Improvements in the dehydrogenation catalysis

 

(57) Abstract:

The invention relates to catalysts used in the dehydrogenation of hydrocarbons, and to methods of using catalysts. Described regenerated catalyst for dehydrogenation of hydrocarbons containing a catalytic component selected from the group consisting of platinum, rhodium, iridium, palladium, ruthenium and osmium deposited on the media containing porous alumina, which has a specific surface of more than 100 m2/g, volume of pores with diameters below 6 nm (60 ) is less than 0.05 cm3/g, volume of pores with diameters in the range from 6 to 35 nm (60-350 ) is more than 0,50 cm3/g, and where the volume of pores with diameters in the range from 6 to 35 nm (60-350 ) is more than 70% of the total pore volume. There is also described a method of producing olefins by dehydrogenation of hydrocarbons using the above catalyst. The technical effect is providing a favorable balance of selectivity, activity and thermal stability of the catalyst. 2 N. and 44 C.p. f-crystals, 1 table.

Description

This application claims the privilege of provisional application U.S. No. 60/151113, filed August 27, 1999, provisional application U.S. No. 60/155877, filed September 24, 1999, and the CoE review and are listed as links.

The scope of the invention

This invention relates to catalysts applicable in the dehydrogenation of paraffins, and to methods of using catalysts. The catalysts according to the invention provide a combination of selectivity, thermal stability and initial activity of the catalytic layer per unit volume, which is very advantageous. In one preferred embodiment of the invention relates to the dehydrogenation essentially linear paraffins having between about 9 and 15 carbon atoms in the molecule, and monoolefins obtained from such paraffins, which finds particular application in the production of biodegradable detergents. Thanks to the use of catalysts and methods according to the invention, it is possible to achieve excellent selectivity of the reaction in the process, which includes the regeneration of the catalyst.

The background to the invention

Many chemical processes that are carried out in practice on an industrial scale, involve the use of one or more catalysts to produce an intermediate or end products. This is, in particular, in oil-dependent branches of engineering. Thanks usually recyclable, large volume, h is further useful effects. Examples of important catalytic processes for the conversion of hydrocarbons include the processes of alkylation, hydrogenation processes, the processes of dehydrogenation and isomerization processes.

Although the catalysts, by definition, not directly consumed in the course of chemical reactions that they promotirovat, in the above-mentioned and other processes in catalysts often gradually become less active during their application through one or more mechanisms, known to specialists in this field. In some cases, taking a particular stage, such as the removal of coke, acid leaching or roasting, to restore most of the lost activity so that the useful service life of the catalyst is prolonged. These stages are often referred to as "regeneration" of the catalyst. Mainly, it is desirable to use catalysts that respond well to regeneration, in order to reduce the costs associated with the replacement of the catalyst. However, in many processes, the regeneration of the catalyst is not feasible. For example, the catalyst, which in other respects could be regenerated by burning the accumulated coke does not have a high enough heat is efficient burning of coke.

This invention relates to catalytic materials, applicable to the dehydrogenation of paraffins (saturated hydrocarbons). The dehydrogenation of paraffins is often carried out with the aim of introducing one or more olefinic bonds, either in order to obtain an olefinic product, which is good in itself, or to provide effective "capture" on the molecule for subsequent reaction with some other substances. The invention in particular relates to a heterogeneously catalyzed the dehydrogenation of paraffins range of detergents (paraffins with the number of carbon atoms in the range 9-15), in order to obtain products that contain only unsaturated bond in the molecule (monoolefinic). The resulting monoolefinic (monoolefinic range of detergents) is applicable to reactions with other organic products, which include aromatic nucleus to get the alkyl benzenes. Such alkyl benzenes having essentially linear alkyl substituents attached to the benzene rings, apply to become alkylbenzenesulfonate that are used in the compositions of detergents for industrial applications, and products in consumer demand. The alkyl benzenes obtained preity have a very high degree of Biodegradability. Used herein, the term "substantially linear" means that the type and degree of branching present in the paraffin, which should be digidrirovanny to obtain olefins for use in the production of alkylbenzenesulfonates, limited to those that provide Las with the degree of Biodegradability, which is acceptable in accordance with existing standards, proclaimed industrial and regulatory agencies. The alkyl benzenes containing a single alkyl substituent attached to the benzene ring (monoalkylbenzenes), are preferred, which are known from the prior art, as they tend to provide favorable characteristics of the detergent. Mixture of alkyl benzenes, consisting mainly of monoalkylbenzenes with linear alkyl substituents, also recognized as preferred, and they are the types most commonly used in the industry of detergents. Such mixtures are commonly referred to as "linear alkylbenzene" or "LAB".

Production monoolefins in the dehydrogenation process typically involves contacting the saturated hydrocarbon with a suitable catalyst in unavoided some formation of undesirable by-products, such as diolefine, aromatic compounds and products of cracking. The number of the resulting diolefin depends mainly on the structure of the paraffin and the degree of conversion, and relatively weak regulation of education diolefin possible through other reaction conditions. The formation of the products of cracking can be minimized by applying a catalyst and exclusions extremely high temperatures. On the formation of aromatic compounds noticeable impact as the selectivity of the catalyst, and the reaction conditions. In the prior art it is well known that large economic benefits can be realized through the use of highly selective dehydrogenation catalyst that minimizes the formation of aromatic compounds at a given level of conversion of paraffin. Specific benefits associated with lower education aromatic compounds include lower consumption of paraffin, lower consumption of monoolefins in adverse reactions with aromatic compounds during production of alkyl benzene, the higher the purity of the recycle paraffin and less extensive inhibition and blockage of the catalyst.

Many Natalie materials contain one or more active metals or metal oxides in powdered form, deposited on the surface of particles of a relatively inert carrier substances, such as silicon dioxide or aluminum oxide. Alternative means known in the art, by means of which the main component(s) of the catalyst or its precursor can be obtained in finely ground condition on the surface of the pretreated appropriate media, include methods such as precipitation, adsorption from aqueous solution and ion-exchange technologies using materials media Zeolite (molecular sieve). Usually after deposition of one or more substances selected media to produce a crude catalyst raw material of the catalyst is subjected to any heat treatment at an elevated temperature for a suitable time, often in the presence of a controlled atmosphere, which may be inert, oxidizing or reducing.

Previous experience is replete with examples of alumina and silica with different particle size, crystal phase structures of pores, etc., in combination with a very wide variety of other components deposited on their surfaces. In many cases precipitated components zaderjkoi as activator, the attenuator or modifier.

Generally, performance of the catalyst is largely determined by the three critical properties are easily recognizable and well-known experts in the field of catalysis. These properties are 1) selectivity, 2) activity, and 3) thermal stability.

In the case of dehydrogenation of paraffin to obtain monoolefins selectivity of the catalyst is a measure of its ability, under appropriate reaction conditions to maximize share just turned paraffin, which turns into monoolefins. Since the increase in the formation of an undesirable by-product leads to reduced formation of monoolefins when this transformation paraffin, selectivity is improved, if the formation of by-product decreases with the conversion of paraffin. Thus, comparison of the selectivity of the catalyst can be carried out according to the amounts of by-products formed during the same turn paraffin in experiments that use different catalysts, but which are essentially equivalent in the sense of other reaction conditions. If you compare different weak acid catalysts, most of paraffin. When comparing selectively in alternative catalysts is particularly convenient to Express the selectivity in comparison with only the standard catalyst. So, for each alternative catalyst to detect an improvement of the selectivity, the degree of improvement can be expressed as the percentage by which alternative catalyst reduces the formation of aromatic compounds in the conversion of paraffin under standard reaction conditions compared to a standard catalyst.

In the case of dehydrogenation of paraffin activity of the catalyst is a measure of its ability to promote the conversion of paraffin. In a continuous process at any particular reaction conditions, the higher the catalyst activity is manifested in higher transformation over a given amount of catalyst. For practical purposes, the most important measure of catalytic activity is the specific activity that indicates the activity per unit volume of the catalyst layer. Under given conditions of continuous reaction of the catalyst with higher volumetric activity capable of providing a higher conversion of paraffin over the catalyst bed zai to obtain a given conversion of paraffin. The factors that significantly affect the volumetric activity of the catalyst include specific surface area, bulk density, types and mass percentages included in the composition of the active metal of the active distribution of metals within the granules of the media and the degree of diffusion resistance caused by the pore structure. As dehydrogenation catalysts lose activity during normal use, compare the activity of different types of catalysts must be carried out with comparable degrees of deactivation of the catalyst. This can be done by comparing the within transformation paraffin for experiments of equal length that begin with the fresh catalyst, using standard reaction conditions.

The dehydrogenation catalyst must have a high degree of thermal stability in order to adequately withstand high temperature, with which he faced during its normal use. High thermal stability is especially important if the catalyst is regenerated by burning off the accumulated coke, i.e., a procedure, which usually tends to the appearance of unusually high local temperatures. Nedostatki high temperatures. One process that contributes to the loss of activity during heat exposure, includes agglomeration (coalescence) of the particles of the active component (components). Another involved process is the degradation of the carrier in such a way that some of the catalytic particles are captured in inappropriate locations within the surrounding layers of material media. In any case, the amount of catalytic surface available for reaction is reduced. Thermal stability of a particular catalyst can be determined by comparing the activities of the submitted samples from the same batch that have been subjected to appropriate treatment, leading to high-temperature aging, and are not subjected to such effect.

It is known that in the catalytic dehydrogenation of paraffins range of detergents interest into monoolefinic in a single pass through the reactor is limited by equilibrium. Although the restriction of the transformation can vary significantly under different reaction conditions, the actual percentage of monoolefins in products is usually not more than about twenty weight percent. It is well known also that is of Reducto, including diolefine, aromatic compounds and hydrocarbons with numbers of carbon atoms below the range of detergents, which are formed in the reactions of cracking. Used herein, the term "transformation" means the mass percentage of paraffin range of detergents in the feedstock that is converted in a single pass in products other than paraffins, in the same range of number of carbon atoms. In cases where the feedstock contains substances other than paraffins range of detergents, these components of the feedstock are ignored in the calculation of conversion and selectivity. As a rule, higher conversion and higher selectivity preferred, but an increase in the transformation leads to a decrease in selectivity.

