Catalyst, method for preparation thereof, and reactions involving it

FIELD: heterogeneous catalysts.

SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.

55 cl, 4 dwg

 

The SCOPE of the INVENTION

The present invention relates to a catalyst containing a porous carrier, a buffer layer and the interfacial layer; a process for the production of catalyst and catalytic processes, in which the used catalyst.

RELATED APPLICATIONS

This application is in part a continuation of US patent 09/123781, which is included in the description of the invention in the form of links.

BACKGROUND of INVENTION

Well-known reaction of conversion of hydrocarbons and hydrogen, such as conversion to water vapor, the reaction conversion of water vapor, methanol synthesis and catalytic combustion. These reactions are usually carried out at a temperature of from 150 to 1000°C. currently on an industrial scale, such reaction is conducted with the use of granular catalyst comprising a catalytically active metal or metal oxide deposited on a ceramic granules with a strongly developed surface.

It is known that foamed or solid catalysts contain three layers: (1) porous media, (2) interfacial layer, and (3) a metal catalyst, as described in [1]. Upon receipt of such catalysts interfacial layer is applied in a variety of ways, including methods of impregnation solution. The catalyst layer may be deposited by impregnation with a solution. The interfacial layer has a wider surface than the porous media, while the porous media has a higher mechanical strength in comparison with the interfacial layer.

Porous media can be a metal or ceramic foam. Metal foam is highly conductive and is easily machined. Mechanical properties inherent in the spongy materials, allow for convenient mounting in the reaction chamber due to mechanical contact. Close values of thermal expansion of the metal foam and the body material of the reaction chamber minimize cracking of the porous medium and the flow of gas around the porous media at elevated temperatures of the reaction. Pestryakov (Pestryakov) with TCS. got catalysts are oxides of transition metals on metal foam media [1] and without [2] the intermediate layer of γ-aluminium oxide for oxidation of n-butane. Kozak (Kosak) [3] investigated several ways dispersion of noble metals on different metal foam, the surface of which was previously protrain HCl solution, and said that the best adhesion of noble metals on the foam media provides nonelectrolytic deposition. Podyacheva (Podyacheva) with TCS. [4] also synthesized perovskites LaCoO3the catalyst on the metal foam carrier with a porous intermediate layer of aluminum oxide for the R methane. Despite all the advantages of the catalysts with metal foam media, metal foam has a low corrosion resistance and non-porous and smooth mesh surface give poor adhesion with the ceramic materials, and these materials due to a mismatch of thermal expansion are prone to cracking interfacial layer after a heat cycle.

To improve the corrosion resistance apply techniques such as diffusion alloying with Al, Cr and Si to create ferrite steels that are commonly used for the production of elements of high-temperature furnaces (about 1200° (C) [5]. When ferrite steel containing aluminum, are subjected to appropriate heat treatment, aluminum is moved to the surface of the alloy and forms a highly adhesive oxide film, resistant to oxygen diffusion. Such films of ferrite steel is used to create metal monoliths containing >10 pores per inch of open cells [6]. However, studies similar foamed alloys with pores, suitable for catalytic purposes (>20 pores per inch, preferably 80 pores per inch), proved fruitless. This applies to imperfect ways to create a thinner pen of Al-ferrite steel, and the lack of source materials to create a pen.

Sledovat is Ino, in the field of catalysts on the media there is a need to create porous media foam, is resistant to corrosion or oxidation and resists cracking interfacial layer.

Literature:

1. A.N.Pestryakov, A.A.Fyodorov, V.A.Shurov, M.S.Gaisinovich, I.V.Fyodorova, React. Kinet. Catal. Lett., 53 [2] 347-352 (1994).

2. A.N.Pestryakov, A.A.Fyodorov, M.S.Gaisinovich, V.A.Shurov, I.V.Fyodorova, T.A.Gubaykulina, React. Kinet. Catal. Lett., 54 [1] 167-172 (1995).

3. J.R.Kosak. A Novel Fixed Bed Catalyst for the Direct Combination of H2and O2to H2About2, M.G.Scaros and M.L.Prunier, Eds., Catalysis of Organic Reactions, Marcel Dekker, Inc. (1995). pi 115-124.

4. O.Y.Podyacheva, A.A.Ketov, Z.R.Ismagilov, A.Bos, H.J.Veringa, React. Kinet. Catal. Lett., 60 [2] 243-250 (1997).

5. A.N.Leonov, O.L.Smorygo and V.K.Sheleg, React. Kinet. Catal. Lett., 60 [2] 259-267 (1997).

6. M.V.Twigg and D.E.Webster. Metal and Coated Metal Catalysts, A Cybulski and J.A.MouliJn, Eds., Structured Catalysts and Reactors, Marcel Dekker, Inc. (1998), p 59-90.

SUMMARY of the INVENTION

The present invention includes a catalyst containing at least three layers: (1) porous media, (2) a buffer layer, (3) interfacial layer and, optionally, (4) a catalytically active layer. In some embodiments a buffer layer located between the porous media and the interfacial layer, contains at least two different composition of the sublayer. Typically, the buffer layer provides a transition coefficient of thermal expansion from the porous media to the interfacial layer, thereby reducing the voltage of thermal expansion as the AK catalyst is heated to high operating temperatures and then cooled. The buffer layer also reduces corrosion and oxidation of porous media and minimizes adverse reactions catalyzed by the surface of the porous media.

