Solid acid catalyst, process for its production and its use

 

(57) Abstract:

The invention relates to a solid molded the catalysts are easily separated from the reactants and re-used in the reactions of alkylation, esterification and isomerization. The method of producing the catalyst comprises (a) receiving media containing a portion of Zirconia and/or hydrated Zirconia and the proportion of aluminum oxide and/or hydrated oxide of aluminum and having a peak diameter in the range of 0.05-1 μm on the distribution curve of pore diameters of 0.05 - 10 μm; applying a sulfur-containing component on the carrier; or (b) receiving the media containing a portion of Zirconia and/or hydrated Zirconia and the proportion of aluminum oxide or hydrated oxide of aluminum and having a volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm, 0.05-0.5 ml/g, and the volume of pores with a diameter greater than 1 μm and not more than 10 μm, average of below 0.05 ml/g; the application of sulfur-containing component on the carrier. Also present solid acid catalyst, method of making acid catalyzed reactions and the way isomerization of hydrocarbons. Improved activity, manipuliruemoy and mechanical strength of the catalyst is of the GLA.

The technical field to which the invention relates

The present invention relates to a solid acid catalyst that is highly active in acid catalyzed reaction system and which is easy to manipulate, and how to obtain it.

Art

In the chemical industry known acid catalyzed reactions, such as alkylation reaction, the esterification reaction and the isomerization reaction. Up to the present time in these reactions used acid catalysts such as sulfuric acid, aluminum chloride, hydrogen fluoride, phosphoric acid and p-toluensulfonate. However, these acid catalysts have corrosive metal properties, so you need the use of expensive corrosion-resistant materials for industrial machines or necessary anticorrosive processing production machines. Usually not only it is difficult to separate the catalyst from the reactants after the reaction, but in addition you must remove the waste acid and also inevitably difficult process, such as alkaline washing. Thus, there are also many problems from the point of view of the environment. Next, ocherednogo solid acid catalyst, containing a sulfate group, which is obtained by contacting the hydroxide or hydrated hydroxide of a metal belonging to group IV of the periodic system of elements, with a solution containing a sulfur-containing component, and annealing the mixture at a temperature of 350-800o(Publication of the Japan patent 59-6181). The solid acid catalyst has a higher acidity than that of 100% sulfuric acid (Hammett acidity of H0is 11,93). Due to its high acidity of the solid acid catalysts exhibit high catalytic ability in various acid catalyzed reactions and possess favorable properties, namely that they exhibit low corrosion activity can be easily separated from the reagents, which do not require removal of waste acids and can be re-used, so I think that they will replace conventional acid catalysts.

It is also known that the catalyst obtained by impregnation of a platinum catalyst, which is obtained by calcination containing sulfur-containing component of the gel Zirconia, has been very active in the isomerization reactions of hydrocarbons (paten the tall collection of platinum and sulfur-containing component and primarily used for the isomerization of hydrocarbons, disclosed are a method, which does not carry out stage of annealing between stages of processing sulfur-containing compound, and coating metal platinum collection; the way in which stage of processing sulfur-containing compound and deposition of the metal platinum collection is carried out in reverse order; and the way in which changed the genus of sulfur-containing compounds according to the publications of the Japan patent 5-29503, 5-29504, 5-29505 and 5-29506.

It is also known that solid acid catalyst obtained by adding sulfur-containing compounds to the hydroxide or aluminum oxide, followed by calcination, exhibits an acidity higher than that of 100% sulfuric acid (published patent application Japan 5-96171, Arata, Trends in Physical Chemistry, volume 2, paragraph 1 [1991]).

In lined with the patent application of Japan 9-38494 disclosed a method of obtaining a molded catalyst based on a metal oxide, processed connection with sulfate groups. The method is characterized by the fact that carry out the preliminary calcining the molded material of the metal hydroxide and boehmite at a temperature of 300-500oAnd then processing the connection with sulfate groups, and it is a method of forming a catalyst with the use of the shaped catalyst, not containing boehmite, due to molding with the addition of boehmite. Also revealed that the molded material obtained through the use of a metal hydroxide and boehmite powder, and then dried at a temperature below 300oWith, can be sprayed and decomposed by adding water, and that the catalyst obtained by mixing a mixture of powder containing platinum, sulfated catalyst based on zirconium dioxide (powdered catalyst formed by Zirconia coated with a platinum and sulfate groups) and boehmite powder with the addition of water, followed by molding and calcination, has substantially reduced catalytic activity.

Used solid catalysts must be molded catalysts are easily separated from the reactants and reused, instead of the powdered form. However, even if the catalysts have sufficient catalytic activity, when they are in powder form, their formation is not possible to achieve mechanical strength, which is necessary during the response/receipt, or their catalytic activity is reduced at the expense of their formation. Therefore clicks the required characteristics as a catalyst and possessing the required mechanical strength.

The invention

In the present invention these problems are solved and it relates to a solid acid catalyst having a sufficiently high activity, sufficient for practical use easy manipuliruemoy and sufficient mechanical strength, although he is a molded product of a solid acid catalyst containing sulfur-containing component; the method of its production and the way of carrying out the reaction using such a catalyst.

As a result of extensive studies on the method of producing a solid acid catalyst, the inventors of the present application now found that mixing with the specific physical properties of zirconium hydroxide having specific physical properties of pseudoboehmite and ammonium sulphate, followed by molding and calcination, can lead to a solid acid catalyst with excellent catalytic activity and sufficient mechanical strength, and further study of the catalyst for completeness of the present invention.

According to the first aspect of the present invention the method according to the zirconium oxide and/or hydrated Zirconia and the proportion of aluminum oxide and/or hydrated oxide of aluminum and having a peak diameter in the range of 0.05-1 μm on the distribution curve of pore diameters from 0.05 μm to 10 μm; and the application of sulfur-containing component to the media.

According to the second aspect of the present invention is a method of obtaining a solid acid catalyst comprises the following stages: receiving media containing a portion of Zirconia and/or hydrated Zirconia and the proportion of aluminum oxide and/or hydrated oxide of aluminum, in which the volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm is 0.05-0.5 ml/g and the volume of pores with a diameter greater than 1 μm and not more than 10 μm is less than 0.05 ml/g; and the application of sulfur-containing component to the media.

