Metal-based catalyst carrier (versions) and method of its preparation (versions)

FIELD: technical chemistry; catalyst carriers for various heterogeneous processes in chemical industry.

SUBSTANCE: proposed carrier has metal base made from chromium and aluminum alloy and/or metallic chromium and coat made from chromium of aluminum oxides or oxides of chromium, aluminum, rare-earth elements or mixture of them. Method of preparation of carrier includes forming of metal powder containing aluminum and other powder-like components and calcination of carrier at solid phase sintering point; used as additional component of metal powder is powder-like chromium; mixture thus obtained is subjected to mechanical activation and is placed in mold accessible for water vapor, after which it is subjected to hydro-thermal treatment and molded product is withdrawn from mold, dried and calcined at respective temperature; then additional layer of aluminum and rare-earth elements oxides or mixture of solutions and suspensions is applied on calcined product followed by drying and calcination.

EFFECT: increased specific surface; enhanced heat resistance of carrier.

8 cl, 1 tbl, 5 ex

 

The invention relates to the field of technical chemistry, namely, carriers for catalysts that can be used in various heterogeneous catalytic processes in the chemical industry, such as full and partial oxidation of hydrocarbons, steam reforming and others, as well as in the energy and automotive industries.

It is known that the use as a carrier for catalysts of metals having high mechanical strength and thermal conductivity, reduces mechanical destruction of the catalyst and to reduce the possibility of local overheating, as well as to produce catalysts in the form of complex cellular structures. The most common problem for metals used as a carrier for catalysts complex forms, is their low specific surface area, which significantly reduces the activity of the catalysts prepared on the basis of such media. To increase the specific surface area of the carriers in metals can cause a highly porous layer of ceramic oxide pre - or together with the active component (catalyst). This layer provides a high dispersion of the active component and the adhesion layer to the metal surface. Thus, the known system, the precursor and the catalyst based on it containing a highly porous layer deposited on the less porous the th or non-porous media from a non-aqueous solvent, containing oxide [US 5472927, B 01 J 021/08, 05.12.1995].

Known thermally integrated monolith containing oxide coating placed on a thin metal plate, forming palikoista structure [WO 0016740, a 61 K 7/50, 23.08.2001]. However, for such high-temperature processes such as combustion of fuels or partial oxidation of hydrocarbons to synthesis gas, an important characteristic is the stability of the catalyst to effect the reaction medium, the time of operation ("life") catalyst [US 4771029, B 01 J 21/04, 13.09.1988]. In particular, the difference of coefficients of thermal expansion of the porous ceramic layer and the metal leads to breakaway from the first surface of the second at high temperatures.

More resistant to high temperatures (heat-resistant) solid media (catalysts) on a metal base formed by applying an intermediate layer between the metal substrate and highly porous oxide coating. These layers not only reduce peeling, but also reduce oxidation of the metal, which is also important for monolithic blocks. Thus, the known method of gas-phase eletrownia cell blocks, made of thin tape-based Fe-Cr-Al alloys type HU-HU at a temperature thermochemical processing >1050°in the saturating mixture containing Al0and AlF [SU 2080458, F 01 N 3/28, 27.05.1997]. The method allows to obtain a dense oxide coating, improving heat resistance 3-10 times. However, eletrownia ready block leads to non-uniformity of the coating on the height of the block [Kinetics and catalysis, 1998, t, B.5: Sevasitan, Cal, Weasle, Anildigital, Ibogaine "improving the heat resistance of the metal blocks, carriers of the catalyst by the method of gas-phase eletrownia", s-717]. This reduces the adhesion of highly porous layer to the substrate and reduces the activity produced from this catalyst carrier.

Also known methods based on cultivation of the intermediate oxide layer from the material of the metal substrate. Thus, the known method of obtaining a dense oxide composite on the surface of aluminum metal by anodic spark oxidation [SU 2103057, B 01 J 21/02, 11.07.1996]. Then on the resulting carrier is applied jointly or separately porous oxides and platinum metals. However, the resulting intermediate oxide layer is porous and consists of a system of intersecting cylindrical macropores with a diameter of from 0.5 to 10 μm [MRS n.497: S.F.Tikhov, G.V.Chernykh, V.A.Sadykov, A.N.Salanov, S.V.Tsybulya, G.M.Alikina, V.F.Lysov "New type of catalytic material based upon alumina epitaxially grown onto thin aluminum foil" p.71-76]. This reduces the stability of the catalyst.