The invention is also a catalyst containing a porous carrier, a buffer layer located between the porous media and megaslim layer; the catalyst is resistant to oxidation, such that when heated in a current of air to 580°With over 2500 minutes the catalyst increases in weight by less than 5%. Alternatively, the catalyst may also be characterized by its resistance to delamination during thermal cycle.

In addition, the invention provides a method of turning at least one reagent, at least one product, wherein the reagent passes through the reaction zone containing the catalyst.

The method of the present invention to obtain a multilayer (at least three-layer) of the catalyst includes the following stages: (1) selecting a porous support, (2) applying a buffer layer on a porous carrier, (3) drawing on it interfacial layer and, optionally, (4) the application of the catalytically active layer on the interfacial layer or with him, where the buffer layer is located between the porous media and the interfacial layer. The best results can be obtained by deposition of the buffer layer and the vapor phase. The catalytically active layer can be applied after or during deposition of the interfacial layer.

The advantages of the present invention, comprising a porous carrier with the buffer layer and the interfacial layer may be as follows: in the best match of coefficients of thermal expansion and better stability to temperature changes, in reducing such adverse reactions as coking, in the required interactions of the metal oxide, solid binding with a strongly developed surface of the interfacial layer and increased protection for the underlying porous media.

The object of the present invention are described in detail and distinctly claimed in the concluding portion of the specification. However, the structure and mode of action of the catalyst, its advantages and objectives of the invention in the best way can be understood using the following description and the attached drawings, in which identical numerals refer to identical elements.

BRIEF DESCRIPTION of DRAWINGS

Figure 1 is an enlarged cross-section of the catalyst.

Figa curve of weight gain (due to oxidation), depending on the time for foam stainless steel (upper line) and for foam stainless steel, coated with titanium dioxide (bottom line), at a temperature of 580°With (dashed line).

Fig.2b curve of weight gain (due to oxidation) in the head of the dependence on time for the Nickel foam (upper line) and for Nickel foam, coated with titanium dioxide (bottom line), at 500°C.

Figure 3 presents two micrograph to compare the effect of thermal cycles on the foam stainless steel with a buffer layer of titanium dioxide and a thin coating of aluminum oxide (left) and on the foam with a thin coating of aluminum oxide (without buffer layer, right).

DESCRIPTION of the PREFERRED EMBODIMENTS (EMBODIMENTS) of the INVENTION

The catalyst presents invention, depicted in figure 1, has a porous carrier 100, a buffer layer 102, the interfacial layer 104 and, optionally, a catalyst layer 106. Any layer can be continuous or interrupted, for example, in the form of zones or drops or as a layer with gaps or holes.

A porous carrier 100 may be a porous ceramic or metal foam. Other porous media suitable for use in the present invention include carbides, nitrides and composite materials. Before the deposition of layers of a porous carrier has a porosity of at least 5%, as determined by the method of mercury porometry, and the average pore size (the sum of the relations of the diameter of pores/pores) from 1 to 1000 μm, as measured using optical and scanning electron microscopy (SEM). Preferably, the porous carrier had a porosity of from about 30 to 99%, more preferably from 70 to 98. The preferred forms of porous media are foams, felts, wool, and combinations thereof. Foam is a structure with a continuous surface, forming pores in its entirety. Felt - fiber structure with an intermediate space between them. Vata structure of tangled threads, as, for example, steel sponge. Less preferably, the porous media can also include other porous medium, such as pellets and otoplasty, provided that they possess the above-mentioned porosity and pore sizes. Open cell metal foams preferably have from about 20 to 3000 pores per inch and more preferably from about 40 to 120 pores per inch. This value represents the largest number of pores per inch (in isotropic materials the direction of measurement does not matter; however, in anisotropic substances, the measurement is carried out in the direction that maximizes the number of pores). In the present invention is "pore per inch measured by scanning electron microscopy. It is established that the porous carrier of the present invention provides compared to the standard bearers of the ceramic granules are a number of advantages, such as low pressure drop, high thermal conductivity, and ease of loading/unloading in chemical reactors.

The buffer layer is 102 differs in composition and/or density of the medium and the interfacial layer and preferably has a coefficient of thermal expansion, intermediate between the coefficients of thermal expansion of the porous support and the interfacial layer. Preferably, the buffer layer represented an oxide or a carbide of the metal. Applicants have found that deposited from the vapor phase layers have the best quality, because they exhibit better adhesion and is resistant to delamination even after several thermal cycles. More preferably, the buffer layers was an Al2About3, TiO2, SiO2and ZrO2or mixtures thereof. More precisely, Al2About3- it α-Al2O3that γ-Al2About3and combinations thereof. α-Al2About3more preferred because of its high resistance to oxygen diffusion. Consequently, it is assumed that the resistance to high temperature oxidation can be enhanced by coating on a porous carrier 100 aluminum oxide. The buffer layer may also be formed by two or more different composition layers. When a porous carrier 100 is a metal, such as foam stainless steel, the preferred embodiment has a buffer layer 102 formed from two different composition of the sublayers (not shown). The first sublayer (in contact with the porous media 100) preferably represents a TiO2because it exhibits good adhesion to porous metal is practical media 100. The second sublayer is preferably α-Al2About3that applied to the TiO2. In the preferred embodiment of the sublayer α-Al2About3is a dense layer, providing high protection to the underlying metal surface. Less dense interfacial layer of aluminum oxide with a strongly developed surface can then be precipitated as a carrier for the catalytically active layer.