A well-known problem encountered in the production of olefins range of detergents by the catalytic dehydrogenation of paraffins, is the loss of catalyst activity during the processing of paraffin. The catalyst may lose activity due to the presence of a strong catalyst poisons such as sulfur compounds in the feedstock, and this loss of activity is usually limited by controlling the purity of the feedstock. However, even when the feedstock content and, due to the formation of coke on the catalytic surfaces. The rate of formation of coke can be widely changed depending on the combination of the selected reaction conditions. As a rule, the lower the rate of formation of coke is preferred as it reduces various costs associated with regeneration or replacement of the catalyst, and facilitates the maintenance of conditions for transformation and other reactions in the optimal range for extended periods of work.

One method used in the processes of dehydrogenation of paraffins prior art to reduce the deactivation of the catalyst, is mixing varying quantities of hydrogen with the vaporized source paraffin feedstock prior to its introduction into the catalytic reaction zone. In U.S. patent 4343724 indicated, for example, that hydrogen plays a "double feature" - as dilution paraffin, and suppress the formation of hydrogen-deficient carbonaceous deposits on the catalyst. In many cases, the number of added hydrogen used in the examples of the patent, was quite large, for example 4 to 8 moles of hydrogen per mole of hydrocarbon. Extreme inconvenience accompany such large supplements of hydrogen, including harmful in the oborudovanie for a given performance and higher costs for energy and maintenance, associated with the extraction, compression, and recycling the hydrogen. So it is advantageous to reduce the molar ratio of hydrogen to hydrocarbon ratio (H2:NS) used in the specified process. In U.S. patent 5324880 proposed a relationship of N2:NS in the range of 0.5 to 1.9, and even lower ratios as those that are in the range of 0.3-0.5, applicable in certain conditions. However, as it seems, some additional amount of hydrogen is always necessary in order to maintain the catalyst in an active state.

Usually the activity of the catalyst for the dehydrogenation of paraffin drops when using it up until the residual activity becomes insufficient to sustain further economic work without prior replacement or regeneration of the catalyst. As the cost of a fresh load of catalyst to the reactor system industrial size can easily reach hundreds of thousands of dollars, it is desirable to extend the useful service life of the layer of catalyst through the regeneration of one or several times before its eventual replacement. Costs, reduce catalyst regeneration include the cost of purchasing new catalyst, mensen noble metal, and compensation of losses of noble metals during the processing of spent catalyst. Moreover, you can avoid the need for expensive equipment to add catalyst without shutting down the reactor, and that happens from time to time episodes catalyst poisoning are less expensive, as the regeneration of the catalyst is often sufficient to restore normal operation.

The ability of the catalyst to effectively regenerated commonly referred to as Regenerist catalyst. In order to be able to be regenerated, the catalyst should have a high degree of thermal stability, so that the loss of activity due to thermal decomposition were minimal during high temperature regeneration, such as the burning of the accumulated coke. Since some loss of activity during each regeneration is inevitable, another requirement for regeneriruemost is enough activity in the fresh catalyst to compensate for the loss of activity that occur during regeneration. The catalyst, which is vysokomehanizirovannym, able to maintain an adequate level of activity on preteenmodeling to assess the degree of regeneriruemost catalyst. However, a reasonable estimate of regeneriruemost can be achieved in the laboratory by measuring the initial activity and thermal stability at temperatures characteristic of the proposed procedure regeneration.

In the production process of monoolefinic the dehydrogenation of paraffins range of detergents significant economic benefits can be realized through the use of a catalyst which has favorable characteristics in terms of selectivity, volume activity, thermal stability and regeneriruemost. In practice, however, the previously known catalysts have disadvantages, at least in relation to one of the specified properties. The catalysts were regenerated, had insufficient selectivity, and catalysts with relatively high selectivity had insufficient volume activity, thermal stability or Regenerist. Thus, the opening of the catalyst with favorable characteristics for all four of these properties, as described here, represents a major advantage in the dehydrogenation of paraffins and in the production of alkyl benzene for use in industrial detergents.

Prior 696160, 3655621, 3234298, 3472763, 3662015, 4409401, 4409410, 4523048, 3201487, 4358628, 4489213, 3751506, 4387259 and 4409412, the entire contents of which is attached to this link. The patents of the prior art relating to catalysts applicable to the dehydrogenation of hydrocarbons, include U.S. patent numbers 3274287, 3315007, 3315008, 3745112 and 4430517, the entire contents of which are shown as links.

Previous experience associated with the dehydrogenation of paraffins range of detergents prior to the formation of monoolefins includes U.S. patent 3761531, which in its entirety is listed as a reference. This patent describes a method of dehydrogenation containing the contacting of the hydrocarbon at dehydrogenation conditions with a catalytic composite containing a combination of catalytically effective amounts of platinum group component, a metal component of group IV-A metallic component of group V-A and alkaline or alkaline-earth metal component with the material of the carrier based on alumina. It specifies that the preferred material of the carrier on the basis of aluminum oxide has a relatively low apparent bulk density, and particularly preferred bulk density in the range from about 0.3 to about 0.4 g/cm3Other patents that relate to catalysts and methods applicable to the dehydrogenation of paraffins range of detergents prior to the formation of monoolefins are U.S. patent numbers 3585253, 3632662, 3920615 and 5324880, which in its entirety are cited as references. The catalysts described in U.S. patent 3920615 are acceptable selectivity, but they are found to be insufficient for volume activity and/or regeneriruemost. The catalysts described in the other three above mentioned patents, is highly appreciated by volume activity and regeneriruemost, but they have insufficient selectivity, which is undesirable low.

SL is the prior art and this invention: 3293319, 3448165 (particularly column 5, lines 26-33); 3576766 (ESP. Art. 5, lines 31 to 60); 3647719 (ESP. Art. 4, line 68 - senior 5, line 4); 3649566 (ESP. Art. 5, lines 13-24); 3761531 (ESP. Art. 4, line 68 - senior 5, line 17); 3767594 (ESP. Art. 2, lines 46-60 and example 1); 3825612 (ESP. Art. 5, lines 26-38); 3998900 (ESP. Art. 5, line 60 - Art. 6, line 3); 4048245 (ESP. Art. 6, lines 39-51); 4070413 (ESP. example 1); 4125565 (ESP. Art. 6, lines 38-51); 4136127 (ESP. Art. 6, lines 41-54); 4172853 (ESP. Art. 6, line 61 - Art. 7, line 6); 4177218 (ESP. example 1 and 3 tbsp., line 56 - senior 4, line 14); 4207425 (ESP. Art. 6, line 33-54); 4216346 (ESP. Art. 6, lines 40-54); 4227026 (ESP. Art. 6, lines 36-50); 4268706 (ESP. Art. 6, lines 38-52, item 7, line 27 - Art. 8, line 59 and Art. 19, lines 3-10); 4312792 (ESP. Art. 6, line 63 - Art. 7, line 9, item 7, line 54 - senior 9, line 19 and Art. 19, lines 22-28); 4341664 (ESP. Art. 6, line 62 - Art. 7, line 8, item 7, line 53 - senior 9, line 18 and 19th century, lines 1-8); 4343724 (ESP. Art. 6, line 61 - Art. 7, line 7, item 7, line 52 - senior 9, line 17 and Art. 19, lines 14-21); 4396540 (ESP. Art. 6, line 61 - Art. 7, line 7, item 7, line 52 - senior 9, line 17 and Art. 19, lines 5-11); 4486547 (ESP. Art. 6, line 56 - Art. 7, line 23); 4551574 (ESP. Art. 6, line 60 - Art. 7, line 25); 4595673 (ESP. Art. 6, line 15-43); 4608360; 4677237 (ESP. Art. 6, lines 25-33) and 4827072 (ESP. Art. 10, line 31 - Art. 11, line 11). The rights to these patents is supposed to be periosteum is acquired, limited inclusion of one or more elements other than platinum group metals, metals of group I-B metals and alkali metals. The remaining U.S. patent 4070413 is the invention limited to the use of specific steamed carrier based on alumina. In each of these patents, the contents of the shape and size of the catalyst particles, and is preferably spheres of 0.16 cm (1/16 inch). In some of these patents (U.S. patents 4268706, 4312792, 4341664, 4343724 and 4396540) indicates that the 1/16 inch extrudates are also preferred. All of the examples used in the sphere of 0.16 cm (1/16 inch), and in these patents, there is no indication that the extrudates even more preferably spheres. Only one of the patents, U.S. patent 4608360, discusses the distribution of pore sizes and there is indication that more than 55% of the total pore volume should be of pores with diameters of 60 nm (600 angstroms) or more. Higher selectivity is attributed to the pore structure in example III of the said patent. An indication of the average pore size is variable and not very specific. The specified limits for the mean diameter of the pores include 2-3 (20-30), 2-30 (20-300) and 2-300 (20-3000) nm (angstroms). The most preferred bulk 3 in all other patents. The limits of bulk density specified for the extrudates were 0.4 to 0.85 or 0.5 to 0.85 grams/cm3.

The following U.S. patents, the contents of which in its entirety is listed as a reference, are also useful to explain the differences between the prior art and this invention: 5677260 (especially column 4, line 50-59); 3458592; 3662018; 3527836; 3274287 (ESP. Art. 3, line 66 - senior 4, line 20 and example IV); 3315007 (ESP. Art. 3, line 25-56 and example I); 3315008 (ESP. Art. 3, line 12-44); 3585253; 3632662 (ESP. Art. 2, lines 50-61 and Art. 3, lines 26-31); 3920615 and 5324880. The catalysts disclosed in U.S. patent 5677260, the rights to which should probably be assigned Indian Petrochemicals include an unusually large number of additional elements, and they have a close affinity with various catalysts, disclosed in patents, rights to which should probably be assigned UOP, LLC. Prioritises areas of 0.16 cm (1/16 inch) with a bulk density of about 0.3 g/cm3. It is mentioned that the preferred pore distribution must be "mesoporous", however, no further definition is not given. In U.S. patent 3458592, 3662018 and 3527836, the rights to which should probably be assigned Texaco and British Petroleum, announced the spacecraft is captured Monsanto Company, most early: 3274287, 3315007 and 3315008 not mention the use of copper in combination with platinum and media, while later: 3585253, 3632662, 3390615 and 5324880 reveal it. In these patents indicate that the volume of macropores (volume enclosed in the pores with average diameters above 70 nm (700 angstroms)) must be at least 0,05 cm3/g and higher amounts of macropores preferred. They say nothing about the bulk density. In U.S. patent 3920615 indicates that the selectivity is improved by annealing to a specific surface area less than 150 m2/, Although this annealing effect on the pore structure, but especially the final pore structure is determined simply by setting the specific surface area. Acceptable changes in the source materials and the order of operations significantly affect the relationship between specific surface area and pore structure.

