Catalyst for catalytic cracking of hydrocarbon, used in obtaining light olefin, and method of obtaining thereof

FIELD: chemistry.

SUBSTANCE: invention relates to catalytic cracking of hydrocarbons. Described is method of obtaining light olefins by catalytic cracking of hydrocarbons with 4 or more than 4 carbon atoms, with boiling point 30-200°C, in presence of catalyst, characterised by the fact that 0.01-5.0 wt % of MnO2 and 1-15 wt % of P2O5 are simultaneously added to catalyst components, where catalyst components contain 1-50 wt % of zeolite, 21-70 wt % of clay and 1-40 wt % of inorganic oxide and where both MnO2 and P2O5 are introduced into (modify) each of catalyst components, such as ZSM-5 zeolite, clay and inorganic oxide.

EFFECT: increase of product outcome.

10 cl, 1 dwg, 6 tbl, 9 ex

 

The technical field to which the invention relates.

The present invention relates to hydrothermally stable porous catalyst with molecular sieve and method thereof, and more particularly to a hydrothermally stable porous catalyst with molecular sieve, which even in an atmosphere with high temperature and humidity has a relatively stable structure and can maintain its catalytic activity, and the method of its production.

The level of technology

Porous inorganic substances, with the frame of the groups Si-OH-Al-widely used in the field of porous catalysts with molecular sieves because they are rich then, have a large specific surface area and a lot of active centers and acid sites.

This catalyst with a porous molecular sieve is used, for example, in heterogeneous catalytic reactions, such as various oxidation reactions/recovery, including catalytic cracking reactions, isomerization reactions, and the esterification reaction, especially heterogeneous catalytic reaction requiring thermal stability in the harsh conditions of the atmosphere with high temperature and humidity. In this case, however, the catalyst causes problems, namely, that when it is placed in an atmosphere of steam at more than 50°C, dealumination its tetrahedral frame, leading to structural degradation, and at the same time, the number of acid sites of the catalyst will decrease, leading to a rapid loss of catalytic activity. In addition, because these catalysts with microporous molecular sieves require high mechanical strength for use in fluidized catalytic petrochemical processes conducted on a large scale, for the catalytic cracking of naphtha to produce spherical catalysts in this area apply inorganic complex and matrix (clay).

Therefore, since the microporous catalyst with molecular sieve contains many components such as a binder, the porous matrix and molecules, maintaining thermal stability of the corresponding component is one of the most important factors for obtaining a suitable microporous catalyst with molecular sieves. For example, the destruction of the structure matrix, which is used to obtain a catalyst with a microporous molecular sieve, greatly reduces the reaction rate of catalytic cracking of naphtha.

On the other hand, to achieve high yield of ethylene and propylene in a method of catalytic cracking of naphtha requires regulation characteristics and acid sites in microporous molecular sieve (zeolite). If the number of acid sites is large or the strength of the acidity is relatively high, the dehydrogenation reaction proceeds faster and therefore the output of saturated hydrocarbons, such as methane, and aromatic hydrocarbons such as benzene, toluene and xylene, is increased.

On the other hand, if the number of acid sites is small or the strength of the acidity is relatively weak, the conversion of hydrocarbon is reduced and therefore reduces the yield of light olefins.

As described above, to effectively produce light olefins from hydrocarbons, such as naphtha, catalytic cracking with catalyst, you want to apply the catalyst having many suitable characteristics. Specifically, it is believed that thermal stability is the most important factor, because the catalytic cracking catalyst is effective under conditions of high temperature and high humidity. Conducted many studies to improve thermal stability.

As for such means of improving thermal stability, in U.S. patent No. 5,039,644 described method of applying phosphate upon receipt of a catalyst which is stable at high temperature and which contains 0.5~15 wt.% P2O5introduced in porous metal oxides, such as TiO2, ZrO 2the mixture of TiO2-ZrO2the mixture of TiO2-Al2O3or a mixture of ZrO2-Al2O3. However, this patent does not describe how to achieve a high yield of light olefins in catalytic cracking of hydrocarbons using zeolite.

In U.S. patent No. 4,977,122 described hydrothermally stable catalyst, which contains (a) a crystalline zeolite; (b) an inorganic oxide matrix (for example, silicon dioxide, aluminum oxide, silicon dioxide-aluminum oxide, magnesium oxide, zirconium dioxide, titanium dioxide, boron oxide, chromium oxide, clay, etc.) and (c) discrete particles of phosphorus-containing alumina, also dispersed in said matrix, and these discrete particles was obtained by contacting alumina with a compound of phosphorus selected from the group consisting of salts of alkaline earth metal (Be, Mg, Ca, Sr, Ba) of phosphoric acid or phosphorous acid, and mixtures thereof.

In U.S. patent No. 6,835,863 described a method of obtaining light olefins by catalytic cracking of naphtha (boiling point: 27-221°C) with the use of pelletized catalyst containing 5-75 wt.% ZSM-5 and/or ZSM-11, 25-95 wt.% silicon dioxide or kaolin and 0.5-10 wt.% phosphorus. However, do not specify a specific source connection phosphorus or hydrothermal stability of the molded catalyst.

Meanwhile, Pat is NTE U.S. No. 6,211,104 described catalyst for catalytic cracking, which contains 10-70 wt.% clay, 5-85 wt.% inorganic oxides and 1-50 wt.% zeolite. The zeolite used in the catalyst consists of 0-25 wt.% Y-zeolite or a REY-zeolite and 75-100 wt.% zeolite of Pancasila (SiO2/Al2O3=15-60 selected from zeolites ZSM-5, ZSM-8 and ZSM-11, containing 2-8 wt.% P2O5and 0.3-3 wt.% Al2O3or MgO or CaO), in which the original substance of the mentioned compounds of aluminum or magnesium, or calcium selected from aqueous solutions of their nitrates, hydrochloride or sulfate. Specifically, the described catalyst, as exhibiting an excellent effect upon receipt of olefins, even in the pre-treatment in an atmosphere of 100% steam at 800°C for 4 to 27 hours. However, in this patent does not describe the method of control/choice and dosage of certain chemical compounds P, added metals limited Al, Mg and Ca and conventional water-soluble salt of the metal is used so that the cations of Al, Mg or Ca, which are generated during the preparation of the catalyst, can be easily subjected to ion exchange with protons of the zeolite, leading to loss of acid sites. For this reason, it is considered that it is not easy to obtain the catalyst, indicated in this patent in these synthesis conditions.

In the publication of U.S. patent No. 2005/0020867 A1 describes a catalyst for obtaining light olefins, and indicated the catalyst gain stages, containing processing ZSM-5 1~10 wt.% P2O5, 0~10 wt.% Re2O3at 0.7~15 wt.% oxides of transition metals (Fe, Co, Mi, Cu, Zn, Mo, Mn), and obtain complete drying, and calcining and then mixing with clay and inorganic binding agents (silicon dioxide, aluminum oxide, a mixture of silicon dioxide-aluminum oxide), followed by spray drying. This ZSM-5 is enriched with silicon dioxide (higher ratio Si/Al), which may reduce the aromatization reaction and transport of hydrogen. However, enriched in silica ZSM-5 is not economical zeolite due to the complicated method of its synthesis, the low efficiency of the matrix and structural stability due to the intensive heat treatment with inorganic binders and clay, which are not stable in the processing of water vapor at high temperature. This may cause a decrease in catalytic kekirawa activity of the zeolite.