Typically a porous carrier 100 has a thermal expansion coefficient different from that of the interfacial layer 104. Therefore, when high-temperature catalysis (T>150° (C) a buffer layer 102 is required to transition between the two coefficients of thermal expansion. In order to obtain a coefficient of expansion compatible with the coefficient of expansion of the porous support and the interfacial layer, thermal expansion coefficient of the buffer layer can be selected by adjusting the composition. Another advantage of the buffer layer 102 is that it provides resistance against side reactions such as coking or cracking caused by the bare surface of the metal foam. For chemical reactions that don't require media with large surface, such as catalytic combustion, a buffer layer 102 stabilizes the metal-catalyst accounts for the strong interaction of metal - the metal oxide. In chemical reactions that require the presence of media with large surface, a buffer layer 102 provides a stronger link with the interfacial layer 104, with a strongly developed surface. Preferably, the buffer layer had no cracks and other damage - this provides the best protection to the underlying media. More preferably, the buffer layer was non-porous. The buffer layer has a thickness which is less than half of the average pore size of the porous media. It is preferable that the buffer layer has a thickness from about 0.05 to 10 μm, more preferably less than 5 microns. The buffer layer should have a thermal and chemical stability at elevated temperatures.

The interfacial layer 104 may include nitrides, carbides, sulfides, halides, oxides, metals, carbon or combinations thereof. The interfacial layer provides highly developed surface and/or provide the desired interaction between the catalyst carrier for catalysts on the media. The interfacial layer may include any substance, usually used as a catalyst carrier. Preferably, the interfacial layer consisted of a metal oxide. Examples of metal oxides include, but are not limited to the list γ-Al2About3, SiO2, ZrO2, TiO2the oxide wills the frame, magnesium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, Nickel oxide, cobalt oxide, copper oxide, zinc oxide, molybdenum oxide, tin oxide, calcium oxide, aluminum oxide, oxide(s) of metals of the lanthanum series, zeolite(s) and mixtures thereof. The interfacial layer 104 may act as catalytically active layer without causing him any further catalytically active substances. Usually, however, the interfacial layer 104 used in combination with a catalytically active layer 106. The interfacial layer may also be formed from two or more different composition of the sublayers. The interfacial layer has a thickness less than half of the average pore size of the porous media. Preferably, the thickness of the interfacial layer ranged from approximately 0.5 to 100 μm, more preferably from about 1 to 50 μm. The interfacial layer may be crystalline or amorphous, and preferably has a surface area determined by BET method of at least 1 m2/year

The catalytically active substance 106 (when present) may be applied on the interfacial layer 104. Alternative catalytically active substance may be applied simultaneously with the interfacial layer. The catalytically active layer (when present) usually dispersed on the interfacial layer. The fact that the catalytically active layer is located at or about Aiden on" interfacial layer, usually means that the microscopic catalytically active particles dispersed on the surface layer of the carrier (for example, the interfacial layer), in the cracks of the layer carrier and open the pores of the layer carrier. The catalytically active layer may include a catalytically active metals, including but not limited to the list of noble metals, transition metals, and combinations thereof; metal oxides included in the list, but not limited to, oxides of alkaline elements, alkaline earth elements, boron, gallium, germanium, arsenic, selenium, tellurium, thallium, lead, bismuth, polonium, magnesium, titanium, vanadium, chromium, manganese, iron, Nickel, cobalt, copper, zinc, zirconium, molybdenum, tin, calcium, aluminum, silicon, item(s) lanthanum series and mixtures thereof; composite materials; zeolite(s); nitrides; carbides; sulfides; halides; phosphates, and combinations of any of the above compounds.

A catalyst comprising a porous carrier, a buffer layer, interfacial layer, and a catalytically active layer, if present) preferably select the largest to be installed in the reaction chamber. Preferably, the catalyst had a through porosity, such that molecules can diffuse through the catalyst. In this preferred embodiment of the invention the catalyst may be placed in the reaction the ion chamber, thus what gases will flow through the catalyst, and not around it. In the preferred embodiment the cross-sectional area of the catalyst is at least 80%, more preferably at least 95%of the cross-sectional area of the reaction zone. In preferred embodiments of the catalytically active substance is distributed on surfaces throughout the catalyst so that the reactants through the catalyst can react everywhere when passing through the catalyst; this is a significant advantage over the granulated catalysts of the type having a significant amount of unused space or catalytically inefficient use of space in the inner part of the granule. The catalyst of the invention are also superior in quality powder catalysts, because compacted powders can cause a sudden pressure drop.

