Light hydrocarbon aromatization process catalyst, method for preparation thereof, and aromatic hydrocarbon production process

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention relates to processes for hydrocarbon feedstock conversion into aromatic hydrocarbons, in particular to light hydrocarbon aromatization process catalysts, to catalyst preparation processes, and aromatic hydrocarbon production processes. A composite light hydrocarbon aromatization process catalyst is described, which contains acidic microporous component with pore size at least 5 Å and oxide component exhibiting dehydrogenation activity and selected from aluminum hydroxide and/or oxide having transportation pore size at least 20 nm, said oxide component having been treated with promoter element compounds. Described are this catalyst preparation method and aromatic compound production process in presence of above-described catalyst.

EFFECT: increased activity and selectivity regarding formation of aromatic hydrocarbons and stabilized functioning of catalyst.

11 cl, 1 tbl, 23 ex

 

The invention relates to methods for hydrocarbon processing, namely, processing of light hydrocarbons to more valuable products - aromatic hydrocarbons, as well as to methods of preparation of the catalyst for aromatic hydrocarbons.

The resulting aromatic compounds can be used as high-octane additives to motor fuels and as raw materials for further processing, as a result of individual aromatic hydrocarbons, solvents, intermediates for the main and fine organic synthesis.

The reaction of formation of aromatic compounds from aliphatic hydrocarbons is a sequence of intermediate reactions as acid mechanism, and represents the reaction of dehydrogenation. Therefore, the aromatization catalyst must have centers, leading both of these reactions. The most common method of obtaining aromatic hydrocarbons is a method of processing hydrocarbon material through aromatization catalyst prepared by introduction of a microporous material having acidic properties promoting additives, which are most commonly used compounds of gallium and/or zinc. As ICRI is a porous material is used most often zeolite with structure of ZSM-5 or ZSM-11. In this connection modifying elements or are introduced into the material during the hydrothermal synthesis, or with the subsequent introduction of modifying additives by impregnation, ion exchange, or other way. Thus obtained microporous material has a bifunctional properties: acidity, which is determined by the presence of acid centers on the surface of the material and within its pores, and also dehydrating properties, which are determined by the presence on the surface or within the microporous material atoms of the respective elements. Therefore, in the composition of the microporous material are the centers of two types: responsible for conducting the reaction of the acid type and are responsible for carrying out the dehydrogenation reaction. Thus, the density of centers per unit surface area and/or volume of the prepared catalyst is substantially increased.

Obviously, the effectiveness of the aromatization catalyst depends on the optimal balance between the centers of both types in the composition of the prepared sample and their optimal locations relative to each other.

There are various ways to prepare catalysts for aromatic hydrocarbons from paraffins and olefins With2and above. As starting material for the preparation produce the ditch using zeolites of the ZSM family, zeolites other structural types, as well as microporous alumophosphate different structural types or other compounds, for example silica gel, amorphous aluminosilicate, and other Source material promotirovat compounds of zinc, gallium, rare or precious metals, which have dehydrating properties. While promoting additive is introduced into the composition of the material or during hydrothermal synthesis starting material, or by impregnation, ion exchange, solid-phase reaction, or any other way, using the existing material. Next, the obtained samples are conducting the reaction for aromatic hydrocarbons, mostly paraffins and/or olefins With2-C6at temperatures below 300°often 400-600°C, at pressures up to 2 MPa and volumetric flow rates of gas mixtures up to several thousand h-1(US 4629818, SS 12/02, 16.12.86; US 4665251, C07C 1/20, 12.05.87; US 4157356, SS 15/02, 05.06.76).

The disadvantages of these methods is that the centers responsible for acid and dehydrating functions are part of the same microporous material. Attempts to introduce an increased content of the modifying additive in the composition of the acidic material will lead to the fact that the metal will block the acid centers on the surface of the material, and also close the entrances into its pores. In addition, povyshen the s content of the metal on the surface of the material leads to coarsening of the particles and the formation of agglomerates of atoms promoting element. This leads to the formation of centers with undesirable properties, leading to adverse reactions. In practice, the main problem of the catalysts for the aromatization of aliphatic hydrocarbons is low stability actions prepared samples due to the formation necesarrily compounds with the catalyst surface. The reason for this may be the sub-optimal concentration ratio of the centers of the two types, the optimal particle size of the promoting element and a non-optimal distance between the different centers on the catalyst surface. Moreover, the atoms of the promoting metals on the surface of the microporous material, often act as centers of coke formation, which leads to a rapid drop in activity of the prepared catalyst.

Closest to the proposed invention in its technical essence and the achieved effect is a method of refining hydrocarbons into aromatic hydrocarbons in the presence of complex (hybrid) catalyst comprising a mixture of zeolite with structure Pancasila, ZSM-5 or ZSM-11, and socializaton representing gallium oxide, deposited oxide, selected from the following group: silicon oxide, aluminum oxide, chromium oxide (US 5135898, B01J 029/28, 25.07.91). It is noted that as a zeolite with structure Penta is the sludge can be used sample, aluminum atoms which is partially or fully substituted with gallium atoms. Further, it is noted that socialization representing the deposited gallium oxide behaves as a hydrogen trap, capturing molecules of hydrogen released during the aromatization of paraffins and olefins. The aromatization reaction proceeds inside the channels of zeolite and formed hydrogen migrates to the particle socializaton outside the zeolite. Thus prepared catalyst is more active and selective in the aromatization of light paraffins and olefins in comparison with standard methods of preparation of catalysts for aromatization. In this case, as shown in the examples, prototype, acetalization may not contain atoms of the promoting element is gallium, and even in this case, the yield of aromatic hydrocarbons is comparable with the result obtained on the classic aromatization catalyst: the catalyst of the process "Cyclar". Thus, in this case the main purpose of socializaton really is pulling the hydrogen molecules from the zeolite as a "hydrogen bomb". From the comparison of the results presented in the prototype, can be seen (tables 1, 2)that the introduction of the hybrid catalyst promoting element, gallium, lead to improvements in the activities of the Oia catalyst, however, this increase is different for different types of "inert oxide material. So, for example, colloidal silica introduction of gallium increases the conversion of n-butane with 90,5 to 98,7% by weight and to increase the yield of aromatic hydrocarbons with 37,7 to 64,3%by weight. However, for neutral aluminum oxide enhancing the conversion of n-butane is from 97.7 to 98.1 wt.%, and the increase in the yield of aromatic hydrocarbons from 33.4 to 42.9 wt.%. Thus, the given examples show that the as-prepared hybrid catalyst depends on the properties of the inert oxide material and the interaction of the promoting element with the surface of the oxide material. In the prototype does not address the impact properties of the used oxide material on the quality of the hybrid catalyst.