In U.S. patent No. 6,613,710 to obtain a catalyst of catalytic cracking reactions used 40~80 wt.% P-modified clay, 1-20 wt.% polienovogo of aluminum oxide and 0.5-15 wt.% ZSM-5. R-modified clay obtained by heating clay and phosphoric acid at 15~40°C for 1~16 hours, polienovy alumina was obtained from a suspension of sodium aluminate and aluminum sulfate at a pH of 7.5~. This catalyst gives more of liquefied petroleum gas by cracking residual oils produced by the distillation or cracking of petroleum and having a boiling point 315-528°C. In this patent has not been proposed a basic catalyst, but offered an additional catalyst for the method of increasing the output of liquefied petroleum gas and do not provide a description of the improved hydrothermal stability and obtaining light olefins.

In U.S. patent No. 5,670,037 ZSM-5 modified rare earth metal, whether with a Sol of aluminum phosphate, proposed for catalytic cracking of hydrocarbons to increase the yield of light olefins. It is obtained by mixing the P2O5and zeolite (the mass ratio of the P2O5the zeolite is 1:5~99) in a solution of phosphate of aluminum, drying, calcining and processing of water vapor. The catalyst after receipt contains 10~35 wt.% zeolite, 5~90 wt.% inorganic oxides (Al2O3, SiO2, Al2O3-SiO2) and 0~70 wt.% the clay. The solution of aluminum phosphate used for the treatment of the zeolite, and there is no explanation for the increase in the yield of light olefins without the use of rare earth metal.

In U.S. patent No. 6,080,698 catalyst zeolite type pentasil to obtain light olefins by catalytic cracking of hydrocarbons obtained from ZSM-5 (SiO2 /Al2O3=15~60), treated with 1~10 wt.% P2O5for 0.3~5 wt.% oxides of alkaline earth metals and 0.3~5 wt.% oxides of transition metals. Indicates the results of the application of Mg, Ni, Zn, Cu and Ca for processing of the zeolite, while the use of magnesium oxide is not explained. Phosphorus is limited only apply for modification of transition metal zeolite.

In U.S. patent No. 6,080,303 zeolite catalyst to obtain light olefins by catalytic cracking of hydrocarbons obtained by treatment with aluminum phosphate (AlPO4). The catalyst was prepared 1) manufacturer and calcining ZSM-5 with the modification of phosphorus, 2) the synthesis of AlPO4by mixing Al(NO3)3and NH4(H2PO4) at pH 7~9, 3) processing of ZSM-5 containing phosphorus, AlPO4and calcining. For applications with AlPO4you can apply AlPO4as in the dried state and in the form of a wet gel. The final catalyst has a composition containing 0.5~10 wt.% P, 1~50 wt.% AlPO4, 5~60 wt.% zeolite and binder or clay (to balance). In this patent P and AlPO4used to improve the hydrothermal stability of the zeolite and explain the advantage of the hydrothermal treatment of n-hexane. However, there is no result of the process without hydrothermal treatment and there is no explanation of the method is stabilizacii binder and clay, when only P and AlPO4used for the treatment of the zeolite.

In U.S. patent 2006/0011513 A1 catalyst made of ZSM-5, beta, mordenite, ferrierite and zeolite (silica/alumina >12), which is treated with a mixed binder of phosphate salts and aluminum salts of phosphates of metals, proposed as an additive in the way the FCC (fluid catalytic cracking). Salt phosphates of metals as a binder selected from phosphates of metals of group IIA, group of lanthanides, Sc, Y, La, Fe, La and Ca, and the phosphate content is more than 5 wt.%, and 4~50 wt.% phosphate is included in typical cases. This patent describes the chemical structure of phosphate salts, which are not active centers, but are binders. In addition, not described also increase the yield of olefins using zeolite obtained by the use of manganese.

In U.S. patent 5,380,690 described catalyst, which contains 0~70% clay, 5~99 wt.% inorganic oxides, such as Al2O3, SiO2, Al2O3-SiO21~50 wt.% zeolite, with the specified catalyst is a zeolite catalyst of pentasil 0~25% zeolite Y, 75~100% P2O5, ZSM-5. The specified catalyst was prepared by mixing to achieve homogeneity ZSM-5 modified 1-30% Re2O3, with a solution of aluminum phosphate is INIA (the mass ratio of Al 2O3:P2O5=1:1~3, P2O5:zeolite = 1:5~99), calcining the mixture, and the treatment with water vapor.

In U.S. patent 2006/0116544 described that the processing of the zeolite type pentasil rare earth metal and manganese or zirconium with phosphorus increases the hydrothermal stability of the catalyst and the yield of light olefins. To enhance the yield of olefin you want manganese or zirconium included in the zeolite with rare earth metal and phosphorus. In addition, as the processing method used direct introduction of rare earth metal and manganese or zirconium and phosphorus in the zeolite. The purpose of this method is a structural improvement that is similar to the previous improvements and there are no comments for stabilization of inorganic binders or the content of the matrix.

In U.S. patent 4,956,075 Y-zeolite catalyst treated with manganese and rare earth metal, is proposed for the catalytic cracking of hydrocarbons to produce gasoline with a higher octane. However, this catalyst gives a lower yield of light olefins and hydrothermal stability is lower than that of catalysts of the type pentasil.

Adding manganese to the ZSM-5 can improve hydrothermal stability, as described in "Studies in Surface Science and Catalysis", V105, 1549 (1996). However, there is an explanation of hydrothermal only when labilnosti, but there is no explanation to obtain light olefins by catalytic cracking of hydrocarbons.

In U.S. patent 6,447,741 aluminophosphate treated with manganese, is used as catalyst for catalytic cracking, whereas in this patent does not indicate the results of the synthesis of the catalyst and its use for cracking hydrocarbons. In addition, in this patent is not described hydrothermal stability and catalytic properties of zeolite, clay and binder.

As explained above, transition metals such as manganese, phosphate and rare earth metals, have been proposed for improving thermal stability of the catalysts and to obtain high yields of light olefins in catalytic cracking of hydrocarbons. However, there are no previous messages, which systematically explains how to obtain catalysts with high thermal stability and high yield of light olefins. That is not previously there were reports offered by the present invention, which describes the creation of acid sites in the zeolite manganese, stabilization inorganic complex and matrix phosphate and manganese to preserve catalytic activity of the catalyst over an extended period of time and increase the yield of light olefins. In addition, in the present invention describe the cost-effective method of manufacturing a catalyst with the exception of the difficult stages of the creation of acid sites and complex processing of spherical catalyst.

As described in the above comparative patents, phosphate exhibits a high ability to increase thermal stability of the zeolite catalyst. Phosphate increases thermal stability stabilization Al through action in the form of phosphate ion ([PO4]3-) in the framework of-Si-OH-Al, which is the centre of acid Branstad, and dealuminated water vapor.

However, thermal stability is strongly influenced by the manner in which injected phosphate in the zeolite. For the introduction of phosphate in the zeolite to improve its thermal stability in the previous methods have attempted to introduce phosphoric acid directly into the zeolite. However, according to these methods, lost a large number of acid centers. Another method is the combined use of phosphoric acid and rare earth metals such as La. By this method large La3+or phosphoric acid reduces reactivity due to their location at the entrance of the pores of the zeolite. In addition, because previous methods tried to make thermally stable only the zeolite, the problem is that the catalyst with a microporous molecular sieve, made of zeolite, does not possess sufficient thermal stability.

Therefore, the present invention describes a method of making the catalyst stability for long periodaverage under conditions of high temperature and high humidity, the way to maximize the yield of light olefins preserving the acid sites of the catalyst after their introduction.

