High-temperature spinel-based shift reaction catalysts

FIELD: shift reaction catalysts.

SUBSTANCE: invention relates to iron oxide-containing catalysts generally used for high-temperature shift reactions wherein gas stream containing water steam and carbon monoxide is passed over catalyst at temperature within a range of 350 to 550°C to convert carbon monoxide into carbon dioxide with simultaneous formation of hydrogen. Catalyst is prepared via precipitation of composition containing ferrous and ferric iron and chromium(III) with a base, ferrous iron being partly oxidized by an oxidant into ferric iron. Further formation of resulting precipitate into formed catalyst blocks is effected at temperature above 200°C. Invention also provides a high-temperature shift reaction process using above catalyst blocks.

EFFECT: avoided need of catalyst restoration stage resulting in improved catalyst strength and activity.

10 cl, 2 tbl, 2 ex

 

The invention relates to catalysts, particularly catalysts containing iron oxide. These catalysts usually used for so-called high-temperature reactions of conversion (HTS), where the gas stream containing water vapor and carbon monoxide is passed over the catalyst at an elevated temperature, typically in the range of 350-550°for the conversion of carbon monoxide to carbon dioxide with simultaneous formation of hydrogen.

Consider the active catalyst usually has a spinel structure of magnetite Fe3O4i.e. Fe(II)O.Fe(III)2O3c ordinary shares, for example 5-15 wt.%, iron, replaced by trivalent metal modifier, such as chromium or manganese. Typically, the catalysts are supplied in the form of granules predecessor, corresponding to the structure of the substituted hematite Fe2O3are regenerated in situ using a process gas. It was found that after recovering the strength of these granules of the catalyst is often insufficient, which leads to the destruction of the granules of the catalyst with the formation of very small particles that cause unacceptable pressure drop when passing through the layer of process gas. For example, if the normal granule precursor has a mean resistance of horizontal rasdall is of about 20 kg, the strength of these pellets after reduction in the active state can be reduced to less than 4 kg, it Was found that, if the recovered catalyst pellet to destroy and re-pelletized, it cannot be retrieved durable products with high activity.

Currently developed a method of producing a catalyst which does not require such a recovery process.

According to this invention, a method for obtaining a molded catalytic converters suitable for high-temperature reaction conversion, involving the deposition of a composition containing divalent and trivalent iron and trivalent metal modifier selected from chromium and manganese from aqueous solution containing iron salts and metal modifier, base and molding the obtained precipitate formed in the catalytic blocks without affecting the specified residue oxidizing atmosphere at temperatures above 200°C.

Although it is known to direct the deposition of magnetite with the use of reason, for example, from solutions of salts of mixed-valence (see Clarke and others, Langmuir,1991, 7, 672) and is known to direct the deposition of magnetite containing trace amounts (<1%) Co, Ni, Zn, Cu, Mn and Cd, by oxidation of iron in the ferric sulfate solution basic potassium nitrate (see P. S. Sidhu and others,J. Inorg. Nucl. Chem.,1978, 40, 429),these documents do not describe a method of obtaining a molded blocks Catholic, containing divalent and trivalent iron and trivalent metal modifier selected from chromium and manganese, suitable for high temperature reactions of transformation.

The proportion used in this invention, salts of chromium and/or manganese is preferably such that the atomic ratio of iron to chromium and/or manganese) is in the range from 5:1 to 20:1, in particular in the range from 7:1 to 15:1. Chromium is preferable manganese. Most preferably, chromium is present in amounts in the range of 5-15 wt.%. I believe that chromium at these levels successfully promotes physical strength of the obtained molded blocks.

The water-soluble salts of iron, chromium and/or manganese can be used as sources of metals. In the first variant embodiment were used salts of divalent and trivalent iron, and salts of trivalent chromium and/or manganese, in particular, in such proportions that the atom of ferrous iron had from 1.5 to 2.5, in particular, about 2 atoms of trivalent metal. In the second variant embodiment were used only ferrous iron salt and a salt of trivalent chromium and/or manganese, ferrous iron was partially oxidized using an oxidant, for example, metal nitrate, so that part is, for example, from half to TLD is-thirds of ferrous iron was converted into trivalent iron. Preferably, two-thirds of ferrous iron oxidizes to ferric iron. In the third variant embodiment using metal salts in the trivalent state and apply the reducing agent in a quantity sufficient to obtain the desired proportions of compounds of divalent and trivalent iron. The reducing agent may be essential, for example, hydrazine, or staple, for example, formaldehyde. In any of the variants of the preferred embodiment of the salts of iron and chromium and/or manganese are the chlorides or sulfates.