Brief description of the invention

Although the patents of the prior art, established and described herein above in the section "Background to the invention", contain a wealth of information relating to the composition and use of various catalysts applicable in the dehydrogenation of paraffins, previous experience, there is nothing that pointed BTI and selectivity still not observed, could be provided with a catalyst in accordance with this invention, which contains one or more elements: platinum, rhodium, iridium, palladium, ruthenium and osmium ("platinum group elements"), deposited on a porous carrier of aluminum oxide, selected so as to provide in the finished catalyst specific surface area of more than 100 m2/g, volume of pores with diameters below 60 angstroms is less than 0.05 cm3/g, volume of pores with diameters in the range from 6 to 35 nm (60-350 angstroms) is more than 0,50 cm3/g, and the volume of pores with diameters in the range from 6 to 35 nm (60-350 angstroms) is more than 70% of the total pore volume. In a preferred embodiment of the invention, the volume of pores with diameters in the range from 6 to 35 nm (60-350 angstroms) is more than 75% of the total pore volume. In a preferred embodiment of the invention the volumetric packing density of the catalyst is more than 0.50 g/cm3. In fact, prior experience leads to the opposite conclusion that such a catalyst should have a relatively low activity and selectivity due to the lack of pores with diameters of more than 60 or 70 nm (600 or 700 angstroms). Therefore, beneficial effects, DOS is receiving, were completely unexpected.

This invention relates to a catalyst applicable to the dehydrogenation of paraffin hydrocarbons, which in one form includes a porous carrier made of alumina and the main catalytic component containing one or more elements selected from the group consisting of platinum, palladium, osmium, ruthenium, iridium and rhodium deposited on the carrier, the said catalyst has a specific surface of more than 100 m2/g, bulk density packing more than 0.50 g/cm3the volume of pores with diameters below 6 nm (60 angstroms) less than 0.05 cm3/g, volume of pores with diameters in the range from 6 to 35 nm (60-350 angstroms) more than 0,50 cm3/g, and the volume of pores with diameters in the range from 6 to 35 nm (60-350 angstroms) more than 70% of the total pore volume.

Disclosed here catalysts possess a combination of thermal stability and specific activity which is essentially comparable to provide the most stable and active catalysts of the prior art, is applicable in the production of monoolefins range of detergents from paraffins range of detergents. So, one of the advantages of the catalysts prepared according to the directions, Katalizator. An additional advantage is that they provide a higher selectivity than the catalysts of the prior art, which have comparable thermal stability and specific activity. Thus, the benefits of the regeneration of the catalyst mentioned above, can always be implemented in conjunction with excellent initial selectivity of the catalyst in the production of monoolefins range of detergents from paraffin raw materials. In addition, in any dehydrogenation process using the catalysts according to this invention, although it contained the regeneration of the catalyst or not, high volume activity of the catalysts prepared according to the invention, can contribute to the achievement of longer reaction cycles, or a higher average conversion in the reactor of a given size. Alternatively, the size of the reactor can be reduced without compromising high performance. In addition, any required fine regulation of the volume of activity can easily be done by changing the loading of Pt. Such improvements are well within the competence of specialists in this field. High selectivity klya achieve either greater performance at a given value of the initial material per pound (unit of mass) of the product, either to reduce consumption of raw materials at a given performance. In a preferred embodiment, the catalysts according to the invention provide high selectivity catalyst, and a relatively low pressure drop. Low pressure drop tends to improve the selectivity of the reaction by providing a lower average pressure response, and this in some cases may also contribute to the reduction associated with the process of total energy intake.

A detailed description of the preferred options

This invention relates to the formation of monoolefins by catalytic dehydrogenation of paraffins having 9 to 15 carbon atoms in the molecule. Monoolefinic, thus obtained, can then be used in the manufacture of detergent compositions based on alkyl benzene. In the catalysts according to this invention used known metals or combinations thereof as a main catalytic component for the dehydrogenation of paraffins in combination with a porous carrier made of alumina, is selected to provide in the finished catalyst the unique and specific combination of structural characteristics. In a preferred embodiment, the main Catalani according to the invention are catalysts on a carrier, i.e., they contain at least one active catalytic material deposited on an inert carrier ("carrier catalyst"). In accordance with this invention, the catalyst carrier is a porous aluminum oxide, selected to provide in the finished catalyst specific physical properties, which has been found to provide advantageous performance characteristics of the catalyst is related to the selectivity, activity and regeneriruemost. Specific physical properties of the finished catalyst according to the invention include restrictions on the microstructure of the finished catalyst, including its specific surface area and pore structure.

It is well known that the microstructure of the finished catalyst depends on the initial material properties of the medium to its original state before exposure to reagents, conditions and operations used in the process of preparation of the catalyst, some of which are well known to specialists in the techniques for the production of catalysts, including impregnating the catalytically active metal (metals), the stage of calcination, hydrothermal treatment, and so on, the microstructure of the initial aluminum oxide can be changed in considerable the ora of the invention should be made strictly on the basis of detailed descriptions, which characterizes the microstructure of the resulting finished catalyst. The original aluminum oxide for use in the catalysts obtained in accordance with the invention may be from any source and can be obtained by a method that ensures that the resulting finished catalyst had a unique set of physical properties that are clearly defined here. It is most preferable to use the original aluminum oxide with a relatively narrow distribution of pore sizes. There are various ways to obtain aluminum oxide with a controlled and narrow distribution of pore sizes. Some of these methods are described in D. L. Trimm and A. Stanislaus in Applied Catalysis 21, 215-238 (1986), which in its entirety is listed as a reference. Especially preferred alumina for the preparation of catalysts according to the invention and achieve the desired combination of physical properties that are installed here is the type manufactured by Engelhard Corporation of Iselin, New Jersey, with the designation of a grade of "AE-30".

The catalysts obtained in accordance with the invention have a marked excellent selectivity in combination with a very low content of pores with diameters of more than 60 nm (600 angstroms). For example, the invention the original media is chosen to ensure that the structure of the finished catalyst, which preferably has a very low volumetric content (less than 20,00% of the total pore volume, including every hundredth percentage between 20,00% 0,00%) of pores with diameters of more than 60 nm (600 angstroms). Based on previous experience in this field of technology, one would expect that such a pore structure will result in undesirable low selectivity of the catalyst. Therefore, high selectivity is achieved in accordance with the invention, in the absence of substantial amounts of such large pores, was a complete surprise.

Relatively high bulk density packaging (more than 0.50 g/cm3and including every hundredth g/cm3between 0.50 to 0.80), presented in the catalysts according to one form of the invention is very advantageous because of its favorable effect for volumetric activity. Although some catalysts of the prior art had a bulk density packaging, comparable with those of this invention, such catalysts of the prior art had insufficient activity per unit mass, selectivity and thermal stability. So that f is the volumetric packing density, providing at the same time excellent activity per unit mass, selectivity and thermal stability, is a noticeable improvement in the technique.

The main catalytic component

The catalysts obtained according to the invention, contain a main catalytic component containing one or more elements selected from the group consisting of ruthenium (Ru), rhenium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt), ("platinum group metals"). Although previous experience related to dehydration, replete with patents that contain claims relating to the use of one or more platinum group metals, in one form or another, deposited on different carriers, Pt is the only metal that is used commercially to any measurable extent, as a main catalytic component for the dehydrogenation of paraffins range of detergents. According to this invention, it is preferable to include platinum and it is most preferable to use platinum and only platinum as a main catalyst component. However, according to this invention, it is also possible to use other the ski component of the catalyst according to the invention. Although the preferred number of the main catalytic component, expressed as a mass percentage based on the total weight of the finished catalyst, here precisely defined for the preferred variants of this invention, any number of the main catalytic component between 0.01% and 3.0% by weight of the total weight of the finished catalyst, including every hundredth percentage between them, covered by the scope of the present invention. In any case, the main catalytic component is located on the media with such distribution, to provide a catalytic surface, which is easily accessible to the reaction mixture.

When the main catalytic component is platinum, the content of platinum in the finished catalyst, expressed in weight percents of the total weight of the finished catalyst, is variable and is preferably in the range from about 0.02% to 2.00%, including every hundredth percentage between them, more preferably between about 0.20% to 1.00%, including every hundredth percentage between them, even more preferably between about 0.40% and 0.70%, including every hundredth percentage between them, it is most preferable to 0.55%. Such levels mogual methods for the specified set empirically variable well-known.

The activating component

Despite the fact that the catalysts obtained in accordance with this invention, may contain only carrier and the main catalytic component, preferably incorporated in the composition of the activating component that functions to improve the performance characteristics of the catalyst. Suitable activating component may be selected from one or more metals, such as scandium, titanium, vanadium, chromium, manganese, iron, cobalt, Nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, silver, lanthanum, hafnium, tantalum, tungsten, ruthenium and gold. However, especially preferably include activating a component that contains one or more metals selected from elements such as copper, silver and gold (Group I-B). The main function of the activating component, which is used here, is to improve the activity and/or selectivity of the catalyst through a variety of impacts on the main catalytic component. For example, the activating component can be used to improve the dispersion of the main catalytic component and/or to improve the distribution of the main catalytic component inside the granules are wearing the Torah, activating the component must be deposited on the catalyst carrier. Regardless of the selected trigger component, the catalyst according to the invention may contain any amount of an activating component of between 0.10% and 5.00% of the total weight of the finished catalyst, including every hundredth percentage between them. However, it is most preferable to use copper only copper as the activating component, since copper is highly effective as an activator, and has a relatively low cost. When using copper, the copper concentration in the material of the finished catalyst, expressed as the mass percentage of the total catalyst, is preferably in the range of about 0,10%-5,00%, including every hundredth percentage between them, more preferably between about 0.50% and is 4.00%, including every hundredth percentage between them, even more preferably between about 1.00% to 3.00%, including every hundredth percentage between them, most preferably about 2,00%. Such concentration in the finished catalyst is easily achievable by experts, without resorting to undue experimentation by conventional techniques used for the deposition of metals on ptx2">In order to provide a catalyst corresponding to the invention, which has the most favorable combination of selectivity, activity and regeneriruemost, it is necessary to control the degree of acidity of the finished catalyst. If the acidity of the catalyst for hydrogenation according to the invention is too high, in the process of dehydrogenation will promotionals acid catalyzed side reactions such as cracking and isomerization, to the extent that it reduces economic indicators of process and production efficiency. According to one form of the invention, as agents controlling the acidity, the preferred alkali metals or their compounds as the oxides of these elements are basic in nature and is highly effective for neutralizing the effects of different acid particles, which are commonly found in or on the catalyst. Other metals, the oxides of which have an alkaline nature, such as alkaline-earth metals, can also be used as agents controlling the acidity, but they are less preferred than alkalis, as they are generally less effective. Regardless of the selected control acidity to agent (s), is using techniques known in the art, and as mentioned here, and the number of controlling the acidity of the agent present in the finished catalyst can be any number between 0,001% and 1,000% by weight of the total weight of the finished catalyst, including every thousandth of a percentage between them.