Moreover, although in accordance with the prototype as the zeolite component of the use of microporous materials prepared in accordance with the patents US 3702886, B01J 20/18, 14.11.1972 and US 3709979, B01J 29/04, 09.01.1973, in the description of these patents indicates that the composition of the prepared zeolites can contain atoms of other elements, such as gallium. This assumption is assumed in the description of the prototype. Thus, in the description of the prototype, there is no unequivocal certainty, whether the source zeolites ZSM-5 and ZSM-11 atoms is Allie in its structure. As can be seen from the data of catalytic tests shown in the prototype, the activity of the original zeolite in the reaction of aromatization of n-butane is quite high, therefore, the original zeolites possess catalytic activity in the aromatization of n-butane, and socializaton only act as a hydrogen trap, dilatory themselves formed of molecules of hydrogen and only thereby improving the performance of the final hybrid catalyst.

The main disadvantage of hybrid catalyst prepared according to the prototype is that the aromatization reaction takes place inside the channels of the zeolite catalyst, as noted in the prototype, and socialization containing gallium oxide, is used only as a hydrogen trap, and this effect is observed even in the absence of the composition of the oxide phase of the promoting element. Accordingly, the centers responsible for the reactions of acid type, and is responsible for the reaction of dehydrogenation, are located on the surface of the microporous material, which leads to difficulty choosing the optimal balance between the concentrations of these centers. Reaction of the acid type proceed with participation of acid sites of the zeolite, located inside the zeolite channels, and on the outer surface of the zeolite crystals. The reaction of dehydrogenation about the ecay on the outer surface of the zeolite crystals with the participation of extra framework metal atoms. Such atoms in addition to perform its direct functions can block the acid sites located on the surface of the zeolite, and close the entrance of the pore; in addition, the extra framework atoms act as centers of coke formation, which leads to a rapid drop in activity of the prepared catalyst.

The disadvantage of the prototype is that as the oxide component of the hybrid catalyst is selected oxide selected from the following group: silicon oxide, aluminum oxide, chromium oxide, which does not have a developed system of transport pores that can contribute to improved mass transfer between the components of hydride catalyst. So, it is well known that almost all of the oxides or hydrated oxides of aluminum have transport then, the average size of which does not exceed 15 nm, and in most cases is 5-10 nm.

The invention solves the problem of creating an improved method of producing aromatic hydrocarbons and improved method of preparation of catalyst for aromatization of aliphatic hydrocarbons, characterized by high activity and selectivity for the formation of aromatic hydrocarbons, as well as increased stability of the catalytic activity.

The problem is solved by a method of processing coal is of Ogorodov 2-C6in aromatic hydrocarbons using bifunctional complex catalyst prepared by mixing the two components, in which the acid function has a microporous component of the catalyst with the size of the micropores is not less than 5 Åand dehydrating function - modifying oxides of the elements supported on a carrier: aluminum oxide and/or hydroxide of aluminum, with a developed system of transport pores, which allow an efficient mass transfer between the two components of the complex catalyst.

Improved in comparison with the prototype performance is achieved due to:

- optimization of the porous structure of the media;

- optimize the balance between acid and dehydrating of functions of a complex catalyst;

- allocation optimization promoting dehydrating component grains of the media;

- increase the activity of the catalyst due to explode acid and dehydrating functions of different constituents of a complex catalyst resulting in the lack of lock promoting component of the acidic centers and openings of the pores of the zeolite;

- increase the stability of the complex catalyst aromatization due to the absence on the surface of the zeolite component atoms of the promoting element, which could the t to represent the additional centers of coke formation.

For the preparation of granules industrial catalyst powder source active material with the desired properties is formed with a binder constituting the oxide and/or hydroxide of one or more elements of aluminum, silicon, magnesium, amorphous aluminosilicate, clay, etc. Usually in the case of preparation of industrial catalysts for the aromatization zeolite material containing compounds of the promoting elements, molded with a binder, usually an oxide or hydroxide of aluminum. Because the binder does not contain in its composition of the active catalyst components, the function of the binder is only in giving strength properties of the final catalyst and, in fact, it represents an inactive component of the catalyst flavoring.

In the course of conducting studies to determine the impact properties of various oxides of aluminum and/or aluminum hydroxide on its possible use as an integral part of a comprehensive aromatization catalyst, in particular as a carrier for the promoting elements, identified the major requirements oxide or aluminum hydroxide and allowing to prepare the active complex catalyst flavoring.

For the implementation of the present invention has been developed a method of obtaining a hydrated oxide is of luminia, with specific porous properties, namely, the branched system of transport pores with an average diameter of about 50 nm by granulation resulting amorphous aluminum oxide with an average diameter of the transport time of not more than 15 nm. The use of biporous hydrated aluminum oxide with wide pores as a carrier for promoting items enables you to evenly apply the promoting elements in the required concentrations, freely to exercise the mass transfer of molecules of the source of hydrocarbons and products of the reaction between the components of the complex catalyst and, consequently, to increase the activity of the prepared catalyst in the reaction of aromatization.

Thus, increased activity and selectivity for the target products proposed in the present invention the complex catalyst in the reaction of aromatization of aliphatic hydrocarbons is a consequence of the interaction between two parts of a catalyst, characterized by its functional purpose. Zeolite component is responsible for the reactions of acid type and an oxide component, treated with compounds of the promoting elements, is responsible for the reaction of dehydrogenation. Optimization of the porous structure of the media for promoting elements bring is to implement easy and effective mass transfer of molecules of raw materials and products of the reaction between the two components of the complex catalyst, and also enables you to evenly distribute the promoting element at grain media. The diversity of catalytic functions in two parts of the complex catalyst allows, moreover, to adjust the ratio of acid and dehydrating component. Moreover, separation of acidic and dehydrating functions of different constituents of a complex catalyst resulting in no lock promoting component of the acidic centers of the zeolite and the input apertures of the pores. Finally, the preparation of complex catalyst leads to an increase in the stability of its actions in the reaction of aromatization due to the absence on the surface of the zeolite component unstructured elements, in particular atoms promoting element, which can be an additional centers of coke formation.