In each case, for the deposition of a composition containing divalent and trivalent iron and trivalent metal modifier, use the base. The deposition can be achieved by adding a base to the solution of iron salts and metal modifier or the addition of iron salts and metal modifier, preferably in aqueous solution, to the aqueous solution of the base. The base is a hydroxide or carbonate of an alkali metal, especially sodium or potassium. Alternatively can be used hydroxide or ammonium carbonate. Preferably the base is an aqueous solution to improve the homogeneity of the deposited composition.

If there are only ferrous iron salt may be used oxidant metal nitrate in a quantity up is sufficient for the oxidation half to two thirds of ferrous iron to ferric iron and thus achieve the optimal ratio of Fe 2+and Fe3+for the formation of magnetite. Preferred such nitrates of alkali metals such as sodium nitrate or potassium. The nitrate of the alkaline metal is preferably in the form of aqueous solution can be connected with a water solution of iron salts and metal modifier before or simultaneously with the Foundation. Preferably the oxidizing agent and the base are added simultaneously, for example, may be used an aqueous solution containing a base and a metal nitrate, to allow for the simultaneous oxidation and deposition of the composition.

The deposition is preferably carried out at a temperature in the range from 30°C to about 100°With (i.e. boiling point), in particular from 40°C to about 100°and at pH in the range of 3.5-9 depending on the way of producing magnetite. For example, if you use salts of iron mixed-valence, the temperature preferably is in the range of 30-80°and a pH in the range of 6-9. Alternatively, if you used the path provides (partial) alkaline oxidation of ferrous iron salts in the presence of nitrate, the preferred temperature is from 60 to 100°and a pH in the range of 3.5-5.

Depending on the starting materials and conditions the compounds of iron and chromium is usually precipitated as oxides, hydroxides or basic carbonates. The preferred route is the way to go with echannel valence, using the appropriate amount of salts of Fe(II) and Fe(III) or alkaline (partially) oxidized salt of Fe(II) for the direct generation of the active oxide magnetic materials.

The precipitate is usually filtered from the mother liquor, washed with, for example, deionized water and acetone and dried. Washing can be carried out using heated water and/or may be performed several washings to reduce to acceptable levels the content in the composition of chloride and sulfate. The air drying is carried out at a temperature below 200°With, in particular, at a temperature in the range of 80-100°to prevent oxidation of magnetite to maghemite or hematite. If precipitated oxidized materials, it is usually not necessary in calcining the dried precipitate, but if accepted, the calcination at temperatures above 200°must be held in the air and in an inert non-oxidizing atmosphere.

One of the advantages of the method of the invention, where use chrome, is that it is possible to avoid the use and/or formation of compounds hexavalent chromium and thus to minimize health risks.

After drying, the precipitate formed into a desired shape of the catalyst, for example, cylindrical granules or tablets, usually using 1-3 wt.% lubricants, such as graphite as an auxiliary is about tabletiruemogo funds. Alternatively, this may be done granulation method, in which the dried precipitate is mixed with a small amount of liquid and the resulting moist mixture granularit or tabletirujut using a granulator. As an alternative, as raw material for pellet mill can be used not precipitate. Alternative sludge can be mixed with a suitable binder, for example, callionymidae cement or clay and a small amount of water and extruded to form extrudates of a suitable size. Preferably the formed catalytic units are the maximum and minimum sizes from 2 to 25 mm and preferably the ratio of the length to the diameter, i.e. the variation of the maximum size and minimum size of less than 2.

In yet another variant embodiment in the formed catalytic units injected copper compounds. This can be done by coprecipitation of copper compounds with compounds of iron and chromium by incorporating a suitable copper salt in the solution of metals. Alternatively, before or after the drying and before the subsequent formation of the precipitate can be impregnated with a solution of a suitable copper compounds. Preferably the number of copper is from 0.5 to 3 wt.% the final catalyst. Copper acts positively on the work of the catalyst in the reaction p is euromania, in particular, at lower operating temperatures.

Characteristics of the formed catalytic converters can be further improved if they are in addition to the precipitated composition containing divalent and trivalent iron, trivalent metal modifier and copper compounds (if present)contain from 2 to 40 wt.% particles having the ratio of length to diameter of at least 2 and an average (by weight) maximum size in the range from 500 to 1500 nm, selected from aluminum oxide, monohydrate alumina, zinc oxide, iron oxide and oxyhydroxide iron. These needle-like particles provide improved physical properties, such as resistance to crushing, thus reducing the probability of formation of dust particles. Methods of introduction of the needle-shaped particles in the catalytic units are disclosed in particular in patent US 5656566, 12.08.1997 (examples 2-9).

The invention is illustrated in the following examples.