According to a third aspect of the present invention is a method of obtaining a solid acid catalyst comprises the following stages: mixing powder containing hydroxide and/or hydrated Zirconia, agglomerated particles which have an average diameter of 0.2-10 μm, with a powder containing hydroxide and/or hydrated oxide of aluminum, having a fibrous form particles; molding the mixture to obtain a carrier; and applying a sulfur-containing component on the carrier. In this case, it is preferable that the above-mentioned media had a peak diameter in the range of 0.05-1 μm on the distribution curve of the diameter of p is Yam of pores with a diameter greater than 1 μm and not more than 10 μm was below 0.05 ml/g It should be noted that a step for media and stage of deposition of sulfur-containing component on the carrier preferably takes place simultaneously in one stage.

The solid acid catalyst according to the present invention is a catalyst which consists of shares of Zirconia and/or hydrated Zirconia and the proportion of aluminum oxide and/or hydrated oxide of aluminum and contains a sulfur-containing component, and which is used in acid catalyzed reactions, the catalyst has a distribution of pore diameters from 0.05 μm to 10 μm with a peak diameter of pores in the range of 0.05-1 μm. Alternatively, it is a catalyst that is formed share of Zirconia and/or hydrated Zirconia and the proportion of aluminum oxide and/or hydrated oxide of aluminum and contains a sulfur-containing component, and which is used in acid catalyzed reactions, and catalyst pore volume with a diameter of not less than 0.05 μm and not greater than 1 μm is 0.05-0.5 ml/g and the volume of pores with a diameter greater than 1 μm and not more than 10 μm is less than 0.05 ml/g In relation to acid catalyzed reactions, the above solid acid catalyste inventions

Powder of Zirconia

Powder, including used for solid acid catalysts hydroxide and/or hydrated Zirconia (hereinafter simply referred to as "powder of zirconium dioxide"), has a high crushing strength, and zirconium dioxide tends to stabilize when the Zirconia powder is converted into the amorphous form, which does not have a defined crystal structure, as shown by x-ray diffraction or electron diffraction analysis. The use of agglomerated particles with an average diameter of 0.2-10 μm, especially 0.2 to 5 μm, particularly 0.5 to 2 μm, is preferred for increasing the activity and mechanical strength of the catalyst. The average diameter of the agglomerated particles can be determined, for example, by a method that includes irradiation with a laser beam of a group of particles dispersed in water, and the calculation of the scattering.

Powder of Zirconia can be obtained in any way, but usually it can be obtained by neutralization or hydrolysis of zirconium salts or ORGANOMETALLIC compounds, such as oxychlorides, alcoholate, chlorides, sulfates, nitrates and oxysulfate. Main components droxia zirconium or hydrated Zirconia.

Further, the powder of zirconium dioxide can be used in the form of a complex metal hydroxide and/or hydrated complex metal hydroxide. The hydroxide and/or gidratirovannom the Zirconia can be added hydroxides and/or hydrated oxides of other metals. Other metals can preferably be used titanium, hafnium, vanadium, chromium, manganese, iron, silicon, tin, gallium, etc., Compounds such other metals can be complex metal compounds. However, as a powder of Zirconia is preferably used such that includes essentially exclusively zirconium as the metal component, more specifically, those which contain zirconium dioxide as the metal in the amount of at least 70 wt.%, especially at least 90 wt.%, with respect to the total mass of metals in the powder of Zirconia.

The alumina powder

The powder, which includes used to obtain the solid acid catalyst is a hydroxide and/or hydrated oxide of aluminum (hereinafter simply referred to as "alumina powder"), preferably has a fibrous form of particles in order to increase the tavern is figurate fibrous shape of the particles is preferably such that what is the ratio of their length to diameter is greater than 10, especially greater than 20. Usually the upper limit of the ratio of length to diameter is about 200. In this case, under the ratio of length to diameter mean the ratio of the lengths of the major axis and minor axis of the particle ([length of major axis/length of minor axis]) and it can be determined, for example, through observation of the alumina powder in a transmission electron microscope or similar, measuring the ratio of the lengths of the minor axis and major axis and calculating their average values. When the particles are spherical, the ratio of length to diameter is 1, which is the lowest value. Usually this form of particles can be obtained in the form of primary particles with the major axis component of 0.1 μm or more, and the secondary particles and the primary particles are oriented in a certain direction. Can also contain particles of other shapes, other than fibrous form, as, for example, lamellar particles, in the least, while the ratio of length to diameter (width), which represents the average value falls within the range of values greater than 10, especially greater than 20.

The alumina powder is preferably in such a form that its agglomerated particles ivlay a fibrous agglomerate particles. As the alumina powder can be used those obtained by various methods. Particularly preferably, the use of hydrated alumina with the structure of boehmite, such as pseudoboehmite, as in this case, it is possible to achieve high catalytic activity. Use or aluminum oxide as alumina powder leads, respectively, to reduce the mechanical strength and the decrease of catalytic activity.

Media

The media, which can be preferably used according to the present invention has a peak diameter in the range of 0.05-1 μm on the distribution curve of pore diameters from 0.05 μm to 10 μm, and especially in the volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm is 0.05-0.5 ml/g and the volume of pores with a diameter greater than 1 μm and not more than 10 μm is less than 0.05 ml/g To increase the mechanical strength of the catalyst preferably, it had a peak diameter in the range of 0.05-1 μm, especially 0.05 to 0.5 micron, but had no other peak in the distribution curve of pore diameters from 0.05 μm to 10 μm, and that the volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm was 0.05-0.5 ml/g, particularly 0.05 to 0.3 raspredelenie pore size can be determined by the method of injection of mercury, in which it is assumed that the boundary angle (wetting) of mercury is 140oand the surface tension is 480 Dyne/cm and all pores are cylindrical. Under with the peak of the distribution of pore sizes imply that the so-called distribution curve of pore sizes obtained by plotting the differential values of the total pore volume in the pore diameter relative to the diameter of the pores has a clear optimal value.

