Zeolite-containing catalyst for coverting hydrocarbons, method of making said catalyst and method of converting hydrocarbon petroleum products using said catalyst

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for converting hydrocarbons, which contains zeolite, method of making said catalyst and method of converting hydrocarbon petroleum products on the catalyst. The zeolite-containing catalyst for converting hydrocarbons, which contains zeolite, heat resistant inorganic oxide and optionally clay, is distinguished by that, the said zeolite has MFI structure, which contains phosphorous and transition metals, or a mixture of said zeolite with MFI structure, containing phosphorous and transition metals, with macroporous zeolite, which contains 75 to 100 wt % of the said zeolite with MFI structure in terms of mass of the mixture, containing phosphorous and transition metals, and 0 to 25 wt % macroporous zeolite; wherein the said zeolite with MFI structure, containing phosphorous and transition metals, in terms of mass of oxide, has the following chemical formula without taking water into account: (0 to 0.3)Na2O·(0.03 to 5.5)Al2O3·(1.0 to 10)P2O5·(0.7 to 15)M1xOy·(0.01 to 5)M2mOn·(0.5 to 10)RE2O3·(70 to 97)SiO2 I or (0 to 0.3)Na2O·(0.3 to 5)Al2O3·(1.0 to 10)P2O5·(0.7 to 15)MpOq·(0.5 to 10)RE2O2·(70 to 98)SiO2 II in which M1 is a transition metal, which is chosen from Fe, Co and Ni, M2 is a transition metal, which is chosen from Zn, Mn, Ga and Sn, M is a transition metal, which is chosen from Fe, Co, Ni, Cu, Zn, Mo or Mn, and RE is a rare-earth metal; x is equal to 1 or 2, where if x equals 1, y equals half the valency of transition metal M1, and when x equals 2, y equals valency of transition metal M1; m equals 1 or 2, when m equals 1, n equals half the valency of transition metal M2, and when m equals 2, n equals valency of transition metal M2; p equals 1 or 2, when p equals 1, q equals half the valency of transition metal M, and when p equals 2, q equals valency of transition metal M; the catalyst also contains an auxiliary component, one or more of which are chosen from a group consisting of IVB group metals, group VIII base metals and rare-earth metals of the period table of elements; in terms of catalyst mass, the said catalyst contains 1 to 60 wt % zeolite, 0.1 to 10 wt % auxiliary component of the catalyst, 5 to 98 wt % heat resistant inorganic oxide and 0 to 70 wt % clay in form of oxides. The method of preparing the catalyst involves mixture and suspension of all or part of the heat resistant inorganic oxide and/or its precursor, water and optionally clay, addition of zeolite and drying the obtained suspension, addition of auxiliary compound before addition of zeolite and before or after addition of clay, addition of acid to establish pH of the suspension equal to 1 to 5, ageing at 30 to 90°C for 0.1 to 10 hours and addition of the remaining heat resistant inorganic oxide and/or its precursor after ageing.

EFFECT: obtained catalyst has high activity and stability and is highly capable of converting petroleum hydrocarbons with high output of propylene, ethylene and lower aromatic hydrocarbons.

20 cl, 24 ex, 5 tbl

 

The technical field

The present invention relates to a catalyst for the conversion of hydrocarbons containing zeolites, the method of its preparation and method of conversion of hydrocarbon oil on the catalyst, more specifically it relates to a zeolite catalyst conversion of hydrocarbons, the method of its preparation and method of conversion of the hydrocarbon oil in the presence of this catalyst.

The level of technology

The lower olefins such as ethylene and propylene, and lower aromatic compounds are valuable raw materials for the petrochemical industry, and the demand for them is increasing day by day. In prior art the old, proven methods for producing ethylene and propylene include methods of thermal conversion of hydrocarbons, for example the methods of thermal cracking of light hydrocarbons with steam in a tubular furnace. When the catalytic cracking or catalytic pyrolysis of heavy hydrocarbons receive a certain amount of ethylene and propylene. In addition, known methods for producing ethylene and propylene from registertimer hydrocarbons by catalytic conversion in the presence of zeolite catalysts. Aromatic compounds receive mainly by the catalytic reforming of distilled gasoline.

Kata is isatori obtain lower olefins from petroleum hydrocarbons by catalytic cracking or pyrolysis can be divided roughly into three classes. One includes catalysts supported on oxides, which can be a SiO2, Al2About3or other oxides and metals that are selected from elements of groups IIB, VB, VIIB and VIII (US 3541179, US 3647682, DD 225135 and SU 1214726). In the course of the cracking process in parallel with the dehydrating activity of deposited metals flow through the condensation reaction and supervivencia. Therefore, this type of catalysts can be used only for processing of a light feedstock with a boiling point below 220°C.

The second class of catalysts is a composite oxides, such as composite, containing mainly ZrO2and/or HfO2and also Al2About3, CR2O3, IGOs, and/or Fe2About3and oxides of alkali or alkaline earth metals (US 3725495 and US 3839485). Other examples are potassium Vanadate, stannate potassium or niobate potassium, which when cracking gasoline give 56 wt.% lower olefins, and the yield of ethylene can reach up to 36.5 wt.% and the yield of propylene can make up 12.5 wt.% (SU 523133, SU 487927 and SU 410037). Another example is the catalyst SiO2·Al2O3containing small amounts of Fe2O3, TiO2, CaO, MgO, Na2O and/or K2Oh, used for cracking of various hydrocarbon fractions (SU 550173, SU 559946). The most commonly used oxide composite is amorphous SiO2·A 2About3(DD 152356).

In addition to extensive use of zeolites in various fields of petrochemical and refining industries, they form a third class of catalysts, i.e. catalysts containing zeolites, particularly catalysts containing zeolites with MFI structure (high-silica zeolites with channels formed five-membered rings).

Patent US 3758403 discloses a method of catalytic cracking of hydrocarbons, which consists in the fact that the hydrocarbon feedstock is brought into contact with the catalyst in the cracking conditions. The specified catalyst contains a mixture of ZSM-5 and zeolite with pore size of more than 0.7 nm. This method increases the octane number of gasoline by increasing the output of olefins, C3=-C4=.

Patent CN 1042201C discloses a cracking catalyst to enhance the yield of udefineu3-C5that contains 10-50% of zeolite Y with dimensions of the unit cell, smaller or equal to 2,450 nm, 2-40% ZSM-5 and zeolite β, modified element selected from P, RE, Sa, SB, N, Al, etc. and their mixtures, and 20-80% semi-synthetic medium consisting of kaolin and a binder of aluminum oxide. This catalyst can increase the yield of ethylene and propylene and to provide a high output gasoline.

Patent CN 1055301C discloses a catalyst for Kraken is to increase the output of isoolefine and gasoline, which contains 5-70% composite binder based on aluminium oxide, 5-65% clay and 23-50% of zeolite. The specified zeolite is a mixture of 15-82% zeolite Y and the rest of the high-silica zeolite containing rare earth element, with channels formed five-membered rings, and/or zeolite HZSM-5 containing 0-10 wt.% phosphorus (as P2O5). In the case when both are high-silica zeolite containing rare earth element, with channels formed five-membered rings, and/or zeolite HZSM-5, the content of the high-silica zeolite containing rare earth element, with channels formed five-membered rings, does not exceed 65%. This catalyst is used mainly to enhance the yield of isoolefine and gasoline.

Patent CN 1102634C discloses a catalyst obtain lower olefins by catalytic pyrolysis, comprising 10-70% clay, 5-85% of a heat-resistant inorganic oxide, 1-50% of zeolite, and the zeolite contains 0-25% zeolite Y, and 75-100% high-silica zeolite with channels formed five-membered rings containing phosphorus and aluminum or magnesium or calcium. This high-silica zeolite is a ZSM-5, -8, or -11, containing 2-8% of phosphorus and 0.3-3% aluminum or magnesium or calcium (in the form of oxide) and having a ratio of the oxides of silicon and aluminum, equal 15-60. This catalyst in the foundations of the om is used to produce ethylene by catalytic pyrolysis.

Patent CN 1317543A discloses a method of producing ethylene and propylene by catalytic pyrolysis of hydrocarbons, which comprises contacting a preheated heavy hydrocarbon oil with a catalyst containing ZSM-5 in a reactor in the presence of high-temperature water vapor at the reaction temperature of 650-750°C, the pressure of the reaction of 1.5-4×105PA, the reaction time of 0.2 to 5 s, the mass ratio of the catalyst/oil 15-40:1 and the mass ratio of steam/oil feedstock 0.3 to 1:1 for carrying out catalytic pyrolysis. The specified zeolite ZSM-5 contains 0.1 to 8 wt.% Hell or si.

Patent US 5006497 discloses a catalyst of several zeolites containing: (1) at least one broad porous zeolite; (2) the zeolite that is selective in the form of molecules of hydrocarbons, with an index of permeability 1-12, substantially not containing components for hydrogenation/dehydrogenation and with activity in the cracking/isomerization; (3) the zeolite that is selective for the shape of the molecule, with an index of permeability 1-12 and activity in the aromatization of paraffins and (4) matrix. These chiropractie molecular sieves are selected from conventional macroporous zeolites of type a zeolite L, zeolite X and zeolite Y. the Specified selective form molecules zeolite with an index of permeability 1-12 selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-48, ZSM-57 and ZSM-5 containing boron, gallium, circus of the deposits and titanium. This catalyst can increase the octane number and the output of gasoline.

Patent US 5236880 discloses a zeolite catalyst for increased conversion of hydrocarbons containing crystalline aluminosilicate with the ratio of SiO2/Al2About3greater than 5 and preferably with the structure of the MFI or MEL. The zeolite contains a metal of group VIIIB, preferably Nickel. The catalyst can be used in the conversion process of the paraffin feedstock for increased activity in the cracking of paraffins, increasing the yield of aromatic fraction in product5-C12gasoline fraction, increasing the calculated octane number products5-C12gasoline fraction and/or enhance the yield of products5-C12gasoline fraction.

Patent CN 1048428C discloses a catalyst containing several zeolites, to obtain lower olefins, which consists of 0-70 wt.% clay, 5-90 wt.% heat-resistant inorganic oxide and 10-35% of zeolite, which comprises 20-75 wt.% the high-silica zeolite with channels formed five-membered rings and containing phosphorus and rare earth element, 20-75 wt. the high-silica zeolite Y, and 1-25 wt.% zeolite Y containing a rare earth element. This catalyst is used mainly to enhance the yield of isobutene and isopentene.

