Method of obtaining olefins

FIELD: chemistry.

SUBSTANCE: description is given of a method of obtaining olefins. The method involves passing a mixture of a hydrocarbon and oxygen containing gas through a catalyst zone, which is capable of maintaining burning over the upper limit the inflammability of the fuel, with obtaining of the above mentioned olefin. The catalyst zone consists of at least, a first layer of catalyst and a second layer of catalyst, where the second catalyst layer is put in the process line after the first catalyst layer, has different content from the first layer and has general formula: M1aM2bM3cOz, where M1 is chosen from IIA, IIB, IIIB, IVB, VB, VIB, VIIB groups of lanthanides and actinoides, M2 is chosen from IIA, IB, IIB, IIIB, IVB, VB, VIB groups, and M3 is chosen from IIA, IB, IIB, IIIB, IVB, VB, VIB and VIIIB groups, a, b, c and z represent atomic ratios of the M1, M2, M3 and O components respectively. The value of a lies in the interval from 0.1 to 1.0, the value of b lies in the interval from 0.1 to 2.0, the value of c lies in the interval from 0.1 to 3.0, and the value of z lies in the interval from 0.1 to 9.0. The catalyst zone has a perovskite type structure.

EFFECT: perfection of the method of obtaining olefins.

9 cl, 4 tbl, 1 dwg, 4 ex

 

The present invention relates to a method for producing olefins from hydrocarbons in which the hydrocarbons are treated autothermal cracking.

Autothermal cracking is a new way of obtaining olefins, in which the hydrocarbon feedstock is mixed with oxygen and passed over the catalyst for autothermal cracking. The catalyst for autothermal cracking capable of supporting combustion beyond the upper Flammability limit of the fuel. On the surface of the catalyst to initiate in situ combustion and generate the heat required to heat the reactants to the process temperature and carrying out the endothermic cracking process. Typically, hydrocarbons and oxygen is passed over a single catalyst layer with obtaining the olefin product. The catalytic layer generally includes at least one metal of the platinum group such as platinum, deposited on a catalyst carrier. The process is autothermal cracking process described in EP 332289 IN, EP-529793 IN, EP-A-0709446 and WO 00/14035.

During autothermal cracking receive the flow of products, which includes not only the number of paraffin and olefin components, but also significant amounts of hydrogen and carbon monoxide. In WO 02/04389 shown that the selectivity of the catalytic zone comprising a catalytic layer (first catalytics the s layer), can be enhanced by the placement of the second catalytic layer containing at least one metal selected from the series comprising Mo, W and the elements of groups IB, IIB, IIIB, IVB, VB, VIIB and VIII of the Periodic table of the elements following the first catalytic layer. Thus, in particular, in WO 02/04389 shown that the application of the catalytic zone, which as the second catalyst layer includes a catalyst, which is almost incapable of supporting combustion beyond the upper Flammability limit of the fuel (i.e. the catalyst, which is virtually inactive in terms of autothermal cracking), and as the first catalytic layer of the catalyst, which is almost capable of supporting combustion beyond the upper Flammability limit of the fuel, typically achieve higher selectivity towards olefins in comparison with that which is achieved using one of the first catalytic layer.

It was found that the selectivity for olefins catalytic zone comprising a catalyst layer (first catalyst layer), can be enhanced by the placement of the second layer of the catalyst of the formula M1aM2bM3cOzin which M1selected from groups IIA, IIB, IIIB, IVB, VB, VIB, VIIB, lanthanides and actinides, M2selected from groups IIA, I, IIB, IIIB, IVB, VB, VIB, and M3selected from groups IIA, IB, IIB, IIIB, IVB, VB, VIB and VIIIB, in the process line after the first catalyst layer.

Accordingly, an object of the present invention is a method of producing olefin, which comprises passing a mixture of hydrocarbon and oxygen-containing gas through a zone of a catalyst capable of supporting combustion beyond the upper Flammability limit of the fuel, to obtain the above-mentioned olefin, and referred to the catalytic zone comprises at least a first layer of catalyst and the second catalyst layer, where the second layer of catalyst is placed in the process line after the first catalyst layer differs in composition from the first catalyst layer and satisfies the General formula

M1aM2bM3cOz,

in which M1selected from groups IIA, IIB, IIIB, IVB, VB, VIB, VIIB, lanthanides and actinides, M2selected from groups IIA, IB, IIB, IIIB, IVB, VB, VIB, M3selected from groups IIA, IB, IIB, IIIB, IVB, VB, VIB and VIIIB, a, b, C, and z represent the atomic ratio of the components respectively M1M2M3and Oh, the value is in the range from 0.1 to 1.0, the value b is in the range from 0.1 to 2.0, the value is in the range from 0.1 to 3.0, and the value of z is in the range from 0.1 to 9.

The first layer of the catalyst includes the t catalyst, capable of supporting combustion beyond the upper Flammability limit of the fuel. In a suitable embodiment, the first layer of the catalyst may include a metal of group VIIIB. Acceptable metals of group VIIIB include platinum, palladium, ruthenium, rhodium, osmium and iridium. In a preferred embodiment, the metal of group VIIIB selected from rhodium, platinum, palladium and mixtures thereof. Especially preferred is platinum, palladium or mixtures thereof. Typical concentrations of the metals of group VIIIB are in the range from 0.01 to 100 wt.%, preferably from 0.01 to 20 wt.%, and more preferably from 0.01 to 10 wt.%, for example, from 1 to 5 wt.%, in particular, from 3 to 5 wt.%. In a suitable embodiment, the first layer of the catalyst includes platinum or palladium, mainly platinum.

