there is Uwe is over, what 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, corresponding to the embodiments of the invention. In addition, if you want composition not containing Kinijit and/or needle-like morphology, use the preferred ranges of these ratios.

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

If the synthesis of ZSM-48 with a significantly lower ratio of silica:alumina do not use heterogeneous seed crystals, inclusions of crystals of ZSM-50 becomes substantially more. When the ratio of the sending agent and silicon dioxide exceed 0.025 usually get agglomerates of mixed phases containing needle-like crystals. The preferred ratio of EOC is allaudio agent and silicon dioxide is approximately 0,022 or less. When the ratio of the sending agent and the silicon dioxide below approximately 0,015 begins the formation of the product containing Kinijit. Kinijit is an amorphous layered silicate, which is a form of natural clay. It does not show the activity of the zeolite type. On the contrary, it is relatively inert under the reaction conditions typically encountered during the processing of raw materials 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. The ratio of Oh:silicon dioxide (or other base:silica) and silica:alumina important for the morphology of the formed crystals, and their purity. The ratio of silica:alumina important for catalytic activity. The ratio of base:silicon dioxide is a factor influencing the formation of keraita. Use hexamethonium directing agent allows to obtain a product containing no fibrous material. The formation of needle-like morphology depends on the ratio of silica:alumina and guide structure agent:silicon dioxide.

Crystals of ZSM-48 synthesized in the form of at least partially dried before use or further about the development. Drying can be accomplished by heating at a temperature of from 100 to 400°C., preferably at a temperature of 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. Binders are stable at the temperature required in the application, and durable. The binder may be catalytically active or inactive and to include other zeolites, other inorganic materials such as clays and metal oxides, such as silicon dioxide, aluminium oxide and silicates. Clays may be kaolin, bentonite and montmorillonite, and they are available for sale. They can be mixed with other materials, such as silicates. In addition to the silicates can be used, and other porous matrix materials, including other binary materials such as magicality, sorosilicate, zirconium silicates, bellosillo and titanosilicates, as well as tricomponent materials, such as maniamerica, chorological, zirconosilicate. The matrix can be in the form of co-gel. The content of ZSM-48 is from 10 to 100% by weight. from the total mass of the bound ZSM-48, with the rest if estvo is binding.

Crystals of ZSM-48 as part of the catalyst, can also be used with metal component for hydrogenation. Metal components for hydrogenation can be selected from Groups 6 to 12 of the Periodic table, based on the IUPAC system, Groups 1-18; but it is preferable metals of Groups 6 and 8-10. Examples of such metals include Ni, Mo, Co, W, Mn, Cu, Zn, Ru, Pt or Pd, Pt or Pd is preferred. You can also use a mixture of metals for hydrogenation, such as Co/Mo, Ni/Mo, Ni/W or 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 also be to use solifidian. The catalyst may be to use subjected to the action of steam.

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 the floor is prohibited 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. The preferred raw waxes and paraffins 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 materials, containing up to 0.2% wt. nitrogen and up to 3.0 wt.%. sulfur based on the total weight 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 1-13), 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 VI is e 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. 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, one of them or in the mixture is from 0.5 to 35 wt.%, by weight of the 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., relative to the weight of the catalyst, and the metal of 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 temperatures of 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 20736 kPa (200 to 3000 pounds per square inch excess.), preferably from 2859 to 13891 kPa (400 to 2000 pounds per square inch excess.); space velocity from 0.1 to 10 h-1preferably from 0.1 to 5 h-1and soothes is the hydrogen supplied to the raw material from 89 to 1780 m 3/m3(from 500 to 10,000 standard cubic feet per barrel), preferably 178 to 890 m3/m3.

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 pounds per square inch excess.), preferably from 1480 to 17339 kPa (200 to 2500 pounds per square inch excess.), the volumetric rate of fluid from 0.1 to 10 h-1preferably from 0.1 to 5 h-1and the number obrabotochka gaseous hydrogen from 45 to 1780 m3/m3(from 250 to 10,000 standard cubic feet per barrel), preferably from 39 to 390 m3/m3(from 250 to 5000 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 finishing hydrobr the processing carried out at a temperature from 150 to 350°C. preferably from 180 to 250°C. the Total pressure is usually from 2859 to 20786 kPa (about 400 to 3000 pounds per square inch excess.). The volumetric rate of fluid is usually from 0.1 to 5 h-1preferably from 0.5 to 3 h-1and the number obrabotochka gaseous hydrogen is 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 one noble metal with a 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, aluminum oxide, silicates 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. Conventional materials media including the indicate amorphous or crystalline oxide materials, such as aluminum oxide, silicon dioxide and silicates. The content of base metals in the catalyst is often higher than about 20% wt. Precious metals are usually present in an amount of not more than 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. Amer. Chern. Soc, 1992, 114, 10834. Examples include MCM-41, MCM-48 and MCM-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. MSM-43 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 bear metal components for hydrogenation, of which minority who she 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.