Patent CN 1053918C discloses a catalyst and the two zeolites to obtain lower olefins, which consists of 0-70 wt.% clay, 5-90 wt.% heat-resistant inorganic oxide and 10-40% of a zeolite, which comprises 25-75 wt.% the high-silica zeolite with channels formed five-membered rings and containing phosphorus and rare earth element, 25-75 wt. the high-silica zeolite Y or zeolite Y containing a rare earth element. This catalyst is used mainly to enhance the yield of propylene, isobutene and isopentene.

CN 1043502C discloses a cracking catalyst in which the carrier is a 0-70 wt.% clay and 5-9 wt.% heat-resistant inorganic oxide, and the active component is a mixture of ZSM-5 and zeolite type Y in the amount of 1-50 wt.%. In the active component ZSM-5 is 75-100 wt.% and zeolite Y is 0-25 wt.%. This catalyst is used to obtain lower olefins, especially propylene and butene, and also production of gasoline and diesel fuel.

CN 1034223C discloses a cracking catalyst, which consists of 0-70% clay, 5-99% heat-resistant inorganic oxide and 1-50% of zeolite, and the zeolite is a mixture of 0-25 wt.% zeolite Y, rare earth element and 75-100 wt.% the high-silica zeolite with channels formed five-membered rings containing phosphorus and rare earth element. This catalyst is used to produce ethylene, propylene and butene, especially propyl is on and butene, and also get gasoline and diesel oil.

The invention

The aim of the present invention is to provide a catalyst active in the conversion of petroleum hydrocarbons in high yields of propylene, ethylene and light aromatic compounds, and method of preparation of the catalyst. Another objective of the present invention is to develop a method of catalytic conversion of hydrocarbon oil products.

The catalyst proposed in the present invention, contains a zeolite, a heat-resistant inorganic oxide and optionally a clay, and the specified zeolite is a zeolite with MFI structure containing phosphorus and transition metals, together with macroporous zeolite that contains, based on the weight of 75-100 wt.% the specified zeolite with MFI structure containing phosphorus and transition metals, and 0-25 wt.% macroporous zeolite. In the calculation of the mass of oxide specified zeolite with MFI structure containing phosphorus and transition metals, has the following chemical formula without water:

or

in which M1 represents a transition metal selected from Zn, Mn, Ga and Sn, M is a transition metal chosen from Fe, Co, Ni, Cu, Zn, Mo or Mn, and RE represents a rare earth metal; x is 1 or 2 when x is 1, the value of y which is half the valence of the transition metal M1, and when x is 2, the value is equal to the valence of the transition metal M1; m is 1 or 2, when m is equal to 1, the value of n is half the valency of the transition metal M2, and when m is 2, the value of n is equal to the valence of the transition metal M2; p is 1 or 2, when p is 1, q is half the valency of the transition metal M, and when p is 2, the value of q coincides with the valence of the transition metal M. the Catalyst also contains an auxiliary component which is one or more selected from the group consisting of alkaline earth metals, metals of group IVB metals, base metals of VIII group metals and rare earth metals of the Periodic table of elements. The specified catalyst contains, based on the weight of the catalyst, 1-60 wt.% zeolite, 0.1 to 10 wt.% a supporting component of the catalyst, 5-98 wt.% heat-resistant inorganic oxide and 0-70 wt.% clay in the form of oxides.

Proposed in the present invention a method for converting hydrocarbon oil comprises contacting the hydrocarbon oil with a catalyst, which is carried out in an atmosphere of water vapor, and conditions specified contact includes contact temperature 450-750°C, the mass ratio of the catalyst/oil, equal 4-40, and the amount of steam equal 1-100 wt.% from the hydrocarbon oil. The specified catalyst and is is raised above the catalyst according to the present invention.

Proposed in the present invention, the method of preparation of the catalyst includes mixing and suspension of all or part of the heat-resistant inorganic oxide and/or its predecessor, water and optionally a clay, the addition of zeolite, drying the resulting suspension and then the annealing, and the auxiliary component is also added prior to the introduction of zeolite and before or after the introduction of clay, add the acid and bring the pH of the suspension to 1-5, aging at a temperature of 30-90°C for 0.1 to 10 hours and add the rest of the heat-resistant inorganic oxide and/or its predecessor after aging. The specified zeolite is a zeolite with MFI structure containing phosphorus and transition metals, or a mixture of the specified zeolite with MFI structure containing phosphorus and transition metals, with macroporous zeolite that contains, based on the weight of the mixture 75-100 wt.% the specified zeolite with MFI structure containing phosphorus and transition metals, and 0-25 wt.% macroporous zeolite. In the calculation of the mass of oxide specified zeolite with MFI structure containing phosphorus and transition metals, has the following chemical formula without water:

or

in which M1 represents a transition metal selected from Fe, Co and Ni, M2 is a transition metal is llom, which are selected from Zn, Mn, Ga and Sn, M is a transition metal chosen from Fe, Co, Ni, Cu, Zn, Mo or Mn, and RE represents a rare earth metal; x is 1 or 2 when x is 1, then the value of y is half of the valency of the transition metal M1, and when x is 2, the value is equal to the valence of the transition metal M1; m is 1 or 2, when m is equal to 1, the value of n is half the valency of the transition metal M2, and when m is 2 the value of n is equal to the valence of the transition metal M2; p is 1 or 2, when p is 1, q is half the valency of the transition metal M, and when p is 2, the value of q coincides with the valence of the transition metal m of these quantities components receive a final catalyst containing the calculation for the weight of the catalyst, 1-60 wt.% zeolite, 0.1 to 10 wt.% a supporting component of the catalyst, 5-98 wt.% heat-resistant inorganic oxide and 0-70 wt.% clay in the form of oxides.

The catalyst proposed in this invention has very good activity and stability and exhibits high ability to convert the hydrocarbon oil with high yields in propylene, ethylene and lower aromatic hydrocarbons, since the catalyst proposed in this invention contains the modified zeolite with MFI structure containing phosphorus and transition metals, or a mixture of zeolite with the MFI structure and macroporous zeolite as an active component, and also includes an auxiliary component of the catalyst as a modifying component.

Disclosure of inventions

The catalyst proposed in the present invention, includes in the calculation for the weight of the catalyst, 1-60 wt.% zeolite, 0.1 to 10 wt.% an auxiliary component, 5-9 wt.% heat-resistant inorganic oxide and 0-70 wt.% the clay. Preferably, the specified catalyst contained 10-50 wt.% zeolite, 0.5 to 8 wt.% an auxiliary component, 10-70 wt.% heat-resistant inorganic oxide and 0-60 wt.% the clay.

Preferably, the calculation of the mass of oxides specified zeolite with MFI structure containing phosphorus and transition metals, had the following chemical formula without water:

or

Preferably, M1 consisted of Fe and M2 represented Zn, and more preferably, M1 consisted of Fe and M2 simultaneously represented Zn. Preferably, M is selected from Fe, Co or Ni.

Specified rare earth metal (RE) preferably represents lanthanum, cerium, or a mixture of rare earth metals containing lanthanum and/or cerium.

These one or more auxiliary components of the catalyst is preferably selected from the group consisting of barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt and Nickel. The specified auxiliary component of the catalyst can the congregation is the substance or in the form of oxides or salts of these metals or in the form of more complex compounds, obtained by the reaction with heat-resistant inorganic oxide and/or clay. The specified auxiliary component of the catalyst may be dispersed in a heat-resistant inorganic oxide or clay or a mixture of oxide and clay.

Specified macroporous zeolite is one or more porous zeolites with a pore size of more than 0.7 nm, for example pajazit, zeolite L, zeolite β, zeolite Ω, mordenite and ZSM-18, especially one or more zeolites, which are selected from zeolite Y, zeolite Y containing phosphorus and/or rare earth element, ultrastable (with respect zeolite Y and zeolite ultrastable (with respect to Y containing phosphorus and/or rare earth element, and zeolite β.

Specified heat-resistant inorganic oxide selected from one or more heat-resistant inorganic oxides used as the matrix and binder component in cracking catalysts, such as aluminum oxide, silicon, and amorphous aluminosilicates. Such heat-resistant inorganic oxides known to specialists in this field.

Found a clay selected from one or more of the clays used as a carrier in cracking catalysts, such as kaolin, halloysite, montmorillonite, diatomaceous earth, Angelica, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. The preferred clay is one or Bo is her clays of kaolin, halloysite and montmorillonite. These clays known in the art.

According to the method of preparation of the catalyst of the present invention, all or part of the heat-resistant inorganic oxide and/or its precursor can be added to the aging stage. To obtain a catalyst with high resistance to abrasion, it is preferable to add a heat-resistant inorganic oxide and/or its predecessor to the stage of aging and after aging to add the rest of the heat-resistant inorganic oxide and/or its predecessor. Pre-added part and the part added later, should be in such a mass ratio to the mass content previously added heat-resistant inorganic oxide and then entered a heat-resistant inorganic oxide in the catalyst was 1:0.1 to 10, more preferably 1:0.1 to 5.

Specified clay can be added both before and after aging, and the implementation of the specified clay does not affect the catalyst activity.

The above acid is one or more selected from water-soluble inorganic or organic acids and the preferred acid is one or more acids from hydrochloric, nitric, phosphoric and carboxylic acids with 1 to 10 carbon atoms. Acid take in such quantity that the pH value of suspense and was 1-5, preferably 1.5 to 4.

The specified temperature aging is 30-90°C., preferably 40-80°C., and the aging time of 0.1-10 h, preferably 0.5 to 8 hours.

The specified predecessor heat-resistant inorganic oxide is one or more substances which are capable of forming a specified heat-resistant inorganic oxide during the preparation of the specified catalyst. For example, the precursor of aluminium oxide can be selected from hydrated aluminum oxide and/or Sol of aluminum oxide, and one or more of these hydrated oxides of aluminum selected from boehmite, pseudoboehmite, three-hydrate of aluminum oxide and amorphous aluminum hydroxide. The precursor of silicon oxide, one or more, you can choose from Zola silicon oxide, silica and soluble glass. The precursor of amorphous silicate, one or more, you can choose from Zola aluminosilicate, and mixtures Zola silicon oxide and a Sol of aluminum oxide and aluminosilicate gel. These predecessors heat-resistant inorganic oxide is known to experts.

The specified auxiliary compound selected from one or more water-soluble or not soluble in water, compounds of alkaline earth metals, metals of group IVB metals, base metals of VIII group metals and rare earth metals, especially one or more moderator is activated or not soluble in water compounds barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt and Nickel, for example the halides, nitrates, sulfates and phosphates of barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt and Nickel. Among these chlorides of barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt and Nickel are preferred chlorides of barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt and Nickel.