The catalysts of this invention can also be characterized by the properties that they exhibit. Factors that can be controlled to influence these properties include the selection of a porous medium, a buffer, an interphase and a catalytically active layer; a gradation coefficients of thermal expansion, the crystallinity, the interaction of the metal carrier, methods of deposition, and other factors that caviano in the light of these descriptions. The use of a buffer layer in combination with the usual experimentation using these factors, allows to obtain catalysts, speeding up a variety of chemical reactions. The preferred embodiment of the catalysts of the present invention exhibit one or more of the following properties: (1) adhesion after three thermal cycles in air, the catalyst gives less than 2% (by area) separation, as determined by scanning electron microscopy; (2) resistance to oxidation. After heating at 580°in air flow over 2500 minutes the catalyst increases in weight by less than 5%; more preferably less than 3%; more preferably after heating at 750°in air flow over 1500 minutes of the catalyst increases in weight by less than 0.5%. Weight gain is determined by the method of thermogravimetric analysis (TGA). Each thermal cycle consists of heating in a current of air from room temperature to 600°C at a heating rate of 10°C/min, holding at a temperature of 600°With over 3000 minutes and cooling at a rate of 10°C/min, it is Preferable that the catalyst had a surface area which is defined by the method of Brunauer-Emmett-teller (BET)greater than about 0.5 m2/g, more preferably greater than about 2.0 m2/year

In addition, the image is etenia is a catalytic process, including passing at least one reactant into the reaction zone containing the catalyst of the invention, the transformation above, at least one reagent, at least one product, and the product yield from the reaction zone. In the preferred embodiment of the catalytic process is carried out in an apparatus having microchannels. Examples of suitable devices with micro-channels and various factors relating to the process described in patents US 5611214, 5811062, 5534328 and patent applications U.S. 08/883643, 08/938228, 09/375610, 09/123779, in patent applications U.S. 09/492246 (case number a patent attorney E-1666B-CIP), 09/375614 (filed August 17, 1999) and 09/265227 (filed March 8, 1999), which is included in the description of the invention in the form of links. In another preferred embodiment the catalyst is a monolith, that is solid, but porous piece of the catalyst with a continuous surface, or several such pieces, folded together (not a layer of compacted powder or granules and is not a coating on the wall of the microchannel), which can be easily inserted and extracted from the reaction zone. A piece or set of pieces of the catalyst preferably has a width of from about 0.1 mm to 2 cm, with a preferred thickness of less than 1 cm, more preferably about 1 to 3 mm, the Catalyst of the invention may have many advantages rolled in the systematic processes such as chemical stability, stability during repeated heat cycle, heat resistance, efficient loading and unloading of the catalyst, a high rate of heat and mass transfer and preservation of the desired catalytic activity.

A metal surface inside the apparatus with micro-channels can be covered or buffer, or interfacial layer, or both. This can be done using any of the methods described here, preferably by deposition from the vapor phase. Preferred coating materials include titanium dioxide and 5-10% SiO2/Al2About3. Covered can the inner surface of the reaction chamber, heat exchanger and other surfaces of the device with microchannels. In some embodiments the walls of the reaction chamber can be coated, if necessary, a buffer layer, interfacial layer, and a catalytically active substance; usually catalytically active substance and the interfacial layer combine to obtain a catalyst on the carrier. Coatings can also be deposited on the metal walls of the tubes and pipelines connected to the device with microchannels or located inside him.

Catalytic processes of the present invention include acetylation, the reactions of addition, alkylation, dezalkilirovania, hydrotalcite is a cation, reductive alkylation, amination, aromatization, atilirovanie, autothermal reforming, carbonylation, decarbonylation, reductive carbonylation, carboxylation, reductive carboxylation, reductive reaction combination reaction, condensation, cracking, hydrocracking, cyclization reaction, cycloaliphatic, dehalogenase, dimerization, epoxidation, esterification, exchange, reaction, Fischer-Tropsch, halogenoalkane, hydrohalogenation, homologation, hydration, dehydration, hydrogenation, dehydrogenation, hydrocarbonylation, hydroformylation, hydrogenolysis, gidrometeorologia, hydrosilation, hydrolysis, hydrobromide, hydrodesulfurization (desulfurization) /gidrogenizirovanii, isomerization, methanol synthesis, methylation, demethylation reaction disproportionation, nitration, oxidation, partial oxidation, polymerization, reaction, recovery, conversion of water vapor and conversion with carbon dioxide, sulfonation, telomerization, transesterification, trimerization, conversion of water vapor and the reverse conversion of water vapor.

The method of preparation of the catalyst of the invention includes selection phase porous media 100, the deposition of the buffer layer 102 on a porous carrier 100 and the deposition of the interfacial layer 104 to buffer the output layer. If necessary, the interfacial layer 104 may be deposited catalytically active layer 106 or interphase and catalytically active layers can simultaneously be applied to the buffer layer 102.

Because the metal has a mesh surface, non-porous and smooth, the deposition of the buffer layer may be difficult. One way to solve this problem is to make the metal surface roughening by chemical etching. For metal catalysts on a carrier of γ-aluminium oxide adhesion to the metal foam is significantly improved when the metal foam becomes rough due to the chemical etching solutions of mineral acids, such as 0.1-1 M HCl solution. Rough mesh surface also exhibits the best stability of the catalytic layer to cracking during thermal cycles. In the preferred embodiment, where the porous media 100 is used, a metal foam, prior to vapor deposition of the buffer layer 102, the metal foam is coated. The etching is preferably carried out by acid, for example HCl.