Crystals of ZSM-48, obtained according to the present 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 an excellent activity and selectivity, as well as provide an excellent yield of the product. They also have environmental advantages, from the point of view of the health effects of crystalline form, and the small size of the crystals is also advantageous in respect of catalytic activity.

In addition to the embodiments described above, in one embodiment the invention relates to the composition of ZSM-48 high purity with a molar ratio of silica:alumina from 70 to 110, and ZSM-48 does not contain seed crystals other than ZSM-48, and fibrous crystals. Preferably crystals of ZSM-48 also has a low content of needle-like crystals or does not contain such crystals. Another embodiment relates to crystals of ZSM-48, which are synthesized in the form include ZSM-48 having a molar ratio of silica:alumina from 70 to 110, and the treatment is carried out from the reaction mixture, containing hexamethonium guide agent at 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 fibrous crystals. Preferably crystals of ZSM-48 also has a low content of needle-shaped crystals, or do not contain acicular crystals.

In yet another embodiment, the crystals of ZSM-48 synthesized in the form of annealed, whereby remove hexamethonium guide the structure of the agent with the formation of ZSM-48 high purity in the Na-form. ZSM-48 in the Na-form also can be subjected to ion exchange with the formation of ZSM-48 in H-form. In yet another embodiment, the crystals of ZSM-48 in synthesized form or annealed crystals of ZSM-48 (Na-form or H-form) is combined with at least one of the components such as a binder and a metal hydrogenation.

And in 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 ratios: dioxide lemnia:aluminium oxide is from 70 to 110, base:silicon dioxide is from 0.1 to 0.3, preferably from 0.14 to 0.8, hexamethonium Sol:silicon dioxide is 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 to form crystals. Perhaps adding to the reaction mixture of seed crystals of ZSM-48. The above procedure allows to obtain crystals of ZSM-48 in synthesized form, which contain hexamethonium guide the structure of the agent.

This invention is illustrated further by the following examples.

Example 1

A mixture was prepared from 1200 g of water, 40 g hexamethonium chloride (56% solution), 228 g of Ultrasil PM (powder precipitated silica from Degussa), 12 g of 45% sodium aluminate solution and 40 g of 50% sodium hydroxide solution. The mixture had the following molar ratios:

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 an autoclave with a volume of 2 l with stirring at 250 rpm for 48 hours. Specialists can recognize that factors such as the size of the autoclave and the type of mechanism for mixing, can give the desired speed of mixing and the time of the process. The resulting product was filtered, washed with deionized (DI) water and dried at a temperature of 250°F (120°C). Roentgenograms of the synthesized material, obtained by the method of RDA, illustrates a typical topology of a pure phase ZSM-48. SAM analysis of the synthesized material shows that the material consists of agglomerates of crystals mixed morphology (needle crystals and crystals of irregular shape). The obtained crystals of ZSM-48 have a molar ratio of SiO2/Al2O3~100/1. Figure 1 shows a micrograph of crystals of ZSM-48. This comparative example with respect to template:silicon dioxide, equal 0,023, shows the presence of a certain amount of needle-shaped crystals.

Example 2

A mixture prepared from water, hexamethonium chloride (55% solution), Ultrasil PM, 45% sodium aluminate solution and a 50% sodium hydroxide solution. The mixture had the following molar ratios:

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 synthesized material obtained by the method of RDA, illustrates a typical topology of a pure phase ZSM-48. SAM analysis of the synthesized material shows that the material consists of agglomerate the small crystals of irregular shape (with an average crystal size of approximately 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 the absence of needle-shaped crystals in ZSM-48 of the present invention.

Example 3

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

SiO2/Al2O3=103

H2O/SiO2=14,3

OH-/SiO2=0,17

Na+/SiO2=0,17

template/SiO2=0,029

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 synthesized material obtained by the method of RDA, illustrates a typical topology of a pure phase ZSM-48. SAM analysis of the synthesized material 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 have a molar ratio of SiO2/Al2O3~95/1. Figure 3 shows a micrograph obtained Crist is low ZSM-48. This comparative example shows the presence of needle-shaped crystals in ZSM-48 synthesized from a reaction mixture having a ratio of template:silicon dioxide, equal 0,029.

Example 4

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

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 synthesized material obtained by the method of RDA, illustrates a typical topology of a pure phase ZSM-48. SAM analysis of the synthesized material shows that the material consists of agglomerates of small crystals of irregular shape (with an average size of crystal <0,05 MK). The obtained crystals of ZSM-48 have a molar ratio of SiO2/Al2O3equal 89/1. Figure 4 shows a micrograph of the obtained crystals of ZSM-48. This example crystals of ZSM-48 really izobreteniya the absence of needle-shaped crystals.