Example 1: obtaining catalytic converters

(a) the path of the mixed-valence: the dichloride tetrahydrate iron(II) (49,7 g) was dissolved in deionized water to obtain 250 ml of solution. Similarly, the uranyl trichloride iron(III) (135,15 g) was dissolved in deionized water to obtain 500 ml of solution. The two solutions were combined and added chloride dihydrate, copper(II) (2.5 g) and gexa the dratha of trichloride chromium(III) (19,07 g). The solution is then heated to 78°to ensure complete dissolution of the salt before adding to the mixed solution of aqueous 1 M sodium hydroxide solution (2600 ml, 104 g of NaOH) over a period of 15 minutes. The solution is then left to cool for approximately 2 hours to room temperature. The resulting suspension was filtered and the solids three times washed with deionized water and twice with acetone before drying in an oven at 50°C for 6 hours, receiving a modified Cr magnetite in the form of powdered black crystalline solid. When using the usual method of washing, as described above, the level of residual Cl was determined approximately 1000 nm Applying a more thorough washing procedure, where the substance was re-suspended in hot (50-80° (C) demineralized water, the levels of residual Cl could significantly fall to about 200 nm Lower levels of residual Cl allows you to extend the use of the catalyst under normal operating conditions.

(b) oxidation: heptahydrate ferrous sulfate (200 g), pentahydrate of copper sulfate(II) (1,11 g) and monohydrate sulfate chromium(III) (24,48 g) was dissolved successively in 1400 ml of deionized water, freed from oxygen by flushing with nitrogen. The solution was heated to 72°and was added dropwise potassium nitrate (20,19 g) and potassium hydroxide (140,27 g), dissolve the built in 750 ml of deionized water, over a period of approximately one hour. After boiling the suspension was continuously barbotirovany nitrogen. The suspension is then boiled under reflux for another 30 minutes and then left to cool to room temperature for the next 90 minutes. The obtained gray-black precipitate three times washed with deionized water until essentially complete release from sulfate, followed by double rinsing with acetone before drying in an oven at 50°C for 6 hours. Alternation above the washing procedure, for example, where the substance is re-suspended in hot (50-80° (C) demineralized water, the residual SO4the catalyst can be significantly reduced (typically a value of about 3000 nm to 600 nm). Reducing residual SO4the catalyst reduces the duration of the initial phase of desulphurization during the process, while improving the efficiency of the process.

(C) Obtaining catalytic converters: molded catalytic units was obtained by mixing modified magnetite samples obtained in examples 1A-1b, 2 wt.% graphite, pre-compacting the material to a density of approximately 1.5-1.6 g/cm3, grinding and sieving the pre-pressed material for producing feed pellets with a particle size between 300 and 850 microns and the formation of g is anal size of 3.6 mm ( ± 0.2 mm) × 5.4 mm in diameter. Each pellet weighed approximately 1.8 grams and had a density of approximately 2.1 to 2.4 g/cm3.

The measurement of average horizontal resistance to crushing (MHCS) were performed on 5 pellets obtained from each of magnetite material using CTS 0,5-ton equipment, calibrated to the load 50 kg For comparison was grained commercially available powder hematite catalyst, modified chromium/copper (comparative 1)using the above method. Pellets of hematite were subjected to stage a recovery in the stream of hydrogen containing gas for the conversion of hematite to magnetite and tested for crushing the same way that the granules of magnetite. The results are shown in table 1.

Table 1
Catalytic units
ExampleMHCS (kg)
Comparative 15,67
1A2,83
1b6,11

The results show that the modified chromium/copper magnetite from the path "oxidation" MHCS provides superior compared to the pre-restored modified chromium/copper hematite material.

Example 2: test kata is eticheskikh blocks

Catalytic units, obtained according to example 1 and comparative catalytic units on the basis of hematite were tested for activity in a laboratory scale high-temperature reaction conversion (HTS). Process gas (containing 14%, 6.5% OF CO2, 55% N2and 24.5% N2+ minor amount of impurities, including methane) and water was supplied to the evaporator at 300°S, which is fed with a mixture of gases electronegativity 1-metre tubular reactor with a nominal internal diameter of 25 mm Reactor working under pressure 27 bar, had a catalyst bed volume of 200 ml 8 ml granules of the catalyst is brought to the required 200 ml mixing with melted flake aluminum oxide. The gas product stream leaving the reactor was applied to the capacitor and then catching the tank from which the samples could be extracted for analysis.

To evaluate the activity of the resulting catalyst mixture of 2 volumes of the above-mentioned process gas and one volume of water vapor was passed through the sample of the catalyst supporting (temperature) 365°and analyzed the escaping gas. The total flow rate was varied between 500 and 2000 l/h.