Alternatively, the first layer of the catalyst may include promoted catalyst, such as promoted catalyst based on a metal of group VIIIB. The promoter may be selected from elements of groups IIIA, IVA and VA of the Periodic table of elements and mixtures thereof. Alternatively the promoter may serve as a transition metal, and this transition metal is a metal other than a catalytic component, such as a metal (metals) of group VIIIB, used as a catalytic component.

Preferred metals of group IIIA include Al, Ga, In and Tl. Of them, preferred is elinee Ga and In. Preferred metals of group IVA include Ge, Sn and Pb. Of them, preferable Ge and Sn, mainly Sn. The preferred metal of group VA is Sb. The atomic ratio between the metal of group VIIIB and a metal of group IIIA, IVA or VA may be 1:0.1 to 50,0, preferably 1:0.1 to 12,0, in particular 1:0.3 to 5.

Acceptable transition metals as promoters can be selected from any one or more of the groups IB to VIII of the Periodic table of elements. Thus, in particular, the preferred transition metals selected from groups IB, IIB, VIB, VIIB and VIII of the Periodic table of elements. Examples of such transition metals as promoters include Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir, Ni, Pt, Cu, Ag, Au, Zn, Cd and Hg. Preferred transition metals as promoters are Mo, Rh, Ru, Ir, Pt, Cu and Zn, mainly Cu. The atomic ratio between the metal of group VIIB and transition metal as a promoter may be 1:0.1 to 50,0, preferably 1:0.1 to 12,0.

Specific examples of promoted catalysts group VIIIB for use as the first layer of the catalyst include Pt/Ga, Pt/In, Pt/Sn, Pt/Ge, Pt/Cu, Pd/Sn, Pd/Ge, Pd/Cu and Rh/Sn. When a metal of group VIIIB is Rh, Pt or Pd, the proportion of Rh, Pt or Pd may be in the range of from 0.01 to 5.0 wt.%, preferably in the range from 0.01 to 2.0 wt.%, and more preferably in the range of 0.05 to 1.0 wt.% from the total mass of the catalyst. The atomic ratio of Rh, Pt Pd and a metal of group IIIA, IVA, VA or transition metal as a promoter can be from 1:0.1 to 50,0, preferably from 1:0.1 to 12,0. For example, the atomic ratio of Rh, Pt or Pd and Sn may be 1:0.1 to 50, preferably 1:0.1 to to 12.0, more preferably 1:0.2 to 3.0mm, and most preferably 1:0.5 to 1.5. The atomic ratio of Pt or Pd and Ge may be 1:0.1 to 50, preferably 1:0.1 to to 12.0, and more preferably 1:0.5 to 8.0 in. The atomic ratio of Pt or Pd and Cu can be 1 is 0.1-3.0, preferably 1:0,2-2,0 and more preferably 1:0.5 to 1.5.

The catalyst of the second layer in General corresponds to the formula

M1aM2bM3cOz,

in which M1selected from groups IIA, IIB, IIIB, IVB, VB, VIB, VIIB, lanthanides and actinides, M2selected from groups IIA, IB, IIB, IIIB, IVB, VB, VIB, and M3selected from groups IIA, IB, IIB, IIIB, IVB, VB, VIB and VIIIB (used in this description refer to groups of the Periodic table of elements borrowed from the notes of CAS, as they are listed in the operation of Cotton and Witkinson Advanced Inorganic Chemistry, fifth edition, 1988).

Preferred values of M1selected from group IIIB, M2choose from group IIA and M3choose from group IB. In the most preferred embodiment, M1denotes yttrium, M2indicates barium, and M3indicates copper.

Materials that reflects privedennaya formula, can be represented in the form of a mixture of individual oxide components, in General corresponding to the formula

M1x1Oy1M2x2Oy2M3X3Abouty3,

in which M1M2and M3have given in the present description above values in which the values of x1, x2, X3, y1, y2 and y3 are in the range from 1 to 7, resulting in three individual oxide components are mixed in suitable proportions with the achievement of atomic ratios for M1M2and M3respectively a, b and C.

The second layer of catalyst in the preferred embodiment is in the form of a perovskite. Structure type perovskite include oxides of yttrium-barium-copper YBa2Cu3O7-δthe oxides of lanthanum-strontium-iron La1-xSrxFeO3-δand oxides of lanthanum-manganese-copper LaMn1-xCuxO3-δin which x is in the range from 0.1 to 0.9, and the δas a rule, is in the range from 0.01 to 1, preferably in the range from 0.01 to 0.25.

The catalyst of the second layer can be promotional adding halide promoters material that meets the General formula

M1aM2bM3cXxAboutz,

in which M1M2and M3, a, b, C and z have the meanings given the data in the present description above, X denotes a halide, preferably the atoms of F or Cl, a x, as a rule, is in the range from 0.05 to 0.5.

The preferred halide promoted by the catalyst of the second layer corresponds to the formula YBa2Cu3O7-δClσin which δ usually is in the range from 0.01 to 0.25, and σ usually is in the range from 0.05 to 0.3.

In addition to the first and second layers of catalyst catalytic zone may include other catalytic layers. For example, catalytic zone may include from 3 to 10, preferably from 3 to 5 layers of catalyst.

When the catalytic zone comprises more than two layers of catalyst, the additional catalyst layer (s) may be the same or different from the catalyst used for any of the first and second layers of catalyst. In a suitable embodiment, the catalyst used for the additional layer (s), is the same as the catalyst of the second catalyst layer.

