Reforming catalyst

FIELD: chemistry.

SUBSTANCE: invention relates to method of reforming with application of catalyst. Described is method of reforming hydrocarbons with water vapour, including contact of supplied gas in reactor of catalytic partial oxidation or installation for autothermal reforming. Reactor operates at temperature 800-1600°C and pressure of 20-100 bar. Egg shell type catalyst, consisting of active compound in form of alloy of nickel and one metal from iridium and ruthenium, on supporter, containing aluminium oxide, zirconium dioxide, magnesium oxide, titanium dioxide or their combinations. Catalyst has cylindrical shape and has one or several through holes, where distance from centre to external catalyst surface constitutes from 10 to 40 mm, catalyst height constitutes from 10 to 40 mm, with diameter of one or several through holes constituting from 3 to 30 mm. At least 90 wt % of iridium or ruthenium in catalyst are located in external envelope which has depth up to 10% of external catalyst surface or to 10% of periphery of one or several through holes of catalyst.

EFFECT: realisation of method of catalytic partial oxidation or autothermal reforming at reduced drop of pressure in catalyst layer without reduction of catalyst activity.

12 cl, 5 dwg, 2 tbl, 5 ex

 

The present invention relates to an improved catalyst for steam reforming, such as tubular reforming, heat exchange reforming, catalytic partial oxidation (CONFERENCE), autothermal reforming and secondary reforming. This invention also relates to a method of producing catalyst and method of reforming process using the catalyst. More specifically, the invention relates to a reforming catalyst for use in the process of autothermal reforming (ATR) or catalytic partial oxidation (CONFERENCE).

As used here, autothermal reforming (APR) covers all variations of this technology, including secondary reformer combustion in air with oxygen. The term secondary reforming process is usually used when the resulting synthesis gas is used as a synthesis gas to produce ammonia. The present invention mainly focused on autothermal reforming process with an oxygen blast. However, it also presents its use for autothermal reforming with air purge and catalytic partial oxidation (CONFERENCE). Typically, the autothermal reforming with air purge is used in factories production of ammonia, and, in General, the operating conditions of the installation autothermal reforming are less demanding�mi because of the decreasing influence of nitrogen in the air at higher relations of water vapor to carbon.

The production of synthesis gas from natural gas, oil, coal, coke, crude oil and other carbon resources is usually carried out through the reaction of steam reforming, autothermal reforming, catalytic partial oxidation, or gasification. The synthesis gas contains hydrogen, carbon monoxide, carbon dioxide and water as main components.

The use of technology autothermal reformer for the treatment of process gas, which was partially subjected to a reforming higher along the flow, is well established. Partially subjected to a reforming gas is usually obtained from the processing of the feed hydrocarbon, which passes through the tubular installation for reforming or heat exchanger installation for reforming. Supplied natural gas can also be directly passed through autothermal system for the reforming process, perhaps after the supplied gas passes through an adiabatic pre-reformer.

In the installation autothermal reforming (ATP), the preheated hydrocarbon feedstock is subjected to exothermic internal combustion in oxygen, partial oxidation with subsequent endothermic steam reforming of the partially oxidized feedstock in a fixed bed of catalyst. Chemical reactions in this type of installation dereference contain a combination of reactions of combustion and steam reforming. Setting the ATR consists roughly of a refractory lined pressure vessel, a combustion chamber and the stationary layer of the catalyst. The burner installed in the upper part of the reactor, provides mixing of the heated hydrocarbon flow, such as a stream enriched in methane, together with the stream containing oxygen, such as air or a mixture of oxygen/water vapor. Oxygen can be served in posteriorities quantities (less than required for full combustion of hydrocarbon feed), and the reaction flame ignition feed hydrocarbon occur in the combustion chamber, located in the upper part of the reactor. The combustion chamber is formed by the region between the burner at the top of the reactor and stationary (s) layer (s) of the catalyst and may also include an area where further conversion of the feed hydrocarbon due to homogeneous reactions in the gas phase. The final conversion of the hydrocarbon occurs through heterogeneous catalysis in one or more fixed beds of a suitable catalyst, arranged in the lower part of the reactor.

The reaction of the ignition flame, representing the partial oxidation of hydrocarbon feed raw materials, are highly exothermic, whereas the final conversion of hydrocarbons in a fixed bed catalyst� is endothermic and is carried out in the presence of, for example, water vapor. The exothermic reaction provides the heat necessary for the endothermic catalytic steam reforming. Apparatus for autothermal reforming of a typical temperature of the process gas leaving the combustion chamber are in the range of 800-1600°C, more specifically, in the range of 900-1400°C. the gas is cooled by the endothermic reaction of steam reforming in the catalyst bed to 850-1100°C. In the area above the fixed bed of catalyst can be achieved the maximum flame temperature 2000-3500°C. the Actual temperature may vary depending on, for example, is blown through the reactor with air or oxygen.

Installation for steam reforming, such as tubular installation for reforming, heat exchange units for reforming, catalytic partial oxidation (CONFERENCE), and especially installations for autothermal reforming usually work with catalysts based on Nickel (Nickel as the sole metal) certain forms, such as catalysts of the round shape. Unfortunately, owing to the harsh conditions prevailing in these plants for the reforming process, especially in installations for autothermal reforming, we observe that there may be a depletion of Nickel on a geometric surface bodies cat�of lysator, and sintering of Nickel and, thus, the loss of a catalytically effective surface area. In General, the catalyst loses stability and activity after some time.

More specifically, the problems associated especially with the work of the Asia-Pacific region, includes evaporation of Nickel and quick sintering of Nickel. As it seems, the volatilization of Nickel is the result of the reaction of Nickel particles of the catalyst for steam reforming in accordance with Ni(t)+H2O=Ni(OH)2(g).

In addition, the apparatus for autothermal reforming is fire-resistant lined, and the catalyst bed is protected by a layer of fire-resistant tiles. A key aspect is to maintain a low pressure drop in the catalyst bed to eliminate the risk of side gas passage in the refractory lining, resulting in local overheating of the reactor shell. Refractory materials based on aluminum oxide and small amounts of aluminum oxide evaporate from these materials at high temperature in the combustion chamber according to equation Al2O3(t)+2H2O (g)=2Al(OH)3(g). These pairs of aluminum oxide is then condensed (or cure or deposited) on the catalyst, which remains relatively cool due to the endothermic reforming reaction. The result is a gradual lowering of the quantity� catalyst, which leads to increasing pressure drop over the catalyst bed.

The patent application U.S. 2005/0089464 discloses a catalyst for partial oxidation-based Rh on alumina and a catalyst for steam reforming Ni-based on aluminium oxide. Download metal is high, i.e. in the range of 5-30 wt.%.

U.S. patent No. 7230035 discloses a catalyst that is provided with porous locking layer between the carrier and the catalytic layer, in which more than 60% of active substances are in the outer shell, i.e. shows a cross-section of the eggshell. The catalytically active material may be iridium, rhenium or rhodium.

The patent application U.S. 2009/0108238 discloses a catalyst for reforming hydrocarbons containing metals such as platinum, palladium, rhodium, iridium, ruthenium, deposited on a carrier, produced from a mixture of the material with low surface area material with high surface area.

The EPO application EP-A-1338335 discloses catalysts for reforming hydrocarbons comprising Ir and Co, or Rh and Co, or Ru and Co in the carrier of cerium oxide and aluminum oxide. The weight content of Ir or Rh or Ru is about the same as Co. This source says nothing about the use of the type catalysts of the eggshell.