The media is not powdery, and has a definite shape and easy to get the carrier with a particle size of 0.5 to 20 mm, it is Generally preferable to use particles having a size (length, cross-sectional) 0.2 to 50 mm, especially 0.5 to 20 mm, the Proportion of aluminum oxide and the proportion of zirconium dioxide are in the media in the form of particle size of 0.01-100 μm. Such media may be obtained by mixing the above-mentioned powder of Zirconia and alumina powder with each other and molding the mixture. However, it can be used these carriers obtained in other ways, insofar as they have a defined porous structure.

Blending can be used kneader machine, usually used in obtaining catalysts. Oba is e add water and mix using a paddle stirrer. However, there are no particular restrictions on the order of addition of raw materials and water. Usually water is added during mixing. However, it is not always necessary to add water, when the powdery raw material is in suspension. Add liquid may be organic solvents such as ethanol, isopropanol, acetone, methyl ethyl ketone and methyl isobutyl ketone. The temperature and time of mixing can vary depending on the raw material powder of Zirconia and alumina powder. However, there are no special restrictions such conditions, insofar as the terms can afford to get the preferred porous structure. Similarly, within the range in which retains the properties of the catalyst according to the present invention, the mixing can be done by adding acid, such as nitric acid, bases such as ammonia, organic compounds, binders, ceramic fibers, surfactants, zeolite, or etc.

Molding after mixing can be performed using the method of molding usually used in obtaining the catalyst. In particular, as it is possible to effectively carry out molding to any W is the W by extrusion, using the extruder worm type. The size of the molded material in particular is not limited. However, it is usually formed so as to reach a length of the cross-section of 0.5-20 mm, for Example, in the case of cylindrical pellets, easy to get those that have a diameter of from about 0.5 to about 10 mm and a length of from about 0.5 to about 15 mm

The annealing after forming is carried out in an atmosphere of gas such as air or nitrogen. It is preferable to perform annealing after the deposition of the carrier sulfur-containing component, as it simplifies the process.

The application of sulfur-containing component

Sulfur-containing component may be supported on a carrier by bringing into contact of the sulfur-containing compounds with the carrier and subsequent heat treatment. As sulfur-containing compounds include, for example, sulfuric acid, ammonium sulfate, sulfurous acid, ammonium sulfite and thionyl chloride. The preferred ammonium sulfate and ammonium sulfite, as they are less aggressive towards production equipment. Sulfur-containing compound can be used the same, or in the form of a solution such as an aqueous solution. Sulfa connection of the creativity you can do with regard to quantities, required for mixing or so on the Amount of added sulfur-containing compounds is preferably such that the amount of sulfur in the final solid acid catalyst was 0.2-10 wt.%, especially 1-10 wt.%.

Drawing on the carrier sulfur-containing compounds preferably takes place simultaneously with the receiving of the media. The catalyst according to the invention can be obtained by mixing powder of Zirconia, alumina powder and sulfur-containing compounds, molding and calcination of the resulting mixture. Mixing and molding can be performed in the same manner as in the case of receiving media. Whereas the catalytic activity it is preferable that the weight of sulfur-containing compounds were 3-40 wt.%, in particular 10-30 wt.%, with respect to the total mass before the annealing. The calcination is preferably carried out at a temperature at which forms a tetragonal crystal structure of Zirconia. This structure can be confirmed by radiography using CuKrays, more specifically, when the ratio of the peaks of x-ray diffraction at 2=28,2oand 2=30,2owhile S30,2 means the square of the peak of the tetragonal crystal Zirconia 2=30,2o) is 1.0 or less, preferably 0.05 or less. The consequence of the absence of essentially monoclinic crystal structure is higher catalytic activity.

When a powder of aluminum oxide using aluminum oxide pseudoboehmite type, the preferred temperature is the temperature of 500-800oS and more preferably 600-800oWith, and preferred time period for annealing is 0.1-20 hours. Too high temperature annealing undesirable, as the proportion of monoclinic crystals in the crystal structure of Zirconia increases and S28,2/S30,2 is the ratio can exceed 1, resulting in reduced catalytic activity. Also junk too low temperature annealing, so as zirconium dioxide cannot crystallize, resulting in can decrease the catalytic activity.

In the case where the receive carrier and then sulfur-containing component is applied to the carrier, sulfur-containing compound can be used in any form, for example in gaseous form or in the form of water is Ino, to sulfur-containing compound was in the form of a liquid due to easier manipulation with it. There are no particular restrictions on the method of contact. However, preferably use the method of impregnation by spraying, dipping, and so on, and the way in which sulfur-containing compound is transferred into the gaseous state and is passed through the catalyst bed. After entering in contact with the sulfur-containing compound, the carrier is calcined at a temperature above 300oBut below 800oWith, preferably above 400oBut below 800oWith, receiving targeted of a solid acid catalyst. The time of annealing is usually 0.5 to 10 hours.

The spent catalyst

According to the present invention as a carrier, you can use the spent solid acid catalyst with low activity. Solid acid catalyst prior to use includes a carrier formed of shares Zirconia with tetragonal crystal structure and the proportion of aluminum oxide and supported on a carrier sulfur-containing component. Preferably, the media is formed of shares Zirconia with tetragonal crystal structure and the proportion of aluminium oxide, where the media does not contain sulfur-containing component.

The solid acid catalyst is preferably obtained by mixing powder of Zirconia, alumina powder and sulfur-containing compounds, molding and calcination. In this case, the mixing and molding can be performed in the same manner as in the case of obtaining the above-mentioned media. In this case, preferably, taking into account the catalytic activity, so that the weight of sulfur-containing compounds were 3-40 wt. %, especially 10 to 30 wt.%, with respect to the total mass before the annealing. The calcination is carried out at a temperature at which can be obtained Zirconia with tetragonal crystal structure.