Each catalyst used in the catalytic zone may not be supported on a carrier or supported on a carrier. In an expedient variant is not supported on a carrier, the catalyst may be in the form of a metal grid. In a preferred embodiment, at least one catalyst in the catalytic zone is a supported on a carrier is utilizator. In a suitable embodiment, each of the catalyst in the catalytic zone is a supported on a carrier catalyst. The media used for catalysts, may be the same or different. Although you can use a number of media materials, usually preferred ceramic media. However, there may be used metallic media.

Suitable ceramic carrier may be any oxide or combination of oxides that are stable at high temperatures, for example, in the range from 600 to 1200°C. the Preferred ceramic material of the carrier has a low coefficient of thermal expansion and resistance to separation of the phases at high temperatures.

Acceptable ceramic substrates include cordierite, socialworker (LAS), aluminum oxide (α-Al2About3stabilized with yttrium oxide zirconium dioxide, titanate, aluminum oxide, nascon and circonspect calcium, and in particular aluminum oxide.

On ceramic substrates can be coated by washing, for example, using γ-Al2About3.

The structure of the material of the carrier is important, because the structure can influence the mode of expiration through the catalyst. This mode of expiration can affect the transport of reactants and products to the surface of a cat who lyst and from it, thereby the influence on the catalyst activity. The material of the carrier, as a rule, can be in the form of particles, such as balls and other spherical granules, or it may be in the form of a foamed material or fibers, in particular, a fibrous layer or pad. In a suitable embodiment, the material of the carrier in the form of particles may consist of balls of aluminum oxide. The preferred form of the medium is the monolith, which is a solid multi-channel ceramic structure. Such monoliths include the structure of a honeycomb, foam or fibrous layers. Pore foamed monolithic structures result in tortuous paths for reactants and products. Such foamed solid carriers may have the presence of from 20 to 80, preferably from 30 to 50 pores per inch. Channel monoliths are usually characterized by a more direct, a pipe-like pores. These pores are usually smaller, so you can have 80 or more pores per linear inch catalyst.

The preferred ceramic foam materials include foamed materials of aluminum oxide.

Alternatively the carrier may be in the form of a thin layer or coating by washing to other media.

When using supported on a carrier, the catalyst metal is a mini-components of the catalyst in the preferred embodiment, distributed throughout the media almost uniformly.

The catalysts used for the execution of the present invention may include additional elements, such as alkali metals. Acceptable alkali metals include lithium, sodium, potassium and cesium.

The catalysts used for the execution of the present invention can be prepared by any method known in the art. For example, you can use helium methods and wet impregnation. The media usually impregnated with one or more solutions, including metals, dried, and then calcined in air. The carrier may be impregnated in one or several stages. In the preferred embodiment, using multiple impregnation stage. In a preferred embodiment, between each impregnation, the carrier is dried and calcined, and then subjected to final annealing, preferably in air. Thereafter calcined carrier can be recovered, for example, heat treatment in a hydrogen atmosphere.

Catalytic zone may be performed by any suitable method, provided that the flow of chemicals (hydrocarbons and oxygen-containing gas) is in contact with the first layer of the catalyst with the formation in the exhaust of the stream (including the interaction products and unreacted starting material), and the above-mentioned exhaust p is the current passes from the first catalyst to the second catalyst bed. A convenient method of performing the catalytic zone is the use of one reactor with the presence of a space between the layers. This space can be created by placing between layers of catalyst essentially inert materials such as alumina, silica and other refractory materials.

Alternatively the space between catalyst is essentially empty.

The gap between the layers of the catalyst with respect to these layers not decisive. However, in the preferred embodiment, this gap should be as small as is practical. In the most preferred embodiment, the gap between catalyst essentially absent, i.e. the layers are interconnected in the vicinity. When the catalytic zone comprises more than two layers, the size of the gap between the layers can be varied.

The size of the layers of catalyst relative to each other can be varied. In a preferred embodiment, the ratio of the size of the first catalyst layer to the size of the second catalyst layer is 1:2.

The catalytic layers can be placed either vertically or horizontally.

As the hydrocarbon may be any hydrocarbon, which created the conditions of partial combustion can be converted into olefin, before occhialino in monoolefins.

The method according to the present invention can be applied for the conversion of olefins in both liquid and gaseous hydrocarbons. Acceptable liquid hydrocarbons include gasoline, ligroin fraction, a gas oil, vacuum gas oil distillation and mixtures thereof. However, in the preferred embodiment, using gaseous hydrocarbons such as ethane, propane, butane and their mixtures. In a suitable embodiment, the hydrocarbon is an original wax material comprising hydrocarbons containing at least two carbon atoms.

The hydrocarbon feedstock is mixed with any acceptable oxygen-containing gas. In a suitable embodiment, the oxygen-containing gas is molecular oxygen, air and/or mixtures thereof. Oxygen-containing gas may be mixed with an inert gas, such as nitrogen and argon.

If necessary, may include additional source components. In a suitable embodiment, in the flow of reagents it is possible to jointly submit methane, hydrogen, carbon monoxide, carbon dioxide or water vapor.

Acceptable any molar ratio of hydrocarbon to oxygen-containing gas under the condition of education in the method according to the present invention the target of the olefin. The preferred ratio of hydrocarbon to oxygen-containing gas ranges from 5 to 16, preferably from 5 to 13.5 Krat article is geometricheskogo, more preferably from 6 to 10 times the stoichiometric ratio of hydrocarbon to oxygen-containing gas required for complete combustion of the hydrocarbon to carbon dioxide and water.