Some available source aluminium oxides contain as impurities enough alkali, such as sodium, for example, to provide an effective degree of control acidity. Therefore, the addition of controlling the acidity of the agent to the original aluminum oxide during the preparation of the catalyst may not be necessary in all cases. However, it is generally preferable to incorporate additional control acidity component containing one or more alkali metals, in order to provide greater protection against potential acidification of the catalyst. If you use add controlling the acidity of the component, it is preferably precipitated on the surface of the medium during preparation of the catalyst, using similar or the same technologies as known in the art and are applicable for the deposition of metals on the catalyst carriers.

According to before mponent added potassium. When using the add potassium, its amount is preferably in the range about 0.01%-2,00%, including every hundredth percentage between them, more preferably in the range of about 0.05%-1,00%, including every hundredth percentage between them, and even more preferably within about 0,10%-0,60%, including every hundredth percentage between them, most preferably about 0.20 per cent. In this description and the attached claims, the amount of added potassium expressed for convenience as the percentage by weight of the total metal weight of finished catalyst, although it is assumed that the potassium must be present in the catalyst in the form of an oxide or salt. If instead of potassium add other alkali metal or mixture of alkali metals, matching their number can easily be determined using the equivalent mass of elements, which should be used, without resorting to undue experimentation.

The shape and size of the catalyst pellet

Specialists in the field of catalysis is known that the size and shape of the granules of catalyst can vary. The catalysts previously used in industry for the dehydrogenation of paraffins range of detergents, had essentially SFU is,32 see Known methods for producing spherical granules of aluminum oxide include techniques such as agglomeration of hydrated alumina powder and oil-drip method (formation of hydrogel spheres from a liquid precursor, produced dropwise in a heated oil bath). The extrudates obtained by transformation of a powder of aluminum oxide in the extrudable batter of various known methods and subsequently extruding the dough through a die under suitable conditions. When the extrudate emerges from the head, it can be cut to any desired length using, for example, a rotating or reciprocating movement of the knife devices at the point of exit of the extruder. The extrudates having a large variety of cross-sections can be obtained by changing the shape of the head. For example, round and three-lobed cross-section are just two of the most often produced by the profiles. It is well known that the size of the granules and form granules have an important impact on the performance of the catalyst. Shorter diffusion path inside the granules are usually associated with higher selectivity of the catalyst, and is anal, which have a higher ratio of surface to volume. However, it is also necessary to consider the impact of the size and shape of the granules on the mechanical strength of the granules and the pressure drop through the catalyst bed. For example, smaller granules of the catalyst resulting in a higher pressure drop, and the form of pellets other than spherical, have a tendency to lower the mechanical strength. Therefore, optimization of the size and shape of the granules for a given process often requires balancing effects on selectivity, pressure drop and durability of the catalyst. The most favorable balance may change significantly when changing technological conditions. However, for any particular case, a better balance will easily identify experts by ordinary experimentation.

A catalyst pellet of any size and forms applicable to the dehydrogenation of paraffins range of detergents that can be used according to the directions, in the practice of this invention. If use areas, the preferred outside diameter of the spheres between 1.0 and about 4.0 millimeters, including every tenth of a millimeter in between, most preferably 2.5 mm, However, claudet with the greatest length in the range between 1.0, and 10.0 mm, including every tenth of a millimeter in between. More preferably, the extrudate having a roughly circular cross-section, a diameter of between about 1.0 and 4.0 millimeters, including every tenth of a millimeter in length and a length sufficient to provide the average ratio of length to diameter in the range of about 1-4. Such extrudates having an average diameter of about 1.60 mm and the average ratio of length to diameter in the range of about 2,00-4,00 (including every hundredth in the interval), are particularly preferred, most preferably the average ratio of length to diameter of 3.00.

The properties of the finished catalysts according to the invention

The finished catalyst obtained in accordance with this invention has a specific surface of more than 100 m2/g, and preferably in the range of 120-200 m2/g, each including a m2/g between them. The range of 135-150 m2/g, including every integer in the interval, is especially preferred.

The catalysts according to the invention can be conveniently characterized as having a specific pore volume, average diameters which lie inside the first range of diameters, and other specific pore volume, average diameter is additionally characterized as a percentage of the total pore volume, related to the specified second range of diameters. In the catalyst according to the invention, the volume of pores having diameters below 6 nm (60 angstroms), less than 0.05 cm3/g, and the volume of pores having diameters below 6 nm (60 angstroms), less than 0.02 cm3/g is more preferred and the volume of pores having diameters below 6 nm (60 angstroms), less than 0.01 cm3/g is preferable. The volume of pores having diameters in the range from 6 to 35 nm (60-350 angstroms), more than 0,50 cm3/g and more preferably within 0,60-0,80 cm3/g, including every hundredth cm3/g between them, and most preferably around 0.69 cm3/,

When the expression in percentage of the total pore volume present in the catalyst according to one variant of the invention, the volume of pores with diameters in the range from 6 to 35 nm (60-350 angstroms) is more than 75,00%. More preferably, the volume of pores with diameters in the range from 6 to 35 nm (60-350 angstroms) more than 80,00%. Even more preferably, the volume of pores with diameters in the range from 6 to 35 nm (60-350 angstroms) more than 84,00% with the most preferred range of 86.00-89,00%, including every hundredth percentage in between. The percentage of pore volume expressed here as a percentage of the total pore volume of the catalyst. Measured the ptx2">According to common understanding of previous experience, the catalysts having the combination of properties (including the distribution of pores), which are the catalysts of this invention were supposed to detect undesirable low selectivity of the catalyst. Moreover, they were supposed to have unacceptably high diffusion resistance due to the lack of pores with diameters of more than about 60 (600) or 70 (700) nm (angstroms). It was therefore unexpected that the catalysts according to the invention, has been found to have excellent selectivity with concomitant low content of large pores.

Other properties of the finished catalyst

Other physical properties are useful to further characterize the catalysts according to the invention, including bulk density packaging. In a preferred embodiment, the catalyst according to the invention has a bulk density of packing more than 0.50 g/cm3. Especially preferred volumetric packing density in the range of 0.50-0.65 g/cm3including every hundredth g/cm3in the interval, with the most preferred volumetric packing density of 0.57 g/cm3. Volumetric packing density higher than 0.50 g/cm3are those the favourable effects in relation to the volume activity of the catalyst.

Bulk density packaging placed here on the basis of measurements made by the following method. The catalyst in amounts in the range 900-1000 ml poured into tared vibrating graduated cylinder 1000 ml Vibration of the cylinder continue as long as the volume does not become permanent. Read the final sample volume of catalyst and determine the mass of the sample catalyst. Volumetric packing density calculated by dividing the sample mass on the final sample volume. The measurements were carried out on samples that were protected from atmospheric moisture after their final annealing during the preparation of the catalyst.

Another characteristic of the catalysts according to the invention is that they are regenerated. For the purposes of this description and the accompanying claims, the catalyst is "recycled" if it is a response to the practical procedure of regeneration is quite favorable, so that it was economically advantageous to regenerate the catalyst at least once during its useful service life. The degree of regeneriruemost can be expressed quantitatively by reducing the cycle time associated with regeneration. For the purposes of this opisie catalyst, is the percentage reduction of the cycle time, which is observed when comparing the first and second cycles, achieved with the same catalyst loading, when two cycles are conducted under conditions that are economically viable, and essentially equivalent in the sense of how the average conversion of paraffins and other working conditions with the exception of the activity of the catalyst. In a pair of cycles, the first cycle begins with the fresh catalyst, continues without regeneration and ends at the point in time selected to provide a cost-effective combination of cycle time and the average conversion of paraffin. The second cycle begins after the first regeneration, continues without additional regeneration and ends at the point in time selected to provide an average conversion of paraffin, approximately the same as during the first cycle. In each case, the periods of downtime inside loops are not included in the calculation of the cycle time or the average transformation. Preferred and/or economically cycle time for a given set of conditions are readily determinable by a professional in the field of catalytic processes.

As for the catalyst, obtained in accordance with the preferred option, where the main catalytic component is Pt, it is well known that the conditions of preparation of the catalyst must be accurately matched to provide the catalyst with adequate mechanical strength and a high degree of dispersion of Pt. According to the invention, any distribution of Pt in the media may be used provided that it will result in a suitable dispersion of Pt, which has adequate thermal stability. Preferably the Pt distribution is as uniform as possible. More specifically, the high local concentration of Pt should pederastia. The purity of the source material of aluminum oxide and conditions of preparation of the catalyst should be selected to ensure adequate thermal stability of the object structure in the finished catalyst; stability should be sufficient to avoid excessive occlusion of Pt during the application of the catalyst. Such considerations are also relevant when using other metals of the platinum group, and these considerations are well-known specialists in the acquisition and application of catalysts on the media.

Obtaining catalyst

As a rule, to obtain catalysts according to the invention can be used in many ways to obtain a catalyst containing a platinum group metal on a carrier of alumina. However, the full processing of the precursor catalyst must agree sufficiently with specified here to produce finished catalyst material having a unique combination of physical characteristics and properties (including the distribution of pore sizes), which lies within a bounded formula of the present invention. A new combination of properties possessed by the catalysts described herein, it is necessary to ensure that such material kata is a major and regeneriruemost. While the preferred method of receiving according to the invention described in example II below, the method of obtaining can be made significant changes, without leaving the scope of the claimed invention that must be understood by the experts after reading this description and the appended claims, since many of the basic principles of obtaining catalysts known in the art, can be applied for preparation of catalysts according to the invention. In any case, it is preferable to select the conditions of impregnation, which result in a favourable distribution of the added components in the media, as well as a high degree of dispersion of the main catalytic component.