Technical problem

The present invention relates to a cracking catalyst in which the components used to stabilize the binder, which is used inorganic oxide, and a matrix component, is added to provide mechanical strength while maintaining the structure of the zeolite, which is the main component of the catalyst at high temperature and high humidity to get cracking catalyst with thermal stability.

Aspect the present invention relates to a method of preparation of the catalyst, which is easily suitable for mass production of the catalyst and which is economical due to the simple method of its synthesis, in contrast to the existing method of producing catalyst.

Technical problem-solving

The catalyst for cracking hydrocarbons to obtain light olefins from C4 hydrocarbon or hydrocarbon, higher than the C4-hydrocarbon, which is characterized in that 0.01 to~5.0 wt.% MnO21~15 wt.% P2O5simultaneously precipitated on the catalyst component, where the component of the catalyst contains 1~50 wt.% zeolite, 21~70 wt.% clay and 1~40 wt.% inorganic oxide.

Proposed pic is b get cracking catalyst to obtain light olefins from C4 hydrocarbon or hydrocarbon, higher than C4 hydrocarbons, and the method comprises the following stages:

(a) mixing the zeolite, clay and predecessor inorganic oxide from a precursor of the phosphor and the predecessor of manganese under stirring to obtain a suspension, and

(b) drying the suspension by spraying with subsequent calculatevalue.

The beneficial effects

The present invention not only improves thermal stability of the catalyst by introduction of manganese and phosphorus in the catalyst containing both zeolite and inorganic oxide and clay, but also allows to obtain a high yield of light olefins in catalytic cracking of hydrocarbons with more than 4 carbon atoms, such as nafta, by protecting the acid sites of the zeolite. Due to the simple method of obtaining a catalyst mass production is easy and cost-effective.

Description of the drawings

Figure 1 is a schematic diagram of the manufacture of the catalyst of the present invention.

The best way of carrying out the invention

Compared with the previous inventions, the present invention describes a new method that will help to produce a catalyst with high thermal stability and to obtain a high yield of light olefins in the field of production of light olefins by catalytic cracking ug is avodarto.

A method of manufacturing the catalyst of the present invention is as follows.

1. To obtain a catalyst with a microporous molecular sieve, maximum protection of the acid sites of the zeolite is carried out by introducing a salt of manganese in the zeolite at a stage of processing of the suspension of the catalyst with a microporous molecular sieve and without the use of zeolite, in which the previously introduced manganese before treatment suspension.

2. To improve the mechanical strength of the catalyst with a microporous molecular sieve in the present invention the inorganic complex is stabilized by introduction of a suitable amount of phosphorus and manganese in the processing phase suspensions of inorganic complex.

3. In the end spend mixing suspensions of zeolite suspensions of inorganic complex and clay, manganese and phosphorus can be introduced into the clay, zeolite and inorganic oxide at the same time, to achieve the maximization of the stability and activity of decomposition.

As described above, although it is well known that the introduction of phosphate or transition metals in the zeolite stabilizes the structure of the catalyst, the present invention first described effective way maximum stabilization of inorganic complex and clay, and preservation of the acid sites of the zeolite by the introduction of both manganese and phosphorus in the zeolite on studyabroad suspension, and not in the previous stages of the immediate processing of zeolite to obtain a high yield of light olefins in catalytic cracking of hydrocarbons with more than 4 carbon atoms.

Described by the present invention a catalyst for obtaining light olefins from hydrocarbons with more than 4 carbon atoms are produced by introducing at the same time of 0.01~5.0 wt.% MnO21~15 wt.% P2O5in the components of the catalyst, which contains 1~50 wt.% zeolite, 21~70 wt.% clay and 1~40 wt.% inorganic oxide.

The above-described catalyst for catalytic cracking receive the following stages: (a) obtaining a mixed suspension by mixing predecessor phosphate and predecessor of manganese zeolite, clay and a precursor of an inorganic oxide; (b) calcining the above mixed suspension after spray drying.

In the examples of this invention, the mixed slurry, which is a precursor of phosphate and predecessor manganese is mixed with zeolite, a clay, a precursor of an inorganic oxide, receive, as illustrated in figure 1, stages, containing (i) obtaining a suspension of zeolite and clay by adding and mixing the clay after mixing zeolite and predecessor of manganese; (ii) obtaining a suspension of inorganic oxide by mixing the precursor fo the veil and the predecessor of the manganese precursor of the inorganic oxide and (iii) mixing to achieve homogeneity of the above suspension of the zeolite/clay and suspension of inorganic oxide.

In other examples of the preparation of the present invention the mixed slurry, which is a precursor of phosphate and predecessor manganese is mixed with zeolite, a clay, a precursor of an inorganic oxide, gain stages, containing (i) obtaining a suspension of the zeolite by mixing zeolite and predecessor of manganese; (ii) obtaining a suspension of inorganic oxide by mixing the precursor phosphate and predecessor of the manganese precursor of the inorganic oxide and (iii) mixing to achieve homogeneity of the above suspension of zeolite suspensions of clay and suspension of inorganic oxide.

In other examples of the preparation of the present invention the mixed slurry, which is a precursor of phosphate and predecessor manganese is mixed with zeolite, a clay, a precursor of the inorganic oxide receive simultaneous mixing zeolite, clay, the precursor of the inorganic oxide, the precursor of phosphate and predecessor of manganese.

Finally, after drying, by spraying the above mixed slurry, the catalyst for catalytic cracking of the present invention is obtained by calcination of the product drying for 5~10 hours at 500~700°C.

The catalyst obtained in this way has not only improved hydrothermal stability, but also provide Bo is its high yield of light olefins in catalytic cracking of hydrocarbons and protection of the acid sites in the zeolite. The activity cannot be guaranteed, if the ratio of each component manganese, phosphorus, zeolite and inorganic oxide when receiving suspensions for spray drying and performing mixing are not appropriate.

The zeolite can be selected from the group consisting of ZSM-5 (Si/Al<200, molar ratio), ZSM-11, ferrite, mordenite, MCM-22, SUZ-4, X-, Y -, and L-zeolite. Zeolite with Si/Al>200 may have reduced activity because of the small number of acid sites, and the synthesis of such zeolite is uneconomical. In the present study the number of the used zeolite is 1~50 wt.% calculated on the total weight of the catalyst.

The predecessor of manganese in this invention can be one from the group of sulfate, nitrate, chloride and manganese acetate, the preferred precursors are chloride and manganese acetate.

An increased yield of light olefins reach by protecting acid sites of the zeolite can be achieved through mixing with the precursor manganese at the stage of obtaining a mixture of suspensions of zeolite, clay and inorganic oxides or at the stage of obtaining suspensions of zeolite.

It is desirable to apply the predecessor of the Mn, so that the content MP was approximately 0.01 to 5.0 wt.% based on the weight of the final catalyst. When the content of MnO2less than 0.01 wt.%, protection kislotno the x centers and hydrothermal stability are reduced. When the content of MnO2more than 5.0 wt.%, protection of the acid sites decreases dramatically, resulting in reduced activity of the catalyst.

In the present invention, the clay can be applied in the range 21~70 wt.% based on the weight of the final catalyst. When the amount of clay is less than 21 wt.%, there are many problems with the regulation of physical properties such as wear resistance and specific gravity. When the amount of clay is more than 70 wt.%, the catalytic activity may decrease.