The hydrocarbon is passed over the catalyst at an average hourly rate of gas supply more than 10000 h-1, more preferably 20000 h-1and most preferably more than 100000 h-1. However, it should be borne in mind that the optimal hourly average gas flow rate usually depends on the pressure and nature of the initial composition.

In a preferred embodiment, the reaction zone together with the hydrocarbon and oxygen-containing gas is fed hydrogen. The molar ratio of hydrogen to oxygen-containing gas can be varied in any effective range, provided that the target is formed olefinic product. In a suitable embodiment, the value of the molar ratio of hydrogen to oxygen-containing gas is in the range from 0.2 to 4, preferably in the range from 1 to 3.

Joint filing of hydrogen is an advantage because in the presence of a catalyst, the hydrogen burns with greater ease than the hydrocarbon, which increases the selectivity of the whole process in respect of the olefin.

In a preferred embodiment, prior to contacting with the catalyst, the reaction mixture of hydrocarbon and color soderzhaschego gas (and optionally together supplied hydrogen is preheated. Usually the reaction mixture is heated to a temperature below the Autoignition temperature of the reaction mixture.

In a suitable embodiment for pre-heating of the reaction mixture prior to contacting with the catalyst it is possible to use the heat exchanger. The heat exchanger allows to heat the reaction mixture to a high temperature pre-heating, such as temperature equal to or above the Autoignition temperature of the reaction mixture. Creating a high temperature pre-heating is an advantage consisting in the fact that it requires less oxygen as a reagent, which leads to savings. Moreover, the creation of high temperature pre-heating can be increased selectivity for olefin product. It was found also that the creation of a high temperature pre-heating increases the stability of the reaction in the mass of the catalyst, leading, thus, to the ability to withstand the increased consumption of raw materials per unit cross section of the stream.

It must be borne in mind that the Autoignition temperature of the reaction mixture depends on the pressure, and the composition of the source material: it is not an absolute value. In the processes autothermal cracking, where the hydrocarbon assetstatus under pressure of 2 ATA, as a rule, you can create a temperature preheating to 450°C.

The method according to the present invention can be effectively carried out at a temperature at the outlet of the catalyst in the range from 600 to 1200°C, preferably in the range from 850 to 1050°and most preferably in the range from 900 to 1000°C.

The method according to the present invention can be performed at any appropriate pressure, in particular under atmospheric pressure or under increased pressure. The method according to the present invention can be realized under a gauge pressure in the range from atmospheric up to 5 bar, but in the preferred embodiment, it is carried out under a gauge pressure above 5 bar. In a more preferred embodiment, the process is autothermal cracking process is performed under a gauge pressure ranging from 5 to 40 bar and expediently in the range from 10 to 30 bar, for example, from 15 to 25 bar.

The interaction products when they come out of the reaction chamber, in the preferred embodiment, cooled rapidly to avoid further reactions. Typically, the product stream is cooled to the range from 750 to 600°within less than 100 MS education, preferably within 50 MS of education, and most preferably within 20 MS of education, for example, within 10 MS of education.

When a process autoarming the first cracking is carried out under a gauge pressure of 15 to 20 bar, products are usually rapidly cooled down and the temperature is reduced to the range from 750 to 600°within 20 MS of education. In a useful embodiment, when the process is autothermal cracking process is performed under a gauge pressure above 20 bar, the products are cooled rapidly and the temperature is reduced to the range from 750 to 600°within 10 MS of education.

The invention is hereinafter described with reference to the drawing.

The drawing shows the reactor (1) autothermal cracking high-pressure reaction zone (2)surrounded by a jacket (3) under pressure. This reactor is made of quartz tubular sheath (4)placed inside a metal holder (5).

The oxygen line (6) and hydrocarbons through line (7) directed to the zone of mixing of gases (8). Next, the mixed gaseous reagents directed into the reaction zone. The reaction zone includes a first layer (9) of the catalyst and a second layer (10) of the catalyst.

When the reactants come into contact with the layers (9) and (10) catalysts, a number of hydrocarbons burns with formation of water and carbon oxides. This combustion reaction is exothermic, and the resulting heat is used for dehydrogenization hydrocarbons with obtaining product stream comprising olefins.

The flow of gaseous products from the reaction zone passes into the zone (11) is the th cooling includes zone (12) of the injection gas in which it is introduced into contact with the high-speed stream of nitrogen at 25°to quickly reduce its temperature and maintaining the selectivity towards olefins.

The invention is further illustrated by the following examples.

Preparation of catalysts

Catalysts 1-3: 3 wt.% platinum on alumina

Catalyst 1: 3 wt.% platinum foamed aluminium oxide

Blocks of foamed aluminum oxide (supplied by the company Hi-Tech Ceramics, new York, with a porosity of 45 pores per inch (IPA)) were subjected to repeated impregnation with an aqueous solution of chloride tetraammineplatinum(II). The chloride solution tetraammineplatinum(II) was prepared using a sufficient amount of salt to achieve nominal concentrations of Pt 3 wt.%, if in the final catalytic composition has introduced a whole metal salt. Between each impregnation, the excess solution from the foam blocks were removed, the foam blocks were dried in air at about 120°C for approximately 30 min and subsequently progulivali in air at 450°C for approximately 30 min (for decomposition on the surface of the foamed material salt Pt to Pt metal). After all the solution foamed material was absorbed, the blocks were dried and spent the final calcination in air at 1200°C for 6 hours

Catalyst 2: 3 wt.%platinum on the balls of aluminum oxide

The experiment according to the method of preparation of the catalyst 1 was repeated using as the carrier balls of aluminum oxide (supplied by the company Condea, with a diameter of 1.8 mm, with a specific surface area of 210 m2/g).