The catalysts obtained in accordance with the preferred form of the invention, contain a carrier, a main catalytic component, controlling the acidity of the component and optionally an activating component. These components are often discussed here only in terms of their constituent elements, but it should be understood that these elements may be present in different oxidation States or as components of various chemical compounds or complexes in various stages of obtaining or use componentui catalyst are considered experts in this field. Some of these methods, which are applicable for the preparation of catalysts containing one or more platinum group metals deposited on a porous carrier made of alumina, can be used for deposition of the added catalyst components (including soluble metal particles bound in complex or non complex) upon receipt of the catalysts according to this invention. For example, a suitable catalyst carrier of aluminum oxide may be immersed in a solution containing one or more decomposing when heated metal salts, which must be used. The activating component and the main catalytic component in one embodiment can be satisfactorily deposited on the catalyst carrier simultaneously using a solution containing both components. In some cases, the best results are obtained if the activating component is applied first, followed by a stage of annealing, after which the calcined material is impregnated with a solution containing main catalyst component. Although it is possible to cause the main catalytic component first and then applying an activating component, this proceduresa, when the activating component and controlling the acidity of the component at the same time add to the media for the first impregnation stage and the main catalytic component is added after the second impregnation stage. As a rule, it is most preferable to add the main catalytic component after any stage of annealing, which significantly reduces the specific surface of the carrier, in order to reduce the risk of wasteful capture some or all of the main catalytic component carrier during calcination.

Despite the fact that, in accordance with the invention can be used any decomposing when heated soluble salts of the metals to be deposited on a carrier of alumina, the best results are usually achieved by the use of salts that do not contain halogen. Containing halogen salt, such as chloroplatinic acid, although applicable, but usually not particularly preferred because their use leads to the fact that the catalyst contains at least some amount of halogen ions, and ions of the halogen in the catalyst material, even in small amounts, can potentially prot-ion is removed from the catalyst material only with difficulty, the presence of sulfate ions in the catalyst even in small quantities may be adversely affected. The most preferred solutions for impregnation of a catalyst containing metals of groups I-B, are solutions containing nitrates, such as copper nitrate or the nitrate of silver, dissolved in aqueous ammonium hydroxide. The most preferred solutions containing platinum metals, are the solutions obtained by dissolution of diamondedition, such as diamondancer platinum, Pt(NH3)2(NO2)2or diamondancer palladium, Pd(NH3)2(NO2)2in aqueous ammonium hydroxide.

When using aqueous ammonia solution diamondinchrist platinum (as in examples I-III below), good results are obtained following the method of preparation of the solution. Diamondancer platinum is dissolved in hot concentrated aqueous ammonium hydroxide solution to obtain a homogeneous intermediate the mother solution in which the concentration of Pt is slightly higher than intended for use for the impregnation of the catalyst. The mother liquor then may not necessarily be maintained at a temperature in the range of about 65-85C ("aged") during the period up to about stuudy in solution. The amount of solution required for impregnation of the catalyst, conveniently provided by diluting a suitable number of intermediate stock solution with deionized water, maintaining at the same time, the temperature suitable for maintaining homogeneity, such as about 65S. If desired, the diluted solution can be heated or cooled to a certain temperature for a stage of impregnation of the catalyst. In any case, it is preferable that the solution was homogeneous, when it is brought into contact with the catalyst carrier. Professionals understand that the most preferred method of preparation may vary, e.g., from the desired particle size of the catalyst. Specialist belongs to the choice of a suitable method and concentrations of solution for a given set of conditions.

During a given stage of the impregnation amount of solution used may vary widely. It is preferable to use relatively large volume of solution to ensure uniform deposition of metal salts. Very satisfactory found the procedure, when in each case, use the volume of solution equal to the amount required for complete saturation of the uterus, just equal to the entire amount of metal present in the solution used for impregnation stage. The amount of solution required to saturate the material of the carrier may be easily determined by tests conducted on a small sample of material media. If the selected metal salt such as the carbonate, the main character, as only one example) in any case not sufficiently soluble to allow precipitate the desired amount of metal in one application, the metal may be applied in several steps with drying and/or calcination of the catalyst material between such stages.

In the various examples shown here, the conditions of annealing is described in the translation to a specific temperature annealing and either at the exact scheduled time of annealing, or the time of calcination, sufficient to ensure the established effect. Professionals it is clear that several excellent temperature annealing could also be used essentially equivalent results. In some cases, could require a compensating change the time of annealing, and such changes are well known in the art. When the calcination is conducted, so that the displacement can be easily tracked by testing samples of the material at appropriate intervals, using known in the art techniques, such as the BET method with nitrogen as the adsorbed substance. When the processing at elevated temperatures is used to remove volatile or decomposing by-products of impregnation, such as nitrites, nitrates, ammonia, etc., similar to the testing of small quantities of granules of the catalyst in selected intervals can be undertaken to assess the success, or, alternatively, specialists can trust the terms of which are well known and recognized as sufficient for such removal, provided that the finished catalyst has physical limitations set forth in the claims. Despite the fact that the annealing in air is shown in various examples, the invention also provides for the use of other atmospheres during calcination, as the use of other atmospheres, including oxidative, reductive and inert atmosphere, people know the usual level in the calcination of the catalysts. The calcination is usually carried out at a temperature between 300 and 1200C, preferably between 400 and 1000C, including every degree of temperature in the specified range. Processing the calcination may be the clock. It is clear that the average temperature during annealing is higher than the average temperature during any dewatering processing.

Example I Prior art

This example illustrates the preparation and use of a dehydrogenation catalyst on a carrier of alumina, corresponding to what is known from the prior art. All used here, parts are parts by weight, except as otherwise specified. Used media aluminum oxide obtained from LaRoche Industries, Inc., grade A-302, sector 5-8 mesh. Technical conditions for the specified media include bulk density of at least 0,673 g/cm3the specific surface of at least 270 m2/g and the volume of macropores at least 0,18 cm3/, In a suitable dryer for coating the catalyst load 104,6 part of the catalyst carrier. The first solution for impregnation is made from 0,666 parts of potassium nitrate, 8,23 part of the three-hydrate nitrate copper (II), 23.0 parts of concentrated aqueous ammonium hydroxide (28% NH3and sufficient deionized water to provide a final solution volume equal to that required to fill the pores of the carrier, as defined by the TEC is R for impregnation is sprayed on the pellets during a period of about seven minutes. After several minutes of treatment in the drum sufficient to accomplish the total absorbance of the solution granules, granules dried at C to a moisture content of 3% or less, and then calcined in air at about C in a period of time sufficient to reduce the specific surface to the range of 180-220 m2/g, as determined by tests on small samples, carried out during the process of annealing. After cooling to ambient temperature, and screening to remove fines resulting calcined intermediate granules are again placed in the drum for coating and impregnating the second time hot (50-60C) water ammonia solution diamondinchrist platinum containing 0,37 part of platinum using a procedure similar to that for the first impregnation. The resulting granules are then dried at C to a moisture content of 5% or less, and then calcined in air at about C in a period of time sufficient to remove decomposing by-products of impregnation, such as nitrites and nitrates. Finally, the pellets are cooled and sieved to obtain 100 parts of the finished catalyst. The resulting catalyst has the following measured properties: 0,25%, 2,1% cu, 0.37% of Pt and the specific surface is t to be found in the table below (Catalyst A).

This catalyst was tested by using it for the dehydrogenation of normal mixture of paraffins, which contains hydrocarbons that contain 10, 11, 12 and 13 carbon atoms per molecule, in a laboratory reactor recycle under the following conditions: the temperature of the catalyst 444-S, excessive pressure of 54.5-55/3 kPa (a 7.9-8.1 psi wt.), the molar ratio of hydrogen to hydrocarbon 0,69-0,71, the consumption of paraffin 79-80 g/g catalyst/hour and the duration of the experiment five hours. Limits reached normal conversion of paraffins to 7.5-11,00% and limits the conversion to aromatic by-products 1,02-1,93%.

Example II

This example illustrates the preparation and use of a dehydrogenation catalyst on a carrier of alumina suitable for the invention. The procedure of example I is repeated except that the carrier serves as the extrudate from Engelhard Corporation, grade AE-30, having a roughly circular cross section with diameters of about 0.16 cm (1/16 inch) and the relationship of length to diameter predominantly in the range 2-4. The duration of the first annealing are chosen so that at least it was a period of time sufficient to remove decomposing by-products of impregnation, and the amount of platinum in vstore. The total number of the medium, and the amount of nitrates of copper (II) and potassium used in the first solution for impregnation, slightly reduced, as required, to ensure that the resulting catalyst having the following properties: 0,23%, 2,07% cu, 0.54% of Pt, the specific surface 144 m2/g, volumetric packing density of 0.57 g/cm3volume of macropores is 0.06 cm3/g, total pore volume 0,78 cm3/g, pore volume zero for pores with diameters below 6 nm (60 angstroms) and pore volume 0,69 cm3/g for pores with diameters in the range from 6 to 35 nm (60-350 angstroms) (equal to 88.5% of the total pore volume).

Characteristics of dehydrogenation for the specified catalyst was tested using the same feedstock and conditions as used in example I. the Limits reached normal conversion of paraffin to 10.9%-15,5%. Increase conversion in comparison with example I is proportional to the increase of the weight of Pt in the reactor. Therefore, there is no loss of efficiency Pt at higher Pt content. Limits conversion to aromatic byproducts of 1.23-2.44 percent, While the conversion of paraffin conversion to aromatic by-products is 36% lower than in example I. Thus, the selectivity of the catalyst according to the invention, CACR CLASS="ptx2">The procedure of example II is repeated except that the use of media other party. The resulting catalyst has the following properties: 0,27%, 2,08% si, 0,52% Pt, the specific surface 143 m2/g, volumetric packing density of 0.56 g/cm3, macropores volume of 0.07 cm3/g, total pore volume 0,78 cm3/g, pore volume zero for pores with diameters below 6 nm (60 angstroms) and a pore volume of 0.68 cm3/g for pores with diameters in the range from 6 to 35 nm (60-350 angstroms) (equal to 87.2% of the total pore volume). Limits reached normal conversion of paraffin to 10.8-15.3% and the limits of transformation to the aromatic by-products 0,92-2,17%. When this transformation paraffin conversion to aromatic by-products is 51% lower than in example I. This further illustrates the advantage of the selectivity of the catalyst according to this invention in comparison with the catalyst of the prior art example I.