The patent application U.S. 2007/0238610 discloses reforming catalysts from the top�willow, applied as potravnyi primer in the form of foams and monoliths for applications in fuel cells. The disclosed two-stage catalysts include catalysts, such as catalyst 2 wt.% Ir - 2 wt.% Ni La2O3with further catalyst containing Pd or Pt, such as 1 wt.% Pd - 5 wt.% Ni. Two-stage catalysts provide higher generation of hydrogen than their single-stage counterparts. Where used Rh, the catalyst comprises Rh, Pt or Pd, and Ni. The addition of Rh, as is believed, improves the stability of the catalyst to sulfur poisoning and coke formation. This source says nothing about the use of the type catalysts of the eggshell.

International application WO-A-9737929 reveals the experimental reactor for carrying out partial oxidation reactions, including the use of monoliths with the catalyst systems comprising the use of Rh in the first catalyst bed and EN in the second layer, or Rh in the first Ni layer and the second layer. There is no disclosure of a catalyst system Rh-Ni or Ir-Ni, neither the use of catalysts of the type eggshell.

International application WO-A-2010078035 describes briefly and widely use of catalysts Ni-Ir in ATR applications, in particular, the catalyst Ni-Ir with 2.5 wt.% Ni and 0.5 wt.% Ir with a variation of about 0.25 wt.% for the optimization. This source says nothing on�individual use of catalysts of the type eggshell.

International application WO-A-2007/015620 discloses the use of deposited Ru catalysts based on Ni for steam reforming, as well as the applied Ir catalysts based on Ni, with the first exhibit excellent activity in the steam reforming. The catalyst prepared in powder form, which is expected to be received by impregnation of Ru or Ir all particles. This source says nothing about the use of the type catalysts of the eggshell.

The patent application U.S. 2008/0265212 reveals resistant to sulphur catalysts for production of synthesis gas and hydrogen via the steam reforming at a temperature of about 500°C for applications in fuel cells. The catalysts are in the form of powders and include Rh-Ni on, among other things, mixed media ceria - alumina. Since the catalyst is in powder form, it is expected that full penetration of the active metal particles inside. Accordingly, this source says nothing about the type catalysts of the eggshell.

U.S. patent number 5616154 broadly discloses the use of Rh and Ru as catalysts on various carriers, including aluminium oxide, for converting liquid organic materials at low temperatures and high pressure (300-450°C, more than 130 atmospheres) in a gas containing methane, etc�carbon monoxide and hydrogen, that is, "methanation". Metals Ir, Pt, and Pd, possibly in combination with the recovered Ni as the second catalyst also indicate how effective the conversion CO - methane. Among the tested catalysts are not bimetallic Ir-Ni and Rh-Ni, and consider the process of "methanation" is a completely different field of use than the present invention.

The patent application U.S. 2008/0197323 discloses the use of catalysts in, for example, autothermal reforming process, where the catalytic activity of the first (upper) layer is increased when used in this layer of catalysts a higher geometric surface area (GPP) than in the subsequent layers. Active metal in the catalyst is a Nickel, which can be replaced by metals, comprising platinum, palladium, iridium, ruthenium and rhodium.

In proceedings of the international conference "Nitrogen and Syngas" 2010, Bahrain 28 II-03 III, 2010, pp. 97-109, is widely proposed to provide the upper part of the catalyst layer in the plant for autothermal reforming catalyst particles having a low GPP, where said particles have more than one through holes, while the lower and major portion of the catalyst layer is provided by smaller particles of catalyst having a higher SE� and also containing more than one through-hole.

The EPO application EP-A-0625481 describes a method of reforming at high temperature, for example, autothermal reforming, in which the layer of catalyst comprises upper and lower layer, and the catalyst in the upper layer have a reduced activity. Decreased activity, as possible while increasing the particle size of the catalyst in the upper layer.

The object of the present invention is to provide a catalyst for use in catalytic partial oxidation (CONFERENCE) or autothermal reforming process (ATR), which has higher activity and more stable than conventional catalysts based on Nickel.

Another object of the present invention is to provide a method of catalytic partial oxidation or autothermal reforming at low pressure drop in the catalyst layer without reducing the activity of the catalyst.

These and other problems are solved by the present invention.

Accordingly, the first object of this invention is provided process, features which also indicated as such in PP.1-15 of claims.

1. Method of steam reforming of hydrocarbons that contains the contact of the injected gas in the reactor, a catalytic partial oxidation (CONFERENCE) or the installation autothermal reformer operating at temperatures�x in the range of 800-1600°C and a pressure of 20-100 bar, with catalyst type eggshell, consisting of the active compounds in the form of an alloy of Nickel and one of iridium metal, rhodium, and ruthenium on a carrier containing aluminum oxide, zirconium dioxide, magnesium oxide, titanium dioxide or combinations thereof.

2. A method according to claim 1, wherein the catalyst has a cylindrical shape and has one or more through holes, where the distance from the center to the outer surface of the catalyst is 10 to 40 mm, the height of the catalyst is 10 to 40 mm, and the diameter of the one or more through holes is from 3 to 30 mm.

3. A method according to claim 1 or 2, wherein the catalyst is in the form of one or more layers of catalyst with respect to a void/(external or geometrical surface area) 1.0-4.5 l/m2.

4. A method according to claim 3 in which the upper layer is a catalyst of the first type with respect to a void/(external or geometrical surface area), which is more than 3 l/m2and at least the second layer is a catalyst of the second type with respect to a void/(external or geometrical surface area), which is less than 3 l/m2.

5. A method according to claim 4, where the ratio of the void/(external or geometrical surface area) of the catalyst of the second type above 2 l/m2.

6. A method according to any one of claims.1-5, has a population�schy at least a third layer of a third type of catalyst, having a void/(external or geometrical surface area) in the range from 1.0 to 4.5.

7. A method according to any one of claims.1-6, in which the active compound is an alloy of Nickel and iridium, or an alloy of Nickel and rhodium, or an alloy of Nickel and ruthenium, where the content of iridium or rhodium or ruthenium in the catalyst is in the range from 0.01 to 0.5 wt.%, as the Nickel content in the catalyst is from 2 to 16 wt.%.

8. A method according to any one of claims.1-7, where the carrier contains aluminum oxide, selected from a-alumina, calcium aluminate, magnesium-aluminum spinel, and combinations thereof.

9. A method according to any one of claims.1-8, where the active compound is an alloy of Nickel and iridium, or Nickel and ruthenium, and at least 90 wt.% iridium or ruthenium in the catalyst is located in an outer shell having a depth of up to 10% of the external surface of the catalyst or up to 10% of the periphery of one or more through holes of the catalyst.

10. A method according to claim 9, in which the local concentration of iridium or ruthenium in the outer shell is from 0.1 to 5.0 wt.%.

11. A method according to any one of claims.1-10, where the active compound in the catalyst in the form of an alloy of Nickel and one of iridium metal, rhodium, and ruthenium has an average crystallite size of below 0.1 μm, when measured by aged or exhausted catalyst.

12. A method according to any�the mu one of claims.1-11, in which the first catalyst prepared by the introduction of Nickel in the media and at the next stage, the addition of iridium or rhodium or ruthenium.

13. A method according to claim 12, wherein the catalyst is obtained by application of a catalyst consisting of Nickel on a carrier, an aqueous solution of iridium, rhodium or ruthenium, and then by calcination in air at 400-600°C and recovery in N2at 350-600°C, preferably 500-550°C.

14. A method according to claim 13, wherein impregnation of the catalyst is carried out with an aqueous solution of IrCl3×H2O or iridium acetate or Ru(NO3)3NO, and the carrier contains aluminum oxide, and preferably is an oxide of aluminum or magnesium-aluminum spinel.