The closest in composition is a carrier selected n the mi as a prototype, consisting of Fe-20Cr-5Al alloy and coating consisting of a sintered powder from a mixture containing, wt.%: 50 Fe and Al with 50 particle size 36-45 mm [US 4783436, B 01 J 21/04, 08.11.1988]. Sintering at high temperature leads to partial oxidation of the metallic base. In particular, in the alloy Fe-Cr-Al aluminium smelted at the surface of the foil and is oxidized, forming an oxide with a structure of corundum the form of elongated crystals. Partially oxidized and the powder, forming additional plates of iron oxide. As a result, the coating is not continuous oxide layer, and a mixed metal oxide composite with a very low specific surface (0.1 m2/g). This leads to the fact that the amount of active component applied from solutions on such media, small and activity derived from such catalysts carriers is low.

The invention solves the problem of increasing the specific surface of the metal carrier while maintaining high heat resistance.

The problem is solved by the composition of the catalyst carrier, which consists of a metal base containing alloys of chromium and aluminum and/or metal chromium, and coatings, which are formed by the oxides of chromium and aluminum (the first option), or the coating formed by the oxides of chromium and aluminum, rare earths or mixtures thereof (the second option). The content of the metal base is in the media is not less than 12.0 wt.%.

The problem is solved through the use of the metallic base of the carrier metal chromium, and alloys of chromium and aluminum as on the basis of solid solutions of aluminum in chrome, and on the basis of intermetallic compounds chromium and aluminium certain structure and stoichiometry (CrAl7, Cr2Al11, CrAl4, Cr4Al9, Cr5Al8, Cr2Al) and other [Pasang "the structure of double alloys", 1973, M.: metallurgy, p.55-57]. The total content of the metal phase (basics) in the medium is not less than 12.0 wt.%, preferably 12,3 reached 98.9 wt.%. As coverage in the media use the oxides of chromium and aluminum, the same structure of corundum with high thermostability. The chromium oxides have moderate activity in oxidation reactions involving hydrocarbons, which increases the activity of the platinum metals when they are applied to the media. A relatively high content of aluminum oxide provides a relatively large porosity of the received media.

The coating of the carrier (the second option) could contain oxides of rare earth elements, or mixtures thereof, which allows to significantly increase their thermostability and activity produced from these catalysts at high temperatures. The term "rare earth elements" is used in a broad sense, as implying f elements, and the side elements IIIb group of the Periodic table (La, Y). The total content of the metal phase (basics) in this medium is not less than 12.0 wt.%, preferably, 12,0-to 98.5 wt.%.

The task is also solved by a method of preparation of the proposed media.

Noted previously, the methods include use as a basis metal strip, which does not allow to obtain media with high specific surface area and porosity without causing additional highly porous substrate [WO 0016740, a 61 K 7/50, 23.08.2001; U.S. Pat. RF 2080458, F 01 N 3/28, 27.05.1997; MRS, n.497: S.F.Tikhov, G.V.Chemykh, V.A.Sadykov, A.N.Salanov, S.V.Tsybulya, G.M.Alikina, V.F.Lysov "New type of catalytic material based upon alumina epitaxially grown onto thin aluminum foil" p.71-76].

More porous composite materials can be obtained from the powdered components. Thus, the known method of preparing the composite material-based aluminium-containing alloy, which comprises a mixture of fibers of alumina and silicon, copper, magnesium, Nickel with molten aluminum in an inert atmosphere [US 41521449, With 22 21/10, 01.05.1979]. This method does not allow to obtain porous composites.

Also known a method of obtaining (ceramometal) cermet grade containing metal particles (less than 30 wt.%) in the matrix of aluminum oxide, deposition from solutions containing aluminum compounds and metal from the group iron, chromium, molyb the ena and others, with subsequent high-temperature annealing and recovery in hydrogen at 1050°With [US 5462903, 04 35/117, 31.10.911995]. This method allows to obtain composite materials with a specific surface area up to 5 m2/, However, the content of the metal phase in the composite is small.

There is also known a method of preparation of the active hromsoderzhashchej composition comprising a mixture of 0.1 to 100 mol.% (in terms of metal) chromium or chromium compounds, various metals, and the material forming the matrix-based alkoxides of aluminum and other metals in an amount of not less than 30 wt.% [WO 0160515, B 01 J 37/00, 23.08.2001]. To obtain a mechanically stable carrier method includes the mandatory annealing in a reducing or inert atmosphere at high temperatures, which significantly complicates the manufacturing process and does not allow to obtain media with a high content of metal, which increases the conductivity of the media.