Example IV

The procedure of example II is repeated except that the use of other media extrusion type of 0.16 cm (1/16 inch), which provides a higher specific surface area in the finished catalyst. The resulting catalyst has the following properties: 0,32%, 2,19% si, 0,65% Pt, the specific surface is diameters below 6 nm (60 angstroms) and a pore volume of 0.48 cm3/g for pores with diameters in the range from 6 to 35 nm (60-350 angstroms) (equal 62,3% of the total pore volume). Limits reached normal conversion of paraffin to 9.3 14.6% and limits the conversion to aromatic byproducts of 1.1 to 3.0%. When this transformation paraffin conversion to aromatic by-products for about 20% lower than in example I. This 20% reduction in the formation of aromatic compounds is substantially less than the reduction by 36% and 51%, as shown in examples II and III. This illustrates a less favourable selectivity, which is achieved when the diameter of the granules remains the same as in examples II and III, but the distribution of pore sizes of the catalyst is not consistent with the invention.

Example V

Two catalyst prepared from different portions of the same batch of granules of aluminum oxide Kaiser KA 101. For catalyst S (standard specific surface area) pellets calcined at 600C for 2 hours to obtain a modified granules with a specific surface area of 190 m2/g volume of macropores of 0.18 cm3/g and a bulk density of 0.67 g/cm3. Modified granules impregnated with aqueous ammonia solution diamondinchrist platinum and copper nitrate (II), dried at 120C and calcined at 450C for two cha it for the dehydrogenation of normal dodecane in a laboratory reactor reciprocating flow of raw materials under the following conditions: the temperature of the catalyst 450C, overpressure 63 kPa (10 psig barg), the molar ratio of hydrogen to hydrocarbon of 8.0, the feed speed dodecane 32 volume liquid volume of catalyst per hour and the duration of the experiment 25 hours. Limits reached normal conversion of paraffin at 13.0-14.3% and limits the conversion to aromatic byproducts of 0.21-0,56%.

For catalyst L (low specific surface area) of the granules are calcined at 1000C for 6 hours to obtain a modified granules with a specific surface area of 48 m2/g, the volume of macropores 0.25 cm3/g and a bulk density 0,69 g/cm3. Use the transformation modified granules in the catalyst, resulting in levels of Pt and si and the test conditions of the catalyst same as catalyst for S, except that they use a higher temperature of the catalyst during the process of dehydrogenation. For catalyst L experience begins when S in an attempt to map the transformation achieved with catalyst S. However, despite the higher the temperature, the higher the achieved transformation is only 14%. Therefore, the specific activity of the catalyst L significantly lower than that of the catalyst S. After 2 hours is no experience. Limits achieved at 450C normal conversion of paraffin from 9.1 to 11.3%. The within transformation to the aromatic by-products for the whole experience 0,04-0,30%. These results show that although the selectivity of the catalyst is improved by annealing the media prior art to reduced specific surface area, as described in patent No. 3920615, improved selectivity accompanied by a significant decrease of activity achieved in a given mass of Pt. This disadvantage is eliminated in the catalyst according to this invention, as illustrated in example II.

Example VI

Catalyst samples of example II and catalyst of the prior art, prepared as described in example I, is subjected to aging for two hours in nitrogen atmosphere at S. Characteristics of dehydrogenation for each of the catalyst before and after the aging test, using the same feedstock and conditions as used in example I. the Conversion of paraffin after 100 minutes of work used for comparisons. For the catalyst of example II an illustrative result of aging is the decrease of the transformation from 12,6% to 11.4%, without aging the decrease of the achieved conversion of 9.5%. For other catalysts pocitovo transformation is 7.2%. This allows us to conclude that both catalyst discover excellent thermal stability. A small difference between two results is considered to be insignificant.

Example VII

The procedure of example II is repeated except that changing the order of addition of metals. In the first stage impregnation only add potassium instead of potassium and copper. On the second impregnation stage is to add copper and platinum instead of only platinum. The resulting catalyst has the following properties: 0,37%, 2,66% si, 0,76% Pt specific surface area of 123 m2/g, volumetric packing density of 0.58 g/cm3, macropores volume of 0.05 cm3/g, total pore volume 0,78 cm3/g, pore volume zero for pores with diameters below 6 nm (60 angstroms) and pore volume 0,69 cm3/g for pores with diameters in the range from 6 to 35 nm (60-350 angstroms) (equal to 88.5% of the total pore volume).

Limits reached normal conversion of paraffin 9.5 to 13.0% and the limits of transformation to the aromatic by-products 0,98-2,04%. When this transformation paraffin conversion to aromatic by-products is 32% lower than in example I. This illustrates the change in the method of producing a catalyst, which is possible in the area covered by the invention without any doubt is the group, the diameter of the carrier increases from about 0.16 cm (1/16 inch) to about 0.32 cm (1/8 inch). The resulting catalyst has the following properties: 0,25%, 2,1% cu, 0.54% of Pt, the specific surface 133 m2/g, volumetric packing density of 0.54 g/cm3, macropores volume of 0.07 cm3/g, total pore volume 0,78 cm3/g, pore volume zero for pores with diameters below 6 nm (60 angstroms) and a pore volume of 0.68 cm3/g for pores with diameters in the range from 6 to 35 nm (60-350 angstroms) (equal to 87.2% of the total pore volume). Limits reached normal conversion of paraffin to 7.8-11.6% and the limits of transformation to the aromatic by-products 0,92-1,92%. When this transformation paraffin conversion to aromatic by-products is 17% lower than in example I. This illustrates the advantage of the selectivity of the catalyst according to this invention in comparison with the catalyst of the prior art example I in the absence of any noticeable differences in the diameter of the pellets.

Example IX

Single-stage adiabatic reactor with piston downflow download two types of catalysts in separate layers. Catalyst R is used for the lower layer and the catalyst N is used for the upper layer. The mass obtained as a result is a lyst of the prior art, prepared as described in example I, and the catalyst is N are prepared in accordance with the invention. Catalyst R has the following properties: 0,24%, and 1.8% cu, 0.46% of Pt, the specific surface 213 m2/g and volumetric packing density of 0.74 g/cm3. Catalyst N has the following properties: 0,30%, and 1.8% cu, 0.54% of Pt, the specific surface 142 m2/g and volumetric packing density of 0.58 g/cm3. In the first working cycle of a hybrid catalytic layer is used for the dehydrogenation of normal paraffin at conditions within the following limits: temperature at the inlet to the catalyst bed 429-S, excessive inlet pressure 57,2-63 kPa (8,3-10.0 psi wt.), the molar ratio of hydrogen to hydrocarbon of 0.47 was 1.06, the consumption of paraffin 4,9-5,3 g/g catalyst/hour and the limits of transformation paraffin 8,25-11,90%. Cycle length 32 days (23 days on C10-13 paraffin and 9 days on SP-14 paraffin) and the average conversion of the paraffin of 10.72%. After the first cycle regenerate the catalyst by burning off the accumulated coke is treated with hydrogen and then used for the second cycle. In the second cycle the operating conditions as follows: temperature at the inlet to the catalyst bed 437-S, excessive pressure at the entrance to 52.4-73,1 kPa (about 7.6-10.6 psi wt.), the molar ratio vodorodych cycle of 29 days (20 days for C10-13 paraffin and 9 days on SP-14 paraffin) and the average conversion of paraffin 10,54%. The comparison of the two cycles shows that regeneration restores a significant part of the activity of the catalyst, which is lost during the first cycle. Moreover, the cycle length and the average transformation fit well within practical operating limits. Therefore, the hybrid layer does not show any lack of regeneriruemost, and the results show an acceptable degree of regeneriruemost catalyst according to the invention.

Structural details

The data presented in the table below for a more detailed discussion of the effects of specific structural changes in the finished catalysts. The catalyst And is best known for the regenerated catalyst prior art for dehydrogenation of paraffins range of detergents. The decrease to zero of aromatic compounds based on the result achieved in example I, and other properties determined using another typical example, which is produced by the method of example I. the Catalyst B-F are the catalysts of examples II, III, IV, VII and VIII respectively. In all cases, a more significant reduction of aromatic compounds is equivalent to a higher selectivity to the of talization selectivity is much higher than for catalyst And prior art. Compared with catalysts b and C, the catalyst E has a selectivity below, obviously, because it is produced using less than optimal order of addition of metals.

Compared to catalysts and catalyst F has a lower selectivity because of the larger diameter of its granules. Compared with the catalyst And the catalyst F has a diameter a little smaller, but the resulting diffusion advantage is greater than the recoverable due to the greater length of its granules. Thus, it is easy to see that the advantage of selectivity at least as much as is shown in the table for catalyst F in comparison with the catalyst And is the result of more favorable porous structure of the catalyst F.

Catalyst D is not in accordance with the invention, as the volume of pores of diameters of 6 nm (60 angstroms) is not within the required range. Compared with the catalyst And catalyst D has a better selectivity due to the smaller diameter of its granules. However, since the catalysts b, C and D have very similar shapes and diameters of the granules, the lower the selectivity of the catalyst D compared to rolled uraemia above comparisons show, the structure of the pores of the catalysts b, C, E and F, prepared in accordance with the invention, provide a higher selectivity than the structure of the pores observed in the catalysts a and D. For catalysts b, C, E and F significantly lower content of pores with diameters below 6 nm (60 angstroms) is, obviously, a very important contribution to higher selectivity. In the catalyst And significantly higher content of macropores >70 nm (>700 angstroms) is not capable of compensating for the adverse effects on the selectivity of the relatively high content of pores of less than 6 nm (60 angstroms). This inefficiency macropores is absolutely amazing and unexpected from the point of view of the previous idea that significant volumes of pores associated with the best selectivity. For example, in U.S. patent No. 4608360 requires that at least 55% of the total pore volume of the catalyst was associated with pores having mean diameters of about 60 nm (600 angstroms) or more.