The problem is solved by the method of preparation of the complex catalyst for aromatization, representing a composite of a microporous material with a pore size not less than 5 Å and hydroxide and/or aluminum oxide with a size of transport has not less than 20 nm, treated with compounds of the promoting elements, and processing of aliphatic hydrocarbons2-C6in aromatic hydrocarbons at the reaction temperature not lower than 400°With, a volumetric flow of feedstock is not more than 10000 h-1 , the pressure is not more than 10 MPa, in the presence of the specified prepared complex catalyst.

As microporous materials having acidic properties and acting as an integral part of the complex catalyst, use of aluminosilicate zeolites having a pore size of not less than 5 Åfor example, zeolites with structure of ZSM-5, ZSM-11, BETA, and others.

The second variant of the method of preparation of complex catalyst flavoring includes the use as a component part of a complex catalyst microporous substituted elementselector containing in its structure boron, iron, gallium, chromium, and having a pore size of not less than 5 Åfor example, having the structure of ZSM-5, ZSM-11, BETA, etc.

As part of a complex oxide catalyst prepared according to any one of two ways, using aluminum hydroxide and/or aluminum oxide, has specially developed an extensive system of transport pores with an average size of not less than 20 nm, allowing easy and efficient mass transfer of molecules of the source of hydrocarbons and products of the reaction between the two components of the complex catalyst. To give the dehydrating properties of the aluminum hydroxide and/or aluminum oxide is treated with compounds of the promoting elements, which are used in isout gallium and/or zinc in certain quantities, to effectively carry out the reaction of aromatization.

The ratio of the microporous and the oxide component is chosen in such a way as to obtain maximum efficiency of the complex catalyst in the reaction of aromatization. In General, the content of the oxide component in the complex catalyst is not more than 50 wt.%, and the content of the promoting elements in the complex catalyst is not more than 10 wt.%.

Microporous component of the complex catalyst may optionally be treated with acid solutions, for example, nitrogen, sulfosalicylic and other

Microporous component of the complex catalyst may optionally be treated with compounds of rare-earth elements, and/or platinum group metals.

The promoting elements on the surface of aluminum hydroxide and/or aluminum oxide contribute by impregnation, or activated impregnation autoclave, or their application from the gas phase, followed by drying and calcining the obtained oxide system.

Next two parts of the complex catalyst are mixed, and a method of mixing two components of the complex catalyst may be different: using a mechanical mixer, a ball mill, etc.

Thus prepared complex catalyst can be used in the de fraction of a certain size or in the form of granules. For the preparation of granules of complex catalyst in the process of mixing can also be liquid, for example water.

Prepared complex catalyst prior to its use in the process of aromatization may be calcined in air at temperatures up to 600°C.

In the process of aromatization using complex catalyst prepared as starting materials are aliphatic hydrocarbons: paraffins and/or olefins with the number of carbon atoms 2-6.

The main distinguishing feature of the proposed method is that the processing of aliphatic hydrocarbons2-C6in aromatic hydrocarbons is carried out in the presence of a complex catalyst comprising a composite of a microporous material with a pore size not less than 5 Åand aluminum hydroxide and/or aluminum oxide with a size of transport has not less than 20 nm, treated with compounds of the promoting elements.

The technical effect of the proposed method is that when the conversion of hydrocarbons With2-C6in the presence of a complex catalyst of the above composition is achieved by increased activity in the conversion of aliphatic hydrocarbons, increasing the selectivity towards formation of aromatic hydrocarbons and invites the stability actions prepared complex catalyst compared to a catalyst for aromatization, prepared by standard known methods.

The method is as follows.

As the source of microporous materials, acting as part of the complex catalyst, use of aluminosilicate zeolites with pore size of not less than 5 Åfor example, zeolites with structure of ZSM-5, ZSM-11, BETA, and others. It is best to use zeolites with structures of ZSM-5 or ZSM-11 with a molar ratio of SiO2/Al2O3not more than 100. In the case of microporous substituted elementselector it can be silicates with pore size of not less than 5 Å introduced during the synthesis of the elements: boron, iron, gallium, chromium, and having the structure of ZSM-5, ZSM-11, BETA, etc.

Microporous component of the complex catalyst may optionally be treated with acid solutions, for example, nitrogen, sulfosalicylic and other

Microporous component of the complex catalyst may optionally be treated with compounds of rare-earth elements, and/or platinum group metals.

As part of a complex oxide catalyst using aluminum hydroxide and/or aluminum oxide with a specially developed an extensive system of transport pores with an average size of not less than 20 nm. The oxide part of the complex catalyst is treated with compounds of promotiedoeleinden, which uses gallium and/or zinc in certain quantities not exceeding 10 wt.% at the mass end of the complex catalyst.

The promoting elements to the surface of the oxide part of a comprehensive catalizadores introduction by impregnation, or activated impregnation autoclave, or their application from the gas phase, followed by drying and calcining the obtained oxide system.

Next two parts of the complex catalyst is mixed. The method of mixing of the two components of the complex catalyst may be different: using a mechanical mixer, a ball mill, etc.

Thus prepared complex catalyst can be used in the form of a fraction of a certain size or in the form of granules. For the preparation of granules of complex catalyst in the process of mixing can also be liquid, for example water.

Prepared complex catalyst prior to its use in the process of aromatization may be calcined in air at temperatures up to 600°C.

The catalyst in the form of fractions or in the form of granules is placed in a flow reactor, rinsed or nitrogen, or hydrogen, or methane, or an inert gas or mixtures thereof at temperatures up to 600°With, then served raw materials with a total expenditure not more than 10 000 h-1that temperature is at least 400 round° With that pressure of not more than 10 MPa.