In the patent [US 4783436, B 01 J 21/04, 08.11.1988], selected as a prototype and method of preparation of the medium described method of preparing a catalyst carrier-based metal having an oxide coating, comprising mixing a metal powder consisting of an alloy of iron and aluminum, marking the metal base, as in examples foil of alloy is Fe-Cr-Al, and calcination of the carrier at a temperature providing a sintering powder with a metal base. This method provides a carrier with a high content of the metal phase, but a small specific surface area.

The proposed method for the preparation of the medium on the metal base includes forming a metal powder containing aluminum and other powdered components, and the roasting carrier when the sintering temperature of the solid phase, as an additional component of the metal powder used powdered chromium, the resulting mixture is subjected to mechanisatie and placed in the mold, available for water vapor, and subjected to hydrothermal treatment, is removed from the mold molded product, which is then dried and calcined at an appropriate temperature (first option), then applied to the calcined product additional layer of aluminum oxide and rare earth elements, or mixtures of solutions or suspensions with subsequent drying and calcination (the second option). The ratio of chromium to aluminum metal powder can be changed within, wt. share: from 75:25 to 99:1.

In the present invention use only the powder components in the form of a mechanical mixture of powders of aluminum and chromium, which is subjected to mechanisatie in energy is abrajano planetary mill during acceleration of the grinding bodies 600-1000 m/s 2[SU 2118669, With 22 33/02, D 22 F 3/16, 20.08.1996]. The ratio of Cr:Al powder ranges (wt. share): from 75:25 to 99:1. At higher content of aluminum powder in the process of mechanisatie is the spontaneous oxidation of aluminum. Then the powder is placed in the mold, providing access water vapor, and treated under hydrothermal conditions. As a result, the adhesion of the powder in a mechanically stable monolith, which is extracted from the mold, dried and calcined in air. The result is a metallic phase based on chromium or chromium and its alloys, which are very resistant to oxidation in air up to 1100°C. On the surface of the metal particles is formed by a coating consisting of oxides of chromium and aluminum with the structure of corundum and providing a sufficiently high specific surface area. Preliminary mechanical activation facilitates the formation of alloys of chromium and aluminum, after annealing. Hydrothermal processing provides the setting in a mechanically stable monolith without calcinations at high temperatures in a reducing or inert atmosphere and contributes to the formation of high specific surface coverage of the carrier. As additional stages may be used, the carrier impregnated with solutions or suspensions containing compounds is s rare earth elements or their mixtures or aluminum and rare earth elements, or mixtures thereof, followed by drying and calcination.

Technical result achieved - high specific surface of a metal carrier and its high resistance to heat.

The essence of the invention is illustrated by the following examples.

Example 1. Chromium powder is mixed with aluminum powder in the ratio (wt. shares) 75:25, is subjected to mechanisatie for 1 min. the resulting powder was placed in a mold made of stainless steel and is subjected to hydrothermal treatment. Mechanically strong monolith is removed from the mold, dried and calcined at 1100°C for 4 h in air. The media contains phase of chromium oxide, aluminum oxide and metallic chromium. The content of the metal phase of 12.8 wt.%.

Example 1A (the second option). Similar to example 1. Characterized in that on the carrier in addition put a cerium oxide from the solution, followed by drying and calcination at 1100°C. the Medium contains phase of chromium oxide, aluminum oxide, cerium oxide and metallic chromium. The content of the metal phase to 12.0 wt.%.

Example 2. Chromium powder is mixed with aluminum powder in the ratio (wt. shares) 80:20, is subjected to mechanisatie within 3 minutes the resulting powder was placed in a mold of largescale and subjected to hydrothermal treatment. Mechanically strong monolith is removed from the mold, dried and calcined at 1100°C for 4 h in air. The media which contains the phase of chromium oxide, aluminum oxide, chromium metal and chromium alloys and aluminum. The content of the metal phase to 12.3 wt.%.

Example 3. Chromium powder is mixed with aluminum powder in the ratio (wt. shares) 80:20, is subjected to mechanisatie within 5 minutes the resulting powder was placed in a mold made of stainless steel and is subjected to hydrothermal treatment. Mechanically strong monolith is removed from the mold, dried and calcined at 1100°C for 4 h in air. The media contains phase of chromium oxide, aluminum oxide, metallic chromium and chromium alloys and aluminum. The content of the metal phase to 35.0 wt.%.