15. A method according to any one of claims.1-14, further comprising removing from the reactor a catalytic partial oxidation (CONFERENCE) or plants for autothermal reforming of synthesis gas for subsequent Fischer-Tropsch synthesis, ammonia synthesis, methanol synthesis and synthesis of simple dimethyl ether (DME).

As used here, a carrier containing aluminum oxide, covers the various forms of alumina such as α-alumina, aluminosilicates of calcium, calcium aluminates, magnesium-aluminum spinel, and combinations thereof.

The terms carrier and substrate are used interchangeably.

As used here when referring to the percent by weight (wt.%) e�means of the weight of the alloy of the metal relative to the total weight of the catalyst, including the media.

As used here, the term catalyst type eggshell refers to the body of catalyst in which the active metal has a significantly different concentration towards the outer surfaces of the catalyst than in the rest of this body. In other words, there is a concentration gradient, or a variation in the concentration of at least one of the active metals from the outer surface of the body of catalyst to the catalyst body. For example, while the Nickel concentration may be constant throughout the body of catalyst (Nickel are uniformly distributed), the concentration of the other metal of the alloy may vary, and preferably to be higher towards the outside of the body of the catalyst. The outer surface is the surface on the catalyst, which is in direct contact with the main flow of the reacting gas passing through the catalyst bed containing the individual catalysts type eggshell. Accordingly, the outer surface may be the surface along the periphery of the through hole in the catalyst, or the surface along the outermost periphery of the catalyst.

We found that the addition of small quantities of noble metals Rh, Ir or Ru applied to the Ni catalysts provides real benefits � their catalytic activity and durability as a result of the stabilization phase of the Nickel against sintering and volatilization at high temperatures and high pressures, for example, reactors in the Asia Pacific region. Noble metal plays a structural role of the activator through the formation of metal alloys with Nickel.

The alloy particles have a slower speed sintering than pure Nickel, and therefore support greater active surface area for longer times during commercial operation. In addition, the alloy particles of compounds with lower vapor pressures, thus more stable against volatilization in the form of, e.g., Ni(OH)2. The result is less loss of Nickel.

Favorable effect of noble metals was originally discovered on promoted Rh catalysts alumina: promoted Rh Nickel catalysts are much more active than their conventional counterparts, such as Nickel catalyst aluminum oxide, aluminates of calcium or magnesium-aluminum spinel. This is due to the higher dispersion of the active phase: for example, an alloy of Ni-Rh also suppresses the volatilization of Nickel near the outer surface of the catalyst rings. The same structural promotion demonstrated after impregnation of small amounts of Ir in conventional catalysts based on Nickel, such as Nickel catalyst aluminum oxide or magnesium-aluminum spinel, and after treatment with�of arena or exposure of the catalysts to industrial conditions that is, in partially exhausted catalysts. Without alloy of Ir or Rh or Pt or Ru with Ni, Ni crystals grow and sintered together, and the effective surface area decreases, leading to decreased activity. We have seen that not many Nickel disappears when it is alloyed with Rh, Ir, Ru or Pt, and that the degree of sintering largely suppressed. Even small amounts of Ir or Rh or Pt or Ru significantly increase the catalytic activity. Therefore, the catalysts according to the invention show a better resistance to deactivation at high temperatures and thus longer service life.

We also found that although iridium has a higher activity than the Nickel in the same degree of dispersion, the resulting catalyst in the form of an alloy of Nickel and iridium on the media shows higher activity than any of the catalyst on the basis of pure Nickel or a catalyst based on pure iridium. Therefore, set an unexpected synergistic effect.

To ensure the profile type of the eggshell with higher local concentrations of metal than Nickel, toward the outer surface of the body of catalyst in the first catalyst is injected Nickel, for example, through impregnation of the substrate containing aluminum oxide, and in the next stage add Ir or Rh or Ru, nab�emer, subsequent application with an aqueous solution of the metal. Preferably, the catalyst is introduced with Nickel is subjected to drying and calcination prior to the subsequent addition of Ir or Rh or Ru. The calcination is preferably carried out at 400-600°C in air, more preferably at 450°C in air.

We also found that especially when using iridium or ruthenium as a noble metal on a carrier containing alumina such as α-alumina, magnesium-aluminum spinel or calcium aluminate, this metal after impregnation on the carrier does not penetrate completely into the body of the catalyst, but rather remains even more on the outer shell of the catalyst body, i.e., toward the external surfaces of the body of the catalyst. Thus, a much simpler and cheaper way of obtaining a new catalyst, without the need for a microporous barrier layer, as for example, in U.S. patent 7230035. The depth in which the noble metal is iridium, up to 2000 μm, preferably up to 1000 μm from the outer surface of the catalyst, more preferably up to 500 microns, most preferably below 400 μm or about 200 μm. The distance from the surface to the surface in the ring formed of the catalyst (from the outer surface of the catalyst to peri�of ETP through holes), or full depth is typically 10000 microns.

Accordingly, in a specific embodiment of the invention, the active compound is an alloy of Nickel and iridium, or Nickel and ruthenium, and at least 90 wt.% iridium or ruthenium in the catalyst is located in an outer shell having a depth of up to 10% of the external surface of the catalyst or up to 10% of the periphery of one or more through holes of the catalyst.

Particles of Ir or Ru remain close to the outer shell of the rings of the catalyst, reaching local concentrations of between 0.1 to 5.0 wt.%, often between 0.1 and 1.0 wt.% when the distances from the outer surface of 1000 μm or below, particularly below 500 microns or even below 400 μm, thereby forming the profile type of the eggshell with a concentration gradient from the surface in the catalyst; the distance from the surface to the surface or full depth is 10000 μm.

The outer surface of the catalyst bodies, even if the body of the catalyst, as such, has a completely cylindrical shape may be different from the round.

Although in the industrial reaction conditions in the plant for autothermal reforming, PRESENTED or occur mainly in the outer shell of the catalyst bodies, some penetration of the active metal is still desirable. We found that the best catalysts are those in which m�Nisha least 90 wt.% active metal, preferably, Ir or Ru, is located within the depth of about 200 μm, for example, from 150 to 250 microns, which corresponds to about 2%, e.g., 1.5 to 2.5% of the external surface of the catalyst or from the periphery of one or more through holes of the catalyst, the catalyst preferably is a ring-shaped catalyst (a through hole) with full depth of 1000 microns.

Preferably, when using iridium impregnation of the catalyst is carried out with aqueous solutions of IrCl3×H2O or Ir(SLA)x(iridium acetate) as precursors. We found that the presence of these sections of the eggshell may be attributed to electrostatic interactions between the anionic particlesIrCl63in solution and the positively charged groups of Al-(OH2)+on the surface of the Al2O3or probably even a Nickel as other fundamental particles, which prevents the penetration of Ir deeper into the body of the catalyst during the impregnation of the pores. The same mechanism of interaction with the surface of the Al2O3as it seems, applies when using the iridium acetate as a precursor for iridium. The iridium acetate is particularly �replication as a precursor of iridium, because he avoids the use of solutions containing Cl-in the course of preparation of the catalyst, and enables the localization of iridium in the catalyst within the layers of a thickness of 200 microns from the surface or below, such as 150 μm, as shown in accompanying Fig.3.

Preferably, when using ruthenium impregnation of the catalyst is carried out EN(NO3)3NO or RuCl3×nH2O as precursors. Ru(NO3)3NO particularly attractive as its predecessor, as it gives the possibility that the thickness of the outer shell EN is below 500 μm concentrations of Ru, usually ranging between 0.3-2.5 wt.%. In the case of RuCl3×nH2O, the thickness of the outer shell EN is usually below 400 μm, and the concentrations of Ru vary typically within the range of 0.2-1.5 wt.%, some more EN also penetrates deeper into the rings to some extent. For example, in the catalyst of Ru/Al2O3obtained RuCl3×nH2O, there is an area of 4000 μm from the outer surface, which contains up to 0.5 wt.% Ru, as shown in accompanying Fig.4.