The various components take in such quantities that the final catalyst contained 1-60 wt.% zeolite, 0.1 to 10 wt.% a supporting component of the catalyst, 5-98 wt.% heat-resistant inorganic oxide and 0-70 wt.% clay based on the weight of the catalyst. It is preferable to take the various components in such amounts that the final catalyst contained 10-50 wt.% zeolite, 0.5 to 8 wt.% a supporting component of the catalyst, 10-70 wt.% heat-resistant inorganic oxide and 0-60 wt.% clay based on the weight of the catalyst.

Method and drying conditions of the suspension. For example, the method of drying may be an air drying, calcining, drying in a stream of air or spray drying, preferably spray drying, and the drying temperature may be from room temperature up to 400°C, preferably 100-350°C. To facilitate spray drying the solids in the society in suspension before drying should preferably be 10 to 50 wt.%, more preferably 20-50 wt.%.

The calcination conditions specified suspension after drying, also known in the art. Generally speaking, the temperature of calcination of the specified suspension after drying is 400-700°C, preferably 450-650°C, and the annealing is at least 0.5 hours, preferably 0.5 to 100 hours and more preferably 0.5 to 10 hours.

The method of obtaining the specified zeolite with MFI structure containing phosphorus and transition metals, includes the introduction of phosphorus and of these transition metals in the zeolite with the MFI structure, whether or not containing rare earth.

Ways of introducing phosphorus and transition metals in the zeolite with the MFI structure, whether or not containing rare earth, can be different, for example, can be added during synthesis of the zeolite with the MFI structure, whether or not containing rare earth, or by means of impregnation, mixing and/or ion exchange. These methods of introducing phosphorus and transition metals in the zeolite with the MFI structure, whether or not containing rare earth, known to specialists in this field.

For example, the zeolite of the formula (I) with the MFI structure, containing phosphorus and transition metals can be prepared in the following way: the zeolite in the sodium form, containing or not containing rare earth obtained by conventional crystallization, to exchange with the rod zeolite/ammonium salt/N 2On with the mass ratio of 1:(0.1 to 1):(5-10) at a temperature of from room temperature to 100°C for 0.3 to 1 hour and then filtered zeolite with the exchange of ammonium ions. Then enter impregnation or ion exchange compound of phosphorus, which is chosen from compounds of Fe, Co and Ni, and a compound selected from compounds of Zn, Mn, Ga and Sn, and then dried and calcined in air or in an atmosphere of steam at 400-800°C for 0.5-8 hours.

If the zeolite with MFI structure in the sodium form contains organic template, the above operation should be performed after removal of the template, and found ammonium salt can be selected from commonly used inorganic ammonium salts such as ammonium chloride, ammonium sulfate and ammonium nitrate, or mixtures thereof.

The above impregnation or ion exchange can be one of the following methods.

Method 1: obtained on the filter zeolite with the exchange of ammonium ions and an aqueous solution of the phosphorus compounds is stirred until a homogeneous mixture at a temperature of from room temperature to 95°C, then dried, and optionally calcined at 400-800°C. the Obtained solid is uniformly mixed with the mixed aqueous solution of a compound of one of the metals Fe, Co and Ni and compounds of one of the metals Zn, Mn, Ga and Sn at a temperature from room temperature to 95 is, then dried and optionally calcined. Two stages of mixing may be reversed.

Method 2: obtained on the filter zeolite with the exchange of ammonium ions and an aqueous solution of the phosphorus compounds is stirred until a homogeneous mixture at a temperature of from room temperature to 95°C, then dried, and optionally calcined at 400-800°C. the Obtained solid is uniformly mixed with an aqueous solution of a compound of one of the metals Zn, Mn, Ga and Sn at a temperature from room temperature to 95°C, then dried and optionally calcined. The sequence of the three stages of mixing can be arbitrary.

Method 3: the filter cake zeolite with the exchange of ammonium ions is stirred until a homogeneous mixture with a mixed aqueous solution of phosphorus compounds, the compounds of one of the metals Fe, Co and Ni and compounds of one of the metals Zn, Mn, Ga and Sn at a temperature from room temperature to 95°C, then dried and optionally calcined.

Method 4: the filter cake zeolite with the exchange of ammonium ions is mixed with a water solution of phosphorus compounds until a homogeneous mixture at a temperature of from room temperature to 95°C, then dried, and optionally calcined at 400-800°C. the Obtained solid is uniformly mixed is with an aqueous solution of a compound of one of the metals Fe, Co and Ni and compounds of one of the metals Zn, Mn, Ga and Sn - ratio solid/liquid 1:5-20, and then exchanged at a temperature of 80-95°C and pH 4-7 2-3 hour with stirring, filtered, dried and optionally calcined. The specified ion exchange can be repeated several times.

The zeolite of the formula (II) with the MFI structure, containing phosphorus and the transition metal can be prepared in the following way: zeolite with MFI structure, whether or not containing rare earth, and an aqueous solution of the phosphorus compounds uniformly mixed at a temperature of from room temperature to 95°C, then dried and calcined at 400-800°C. the Obtained solid is uniformly mixed with an aqueous solution of the compound of the transition metal M at a temperature of from room temperature to 95°C, then dried. Alternative zeolite with MFI structure, whether or not containing rare earth uniformly mixed with an aqueous solution of the compound of the transition metal M at a temperature of from room temperature to 95°C and then dried. The obtained solid is uniformly mixed with an aqueous solution of phosphorus compounds at a temperature of from room temperature to 95°C and then dried. Alternative zeolite with MFI structure, whether or not containing rare earth uniformly mixed with the mixed aqueous solution of compounds perehodnik the metal M and phosphorus compounds at a temperature from room temperature up to 95°C and then dried. Alternative zeolite with MFI structure, whether or not containing rare earth uniformly mixed with an aqueous solution of phosphorus compounds at a temperature from room temperature up to 95°C, then dried and calcined at 400-800°C. the Obtained solid is uniformly mixed with an aqueous solution of the compound of the transition metal M with a ratio of solid/liquid 1:5-20, and then exchanged at least once at a temperature of 80-95°C and pH 4-7 2-3 hours with stirring, then filtered and dried.

Specified one or more phosphorus compounds selected from water-soluble compounds of phosphorus, preferably phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrophosphate and ammonium phosphate.

These compounds Fe, Co and Ni, and Zn, Mn, Ga and Sn are selected from their water-soluble salts, such as sulphates, nitrates and chlorides. The connection specified transition metal M selected from the water-soluble salts, for example one or more of chlorides, nitrates, sulfates or carbonates. Preferably, when the specified one or more compound of the transition metal M selected from the group consisting of sulphate of iron(III)sulfate iron(II)nitrate iron(III), iron chloride(III), iron chloride(II), cobalt sulfate, cobalt nitrate, cobalt chloride, Nickel sulfate, Nickel nitrate and Nickel chloride.

Ways the specified drying after impregnation or ion exchange can be any method of drying, for example, air drying, calcination, etc. drying Temperature may be from room temperature to 400°C., preferably 100-200°C. the Temperature of annealing after drying is a traditional temperature calcination, usually 400-800°C, preferably 450-700°C.

The various components should be taken in such quantities as to be sure that the composition of the obtained zeolite with MFI structure containing phosphorus and transition metals, corresponds to the chemical formula of the zeolite without water. If the sodium content in it does not meet the specified requirements, the sodium can be removed by washing or by exchange with ammonium ions. The removal of sodium by washing or by exchange with ammonium ions known to specialists in this field.

The method of converting hydrocarbon oil proposed in the present invention can be carried out in different reactors, for example in a column, fluidized bed reactor, a reactor with a fixed bed or in a reactor with a moving bed.

These contact conditions include the temperature of the contact 450-750°C, the mass ratio of the catalyst/oil 4-40 and water vapor in the amount of 1-100 wt.% from the feed oil. Preferably, these contact conditions included a contact temperature of 500-700°C, the mass ratio of the catalyst/oil -30 and water vapor in the amount of 10-90 wt.% from the feed oil.

For fluidized bed reactor, a reactor with a fixed bed or reactor with a moving bed these contact conditions also include a mass hourly space velocity of 5-30 h-1preferably 5-25 h-1. For a reactor column type specified contact conditions also include the reaction time is 0.1 to 5.0, preferably from 0.2 to 3.5 C.

The catalyst proposed in the present invention can be used in the technology of catalytic cracking or catalytic pyrolysis to obtain lower olefins and enhance the yield of lower olefins, especially increasing the yield of propylene and ethylene, and at the same time improve the lower content of aromatic compounds in gasoline. This catalyst can also be used in completely new technologies from the conversion of hydrocarbons to catalytic conversion of heavy petroleum fractions into lower olefins, especially propylene and ethylene, and lower aromatic compounds.

The way of transformation of a hydrocarbon oil, in the present invention, provides the ability to catalytically convert the hydrocarbon oil into lower olefins, especially propylene and ethylene, and at the same time to increase the lower content of aromatic compounds in gasoline or receive lower olefins, especially propylene and ethylene, and lower aromatic compounds is of. Specified one or more hydrocarbon oil selected from the group consisting of crude oil and its various fractions, especially oil and fractions with boiling points higher than 330°C., for example oil atmospheric distillation of crude oil, fuel oil, vacuum distillation, vacuum gas oil, atmospheric gas oil, gas oil straight race, deasphalting oil and gas oil coking.

The following examples provide further description of the present invention, but not limit the present invention.

Examples 1-8 illustrate the zeolites of formula (I) with the MFI structure, containing phosphorus and transition metals, and methods for their preparation.

Examples 1'-8' illustrate the zeolites of the formula (II) with the MFI structure, containing phosphorus and the transition metal, and methods for their preparation.

Example 1

2 kg of NH4Cl was dissolved in 100 kg of water and to the solution was added 10 kg (dry basis) of the zeolite ZRP-1 zeolite with MFI structure containing rare earth obtained from The Zhoucun Catalyst Plant, Qilu Petrochemical Co., with a molar ratio of SiO2/Al2O3equal to 30, the content of oxides of the rare earths RE2O3equal to 4.0 wt.%, in which the content of the oxide of lanthanum was 2.1 wt.%, cerium oxide of 0.52 wt.% and other rare earth oxides of 1.36 wt.%, and the content of Na2O 1.7 wt.%), spent ion exchange at 90°C for 0.5 hour and then filtered. Otherthrow the hydrated precipitate uniformly mixed with 9.8 kg of a mixed solution, containing 0,34 kg N3RHO4, 0,29 kg Fe(NO3)3and 1.5 kg of Zn(NO3)2was dried at 120°C, probalily at 550°C for 2 hours and got zeolite Z1 with the MFI structure, containing phosphorus and metals such as iron and zinc. Chemical formula Z1 without water: 0,1Na2O·4,9l2O3·2,4R2O5·0,9F2About3·0,6ZnO·3,8R2O3·87,3SiO2. Chemical formula without water zeolite with MFI structure containing phosphorus and metals such as iron and zinc, obtained by determining the elemental composition of the zeolite by x-ray fluorescence spectroscopy with the following calculation.