Applying a buffer layer 102 is preferably carried out by deposition from the vapor phase, which includes, but is not limited to a list, chemical vapor deposition, physical vapor deposition or Oceania. It has been unexpectedly discovered that the vapor deposition, which is usually carried out at high temperatures, leads to polycrystalline or amorphous phases, which ensures good adhesion of the buffer layer to the surface of the porous media. This method is especially preferable for the adhesion of the buffer layer of the metal oxide to the metal porous media. Alternative buffer layer 102 can be obtained by precipitation from a solution. For example, deposition from a solution includes the stage of activation of the metal surface during exposure of the metal surface with water vapor for the formation of surface hydroxyl groups, then the surface reaction and the hydrolysis of the alcoholate to obtain coverage from a metal oxide. Such a deposition from a solution may be preferred as a less expensive method of applying a buffer layer 102.

The interfacial layer 104 preferably is produced by deposition from the vapor phase or from a solution, using the original substance known for these techniques. Suitable source agents are ORGANOMETALLIC compounds, halides, carbonyl compounds, acetonate, acetates, metals, colloidal dispersions of metal oxides, nitrates, clay, etc. for Example, a porous interfacial layer of aluminum oxide may be coated with a thin layer of colloidal disperse and aluminum oxide brand PQ (Nyacol Products, Ashland, MA) with subsequent drying in vacuum overnight and calcination at 500°C within 2 hours.

The catalytically active substance can be applied in any suitable way. For example, the catalyst precursor is applied on the colloidal particles of the metal oxide that is pre-printed on porous media as a buffer layer, then dried and turned into the desired shape.

Example 1

In order to demonstrate the main advantages of the buffer layer of the present invention, an experiment was conducted.

Neprotivleniya foam stainless steel (Astromet, Cincinnati HE was covered with a layer of TiO2a thickness of 1000 angstroms by chemical vapour deposition. Isopropoxide titanium (Strem Chemical, Newburyport, MA) was deposited from the vapor phase at temperatures ranging from 250 to 800°C, and at pressures from 0.1 to 100 mm Hg Coating of titanium dioxide, which has an excellent adhesion to the foam were obtained at the temperature of deposition 600°and the pressure in the reactor 3 mm Hg

Analysis using SEM (scanning electron microscope) showed that γ-aluminum oxide with a buffer layer of TiO2printed on foam stainless steel, does not cracking after a few (3) thermal cycles at temperatures ranging from room temperature to 600°C. In a control experiment with Penn the m carrier stainless steel covered γaluminum oxide without the buffer layer of TiO2observed strong delamination or cracking γ-alumina under the same experimental conditions. Resistance to high temperature oxidation shown in figa and 2b. As you can see from figa, steel foam without the buffer layer is rapidly oxidized, which was accompanied by increase in weight (i.e. values of heat gain), whereas steel, coated with titanium dioxide, oxidized relatively slow. As can be seen from fig.2b, Nickel foam without the buffer layer is oxidized, whereas Nickel foam, coated with titanium dioxide, in the same conditions showed no oxidation (i.e. oxidation, not detectable).

CONCLUSION

Although in the description shown and described the preferred embodiment of the present invention, for specialists in this area it is obvious that changes and modifications without departure from the invention in its broader aspects. Therefore, the attached claims is intended to include all such changes and modifications as are within the true nature and scope of the invention.

1. The catalyst containing porous metal media, a buffer layer, interfacial layer, and a catalytically active layer on the surface of the porous metal wear the ü has an average pore size from 1 to 1000 microns and the porous metal media is chosen from the group consisting of foam, felt, wool, or combinations thereof; a buffer layer located between the porous media and the interfacial layer, the interfacial layer is located between the catalytically active layer and the buffer layer.

2. The catalyst according to claim 1, where the catalyst is stable during thermal cycle, such that after three thermal cycles in air, the catalyst exhibits less than 2% of the delamination.

3. The catalyst according to claim 1, where the catalyst is resistant to oxidation, such that when heated in a current of air at 580°With over 2500 min the catalyst increases in weight by less than 5%.

4. The catalyst according to claim 1, where the catalyst is resistant to oxidation, such that when heated in a current of air at 750°With over 1500 rpm catalyst increases in weight by less than 0.5%.

5. The catalyst according to claim 1, where the porous media is a metal and the catalytically active layer is distributed over the entire surface of the catalyst so that the reactants through the catalyst, can interact with the catalyst across its surface.

6. The catalyst according to claim 1, where the specified buffer layer is non-porous.

7. The catalyst according to claim 1, where the interfacial layer has a surface area determined by BET method of at least 1 m2/year

8. The catalyst according to claim 1, where the interfacial layer contains a substance in the curse of the group, consisting of nitrides, carbides, sulfides, halides, and coal.

9. The catalyst according to claim 1, resistant to oxidation, such that when heated in a current of air at 750°With over 1500 rpm catalyst increases in weight by less than 0.5%.

10. The catalyst according to claim 1, where the porous media is made in the form of foam.

11. The catalyst according to claim 1, where the porous metal media has an average pore size from 1 to 500 microns.

12. The catalyst according to claim 1, where the interfacial layer has a thickness of from 1 to 50 microns.

13. The catalyst containing porous metal media, the buffer layer and the interfacial layer, where the porous metal media has an average pore size from 1 to 1000 microns and the porous metal media are selected from the group consisting of foam, felt, wool, or combinations thereof; a buffer layer consists of at least two compositionally different sublayers and is located between the porous media and the interfacial layer.