Noted that after annealing the ball diameter was reduced to approximately 1.2 mm

Catalyst 3: 3 wt.% platinum foamed aluminium oxide

The experiment according to the method of preparation of the catalyst 1 was repeated using as the carrier blocks of foamed aluminum oxide with a porosity of 30 IPA (supplied by company Hi-Tech, new York).

Catalysts 4-6: catalysts based on mixed oxides of metals

Catalyst 4: oxide of Y-Ba-Cu oxide aluminum

2,084 g of uranyl nitrate yttrium (99,9%of the firm Aldrich), 2,835 g of barium nitrate (99+%of the firm Aldrich) and 3,975 g hemipentahydrate nitrate copper(II) (99,99+%firm Aldrich) was dissolved in 50 cm3deionized water.

This solution was subjected to re-impregnation balls of aluminum oxide (supplied by the company Condea, with a diameter of 1.8 mm, with a specific surface area of 210 m2/g). Between the excess impregnation solution with the beads was removed, the beads were dried in air at about 120°C for 10 min and subsequently progulivali in air at 450°C for approximately 30 minutes After all the solution was absorbed by the balls, their drying and spent the final calcination in air at 1200° With over 6 hours

Noted that after annealing the ball diameter was reduced to approximately 1.2 mm

Catalyst 5: oxide of Y-Ba-Cu

the 3.65 g of uranyl nitrate yttrium (99,9%of the firm Aldrich), with 5.22 g of barium nitrate (99+%of the firm Aldrich) and 7,248 g hemipentahydrate nitrate copper (II) (99,99+%of the firm Aldrich) were thoroughly mixed and placed on the tray of the silicon dioxide in the drying cupboard, which stood at 150°C for 2 hours during this period was the dissolution and mixing of salts in their crystallization moisture.

Next, the mixture was progulivali in air at 350°C for 1 h, then the temperature was linearly increased at a rate of 10°C/min up to 950°C, after which it was maintained for 4 h and then cooled.

The obtained solid material was crushed using a mortar and pestle, vypressovyvaniem of discs with a diameter of 22 mm under a 20-ton pressure, then crushed and sieved to particles of 1 to 2 mm.

Catalyst 6: F doped oxide of Y-Ba-Cu

11,584 g of uranyl nitrate yttrium (99,9%of the firm Aldrich), 15,806 g of barium nitrate (99+%of the firm Aldrich), 21,338 g hemipentahydrate nitrate copper(II) (99,99+%company Atdrich) and 0,245 g of copper fluoride (Aldrich company, 99,999%) were thoroughly mixed and placed on the tray of the silicon dioxide in the drying cupboard, which stood at 350°C for 3 hours

The obtained solid material is by using a mortar and pestle grinds, then progulivali in air at 950°C for 6 hours Then the mixture was left to cool, and then crushed using a mortar and pestle to powder. Then this powder vypressovyvaniem disks with a diameter of 22 mm under a 20-ton pressure, then crushed and sieved to particles of 1 to 2 mm and, finally, before the test was re-progulivali in air at 950°C for 6 hours

Example 1

In the autothermal reactor cracking of high pressure, as shown in the drawing, includes the first layer catalyst comprising alumina containing 3 wt.% platinum (catalyst 1), maintained a gauge pressure of 10 bar. The thickness of the first catalyst layer was 30 mm In the autothermal reactor was sent ethane, oxygen, hydrogen and nitrogen and the reaction conditions were adjusted in such a way as to support the conversion of ethane at the level of 50%. The resulting product stream was analyzed, its composition is presented in table 1.

This example was repeated using autothermal reactor, comprising a first layer of a catalyst comprising alumina containing 3 wt.% platinum (catalyst 2), and the second layer catalyst comprising a mixed oxide of yttrium-barium-copper (catalyst 4). The thickness of the second catalyst layer was 60 mm, the Resulting product stream also is analyzed, its composition is presented in table 1.

The data in table 1 show that when combined with the first catalyst layer using the second layer of the catalyst, the selectivity for ethylene increases, the selectivity for carbon monoxide is reduced, and the conversion of oxygen is increased.

Example 2

Example 1 was repeated with the creation of a gauge pressure of 20 bar and the use of the catalysts listed in table 2. The results are presented in table 2. Again you can see that when combined with the first catalyst layer using the second layer of the catalyst, the selectivity for ethylene increases, and the selectivity for carbon monoxide is reduced.

Example 3

The experiment of this example was performed under a gauge atmospheric pressure (0 bar) in the autothermal reactor consisted of a quartz reactor in a furnace with an electric heater, as disclosed in WO 02/04389. Positioning the first layer catalyst comprising alumina containing 3 wt.% platinum (catalyst 3), in this autothermal reactor was sent ethane, oxygen, hydrogen and nitrogen and the reaction conditions were adjusted in such a way as to support the conversion of ethane at a level of approximately 40%. The resulting product stream was analyzed, its composition is presented in table 3.

This PRIMEPOWER using the first catalyst layer, including alumina containing 3 wt.% platinum (catalyst 3), and the second catalyst layer, comprising a mixed oxide of yttrium-barium-copper (catalyst 5). The resulting product stream is also analyzed, its composition is presented in table 3.