Example 2

5 kg NH4Cl was dissolved in 100 kg of water and added to 10 kg (dry basis) of the zeolite ZRP-1 (the same as in example 1), spent ion exchange at 85°C for 0.5 hour and then filtered. The filter cake is evenly mixed with 6.8 kg of a solution containing 0.8 kg NH4H2RHO4was dried at 120°C and probalily at 550°C for 2 hours. Spent ion exchange of the calcined sample is mixed with a solution of 6.5 wt.% Fl3and 4.7 wt.% ZnCl2when the ratio of liquid/solid 5:1 at 80-90°C for 2 h, then was filtered and the spent ion exchange in the same conditions until the desired amount of substance, dried at 120°C, again probalily at 550°C for 2 hours and got zeolite Z2 with what ructural MFI, containing phosphorus and metals such as iron and zinc. Chemical formula Z2 without water: 0,3Na2O·4,7Al2O3·4,5P2O5·1,6F2O3·1,4ZnO·3,7R2O3·84,1SiO2.

Example 3

2 kg of NH4Cl was dissolved in 100 kg of water and to the solution was added 10 kg (dry basis) of the zeolite ZRP-5 (zeolite with MFI structure, obtained from The Zhoucun Catalyst Plant, Qilu Petrochemical Co., with a molar ratio of SiO2/Al2O360), spent ion exchange at 90°C for 0.5 h and was filtered. The filter cake is evenly mixed with 6,7 kg of a solution containing 0,69 kg NH4H2PO4and dried at 120°C. Then the dried sample was evenly mixed with 11.3 kg of a solution containing 2.26 kg FeSO4was dried at 120°C and probalily at 550°C for 2 hours. The calcined sample was evenly mixed with 9.5 kg of a solution containing 0,47 kg ZnSO4was dried at 120°C, probalily at 550°C for 2 hours and got zeolite Z3 with the MFI structure, containing phosphorus and metals such as iron and zinc. Chemical formula Z3 without water: 0,1Na2O·2,3Al2About3·3,6P2O5·10,0Fe2O3·2,0ZnO·82,0SiO2.

Example 4

8 kg NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-5 (the same as in example 3), spent ion exchange at 85°C for 0.5 hour and then was filtered. Otfit is consistent precipitate uniformly mixed with 6,7 kg of solution, containing 0,69 kg NH4H2PO4and dried at 120°C. the Dried sample was evenly mixed with 9.7 kg of a solution containing 0.49 kg Fe(NO3)3and 0.24 kg MP(NO3)2was dried at 120°C, probalily at 600°C for 2 hours and got zeolite Z4 with the MFI structure, containing phosphorus and metals - iron and manganese. Chemical formula Z4 without water: 0,1Na2O·2,6l2O3·4,0 P2About5·1,5F2O3·1,1MP2About3·90,7SiO2.

Example 5

8 kg NH4Cl was dissolved in 100 kg of water and to this solution was added 10 kg (dry basis) of the zeolite ZRP-5 (zeolite with MFI structure, obtained from The Zhoucun Catalyst Plant, Qilu Petrochemical Co., with a molar ratio of SiO2/Al2About3equal to 70), spent ion exchange at 85°C for 0.5 hour and then was filtered. The filter cake is evenly mixed with 6.3 kg of a solution containing 0.26 kg NH4H2PO4and dried at 120°C. the Dried sample was evenly mixed with 10.1 kg of a solution containing 0.8 to 2 kg (NO3)2and 0.24 kg MP(NO3)2was dried at 120°C, probalily at 600°C for 2 hours and got zeolite Z5 with the MFI structure, containing phosphorus and the metals cobalt and manganese. Chemical formula Z5 without water: 0,1Na2O·2,2Al2O3·1,5P2O5·3,so2O3·1,1MP2O3·91,6SiO2.

Primer

8 kg NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-5 (the same as in example 3), spent ion exchange at 85°C for 0.5 hour and then was filtered. The filter cake is evenly mixed with 6,7 kg of a solution containing 0.70 kg (NH4)2HPO4, and was dried at 120°C. the Dried sample was evenly mixed with 9.7 kg of a solution containing 0,52 kg Ni(NO3)2and 0.22 kg MP(NO3)2was dried at 120°C, probalily at 600°C for 2 hours and got zeolite Z6 with the MFI structure, containing phosphorus and metals - Nickel, and manganese. Chemical formula Z6 without water: 0,1Na2O·2,6Al2O3·3,5P2O5·2,0NiO·1,0Mn2O3·90,8SiO2.

Example 7

8 kg NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-1 (the same as in example 1), spent ion exchange at 85°C for 0.5 h and was filtered. The filter cake is evenly mixed with 6.5 kg of a solution containing 0,47 kg (NH4)2NRA4, and was dried at 120°C. the Dried sample was evenly mixed with 9.8 kg of a solution containing 0,51 kg Fe(NO3)3and 0.32 kg GA(NO3)3was dried at 120°C, probalily at 600°C for 2 hours and got zeolite Z7 with the MFI structure, containing phosphorus and metals - iron and gallium. Chemical formula Z7 excluding the odes: 0,1Na 2O·4,9l2O3·2,4R2O5·1,6F2O3·1,1G2O3·3,8R2O3·86,1SiO2.

Example 8

8 kg NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-5 (the same as in example 3), spent ion exchange at 85°C for 0.5 h and was filtered. The filter cake is evenly mixed with 7.0 kg of a solution containing 0,95 kg NH4H2PO4and dried at 120°C. the Dried sample was evenly mixed with 9.5 kg of a solution containing 0.35 kg Fl3and 0.14 kg SnCl2was dried at 120°C, probalily at 600°C for 2 hours and got zeolite Z8 with the MFI structure, containing phosphorus and metals - iron and tin. Chemical formula Z8 without water: 0,07Na2O·2,5Al2O3·5,4P2O5·1,6Fe2O3·1,0SnO2·89,4SiO2.

Example 1'

2 kg of NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-1 (the same as in example 1), spent ion exchange at 90°C for 0.5 h and was filtered. 9,88 kg of a mixed solution containing 0,34 kg N3RHO4, 0.48 kg Fe(NO3)3uniformly mixed with the filtered precipitate was dried at 120°C, probalily at 550°C for 2 hours and got zeolite Z1' with the MFI structure, containing phosphorus and metal - iron. Chemical formula Z1' without water: 0,1Nasub> 2O·4,9Al2O3·2,4P2O5·1,5Fe2O3·3,8RE2O3·87,3SiO2.

Example 2'

5 kg NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-1 (the same as in example 1), spent ion exchange at 85°C for 0.5 h and was filtered. The filter cake is evenly mixed with 6.8 kg of a solution containing 0.8 kg NH4H2PO4was dried at 120°C and probalily at 550°C for 2 hours. With the calcined sample of spent ion exchange with 5 wt.% a solution of Fe(NO3)3when the ratio of liquid/solid 5:1 at 80-90°C for 2 h, then was filtered, spent ion exchange in the same conditions until the desired amount of iron in the sample was dried at 120°C, again probalily at 550°C for 2 hours and got zeolite Z2' with the MFI structure, containing phosphorus and metal - iron. Chemical formula Z2' without water: 0,03Na2O·4,7Al2O3·4,5P2O5·3,0Fe2O3·3,7RE2O3·84,1SiO2.

Example 3'

2 kg of NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-5 (the same as in example 3), spent ion exchange at 90°C for 0.5 h and was filtered. The filter cake is evenly mixed with 12.8 kg of a solution containing 0.32 kg N3RHO4and 3,42 kg Fe(NO3)3th is was made at 120°C, he probalily at 550°C for 2 hours and got zeolite Z3' with the MFI structure, containing phosphorus and metal - iron. Chemical formula Z3' without water: 0,1Na2O·2,4Al2O3·2,0P2O5·10Fe2O3·85,5SiO2.

Example 4'

8 kg NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-5 (the same as in example 3), spent ion exchange at 85°C for 0.5 h and was filtered. The filter cake is evenly mixed from 6.89 kg of a solution containing 0.89 kg NH4H2PO4and dried at 120°C. the Dried sample was evenly mixed with 9.52 kg of a solution containing 0.52kg FeSO4·6H2O, dried at 120°C, probalily at 600°C for 2 hours and got zeolite Z4' with the MFI structure, containing phosphorus and metal - iron. Chemical formula Z4' without water: 0,1Na2O·2,6l2About3·5,1R2O5·1,5Fe2O3·90,7SiO2.

Example 5'

8 kg NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-5 (the same as in example 5), spent ion exchange at 85°C for 0.5 h and was filtered. The filter cake is evenly mixed from 6.89 kg of a solution containing 0.89 kg NH4H2PO4and dried at 120°C. the Dried sample was evenly mixed with 9.35 kg of a solution containing 0.35 kg FeSO4·6H2O, who left the house taking at 120°C, he probalily at 600°C for 2 hours and got zeolite Z5' with the MFI structure, containing phosphorus and metal - iron. Chemical formula Z5' without water: 0,1Na2O·2,2Al2O3·5,1P2O5·1,0F2About3·91,6SiO2.

Example 6'

8 kg NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-5 (the same as in example 3), spent ion exchange at 85°C for 0.5 h and was filtered. The filter cake is evenly mixed with 6.9 kg of a solution containing 0.9 kg (NH4)2HPO4and was dried at 120°C. the Dried sample was evenly mixed with 9,83 kg of a solution containing 0.83 kg Ni(NO3)2·6N2O, dried at 120°C, probalily at 600°C for 2 hours and got zeolite Z6' with the MFI structure, containing phosphorus and metal is Nickel. Chemical formula Z6' without water: 0,1Na2O·2,6Al2O3·4,5P2O5·2,0NiO·90,8SiO2.

Example 7'

8 kg NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-1 (the same as in example 1), spent ion exchange at 85°C for 0.5 h and was filtered. The filter cake is evenly mixed from 6.84 kg of a solution containing 0,84 kg (NH4)2HPO4and dried at 120°C. the Dried sample was evenly mixed with 9,39 kg of a solution containing 0,39 kg Ni(NO3)2·6N2 O, dried at 120°C, probalily at 600°C for 2 hours and got zeolite Z7' with the MFI structure, containing phosphorus and metal is Nickel. Chemical formula Z7' without water: 0,1Na2O·4,9Al2O3·4,1P2O5·1,0NiO·3,8RE2O3, 86,1SiO2.