In the present invention, the Al2O3, SiO2or Al2O3-SiO2can be used as inorganic oxidized precursor of the binder. The precursor of the inorganic oxide catalyst for catalytic cracking in the present invention has the form of a Sol, gel, or solution, including Al2O3, SiO2or Al2O3-SiO2. The required amount of inorganic oxide is in the range of 1~40 wt.% based on the weight of the final catalyst. When the amount of inorganic oxide is less than 1 wt.%, wear microspherical catalyst may be insufficient, whereas when the amount of inorganic oxidized substances more than 40 wt.%, the activity of the catalyst kataliticheski the first cracking is reduced.

As for the predecessor of phosphorus to the present invention, it can be used in the form of an aqueous compound, which is selected from the group of H3PO4, (NH4)3PO4, H(NH4)2(PO4and H2(NH4PO4), and it is desirable to use in such quantity that he had the contents of P2O5in the final catalyst in the range of 1~15 wt.%. When the content of P2O5in the final catalyst is less than 1 wt.%, hydrothermal stability of the zeolite is reduced, whereas when the content of P2O5in the final catalyst is greater than 15 wt.%, the activity of the catalyst for catalytic cracking is reduced due to excessive loss of acid sites.

Phosphorus and manganese contained in the mixed suspension, are in the dissolved form, they are all substances of zeolite, clay and inorganic oxidized substances. These components protect the acid sites of the zeolite and increase the hydrothermal stability of the zeolite, clay and inorganic oxidized substances, thereby maximizing stability and activity of the catalyst.

Finally, the catalyst for catalytic cracking of the present invention is produced by spray drying and calcining the above mixed suspension at 500~700°C during the 5~10 hours.

The catalyst obtained according to the present invention, applied in the form of molded microspheroidal catalyst for fluidized catalytic method of producing ethylene and propylene from a hydrocarbon (number of carbon atoms is 4 or more) with high yield and high selectivity. In this way, these hydrocarbons (number of carbon atoms is 4 or more) means hydrocarbons that have a boiling point of 30~200°C.

In addition, even in conditions of high humidity and high temperature, the catalyst according to the present invention has a high craterous activity and stability. Due to this characteristic, the present catalyst can be used not only for the reaction of catalytic cracking, but also for the reactions of isomerization, alkylation reaction, the esterification reaction and the oxidation reaction/recovery, require high hydrothermal stability.

The implementation of the invention

Hereinafter the present invention will be described in more detail by means of examples. It should be clear, however, that these examples should not be construed as limiting the scope of the present invention.

Comparative example 1: obtaining P-La-Mn/ZSM-5

40,5 g MnCl2·4H2O was dissolved in 3000 ml of distilled water. To the solution was slowly added 200 g of ZSM-5 when the AC is shivani for about 3 hours at room temperature. Then the solution was dried by vacuum drying and subsequent calcination (650°C, 6 hours). 89 g of La(NO3)3·6H2O was dissolved in 3000 ml of distilled water and to the solution was added 200 g of calcined sample, followed by stirring for 3 hours at room temperature. Then the solution was dried by vacuum drying and subsequent calcination (650°C, 6 hours). of 25.5 G. of 85% H3PO4was dissolved in 3000 ml of distilled water and 200 g of calcined sample was added to the solution followed by stirring for 3 hours at room temperature. Then the solution was dried by vacuum drying and subsequent calcination (650°C, 6 hours).

Comparative example 2: obtain the P-Mn/ZSM-5

40,5 g MnCl2·4H2O was dissolved in 3000 ml of distilled water and to the solution was added 200 g of ZSM-5, followed by stirring for 3 hours at room temperature. Then the solution was dried by vacuum drying and subsequent calcination (650°C, 6 hours). of 25.5 G. of 85% H3PO4was dissolved in 3000 ml of distilled water and to the solution was added 200 g of calcined sample, followed by stirring the mixture for 3 hours at room temperature. Then the solution was dried by vacuum drying and subsequent calcination (650°C, 6 hours).

Comparative example 3: obtaining the P/ZSM-5

of 25.5 G. of 85% H3PO4races shall varali in 3000 ml of distilled water and to the solution was added 200 g of ZSM-5, followed by stirring for 3 hours at room temperature. Then the solution was dried by vacuum drying and subsequent calcination (650°C, 6 hours).

Comparative examples 4-6

Microspheroidal catalyst for catalytic cracking was obtained with the application of the sample of comparative examples 4-6 the following procedure.

To obtain suspensions of zeolite, 120 g of the sample of comparative example 1 was added to 200 g of distilled water, followed by stirring. To obtain a suspension of clay, 144 g of clay was added to 176 g of distilled water, followed by stirring. To bind the zeolite and clay was applied 439 g Zola aluminum oxide (solids content of 8.4%, pH 2~3), while receiving microspheroidal catalyst. Suspension of zeolite, a clay suspension and the Sol of aluminum oxide were mixed to achieve homogeneity, followed by spraying and drying. Then, the thus obtained substance was caliciviral at 650°C for 6 hours with the formation of the molded catalyst of comparative example 4. The same technique and the same way molded catalysts of comparative examples 5 and 6 were obtained using zeolite of comparative examples 2 and 3.

Comparative example 7

To obtain suspensions of zeolite, 120 g of the sample of comparative example 1 was slowly added to 200 g of distilled water, followed by stirring. To obtain the suspension is Lina, 144 g of clay was slowly added to 176 g of distilled water, followed by stirring. To obtain the inorganic binder used for the manufacture microspheroidal catalyst, 439 g Zola aluminum (solids content of 8.4%, pH 2-3) and 33.1 g of 85% H3PO4mixed to achieve homogeneity. Suspension of zeolite, a clay suspension and the mixture Sol alumina-N3RHO4mixed to achieve homogeneity, followed by drying the mixture by spraying. Then this mixture was caliciviral at 650°C for 6 hours and got molded catalyst of comparative example 7.

The chemical composition of the catalysts of comparative examples 4-7 are summarized below in table 1.

Table 1
The catalyst composition, wt.%Comparative example 4Comparative example 5Comparative example 6Comparative example 7
Zeolite29,333,937,027,5
Clay47,947,9 47,944,8
Al2O312,312,312,311,5
SiO2----
P2O52,92,92,99,1
LaO5,1--the 4.7
MnO22,63,0-2,5

Examples 1-2

4.5 g MnCl2·4H2O was added to 376 ml of distilled water and to this solution was added 120 g of ZSM-5, followed by stirring the mixture at 60°C for 6 hours. Then to this solution was slowly added 144 g of clay using the mixer for slurry with high viscosity and the mixture was stirred for 3 hours. To obtain an inorganic binder, 439 g Zola aluminum (solid content of 8.4%, pH 2~3), 30.5 g of 85% H3PO4and 1.8 g of MnCl2 2O were mixed at 35°C for 8 hours. The above suspension of zeolite-clay and inorganic binder were mixed to achieve homogeneity, followed by spray drying. Then after calcination at 650°C for 6 hours has been the catalyst of example 1.

Used the same procedure as in example 1, except that used other samples (11.2 g MnCl2·4H2O for treatment of ZSM-5, 3.1 g MnCl2·4H2O and 43.8 g H3PO4used for processing inorganic binder), to obtain the catalyst of example 2.