The following examples describe in detail the present invention.

Example 1. Synthesis of microporous materials to illustrate examples of the invention, different chemical and structural properties was carried out in accordance with the techniques described in the patents of the Russian Federation 2174952, 20.10.2001 and 2214965, 27.10.2003.

Example 2 (comparative). Powdered aluminosilicate zeolite ZSM-5 prepared according to the method indicated in example 1, to prepare a fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) for 1 h at 550°With, then stop the flow of nitrogen and at the same temperature and at a pressure of 0.4 MPa begin feeding n-butane with a bulk velocity of 750 h-1. Data of catalytic tests are shown in table 1.

The example shows that the aluminosilicate zeolite has a very small activity in the reaction of aromatization of n-butane.

Example 3 (comparative). 15 g of the powder aluminosilicate zeolite ZSM-5 is mixed with gidratirovannym aluminum oxide (pseudoboehmite) ratio of 20 wt.% Al2O3in the final catalyst, and then calcined at 550°and prepare the fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) for 1 h at 550°With, then stop the flow of nitrogen and at the same temperature and at a pressure of 0.4 MPa begin feeding n-butane with a bulk velocity of 750 h -1. Data of catalytic tests are shown in table 1.

The example shows that the aluminosilicate zeolite is mixed with aluminum oxide has a low activity in the reaction of aromatization of n-butane.

Example 4. (the prototype). Hydrated alumina is impregnated with nitrate gallium to gallium content of 10 wt.%.

15 g of the powder aluminosilicate zeolite ZSM-5 is mixed with gidratirovannym aluminum oxide containing gallium, the ratio of 20 wt.% Al2About3in the final catalyst, and then calcined at 550°and prepare the fraction of 0.2 to 0.8 mm, the catalyst contains 2.0 wt.% gallium.

4 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) for 1 h at 550°With, then stop the flow of nitrogen and at the same temperature and at a pressure of 0.4 MPa begin feeding n-butane with a bulk velocity of 750 h-1. The example shows that the aluminosilicate zeolite is mixed with aluminum oxide containing gallium, has a high activity in the reaction of aromatization of n-butane, compared with catalyst without gallium.

Example 5. Solution of colloidal silica Ludox AS-40 (DuPont Corp.) carefully dried on a hot surface until dry, and then made red-hot at 550°C.

15 g of the powder aluminosilicate zeolite ZSM-5 is mixed with procula the major colloidal silica ratio of 20 wt.% SiO 2in the final catalyst, after which the sample annealed at 550°and prepare the fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) for 1 h at 550°With, then stop the flow of nitrogen and at the same temperature and at a pressure of 0.4 MPa begin feeding n-butane with a bulk velocity of 750 h-1.

The example shows that the aluminosilicate zeolite is mixed with silicon oxide has a very small activity in the reaction of aromatization of n-butane.

Example 6 (the prototype). Solution of colloidal silica Ludox AS-40 (DuPont Corp.) carefully dried on a hot surface until dry, made red-hot at 550°and then impregnated with a solution of gallium nitrate at the rate of 10 wt.% gallium.

15 g of the powder aluminosilicate zeolite ZSM-5 is mixed with calcined colloidal silicon oxide containing gallium, the ratio of 20 wt.% SiO2in the final catalyst, after which the sample annealed at 550°and prepare the fraction of 0.2 to 0.8 mm, the catalyst contains 2.0 wt.% gallium.

4 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) for 1 h at 550°With, then stop the flow of nitrogen and at the same temperature and at a pressure of 0.4 MPa begin feeding n-butane with a bulk velocity of 750 h-1. the C example shows, what aluminosilicate zeolite is mixed with silicon oxide containing gallium, has a high activity in the reaction of aromatization of n-butane, compared with catalyst without gallium.

Example 7 (comparative). 25 g of the powder aluminosilicate zeolite ZSM-5 pour 0.5 liters of a solution containing 20 g of gallium nitrate. The resulting suspension is boiled with stirring and reflux for 10 h, after which the powder is separated on a filter and washed repeatedly with distilled water. The sample obtained is dried at room temperature and calcined at 500°C. the Zeolite contains 1.6 wt.% gallium.

The prepared sample is mixed with alumina ratio of 20 wt.% Al2O3in the final catalyst, and then calcined at 550°and prepare the fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) for 1 h at 550°With, then stop the flow of nitrogen and at the same temperature and at a pressure of 0.4 MPa begin feeding n-butane with a bulk velocity of 750 h-1.

The example shows that the processing of the aluminosilicate zeolite promoting element, gallium, leads to an increase in the activity of the catalyst in the reaction of aromatization of n-butane.

Example 8. Ga-containing aluminosilicate zeolite of example 5 is mixed with calcined colloidal oxide to Omnia ratio of 20 wt.% SiO 2in the final catalyst, after which the sample annealed at 550°and prepare the fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) for 1 h at 550°With, then stop the flow of nitrogen and at the same temperature and at a pressure of 0.4 MPa begin feeding n-butane with a bulk velocity of 750 h-1.

Example 9 (prototype). 2.3 g of gallium nitrate was dissolved in 5 ml of water. This solution was added 4.5 g of a solution of colloidal silica Ludox AS-40 (DuPont Corp.), and the resulting solution was stirred for a few minutes, and then dried on a hot surface and annealed at 550°C.

15 g of the powder aluminosilicate zeolite ZSM-5 is mixed with the calcined mixed oxide ratio of 20 wt.% SiO2in the final catalyst, after which the sample annealed at 550°and prepare the fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) for 1 h at 550°With, then stop the flow of nitrogen and at the same temperature and at a pressure of 0.4 MPa begin feeding n-butane with a bulk velocity of 750 h-1.

Example 10 (comparative). 30 g of the powder of the aluminosilicate with the structure of ZSM-11 prepared in accordance with the method specified in example 1 is impregnated with an aqueous solution of zinc acetate, the rate of 3.5 wt.% zinc in the end the second catalyst. The sample obtained is dried at 100°and calcined at 550°C. the Prepared sample formed with gidratirovannym alumina ratio of 20 wt.% Al2About3in the final catalyst, making granules, and then calcined at 550°and prepare the fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor.