Example 8'

8 kg NH4Cl was dissolved in 100 kg of water and added to this solution 10 kg (dry basis) of the zeolite ZRP-5 (the same as in example 3), spent ion exchange at 85°C for 0.5 h and was filtered. The filter cake is evenly mixed from 6.89 kg of a solution containing 0.89 kg NH4H2PO4and dried at 120°C. the Dried sample was evenly mixed with 10,06 kg of a solution containing 1.06 kg FeSO4·6N2O, dried at 120°C, probalily at 600°C for 2 hours and got zeolite Z8' with the MFI structure, containing phosphorus and metal - iron. Chemical formula Z8' without water: 0,07Na2O·2,5Al2O3·5,0P2O5·3,0Fe2O3·89,4SiO2.

Example 9

This example illustrates the catalyst proposed by the present invention, and the method of its preparation.

0,34 kg VA(NO3)2dissolved in 18 kg decationizing water, added 4.2 kg halloysite (industrial product Suzhou Kaolin Co. with a solids content 71,6 wt.%) and mixed. To the resulting suspension was added 3.2 kg of pseudoboehmite (industrial product Shandong Alumina Plant is the solid content 62,0 wt.%) and established pH 2 using hydrochloric acid. The suspension was mixed until smooth and kept at 70°C for 1 hour for aging and then added 3.7 kg Zola aluminum oxide (the product of the Zhoucun Catalyst Plant, Qilu Petrochemical Co. with the content of Al2O3of 21.5 wt.%, moreover, before and after aging add such quantity of the precursor of the heat-resistant inorganic oxide, so that the ratio of the heat-resistant inorganic oxide before and after aging was 1:0,4). After uniform mixing added to 11.4 kg of a suspension obtained by suspendirovanie a mixture of 3.5 kg (dry basis) of the zeolite with the MFI structure, containing phosphorus and metals such as iron and zinc, zeolite Z1 obtained in example 1 and 0.5 kg (dry basis) of ultrastable (with respect zeolite Y (industrial brand DASY2.0, the product of the Zhoucun Catalyst Plant, Qilu Petrochemical Co. with cell size 2,446 nm and the content of oxides of the rare earths RE2O32.0 wt.%, moreover, the content of lanthanum oxide was 1.06 wt.%, cerium oxide 0.26 wt.% and other rare earth oxides of 0.68 wt.%) in water, evenly mixed and obtained a suspension with a solids content of 24.5 wt.%. The resulting suspension was spray dried and formed into particles with a diameter of 20-150 μm at 250°C, which was probalily at 550°C for 2 hours and got the catalyst C1, proposed in the present invention. The composition of C1 is given in table 1.

Example 10

This example illustrates a catalyst is, proposed in the present invention, and the method of its preparation.

The catalyst C2 was prepared according to the method of example 9 except that 0,34 kg VA(NO3)2replaced by 0.46 kg Ll3·7H2O and Z1 is replaced by an equal amount of zeolite with MFI structure containing phosphorus and metals such as iron and zinc, Z2, obtained in example 2. Composition C2 are given in table 1.

Example 11

This example illustrates the catalyst proposed in the present invention, and the method of its preparation.

Catalyst C3 was prepared according to the method of example 9 except that 0,34 kg VA(NO3)2replaced by 0.17 kg Ba(NO3)2and 0.34 kg Fl3·6N2O and Z1 is replaced by an equal amount of zeolite with MFI structure containing phosphorus and metals iron and gallium, Z7, obtained in example 7. Composition C3 are shown in table 1.

Example 9'

This example illustrates the catalyst proposed in the present invention, and the method of its preparation.

Catalyst C1' was prepared by the method of example 9 except that Z1 is replaced by an equal amount of zeolite with MFI structure containing phosphorus and metal - iron, Z1', obtained in example 1'. Composition C1' are shown in table 1.

Example 10'

This example illustrates the catalyst proposed in the present invention, and the method of its preparation.

Catalysators' was prepared by the method of example 10 except that Z2 is replaced by an equal amount of zeolite with MFI structure containing phosphorus and metal - iron, Z2', obtained in example 2'. Composition C2' are shown in table 1.

Example 11'

This example illustrates the catalyst proposed in the present invention, and the method of its preparation.

Catalyst C3' was prepared by the method of example 11 except that the Z7 was replaced by an equal amount of zeolite with MFI structure containing phosphorus and metal - Nickel, Z7', obtained in example 7'. Composition C3' are shown in table 1.

Comparative example 1

This comparative example illustrates the catalyst for comparison containing zeolite with MFI structure that does not contain phosphorus and transition metals, and the method of its preparation.

The catalyst comparison SW was prepared according to the method of example 9 except that the zeolite with MFI structure containing phosphorus and metals such as iron and zinc, Z1 obtained in example 1 was replaced by zeolite ZRP-1 (the same as in example 1). The composition SV are shown in table 1.

Comparative example 2

This comparative example illustrates the catalyst of comparison that does not contain an auxiliary component of the catalyst, and the method of its preparation.

The catalyst comparison SW was prepared according to the method of example 9 except that didn't add VA(NO3)2and the number of Zola alumina status is ulala 4,7 kg The composition SV are shown in table 1.

Comparative example 3

This comparative example illustrates the catalyst for comparison containing zeolite with MFI structure, not containing phosphor and transition metal and an auxiliary component of the catalyst, and the method of its preparation.

The catalyst comparison SW was prepared according to the method of example 9 except that didn't add VA(NO3)2the number Zola alumina was 4.7 kg and zeolite with MFI structure containing phosphorus and metals such as iron and zinc, obtained in example 1, Z1, substituted zeolite ZRP-1 (the same as in example 1). The composition SV are shown in table 1.

Table 1
Example No.Example 9Example 10Example 11Example 9'Example 10'Example 11'EUR. example 1EUR. example 2EUR. example 3
CatalystC1C2C3C1'C2'SVSVSV
The type of clayHalloysiteHalloysiteHalloysiteHalloysiteHalloysiteHalloysiteHalloysiteHalloysiteHalloysite
The clay content, wt.%303030303030303030
Type components. neorg. oxideAluminium oxideAluminium oxideAluminium oxideAluminium oxideAluminium oxideAluminium oxideAluminium oxideAluminium oxideAluminium oxide
The content of the heat-resistant neorg. oxide, wt.%2828282828283030
Type support. component catalystVALaFe + BaVALaFe + BaVA
The content of the support. component catalyst (oxide), wt.%2222222
The type of zeolite with MFI structureZ1Z2Z7Z1'Z2'Z7'ZRP-1Z1ZRP-1
The content of the zeolite with the MFI structure, wt.% 353535353535353535
Type macroporous zeoliteDASY2.0DASY2.0DASY2.0DASY2.0DASY2.0DASY2.0DASY2.0DASY2.0DASY2.0
The content of the macroporous zeolite, wt.%555555555

Example 12

This and the following examples illustrate the catalyst according to the present invention and the method of its preparation.

0,17 kg VA(NO3)2dissolved in 12.5 kg decationizing water, to which was added 4.0 kg of pseudoboehmite (same as in example 9), and established pH 2 with nitric acid.

The resulting suspension was evenly mixed, held at 50°C for 5 hours for aging, and is Lucile aged product.

1.9 kg Zola aluminum oxide (the same as in example 9, the predecessor of thermotolerant inorganic oxide added before and after aging in an amount such that the mass ratio of the heat-resistant inorganic oxide before and after aging was 1:0,16) was added to 2.5 kg decationizing water, to which was added 4.0 kg of kaolin (containing 76 wt.% solids production Suzhou Kaolin Co.), and the resulting suspension is evenly mixed. To the aged, as described above, the product is then added to 11.4 kg of a suspension, obtained from 3 kg (dry basis) of the zeolite with the MFI structure, containing phosphorus and metals such as iron and zinc, Z3, obtained in example 3, 1 kg (dry basis) of ultrastable (with respect zeolite Y (industrial brand USY, the product of the Zhoucun Catalyst Plant, Qilu Petrochemical Co., with the size of the unit cell from 2.445 nm, the content of sodium oxide to 0.36 wt.%) and water are uniformly mixed and obtained a suspension with a solids content equal to 27.4 wt.%. The resulting slurry was spray dried and sformovat in the particle diameter of 20-150 μm at 220°C, which was probalily at 520°C for 4 hours, and got the catalyst C4, proposed by the present invention. Composition C4 is given in table 2.

Example 13

0,17 kg Ba(NO3)2dissolved in 18 kg decationizing water, to which was added 3.0 kg halloysite (the same as in example 9) and 0.9 kg m is norilana (with a solids content of 95 wt.% production Zhejiang Fenghong Chemical Clay Ltd.) and mixed. Then added 4.0 kg of pseudoboehmite (the same as in example 9) and set the pH to 3.5 with hydrochloric acid. The resulting suspension was evenly mixed and added sulfuric acid in the same molar amount that VA(NO3)2for a full education precipitate of barium sulfate. The suspension stood at 75°C for 5 hours for aging, and added 1.8 kg Zola aluminum oxide (the same as in example 9, the predecessor of thermotolerant inorganic oxide added before and after aging in an amount such that the mass ratio of the heat-resistant inorganic oxide added before and after aging was 1:0,16) and uniformly mixed. Then added 11,4 kg suspension obtained from 3.0 kg (dry basis) of the zeolite with the MFI structure, containing phosphorus and metals such as iron and manganese, Z4, obtained in example 4, 1.0 kg (dry basis) of the zeolite HY containing rare earth (industrial brand REHY, the product of the Zhoucun Catalyst Plant, Qilu Petrochemical Co., with the size of the unit cell 2,465 nm, the content of sodium oxide to 3.2 wt.%, the content of rare earth oxides to 7.0 wt.%, moreover, the content of lanthanum oxide was 3,71 wt.%, cerium oxide of 0.91 wt.% and other rare earth oxides of 2.38 wt.%) and water are uniformly mixed and obtained a suspension with a solids content of 25.5%by weight. The resulting slurry was spray dried and sformovat in the form of Castelvetro 20-150 microns at 280°C, which probalily at 580°C for 2.5 hours, and received the catalyst C5, proposed by the present invention. The composition of the C5 are shown in table 2.

Example 14

0.22 kg l3·7H2O was dissolved in 5.0 kg decationizing water, 7,0 kg halloysite (the same as in example 9) was impregnated with the obtained solution, and then dried at 120°C and received halloysite containing 2.0 wt.% SEO2.