Again you can see that when combined with the first catalyst layer using the second layer of the catalyst, the selectivity for ethylene increases, and the selectivity for carbon monoxide is reduced.

Example 4

Example 3 was repeated, but using a second catalyst layer including doped fluoride mixed oxide of yttrium-barium-copper (catalyst 6). The results are presented in table 4. Again you can see that when combined with the first catalyst layer using the second layer of the catalyst, the selectivity for ethylene increases, and the selectivity for carbon monoxide is reduced.

Table 1
Autothermal cracking of ethane under a gauge pressure of 10 bar with the joint supply of hydrogen at about 50%conversion of ethane
The catalyst layer 1Catalyst 1Catalyst 2
The catalyst layer 2-Rolled the ATOR 4
The flow velocity of the source
ethane, g/min101,2099,85
hydrogen, g/min
oxygen, g/min37,0535,89
nitrogen in the reactor, g/min11,0811,10
Nitrogen for rapid cooling147,9750,06
Gauge pressure, bar10,029,99
Preheating the raw material, °158182
The catalyst, °898898
After the abrupt cooling in nitrogen, °495520
The conversion of ethane, %48,0950, 20mm
The transformation of oxygen, %90,8299,65
Selectivity (g/100 g converted ethane) against
hydrogen5,495,03
methaneof 10.259,01
ethylene61,0967,59
acetylene0,220,26
propane1,740,91
propylene3,602,84
Bhutan2,91of 1.34
of butenes0,660,52
butadiene0,760,94
C5-C70,570,17
aromatic compounds0,160,11
carbon monoxide22,7113,76
carbon dioxideof 4.4412,31

Table 2
Autothermal cracking of ethane under a gauge pressure of 20 bar with the joint supply of hydrogen at about 50%conversion of ethane
The catalyst layer 1Catalyst 1Catalyst 2
The catalyst layer 2-Catalyst 4
The flow velocity of the source
ethane, g/min199,87198,06
hydrogen, g/min4,485,18
oxygen, g/min71,6871,95
nitrogen in the reactor, g/min11,1211,09
Gauge pressure is the bar20,0219.93 per
Preheating the raw material, °162156
The temperature of the catalyst No. 1, °909903
After the abrupt cooling in nitrogen, °696527
The conversion of ethane, %49,9050,94
The transformation of oxygen, %99,6599.89 per
Selectivity (g/100 g converted ethane) against
methane11,1712,08
CO21,4418,96
CO24,087,05
ethylene56,1758,29
acetylene0,180,26
propylene4,60br4.61
propane1,421,22
MAPD0,050,00
Bhutan3,061,93
of butenes1,361,17
butadienethe 1.441,28
C5-C71,901,19
aromatic compounds1,351,06
Table 3
Autothermal cracking of ethane under a gauge pressure of 0 bar with the joint supply of hydrogen at approximately 40%conversion of ethane

/tr>
The catalyst layer 1Catalyst 3Catalyst 3
The catalyst layer 2Catalyst 5
The flow velocity of the source
ethane, g/minto 4.98to 4.98
hydrogen, g/min0,200,20
oxygen, g/min1,601,60
nitrogen, g/min1,030,98
Gauge pressure, bar0,000,00
Preheating the raw material, °348323
The catalyst, °823825
The conversion of ethane, %41,644,7
The transformation of oxygen, %98,4100,0
Selectivity (g/100 g converted ethane) against
methane6,114,35
ethylene71,3475,77
acetylene0,000,00
propane1,040,39
propylene1,270,75
Bhutan1,950,57
of butenes0,170,14
butadiene0,230,74
C5-C70,050,02
aromatic compounds0,000,00
carbon monoxide17,0212,53
carbon dioxideto 7.5912,09

Table 4
Autothermal cracking of ethane under a gauge pressure of 0 bar with the joint supply of hydrogen at approximately 40%conversion of ethane
The catalyst layer 1Catalyst 3Catalyst 3
The catalyst layer 2-Catalyst 6
The flow velocity of the source
ethane, g/min4,464,46
hydrogen, g/min0,22
oxygen, g/min1,781,78
nitrogen, g/min1,020,99
Gauge pressure, bar0,000,00
Preheating the raw material, °219229
The catalyst, °827887
The conversion of ethane, %41,141,4
The transformation of oxygen, %94,7100,0
Selectivity (g/100 g converted ethane) against
methane5,773,49
ethylene72,7076,65
acetylene0,000,00
propane1,220,35
propylene1,550,69
Bhutan2,410,75
of butenes0,400,19
butadiene0,070,41
C5-C70,020,12
aromatic compounds0,000,00
carbon monoxide15,2611,19
carbon dioxide 4,0713,92

1. A method of producing olefin, comprising passing a mixture of hydrocarbon and oxygen-containing gas through the catalytic zone, including at least the first layer of catalyst and the second catalyst layer, and the first catalyst layer includes a catalyst capable of supporting combustion beyond the upper Flammability limit of the fuel, and the second layer of catalyst is placed in the process line after the first catalyst layer differs in composition from the first catalyst layer and satisfies the General formula

M1aM2bM3cOz,

in which M1selected from groups IIA, IIB, IIIB, IVB, VB, VIB, VIIB, lanthanides and actinides; M2selected from groups IIA, IB, IIB, IIIB, IVB, VB, VIB; M3selected from groups IIA, IB, IIB, IIIB, IVB, VB, VIB and VIIIB, a, b, C, and z represent the atomic ratio of the components respectively M1M2M3and About; the value is in the range from 0.1 to 1.0, the value b is in the range from 0.1 to 2.0, the value is in the range from 0.1 to 3.0, and the value of z is in the range from 0.1 to 9, and has a perovskite structure type.