Rh/Ir/Ru (Rh or Ir, or Ru) in fresh catalyst based on Nickel will be during heating, and after start-up, to form the alloy, penetrating into the Nickel particles. While pure Ni will be sintered with a higher speed through as�e, the catalyst promoted with a noble metal to be sintered with a slower speed and thereby maintain a large active surface area for longer periods of time with a concomitant increase in the service life of catalyst loading. We observed smaller size of the metal particles in the spent catalysts promoted with noble metals, in comparison with catalysts based on pure Nickel. Active compound in the form of an alloy of Nickel and noble metals has an average crystallite size of below 0.1 μm in the measurement of aged or exhausted catalyst, while the catalyst with particles of Nickel without noble metal has a mean crystallite size of more than 0.1 μm, often in the range of 0.1-0.8 μm or more, as measured by analysis of scanning electron microscopy (SEM).

In accordance with the invention, the preferred catalyst showing high activity and stability, is a catalyst carrier comprising α-alumina with a 2.0 or 3.0 wt.% Ni and 0.1 wt.% 1 G. Thus, in a preferred embodiment of the invention, the weight ratio Ir/Ni is 1/20 or 1/30, but lower the number of Ir relative to Ni are also applicable, such as weight ratio Ir/Ni as low as 1/60. Weight ratio of Rh/Ni may also bytestor low, as 1 / 70th of an. More preferred interval for the media containing α-alumina, is 0.04-0.15 wt.% Ir/Rh.

The term Ir/Rh denotes Ir, or Rh. The term Rh/Ir denotes Rh or Ir.

A carrier comprising α-alumina, 0.01-0.5 wt.% Rh/Ir, but is preferably from 0.03 to 0.5 wt.% Rh/Ir.

In another preferred embodiment of the invention, the carrier containing spinel MgAl2O4works well in terms of activity and stability as with 8 wt.% Ni, and 0.25 wt.% Ir/Rh, and 12 wt.% Ni and 0.25 wt.% Ir/Rh, which corresponds to the Ir/Ni=1/32 and 1/48, respectively. The media containing spinel MgAl2O4works also with 0.01-0.5 wt.% Rh/Ir, preferably 0.03 to 0.5 wt.% Rh/Ir.

As described above, condensation of aluminum oxide in the plant for reforming causes the voids of the catalyst layer to decrease, and thereby increases the pressure drop in the catalyst bed. Lowering this emptiness is sharper than linear, the effect of relatively increasing the pressure drop.

This emptiness is the volumetric portion of the catalyst layer, where the process gas can flow freely and is not obstructed by the material of the catalyst bodies.

The emptiness of the catalyst layer is a for this purpose defined as the number of liters of volume of the catalyst layer that is outside or external geometric p�surface of the bodies of catalyst per unit volume of the catalyst layer.

External or geometrical surface area (GPP) of the bodies of catalyst is a for this purpose defined as the number of m2external or geometrical surface area of the bodies of catalyst per unit volume of the catalyst layer.

According to the invention the problem of deposition is further facilitated by the work of more space for condensation/deposition of aluminum oxide in the choice of the catalyst to the upper part of the catalyst layer with the shape of the body, characterized by a high ratio between the void and the external or geometric surface area; that is, emptiness, divided by external or geometrical surface area in units of l/m2that follows from the definitions above. This again leads to the fact that the catalyst is a simple annular body shape, i.e. a cylinder with a single through hole, preferred over other more complex forms with many through holes. Therefore, in another preferred embodiment of the invention, the upper layer is a first type of catalyst with a single through hole.

Preference above would be contrary to the normal first choice for body shape of the catalyst, operating at conditions with strong diffusion limitations of pores, where the experts will have a tendency to�the collection of a body shape of the catalyst with high external or geometric surface area per unit catalyst layer. This item is explained below the table, providing key figures on some body shapes of catalyst used in autothermal reforming process.

Obviously, contrary to traditional loading schemes in the present invention, the upper layers containing only one through hole, represent the lowest geometric surface area.

Therefore, combining the use of catalysts of the type eggshell with Nickel and one of the metals iridium, rhodium, and ruthenium, with special shapes, as determined by the void/geometric surface area, it is possible to limit the pressure drop, and at the same time, at least to maintain catalytic activity and stability in at least the upper layer of the catalyst layer.

It would be understood that the term catalyst layer or the fixed layer forms an agglomeration of bodies of catalyst particles dispersed inside the reactor, which leads to a layer having this thickness along the length of the reactor. It would also be clear that the catalyst may contain one or more layers or sublayers of the catalyst.

void/(EXT. or Zh. square surface)Void EXT. or Zh. the surface area, UPF(EXT. or Zh. the surface area)/(volume of the layer)
l/m2m2/m3m2/l
7 resp. 16×11 mm1,07 (1,04)0,5265040,50
7 resp. 20×18 mm1,38 (1,36)0,5454010,40
ring 25/11-20 mm2,22 (2,15)To 0.4482080,21
ring 35/16-27 mm3,14 (3,07)0,4621500,15

Ring 25/11-20 mm is the catalyst in the form of a ring (a through hole) with an outer diameter of 25 mm, an inner diameter (diameter of through hole) 11 mm and height 20 mm 16×11 mm with 7 holes indicates a catalyst with 7 through holes (or the equivalent through holes 7), an outer diameter of 16 mm diameter hole�Oia 3 mm, height of 10 mm.

The magnitude of the relationship for a void/(external or geometrical surface area), for example, 2,22 l/m2for catalyst particles in the form of rings 25/11-20 mm, calculated using standard empirical formulae for determination of the void, while the values in parentheses are calculated using formula from the open literature.

In particular, the size of voids of the table and the values in parentheses for the relationship a void/(external or geometrical surface area), for example 2.15 for catalyst particles in the form of rings 25/11-20 mm calculated according to the formula Max Leva for the calculation of the void (1. Leva, M.; Chem. Eng. may, pp. 115-117 (1949), 2. Leva, Max; Grammer, Milton. "Pressure Drop Through Packed Tubes: Part III Prediction of Voids in Packed Tubes." Chemical Engineering Progress, vol. 43, No. 12, pp. 713-718. Pittsburgh, PA: 1947), in which emptiness=external void+internal void, and external emptiness=0,30675+0,6885 (Dp/Dt), where Dp is the particle size and Dt is the inside diameter of the reactor or pipe.

Accordingly, the upper layer is a first type of catalyst with respect to a void/(external or geometrical surface area) - ratio which is above 3 l/m2and at least the second layer is a second type of catalyst with respect to a void/(external or geometrical surface area) - ratio which is below 3 l/m2. Preferably, the ratio of the void/(out�average or geometric surface area) of the second type of catalyst is above 2 l/m 2. In these specific conditions, the invention enables, in spite of the patent application EPO EP-A-0625481, low pressure drop in the catalyst bed, while at the same time able to maintain or increase the catalytic activity at least its in the upper layers of the catalyst layer. Accompanying Fig.5 shows a lower pressure drop in the plant for autothermal reforming compared to conventional loading of the catalyst.