The specified halloysite containing SEO2added to 21,8 kg decationizing water and stirred it up, then, to the suspension was added to 3.9 kg pseudoboehmite (the same as in example 9, the precursor of the heat-resistant inorganic oxide was added before aging) and established pH 3 using hydrochloric acid. The resulting suspension was evenly mixed, stood at 60°C for 2 hours for aging, and added 7,2 kg suspension obtained from 2.0 kg (dry basis) of the zeolite with MFI structure containing phosphorus and the metals cobalt and manganese, Z5, obtained in example 5, 0.5 kg (dry basis) of the zeolite ultrastable (with respect to Y (the same as in example 9) and water are uniformly mixed and obtained a suspension with a solids content of 25.2 wt.%. The resulting slurry was spray dried and sformovat in the particle diameter of 20-150 μm at 250°C, which was probalily at 600°C for 1 hour, and received the catalyst C6, proposed by the present invention. The composition C6 bring the n in table 2.

Example 15

1.44 kg Zr (SO4)2·4H2Oh was dissolved in 18 kg decationizing water was added 5.6 kg halloysite (the same as in example 9) and mixed, then added 3.2 kg of pseudoboehmite (the same as in example 9) and set the pH to 4 with hydrochloric acid. The resulting suspension was evenly mixed, stood at 60°C for 1 hour for aging and added 2.3 kg Zola aluminum oxide (the same as in example 9, the predecessor of thermotolerant inorganic oxide added before and after aging in an amount such that the mass ratio of the heat-resistant inorganic oxide added before and after aging was 1:0,25) and uniformly mixed. Then added 8.6 kg suspension obtained from 2.5 kg (dry basis) of the zeolite with the MFI structure, containing phosphorus and metals - Nickel and manganese, Z6, obtained in example 6, and 0.5 kg (dry basis) of the zeolite ultrastable (with respect to Y (the same as in example 9) and water are uniformly mixed and obtained a suspension with a solids content of 25.6 wt.%. The resulting slurry was spray dried and sformovat in the particle diameter of 20-150 μm at 220°C, which was probalily at 550°C for 2 hours, and got the catalyst C7, proposed by the present invention. The composition C7 are shown in table 2.

Example 16

0.43 kg VA(NO3)2and 0.57 kg LaCl3·7H2O dissolved is 12 kg decationizing water, added 3.2 kg of pseudoboehmite (the same as in example 9), was mixed and set pH 3 using hydrochloric acid. The resulting suspension was evenly mixed and kept at 55°C for 6 hours for aging, added 25,0 kg Zola silicon oxide (content of silicon oxide 16.6 wt.%, received at the plant Beijing Chemical plant) and 2.3 kg Zola aluminum oxide (the same as in example 9, the predecessor of thermotolerant inorganic oxide added before and after aging in an amount such that the mass ratio of the heat-resistant inorganic oxide added before and after aging was 1: 2,25) and uniformly mixed. Then added 8.6 kg suspension obtained from 3.0 kg (dry basis) of the zeolite with the MFI structure, containing phosphorus and metals - iron and tin, Z8, obtained in example 8, and the water is evenly mixed and the obtained suspension with a solids content of 19.2 wt.%. The suspension was spray dried and sformovat in the particle diameter of 20-150 μm at 250°C, which was probalily at 550°C for 2 hours, and got the catalyst C8 offered by the present invention. The composition of C8 are shown in table 2.

Example 12'

Catalyst C4' was prepared by the method of example 12 except that the Z3 was replaced by an equal amount of zeolite Z3' with the MFI structure, containing phosphorus and metal - iron obtained in example 3'. Composition C4' are given in Alice 2.

Example 13'

The catalyst C5' was prepared by the method of example 13 except that the Z4 replaced by an equal amount of zeolite Z4' with the MFI structure, containing phosphorus and metal - iron obtained in example 4'. The composition of the C5' are shown in table 2.

Example 14'

The catalyst C6' was prepared by the method of example 14 except that the Z5 was replaced by an equal amount of zeolite Z5' with the MFI structure, containing phosphorus and metal - iron obtained in example 5'. The composition of the C6' are shown in table 2.

Example 15'

The catalyst C7' was prepared by the method of example 15 except that the Z6 was replaced by an equal amount of zeolite Z6' with the MFI structure, containing phosphorus and metal - iron, obtained in example 6'. The composition C7' are shown in table 2.

Example 16'

The catalyst C8' was prepared by the method of example 16 except that the Z8 was replaced by an equal amount of zeolite Z8' with the MFI structure, containing phosphorus and metal - iron obtained in example 8'. The composition of C8' are shown in table 2.

Example 13'
Table 2
Example No.Example 12Example 13Example 14Example 15Example 16Example 12'Example 14'Example 15'Example 16'
CatalystC4C5C6C7C8C4'C5'C6'C7'C8'
The type of clayKaolinHalloysite + montmorilloniteHalloysiteHalloysite-KaolinHalloysite + montmorilloniteHalloysiteHalloysite-
The clay content, wt.%30305040-30305040-
The type of heat-resistant norgan. oxideHydroxy is aluminum. The oxide of aluminum.The oxide of aluminum.The oxide of aluminum.The oxide of aluminum. + silicon oxideThe oxide of aluminum.The oxide of aluminum.The oxide of aluminum.Aluminium oxideThe oxide of aluminum. + silicon oxide
The content of the heat-resistant norgan. oxide, wt.%29292425652929242565
Type support. componentBaBaCeZrBa + LaBaBaCeZrBa + La
The content of the support. component catalyst (oxide), wt.%1115 511155
The type of zeolite with MFI structureZ3Z4Z5Z6Z8Z3'Z4'Z5'Z6'Z8'
The zeolite with structure. MFI, wt.%30302025303030202530
Type macroporous zeoliteUSYREHYDASY2.0DASY2.0-USYREHYDASY2.0DASY2.0-
The content of the macroporous zeolite, wt.%10 1055-101055-

Examples 17-19

The following examples show the activity of the catalyst, proposed by the present invention.

Catalysts C1-C3 pre-treated with 100% steam at 800°C for 17 hours, loaded in a small fluidized bed reactor in the amount of 180 g and then introduced a mixture of vacuum gas oil, are shown in table 3, and the water vapor at the reaction temperature of 580°C. the mass ratio of the catalyst/oil equal to 10, a mass hourly flow rate 10 h-1and the quantity of water vapor was 25 wt.% from vacuum gas oil. The results are shown in table 4.

Examples 17'-19'

The following examples show the activity of the catalyst, proposed by the present invention.

The catalytic conversion is carried out according to the method of example 17 with the same raw material, except that the catalysts were C1', C2' and C3'. The results are shown in table 4.

Comparative examples 4-6

The following examples show the activity of the catalyst, proposed by the present invention.

The catalytic conversion is carried out according to the method of example 17 with the same raw materials except the catalysts were SW, SW and SW. The results are shown in table 4.

Table 3
Raw materials from petroleumVacuum gasoilOil atmospheric distillation
Density (20°C)g/cm30.87300.8909
Viscosity, mm2/s8.04At 24.84
Asphalt, wt.%-0.8
Coke balance0.154.3
Conradson, wt.%
The boiling range
IBP346282
10%411370
30%437482
50% 462553
70%489-
90%523-
FBP546-

Table 4
Example No.Example 17Example 18Example 19Example 17'Example 18'Example 19'Compare. example 4Compare. example 5Compare. example 6
CatalystC1C2C3C1'C2'C3'SVSVSV
Conversion, wt.%92.292.091.992.091.9 91.086.891.788.1
Product distribution, wt.%
Gas cracker67.567.067.267.366.866.763.466.863.9
Gasoline (C5-221°C)18.818.718.618.718.617.918.518.419.1
Light cycle oil (221-330°C)4.54.64.64.84.75.58.1 4.86.9
Heavy diz. fuel (>330°C)3.33.43.53.23.43.55.13.55.0
Coke residue5.96.36.16.06.56.44.96.55.1
Including propylene31.331.031.431.530.931.728.329.527.8
Including ethylene10.210.19.910.310.19.88.89.28.6
Including WITH*6.16.05.95.95.86.05.75.85.7
*WITH means benzene, toluene and xylene.

Table 4 shows that in contrast to zeolite with MFI structure that does not contain phosphorus and transition metals, which was pretreated under the same conditions and contained the same amount of zeolite catalyst, proposed by the present invention are significantly more active in the conversion of heavy petroleum products at higher gas outlets cracking, especially propylene, ethylene and VTH. Compared with the catalyst containing the same amount of zeolite of the same type, but does not contain an auxiliary component of the catalyst, the catalyst of this invention gives higher yields of propylene, ethylene and VTH and reduced the number of coke. This shows that the catalyst proposed in the present invention, has an exceptional activity, stability and selectivity.

Examples 20-24

The following examples show the activity of the catalyst, proposed by the present invention.

Catalytic con is the version conducted by way of example 17 with the same raw materials except the catalyst C1 was replaced by the catalyst C4-C8, respectively, and the raw material was oil atmospheric distillation, as shown in table 3. Reaction conditions and results are shown in table 5.

Examples 20'-24'

The following examples show the activity of the catalyst, proposed by the present invention.

The catalytic conversion is carried out according to the method of example 17 with the same raw materials except that the catalyst C1 was replaced by the catalyst C4'-C8' respectively, and the raw material was oil atmospheric distillation, as shown in table 3. Reaction conditions and results are shown in table 5.

td align="center"> 80 19.4
Table 5
Example No.Example 20Example 21Example 22Example 23Example 24Example 20'Example 21'Example 22'Example 23'Example 24'
CatalystC4C5C6C7C8C4' C5'C6'C7'C8'
The reaction temperature, °C550580620620680550580620620680
The catalyst/oil, wt. ratio10101015251010101525
Mass hours. space velocity, h-110101515201010151520
Steam/oil, wt. ratio252550802525508080
Conversion, wt.%79.883.486.488.592.479.983.686.688.692.5
Product distribution, wt.%
The cracking gas50.153.554.957.661.550.153.455.157.661.7
Gasoline (C5-221°C)21.620.218.316.421.520.419.318.216.1
Light cycle oil (221-330°C)12.610.59.07.55.912.610.38.97.66.0
Heavy products (>330°C)7.66.14.64.01.77.56.14.53.81.5
Cox8.19.712.112.614.58.39.812.212.814.7
Including propylene 21.323.224.125.322.821.523.424.225.622.9
Including ethylene7.610.112.312.921.57.710.212.412.821.8
Including WITH*6.26.86.97.16.86.06.66.77.06.7
*WITH means benzene, toluene and xylene.