Example 3-4

4.5 g MnCl2·4H2O was added to 376 ml of distilled water and to this solution was added 120 g of ZSM-5, followed by stirring the mixture at 60°C for 6 hours. Then to this solution was slowly added 144 g of clay using the mixer for slurry with high viscosity for 3 hours. 56.7 g of pseudoboehmite (the content of Al2O372%) were dispersible in 498 g of distilled water. Then, to obtain the precursor of the inorganic binder this solution dispersed pseudoboehmite, 30.5 g of 85% H3PO4and 1.8 g of MnCl2·H2O were mixed at 35°C for 8 hours. To obtain the inorganic binder to the mixture was added 5.32 g of formic acid and the mixture was stirred to those who long until it became stable. The above suspension of zeolite-clay and inorganic binder were mixed to achieve homogeneity, followed by spray drying. Then after calcination at 650°C for 6 hours has been the catalyst of example 3.

Used the same procedure as in example 3, except that used other samples (15.5 g MnCl2·4H2About used for treatment of ZSM-5, 4.8 g MnCl2·4H2O and 51.3 g H3PO4used to obtain the inorganic binder), thus obtaining the catalyst of example 4.

Example 5-6

4.5 g MnCl2·4H2O was added to 376 ml of distilled water and to this solution was added 120 g of ZSM-5, followed by stirring the mixture at 60°C for 6 hours. Then to this solution was slowly added 144 g of clay using the mixer for slurry with high viscosity for 3 hours. To 199 g of a solution of aluminum sulfate (8% Al2O3) was added to 23.6 g of water glass (29% SiO2) and the mixture was stirred. Then, to obtain an inorganic binder 15,95 g H3PO4and 1.8 g of MnCl2·4H2O were mixed at 35°C for 8 hours. The above suspension of zeolite-clay and inorganic binder were mixed to achieve homogeneity, followed by spray drying. Then after ka is itinerary at 650°C for 6 hours has been the catalyst of example 5.

Used the same procedure as in example 5, except that used other samples (11.4 g MnCl2·4H2O used for treatment of ZSM-5, 5.8 g MnCl2·4H2O and 71.2 g H3PO4used for processing inorganic binder), thus obtaining the catalyst of example 6.

The chemical composition of the catalysts of examples 1-6 are summarized below in table 2.

Table 2
The catalyst composition, wt.%Example 1Example 2Example 3Example 4Example 5Example 6
Zeolite37,235,936,734,840,235,5
Clay44,7to 43.144,141,648,142,6
Al2O311,411,0 12,511,85,3the 4.7
SiO2----2,32,0
P2O55,88,15,89,23,313,0
LaO------
MnO20,91,90,92,60,82,2

Examples 7-8

4.5 g MnCl2·4H2O was added to 376 ml of distilled water and to this solution was added 90 g of ZSM-5, followed by stirring the mixture at 60°C for 6 hours. Then to this solution was slowly added 144 g of clay using the mixer for slurry with high viscosity for 3 hours. To 220 ml of distilled water was added of 62.4 g of Al(NO 3)3·9H2O, then added a 21.5 grams of 85% H3PO4and 1.3 g of MnCl2·H2O and the mixture was stirred at 35°C for 8 hours. The above suspension of zeolite-clay and the solution was mixed to achieve homogeneity, followed by spray drying. Then after calcination at 650°C has been the catalyst of example 7.

Used the same procedure as in example 7, except that used other samples (used 120 grams of ZSM-5, 11.4 g MnCl2·4H2O used for treatment of ZSM-5, 5.8 g MnCl2·4H2O and to 61.2 g H3PO4used to obtain the inorganic binder), thus obtaining the catalyst of example 8.

Comparative example 8

120 g of ZSM-5 was mixed with 376 ml of distilled water at room temperature for 6 hours. Then to this solution was slowly added 144 g of clay using the mixer for slurry with high viscosity for 3 hours. To 220 ml of distilled water was added of 62.4 g of Al(NO3)3·9H2O, followed by stirring with 21.5 grams of 85% H3PO4. The above suspension of zeolite-clay and the solution was mixed to achieve homogeneity, followed by spray drying. Then after calcination at 650°C for 6 hours has been the catalyst of comparative example 8.

Comparative example 9

of 13.2 g of 85% H3PO4added to 576 ml of an aqueous solution (dissolved 22,8 g MnCl2·4H2O and 222,6 g AlCl3·6H2O), followed by stirring for 3 hours. This solution was titrated ammonia water to achieve a pH=11. After removal of the precipitate, drying at 100°C and calcination at 650°C for 5 hours received MnAlPOx. 32,6 g MnAlPOx and 120 g of ZSM-5 was added to 200 g of distilled water and the mixture was stirred with formation of a suspension MnAlPOx/ZSM-5. To obtain suspensions of clay used byr111.4 g clay and 176 g of distilled water on the above methodology. 439 g Zola aluminum oxide (solids content of 8.4%, pH 2~3), the suspension of zeolite and the clay suspension was stirred until homogeneity followed by spray drying and calcining at 650°C for 6 hours, thus obtaining a catalyst of comparative example 9.

The chemical composition of the catalysts of examples 7-8 and comparative examples 8-9 are summarized below in table 3.

Table 3
The catalyst composition, wt.%Example 7Example 8Comparative example 8Comparative example 9
Zeolite 34,8of 37.842,039,9
Clay55,845,350,437,0
Al2O33,32,73,020,0
SiO2----
P2O55,111,94,61,4
LaO----
MnO21,02,38-1,7

Evaluation of catalyst activity

To assess the activity of the catalyst, samples, 14 of the catalysts of the above comparative examples 4-9 and examples 1-8 was treated with steam at 760°C in an atmosphere of 100% water vapor for 24 hours. The test conditions are DL the evaluation activity were as follows: the reaction temperature was 675°C, volume-mass velocity (WHSV) was 8 per hour, the catalyst loading was 6 g and as a reagent used naphtha (boiling point 30-135°C). The test results are summarized in tables 4-6.

From these results it becomes apparent that high reaction conversion and a high yield of light olefins was obtained by introduction of Mn and P in obtaining microspherical catalyst according to the present invention. Mn and P are effective to stabilize the zeolite, an inorganic binder and clay. In addition, Mn and P protect the acid sites of the zeolite, which allows to obtain a high yield of light olefins.

Table 4
The distribution of components, wt.%Compare. example 4Compare. example 5Compare. example 6Compare. example 7Compare. example 8Compare. example 9
With2=16,514.4V13,513,311,214.4V
With3= 19,619,419,419,218,119,2
With2-7,87,08,56,45,67,5
With3-a 4.94,36,03,22,34,1
With410,610,810,2the 10.19,510,7
With5(ISO-C5the h5)7,49,310,610,612,36,8

Table 5
The distribution of components, wt.%Example 1Example 2 Example 3Example 4Example 5
With2=19,519,421,821,720,5
With3=21,420,920,019,8a 21.5
With2-9,19,6the 10.1the 10.19,1
With3-5,85,84,54,3a 3.9
With4-9,3the 9.77,47,38,4
With5(ISO-C5n-C5)4,44,21,61,43,6

Table 6
The distribution of components, wt.%Example 6Example 7Example 8
With2=20,821,7of 21.9
With3=20,321,022,3
With2-9,89,59,8
With3-the 4.73,74,1
With48,57,67,0
With5(ISO-C5the h5)2,02,42,4

As described above, the catalyst according to the present invention is characterized by the fact that to achieve a high yield of light olefins acid sites of the zeolite is treated with Mn and to achieve the thus treated zeolite of high activity in the structure of the catalyst, P and Mn are used for stabilization is used as the St is based on inorganic oxide matrix component. The present method of producing catalyst has advantages from the point of view of costs compared with the methods of the prior art, which typically contain advanced stage of introducing these components in the zeolite.