Can be provided for at least the next, the third layer of the third type of catalyst, where the specified third type of catalyst freely formed with adequate effective catalytic activity and characteristics of pressure drop to effect the conversion of the reforming process and requirements for initial pressure drop. Such catalysts are preferably catalysts with respect to a void/(external or geometrical surface area) in the range from 1.0 to 4.5 l/m2more preferably, the catalysts with respect to a void/(external or geometrical surface area) that is lower than 1.5 l/m2such as catalysts cylindrical shape with through holes 7 (or equivalent 7 through holes) having a void/(external or geometrical surface area) in the range of 1.0-1.4, more specifically, to 1.36 and 1.4 l/m 2as shown in the table above.

Preferably, the top layer is 5-30% of the total depth of the catalyst layer.

The second object of the invention, as defined in clauses 16 to 22, the invention also covers the catalyst as such.

Therefore, this invention also provides catalyst type eggshell, consisting of the active compounds in the form of an alloy of Nickel and one of iridium metal, rhodium, and ruthenium on a carrier containing aluminum oxide, zirconium dioxide, magnesium oxide, titanium dioxide or combinations thereof.

Preferably, the content of iridium or rhodium or ruthenium in the catalyst is in the range from 0.01 to 0.5 wt.%, as the Nickel content in the catalyst is from 2 to 16 wt.%.

Preferably, the carrier containing aluminum oxide, selected from α-alumina, calcium aluminate, magnesium-aluminum spinel, and combinations thereof.

Preferably, the catalyst has a cylindrical shape and has one or more through holes, where the distance from the center to the outer surface of the catalyst is 10 to 40 mm, the height of the catalyst from 10 to 40 mm, and the diameter of the one or more through holes from 3 to 30 mm.

Preferably, the active compound is an alloy of Nickel and iridium, or Nickel and ruthenium, and at least 90 wt.% iridium or ruthenium in the catalysate�ré is located in the outer shell, having a depth of up to 10% of the external surface of the catalyst or up to 10% of the periphery of one or more through holes of the catalyst.

Preferably, the local concentration of iridium or ruthenium in the outer shell is from 0.1 to 5.0 wt.%.

Preferably, the catalyst prepared, first introducing Nickel in the media, and in the next stage by adding iridium or rhodium or ruthenium. More preferably, the catalyst is obtained by application of a catalyst consisting of Nickel on a carrier, an aqueous solution of iridium, rhodium or ruthenium, and then by calcination in air at 400-600°C and recovery in N2at 350-600°C, for example, at 500-550°C. in Other words, the invention encompasses therefore also a method for producing the catalyst type eggshell containing stage: (a) the introduction of Nickel in a carrier containing aluminum oxide, zirconium dioxide, magnesium oxide, titanium dioxide, magnesium aluminum spinel, and combinations thereof; (b) adding one metal of iridium, rhodium or ruthenium to the catalyst of stage (a). Preferably, step (a) comprises the step of impregnating the carrier with Nickel and then drying and calcination, where the calcination is preferably carried out at 400-600°C in air, more preferably at 450°C in air.

Preferably, impregnation of the catalyst is carried out with an aqueous solution of IrCl 3×H2O or iridium acetate or Ru(NO3)3NO, and the carrier contains aluminum oxide, preferably α-alumina or magnesium-aluminum spinel. These predecessors are getting the best gradients in the concentration of metals. While Rh represents the variation in concentration of all the catalyst bodies, but actually peaks far away from the outer surface of the catalyst, Ir and Ru finely dispersed toward the outer surfaces of the catalyst bodies, as seen in Fig.3 and 4.

The preferred catalyst for use in the steam reforming of hydrocarbons, such as adiabatic pre-reforming process and a primary reforming process, is preferred for use in the reforming of hydrocarbons in a catalytic partial oxidation (CONFERENCE) or the setting for autothermal reforming, the most preferred for use in the reforming of hydrocarbons in a catalytic partial oxidation (CONFERENCE) or the installation autothermal reformer operating at temperatures in the range of 800-1600°C and a pressure of 20-100 bar.

Fig.1 shows the activity of the reformer (mol/g/h) aged promoted Ir catalysts at 450 and 500°C.

Fig.2 shows the activity of the reformer (mol/g/h) aged promoted Rh catalysts at 450 and 500°C.

Fig.3 while�device linear scanning microprobe, measured along the cross section of Nickel on α-alumina with Ir 0,1 (A), of Nickel on magnesium-aluminum spinel with Ir 0,1 (In), Nickel on α-aluminum oxide with Rh 0,1 (C) and magnesium-aluminum spinel with Rh 0,1 (D); ring of the catalyst from the outer to the inner surface (the outer surface of the catalyst to the outer surface of the through holes of the catalyst). Ring was measured in aged condition. X axis: distance in microns from the outer surface of the catalyst to the outer surface of the through holes of the catalyst, Y-axis: wt.% iridium (A, b) or rhodium (C, D).

Fig.4 shows the linear scanning microprobe measured along the cross section of Nickel on α-alumina, impregnated with 0.1 wt.% Ru, or using [Ru(NO3)3NO] (Fig.4A), or RuCl3×nH2O (Fig.4B) as precursors; the rings of the catalyst from the outer to the inner surface (the outer surface of the catalyst to the outer surface of the through holes of the catalyst). X axis: distance in microns from the outer surface of the catalyst to the outer surface of the through holes of the catalyst, Y-axis: wt.% ruthenium.

Fig.5 shows the effect of catalyst loading according to the invention in an industrial setting for autothermal reforming working when the ratio of steam to carbon of 0.60. The lowest working line: �pressure drop range of the present invention.

Example 1:

The catalysts were prepared by obtaining fractions of the substrate α-Al2O30,42-0,50 mm, then application then a 3.5 wt.% Ni, followed by drying and calcination at 450°C in air. Particles within this interval, the small size of 0.42-0.50 mm is used to ensure full penetration of the catalytic material and thereby have a measure of the internal catalytic activity. Then carried out impregnation of the pores of the catalyst with aqueous solutions of IrCl3×H2O or Rh(NO3)2to reach downloads from 0.05 to 1.0 wt.% noble metal (Ir or Rh), and then drying and calcination at 450°C in air. In impregnowanych applied a 5% excess volume of solution predecessor. The catalyst was then recovered in pure H2at 525°C.

Aged catalysts:

Experiments on aging was performed for 10 days at 850°C, a pressure of 30 bar (gauge) and the atmospheres of H2O/N2(6:1) to investigate the effect of promoters Rh and Ir on the sintering of Nickel, and the interaction between them.

An overview of catalysts shown in the table below:

The samples of example 1:
Code sampleMac.% Niwt.% Belgorod�CSO metal (Rh or Ir) Weight ratio of Ni/noble metal
Matt. Ni_3,53,5-
Ni 3,5_Ir 0,053,50,05 Ir70
Ni3,5_IrO,l3,50,1 Ir35
Ni 3,5_Ir 0,253,50,25 Ir14
Ni 3,5_Ir 0,53,50,5 Ir7
Ni3,5_Ir 1,03,51,0 Ir3,5
Matt. Ir_0,25-0,25 Ir
Ni 3,5_Rh 0,053,5Of 0.05 Rh70
Ni 3,5_Rh 0,13,50,1 Rh35
Ni 3,5_Rh 0,253,5 0,25 Rh14
Ni 3,5_Rh 0,53,50,5 Rh7
Ni 3,5_Rh 1,03,51,0 Rh3,5
Matt. Rh_0,250,25 Rh

Fig.1 shows the activity of the reforming aged catalysts with different weight relationship of Ni/Ir. Observe that the comparative catalyst containing iridium (Matt. Ir_0,25), at 450 To quickly deactivate after 1 h of reforming reaction leading to complete loss of activity. Yet we find the increase in activity with increasing load Ir, which is very pronounced due to the synergistic effect obtained after the formation of alloys, Ir-Ni. Iridium plays a role as a structural promoter in the formation of bimetallic particles of Ni-Ir, which are more resistant to sintering during the aging treatments. Therefore, the activity of the catalysts is significantly improved due to the higher dispersion of the metal in aged promoted Ir catalyst than in the comparative Ni catalyst. This effect becomes most pronounced when using�AI weight relationship of Ni/Ir below 14.