Solid acid catalyst

The solid acid catalyst according to the present invention is a catalyst comprising a carrier, which is formed of shares of Zirconia and/or hydrated Zirconia (hereinafter also referred to as "the proportion of Zirconia") and the proportion of aluminum oxide and/or hydrated aluminum oxide (hereinafter referred to as "the proportion of aluminum oxide") and sulfur-containing component supported on a carrier, and which is m in particular, the volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm is 0.05-0.5 ml/g and the volume of pores with a diameter greater than 1 μm and not more than 10 μm is less than 0.05 ml/g The porous structure of the catalyst can be determined in the same manner as the carrier, and a porous structure with a pore size of 0.05 μm or more is essentially the same before applying the sulfur-containing component. In particular, for increasing the mechanical strength of the catalyst preferably, there was a peak diameter in the range of 0.05-1 μm, particularly 0.05 to 0.5 micron, but there was no other peak in the distribution curve of pore diameters from 0.05 μm to 10 μm, and that the volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm was 0.05-0.5 ml/g and the volume of pores with a diameter greater than 1 μm and not more than 10 μm was below 0.05 ml/g, in particular lower than 0.02 ml/g

The distribution of pores with a diameter of not more than 0.05 microns can be determined by adsorption of nitrogen or the like. In this area, it is preferable that the pores had an average diameter in accordance with the size of the target reaction of compounds and it is usually in particular Crystalline structure of the proportion of zirconium dioxide in the catalyst has S28,2/30,2-ratio of not greater than 1.0, especially not more than 0,05. Having essentially no monoclinic crystal structure provides a higher catalytic activity. Solid acid catalyst saikoroshi Hammett H0is 11,93).

More preferably, the weight proportion of aluminum oxide in the total mass fraction of aluminum oxide and the proportion of zirconium dioxide in the catalyst was 5-90 wt. %, preferably 5-50 wt.%, and more preferably 10-40 wt.% Below this range, the mechanical strength of the catalyst is reduced and the Zirconia is difficult to stabilize. Above this range, the catalytic activity is relatively low. The total mass fraction of Zirconia and the proportion of aluminum oxide in the catalyst is preferably not less than 70 wt.%, in particular at least 80 wt.%, from such points of view, both the catalytic activity and durability of molded material.

The solid acid catalyst according to the present invention, if it is desirable, preferably may contain metal components selected from groups 8, 9 or 10 (periodic system of elements), when used in the conversion reactions such as isomerization. As used for the catalyst according to the present invention, metal components selected from groups 8, 9, or 10 can be used, respectively, platinum, palladium, ruthenium, Nickel, etc. are preferably used in the form of soy anhydrous condition, either in the form of hydrates. Next, the metal compounds may be used individually or as mixtures of two or more of these compounds. With regard to the amount of the added metal compounds, it is preferable to be added so that the total number of elements of groups 8, 9 or 10 in the solid acid catalyst was 0.05-10 wt.%, in particular 0.1 to 5 wt.%

There are no particular restrictions on the method of application of metal components. However, preferably can be used in the impregnation method, such as spraying or dipping, ion exchange method, etc. of the Above caused the catalyst was calcined in a gas atmosphere, such as air or nitrogen, at a temperature of 300-700oC for 0.1 to 20 hours, to improve the catalyst activity.

The catalyst according to the present invention is not in powder, and in a certain shape (molded), so could easily be the catalyst size particle diameter of 0.5 to 20 mm is Usually used catalyst with an average particle diameter of 0.2 to 50 mm, especially 0.5 to 20 mm

The mechanical strength of the obtained catalyst, as the crushing strength side Powergen 4-20 kg Molded solid acid catalyst according to the present invention retains its shape after aging in water. Granules that do not retain their shape in the water, are the cause of turning in powder or cracking during the stage of application upon receipt of the catalyst or during the catalytic reactions that can lead to reduced output or difficulties in the process, so that these granules in practice undesirable.

Acid catalyzed reaction

Acid catalyzed reaction, where applicable solid acid catalyst according to the present invention includes, generally acid catalyzed reaction using a Lewis acid as a catalyst, usually catalysts based on aluminium chloride, or acid Bronsted as a catalyst, usually sulfuric acid. Examples of such reactions include various reactions, such as isomerization, disproportionation, nitration, decomposition, alkylation, etherification, acylation, the formation of ester and polymerization. More specifically, the catalyst according to the present invention can be used in the esterification reaction of methacrylic acid and so on, the cycle of tetrahydrofuran, decomposition reaction of freon, the reaction of oxidative dehydrocondensation methane, etc., In particular it can preferably be used in the conversion reactions such as isomerization, decomposition, acylation, education simple ether and etherification. The main object of the reactions are hydrocarbons, i.e. hydrocarbons and derivatives of hydrocarbons, such as derivatives obtained by introducing substituents in hydrocarbons, particularly hydrocarbons or oxygen-containing hydrocarbon compounds. In particular, the catalyst according to the present invention is preferably used in the conversion reactions of hydrocarbons. Examples of the reaction conversion is isomerization, decomposition, acylation, education simple ether and alkylation, etc.

The object of isomerization are preferably hydrocarbon oil fractions with a boiling point in the range of about -20oWith up to 150oC. In particular, the catalyst according to the present invention is preferably used in the reaction, in which the paraffin (saturated hydrocarbons) with a linear chain isomerized in the branched paraffin or olefin or aromatic compound hydronaut education facilitiesbeautifully temperature is in the range of 100-300oWith, especially 120-240oWith the preferred pressure is the value in the field of 1-50 kg/cm2preferred hourly space velocity of the liquid is in the range of 0.2-10/h and the preferred ratio of hydrogen/feedstock has a value in the range of 0.2-10 mol/mol.

Treatment in oxidizing atmosphere

The catalytic activity of the catalyst according to the present invention can be increased by heat treatment in an oxidizing atmosphere before or after use. Usually, the heat treatment is carried out at a temperature of 300-500oC in an atmosphere with oxygen, such as air. The oxygen content in the atmosphere is preferably 0.1 to 50 vol.%, in particular, 1-30 wt.% Preferably can be used a mixture of nitrogen with oxygen and nitrogen from air, the air, etc., particularly preferred temperature processing 350-480oWith a processing time of 0.1-100 hours. The pressure in the processing may be reduced pressure, atmospheric pressure and a pressure higher than atmospheric. Suitable and preferred treatment at atmospheric pressure. Since processing in an oxidizing atmosphere is carried out for drying the catalyst and oxidation and removal after this adsorber who would have used the air contained much lower amounts of impurities, such as moisture, especially before the application of the catalyst. More specifically, preferably can be used dry atmosphere, the relative humidity of which is at a temperature of 20oReduced to a value not higher than 5%. If the treatment temperature is too high, the properties of the catalyst for change, while at a very low temperature processing get enough of the dried catalyst. In any case, the activity of the catalyst decreases. This treatment is effective for the catalyst, which is kept in the atmosphere of air for a period of time not less than 1 day, especially not less than 10 days after heat treatment such as annealing, in the process of preparation of the catalyst or catalyst used in acid catalyzed reactions. When the processing is carried out in a non-oxidizing atmosphere (in air flow that does not contain oxygen), the catalyst activity is also reduced.