1. The method of obtaining light olefins by catalytic cracking of hydrocarbons with 4 or more than 4 carbon atoms having a boiling point of 30-200°C, in the presence of a catalyst, wherein the catalyst is characterized by the fact that 0.01-5.0 wt.% MnO2and 1-15 wt.% P2O5at the same time add to the components of the catalyst, where the components of the catalyst containing 1-50 wt.% zeolite, 21-70 wt.% clay and 1-40 wt.% inorganic oxide and where both MnO2and P2O5enter (modify) each of the components of the catalyst, such as ZSM-5 zeolite, clay and inorganic oxide.

2. The method according to claim 1, characterized in that the zeolite has a molar ratio Si/Al is less than 200, or equal to 200.

3. The method according to claim 1, wherein the inorganic oxide is Al2O3, SiO2or Al2O3-SiO2.

4. The method according to claim 1, characterized in that the hydrocarbons consist of naphtha.

5. The method according to claim 1, characterized in that the catalyst prepared by the method comprising the following stages:
(a) mixing the zeolite ZSM-5, clay and predecessor inorganic oxide is predecessor of phosphorus and predecessor of manganese under stirring to obtain a slurry mixture, and
(b) spray drying the slurry mixture, followed by calcination,
where stage (a) contains stages:
(i) mixing the zeolite ZSM-5 precursor manganese followed by the addition of clay and stirring the mixture to obtain a suspension of zeolite ZSM-5/clay;
(ii) mixing the precursor of the inorganic oxide with the predecessor of phosphorus and predecessor of manganese under stirring to obtain a suspension of inorganic oxide and
(iii) mixing the suspension of zeolite ZSM-5/clay and suspension of inorganic oxide to obtain a homogeneous suspension.

6. The method according to claim 1, characterized in that the catalyst was prepared according to the method containing the following steps:
(a) mixing the zeolite ZSM-5, clay and predecessor inorganic oxide from a precursor of the phosphor and the predecessor of manganese under stirring to obtain a slurry mixture;
(b) spray drying the slurry mixture, followed by calcination,
where stage (a) includes the steps:
(i) mixing the zeolite ZSM-5 precursor manganese to obtain a suspension of the zeolite;
(ii) mixing the precursor of the inorganic oxide with the predecessor of phosphorus and predecessor of manganese under stirring to obtain a suspension of inorganic oxide and
(iii) mixing the suspension of zeolite ZSM-5, the suspension of inorganic oxide and clay up to the achievements of homogeneity.

7. The method according to claim 1, characterized in that the catalyst was prepared according to the method that contains the stage:
(a) mixing the zeolite ZSM-5, clay and predecessor inorganic oxide from a precursor of the phosphor and the predecessor of manganese under stirring to obtain a slurry mixture;
(b) spray drying the slurry mixture, followed by calcination,
where stage (a) is conducted by mixing the ZSM-5 zeolite, clay and predecessor inorganic oxide, the precursor of phosphorus and predecessor of manganese at the same time with stirring.

8. The method according to any of pp.5-7, characterized in that the precursor of the inorganic oxide contains Al2O3, SiO2or Al2O3-SiO2and has the form of a Sol, gel, or solution.

9. The method according to any of pp.5-7, in which the precursor manganese is sulfate, nitrate, chloride or acetate compound of manganese.

10. The method according to any of pp.5-7, characterized in that the precursor of phosphorus is the water connection of phosphorus selected from the group of H3PO4, (NH4)3PO4, H(NH4)2(PO4and H2(NH4)PO4.



 

Same patents:

FIELD: process engineering.

SUBSTANCE: invention relates to oil processing industry, particularly, to oil fractions cracking catalyst. Proposed catalyst comprises ultra stable zeolite Y in cation-decationated form with lattice module of 5.2-6.0 containing 1.0-1.5 wt % of sodium oxide, 10-14 wt % of rare-earth metal oxides, and/or ultra stable zeolite with lattice module of 6.0-10.0 containing 0.5-1.0 wt % of sodium oxide, 7-10 wt % of rare-earth metal oxides, and matrix wherein amorphous alumina silicate, aluminium hydroxide and bentonitic clay making its components in the following ratio in wt %: zeolite Y or mix of zeolites Y 15-30, amorphous alumina silicate 20-45, aluminium hydroxide 10-40, and bentonitic clay 10-40. Proposed method comprises conducting ionic replacement by cations of rare-earth metals and ammonium on zeolite NaY, ultra stabilisation of zeolite by steam, mixing zeolite with matrix components, i.e. amorphous alumina silicate, aluminium hydroxide and bentonitic clay, spray drying, calcining and making catalyst. Note here that ultra stabilisation of zeolite is conducted in rotary kiln one or two times unless mixing with matrix components. Note also that zeolite filtration is carried out in countercurrent. Note that filtrates of next stages of ionic replacement is used as flushing fluids at previous stages while ionic replacement of sodium cations in zeolite by ammonium cations is conducted two or three times.

EFFECT: high activity of catalyst and high octane number of gasoline.

4 cl, 2 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to catalyst and method of preparing microspheric bizeolite catalyst of vacuum gasoil cracking. Described is catalyst, including ultrastable zeolite Y with matrix constant from 24.30 to 24.55 Å and content of rare earth elements 3.0-6.0 wt %, zeolite HZSM-5 with silica module from 25 to 40 and matrix, in which as components used are bentonite clay, aluminium hydroxide and amorphous alumosilicate. Catalyst contains in wt %:zeolite Y 15-25; zeolite HZSM-5 1-5; bentonite clay 15-30; aluminium hydroxide 15-30; amorphous alumosilicate 20-45. Also disclosed is method of preparation of said catalyst, including application of zeolite Y with matrix constant from 24.30 to 24.55 Å, carrying out ionic exchanges on ammonium cations and rare earth elements on zeolite Y until content of rare earth elements in zeolite is 3.0-6.0 wt %, ammonium 7.0-8.0%, zeolite ultrastabilisation in water vapour medium, after ultrastabilisation third ionic exchange on ammonium cations and further mixing of zeolite with matrix components are carried out.

EFFECT: simultaneous increase of petrol output and octane number of cracking petrol.

2 cl, 2 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the oil refining industry and specifically to preparation of catalysts for cracking oil fractions. Described is a microspherical catalyst for reducing sulphur content in cracked gasoline, which contains ultrastable zeolite Y in a cation-decationated form and a matrix whose components are bentonite clay, aluminium hydroxide, amorphous aluminosilicate and a magnesium-aluminium spinel with molar ratio Mg:Al of (2-3):1 or a zinc-magnesium-aluminium spinel with molar ratio Zn:Mg:Al of (1-2):(1-2):1, with the following content of components, wt %: zeolite Y 15-25; bentonite clay 15-25; aluminium hydroxide 15-25; amorphous aluminosilicate 25-40; magnesium-aluminium or zinc-magnesium-aluminium spinel 5-15. Described is a method of preparing said catalyst, involving ion exchange of ammonium cations and rare-earth elements on zeolite Y, ultrastabilisation of the zeolite in water vapour medium, mixing the zeolite with matrix components in form of bentonite clay, aluminium hydroxide, amorphous aluminosilicate and magnesium-aluminium hydrotalcite with molar ratio Mg:Al of (2-3):1 or zinc-magnesium-aluminium hydrotalcite with molar ratio Zn:Mg:Al of (1-2):(1-2):1, obtaining a composition and spray drying, followed by calcination.

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2 cl, 2 tbl, 8 ex

FIELD: process engineering.

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EFFECT: great volume of catalyst's pores, high capability of cracking heavy oil products and high stability of coving.