Fig.2 shows the activity of the aged catalysts reforming various weight relationship of Ni/Rh. The increase in activity with increasing load Rh is also very pronounced due to the synergistic effect obtained by the formation of alloys of Rh-Ni. Rh also plays a role as a structural promoter and the formation of bimetallic particles of Ni-Rh, which is more resistant to sintering during the aging treatments. Therefore, the activity of the catalysts is significantly improved due to the higher dispersion of the metal in aged promoted Rh catalyst than in the comparative Ni catalyst. This effect is noticeable even when using such a high weight relationship of Ni/Rh, 70.

The figures above show that the use of Rh or Ir in combination with Ni leads to an excellent reforming catalysts with higher resistance to sintering and, therefore, with a longer catalyst life. The increase in activity, again attributable to the structural promotion, was obtained through the formation of bimetallic particles of Ni-Ir and Ni-Rh.

Rh and Ir, are known to be catalytically active in the reforming reaction; in particular, Rh is more active than Ni. Increased activity, however, is attributed to the increased dispersion of the metal, gained after obra�Otok aging. The effect of promotion, therefore, receive during the aging treatment after the formation of particles of an alloy of Rh-Ni, which can be sintered at lower speed, than the particles of pure Nickel.

Example 2:

The distribution of Ir and Rh along the cross sections of the rings were studied by analysis of the internal combustion engine (spectroscopy of dispersion wavelengths). Fig.3 shows some representative examples of linear scans measured on the aged Nickel catalyst deposited on α-aluminum oxide and magnesium-aluminum spinel promoted with Ir (Fig.3A and 3B) and Rh (Fig.3C and 3D).

Promoted Rh catalysts are also profiles the type of eggshell. However, Rh is not only present in the outer shell, i.e., near or on the external catalyst surface, but also penetrates deeper into the rings. For example, magnesium-aluminum _Rh 0,1 reaches high concentrations in Rh 2000 μm from the outer shell (Fig.3C). Without being linked by any theory, it is believed that this is due to the weak interaction between [Rh(H2O)6]3+or other cationic particles in the solution and the substrate Al2O3. Consequently, an aqueous solution of Rh(NO3)2less suitable as a precursor, as the fraction of Rh is wasted inside the ring-shaped catalysts.

On the other hand, Ir particles unexpectedly remain close to naru�Noah shell rings often below 1000 μm, especially below 500 μm or below 400 μm, reaching local concentrations between 0.1 and 1.0 wt.%. The distance from the surface to the surface or full depth is as shown in Fig.3, about 10,000 microns. Without being linked by any theory, the location of these profiles type eggshells are considered to be the result of electrostatic interactions between anionic particlesIrCl63in solution and positively charged groups (HE2)+on the surface of the Al2O3that prevents the penetration of Ir deeper into the body of the catalyst (catalysts in the form of a ring) during the impregnation of the pores.

Similar or even better results were obtained using aqueous solutions of acetate Ir (Ir(OAc)xas a precursor to Ir, as we have also seen profiles type egg shell with very thin layers of less than 200 microns.

Similar concentration profiles were obtained for all aged catalysts.

Example 3:

The distribution of EN along the cross-section of the various rings of the catalyst Ru/Al2O3obtained with different precursors of Ru studied by the analysis engine. Fig.4 shows two typical examples of linear scans, measured� catalysts recovered from Nickel, deposited on α-alumina, which is then impregnert 0.1 wt.% Ru, or precursors Ru(NO3)3NO (Fig.4A), or RuCl3×nH2O (Fig.4B).

While the average Ni concentration along the cross section of the rings remains fairly constant (average of 2.5 wt.% Ni), both catalysts present higher concentration of Ru in the outer shell, i.e., near or in the outer body surface of the catalyst. In the case of precursor Ru(NO3)3NO, the thickness of the outer shell EN usually below 500 μm concentrations of Ru, usually ranging between 0.3-2.5 wt.%. In the case of RuCl3×nH2O, the thickness of the outer shell EN usually below 400 μm, and the concentration of Ru vary typically within the range of 0.2-1.5 wt.%.

In both cases (especially in the catalyst prepared from RuCl3×nH2O) a certain amount of Ru also penetrates deeper into the rings to some extent. For example, in the catalyst of Ru/Al2O3obtained RuCl3×nH2O, there is an area of 4000 μm from the outer surface, which contains up to 0.5 wt.% EN (Fig.4B).

Example 4:

The calculation of the ratio of the void/(external or geometrical surface area).

Used the formula max Lev (Max Leva) for the calculation of the void (1. Leva, M.; Chem. Eng. may, pp. 115-117 (1949), 2. Leva, Max; Grummer, Milton. "Pressure Drop Through Packed Tubes: Part III Prediction of Voids in Paced Tubes." Chemical Engineering Progress, T. 43, No. 12, pp. 713-718. Pittsburgh, PA: 1947).

Void=emptiness-external+void-internal.

Void - external=0,30675+0,6885×(Dp/Dt), where Dp is the particle size, a Dt is the inner diameter of the tube or reactor.

If the catalysts are of cylindrical form, Dp is calculated as the equivalent diameter of the sphere by the equation Dp=(3/2×Dcyl2×Hcyl)1/3,

where Dcyl is an outer diameter of the cylinder, a Hcyl represents its height.

In the case of catalysts in the form of a ring (a through hole) or a plurality of through holes in the catalyst in the form of a cylinder, the outer void is calculated by the formula:

Emptiness-inner=(1-emptiness-external)×Nholes×(Dhole/Dcyl)2where Nholes is the number of through holes in the catalyst, a Dhole is the diameter of the through holes.

Emptiness, therefore,

Void=emptiness-full=void-external+void-internal

External or geometrical surface area (GPP) is determined as the number of m2external or geometrical surface area of the bodies of catalyst per unit volume of the catalyst layer. GPP has dimension m2/m3and it is calculated based on the number of solids (catalyst particles) on its volume and bulk density, which is first calculated on the basis of measurable density of the material of the catalyst, usually about 2200 kg/m3. The number �ate on the volume calculated from the measurable weight of the catalyst and the bulk density:

Body per volume (#/m3)=bulk density/weight of one body of catalyst.

bulk density=(1-void)×(density of the catalyst particles).

AOP on the body=GPC=π(Dcyl2-Nholes×Dhole2)+π×Hcyl×(Dcyl+Nholes×Dhole)

Then calculate GPP

GPP=(Body volume)×(GPC)

The calculation of the ratio of the void/PPG then direct.

Example for catalysts in the form of a ring 25/11-20 mm:

Ring 25/11-20 mm is the catalyst in the form of a ring (a through hole, Nhole=1) with an outer diameter of 25 mm, Dcyl, an inner diameter (diameter of through holes. Dhole) 11 mm and a height (Hcyl) 20 mm.