14. The catalyst according to item 13, additionally containing a catalytically active layer on the interfacial layer.

15. The catalyst according to item 13, where specified, at least two sublayers include a first sublayer of TiO2in contact with a porous carrier, and the second sublayer consisting of α-Al2About3.

16. The catalyst according to item 15, where the interfacial layer contains aluminium oxide layer with a strongly developed surface is less dense than the second sublayer.

17. The catalyst according to item 16, further containing catalyst deposited on the interfacial layer.

18. The catalyst according to item 13, where the interfacial layer comprises a metal oxide.

19. The catalyst according to item 13, where the interfacial layer can serve as a catalytically active layer without any applied more catalytically active substances.

20. The catalyst according to item 13, where the interfacial layer consists of at least two different composition of the sublayers.

21. The catalyst according to item 13, where the porous media has a porosity of from 70 to 98%.

22. The catalyst according to item 13, where the porous media is made in the form of foam.

23. The catalyst according to item 13, where the interfacial layer has a thickness of from 1 to 50 microns.

24. The catalyst containing porous metal media, the buffer layer and the interfacial layer, where the porous metal media has an average pore size from 1 to 1000 microns and the porous metal media are selected from the group consisting of foam, felt, wool, or combinations thereof; a buffer layer located between the porous media and the interfacial layer; and the catalyst is stable during thermal cycle, such that after three thermal cycles in air, the catalyst exhibits less than 2% of the delamination.

25. The catalyst according to paragraph 24, where the porous media is a metal and the catalyst, in addition, ladet resistance to oxidation, such that when heated in a current of air at 580°With over 2500 rpm weight of the catalyst increases by less than 5%.

26. The catalyst A.25, where the buffer layer has a thickness of from 0.05 to 10 μm.

27. The catalyst according to paragraph 24, where the catalyst is a monolith having a width of from about 0.1 mm to 2 cm and a thickness of less than 1 cm

28. The catalyst according to paragraph 24, where the porous media has a porosity in the range of from 70 to 98%.

29. The catalyst according to paragraph 24, where the porous media is made in the form of foam.

30. The catalyst according to paragraph 24, where the porous metal media has an average pore size from 1 to 500 microns.

31. The catalyst according to paragraph 24, where the interfacial layer has a thickness of from 1 to 50 microns.

32. A method of producing a catalyst, which includes stages

the selection of a porous carrier selected from the group consisting of foam, felt, wool, or combinations thereof;

the vapour deposition of the buffer layer to the specified porous media;

the deposition of the interfacial layer to the specified buffer layer.

33. The method according to p where the specified buffer layer is a titanium dioxide.

34. The method according to p, where the catalytically active material is applied simultaneously with the interfacial layer.

35. The method according to p, where the interfacial layer is precipitated from the solution.

36. The method according to p, where stage vapour deposition include chemical vapor deposition.

37. The method according to p, where the carrier includes a metal foam and chemical vapor deposition is carried out at a temperature of from 250 to 800°C.

38. The method according to p, where the original connection for the chemical deposition from the vapor phase selected from the group consisting of ORGANOMETALLIC compounds, halides, carbonyl compounds, acetone and acetates.

39. The method according to p, which includes stages of vapour deposition of a layer of TiO2; deposition from the vapor phase on a layer of TiO2a dense layer of aluminum oxide and the deposition of a thick layer of aluminum oxide is less dense layer of aluminum oxide with a highly developed surface.

40. The method according to p, where the porous medium consists of a metal foam and the catalyst has a surface area of more than 2.0 m2/year

41. The method according to p, where the porous medium consists of a metal foam or metal foam is coated before the vapor deposition of the buffer layer.

42. The method according to p, where the porous medium contains a metal selected from the group consisting of foam, felt and wool; and the catalyst is resistant to oxidation, such that when heated in a current of air at 750°With over 1500 rpm catalyst increases in weight by less than 0.5%.

43. The method according to p, where the porous media has a porosity in the range of from 70 to 98%.

44. The method according to p where stage vapour deposition include chemical vapor deposition.

45. The method of turning at least one reagent, at least one product, including

passing at least one reactant in the reaction zone, which contains the catalyst according to claim 1;

the transformation of the specified at least one reagent, at least one product and

the product yield from the reaction zone.

46. The method according to item 45, where the specified method selected from the group consisting of acetylation, addition reactions of, alkylation, dealkylation, hydrodealkylation, reductive alkylation, amination, flavoring, arilirovaniya, Autoterminal reforming, carbonylation, decarbonylation, restorative decarbonylation, carboxylation, reductive carboxylation, reductive reactions combination reactions of condensation, cracking, hydrocracking, cyclization reactions, cycloaliphatic, dehalogenase, dimerization, epoxidation, esterification, exchange, reaction, Fischer-Tropsch, halogenation, hydrohalogenation, homologation, hydration, dehydration, hydrogenation, dehydrogenation, hydrocarbonsoluble, hydroformylation, hydrogenolysis, gidrometeorologia, hydrosilation, hydrolysis, hydrobromide, hydrodesulfurization (desulfurization)/gidrogenizirovanii, Isom the polarization, for methanol synthesis, methylation, demethylation, disproportionation reactions, nitration, oxidation, partial oxidation, polymerization reactions, recovery, conversion with steam and conversion with carbon dioxide, sulphonation, telomerization, transesterification, trimerization, the conversion of water vapor and reverse conversion of water vapor.