1. Zeolite-containing catalyst for conversion of hydrocarbons containing zeolite, a heat-resistant inorganic oxide and optionally a clay, characterized in that the zeolite is a zeolite with MFI structure containing phosphorus and transition metals, sludge is a mixture of the specified zeolite with MFI structure, containing phosphorus and transition metals, with macroporous zeolite, which contains calculated on the weight of the mixture 75-100 wt.% the specified zeolite with MFI structure containing phosphorus and transition metals, and 0-25 wt.% macroporous zeolite, and in the calculation of the mass of oxide specified zeolite with MFI structure containing phosphorus and transition metals, has the following chemical formula without water:

or

in which M1 represents a transition metal selected from Fe, Co and Ni, M2 is a transition metal chosen from Zn, Mn, Ga and Sn, M is a transition metal chosen from Fe, Co, Ni, Cu, Zn, Mo or Mn, and RE represents a rare earth metal; x is 1 or 2, and when x is 1, the value is half of the valency of the transition metal M1, a when x is 2, the value is equal to the valence of the transition metal M1; m equal to 1 or 2 when m is equal to 1, the value of n is half the valency of the transition metal M2, and when m is 2, the value of n is equal to the valence of the transition metal M2; p is 1 or 2, when p is 1, q is half the valency of the transition metal M, and when p is 2, the value of q coincides with the valence of the transition metal M; the catalyst also contains an auxiliary component, one or more of which is selected from the group consisting of metals of group IVB metals, base metals of VIII group metals and rare earth metals of the Periodic table of elements; based on the weight of the catalyst specified catalyst contains 1-60 wt.% zeolite, 0.1 to 10 wt.% a supporting component of the catalyst, 5-98 wt.% heat-resistant inorganic oxide and 0-70 wt.% clay in the form of oxides.

2. The catalyst according to claim 1, characterized in that the calculation of the mass of catalyst it contains 10-50 wt.% zeolite, 0.5 to 8 wt.% an auxiliary component, 10-70 wt.% heat-resistant inorganic oxide and 0-60 wt.% the clay.

3. The catalyst according to claim 1, characterized in that the calculation of the mass of oxide zeolite with MFI structure containing phosphorus and transition metals, has the following chemical formula without water:

or

4. The catalyst according to claim 1, wherein M1 represents Fe.

5. The catalyst according to claim 1, wherein M2 represents Zn.

6. The catalyst according to claim 1, wherein M1 represents Fe, a M2 represents Zn.

7. The catalyst according to claim 1, wherein M selected from Fe, Co or Ni.

8. The catalyst according to claim 1, characterized in that one or more of the auxiliary catalyst components selected from the group consisting of zirconium, titanium, lanthanum, cerium, iron, cobalt and Nickel.

. The catalyst according to claim 1, characterized in that one or more of the macroporous zeolites are selected from the group consisting of faujasite, zeolite L, zeolite β, zeolite Ω, mordenite and ZSM-18.

10. The catalyst according to claim 9, characterized in that one or more of the macroporous zeolites are selected from the group consisting of zeolite Y, zeolite Y containing phosphorus and/or rare earth, ultrastable (with respect zeolite Y, ultrastable (with respect zeolite Y containing phosphorus and/or rare earth, and zeolite β.

11. The catalyst according to claim 1, characterized in that one or more of the heat-resistant inorganic oxide selected from the group consisting of aluminum oxide, silicon oxide and amorphous aluminosilicate.

12. The catalyst according to claim 1, characterized in that one or more clays selected from the group consisting of kaolin, halloysite, montmorillonite, diatomaceous earth, anelita, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.

13. The method of preparation of the catalyst according to claim 1, which comprises mixing and suspension of all or part of the heat-resistant inorganic oxide and/or its predecessor, water and optionally a clay, the addition of zeolite and drying the resulting suspension, adding an ancillary compound before adding the zeolite and before or after addition of the clay, adding acid to establish a pH-value of the suspension, equally the m 1-5, aging at 30-90°C for 0.1 to 10 h and adding the remaining heat-resistant inorganic oxide and/or its predecessor after aging.

14. The method according to item 13, wherein before aging add first part of the heat-resistant inorganic oxide and/or its predecessor, and after aging add the remaining heat-resistant inorganic oxide and/or its predecessor; added first portion and further added portion take such that the mass ratio of the first added portions and then add a portion of the heat-resistant inorganic oxide in the catalyst was 1:0.1 to 10.

15. The method according to 14, characterized in that the aforementioned ratio is 1:0.1 to 5.

16. The method according to item 13, wherein the acid is selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, and carboxylic acids with 1 to 10 carbon atoms, and the amount of acid allows you to set the pH of the suspension is equal to 1.5 to 4.

17. The method according to item 13, wherein the aging temperature is 40-80°C and the duration of aging 0.5-8 hours

18. The method according to item 13, wherein the one or more ancillary compounds selected from the group consisting of halides, nitrates and phosphates of zirconium, titanium, lanthanum, cerium, iron, cobalt and Nickel.

19. A method of converting coal is hydrogen petroleum products, which comprises contacting the hydrocarbon oil with the catalyst according to claims 1 to 12, and the contacting is carried out in an atmosphere of water vapor and conditions specified contact includes contact temperature 450-750°C, the mass ratio of the catalyst/oil, equal 4-40, and the amount of water vapor 1-100 wt.% from the hydrocarbon oil product.

20. The method according to claim 19, characterized in that the contact conditions include a contact temperature of 500-700°C, the mass ratio of the catalyst/oil, equal 5-30, and the amount of water vapor equal to 10-90 wt.% from the hydrocarbon oil.



 

Same patents:

The invention relates to the refining of oil, in particular, to the hydrofining of petroleum fractions

The invention relates to a method for the catalytic dewaxing of lubricating oils

The invention relates to a method of hydrocracking a hydrocarbon feedstock with the aim of obtaining basic component of the lubricating oil

The invention relates to the refining, in particular, to methods for nitrosative oils, hydraulic fluids, diesel and aviation fuels

FIELD: chemistry.

SUBSTANCE: cracking catalysts contains aluminium oxide, phosphorus and molecular sieves with clay or without clay whereat said aluminium oxide is η-aluminium oxide or mixture of η-aluminium oxide and χ-aluminium oxide and/or γ-aluminium oxide with general composition per all catalyst, wt: % η-aluminium oxide 0.5-50; χ-aluminium oxide and/or γ-aluminium oxide 0-50; molecular sieves 10-70; clay 0-75; and phosphorus in the form of P2O5 0.1-8. The method for catalysts preparation includes: drying of the suspension containing aluminium compound, molecular sieves and water with clay or without clay and calcination of the said suspension with following adding of phosphorus compound. The said aluminium compound is aluminium compound able to form η-aluminium oxide or mixture of the aluminium compound able to form η-aluminium oxide with compound able to form χ-aluminium oxide and/or γ-aluminium oxide with every component using in such amount that resulting catalyst agrees aforementioned composition. The methods for catalysts preparation are described also providing additional inlet of rare earth metal or usage in the quality of molecular sieves of the zeolites mixture containing zeolite Y and zeolite with structure MFI whereat content of zeolite Y is 30-90% wt and content of zeolite with structure MFI is 10-70% wt per total amount of zeolites mixture.

EFFECT: increase of catalyst activity and quality enhancing of the petrol containing in the cracking products.

23 cl, 26 tbl, 52 ex

FIELD: chemistry.

SUBSTANCE: mould catalyst for hydrocracking contains at least zeolite Y and inorganic high-melting oxide with monomodal pores distribution (by mercury porosimetre) whereat at least 50% of total volume is represented with pores having diametre in the range from 4 to 50 nm and the volume at least 0.4 ml/g. The method for carrier preparation and the carrier obtained with this method are described; the said method includes moulding of the mixture containing at least zeolite Y and high-melting oxide with calcinations losses in the range (LIR) from 55 to 75%. The catalytical composition for hydrocracking includes said carrier, at least one component of hydrogenating metal selected from the metal of groups V1B and group V111 and optionally at least one promoting element selected from silicon boron in the case when carrier virtually does not contain the alumosilicate zeolite. The method for catalytical composition preparation and composition obtained with this method are described; the said method includes optional calcinations of the said carrier, precipitation of the at least one hydrogenating metal selected from described above ones in the corresponding amount; the said precipitation is carried out by impregnation with solution containing organic compound having at least two functional groups selected from carboxyl, carbonyl and hydroxyl groups. The hydrocracking method with application of the aforementioned catalytical composition is described.

EFFECT: enhancing of the catalytical composition activity, selectivity and hydrogenation ability.

18 cl, 5 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to field of oil processing, in particular CO oxidation catalysts, used as additive to cracking catalyst for oxidising oxygen into carbon dioxide in process of cracking catalyst regeneration. Claimed catalyst for CO oxidation in process of cracking catalyst regeneration contains manganese compounds, aluminium oxide and natural bentonite clay, with the following component content, wt %: manganese in terms of MnO2 6-20, bentonite clay - 24-44, Al2O3 - the remaining part, and has microspherical form of particles with average size 70 mc, wear resistance 92-97%, bulk density 0.7-0.8 g/cm3. Described is method of preparing catalyst for CO oxidation in process of cracking catalyst regeneration, which includes mixing manganese (IV) hydroxide, obtained by precipitation of manganese nitrate from water solution with ammonium, with composition, which consists of aluminium hydroxide and bentonite clay, preliminarily processed with concentrated nitric acid (12.78 mole/l), composition drying and burning, which is carried out step by step: at temperature 500°C during 4-6 hours, and then at temperature 950-970°C during 4 hours.

EFFECT: increase of catalyst activity and wear-resistance.

2 cl, 1 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of chemical industry, in particular, to creation of highly active homogenous catalysts. Described is catalyst based on binary bridge bis(phenoximine) complex of titanium, in which as bridge between phenyl substituents of imine nitrogen it contains n - phenylene group, and corresponds to the following formula: . Described is method of preparing described above catalyst by interaction of tetradentate diimine ligand with compound of transitive metal, in which as components for ligand preparation used is 4,4"-diamino-l-terphenyl and 3,5-dicumylsalicilic aldehyde, and as compound of transitive metal used is titanium diisopropoxydichloride TiCl2(OPr)2. Described is process of ethylene polymerisation in medium of hydrocarbon solvent in presence of catalyst obtained by claimed method with co-catalyst.

EFFECT: increase of polymerisation process economy due to lower catalyst consumption; obtaining of linear polyethylene with high and extra-high molecular mass, with temperature of melting 140-142°C, improved morphology of polymer powder and absence of its adhering on reactors wall.

4 cl, 2 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: invention refers to the improved method for oxidising of aromatic hydrocarbon such as para-xylol, meta-xylol, 2,6-dimethylnaphthalene or pseudocumene with forming of corresponding organic acid. The oxidation is implemented by the source of molecular oxygen in liquid phase at temperature range from 50°C to 250°C in the presence of catalyst being a) oxidation catalyst based on at least one heavy metal representing cobalt and one or more additive metals being selected from manganese, cerium, zirconium, titanium, vanadium, molybdenum, nickel and hafnium; b) bromine source; and c) unsubstituted polycyclic aromatic hydrocarbon. The invention refers also to the catalytic system for obtaining of organic acid by the liquid-phase oxidation of aromatic hydrocarbons representing: a) oxidation catalyst based on at least one heavy metal representing cobalt and one or more additive metals being selected from manganese, cerium, zirconium, titanium, vanadium, molybdenum, nickel and hafnium; b) bromine source; and c) unsubstituted polycyclic aromatic hydrocarbon.