Example 5

A mixture prepared from water, hexamethonium chloride (56% solution), modified Ultrasil Modified, 45% sodium aluminate solution, 50% sodium hydroxide solution and 3.5% wt. (on silica) seed crystals of ZSM-48. The mixture had the following molar ratios:

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 synthesized material obtained by the method of RDA, shows a mixture of ZSM-48 and traces of impurities keraita.

Example 6

A mixture prepared from water, hexamethonium chloride (56% solution), modified Ultrasil Modified, 45% sodium aluminate solution, 50% sodium hydroxide solution and 3.5% wt. (on silica) seed crystals of ZSM-48. The mixture had the following molar ratios:

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 obtained by the method of RDA synthesized material obtained from the reaction mixture with a ratio of base:silicon dioxide, equal to 0.20, shows a mixture of ZSM-48 and impurities keraita.

Example 7

A mixture prepared from water, hexamethonium chloride (56% solution), Ultrasil PM, 45% sodium aluminate solution, 50% sodium hydroxide solution and 3.5% wt. (on silica) seed crystals of ZSM-48. The mixture had the following molar ratios:

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 synthesized material obtained by the method of RDA, shows a typical topology of a pure phase ZSM-48.

Example 8

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

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 synthesized material obtained by the method of RDA, shows a typical topology of the phase ZSM-48 and traces of impurities ZSM-50. The product is an acicular morphology.

Example 9

65 parts (base: annealing 586°C) crystals of ZSM-48 high activity (Example 4) was mixed with 35 parts pseudoboehmite aluminum oxide (basis: annealing at 586°C) in a machine for molding mixture 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 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 annealed in nitrogen at 538°C. to decompose and remove the organic template. Annealed in the nitrogen product extrusion 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 (sample: <500 ppm Na). After treatment with ammonium nitrate extrudate was washed with deionized water to remove the remaining ions nitrate before drying. The extrudate after ammonium exchange was dried at a temperature of 121°C during the night and annealed in air at 538°C. After air annealing 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 annealed in air at 360°C for conversion of nitrate salts tetramine in the oxide of platinum.

Example 10

Deparaffinizing the 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 a ratio of silica:alumina of approximately 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, hexameta the rd chloride (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 ratios:

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 synthesized material obtained by the method of RDA shows the topology of a pure phase ZSM-48. The crystals in the synthesized form was 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 annealed 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 5% wt. the seed of beta-crystals (on silica). Heterostructural the nucleation when using beta crystals are described in U.S. patent No. 6923949. The mixture were prepared from 1000 g of water, 25 g hexamethonium chloride (56% races the thief) 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/Al2O3~35,5/1) as a seed. The mixture had the following molar ratios:

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 synthesized material obtained by the method of RDA shows the topology 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 annealed 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 the preparation of ZSM-48 with 10% wt. the seed of beta-crystals (on silica). Used reagents, the amount of reagents and about what Edery, described in Example 2, but as the directing agent used double the amount of beta crystals. Radiograph of the synthesized material obtained by the method of RDA shows the topology 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 annealed 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. Annealed 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. 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 of the activity of the catalyst relative activity compared the sustained fashion catalyst. The results of the analysis are presented in the table.

Table
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-hexa is as in Examples 12 and 13, as well as increasing the value of alpha for catalysts for the growth of crystals of the percentage of beta. The increase in the magnitude of adsorption of n-hexane and alpha values shows that the crystals of ZSM-48 with heterogeneous seed have a different reactivity than the crystals of ZSM-48 with homogeneous seed.

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 high 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 the volume obrabotochka gas 459 m3/m3(250 standard cubic feet per barrel). Figure 6 shows the dependence of the temperature is s in the reactor temperature, required to meet temperature fluidity 370°C+. Figure 6 the difference between the top line (representing ZSM-48 with a high ratio of silica:alumina) and bottom line (ZSM-48 of the present invention) gives an idea about the advantage in the activity.

1. Catalytic composition for dewaxing a hydrocarbon feedstock, comprising crystals of ZSM-48 having a molar ratio of silica: alumina equal to 110 or less, which does not contain the seed crystals other than ZSM-48, and does not contain crystals of ZSM-50.

2. The composition according to claim 1, in which crystals of ZSM-48 do not contain crystals having a fibrous morphology.

3. The composition according to claim 2, in which crystals of ZSM-48 do not contain crystals having a needle-like morphology.

4. The composition according to claim 1, in which crystals of ZSM-48 does not contain Kinijit.

5. The composition according to claim 1, in which crystals of ZSM-48 has a ratio of silica : alumina less than 100.

6. The composition according to claim 1, in which crystals of ZSM-48 do not contain crystals other than ZSM-48.

7. The composition according to claim 1, additionally containing at least one of the components such as a binder and a metal hydrogenation.