Example 4. Chromium powder is mixed with aluminum powder in the ratio (wt. shares) 80:20, is subjected to mechanisatie within 10 minutes the resulting powder was placed in a mold made of stainless steel and is subjected to hydrothermal treatment. Mechanically strong monolith is removed from the mold, dried and calcined at 1100°C for 4 h in air. The media contains phase of chromium oxide, aluminum oxide, metallic chromium and chromium alloys and aluminum. The content of the metal phase of 74.0 wt.%.

Example 5. Chromium powder is mixed with aluminum powder in the ratio (wt. shares) 99:1, put mechanisatie within 10 minutes the resulting powder was placed in a mold of largescale and subjected to hydrothermal treatment. Mechanical the ski durable monolith is removed from the mold, dried and calcined at 1100°C for 4 h in air. The media contains phase of chromium oxide, aluminum oxide, metallic chromium and chromium alloys and aluminum. The content of the metal phase that 98.9 wt.%.

Example 5A (the second option). Similar to example 5. Characterized in that on the carrier in addition put the oxides of cerium, lanthanum and aluminum in the slurry, followed by drying and calcination at 1100°C. the Medium contains phase of chromium oxide, aluminum oxide, oxides of rare earth elements, metal chromium and chromium alloys and aluminum. The content of the metal phase to 98.5 wt.%.

The basic properties of the obtained media presented in the table.

As can be seen from the table, the specific surface area obtained media is 0.5-1.9 m2/year the Total volume available for the gas phase then is 0,27-0,11 cm3/, While the share of pore size less than 0.1 μm is 2.1-25,0% vol. of the total number of available pores, which provides a high diffusive permeability of the received media. The most optimal from the point of view of mechanical strength, specific surface area and porous structure are the media containing 12,3-74,0 wt.% the metal phase.

Table.

Basic properties of the catalyst carrier.
No. The composition of the powder, by weight. Rel. Cr:AlTime megachilidae powder, minThe phase composition of the metallic baseThe coating compositionThe content of the metallic base in the media, wt.%The specific surface the terrain of media, m2/gTotal pore volume, cm3/gThe amount of pore size <1000Åcm3/gThe strength of granules, MPa
175:251Cr0Al2About3,12,81,80,26of 0.0815,8
Cr2O3,
175:251Cr°Al2O3,to 12.03,20,280,0895,8
andCr2O3,
SEO2
280:203Cr°,Al2O3,12,30,90,270,0614,2
alloyCr2About3,
Cr-Al,
380:205Cr0,Al2O3,35,01,90,110,01322,6
alloyCr2About3,
Cr-Al,
480:2010Cr°,Al2About3 74,01,60,140,01019,7
alloyCr2About3,
Cr-Al,
599:110Cr°,Al2O3,the 98.90,50,180,0092,4
alloyCr2O
Cr-Al,
599:110Cr°,Al2O3,98,51,60,190,0192,4
andalloyC 2About3,
Cr-Al,La-
SEOx

1. Catalyst carrier consisting of a metal base, chromium, and coatings containing aluminum, wherein the metal base includes alloys of chromium and aluminum and/or metallic chromium, and the coating formed by the oxides of chromium and aluminum.

2. The carrier according to claim 1, characterized in that the content of the metallic base in the medium is not less than 12.0 wt.%.

3. The method of preparation of the catalyst carrier on a metal basis, including the formation of a metal powder containing aluminum and an additional powder component, the roasting carrier when the sintering temperature of the solid phase, characterized in that as an additional component of the metal powder used powdered chromium, the resulting mixture is subjected to mechanisatie, then poluchenno the mixture placed in the mold, available for water vapor, and subjected to hydrothermal treatment, is removed from the mold molded product, which is then calcined at an appropriate temperature.

4. The method according to claim 3, characterized in that the ratio of chromium to aluminum metal powder can be changed within, parts by weight: 75:25÷99:1.

5. Catalyst carrier consisting of a metal base, chromium, and coatings containing aluminum, wherein the metal base includes alloys of chromium and aluminum and/or metallic chromium, and the coating formed by the oxides of chromium and aluminum, rare earths or mixtures thereof.

6. The carrier according to claim 5, characterized in that the content of the metallic base in the medium is not less than 12.0 wt.%.

7. The method of preparation of the catalyst carrier on a metal basis, including the formation of a metal powder containing aluminum and an additional powder component, and the roasting carrier when the sintering temperature of the solid phase, characterized in that as an additional component of the metal powder used powdered chromium, the resulting mixture is subjected to mechanisatie and placed in the mold, available for water vapor, and subjected to hydrothermal treatment, is removed from the mold molded product, which is then su is at and calcined at an appropriate temperature, then put on the calcined product additional layer of aluminum oxide and rare earth elements or their compounds from solutions or suspensions, followed by drying and calcination.