After treatment in the oxidizing atmosphere is necessary to prevent adsorption of moisture by the catalyst. For this purpose it is preferable to carry out the processing after the introduction of the catalyst into the reaction apparatus or reactor and start acid catalyzed reaction essentially without the introduction is aroda, it is preferable not to start the reaction before the atmosphere can be replaced with an inert atmosphere such as an inert gas, such as nitrogen or a noble gas such as argon. It should be noted that, since the catalyst is not significantly reduced when it is kept on the air for a time period of about 1 day in the case of small-sized reaction apparatus processing in an oxidizing atmosphere can be performed outside the reactor and then to introduce the catalyst into the reactor.

The processing in the above-mentioned oxidizing atmosphere can be used for regeneration of the catalyst, which was used in the reaction apparatus or reactor and whose activity is reduced. In particular, when the carbonaceous substance, such as a substance called "coke", was deposited on the catalyst, it is preferable to bring the oxygen concentration to 0.1-20 vol.%, especially 0.2 to 5 vol.%, so that carbonaceous matter has not been oxidized.

Information confirming the possibility of carrying out the invention

EXAMPLES

Below the invention is explained in more detail using examples.

Used in the examples of measurement methods and the like described below.

Example 1

Example 2

Method of determining the ratio of length to diameter

The powder was observed in the transmission electron microscope H-9000UHR, manufactured by Hitachi Ltd., and randomly chose 10 of the particles in the image field of the particles was determined by the relationship of the major and minor axes of the respective particles and expected average value.

Example 3

The method of determining the distribution of pore sizes

The range of pore diameters of 0.05-10 μm was determined by the method of injection (injection) of mercury, using the analyzer type AutoPore 9200, manufactured by Micromeritics Co. The range of pore diameters of 0.05 μm or less was determined by the method of nitrogen adsorption using the analyzer type ASAP2400 manufactured by Micromeritics Co.

Example 4

Test resistance

50 Cylindrical pellets with a diameter of 1.5 mm and a length of 5 mm, selected at random, was immersed in 10 ml of water at room temperature and kept for 15 minutes, was determined changes in the form of the ode, without turning in powder or cracking.

Example 5

The method of determining the average crushing strength

The crushing strength of the lateral surface of the sample, having obtained by extrusion of a cylindrical shape, dried and calcined, was determined on the instrument for measuring the crushing strength of the tablets TN-SR manufactured by Toyama Sangyo Co., Ltd. Used to measure the probe was the thin end of a cylindrical shape with a diameter of 4.5 mm, the Operation of application of the measured sample is carried to the center of the side surface of the cylindrical surface and was repeated 20 times and the obtained values was calculated the average value.

Example 6

The method of calculating S28,2/S30 2

Peaks of tetragonal crystal and monoclinic crystal Zirconia was isolated (cut from x-rays, and computed the ratio of the peak area of monoclinic Zirconia at 2=28,2othe peak area of tetragonal Zirconia at 2=30,2o. When the ratio S28,2/S30 2 was not more than 0,02, the peak of the monoclinic crystal was fuzzy and undefined. The radiograph was obtained under the following conditions:

a device for measuring x-rays under Bo is her, placed into the body tube of the type Cu-lamp (power output of 30 kV, 20 mA, wavelength

measuring range (2): 3-90o;

step width: 0,02o;

scan speed: 4o/min;

slit width: deflecting the slit (DS)=1o;

the scattering slit (SS)=1o;

the receiving slit (RS)=0.33 mm;

the condition of equalization: 15-point gravimetric method alignment Savitzky, Golay's;

used to select peaks range 2(2): 26,5o-32,5o;

the number of allocated target peaks: 4 (2 peaks of monoclinic crystal, 1 peak of tetragonal crystal, 1 the peak of the amorphous state);

the peak used to calculate the ratio of crystal types:

monoclinic; 2=28,2 (d=3,163, hkl=111);

tetragonal: 2=30,2 (d=2,960, hkl=111).

Example 7

The catalyst AND

From commercially available preparative forms of dry hydrated Zirconia used a powder with an average particle diameter of 1.2 μm as a powder of zirconium dioxide. Also from commercially available powders of aluminum oxide (pseudoboehmite) used a powder of aluminum oxide, having a fibrous form of particles. The alumina powder had a length to diameter fibers 58, average particle diameter 10 μm. Combined 1200 g of powder of zirconium dioxide, 800 g of the powder of the oxide Amosu blade mixer adding water. The resulting mixing product extrudible through an extruder with a round hole with a diameter of 1.6 mm for forming cylindrical pellets, which were dried at a temperature of 110oFrom getting dry granules. Dry granules were tested for resistance. As a result, all of the granules is not cracked or has turned into powder and preserved in its original form. Then dry granules were progulivali at a temperature of 650oWith over two hours, receiving catalyst A.

Determination (estimation) of the distribution of pore sizes of the catalyst And for pores with a diameter of 0.05-10 μm showed a distribution of pore sizes, which was a clear peak value of the pore diameter of 0.18 μm, but there was no other clear peak. The volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm amounted to 0.18 ml/g and the volume of pores with a diameter greater than 1 μm and not more than 10 μm was 0.01 ml/g or less. Determination of the distribution of pore sizes for pores with a diameter of not more showed an average pore diameter of

Molded catalyst And had a cylindrical shape particles with an average diameter of 1.5 mm and an average length of 5 mm and a test of the resistance showed that all the pellets retained their original shape without rastreskivanie the kg Attitude S28,2/30,2 for catalyst And was 0.04, and essentially monoclinic structure was absent.