47. The method according to item 45, where the specified reaction zone having a wall and at least one of these walls has a deposited buffer layer, interfacial layer, and a catalytically active layer.

48. The method of turning at least one reagent, at least one product, including

passing at least one reactant in the reaction zone, which contains the catalyst according to item 13;

the transformation of the specified at least one reagent, at least one product and

the product yield from the reaction zone.

49. The method according to p, where the specified method selected from the group consisting of acetylation, addition reactions of, alkylation, dealkylation, hydrodealkylation, reductive alkylation, amination, flavoring, arilirovaniya, Autoterminal reforming, carbonylation, decarbonylation, restorative decarbonylation, carboxylation, reductive carb is calironia, reactions restorative combinations, reactions, condensation, cracking, hydrocracking, cyclization reactions, cycloaliphatic, dehalogenase, dimerization, epoxidation, esterification, exchange, reaction, Fischer-Tropsch, halogenation, hydrohalogenation, homologation, hydration, dehydration, hydrogenation, dehydrogenation, hydrocarbonsoluble, hydroformylation, hydrogenolysis, gidrometeorologia, hydrosilation, hydrolysis, hydrobromide, hydrodesulfurization (desulfurization)/gidrogenizirovanii, isomerization, methanol synthesis, methylation, demethylation, disproportionation reactions, nitration, oxidation, partial oxidation, polymerization reactions, recovery, conversion with steam and conversion with carbon dioxide, sulphonation, telomerization, transesterification, trimerization, the conversion of water vapor and reverse conversion of water vapor.

50. The method of turning at least one reagent, at least one product, including

passing at least one reactant in the reaction zone, which contains the catalyst according to point 24;

the transformation of the specified at least one reagent, at least one product and

the product yield from the reaction zone.

51. The method according to item 50, where the specified method selected from gr is PPI, consisting of acetylation, addition reactions of, alkylation, dealkylation, hydrodealkylation, reductive alkylation, amination, flavoring, arilirovaniya, Autoterminal reforming, carbonylation, decarbonylation, restorative decarbonylation, carboxylation, reductive carboxylation, reductive reactions combination reactions of condensation, cracking, hydrocracking, cyclization reactions, cycloaliphatic, dehalogenase, dimerization, epoxidation, esterification, exchange, reaction, Fischer-Tropsch, halogenation, hydrohalogenation, homologation, hydration, dehydration, hydrogenation, dehydrogenation, hydrocarbonsoluble, hydroformylation, hydrogenolysis, gidrometeorologia, hydrosilation, hydrolysis, hydrobromide, hydrodesulfurization (desulphurization)/gidrogenizirovanii, isomerization, methanol synthesis, methylation, demethylation, disproportionation reactions, nitration, oxidation, partial oxidation, polymerization reactions, recovery, conversion with steam and conversion with carbon dioxide, sulphonation, telomerization, transesterification, trimerization, the conversion of water vapor and reverse conversion of water vapor.

52. Device with microchannels, in which, at least on the at from the inner walls are covered with the buffer layer, which is caused by deposition from the vapor phase.

53. The apparatus according to paragraph 52, optionally containing interfacial layer deposited on the buffer layer.

54. The apparatus according to item 53, where the buffer layer is deposited by means of chemical deposition from the vapor phase.

55. The apparatus according to paragraph 52, where the said walls include at least one wall of the reaction chamber, and on the interfacial layer additionally deposited catalytically active substance.



 

Same patents:

FIELD: chemistry of organochlorine compounds, chemical technology.

SUBSTANCE: method involves treatment of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane with solid calcium hydroxide or a mixture of solid calcium hydroxide and solid sodium hydroxide with the content of sodium hydroxide in mixture 30%, not above, in the molar ratio 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane to alkali = 1:(1.5-1.75) at heating in the presence of catalyst. As catalysts method involves benzyltrialkyl ammonium halides, preferably, benzyltriethyl ammonium chloride or benzyltrimethyl ammonium bromide, tetraalkyl ammonium halides, preferably, tetrabutyl ammonium bromide taken in the amount 0.0005-0.005 mole. Invention provides the development of a new method for preparing 1,1-dichloro-2,2-bis-(4-chlorophenyl)-ethylene allowing to enhance ecological safety of technological process and to improve quality of the end product.

EFFECT: improved method preparing.

2 cl, 15 ex

FIELD: industrial organic synthesis.

SUBSTANCE: gas-phase thermal dehydrochlorination of 1,2-dichloroethane is conducted in presence of hydrogen chloride as promoter dissolved in feed in concentration between 50 and 10000 ppm.

EFFECT: increased conversion of raw material and reduced yield of by-products.

4 cl, 1 tbl, 8 ex

FIELD: petrochemical processes.