Example 11 (comparative). 30 g of the powder zhelezohromovye with the structure of ZSM-11 prepared in accordance with the method specified in example 1 is impregnated with an aqueous solution of gallium nitrate at the rate 2.5 wt.% gallium in the final catalyst. The sample obtained is dried at 100°and calcined at 550°C. the Prepared sample formed with gidratirovannym alumina ratio of 20 wt.% Al2O3in the final catalyst, making granules, and then calcined at 550°and prepare the fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor.

Example 12 (comparative). 20 g of the powder barelypolitical with the structure of ZSM-5, prepared in accordance with the method specified in example 1 is impregnated with an aqueous solution of zinc acetate, the rate of 2.2 wt.% zinc in the final catalyst. The sample obtained is dried at 100°and calcined at 550°C. the Prepared sample is mixed with gidratirovannym alumina ratio of 20 mA is.% Al 2O3in the final catalyst, and then calcined at 550°and prepare the fraction of 0,2-0,8 mm 4 g of the obtained catalyst is placed in a flow reactor.

Example 13. Preparation of zinc-containing oxide part of the complex catalyst. Hydrated aluminum oxide with an average size of transport has not less than 20 nm is impregnated with an aqueous solution of zinc acetate on the basis of 14 wt.% zinc, then dried and calcined at 500°C.

Example 14. Preparation of gallium-containing oxide part of the complex catalyst. Hydrated aluminum oxide with an average size of transport has not less than 20 nm is impregnated with an aqueous solution of gallium nitrate at the rate of 10 wt.% gallium, and then dried and calcined at 500°C.

Example 15. Preparation of zinc-gallium-containing oxide part of the complex catalyst. 25 g of hydrated aluminum oxide with an average size of transport has not less than 20 nm and 8 g of zinc nitrate dissolved in 50 g of water, loaded into an autoclave and heated at a temperature of 175°C for 10 h, and then dried and calcined at 500°C. the Content of zinc in the final aluminum oxide and 9.5 wt.%.

Example 16. Preparation of zinc-containing oxide part of the complex catalyst. Hydrated aluminum oxide with an average size of transport has not less than 20 neradovac nitrogen, containing a pair of zinc acetylacetonate at a temperature of 250°C. After the number passing through the sample acetylacetonate zinc will match the content of zinc in the sample 6 wt.%, stop the supply of nitrogen and purge the sample air at a temperature of 560°C for 3 hours

Example 17. 25 g of the powder aluminosilicate zeolite ZSM-5 prepared in accordance with the method specified in example 1 is mixed with the zinc-containing alumina from example 11, method to obtain a 25 wt.% Al2About3in the final catalyst, which corresponds to 3.5 wt.% zinc in the final sample. The catalyst calcined at 500°With, then draw a fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor.

Example 18. 30 g of the powder of the aluminosilicate with the structure of ZSM-11 is formed with the aluminum oxide from example 11, containing zinc, from calculation to obtain a 25 wt.% Al2O3in the final catalyst, which corresponds to 3.5 wt.% zinc in the final sample. The catalyst calcined at 500°With, then draw a fraction of 0,2-0,8 mm 4 g of the obtained catalyst is placed in a flow reactor.

Example 19. 25 g of the powder zhelezohromovye with the structure of ZSM-11 is formed with the aluminum oxide of example 12 containing gallium, calculated to obtain a 20 wt.% Al2O3in to enom catalyst, which corresponds to 2.0 wt.% gallium in the final sample. The catalyst calcined at 500°With, then draw a fraction of 0,2-0,8 mm 4 g of the obtained catalyst is placed in a flow reactor.

Example 20. 20 g of barelypolitical with the structure of ZSM-5, prepared in accordance with the method specified in example 1 is mixed with aluminum oxide from example 13 containing zinc thus, to obtain 2.2 wt.% zinc in the final sample. The catalyst calcined at 500°With, then draw a fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor.

Example 21. 25 g of the powder aluminosilicate zeolite ZSM-5 is mixed with aluminum oxide from example 14, containing zinc, and aluminum oxide from example 12 containing gallium, from calculation to obtain the total content of 2.0 wt.% zinc and 1.0 wt.% gallium in the final sample. The catalyst calcined at 500°With, then draw a fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor.

Example 22. 20 g of zeolite with structure BETA is mixed with aluminum oxide of example 7 containing zinc thus, to obtain 1.9 wt.% zinc in the final sample. The catalyst calcined at 500°With, then draw a fraction of 0,2-0,8 mm 4 g of the obtained catalyst is placed in a flow reactor.

Note the R 23. 30 g rosilicate ZSM-5 prepared in accordance with the method specified in example 1 is mixed with aluminum oxide from example 14, containing the zinc thus, to obtain 2.4 wt.% zinc in the final sample. The catalyst calcined at 500°With, then draw a fraction of 0,2-0,8 mm

4 g of the obtained catalyst is placed in a flow reactor.

/tr>
Table 1.

Conditions for the aromatization of n-butane and catalytic data of the test samples prepared according to examples 1-21. Tthe reactions- 550°C, the volumetric feed rate of n-butane - 750°C. CONV. - conversion of n-butane, wt.%; The output AU - the yield of aromatic hydrocarbons in terms served raw materials, wt.%.
SampleDuring the experiment, h
example No.2468
2
Conversion54,352,653,151,6
Outlet AUthe 10.19,49,8
3
Conversion46,246,7to 45.445,3
Outlet AU9,98,29,18,7
4
Conversion67,263,962,261,0
Outlet AU27,326,926,125,4
5
Conversion45,943,044,8to 43.1
Outlet AU9,18,89,48,9
6
Conversionof 60.5of 58.958,456,9
Outlet AU26,026,425,725,5
7
Conversion84,280,773,364,0
Outlet AU30,928,426,823,2
8
Conversion77,972,268,663,9
Outlet AU25,623,121,3to 19.9
9
Conversion68,765,4of 57.555,0
Outlet AU16,914.4V12,411,2
10
Conversion89,684,178,872,3
Outlet AUthe 33.431,930,128,8
11
Conversion85,083,179,272,6
Outlet AUof 31.429,727,225.5
12
Conversion80,378,675,471,7
Outlet AU29,628,125,224,0
17
Conversion95,7a 94.293,292,4
Outlet AU39,740,639,538,8
18
Conversion97,397,096,395,7
Outlet AU41,3of 40.940,639,9
19
Conversion91,7for 91.390,089,2
Outlet AUof 37.838,137,736,9
20
Conversion95,794,9a 94.292,9
Outlet AU39,138,437,536,4
21
Conversion96,996,696,195,5
Outlet AU40,840,6of 40.940,4
22
Conversion98,897,395,993,3
Outlet AUto 43.141,439,537,7
23
Conversion94,494,193,592,9
Outlet AU38,737,737,237,0