2. The method according to claim 1, in which the first catalyst layer includes a metal of group VIIIB.

3. The method according to claim 2, in which the catalyst of the first layer is chosen from the series, on the expectation Pt/Ga, Pt/In, Pt/Sn, Pt/Ge, Pt/Cu, Pd/Sn, Pd/Ge, Pd/Cu and Rh/Sn.

4. The method according to claim 1, in which the catalyst of the second layer can be promotional adding halide promoters material that meets the General formula

M1aM2bM3cXxOz,

where X denotes a halide, and a value x is in the range from 0.05 to 0.5.

5. The method according to one of the preceding paragraphs, in which M1selected from group IIIB, M2choose from group IIA and M3selected from groups IB.

6. The method according to claim 5, in which M1denotes yttrium, M2denotes the barium and M3indicates copper.

7. The method according to one of claims 1 to 4, in which the hydrocarbon is an original wax material comprising hydrocarbons containing at least two carbon atoms.

8. The method according to one of claims 1 to 4, in which the molar ratio of hydrocarbon to oxygen-containing gas is 5 to 16 times the stoichiometric ratio of hydrocarbon to oxygen-containing gas required for complete combustion of the hydrocarbon to carbon dioxide and water.

9. The method according to one of claims 1 to 4, which together with the hydrocarbon and oxygen-containing gas in a reaction zone serves hydrogen.



 

Same patents:

FIELD: petrochemical processes.

SUBSTANCE: method consists in that interaction of initial hydrocarbon and molecular hydrogen-containing gas in reaction zone in presence of catalyst results in formation of reaction product wherein concentration of oxygen is equal, close or superior to inflammability limit, after which reaction decay is determined using thus obtained signal to activate measures directed to reduce explosion risk outside of reaction zone. Reaction decay is, for example, determined from sudden increase in concentration of oxygen in reaction product stream and/or from sudden product temperature drop. A similar olefin production method is also described as well as reactor used for conversion of hydrocarbons.

EFFECT: reduced risk associated with possible explosion in equipment located outside reaction zone, where hydrocarbon oxidation occurs.

36 cl, 4 ex

The invention relates to a method for producing olefins from hydrocarbons

The invention relates to a method of producing monoolefins of hydrocarbons containing one or more hydrocarbons of the paraffin series having at least two carbon atoms

FIELD: petroleum processing and catalysts.

SUBSTANCE: invention relates to catalyst for steam cracking of hydrocarbons, which catalyst contains KMgPO4 as catalyst component. Catalyst is prepared by dissolving KMgPO4 precursor in water and impregnating a support with resulting aqueous solution of KMgPO4 precursor or mixing KMgPO4 powder or its precursor with a metal oxide followed by caking resulting mixture. Described is also a light olefin production involving steam cracking of hydrocarbons.

EFFECT: increased yield of olefins, reduced amount of coke deposited on catalyst, and stabilized catalyst activity.

21 cl, 4 tbl, 14 cl

The invention relates to a method for producing liquid products of thermal cracking of petroleum residues and can be used in the refining industry
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FIELD: petroleum processing and petrochemical process catalysts.

SUBSTANCE: hydrofining catalyst is composed of, wt %: NiO 2.5-4.0, MoO3 8.0-12.0, Na2O 0.01-0.08, La2O3 1.5-4.0, P2O5 2.0-5.0, B2O3 0.5-3.0, and Al2O3 the rest. Preparation of the catalyst involves impregnation of sodium oxide-containing carrier with active components: nickel nitrate and ammonium paramolybdate solution followed by drying and calcination. In particular, sodium oxide-containing aluminum hydroxide is mixed with boric acid solution and nitric acid solution of lanthanum carbonate, resulting carrier is dried and calcined, after which impregnated with nickel nitrate and ammonium paramolybdate solution at pH 1.5-3.0 and temperature 40-80°C in presence of phosphoric acid.

EFFECT: enhanced efficiency of hydrofining raw materials comprising elevated amounts of unsaturated hydrocarbons.

2 cl, 2 ex

FIELD: hydrogenation-dehydrogenation catalysts.

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

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

18 cl, 2 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: catalyst designed for using in petroleum fraction hydrofining, which contains oxides of cobalt, molybdenum, phosphorus, lanthanum, boron, and aluminum, is prepared by mixing aluminum hydroxide with boric acid solution and nitric acid solution of lanthanum carbonate followed by drying, calcination, impregnation of resulting carrier with cobalt nitrate and ammonium paramolybdate solution in nitric acid at pH 2.0-3.5 and 40-80°C in presence of phosphoric acid followed by drying and calcination at elevated temperature.

EFFECT: enabled production of hydrogenate with reduced content of sulfur compounds.

2 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides petroleum fraction hydrofining catalyst with following chemical analysis, wt %: CoO 2.5-4.0, MoO3 8.0-12.0, Na20.01-0.08, La2O3 1.5-4.0, P2O5 2.0-5.0, B2O3 0.5-3.0, Al2O3 - the balance.

EFFECT: enhanced hydrofining efficiency in cases of feedstock containing elevated amount of unsaturated hydrocarbons.

2 ex

FIELD: hydrogen power engineering; the catalytic method of realization of the dimethyl ether steam conversion reaction.