The weight of the catalyst (tablet weight)=17,4 g

The particle density=2200 kg/m3

The pipe inner diameter=2000 mm

Following the formula above:

Emptiness external=0,316

Void internal=0,132

Emptiness=0,316+0,132=to 0.448

Bulk density=1188 kg/m3

Pills volume=68188/m3

GPC=30.5 cm2

GPP=30,5×68188/10000=208 m2/m3

Emptiness/PPG=to 0.448/208×1000=2,15 l/m2

Example 5:

Reference is made to Fig.5. Here shows the influence of the load according to the invention in an industrial setting for autothermal reforming working when the ratio of steam to carbon of 0.60. Improved loading of the catalyst, in which the top and second layers are catalysts in the form of a ring, dramatically reduces the rate grew�and pressure drop. Vapor deposition of aluminum oxide on the catalyst is thus reduced to such an extent that the pressure drop remains low or at least greatly reduced. The operating conditions of the installation for autothermal reforming working when the ratio of steam to carbon of 0.60, is particularly demanding, because the low ratio of water vapor to carbon means higher temperatures in the combustion chamber.

1. Method of steam reforming of hydrocarbons, including
contacting feed gas in the reactor, a catalytic partial oxidation or installation autothermal reformer operating at temperatures in the range of 800-1600°C and a pressure of 20-100 bar, with catalyst type eggshell, consisting of the active compounds in the form of an alloy of Nickel and one metal of iridium and ruthenium on a carrier containing aluminum oxide, zirconium dioxide, magnesium oxide, titanium dioxide or combinations thereof,
moreover, the catalyst has a cylindrical shape and has one or more through holes, where the distance from the center to the outer surface of the catalyst is 10 to 40 mm, the height of the catalyst is 10 to 40 mm, and the diameter of the one or more through holes is from 3 to 30 mm,
and being used as a carrier of aluminum oxide selected from α-�of aluminum oxide, aluminate of calcium, magnesium-aluminum spinel, and combinations of them,
at least 90 wt. % of iridium or ruthenium in the catalyst are placed in an outer shell having a depth of up to 10% of the external surface of the catalyst or up to 10% of the periphery of one or more through holes of the catalyst.

2. A method according to claim 1, wherein the catalyst is in the form of one or more layers with respect to a void/(external or geometrical surface area) 1.0-4.5 l/m2.

3. A method according to claim 2, wherein the top layer is the catalyst of the first type with respect to a void/(external or geometrical surface area), which is more than 3 l/m2and less than 4.5 l/m2and at least the second layer is a catalyst of the second type with respect to a void/(external or geometrical surface area), which is less than 3 l/m2and more than 1.0 l/m2.

4. A method according to claim 2, in which the ratio of the void/(external or geometrical surface area) of the catalyst of the second type above 2 l/m2and less than 4.5 l/m2.

5. A method according to claim 2, in which use at least an additional third layer of a third type of catalyst having a void/(external or geometrical surface area) in the range from 1.0 to 4.5.

6. A method according to claim 1, wherein AK�active compound is an alloy of Nickel and iridium, or an alloy of Nickel and ruthenium, where the content of iridium or ruthenium in the catalyst is in the range from 0.01 to 0.5 wt. % and the Nickel content in the catalyst is from 2 to 16 wt. %.

7. A method according to claim 1, wherein the concentration of iridium or ruthenium in the outer shell is from 0.1 to 5.0 wt. %.

8. A method according to claim 1, wherein the active compound in the catalyst in the form of an alloy of Nickel and one metal of iridium and ruthenium has an average crystallite size of below 0.1 μm in the measurement of aged or exhausted catalyst.

9. A method according to claim 1, wherein the first catalyst prepared by the introduction of Nickel in the media and at the next stage, the addition of iridium or ruthenium.

10. A method according to claim 9 in which the catalyst is obtained by application of a catalyst consisting of Nickel on a carrier, an aqueous solution of iridium or ruthenium, and then by calcination in air at 400-600°C and recovery in N2at 350-600°C.

11. A method according to claim 10, in which the impregnation of the catalyst is carried out with an aqueous solution of IrCl3×N2Oh, or iridium acetate or Ru(NO3)3NO, the carrier contains aluminum oxide, selected from α-alumina and a magnesium-aluminum spinel.

12. A method according to any one of claims. 1-11, further comprising removing from the reactor a catalytic partial oxidation or plants for autothermal reforming syngas for p�next downstream of the Fischer-Tropsch synthesis, ammonia synthesis, methanol synthesis and the synthesis of dimethyl simple ether.



 

Same patents:

FIELD: oil and gas industry.

SUBSTANCE: invention relates to the field of petrochemistry and more specifically to a method of producing synthesis gas which is used as the feedstock, for example, for the synthesis of methanol, dimethyl ether, hydrocarbons by Fischer-Tropsch method. The method of producing synthesis gas comprises oxidative conversion of methane-containing gas at a temperature more than 650°C in through-flow riser, using as oxidant the microspherical or crushed catalyst based on metal oxides, capable of multiple redox transitions, at that the catalyst is continuously passed through the riser upwards in the methane-containing gas flow with a residence time of the feedstock in the reaction zone of 0.1-10 s, separating the catalyst passing from the reactor from the product and regeneration of the catalyst by oxidation with carbon dioxide in the regenerator from which the regenerated catalyst enters the reactor. The oxidative conversion of methane-containing feedstock and regeneration of regenerated catalyst is carried out simultaneously and continuously.

EFFECT: invention enables to improve the removal rate of the product, to reduce energy consumptions for transportation of oxygen-containing agent, to reduce the risk of explosion and ignition, as well as to adjust the composition of the synthesis gas.

7 cl, 1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention can be used in obtaining hydrogen from reagents, including liquid hydrocarbons, gaseous hydrocarbons and/or oxygen-containing compounds, including those, obtained from biomass, and their mixture. In order to obtain hydrogen used are: section of reagents heating; section of catalytic partial oxidation with short contact time, in which synthesis-gas is obtained; section of heat recuperation; section of converting carbon monoxide, present in synthesis-gas, into carbon dioxide by reaction of water gas conversion; section of said carbon dioxide removal; section of condensate cooling and removal.

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17 cl, 2 dwg, 5 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: a copper-chromium-zinc catalyst for heterogeneous reactions, which includes copper, chromium, zinc and aluminium oxides and an additional component is disclosed. The catalyst contains, as the additional component, 0.5-5 wt % of a silicon compound with respect to the oxide and the catalyst is formed via heat treatment of aluminium hydroxide together with compounds of said components, and has a porous structure with total specific pore volume of not less than 0.25 cm3/g and content of mesopores with a diameter of 10-40 nm higher than 60%, and the catalyst has the following composition, with respect to oxides, wt %: CuO 50.0-57.0; Cr2O3 11.0-16.0; ZnO 9.5-13.0; SiO2 0.5-5.0; aluminium oxide - the balance.

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6 cl, 2 tbl, 8 ex

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SUBSTANCE: invention can be used during HCs production from natural or associated petroleum gas. Method of oxygenates cleaning from reaction water generated at stage of HCs synthesis from syngas during GTL process includes conversion of even part of the contained oxygenates under conditions of syngas chilling by even part of the reaction water at temperature over 500°C upon contact with catalyst of the oxygenates steam conversion. Further syngas cooling temperature below 400°C is performed by the cleaned water injection in the syngas flow. Method of use of the reaction water generated at stage of HCs synthesis from syngas during GTL process includes its cleaning of the oxygenates under conditions of the syngas chilling at temperature over 500°C upon contact with catalyst of the oxygenates steam conversion, cleaned water degassing. The cleaned degassed water is used to cool the syngas to temperature below 400°C and produce the water steam.

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4 cl

FIELD: chemistry.

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22 cl, 5 dwg, 4 tbl

FIELD: chemistry.

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5 cl, 3 tbl, 8 ex

FIELD: oil and gas industry.

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2 cl, 7 dwg, 1 tbl

FIELD: chemistry.

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EFFECT: claimed invention makes it possible to obtain target products by the improved combined method of ethane cracking and OTO technology.