1. The catalyst for aromatization of light hydrocarbons, which is a complex catalyst containing microporous component having acidic properties and pore sizes of at least 5 Åand an oxide component having dehydrating properties, characterized in that the oxide component contains a hydroxide and/or aluminum oxide with a size of transport has not less than 20 nm, treated with compounds of the promoting elements.

2. The catalyst according to claim 1, characterized in that the microporous component, have the its acidic properties and acting as an integral part of the complex catalyst, it contains aluminosilicate zeolites, preferably, with the structure of ZSM-5, ZSM-11, BETA.

3. The catalyst according to claim 1, characterized in that the microporous component having acidic properties and acting as an integral part of the complex catalyst, it contains microporous elementobject containing in its structure at least one element from the set: boron, iron, gallium, chromium, and having the structure, preferably ZSM-5, ZSM-11, BETA.

4. The catalyst according to claim 1, characterized in that the size of the transport pores in the hydroxide and/or aluminum oxide is preferably 40-50 nm.

5. The catalyst according to claim 1, characterized in that as the promoting elements it contains gallium and/or zinc in an amount of not more than 10 wt.% at the mass end of the complex catalyst.

6. The method of preparation of the complex catalyst for aromatization of light hydrocarbons mixture of microporous component having acidic properties and pore sizes of at least 5 Åand an oxide component having dehydrating properties, characterized in that the oxide component using a hydroxide and/or aluminum oxide with an average size of transport has not less than 20 nm, treated with compounds of the promoting elements.

7. The method according to claim 6, characterized in that the microporous to mponent use of aluminosilicate zeolites, preferably, with the structure of ZSM-5, ZSM-11,BETA.

8. The method according to claim 6, characterized in that the microporous component using microporous elementobject containing in its structure at least one element from the set: boron, iron, gallium, chromium and having the structure, preferably ZSM-5, ZSM-11, BETA.

9. The method according to claim 6, characterized in that the size of the transport pores in the hydroxide and/or aluminum oxide used to prepare the complex catalyst is preferably 40-50 nm.

10. The method according to claim 6, characterized in that the oxidic part of the complex catalyst, namely hydroxide and/or aluminum oxide, to the point of mixing with the porous component is treated with compounds of the promoting elements, which use gallium and/or zinc in an amount of not more than 10 wt.%. at the mass end of the complex catalyst.

11. The method according to claim 6 or 10, characterized in that the promoting elements to the surface of the oxide part of the complex catalyst making method of impregnation, or activated impregnation autoclave, or their application from the gas phase, followed by drying and calcining the obtained oxide component.

12. The method of obtaining aromatic hydrocarbons, which consists in the conversion of aliphatic hydrocarbons With2-C6when the temperature is neither the e 400° With that pressure of not less than 0.5 MPa, a volumetric flow of hydrocarbons From2-C6not more than 10 000 h-1in the presence of a complex catalyst comprising a mixture of microporous component and an oxide component, characterized in that as a complex catalyst using the catalyst according to any one of claims 1 to 11.



 

Same patents:

The invention relates to the field of preparation of the catalyst used in the production of aromatic hydrocarbons

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention provides catalyst based on iron oxide and lanthanide compound wherein at least part of iron oxide is prepared via a method including thermal decomposition of iron halide and which contains lanthanide in amount corresponding to 0.07 to 0.15 mole per mole iron oxide found in catalyst (calculated as Fe2O3). A catalyst is also described wherein part of iron oxide contains residual halide. Preparation of catalyst involves providing a mixture containing sufficient amounts of at least iron oxide and lanthanide compound followed by calcination of the mixture. Alkylaromatic compound dehydrogenation process is further described involving contact of raw feed containing alkylaromatic compound with above-described catalyst as well as polymer or copolymer production process involving production of alkenylaromatic compound as described above and subsequent polymerization thereof or copolymerization with a monomer.

EFFECT: enabled production of alkenylaromatic compounds with improved characteristics owing de decreased formation of by-products.

18 cl, 2 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: catalyst preparation method comprises: mixing high-silica Pentasil ZSM-5-type zeolite in ammonium form with distilled water, zinc nitrate, aluminum hydroxide, and boric acid; evaporating resulting mass; molding granules; drying; and treating granules with laser emission at power 40-50 W in three passes across monolayer of catalyst granules at scanning rate 800-1000 mm/min.

EFFECT: increased yield of aromatic hydrocarbons.

1 tbl, 11 ex

FIELD: petrochemical process catalyst.

SUBSTANCE: invention relates to a method of preparing catalyst for use in Fischer-Tropsch process and to catalyst obtained according present invention. Preparation of catalyst suitable for conversion at least one synthesis gas component comprises: providing aqueous solution of organic acid; adding iron metal to acid solution; passing oxidant through the solution until iron metal is consumed and iron-containing slurry formed; grinding resulting slurry to achieve average particle size less than about 2 μm; adding at least one promoter to ground iron-containing slurry to form product suspension, concentration of said promoter being such as to obtain said product suspension containing solid phase constituting from about 10 to about 40% of the weight of suspension, including said promoter; performing spray drying of suspension to obtain particles; and calcining these particles to obtain desired catalyst.

EFFECT: optimized catalyst preparation procedure.

23 cl, 2 dwg, 1 tbl, 12 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides high-silica zeolite catalyst comprising molybdenum and a second modifying element, namely nickel, content of the former in catalyst being no higher than 4.0 wt % and that of the latter from 0.1 to 0.5 wt %. Preparation of the catalyst involves modifying zeolite with molybdenum and second promoting element, the two being introduced into zeolite in the form of nano-size metal powders in above-indicated amounts.