SUBSTANCE: the invention is pertaining to the catalytic method of realization of the dimethyl ether (DME) steam conversion reaction for the purpose to produce the hydrogen-enriched gas mixture, which may be used in the hydrogen power engineering, in particular, as the fuel for feeding the fuel cells of the different designation. The invention presents the bifunctional catalyst of the dimethyl ether (DME) steam conversion containing the acidic centers for hydration of DME into the methanol, and the copper-containing centers for the steam conversion of methanol, and representing by itself the copper-ceric oxide deposited on the aluminum oxide. The invention also presents the method of production of the hydrogen-enriched gas mixture by interaction of DME and steam at the temperature of 200-400°C, pressure of 1-100 atm, molar ratio of H2О/DME equal to 2-10 at presence of the described above catalyst. The technical result of the invention is the high hydrogen efficiency, production of the hydrogen-containing gas with the low contents of carbon oxide at the ratio steam/DME equal to the stoichiometric (H2O/DME=3), that has the relevant technological value.

EFFECT: the invention ensures the high hydrogen efficiency, production of the hydrogen-containing gas with the low contents of carbon oxide at the suitable ratio steam to DME, that has the relevant technological value.

5 cl, 15 ex, 6 tbl

FIELD: chemical industry; catalyzers for dehydrogenation of the alkyl-aromatic hydrocarbons.

SUBSTANCE: the invention presents the catalyzer used for dehydrogenation the alkyl-aromatic hydrocarbons of the following composition (in mass%): potassium compounds (in terms of potassium oxide) - 8.0-25.0; magnesium compounds and-or calcium compounds (in terms of magnesium oxide and-or calcium oxide) - 0.2-7.0; molybdenum oxide - 0.7-7.0; cerium oxide - 1.0-15.0; Portland cement - 0.5-12.0; lanthanum oxide and-or neodymium oxide - 0.01-7.0; iron oxide - the rest. The technical result of the invention is the increase of activity, selectivity of the catalyzer, as well as the thermal stability, which increases the catalyzer service life.

EFFECT: the invention ensures the increase of activity, selectivity, thermal stability and the service life of the catalyzer.

4 cl, 20 ex, 2 tbl, 2 dwg

FIELD: oxidation catalysts.

SUBSTANCE: invention relates to oxidation catalysts that can be, in particular, used for complete oxidation of volatile organic compounds into CO2 and H2O. Catalyst according to invention contains mixed copper, manganese, and lanthanum oxides, wherein metals can assume multiple oxidation states and whose chemical analysis expressed for metals in lowest oxidation states is the following: 35-40% CuO, 50-60% MnO, and 2-15% La2O3.

EFFECT: enhanced stable catalytic activity and resistance to caking.

11 cl, 2 tbl, 2 ex

FIELD: catalyst preparation methods.

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EFFECT: prevented deactivation of copper-containing catalyst operated with process gas containing chlorine compounds.

11 cl, 3 tbl, 7 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: catalyst contains, wt %: potassium oxide and/or rubidium oxide, cesium oxide 10-40, magnesium oxide 2-10, cerium(IV) oxide 2-20, sulfur 0.2-5, and ferric oxide the rest.

EFFECT: increased selectivity and mechanical strength of catalyst.

1 tbl, 17 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention is dealing with catalyst applicable in saturated hydrocarbon ammoxidation process resulting in corresponding unsaturated nitrile. Catalyst composition of invention comprises complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one of nickel and magnesium, and at least one of lithium, sodium, potassium, rubidium, and thallium and is described by following empirical formula: AaBbCcFedBieCofCegSbhMomOx, wherein A represents at least one of Cr, P, Sn, Te, B, Ge, Zn, In, Mn, Ca, W, and mixtures thereof; B represents at least one of Li, Na, K, Rb, Cs, Ti, and mixtures thereof; C represents at least one of Ni, Mg, and mixtures thereof; a varies from 0 to 4.0, b from 0.01 to 1.5, c from 1.0 to 10.0, d from 0.1 to 5.0, e from 0.1 to 2.0, f from 0.1 to 10.0, g from 0.1 to 2.0, h from 0.1 to 2.0, m from 12.0 to 18.0, and m is a number determined by requirements of valences of other elements present. Ammoxidation processes for propylene, ethylene, or their mixtures to produce, respectively, acrylonitrile, methacrylonitrile, or their mixtures in presence of above-defined catalytic composition is likewise described.

EFFECT: increased olefin conversion.

9 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: catalyst for dehydration of alcylaromatic hydrocarbons containing oxides of iron, alkaline-earth metals, cerium (4), molybdenum, titanium and/or vanadium and potassium is described. The diffraction pattern of said catalyst contains reflexes of potassium polyferrite and hematite phase related to iron (3) oxide in α-form. The relative intensities of said reflexes are (1÷40) and 100% respectively. Catalyst component ratio may be as follows: potassium oxide 5-30 Wt%; oxides of alkaline-earth metals 1-10 Wt%; cerium (4) oxide 5÷20 Wt%; molybdenum oxide 0.2-5 Wt%; titanium and/or vanadium oxide 0.2-5 Wt%; iron (3) oxide - the rest. Additionally catalyst can contain up to 30 Wt% of rubidium oxide and/or cesium oxide. The catalyst is prepared by calcinating at temperatures 500-750°C during 1-3 hr and 800-900°C during 0.5-1.5 hr. Bulk density of catalyst is in the range 0.95-1.5g/sm2.

EFFECT: development of catalyst providing high conversion and selectivity in relation of end products in the process of alcylaromatic hydrocarbons dehydration; increasing of catalyst service cycle.

5 cl, 1 tbl, 15 ex

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