25 cl, 4 tbl, 11 ex, 1 dwg

FIELD: oil and gas industry.

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3 cl, 2 tbl, 5 ex

FIELD: process engineering.

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28 cl, 1 tbl, 7 ex, 4 dwg

FIELD: petrochemistry.

SUBSTANCE: this invention relates to the catalyst of the catalytic cracking which is appropriate for reduction of sulphur concentration in the catalytic cracking liquid products in particular in benzine products produced upon the implementation of the method of catalytic cracking, preferably the method of catalytic cracking in the fluidized layer of the catalyst; the method describes the catalyst containing zeolite, zinc and at least one rare earth element having the ion radius less than 0.95 A with the coordinate number 6; the summary describes the method of reduction of sulphur concentration in the catalytically cracked oil fraction at high temperatures in presence of the above catalyst.

EFFECT: reduction of sulphur concentration upon the execution of catalytic cracking.

42 cl, 4 tbl, 7 ex, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing ethylene and propylene using starting material having high concentration of diolefins by bringing hydrocarbon substance containing at least one olefin which contains 4-12 carbon atoms in amount of at least 20 wt % and where the hydrocarbon substance contains at least one diolefin compound containing 3-12 carbon atoms in amount of 1.26-2.5 wt % in terms of the weight of the hydrocarbon substance, into contact with a zeolite-containing moulded catalyst in a reactor for catalytic conversion of at least one olefin containing 4-12 carbon atoms, where the zeolite in the zeolite-containing moulded catalyst satisfies conditions (1), (2), (3) and (4): (1) the zeolite is an intermediate pore size zeolite with pore size from 5 to 6.5 Е, (2) the amount of protons in the zolite is equal to or less than 0.02 mmol per gram of zeolite, (3) the zeolite contains at least one metal selected from a group comprising group IB metals, (4) the zeolite has molar ratio of silicon oxide to aluminium oxide (SiO2/Al2O3) ranging from 800 to 2000.

EFFECT: method enables stable production of ethylene and propylene with high output using raw material which contains diolefin.

7 cl, 3 ex, 4 tbl, 1 dwg

FIELD: oil and gas production.

SUBSTANCE: invention refers to procedure for production of motor fuel by oil fraction cracking at presence of ball alumo-silicate platinum-zeolite-containing catalyst obtained by forming hydro-gel in mineral oil, synthesised mixing solutions of sodium silicate and aluminium sulphate with water suspensions of fine dispersed powders of zeolite of type Y and filler - aluminium oxide with contents α-Al2O3 not over 85 wt %, stabilised dispersers and containing platinum-hydrochloric acid, by activation, washing, drying and baking in atmosphere of water steam. The distinguished feature of the procedure is like follows: for preparation of catalyst there is used ultra-stable zeolite Y in hydrogen or hydrogen-rare earth form - at degree of crystallinity as high, as 85%, mole ratio SiO2/Al2O3=10÷15. The degree of exchange to cations of rare earth elements of ultra-stable zeolite Y in hydrogen-rare earth form is not more, than 60%. Preliminary raw stock of catalytic cracking is hydro-fined to contents of sulphur not over 0.3 % wt. Catalytic cracking is performed with extraction of fractions of motor fuel and heavy fraction of product of catalytic cracking with temperature of beginning of boiling point above 360°C which is directed to re-cycle into source raw stock to ensure content as high, as 5 % wt.

EFFECT: increased output of benzene fraction and its octane number.

1 tbl

FIELD: oil and gas production.

SUBSTANCE: invention refers to procedure for catalytic conversion of hydrocarbons. The procedure consists in contacting source hydrocarbons with catalyst of hydrocarbon conversion to ensure reaction of catalytic cracking in a reactor. Further, products of reaction are withdrawn from the reactor and are divided into fractions to produce light olefines, gasoline, diesel fuel, heavy diesel fuel and other saturated low-molecule hydrocarbons. Also, catalyst of hydrocarbons conversion contains (of total weight of catalyst): 1-60 % wt of mixture of zeolite, 5-99 % wt of heat-resistant non-organic oxide and 0-70 % wt of clay. Mixture of zeolite contains (from total weight of mixture): 1-75 % wt of beta-zeolite modified with phosphorus and transition metal M, 25-99 % wt of zeolite with MF-structure and 0-74 % wt of zeolite of large pores. Waterless chemical composition of beta-zeolite modified with phosphorus and transition metal M is of the following kind: (0-0.3)Na2O·(0.5-10)Al2O3·(1.3-10)P2O5·(0.7-15)MxOy·(64-97)SiO2 (in brackets there are indicated wt percents of oxides) where transition metal M is one or several metals chosen from a group consisting of Fe, Co, Ni, Cu, Mn, Zn and Sn; x is number of atoms of transition metal M, and y is number ensuring valence corresponding to a degree of transition metal M oxidation.

EFFECT: increased conversion of hydrocarbons of oil and higher output of light olefines, particularly, propylene.

17 cl, 43 ex, 8 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts. Described are methods of producing a cobalt Fischer-Tropsch synthesis catalyst, which involve preparation of a granular support from starting material - oxides of group III and IV metals, mixing the latter with modifying additives, followed by calcining, saturation with cobalt compounds, followed by calcining and activation of the catalyst in a current of a hydrogen-containing gas during Fischer-Tropsch synthesis.

EFFECT: low power consumption of the Fischer-Tropsch synthesis process.

2 cl, 11 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: method of producing a Fischer-Tropsch synthesis catalyst, involving calcining material: nitrate, oxonitrate, hydroxide or oxohydroxide of aluminium, zirconium, silicon or titanium, at temperature of 400-800°C, grinding particles to size of not more than 0.5 mm, granulating, calcining the granules at temperature of 400-800°C, saturating with a solution of cobalt compounds in amount of 20-30 wt % and promoters selected from: Re, Ru, followed by calcination at temperature of 270-450°C, grinding the granules to particle size of not more than 0.5 mm, mixing with a zeolite selected from: ZSM-5, Y, β, content of which ranges from 30 to 70% of the mass of the ready catalyst, granulating the obtained mixture together with boehmite, the mass of which ranges from 10 to 20% of the mass of the mixture, and calcining at temperature of 400-600°C, ion exchange of the granules with soluble compounds of palladium or Fe, Co, Ni, with content thereof of 0.5-8.0% of the mass of the ready catalyst, in a suspension of granules and a solution of said metal compounds at temperature of 60-80°C for 1-3 hours, drying the suspension at temperature of 80-150°C and calcining the residue at temperature of 300-500°C, activating the catalyst with hydrogen at 250-500°C in a fixed bed Fischer-Tropsch synthesis reactor while passing hydrogen with volume rate of 3000 h-1 at atmospheric pressure.

EFFECT: low cost of the catalyst, high stability of the catalyst.

1 tbl, 48 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of ion-exchange moulded catalysts. Described is an ion-exchange moulded catalyst for organic synthesis, which contains a mixture of copolymers with a macroporous and gel structure, a sulphonated copolymer of styrene and divinyl benzene, and a thermoplastic binding component - polypropylene, wherein the weight ratio of the gel and macroposous components is equal to (3.7-14.0):1, respectively, with respect to the dry catalyst, the amount of the binding component is equal to 20-30 wt % with respect to the dry catalyst, the starting components are taken with residual moisture content of not more than 10 wt % and fractional composition of not less than 95% of a fraction of particles with size in the range of 50-200 mcm. Described is a method of producing said catalyst.