EFFECT: enhanced efficiency of non-oxidative methane conversion process due to increased activity and stability of catalyst.

3 cl, 1 tbl, 7 ex

FIELD: alternate fuel production.

SUBSTANCE: invention relates to synthesis of hydrocarbons from CO and H2, in particular to catalysts and methods for preparation thereof in order to carrying out synthesis of hydrocarbons C5 and higher according to Fischer-Tropsch reaction. Method resides in that non-calcined zeolite ZSM-12 in tetraethylammonium-sodium form is subjected to decationation at pH 5-9, after which decationized zeolite (30-70 wt %) is mixed with alumina binder while simultaneously adding cobalt (7.5-11.5 wt %) as active component and modifier, in particular boron oxide (3-5 wt %). Proposed method allows catalyst preparation time to be significantly reduced owing to combining support preparation and deposition of active component and modifier in one stage with required catalytic characteristics preserved. In addition, method is environmentally safe because of lack of waste waters, which are commonly present when active components are deposited using impregnation, coprecipitation, and ion exchange techniques.

EFFECT: reduced catalyst preparation time and improved environmental condition.

1 tbl, 10 ex

FIELD: petrochemical processes.

SUBSTANCE: catalyst, containing high-silica zeolite of the H-ZSM-5 type having silica modulus SiO2/Al2O3 = 20 to 160 in amount 60.0-90.0%, contains (i) as modifying component at least one oxide of element selected from group: boron, phosphorus, magnesium, calcium, or combination thereof in amount 0.1-10.0 wt %; and (ii) binding agent: alumina. Catalyst is formed in the course of mechanochemical and high-temperature treatments. Described is also a catalyst preparation process comprising impregnation of decationized high-silica zeolite with compounds of modifying elements, dry mixing with binder (aluminum compound), followed by mechanochemical treatment of catalyst paste, shaping, drying, and h-temperature calcination. Conversion of methanol into olefin hydrocarbons is carried out in presence of above-defined catalyst at 300-550°C, methanol supply space velocity 1.0-5.0 h-1, and pressure 0.1-1.5 mPa.

EFFECT: increased yield of olefin hydrocarbons.

3 cl, 1 tbl, 15 ex

FIELD: carbon monoxide conversion catalysts.

SUBSTANCE: preparation of middle-temperature carbon monoxide conversion catalysts, which can be used in industrial production of ammonia synthesis destined nitrogen-hydrogen mixture, comprises mechanical activation of iron-containing component with calcium and copper oxides, mixing with water to form plastic mass, extrusion forming, drying, and calcination, said iron-containing component being iron metal powder and said mechanical activation of components being accomplished by passing air enriched with oxygen to 30-100%. Under these circumstances, catalyst activity rises by 19.4-23.1%.

EFFECT: increased catalyst activity, eliminated formation of waste waters and emission of toxic nitrogen oxides, and reduced (by 30%) number of process stages.

1 tbl, 3 ex

FIELD: gas treatment processes and catalysts.

SUBSTANCE: invention relates to catalyst for selectively oxidizing hydrogen sulfide to sulfur in industrial gases containing 0.5-3.0 vol % hydrogen sulfide and can be used at enterprises of gas-processing, petrochemical, and other industrial fields, in particular to treat Claus process emission gases, low sulfur natural and associated gases, chemical and associated petroleum gases, and chemical plant outbursts. Catalyst for selective oxidation of hydrogen sulfide into elementary sulfur comprises iron oxide and modifying agent, said modifying agent containing oxygen-containing phosphorus compounds. Catalyst is formed in heat treatment of α-iron oxide and orthophosphoric acid and is composed of F2O3, 83-89%, and P2O5, 11-17%. Catalyst preparation method comprises mixing oxygen-containing iron compounds with modifying agent compounds, extrusion, drying, and heat treatment. α-Iron oxide used as oxygen-containing iron compound is characterized by specific surface below 10 m2/g, while 95% of α-iron oxide have particle size less than 40 μm. Orthophosphoric acid is added to α-iron oxide, resulting mixture is stirred, dried, and subjected to treatment at 300-700°C. Hydrogen sulfide is selectively oxidized to elemental sulfur via passage of gas mixture over above-defined catalyst at 200-300°C followed by separation of resultant sulfur, O2/H2S ratio in oxidation process ranging from 0.6 to 1.0 and volume flow rate of gas mixture varying between 900 and 6000 h-1.

EFFECT: increased yield of elemental sulfur.

9 cl, 5 tbl, 9 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: group of inventions relates to conversion of hydrocarbons using micro-mesoporous-structure catalysts. A hydrocarbon conversion process is provided involving bringing hydrocarbon raw material, under hydrocarbon conversion conditions, into contact with micro-mesoporous-structure catalyst containing microporous crystalline zeolite-structure silicates composed of T2O3(10-1000)SiO2, wherein T represents elements selected from group III p-elements and group IV-VIII d-elements, and mixture thereof, micro-mesoporous structure being characterized by micropore fraction between 0.03 and 0.40 and mesopore fraction between 0.60 and 0.97. Catalyst is prepared by suspending microporous zeolite-structure crystalline silicates having above composition in alkali solution with hydroxide ion concentration 0.2-1.5 mole/L until residual content of zeolite phase in suspension 3 to 40% is achieved. Thereafter, cationic surfactant in the form of quaternary alkylammonium of general formula CnH2n+1(CH3)3NAn (where n=12-18, An is Cl, Br, HSO4-) is added to resulting silicate solution suspension and then acid is added formation of gel with pH 7.5-9.0. Gel is then subjected to hydrothermal treatment at 100-150°C at atmospheric pressure or in autoclave during 10 to 72 h to produce finished product.

EFFECT: enlarged assortment of hydrocarbons and increased selectivity of formation thereof.

16 cl, 2 dwg, 2 tbl

FIELD: oil refining; methods of production of cracking globular catalysts.