Example 8

The catalyst IN

From commercially available preparative forms of dry hydrated Zirconia used a powder with an average particle diameter of 15 μm as a powder of zirconium dioxide. Also from commercially available powders of hydrated aluminum oxide (pseudoboehmite) used the alumina powder having a plate-like particle shape. The alumina powder had a particle ratio of length to width is 2, the average particle diameter was 20 μm. The catalyst was obtained in the same manner as catalyst A, except for the use of these powder of Zirconia and alumina powder. Dry granules after getting tested for water resistance, which showed that all the pellets turned into powder.

Determination (estimation) of the distribution of pore sizes of the catalyst for pores with a diameter of 0.05-10 μm showed a distribution of pore sizes, which was a clear peak is related to the pore diameter of 1.7 mm, but there was no other clear peak. The volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm was 0.07 m then, for pores with a diameter of not more showed an average pore diameter of

Molded catalyst had a cylindrical shape particles with an average diameter of 1.5 mm and an average length of 5 mm and a test of the resistance showed that 10 out of 50 pellets cracked or has turned into powder. It also shows that the average crushing strength is 2.8 kg Ratio S28,2/30,2 for catalyst was 0.04, and essentially monoclinic structure was absent.

Example 9

The catalyst WITH

50 g of catalyst And was applied by spraying an aqueous solution of hexachloroplatinic acid so that the amount of platinum in the catalyst was 0.5%. After drying, the catalyst was progulivali at a temperature of 550oWith over two hours, receiving catalyst C. the Distribution of pore sizes and the crystal structure of the catalyst were essentially the same as those of catalyst A. the Test for the resistance of the catalyst showed that all the pellets retained their original shape without cracking or conversion into powder. The average crushing strength was equal to 4.0 kg

Example 10

Catalyst D

50 g of catalyst was applied by spraying an aqueous solution of hexachloroplatinic ctor was progulivali at a temperature of 550oWith over two hours, receiving catalyst D. the Distribution of pore sizes and the crystal structure of catalyst D were essentially the same as those of catalyst C. Test the resistance of the catalyst D was shown that 8 out of 50 pellets cracked or has turned into powder. The average crushing strength was 2.5 kg

Example 11

Catalysts E, F

As a powder of Zirconia used dry powder of hydrated zirconium dioxide with an average particle diameter of 1.2 μm, obtained by drying a commercially available powder of zirconium hydroxide. Also from commercially available powders of hydrated aluminum oxide (pseudoboehmite) used a powder of aluminum oxide, having a fibrous form of particles. The alumina powder had a ratio of length to diameter of the particles 58 and the average particle diameter of 10 μm. Combined 1500 g of powder of zirconium dioxide, 500 g of powder of aluminum oxide and, further, 383 g of ammonium sulfate and mixed for 45 minutes in a kneader machine with stirring using a paddle stirrer while adding water. The resulting mixing product extrudible through an extruder with a round hole, Diametro the industry. As a result, all of the granules is not cracked or has turned into powder and preserved in its original form. Then dry granules were progulivali at a temperature of 650oWith over two hours of receiving the catalyst E, which was a catalyst molded material based on zirconium dioxide, which inflicted then sulfur-containing component.

Determining the distribution of pore sizes of the catalyst E for pores with a diameter of 0.05-10 μm showed a distribution of pore sizes, which was a clear peak value of the pore diameter of 0.22 μm, but there was no other clear peak. The volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm amounted to 0.18 ml/g and the volume of pores with a diameter greater than 1 μm and not more than 10 μm was 0.01 ml/g determination of the distribution of pore sizes for pores with a diameter of not more showed an average pore diameter of

Molded catalyst E had a cylindrical shape particles with an average diameter of 1.5 mm and an average length of 5 mm and a test of the resistance showed that all the pellets retained their original shape without cracking or conversion into powder. It was also found that the average crushing strength is 3.5 kg S28,2/30,2 is the Ratio of katibasti 125 ml of an aqueous solution of hexachloroplatinic acid thus that the amount of platinum in the catalyst was 0.5%. After drying, the catalyst was progulivali at a temperature of 550oWith over two hours of receiving the catalyst F, which was a catalyst formed containing platinum sulfated molded material based on Zirconia/alumina. The distribution of pore sizes and the crystal structure of catalyst F were essentially the same as those of the catalyst that is a test of the resistance of the catalyst F was shown that all the pellets retained their original shape without cracking or conversion into powder. The average crushing strength was 3.3 kg

Example 12

Catalyst G

From commercially available preparative forms of dry hydrated Zirconia used a powder with an average particle diameter of 1.2 μm as a powder of zirconium dioxide. Also from commercially available powders of hydrated aluminum oxide (pseudoboehmite) used a powder of aluminum oxide, having a fibrous form of particles. The alumina powder had a particle ratio of length to diameter 58 and the average particle diameter was 10 μm. United 300 g of the powder diocesian using a blade mixer adding water. The resulting mixing product extrudible through an extruder with a round hole with a diameter of 1.6 mm for forming cylindrical pellets, which were dried at a temperature of 110oFrom getting dry granules. After this dry granules were progulivali at a temperature of 650oC for two hours, getting media G.

Determining the distribution of pore sizes of the carrier of G for pores with a diameter of 0.05-10 μm showed a distribution of pore sizes, which was a clear peak value of the pore diameter of 0.25 μm, but there was no other clear peak. The volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm was to 0.20 ml/g and the volume of pores with a diameter greater than 1 μm and not more than 10 μm is not more than 0.01 ml/g determination of the distribution of pore sizes for pores with a diameter of not more showed an average pore diameter of

Molded carrier G had a cylindrical shape particles with an average diameter of 1.5 mm and an average length of 5 mm and a test of the resistance showed that all the pellets retained their original shape without cracking or conversion into powder. It was also found that the average crushing strength is 4.8 kg Ratio S28,2/30,2 carrier G was not more than 0,02, and creatures who stevedorage acid thus that the amount of platinum in the catalyst was 0.5%. After drying, was added 125 ml of an aqueous solution of sulfuric acid with a concentration of 0.5 mol/l, and again it was dried, and then the catalyst was progulivali at a temperature of 600oWith over two hours, receiving catalyst G. Molded catalyst G had a cylindrical shape particles with an average diameter of 1.5 mm and an average length of 5 mm, the Ratio S28,2/S30 2 catalyst G was not more than 0,02, and essentially monoclinic structure was absent.