EFFECT: activation of the aromatic hydrocarbons oxidation increasing the yield of target products and allowing to decrease the catalyst concentration and the temperature of the process.

45 cl, 4 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: described is catalyst for isomerisation of xylols, which includes in wt %: zeolite ZSM-5 - 10-35, calcium 0.05-1.0, calculated per zeolite, sodium 0.05-0.12, calculated per zeolite, aluminium oxide - the remaining part. Also described is method of preparing said catalyst, which includes mixing of aluminium hydroxide with zeolite ZSM-5, processing of obtained mixture with water solutions of calcium and, possibly, sodium compounds, with following forming and burning of obtained extrudates.

EFFECT: ensuring of xylol isomerisation until equilibrium composition of isomer is achieved, reduction of xylol loss at isomerisation temperature 400-460°C, increase of level of ethyl benzene, n-Nona and cumene conversion.

3 cl, 1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to the production of catalyst for hydrocarbon conversion. The said catalyst includes nickel, titanium, boron, manganese, lanthanum and aluminium oxides with following components content, wt %: nickel oxide - 8.5-24.5; titanium oxide - 0.05-2.1; boron oxide - 0.1-3.0; manganese oxide - 0.01-2.8; lanthanum oxide - 0.1-5.0; aluminium oxide constitutes the remaining percentage. The method of catalyst obtaining consists of following stages: 1) preparation of the batch mixture including alumina, titanium oxide, boric acid, manganese oxide, lanthanum oxide; 2) addition of the binder including paraffin, wax and oleinic acid; 3) moulding of the carrier pellets by slip casting at excessive pressure 0.4-2 MPa and temperature 70-80°; 4) air-seasoning and two-stage calcination of the obtained carrier whereat the first stage is carried out in ceramic forms in alumina bed at temperature 1100-1200°C during 4-8 hrs, then the temperature is increased during 1 hour up to 1350-1420°C, and the calcination is carried out at this temperature during 2-4 hrs; 5) carrier impregnation with nickel and aluminium and/or lanthanum nitrates; 6) drying and calcination of catalyst mass at 400-500°C.

EFFECT: preparation of catalyst with enhanced activity and mechanical reliability, decreasing of catalyst bed hydraulic resistance

7 cl, 1 tbl, 19 ex

FIELD: chemistry.

SUBSTANCE: description is given of a method of obtaining an active phase of a heterogeneous catalyst based on oxides or mixed oxides of transition metals, chosen from a group containing Mo, V, Te, Nb, through successive mixture of aqueous solutions of molybdenum tellurate, vanadium sulphate and niobium oxalate. An aqueous solution of vanadium sulphate is added to the molybdenum tellurate solution first, obtaining a suspension after mixing, which is then added to niobium oxalate. The obtained mixture is further intensively stirred for 10 minutes, kept in an autoclave at 175°C for 50 hours and after filtration and washing, roasted at 600°C in a stream of inert gas. The heterogeneous catalyst for oxidative dehydrogenation of gaseous mixtures of hydrocarbons is a composite material in form of a mechanical mixture of solid dispersion powders obtained from an active phase and an inactive phase with specific surface area of 1-10 m²/g, relative the active dispersion matrix. The method of obtaining the catalyst involves mechanical mixture of powders of active and inactive phases with subsequent pressing, crushing and grading the particles through sieving. Described also is a method of oxidative dehydrogenation of ethane, in which a gas mixture, containing oxygen and ethane in ratio ranging between 1:2.5 and 1:3.5, is fed at pressure of 1 atm and bulk speed of 500-30000 h-1 into a flow reactor with a stationary layer of the heterogeneous catalyst described above, heated to 380-420°C.

EFFECT: increased output of the dehydrogenation process, while maintaining high conversion and selectivity.

11 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention refers to catalyst preparation of the low temperature conversion of carbon oxide with water vapour including: mixing of the components containing copper and zinc; mechanic activation during passing-through of the gas mix containing ammonia, carbon dioxide and water vapour; additional activation with pass of water vapour containing the additives of alkali metals carbonates and calcium aluminate at mass ratio (on oxide basis): CuO:ZnO:CaAl2O4:Me2O-(42-60):(24-42):(13-15):(1-3), where Me-K, Rb, Cs; 4) pellets moulding and calcination.

EFFECT: enhancing of catalyst selectivity and durability at retaining of its high activity.

1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: method of producing cumene includes interaction of benzene with acetone and hydrogen with catalytic compound added as containing one or more zeolite in acid form or preferentially acid form, copper and, optionally, one or more element chosen from elements of groups IIIA, VIB, VIIB. Additionally the given invention concerns method of producing phenol with using cumene prepared by the method as described, catalytic compound for production cumene, and also methods of producing catalytic compound for cumene.

EFFECT: application of the methods and catalytic compounds specified above allows simplifying considerably producing phenol from cumene, allowing for simultaneous one-stage reaction for all chemical transformations required to produce high-yield cumene from acetone, benzene and hydrogen with minimum amount of secondary reactions of various reagents, intermediate compounds and products.

69 cl, 16 ex, 2 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a packet of catalyst grids for converting ammonia in a gas mixture containing oxygen, made from platinoid alloys, and can be used in nitric and hydrocyanic acid, as well as hydroxylaminosulphate plants. The packet of catalyst grids for converting ammonia in a gas mixture containing oxygen, includes a grid layer made from platinoid alloys with low 70 to 85% and high 90 to 95% concentration of platinum, distinguished by that, the packet consists of three layers, where the first layer along the path of the gas mixture has grids made from an alloy with low concentration of platinum, the number of which is 1/6 to1/3 of the total number of grids in the packet, the second layer has grids made from an alloy with high concentration of platinum, numbering from 1/3 to 2/3 of the total number of grids in the packet, and the third layer has grids made from an alloy with low and/or with high concentration of platinum.

EFFECT: invention allows for reducing mass of platinoids, included in the packet of catalyst grids and their loss when using the packet without reducing degree of conversion of ammonia to the target product.

4 cl, 18 ex, 2 tbl, 1 dwg

Catalytic element // 2362624

FIELD: technological processes.

SUBSTANCE: invention is related to catalytic elements of regular structure for different catalytic processes. Catalytic element was described that represents a single block structure made of separate components - catalytic rods that are distanced from each other by spacer device. Catalytic rods may have different shape of section and diametres, and may also represent different catalysts. Rods in single block structure may create layers installed parallel, perpendicular or at the angle to each other and flow of reagents.

EFFECT: provision of manufacturability of making, low resistance to flow, good missing and turbulisation of reagents flow, high mass- and heat-exchange properties, without disadvantages inherent in these types of catalysts.

6 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention refers to making heat-resistant sulphocation catalysts. There is disclosed method for making heat-resistant sulphocation catalysts containing aromatic rings chemically combined with solid polymer base, at least two groups -SO2OH, by sulphonation of aromatic rings of polymer base followed by desulfonation at higher temperature of those aromatic rings having only one group -SO2OH whereat heat-resistant polymer base is sulphonated, while aromatic rings are sulphonated in two or more stages with gradually increasing sulphonation hardness. The first stage involves soft sulphonation with aqueous sulphuric acid solution concentrated 95 wt % and more at temperature 90°C and less, preferentially 70°C and less. The last stage implies sulphonation with aqueous sulphuric acid solution concentrated 90 wt % and more or with oleum with SO3 concentrated 1 to 30 wt % higher than chemically combined in acid. The catalyst is sequentially washed by dissolved sulphuric acid solution, then by water. Thereafter it contacts at temperature 150 to 200°C with an inert solvent not containing groups neutralising -SO3OH groups and introduced in amount required to remove groups -SO2OH from the aromatic rings containing one group -SO2OH only.

EFFECT: making heat-resistant catalyst of required dimension and/or shape.

8 cl, 1 tbl, 5 ex

FIELD: mechanics.

SUBSTANCE: invention relates to heterogeneous catalytic reactors designs. The catalytic reactors include inlet, outlet and reactor wall. Inner volume of rector accommodates framed structure located along reactor axis and rector containment structure being located near reactor wall. Both structures are different from each other to ensure catalysis and heat transfer process. In order to allow fluid hitting against reactor wall, type 1 devices are implemented on the framed structure to direct fluid in centrifugal direction. To enable fluid out-flowing from reactor wall while it flows from reactor inlet to its outlet, type 2 devices are available in the framed structure.

EFFECT: effective heat transfer in reactor volume, especially near catalytic reactor walls or other solid wall being in cross section.

37 cl, 8 dwg

FIELD: metallurgy.

SUBSTANCE: invention relates to metallurgy field, particularly to receiving of steel sheet and foil with high content of aluminium by method of flow line production with low cost. On at least one surface of basic steel sheet, containing aluminium in amount from 3.5 up to less than 6.5 wt %, it is applied aluminium or aluminium alloy for receiving of laminated material. It is subject to cold working for giving of operating voltage and diffusive heat processing. It is received steel sheet, containing from 6.5 up to 10 wt % of aluminium, allowing texture with crystal plane aggregate α-Fe {222}, compound from 60 up to 95%, and/or planes {200}, compound from 0.01 up to 15%, relative to surface of steel sheet. Sheet is subject to additional cold rolling with receiving of foil.

EFFECT: treatability improvement, that provides receiving of products of different forms without additional operations.

21 cl, 2 dwg, 6 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to the improved method of catalytic liquid phase hydrogenation of 2',4',4-trinitrobenzanilide. The obtained compound can be used as an intermediate product when making dyes, heat-resistant polymers, synthesis of high-strength fibers etc. Liquid phase hydrogenation of 2',4',4-trinitrobenzanilide takes place when heating in a medium of a mixture of isopropyl and toluene, with ratio (weight parts) from 3:7 to 7:3 on a block highly-porous honeycomb catalyst with porosity not less than 80-90%. The catalyst consists of a carrier based on α-aluminium oxide with an active substrate from sulphated zirconium dioxide and an active component - palladium. The active substrate from zirconium dioxide is taken in quantity not more than 8.0 wt %.

EFFECT: use of the proposed invention cuts reaction time by 4-10 times, increases load on the catalyst by up to 5 times and allows for continuous catalytic liquid phase hydrogenation of 2',4',4-trinitrobenzanilide.

9 ex

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