The loss continued a strong confidence to very large pores in communication with the instructions of the invention is advantageous because some of the shortcomings inherent in very large pores. Compared with smaller pores very large pores sadkach it is no longer considered necessary for the high selectivity of the reaction. Counting per unit volume of catalyst, a very large pores provide less surface area of the carrier, which is necessary to properly stabilize the fine crystallites of platinum, which is required for high catalytic activity. Therefore, in the catalyst with a high content of very large pores increasing filling platinum, in order to provide a higher initial activity, leads to so close to picking up crystallites that it has a harmful effect on thermal stability of the dispersion of platinum. Another disadvantage of very large pores is their tendency to reduce the mechanical strength of the granules of the catalyst.

In catalysts b, C, E and F are very high content of pores in the range of 6-35 nm (60-350 angstroms) is not associated with low selectivity. Therefore, we can conclude that the pores in this range is surprisingly capable of very effectively contribute to the low diffusion resistance, which is necessary for high selectivity.

The other amazing aspect of the catalysts according to this invention, which no doubt will be taken into account by the experts after reading and understanding this specification, is a large degree, Atrem). Some of the catalysts obtained in accordance with the invention, essentially no such micropores. Although it was previously known that the selectivity could be increased through a more stringent annealing, obviously, by reducing the content of micropores, all previous attempts in this direction gave relatively poor results. If the calcination was rigid enough to provide a significant increase in selectivity, the specific surface area was decreased so much that the activity and thermal stability were undesirable low. If the annealing was less stringent, increasing the selectivity was less than desirable. Now found that a very high degree of reduction of the micropores and the increase in selectivity can be achieved in combination with the final specific surface area sufficient to provide both high activity and high thermal stability.

Volumetric packing density of the catalyst according to the invention is higher than most of the dehydrogenation catalysts of the prior art. This property combined with a new porous structure makes it possible to achieve very high in the of MNA density, low volume of macropores and low micropore volume are the result of a previously unavailable level of favorably located specific surface area of the medium per unit of reaction volume.

This makes possible the introduction of a large number of platinum in the reactor of a given size without any significant damage to the average efficiency per unit mass of platinum.

Useful characteristics of the process

Any of various combinations of equipment, raw materials and working conditions, which can be used with the catalysts of the prior art to obtain monoolefins range of detergents by dehydrogenation of paraffins, can also be used with the catalysts according to the invention. However, it is preferable to use a process that provides for the regeneration of the catalyst through cost-effective intervals. The following sections describe various preferred features of the process for a process that provides for the regeneration of the catalyst.

The design of the reactor

For the implementation in practice of the present invention is used, the reactor or reactors should be preferably designed for adiabatic high degree of conversion to the hotter walls leads to lower selectivity of the reaction. Another reason is that the impact of such mixture to higher temperatures of the catalyst, existing near the inlet adiabatic reactor, leads to the decrease of selectivity of the reaction, and causes an unacceptably high degree of deactivation of the catalyst under the conditions specified process. Another reason is that the selectivity tends to be higher when any increase in the degree of conversion occurs at the lowest possible mean ratio of olefin to paraffin, i.e., when the back-mixing is minimized. The fourth reason is that part of the adiabatic reactor downstream from the site where the greatest transformation, provides a more favorable low-temperature environment, where it may remain the preferred excess of the initial activity of the catalyst.

Any other structural elements of the reactor, suitable for use for platinum catalyzed dehydrogenation of paraffins range of detergents, can also be used in the practice of this invention. The direction of flow may be downward, upward or radial. The ratio of the depth of the layer in the direction of flow to the area of the transverse and rolling, but it should not be fluidized, as this would be incompatible with the work when the piston flow.

It is preferable to use a cylindrical reactor of continuous operation with a fixed layer and a downward direction with the ratio of length to diameter is chosen so as to minimize problems with parietal effects, the formation of local end-to-end flows, excessive back-mixing, the excess thermal feedback or insufficient turbulence outside the granules of the catalyst. It is preferable that the feed paraffin was completely vaporized and uniformly mixed with the added hydrogen prior to contact with the catalyst bed.

Paraffin feedstock

Paraffin range of detergents that are used as raw material may be of any origin and any variety, suitable for use in platinum catalyzed the dehydrogenation. Paraffins, used as a raw material for the dehydrogenation using catalysts according to the invention include all of paraffins having from 2 to 20 carbon atoms per molecule, whether paraffins with a straight chain or branched. Although it is assumed that any paraffin, colorlove in accordance with the invention, the preferred starting material are paraffins suitable for obtaining alkyl benzenes as intermediates in the production of sulfonated alkyl benzenes for detergents, and normal paraffins are particularly preferred feedstock. "Paraffin range of detergents" means paraffins with a total number of carbon atoms in the range from 9 to 15 inclusive, i.e., saturated hydrocarbon molecules that contain 9, 10, 11, 12, 13, 14 or 15 carbon atoms per molecule. The total number of carbon atoms ranging from 10 to 14 is particularly preferred. Can be used in mixture with the range of numbers of carbon atoms, and preferably to limit the width of the range of numbers of carbon atoms in such compounds with four carbon atoms or less. Used paraffins can be fresh (not previously used in the process of dehydrogenation) or recycle (neprevzaidennymi paraffin extracted from an earlier product of dehydrogenation). Mixtures containing fresh and recycle paraffins in any proportions, can also be used.

Since different ranges established in this description and the attached claims, it is useful to define all the established range of the zone. For example, the expression "any number of carbon atoms between 9 and 15" means 9, 10, 11, 12, 13, 14 and 15. Similarly, the percentage ranges also include the extreme values used to limit the range.

The number of stages and the number of catalyst

It is preferable to use either a single stage reaction, or two successive stages with suitable means for reheating between stages. If you use two stages, various aspects of reactor designs and operating conditions may be similar or different. In a preferred method of operation of a series of many cycles and punctuating their regenerations of the catalyst can be completed without any interruption to add or remove catalyst. At the beginning of this series, the type and amount of catalyst loaded in the reactor or the reactor shall be such that there is an excess of catalyst activity. This excess of the initial activity necessary to compensate for the deactivation of the catalyst, which occurs during each working cycle and from cycle to cycle. The preferred excess of the initial activity is the excess, which provides the most favorable known by experience, at the beginning of each cycle due to excessive activity.

The conversion of paraffin

Any degree of conversion per pass and any controls transformations which are appropriate for the platinum catalyzed dehydrogenation of paraffins range of detergents that can be used in the practice of this invention. Turning over one stage could be very low in some cases, for example about 1%. The total transformation throughout all stages of the process of dehydrogenation could reach 20% or higher. The preferred range of turning of the wax throughout the United stages from about 5% to about 20%. The transformation can be maintained almost constant during the processing cycle or changed in any desired manner. The best program for the regulation of transformation on the basis of the time within a work cycle greatly depends on other conditions used and may be determined by ordinary experimentation.

Various methods of control transformations during the processing cycle is well known. Such methods include adjusting the reaction temperature, reversible poisoning of the catalyst, periodic or continuous doba is gained. In a preferred method of processing cycles begin with a substantial excess of activity of the layer of catalyst and operating conditions closer to the beginning of the cycle limit relatively low temperature range, which provides a high tolerance to excess activity of the catalyst. Thus can be achieved good results without relying on any reversible poisoning, nor the addition of the catalyst during processing.

Regeneration and treatment with hydrogen catalyst

The preferred method of regeneration of the catalyst is burning the accumulated coke using diluted source of oxygen, such as a mixture of air with nitrogen and/or recycle the products of combustion of coke. The oxygen content and the temperature of the inlet gas can be adjusted to provide a suitable peak temperature within the combustion zone of coke. In a preferred method of operation after burning coke and before the introduction of the original paraffin catalyst process clean or recycle hydrogen for about an hour or more at a temperature comparable with that which must be at the beginning of the next processing cycle. The treatment with hydrogen is also used to podgotovity specific circumstances can be determined by ordinary experimentation.

The added hydrogen

It is known that traditional industrial dehydrogenation of paraffins range of detergents certain amount of hydrogen added to the initial mixture for dehydrogenation, in order to maintain the catalyst in an active state. Without regard to any theory it is usually assumed that the action of hydrogen beyond simple dilution. In particular, hydrogen, likely plays a role in suppressing the formation of coke on the surfaces of the catalyst and maintaining platinum necessary in the metallic state.

The number of added hydrogen can be widely changed, and the ratio of N2:The national Assembly may be constant or variable over the cycle of the reaction. The relation of H2:The NA is defined here as the molar ratio of added hydrogen to hydrocarbon range of detergents in the feed mixture. Although there may be used a much higher ratio, it is preferable to use a relatively low ratio H2:NS within about 0.3 to 1.9. Particularly preferable to use a relationship of H2:NS in the range of about 0.4 to 1.0. Among the advantages of relatively low relationship of H2:NS can be called the smaller the Rev is e low operating temperatures is particularly advantageous near the beginning of the cycles, when there are large amounts of excess activity of the catalyst.

The hydrogen used in this invention may be from any source and of any kind, suitable for use in platinum catalyzed the dehydrogenation of paraffins. Suitable types include hydrogen, obtained by another process; hydrogen formed during the dehydrogenation, dedicated or recycled, and the various hydrogen purity. For economic reasons it is generally preferable to use hydrogen generated in the process. The degree of purification or treatment of recycle hydrogen before its reuse should be selected to optimize the overall efficiency of the process.

Temperature and pressure

Any temperature at the inlet to the catalyst bed suitable for platinum catalyzed dehydrogenation of paraffins range of detergents that can be used in the practice of this invention. For operations with a single stage reaction, it is preferable to use the temperature at the entrance, which does not exceed S. For operations with two or more stages of the reaction it is preferable to use the temperature at the entrance, which does not exceed 450C. The advantages of casenergy, reduced the rate of formation of coke, reduced maintenance costs of the equipment and the improved efficiency of the catalyst.