Determining the distribution of pore sizes of the catalyst G for pores with a diameter of 0.05-10 μm showed a distribution of pore sizes, which was a clear peak value of the pore diameter of 0.22 μm, but there was no other clear peak. The volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm amounted to 0.18 ml/g and the volume of pores with a diameter greater than 1 μm and not more than 10 μm is not more than 0.01 ml/g determination of the size distribution of pores with a diameter of not more showed an average pore diameter of

Molded catalyst G had a cylindrical shape particles with an average diameter of 1.5 mm and an average length of 5 mm and a test of the resistance showed that all the pellets retained their original shape without cracking or becoming 0.2 G media amounted to no more than 0,02, and essentially monoclinic structure was absent.

Example 13

The deactivated catalyst N

40 g of Catalyst G was treated at a temperature of 450oC for 24 hours in a stream of hydrogen at 10 kg/cm2-G and 600 ml/min, getting deactivated catalyst N. The distribution of pore sizes and the crystal structure of the deactivated catalyst H was essentially the same as those of catalyst G. a test of the resistance of the deactivated catalyst H showed that all the pellets retained their original shape without cracking or conversion into powder.

Example 14

The treated catalyst I

10 g of the Deactivated catalyst H was progulivali at a temperature of 550oC for two hours in the air, receiving the treated catalyst I. the Distribution of pore sizes and the crystal structure of the treated catalyst I were essentially the same as those of catalyst G. a test of the resistance of the treated catalyst I showed that all of the granules retained their original shape without cracking or conversion into powder.

Example 15

The treated catalyst J

To 10 g deaktivirovannovo and then an excess of an aqueous solution of sulfuric acid was removed by filtration, was dried and progulivali at a temperature of 550oC for two hours, getting treated catalyst J. the Distribution of pore sizes and the crystal structure of catalyst J were essentially the same as those of catalyst G. a test of the resistance of the treated catalyst J showed that all the pellets retained their original shape without cracking or conversion into powder.

Example 16

The treated catalyst TO

To 10 g of the deactivated catalyst was added 150 ml of an aqueous solution of ammonium sulfate with a concentration of 0.5 mol/l for a contact and then an excess of an aqueous solution of ammonium sulfate was removed by filtration, was dried and progulivali at a temperature of 550oC for two hours, getting treated catalyst K. the Distribution of pore sizes and the crystal structure of the treated catalyst To essentially were the same as those of catalyst G. a test of the resistance of the treated catalyst To showed that all the pellets retained their original shape without cracking or conversion into powder.

Example 17

The acylation reaction

to 20.0 g of the Catalyst, powdered autoclave and subjected to pre-treatment at a temperature of 400oC for 1 hour in an atmosphere of air. After that inside of the autoclave was created an atmosphere of nitrogen without the introduction of outside air and added 225 g of chlorobenzene and 35 g of p-chlorobenzylchloride, and then carried out the reaction at a temperature of 135oWith under stirring. After reaction for three hours the reaction mixture was analyzed by gas chromatography.

The output of dichlorobenzophenone, acylated form, was 27%, if used, the catalyst And, 24%, if used, the catalyst, and 29%, if used, the catalyst E. For comparison, the acylation reaction was performed in the same manner as above, except that the used catalyst E and atmosphere pre-treatment was nitrogen, with the result that the output dichlorobenzophenone was 26%.

Example 18

The reaction of isomerization of n-hexane 1

4 cm3each of the catalysts (catalysts C and D), granular 16-24 mesh was introduced into the reactor flow-type fixed layer with a length of 50 cm and an inner diameter of 1 cm and subjected to pre-treatment, after which carried out the reaction of isomerization of n-hexane. Pre-processing was carried out under the following conditions: teeacher have established a nitrogen atmosphere without the introduction of air and then the atmosphere of hydrogen until the beginning of the isomerization reactions.

The reaction of isomerization of n-hexane was carried out under the following conditions: reaction temperature: 200oWith the reaction pressure (gauge pressure): 10 kgf/cm2; hourly space velocity of the liquid: 1.5/h and the ratio of hydrogen/oil (N2/oil): 5 (mol/mol).

The speed of conversion and selectivity, which show the activity of the catalyst was calculated and evaluated by subsequent use, the rate of conversion in n-hexane and the values of the ratio of 2,2'-dimethylbutan/acyclic hydrocarbon with 6 carbon atoms:

the speed of conversion in n-hexane = [1-( wt.% n-hexane in the resulting oil/ wt. % n-hexane in the original oil)]100 (%); 2,2'-dimethylbutan/acyclic hydrocarbon with 6 carbon atoms = (wt.% 2,2'-Dimethylbutane the resulting oil/ wt.% all of acyclic hydrocarbons containing 6 carbon atoms in the obtained oil)(100 (%).

The composition of the stream of oil coming out of the reaction tube after 20 hours after start of the reaction were analyzed by gas chromatography, as a result it was found that the rate of conversion of n-hexane is 88.6% in the case of the catalyst and 86.3% in the case of catalyst D and the ratio of 2,2'-dimethylbutan/acyclic hydrocarbon with 6 the R> The reaction of isomerization of n-hexane 2

When using catalyst F was carried out by reaction of conversion of n-hexane, like the above-mentioned reaction of isomerization of 1 under the following conditions: reaction temperature: 180oC; the reaction pressure (gauge pressure): 10 kgf/cm2; hourly space velocity of the liquid: 1.5/hour; the ratio of hydrogen/oil (N2/oil): 5 (mol/mol); and under the changed conditions of pretreatment. The composition of the stream of oil coming out of the reaction tube after 20 hours after start of the reaction were analyzed by gas chromatography for the reactions, which changed the conditions of temperature, atmosphere and pressure pre-treatment. The results obtained are presented in table 1.