EFFECT: obtaining a catalyst in which there is no blocking of the adsorption space of the catalyst and premature evaporation of water.

4 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalytic chemistry, particularly a method of producing aluminium-nickel-molybdenum catalysts for hydrofining diesel fuel by self-propagating high-temperature synthesis through an intermetallic alloy step. The method of producing the catalyst involves mixing dry powder of nickel, molybdenum and aluminium oxides in ratio of 35-67% molybdenum oxide, 9-17% nickel oxide, aluminium oxide - the balance; the obtained mixture is used to mould pellets of given size and mass, which are then placed into a refractory mould with an inner high-temperature protective coating; said mould is placed a centrifuge and then rotated with centrifugal acceleration of 4-80 g, where g gravitational acceleration; during rotation of the centrifuge, the pellets are burnt and the combustion process is maintained in an air atmosphere at temperature higher than the melting point of components of the mixture of the pellets until an intermetallic alloy is obtained; after removing from the centrifuge, the obtained alloy is then successively leached from aluminium with an alkali metal hydroxide solution for 20-60 minutes, washed and stabilised with 10% citric acid solution and 1% hydrogen peroxide solution.

EFFECT: fewer steps of preparing the catalyst and obtaining a highly active catalyst.

4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalytic processes. Described is a method for synthesis of a catalyst for oxidative cracking of organic material, including biomass, involving heating water containing 1-10% lower alcohol to 58-75°C, adding FeCl3×6H2O and soda with weight ratio of iron chloride to soda of 1.5-80, holding the aqueous solution at temperature of 58-75°C for at least 10 minutes while stirring and leaving the aqueous solution until complete precipitation of Fe3+. Described is use of a catalyst obtained using said method for oxidative cracking of organic material.

EFFECT: high catalyst activity.

14 cl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of polymers, specifically metal complex polymerisation catalysts, and can be used to produce trans-1,4-polyisoprene. Described is a method of obtaining a modified titanium-magnesium nanocatalyst for polymerisation of isoprenate by reacting magnesium with titanium tetrachloride and butyl chloride in volume ratio of 1/(63-190), followed by washing and further modification with phosphine of general formula R3P, where R=aryl, alkyl or a thiol of general formula R1SR2, where R1, R2=aryl, alkyl or carbon disulphide. In the nanocatalyst, the ratio phosphorus/titanium in the case of phosphine or sulphur/titanium in the case of thiol or carbon disulphide ranges from 1 to 20 mol/mol.

EFFECT: high stereospecificity of the catalyst with respect to isoprene and reduced amount of low molecular weight fractions in polyisoprene.

3 cl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing carbon catalyst supports. Described is a method of producing a carbon catalyst support involving use of soot as starting material, characterised by that the soot is mixed with petroleum pitch and a solvent, the obtained mixture is granulated, the granules are stabilised in a gas medium at temperature not higher than 250°C and carbonised at temperature of 600-1200°C, followed by cooling.

EFFECT: cheap carbon catalyst support with low ash content and high mechanical strength of granules.

1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for selective synthesis of high-quality gasoline fractions from synthesis gas and a method for production thereof. Described is a highly selective catalyst for producing high-quality gasoline fractions from synthesis gas, which consists of cobalt, a promoter and a molecular sieve, wherein the weight content of cobalt is 1-30%, the weight content of the promoter is 0.01-5%, and the remaining part is a molecular sieve, with respect to the weight of the catalyst, wherein the molecular sieve is one or more molecular sieves selected from molecular sieves Beta, ZSM-5, MOR, Y and MCM-22, wherein acidity of the molecular sieve is expressed through the amount of adsorbed NH3, and the adsorption capacity of the molecular sieve ranges from 0.16 to 0.50 mmol NH3/g; the molecular sieve has a microporous-mesoporous structure, wherein the micropores have diameter of 0.4-0.9 nm, and the mesopores have diameter of 2-30 nm, the specific surface area of the molecular sieve is 100-900 m2/g and the volume of micropores and mesopores is 0.1-0.6 cm3/g, respectively. Described is a method of producing a highly selective catalyst used for synthesis of high-quality gasoline fractions from synthesis gas by Fischer-Tropsch synthesis, involving the following steps: (1) preparing a weighed portion of a cobalt salt according to content of components given above, mixing with a solvent which is deionised water, alcohol or a ketone, to obtain a solution which contains a cobalt salt with concentration of 0.5-20 wt %; (2) preparing a weighed portion of a promoter according to content of components established above, adding to the prepared solution a cobalt salt and stirring for 0.5-3 hours; (3) preparing a weighed portion of a molecular sieve according to content of components established above, adding the molecular sieve to the prepared solution of cobalt salt, stirring for 0.1-15 hours and holding for 0.1-24 hours; (4) evaporating the suspension at temperature of 40-100°C and drying the obtained solid substance under a vacuum at temperature of 30-100°C for 1-24 hours; (5) calcining the dried substance on air at temperature of 300-550°C for 2-10 hours; (6) moulding the calcined powder as a catalyst precursor; (7) reducing the catalyst precursor in a hydrogen atmosphere or a mixture of hydrogen and an inert gas at temperature of 300-550°C for 1-10 hours.

EFFECT: described is a highly selective catalyst for producing high-quality gasoline fractions from synthesis gas.

13 cl, 17 tbl, 16 ex

FIELD: process engineering.

SUBSTANCE: invention relates to catalyst, methods of its production and application for cleaning off-gases of NOx in oxidative conditions in the presence of hydrocarbon. Catalyst for cleaning off-gases of nitrogen oxides by catalytic reduction of methane in oxidative medium comprises 1.75-2.0 wt % of palladium applied on carrier. The latter represents Mg(Sr)-Al-O oxide composition containing 4-14 wt % of Mg(Sr)O with specific surface (3.8 - 9.0) m2/g and moisture content of (0.35-0.65) ml/g. Invention covers the method of making the catalyst including manufacturing Mg-Al-O and Sr-Al-O carriers and that of cleaning off-gases from nitrogen oxides by catalytic reduction by hydrocarbons in oxidative atmosphere in the presence of above described catalyst including palladium applied on Mg-Al-O or Sr-Al-O carrier.

EFFECT: efficient cleaning.

4 cl, 21 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to petrochemical industry. Described is a method of preparing a titanium catalyst for stereospecific polymerisation of isoprene in the presence of a catalyst system TiCl4-Al(i-C4H9)3-diphenyloxide-piperylene by mixing toluene solutions of titanium tetrachloride, which contains phenyl oxide, and triisobutylaluminium, which contains piperylene, in molar ratio of the titanium and aluminium components of the catalyst to diphenyl oxide and piperylene of 1:0.15, at temperature of (-20)-(-10)°C, followed by circulation of the catalyst on an outer loop with collection of isoprene for polymerisation, wherein a small tubular turbulent reactor with a diffuser-confusor design is mounted at the step for circulation on the outer mixing loop.

EFFECT: method enables to reduce consumption of the titanium catalyst during isoprene polymerisation.

1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to zeolite structures. Described are zeolite secondary structures obtained using a method which involves producing zeolite primary particles, heating the zeolite primary particles to temperature higher than about 800°C at an average rate of at least about 10°C/min under pressure of at least 5.0 MPa, to form a zeolite secondary structure having ultimate tensile stress of at least about 0.40 MPa. Described is use of said zeolite structures as hydrocarbon isomerisation catalysts.

EFFECT: higher strength of zeolite structures.

18 cl, 1 tbl, 2 dwg, 1 ex

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