SUBSTANCE: method provides for three-stage isolation of aromatic hydrocarbons in the separation, absorption, and separation stages using, as absorbent, ethylbenzene rectification bottom residue. Loaded absorbent containing diethylbenzene isomer mixture serves as starting material for production of alkylaromatic hydrocarbons including divinylbenzene.

EFFECT: reduced loss of aromatic hydrocarbons and improved economical efficiency of styrene production process.

2 dwg, 1 tbl, 5 ex

FIELD: chemical industry branches, possibly manufacture of calcium carbide, calcium oxide, acetylene, carbonic acid and slaked lime.

SUBSTANCE: coal-carbonate mineral raw material - lime is fired in reactor 1 with use of acetylene as high-temperature energy carrier. Lime produced in reactor 1 is fed to user and(or) to second reactor 2 and adding coke or coal with fraction size 20 -25 mm and with sulfur content less than 1% into reactor 2. Some part of acetylene further produced is also added to reactor 2. Ready calcium carbide is removed out of reactor 2 and it is fed to user and(or) to fourth reactor 4 where after contact with water acetylene and slaked lime are formed. Acetylene is fed through pipeline 15 to user and(or) to reactors 1 and 2. Ready slaked lime is fed to user. Gaseous products such as carbon dioxide from reactor 1 and carbon oxide from reactor 2 are fed to third reactor 3 where after contact with water carbonic acid is formed and fed to user as "dry ice" or in liquefied state.

EFFECT: possibility for producing wide assortment of commercial products in one waste-free cycle, elimination of environment contamination.

2 cl, 1 dwg

FIELD: petrochemical processes catalysts.

SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on granulated halumine may further contain promoters selected from oxides ZrO2 and HfO2 and metals Ru, Pd, and Pt.

EFFECT: increased selectivity and productivity.

2 cl, 3 tbl, 2 ex

FIELD: petrochemical process catalysts.

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2 cl, 2 tbl, 2 ex

FIELD: detoxification methods.

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EFFECT: essentially increased waste processing productivity with minimum formation of secondary toxic substances.

5 cl, 1 tbl, 12 ex

FIELD: industrial organic synthesis.

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EFFECT: reduced amount of process waste and increased production of isoprene without increase in consumed raw material.

3 cl, 1 tbl, 4 ex

FIELD: industrial organic synthesis.

SUBSTANCE: first stage of the process comprises synthesis of 4,4-dimethyl-1,3-dioxan via isobutylene/formaldehyde condensation in presence of acid catalyst at 80-100ºC and pressure 1.6-2.0 MPa. Product and high-boiling by-product mixture are isolated from oil layer of reaction mixture. 4,4-Dimethyl-1,3-dioxan is then decomposed on calcium phosphate catalyst at 290-380°C and pressure 0.12-0.16 MPa in presence of water steam. Contact gas is further processed to produce isoprene. High-boiling by-product mixture is distilled on two in series connected vacuum rectification columns. On the first column, 60-70% of distillate is recovered based on the weight of feed. Second distillation on the second column gives second distillate (75-90%) and bottom product, which is recycled into 4,4-dimethyl-1,3-dioxan synthesis zone. Second-column distillate is decomposed into isoprene on ceramic filling at 400-450°C and pressure 0.12-0.16 MPa in presence of water steam supplied at (2-5):1 weight ratio to high-boiling by-product mixture. Contact gas obtained after decomposition of this mixture is processed jointly with contact gas obtained after decomposition of dimethyldioxan.

EFFECT: reduced amount of process waste and increased production of isoprene without increase in consumed raw material.

3 cl, 1 dwg, 1 tbl, 4 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to catalysts used in isoamylenes-into-isoprene dehydrogenation process and contains, wt %: iron oxide 62-75.4, potassium carbonate 12-21.5, chromium oxide 1-3, potassium hydroxide 0.5-2.5, sulfur 0.1-2.0, ammonium nitrate 0.1-2.0, silicon dioxide 1-5, calcium carbonate 1-5, and cerium nitrate 1-3.

EFFECT: increased mechanical strength, resistance to saturated steam and moisture, and stability during long-time operation.

3 ex

The invention relates to new phosphorus ylides F.-ly (I)

< / BR>
in which R1, R2and R3represent the amino group R R N, where R' and R" are C1-C6alkyl; R4- H, Me; R5polymer media polystyrene type f crystals of (S)

< / BR>
where n, n' and m are integers greater than or equal to 1

The invention relates to an improved method of hydrogenation of unsaturated cyclic compounds such as benzene and aniline, or cyclohexylaniline and dicyclohexylamine, obtaining, for example, cyclohexylaniline or cyclohexane

The invention relates to organic chemistry, in particular to a method for producing N-(1-propenyl)ndimethylacetamide by isomerization of N-(2-propenyl)ndimethylacetamide in the presence of catalytically active carbonyl complex of a metal of group VIII, at room temperature

The invention relates to an improved process for the preparation of pyrazole and its derivatives of the formula I

< / BR>
in which the radicals R1-R4have the meanings specified below,

from,- unsaturated carbonyl compounds of the formula II

< / BR>
and hydrazine or hydrazine derivatives of formula III

H2N-OTHER4

The invention relates to petrochemistry, in particular to the two-stage dehydrogenation of isopentane, and can be used to improve cooling unit in those industries in which there are processes of heat transfer
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