Example 20

The reaction of isomerization of n-hexane 3

Was carried out by activating the processing is deactivated after the reaction catalyst. Catalyst F was used in the above reaction of isomerization of 2 for 100 hours for deactivation of the catalyst, using nitrogen instead of hydrogen. The catalyst was subjected to preliminary processing in different atmosphere and measured the change of activity. As the atmosphere used an atmosphere of hydrogen, nitrogen atmosphere, and nitrogen, the soda the century The activity was evaluated by implementing the same reaction as above, the reaction of isomerization of 2, and the composition of the stream of oil coming out of the reaction tube after 20 hours after start of the reaction were analyzed by gas chromatography. The results are presented in table 2.

Example 21

The reaction conversion in n-heptane

One (1) g molded in the form of grains from 16 to 24 mesh catalyst was introduced into the reactor flow-type fixed layer with a length of 50 cm and an inner diameter of 1 cm and the reaction was carried out under the following conditions: reaction temperature: 200oC; reaction pressure: 4 kg/cm2- G; space velocity: 3,4/h, and the ratio of hydrogen/feedstock (H2/oil): 5 mol/mol. As a pre-treatment of the catalyst to the reaction conversion was carried out the repair using hydrogen at a temperature of 300oC for 1 hour. The conversion speed, which shows the activity of the catalyst was calculated using the speed of conversion in n-heptane as described below and evaluated: the conversion speed in n-heptane = [1-(wt.% n-heptane obtained in the oil/ wt.% n-heptane in the original oil)]100 (%).

By analyzing the speed of conversion in n-heptane 2 hours after the beginning realize 3.

Applicability in industry.

The present invention relates to a molded solid acid catalyst, comprising a carrier with a precisely defined pore structure, and the catalyst may have sufficient mechanical strength and at the same time has excellent catalytic activity due to the presence of a precisely defined pore structure in the molded catalyst. As it is a molded material, the catalyst can be easily separated from the reactants, which allows reuse of the catalyst, as well as facilitates the disposal of spent catalyst.

The solid acid catalyst according to the present invention is suitable for a variety of acid catalyzed reactions such as isomerization, disproportionation, alkylation, etherification, acylation, the formation of ester and polymerization.

1. A method of obtaining a solid acid catalyst, comprising the stage of receiving the media containing a portion of Zirconia and/or hydrated Zirconia and the proportion of aluminum oxide and/or hydrated oxide of aluminum and having a peak diameter within the management 500 - 800oC for 0.1 to 20 hours, while the volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm is 0.05-0.5 ml/g, and the volume of pores with a diameter greater than 1 μm and not more than 10 μm is less than 0.05 ml/g, and deposition of sulfur-containing component to the media.

2. A method of obtaining a solid acid catalyst under item 1, in which the temperature of annealing is 600 - 800oC.

3. A method of obtaining a solid acid catalyst under item 1 or 2, wherein the stage of receiving media is a stage, comprising a mixture of powder containing a hydroxide and/or hydrated Zirconia, agglomerated particles which have an average diameter of 0.2-10 μm, with a powder containing hydroxide and/or hydrated oxide of aluminum, having a fibrous form of particles, and molding the mixture.

4. A method of obtaining a solid acid catalyst according to any one of paragraphs. 1-3, in which the receiving medium and the application of sulfur-containing component on the carrier is carried out in one stage.

5. A method of obtaining a solid acid catalyst according to any one of paragraphs. 1-3, in which stage of deposition of sulfur-containing component on the carrier includes, after receiving the media introduction to contact gray is.

6. A method of obtaining a solid acid catalyst according to any one of paragraphs. 1-5, in which the solid acid catalyst contains at least one metal component selected from groups 8, 9 and 10 of the periodic system of elements).

7. A method of obtaining a solid acid catalyst, comprising the stage of deposition of sulfur-containing component, representing the introduction of contact between the solid acid catalyst obtained by the method according to any of paragraphs. 1-5 and used up to reduce its activity as a carrier with a sulfur-containing compound and calcining the carrier at a temperature above 300oWith and below 800oC.

8. A method of obtaining a solid acid catalyst under item 7, in which the solid acid catalyst contains at least one metal component selected from groups 8, 9 and 10 of the Periodic system of elements.

9. A method of obtaining a solid acid catalyst, comprising the stage of processing of solid acid catalyst obtained by the method according to any of paragraphs. 1-8 and used up to reduce its activity, in an oxidizing atmosphere at a temperature of 300-500oC.

10. Solid acid Katalizator of hydrated zirconium dioxide, the proportion of aluminum oxide and/or hydrated aluminum oxide, and sulfur-containing component and having a peak diameter in the range of 0.05-1 μm on the distribution curve of pore diameters from 0.05 to 10 μm, the volume of pores with a diameter of not less than 0.05 μm and not greater than 1 μm is 0.05-0.5 ml/g, volume of pores with a diameter greater than 1 μm and not more than 10 μm is less than 0.05 ml/g, and the peak x-ray diffraction at 2 = 28,2related to Zirconia to monoclinic crystal structure, the peak at 2 = 30,2related to Zirconia with tetragonal crystal structure, is 1 or less.

11. Solid acid catalyst under item 10, in which the ratio of the peak x-ray diffraction at 2 = 28,2related to Zirconia to monoclinic crystal structure, the peak at 2 = 30,2related to Zirconia with tetragonal crystal structure, is 0.05 or less.

12. Solid acid catalyst under item 10 or 11, used in acid catalyzed reactions the conversion of hydrocarbons.

13. The solid acid catalyst according to any one of paragraphs. 10-12, which contains extremely 14. Way for acid catalyzed reactions, including the implementation of the acid catalyzed reaction using a solid acid catalyst according to any one of paragraphs. 10-13, which use up to reduce its activity and process in the oxidizing atmosphere at a temperature of 300-550oC.

15. Way for acid catalyzed reactions, characterized in that it includes the loading of the solid acid catalyst according to any one of paragraphs. 10-13, the processing of the above catalyst at a temperature of 300-550oC in oxidizing atmosphere and implementation of acid catalyzed reactions.

16. The way isomerization of hydrocarbons, characterized in that it includes the loading of the solid acid catalyst according to any one of paragraphs. 10-13, the processing of the above catalyst at a temperature of 300-550oIn oxidizing atmosphere, replacement oxidizing atmosphere, an inert atmosphere and introducing a contact of the catalyst with a hydrocarbon in a hydrogen atmosphere.

 

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