8 cl, 1 dwg, 5 tbl, 1 ex

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17 cl, 3 dwg

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12 cl, 2 dwg, 14 tbl, 11 ex

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4 cl, 2 dwg, 4 tbl

FIELD: chemistry.

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EFFECT: obtaining catalysts with a longer service life, selectivity and activity.

17 cl, 2 tbl, 14 ex

FIELD: oil and gas industry.

SUBSTANCE: invention is related to oil processing, in particular to manufacturing method of cracking catalyst for heavy and bottom fractions. The claimed method for manufacturing of granulated cracking catalyst includes introduction of Y-type zeolite to the carrier containing colloidal components and/or their precursors, formation and thermal treatment. At that colloidal components and/or their precursors are interaction products of nanoscale compounds of tetrahedron type of [SiO4]- and [AlO4]+ composed of natural and/or synthetic aluminosilicates with acids or salts, mixtures are made by extrusion at sol-gel stage and thermal treatment is preceded by hold-up time without heating.

EFFECT: suggested method allows production of granular catalysts with high mechanical properties and high activity as well improvement of the technology and increase in productivity.

6 cl, 4 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of catalysis. Described is method of manufacturing geometrical moulded products from catalyst K, in which active mass represents multi-element oxide, which contains Mo element, Bi and/or V elements, as well as one or several elements from series Co, Ni, Fe, Cu and alkali metals, in which highly dispersed mixture is obtained by means of sources of different elements, said mixture is coarsened to powder by pressing, and moulded product V is formed from said coarser powder by agglomeration; said products are divided into undamaged moulded products V+ and damaged moulded products V-, undamaged moulded products V+ are made into moulded products from catalyst K, and damaged moulded products V- are crushed and returned into production of highly dispersed mixture.

EFFECT: reduction of material loss in the process of catalyst production, improvement of working characteristics of catalyst.

5 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts designed for conducting heterogeneous catalytic reactions, e.g. oxidation of sulphur dioxide etc. Described is a catalyst element for conducting heterogeneous catalytic reactions with an internal opening; there are protrusions on the inner and outer surfaces of the element which are arranged into a circle with equal spacing from each other, wherein the shortest distance from the central axis of said circle to the point on the protrusion on the outer surface of the element that is furthest from said axis is the same for each protrusion, wherein the element has a shape which is elongated in the longitudinal direction; the wall of the element formed by the inner surface and the outer surface has the same thickness on the entire periphery of the element, wherein the thickness of the wall is equal to 0.1-0.25 times the diameter of an arbitrary circle passing in the cross-section of the element on protrusions on the outer surface of the element, and the height of each protrusion is equal to 0.15-0.35 times the diameter of said circle.

EFFECT: high degree of utilisation of the inner surface, ensuring uniform distribution of gas in the volume of the element, low flow resistance.

5 cl, 3 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to moulded catalysts. Described is a catalyst element having a cylinder with length C and diameter D, wherein said element has five openings with circular cross-section with diameter d' in the range of 0.1D-0.3D, lying in a pentagonal pattern, which pass through longitudinally, with five grooves passing along the length of the element, wherein said grooves lie equidistant from neighbouring openings of said pentagonal pattern. Described is a method of making said catalyst element and use thereof.

EFFECT: larger active surface of the catalyst element and strength thereof.

18 cl, 3 dwg, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to moulded heterogeneous catalysts. Disclosed is a catalyst element in form of a cylinder, having length C and diameter D, which has one or more through-openings, where said cylinder has dome-shaped ends of sections A and B, such that (A+B+C)/D lies in the range of 0.50-2.00, and (A+B)/C lies in the range of 0.40-5.00. Disclosed also is a method of producing the catalyst and a catalytic method using the catalyst element.

EFFECT: obtaining catalysts with a large geometric surface area and given porosity.

22 cl, 2 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to moulded catalysts, production and use thereof. Described is a catalyst component in form of a cylindrical pellet, having cylinder length C and cylinder diameter D, wherein the outer surface of the component has two or more grooves running along its length, wherein said cylinder has dome-shaped ends of lengths A and B, such that (A+B+C)/D is in the range of 0.50-2.00, and (A+B)/C is in the range of 0.40-5.00. Described is a method of producing said catalyst component, comprising steps of: (i) feeding powdered material, optionally with a pelletising additive, into a pellet mould, (ii) pressing the powder to form a moulded component and then (iii) optionally heating the moulded component to form a moulded catalyst component, wherein said mould has such a shape that the catalyst component has the shape of a cylindrical pellet, having cylinder length C and cylinder diameter D, wherein the outer surface of the component has two more grooves passing along its length, wherein said cylinder has dome-shaped ends with lengths A and B, such that (A+B+C)/D is in the range of 0.50-2.00, and (A+B)/C is in the range of 0.40-5.00.

EFFECT: descried is a catalytic method using said catalyst component, which provides contact between a reaction mixture with the catalyst component in catalysed reaction conditions.

24 cl, 3 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of filling a longitudinal section of a contact pipe with a homogeneous part of a solid catalyst bed. The method of filling a longitudinal section of a contact pipe with a homogeneous part of a solid catalyst bed, the active mass of which is at least one multielement oxide which contains a) elements Mo, Fe and Bi, or, b) elements Mo and V, or c) element V, and additionally P and/or Sb, or the active mass of which contains elementary silver on an oxide support-article, and which consists of only one type Si, or a homogenised mixture of various types Si of catalytically active moulded articles of a defined geometrical shape or catalytically active moulded articles and inert moulded articles of a defined geometrical shape, wherein the median of the maximum longitudinal dimensions Lsi of the articles of a defined geometrical shape of type Si is characterised by the value Dsi, at least within one type Si of moulded articles of a defined geometrical shape, the following set of conditions M is satisfied, such that 40 to 70% of the total number of moulded articles of a defined geometrical shape belonging to S1, have a maximum longitudinal dimension Lsi, for which the inequality 0.98·Dsi≤Lsi≤1.02·DSi holds, at least 10% of the total number of moulded articles of a defined geometrical shape belonging to Si have a maximum longitudinal dimension Lsi, for which the inequality 0.94·Dsi≤Lsi<0.98·Dsi holds, at least 10% of the total number of moulded articles of a defined geometrical shape belonging to S1 have a maximum longitudinal dimension Lsi for which the inequality 1.02·Dsi<Lsi≤1.10·Dsi holds, less than 5% of the total number of moulded articles of a defined geometrical shape belonging to Si have a maximum longitudinal dimension Lsi for which the inequality 0.94·Dsi>Lsi holds, and less than 5% of the total number of moulded articles of a defined geometrical shape belonging to Si have a maximum longitudinal dimension Lsi for which the inequality 1.10·Dsi<Lsi holds, wherein the sum of all moulded articles of a defined geometrical shape belonging to Si is 100%; described also is a method of loading a contact pipe with a solid catalyst bed, a shell-and-tube reactor, a method for oxidation of an organic compound and a method for synthesis of separate organic compounds.

EFFECT: high selectivity of moulding the final synthesis product.

17 cl, 3 ex

FIELD: process engineering.

SUBSTANCE: invention relates to filter designed to remove solid particles and nitrogen oxides from exhaust gases. Filter comprises porous substrate with inlet and outlet surfaces and substrate pores of the first average size. Note here that said porous substrate is coated by material increasing the surface area. Said material includes molecular sieve promoted by transition metal wherein aforesaid coat represents a porous untreated coat on inlet and/or outlet surface. One of plies has pores of the second average size, smaller than the first one.

EFFECT: balanced backpressure, efficient filtration and catalytic activity.

17 cl, 7 dwg, 3 ex

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