8. The method according to claim 7, characterized in that the ratio of chromium to aluminum metal powder can be changed within, parts by weight: 75:25÷99:1.



 

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1 ex

FIELD: technology for silicium dioxide production useful as additive for polymer reinforcement.

SUBSTANCE: claimed method includes silicate reaction with acidifying agent to produce silicium dioxide slurry separation and drying of said slurry, wherein reaction is carried out according to the next steps: i) providing base aqueous solution with pH from 2 to 5, preferably from 2.5 to 5; ii) simultaneous addition silicate and acidifying agent to said base solution maintaining solution pH from 2 to 5, preferably from 2.5 to 5; iii) addition silicate only without acidifying agent to produce pH from 7 to 10, preferably from 7.5 to 9.5; (iv) simultaneous addition silicate and acidifying agent to reaction medium to maintain pH from 7 to 10, preferably from 7.5 to 9.5; (v) addition acidifying agent only without silicate to produce reaction medium pH below 6. Obtained high structured silicium dioxides have the next characteristics: CTAB specific surface (SCTAB) is 40-525 m2/g; BET specific surface (SBET) is 45-550 m2/g; width Ld ((d84-d16)/d50) of particle size distribution measured by XDC grading analysis after ultrasound grinding is at least 0.92; and such pore distribution that V(d95-d50)/V(d5-d100) is at least 0.66.

EFFECT: improved material for polymer reinforcement.

FIELD: production of carbon carrier for catalysts.

SUBSTANCE: proposed method includes heating of moving layer of granulated furnace black used as backing, delivery of gaseous or vaporous hydrocarbons into soot layer followed by their thermal decomposition on soot surface forming layer of pyrocarbon at forming of layer of pyrocarbon and activation of material compacted by pyrocarbon at temperature of 800-900°C and unloading of finished product. Granulated furnace black at specific surface of 10-30 m2/g and adsorption rate of 95-115 ml/100 g is used as backing for compacting with pyrocarbon. Then, product is subjected to activation for obtaining total volume of pores of 0.2-1.7 cm3/g. Black is compacted by pyrocarbon at two stages: at first stage, granulated black is compacted to bulk density of 0.5-0.7 g/cm3, after which material is cooled down and screened at separation of fraction of granules of 1.6-3.5 mm; at second stage, this fraction is subjected to repeated pyrolytic compacting to bulk density of granules of 0.9-1.1 g/cm3.

EFFECT: enhanced economical efficiency; increased productivity of process.

3 ex

FIELD: composite materials.

SUBSTANCE: invention relates to catalyst carriers and methods for preparation thereof. Novel porous composite material particles are proposed comprising alumina component and swelled clay component finely dispersed in alumina component in amount effective to raise hydrothermal stability, pore volume, and/or pore mode in the mesopore region in composite material particles as compared to swelled clay-free material. Also proposed are composite material particles and agglomerate particles obtained therefrom as well as a method for hydroprocessing of petroleum feedstock using agglomerates as hydroprocessing catalyst carrier.

EFFECT: increased hydrothermal stability and pore volume.

44 cl, 24 dwg, 19 tbl, 28 ex

FIELD: inorganic compounds technologies.

SUBSTANCE: invention provides porous composite particles containing alumina component and residue of at least one additional crystal growth inhibitor component dispersed within alumina component, wherein indicated composite particles have (A) specific surface area at least 80 m2/g; (B) average nitrogen-filled pore diameter 60 to 1000 Å; (C) total nitrogen-filled pore volume 0.2 to2.5 cm3/g and (D) average particle size 1 to 15 μm, and where, in indicated composite particles, (i) alumina component contains at least 70 wt % of crystalline boehmite with average crystallite size 20 to 200 Å, γ-alumina obtained from indicated crystalline boehmite, or mixture thereof; (ii) residue of additional is obtained from at least one ionic compound containing ammonium, alkali metal, alkali-earth metal cation, or mixtures thereof and wherein anion is selected from group comprising hydroxyl, silicate, phosphate, sulfate, or mixtures thereof and is present in composite particles in amounts between 0.5 and 10 % of the summary weight of alumina and additional components. Invention also provides a method to obtain composite particles, agglomerated particles prepared therefrom, and a method for hydroprocessing of petroleum feed using above-mentioned agglomerates.

EFFECT: avoided unnecessary calcination before addition of metals to increase average pore size and use of organic solvents for azeotropic removal of water.

36 cl, 2 tbl, 22 ex

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