For best results it is usually necessary to change the temperature at the inlet during the working cycle. Usually the lowest temperature used in the beginning of the cycle to suppress excessively deep reaction and higher temperatures are used later to compensate for the decrease in catalyst activity. In each moment of time during the working cycle, the inlet temperature required for the particular stage of the reaction strongly depends on reinforcing desirable transformations during the step, the desired transformation on the output stage, the General pressure relationships:NA, everything is interconnected with the inlet temperature and determines whether the temperature of the output stage is high enough to provide the desired transformation, which must be achieved before the transformation will be prevented by the effects of the equilibrium reaction. For any particular situation the optimal program adjustments temperatures at the inlet can be determined by ordinary experimentation specialist with regard to this specification.

MCOR

Mass time volume flow (MCAR) is defined here as the mass of the original paraffin arriving at a specific layer of catalyst per hour per unit mass of catalyst in this layer (both masses measured in the same units). When MTOR increases, the conversion in the catalyst layer of the specified activity tends to decrease. The choice of values MCAR also captures the magnitude of these alternative options, as time volumetric flow rate (CORE) or contact time. Any MCOR, suitable for platinum catalyzed dehydrogenation of paraffins range of detergents that can be used in the practice of this invention. Values in the range from about 1 to about 20 predosterezheniyam given this description.

Work cycles

Action process with a specific layer of the catalyst from the time it was loaded or regeneration to remove or regenerating the designated here as the duty cycle. The duration of such a cycle refers to the time spent on processing the source material and does not include periods of inactivity. The cycle length can vary widely, and the most favorable cycle time significantly depends on the lifetime of the catalyst at the beginning of the cycle, and the operating conditions used during the cycle. Although it may be used with any cycle, it is preferable to use a cycle time of more than about 200 hours, as the shorter cycles lead to an excessive decrease in the percentage of time during which the reactor is available for processing of paraffin. Possible much longer cycles, for example, 1000 hours or more. When the cycle length increases, it becomes more difficult to support the transformation and working conditions in the optimal range, the catalyst is deactivated.

The derivation and application of the product

The olefins obtained in accordance with ganachaud becoming an alkyl benzenes for use in detergents and transformation in various other products. Suitable methods of extraction of the product include various effective combination of stages selected from the condensation, separation of gas-liquid fractional distillation, selective adsorption, solvent extraction and selective chemical reactions. In a preferred method, the gaseous reaction mixture dehydrogenation is cooled to obtain the enriched hydrocarbon liquid phase enriched in hydrogen gaseous phase. Gaseous phase partially divert and partially recycle, with additional cleaning or without, in the process of dehydrogenation. The liquid phase is not necessarily subjected to selective hydrogenation to convert diolefins in monoolefinic and, in any case, fractionary to remove low-boiling products of cracking. The rest of the mixture containing olefins and paraffins range of detergents, bring into contact with benzene and acid catalyst in a suitable alkylation conditions to convert olefins, mainly in the alkyl benzene. The alkylation mixture is then divided by appropriate means, including fractional distillation, the product fraction alkylbenzene fraction neprevyshenie wax fraction neprevyshenie benzene and other components, such as niceley cleaning or Stripping or without it, at the stage of alkylation and dehydrogenation, respectively. In a particularly preferred method, the acidic alkylation catalyst is hydrofluoric acid, which is extracted from a mixture of alkylation at least partially purify and return to the stage alkylation.

Although the invention is shown and described with respect to specific preferred embodiments, it is obvious that equivalent alterations and modifications may become apparent to specialists after reading and understanding this specification and the accompanying claims. This invention includes all of these modifications and modifications and is limited only by the following claims.

1. Regenerated catalyst applicable to the dehydrogenation of hydrocarbons containing main catalyst component that contains one or more elements selected from the group consisting of platinum, rhodium, iridium, palladium, ruthenium and osmium deposited on a solid medium containing porous aluminum oxide, characterized in that the regenerated catalyst has a specific surface of more than 100 m2/g, volume of pores with diameters below 6 nm (60 ) is less than 0.05 cm2. The catalyst p. 1, additionally containing controlling the acidity component selected from the group consisting of alkali metals and alkaline earth metals deposited on the specified media.

3. Catalyst under item 1 or 2, additionally containing an activating component containing one or more elements selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, Nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, silver, lanthanum, hafnium, tantalum, tungsten, rhenium, and gold deposited on the specified media.

4. The catalyst according to any one of paragraphs.1-3, where the specified main catalytic component contains platinum.

5. The catalyst according to any one of paragraphs.1-4, where the specified main catalytic component comprises a mixture of at least two different elements selected from the group consisting of platinum, rhodium, iridium, palladium, ruthenium and osmium.

6. The catalyst according to any one of paragraphs.2-5, where controlling the acidity of the component is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium.

7. The catalyst according to p. 6 for controlling the acidity of the component is potassium.

8. Kataliza, selected from the group consisting of alkali metals and alkaline earth metals.

9. The catalyst according to any one of paragraphs.3-8, where the activating component is selected from the group consisting of copper, silver and gold.

10. The catalyst p. 9, characterized in that said activating component is copper.

11. The catalyst according to any one of paragraphs.1-10, where the catalytic component is present in amounts of between 0.01 and about 3.00% by weight of the total catalyst, including every hundredth percentage in between.

12. The catalyst p. 4 or any dependent of him item that contains between 0,002 and 2,000% platinum by weight of the total catalyst, including every hundredth percentage in between.

13. The catalyst according to p. 12, which contains between 0.20 and 1.00% platinum by weight of the total catalyst, including every hundredth percentage in between.

14. The catalyst p. 13, which contains between 0,40 and 0.70% platinum by weight of the total catalyst, including every hundredth percentage in between.

15. The catalyst according to any one of paragraphs.2-14, where the specified controlling the acidity of the component is present in any amount between 0.001 and 1,000% of the total mass of the catalyst, including every thousandth procentov amount ranging from about 0.10 to about 0.60 percent of the total weight of the finished catalyst, including every hundredth percentage in between.

17. The catalyst according to any one of paragraphs.3-16, where activating the specified component is present in amounts of between 0.10 and 5.00% of the total mass of the catalyst, including every hundredth percentage in between.

18. The catalyst p. 10 or any dependent of him to the point where the copper is present in amounts of from 1.00 to 3.00% of the total mass of the catalyst, including every hundredth percentage in between.

19. The catalyst according to any one of paragraphs.1-18, where the volumetric packing density of more than 0.50 g/cm3.

20. The catalyst according to any one of paragraphs.1-19, where the volume of pores with diameters in the range from 6 to 35 nm (60-350 A) is more than about 75% of the total pore volume.

21. The catalyst according to p. 20, where the volume of pores with diameters in the range from 6 to 35 nm (60-350 A) is more than 80% of the total pore volume.

22. The catalyst according to any one of paragraphs.1-21, where the reduction of the cycle time associated with the first regeneration of the catalyst is not more than 50% of the duration of the first cycle.

23. The catalyst according to p. 22, where the reduction of the cycle time associated with the first regeneration of the catalyst is not more than 35% of the duration of the first cycle.

24. Cataflam not more than 20% of the duration of the first cycle.

25. The catalyst according to any one of paragraphs.1-24, where the catalyst is in the form of spheroids with diameters in the range of 1.0 to 4.0 mm, including every tenth of a millimeter in between.

26. The catalyst according to any one of paragraphs.1-24, where the catalyst is in the form of the extrudate with the largest diameter of 1.0 - 10.0 mm, including every tenth of a millimeter in between.

27. The catalyst according to any one of paragraphs.1-26, where the specific surface is in the range from 135 to 150 m2/g, each including a 1 m2/g in the interval.

28. The method of producing olefins by dehydrogenation of a hydrocarbon, which contains stage a) obtaining a hydrocarbon; (b) preparation of the catalyst according to any one of the preceding paragraphs; and (c) contacting the specified catalyst with a specified hydrocarbon under conditions effective to cause the dehydrogenation of the specified hydrocarbon with obtaining the olefin.

29. The method according to p. 28, where the hydrocarbon is a paraffin wax.

30. The method according to p. 29, where the paraffin is a straight or branched chain and is paraffin range of detergents.

31. The method according to p. 30, where the specified contains paraffin hydrocarbon straight chain range of detergents.

32. The method according to p. 28, where the hydrocarbon contains at manageportal, where unsaturated hydrocarbons are present in amounts less than 25,00% of the total mass of the hydrocarbon.

34. The method according to p. 33, where the hydrocarbon comprises a mixture of hydrocarbons, where the unsaturated hydrocarbons comprise at least 50,00% mixture by weight of the total hydrocarbon.

35. The method according to any of paragraphs.28-34, where the specified catalyst placed inside the reactor, where the reactor includes a) an input portion, which serves the flow of raw materials containing gaseous hydrocarbon; (b) means for maintaining the catalyst essentially in a stationary position, and c) the output part, where the exhaust gases containing at least one olefin, leave the specified reactor.

36. The method according to p. 35, where the hydrocarbon contains a saturated hydrocarbon.

37. The method according to p. 35 or 36, further containing stage d) extraction of paraffin from these exhaust gases.

38. The method according to p. 35 or 36, further containing stage d) extracting monoolefins of these exhaust gases.

39. The method according to any of paragraphs.35-38, optionally containing stage e) extracting monoolefins of these exhaust gases to get depleted exhaust stream that contains a smaller percentage of monoolefins than specified the tee.

40. The method according to p. 39, additionally containing a stage of adding gaseous hydrocarbon to depleted exhaust stream at the stage of re-direction of this depleted exhaust flow to a specified input part.

41. The method according to any of paragraphs.35-40, where the specified stream feedstock contains hydrogen in an effective amount to maintain the specified catalyst in an active state.

42. The method according to p. 41, where the molar ratio of hydrogen to hydrocarbon is in the range of 0.3 to 1.9.

43. The method according to any of paragraphs.35-42, where the hydrocarbon is a paraffin and which further comprises a stage

d) extraction of unreacted paraffins from the specified waste stream, and e) re-direction of unreacted paraffins to a specified input part of the reactor.

44. The method according to any of paragraphs.35-42, optionally containing stage d) extraction of unreacted paraffins from the specified waste stream; (e) mixing fresh paraffins with these unreacted paraffins to the formation of the mixture and (f) the filing of this mixture to the specified input part.

45. The method according to any of paragraphs.28-44, optionally containing phase regeneration in the e catalyst in oxygen-containing atmosphere to a temperature sufficient to cause oxidation of at least part of the coke present on the surface of a specified catalyst.

Priority items:

27.08.1999 on PP.1-27;

03.02.2000 on PP.28-46.

 

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