8. The composition according to claim 7, in which the metal hydrogenation is a noble metal.

9. The composition according to claim 1, in which crystals of ZSM-48 are Na, in the H-form or in synthetic form.

10. The composition according to claim 1, in which crystals of ZSM-48 obtained from a mixture containing hexamethonium guide the structure of the agent at a molar ratio of the guide structure agent : silicon dioxide from 0.01 to 0.05.

11. The composition of claim 10 in which the molar ratio of the guide structure agent : silicon dioxide is between 0.015 to 0.025.

12. The composition according to claim 1, in which crystals of ZSM-48 in synthesized form has a ratio of silica : alumina 100 or less.

13. The composition according to claim 1, in which crystals of ZSM-48 in synthesized form has a ratio of silica : alumina of at least 70.

14. The method of producing crystals of ZSM-48 synthesized in the form included in the composition according to any one of claims 1 to 13, containing hexamethonium guide the structure of the agent, where the crystals of ZSM-48 synthesized in the form does not contain crystals of ZSM-50 and the seed crystals other than ZSM-48, including: the preparation of an aqueous mixture of silicon oxide or salt of silicic acid, aluminum oxide or aluminum acid, hexamethonium salt and an alkaline base, where the mixture has the following molar ratios: silica : alumina from 70 to 110, base : silicon dioxide from 0.1 to 0.3 and hexamethonium Sol : silicon dioxide from 0.01 to 0.05 and the mixture heated Ave is stirring in the course of time and at a temperature sufficient for the formation of crystals.

15. The method according to 14, in which the mixture has a molar ratio of base : silicon dioxide from 0.14 to 0.18.

16. The method according to 14, in which the mixture has a molar ratio hexamethonium Sol : silicon dioxide between 0.015 to 0.025.

17. The method according to 14, in which crystals of ZSM-48 synthesized in the form of annealed to remove hexamethonium guide the agent framework.

18. The method according to 14, in which crystals of ZSM-48 in synthesized form is mixed with at least one of the components such as a binder and a metal component for hydrogenation.

19. The method according to 14, in which the synthesized crystals of ZSM-48 produced using seed crystals of ZSM-48.

20. The method according to 14, in which the synthesized crystals of ZSM-48 has a ratio of silica : alumina from 70 to 110.

21. The method of dewaxing a hydrocarbon feedstock, comprising bringing the feedstock into contact with a catalyst of the ZSM-48 under conditions of catalytic dewaxing to obtain deparaffinizing raw materials, and the catalyst includes crystals of ZSM-48 with a molar ratio of silica : alumina from 70 to 110, not containing seed crystals, non-ZSM-48, not containing crystals of ZSM-50, and these crystals of ZSM-48 obtained by the method according to any of p-20.

22. --- The on item 21, in which crystals of ZSM-48 do not contain crystals having a fibrous morphology.

23. The method according to item 22, in which crystals of ZSM-48 do not contain crystals having a needle-like morphology.

24. The method according to item 21, in which crystals of ZSM-48 does not contain Kinijit.

25. The method according to item 21, in which the raw materials before bringing into contact with a catalyst of the ZSM-48 is subjected to hydrobromide under conditions of hydrobromide.

26. The method according to item 21, in which deparaffinization raw material is subjected to finish hydrobromide under conditions of finishing hydrobromide.

27. The method according to item 21, 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 to 3000 pounds per square inch excess.), the volumetric rate of fluid from 0.1 to 10 h-1and the number obrabotochka gaseous hydrogen from 45 to 1780 m3/m3(from 250 to 10,000 standard cubic feet per barrel).

28. The method according A.25, 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 to 3000 pounds per square inch excess.), space velocity from 0.1 to 10 h-1and the ratio of hydrogen supplied to the raw material from 89 to 1780 m3/m3(from 500 to 10,000 standard cubic feet per barrel).

29. The method according to p in which conditions finishing hydrobromide include a temperature of from 150 to 350°C., a total pressure from 2859 to 20786 to the a (from 400 to 3000 lbs/sq. inch excess), space velocity in the range from 0.1 to 5 h-1and the ratio of hydrogen supplied to the raw material from 44.5 to 1780 m3/m3(from 250 to 10,000 standard cubic feet per barrel).



 

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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

The invention relates to a method for the catalytic dewaxing of hydrocarbon raw material containing molecules of paraffin and more than 500 weight

FIELD: chemistry.

SUBSTANCE: invention relates to synthesis of zeolites. A method is described for synthesis of zeolite beta, in which the template used is a mixture which contains diethylenetriamine and a compound with tetraethylammonium cations. The reaction mixture, which contains sources of silicon, aluminium and the template, is kept at 70-200°C until formation of zeolite beta crystals.

EFFECT: obtaining zeolite beta with improved filterability.

11 cl, 8 ex

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