SUBSTANCE: proposed method includes mixing aqueous suspension of zeolite Y in cation-exchange form with alumina suspension in aqueous solution of sodium silicate and aluminum sulfate solution, introducing platinum into aluminum sulfate solution or into aqueous suspension of zeolite fed for molding, forming catalyst granules in column filled with mineral oil, successive activation with solutions of aluminum sulfate and mixture of nitrates of rare-earth elements, washing-off with condensate water containing cations of iron, calcium and magnesium for removal of salts and calcination of granules in atmosphere of flue gases and water steam. For obtaining catalyst possessing enhanced activity, mechanical strength and bulk density, type Y zeolite is added into catalyst in hydrogen or hydrogen-rare-earth form; alumina is also added in the amount of 3-65 mass-%: with size of particles lesser than 10 mcm, 95-100 mass-%; lesser than 5 mcm, 40-80 mass-%. Catalyst has following composition in terms of oxides, mass-%: aluminum, 10.0-67.0; rare-earth elements, 0.5-3.5; platinum, 0.0001-0.01; iron, 0.01-0.2; calcium, 0.01-0.2; magnesium, 0.01-0.2; sodium, 0.01-0.3; the remainder being silicon. Catalyst has mechanic crushing strength of 22-40 kg/ball, wear resistance 900-1400 s, bulk density, 720-11000 kg/m3 and catalytic activity by gasoline yield, mass-%: 62.0-64.9 in cracking of kerosene-gas oil fraction and 41.5-45.7 in cracking of vacuum gas oil.

EFFECT: enhanced efficiency.

FIELD: petrochemical process catalysts.

SUBSTANCE: catalyst preparation method comprises: mixing high-silica Pentasil ZSM-5-type zeolite in ammonium form with distilled water, zinc nitrate, aluminum hydroxide, and boric acid; evaporating resulting mass; molding granules; drying; and treating granules with laser emission at power 40-50 W in three passes across monolayer of catalyst granules at scanning rate 800-1000 mm/min.

EFFECT: increased yield of aromatic hydrocarbons.

1 tbl, 11 ex

FIELD: petrochemical processes.

SUBSTANCE: catalyst, containing high-silica zeolite of the H-ZSM-5 type having silica modulus SiO2/Al2O3 = 20 to 160 in amount 60.0-90.0%, contains (i) as modifying component at least one oxide of element selected from group: boron, phosphorus, magnesium, calcium, or combination thereof in amount 0.1-10.0 wt %; and (ii) binding agent: alumina. Catalyst is formed in the course of mechanochemical and high-temperature treatments. Described is also a catalyst preparation process comprising impregnation of decationized high-silica zeolite with compounds of modifying elements, dry mixing with binder (aluminum compound), followed by mechanochemical treatment of catalyst paste, shaping, drying, and h-temperature calcination. Conversion of methanol into olefin hydrocarbons is carried out in presence of above-defined catalyst at 300-550°C, methanol supply space velocity 1.0-5.0 h-1, and pressure 0.1-1.5 mPa.

EFFECT: increased yield of olefin hydrocarbons.

3 cl, 1 tbl, 15 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: process comprises contacting hydrocarbon blend with solid porous phase, namely with methanol decomposition catalyst or methanol-to-hydrocarbons and water conversion catalyst. Contact is conducted such that at least part of hydrocarbon blend comes into contact with catalyst under suitable conditions for conversion of at least part of methanol at volumetric feed flow rate 3-15 h-1.

EFFECT: enabled removal of methanol without disturbing composition of hydrocarbon blend.

4 cl, 7 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to petrochemical processes, in particular production of ethylbenzene via alkylation of benzene with ethylene catalyzed by solid acid catalyst, and provides elevated-strength (cleavage strength above 2 kg/mm diameter) catalyst showing high characteristics regarding activity (theoretical yield of ethylbenzene 65.83-70.7%) and selectivity (yield of ethylbenzene based on converted benzene 68,18-71.4%). This is achieved by way of mixing Pentasil-type zeolite with binder, said zeolite having been preliminarily subjected to exchange of cations: consecutively ammonium and calcium or magnesium. As binder, pseudoboehemite-structure aluminum hydroxide, to which inorganic acid was add to pH 2-4, is utilized. Molding mass is characterized by calcination loss 35-45 wt %. Heat treatment is effected in one to three steps.

EFFECT: improved strength, activity and selectivity of catalyst.

2 tbl, 5 ex

FIELD: alternate fuel production and catalysts.

SUBSTANCE: synthesis gas containing H2, CO, and CO2 is brought into contact, in first reaction zone, with bifunctional catalyst consisting of (i) metal oxide component containing 65-70% ZnO, 29-34%, Cr2O3, and up to 1% W2O5 and (ii) acid component comprised of zeolite ZSM-5 or ZSM-11, beta-type zeolite or crystalline silica-alumino-phosphate having structure SAPO-5 at silica-to-alumina molar ratio no higher than 200, whereas, in second reaction zone, multifunctional acid catalyst is used containing zeolite ZSM-5 or ZSM-11 and having silica-to-alumina molar ratio no higher than 200.

EFFECT: increased selectivity with regard to C5+-hydrocarbons and increased yield of C5+-hydrocarbons based on synthesis gas supplied.

7 cl, 2 tbl, 15 ex

FIELD: production of catalysts for alkylation of benzole with olefin hydrocarbons.

SUBSTANCE: proposed catalyst is made on base of crystalline zeolite in hydrogen form ZSM-5 contains additionally tin at the following ratio of components, mass-%: SiO2, 60-60.7; Al203, 30-35; Sn, 0.01-0.1; the remainder being H2O.

EFFECT: enhanced efficiency.

1 tbl, 3 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to composition suitable for use in reaction zone wherein aniline is brought into contact with nitrobenzene to produce 4-aminodiphenylamine synthesis intermediates, which composition contains zeolite having internal channels with a base introduced therein to take part in above reaction. Dimensions of cross-section of channels is such that a limited reaction transition state is ensured thereby improving selectivity of reaction with regard to desired intermediates. Invention also related to the title process using above defined composition.

EFFECT: improved selectivity of 4-aminodiphenylamine intermediates production.

9 cl, 12 dwg, 7 tbl, 8 ex

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