The main criterion for the activity of the catalyst is % conversion of carbon monoxide. Thus, the % conversion of carbon monoxide correlated sobsey speed gas flow, to determine the flow rate for each catalyst, which provided a 15 %conversion of CO (whenever 365°). As the flow rate associated with the time of contact between the reacting gases and the catalyst, these data are relative criterion observed activity, a higher flow rate shows superior catalytic activity. Were tested pellets from example 1(b), comparative example 1 and the second comparative catalyst consisting of commercially available pellets of catalyst based on hematite (comparative 2). Hematite catalysts (comparative 1 comparative 2) before the test were subjected to a stage of recovery, including exposure to the process gas at 1250 l/h, when the ratio of the volume of steam:gas 1:1 and the temperature change as follows:

(i) the temperature of an inclined reactor (Ramp reactor) 250°With up to 440°C for 16 hours;

(ii) the temperature of the supported reactor (Maintain reactor) at 440°C for 4 hours.

The results are shown in table 2.

Table 2
The activity of the catalytic unit and a residual resistance to crushing
ExampleThe flow rate to 15%is reversine WITH (l/h) MHCS (kg)
Comparative 112671,22
Comparative 29432,31
1b11942,74

These results show that the path of "oxidation" magnetite material gives superior MHCS compared to hematite materials testing HTS. The flow rate for equivalent conversion for catalyst path "oxidation" was almost as good as for granulated in a laboratory hematite material (but with more than double MHCS) and superior in comparison with commercially available granular catalyst based on hematite.

In addition, the catalytic units of the present invention do not undergo significant volume changes (e.g., shrinkage)due to the stage of recovery required for catalysts on the basis of hematite. Stable volumes of catalyst provide some benefits, such as better tab, lower pressure drop, and potentially higher loading of the active catalyst in this vessel.

1. A method of obtaining a molded catalytic converters for high temperature reaction conversion, involving the deposition of a composition containing divalent and trivalent iron and trivalent chromium from water, R is the target, containing salts of divalent iron and trivalent chromium, base and ferrous iron is partially oxidized using an oxidant, which converts some of the ferrous iron to ferric iron, and molding the resulting sludge formed in the catalytic blocks without affecting the specified residue oxidizing atmosphere at a temperature above 200°C.

2. The method according to claim 1, where the oxidizing agent are added simultaneously to the base.

3. The method according to claim 1 or 2, where the oxidizer is a nitrate of an alkali metal in an amount sufficient to convert from half to two thirds of ferrous iron to ferric iron.

4. The method according to claim 1 or 2, where the deposition is carried out at temperatures in the range between 60°and 100°C.

5. The method according to claim 1 or 2, where the formed catalytic unit is a beads, granules, tablet or extrudate.

6. The method according to claim 1 or 2, where the formed catalytic unit contains divalent copper.

7. The method according to claim 1 or 2, where the formed catalytic blocks contain acicular particles having a length to diameter of at least 2 and an average (by weight) maximum size in the range from 500 to 1500 nm, selected from aluminum oxide, monohydrate alumina, zinc oxide, iron oxide and oxyhydroxide iron in an amount of from 2 to 40 wt. from the molded blocks.

8. The method according to claim 1, where in aqueous solution provides a number of salts of iron and chromium, sufficient to besieged composition had an atomic ratio of iron to chromium in the range from 5:1 to 20:1.

9. The method according to claim 1, where in an aqueous solution to provide a salt of chromium, is sufficient for the specified chromium was present in the specified precipitated compositions in amounts in the range from 5 to 15 wt.%.

10. Method of high-temperature conversion, involving passing a mixture of carbon monoxide and water vapor at a temperature of from 350°550°With over a layer formed catalytic converters, obtained according to the method according to any one of claims 1 to 9.



 

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5 cl, 1 tbl, 6 ex

FIELD: chemical industry; methods of manufacture of the composites, catalytic agents, the materials for the gases storing.

SUBSTANCE: the invention is pertaining to the method of the selective manufacture of the ordered carbonic nanotubes in the boiling layer and may be used at the composites, catalytic agents, the materials for the gases storing. First manufacture the catalytic agent by deposition of the transition metal particles on the grains of the carrier in the "boiling bed" in the deposition reactor at the temperature of 200-300°C. The particles of the metal have the average size of 1-10 nanometers metered after the action of the temperature of 750°C. The grains of the catalytic agent contain 1-5 % of the mass particles of the metal. Fragments of metal also have the average size of 10-1000 μ. The carrier has the specific surface above 10 m2/g and is selected from the activated charcoal, silica, silicate, magnesium oxide or titanium oxide, zirconium oxide, zeolite oxide or the mixture of the grains of several of these materials. The ordered carbonic nanotubes are manufactured by decomposition of the gaseous source of carbon, for example, hydrocarbon, at its contact with at least of one solid catalytic agent. The decomposition is conducted in the "boiling" bed of the catalytic agent in the growth reactor at the temperature of 600-800°C. The invention allows to increase the output of the pure nanotubes with in advance calculated sizes.

EFFECT: the invention allows to increase the output of the pure nanotubes with in advance calculated sizes.

31 cl, 5 dwg, 3 tbl, 15 ex

FIELD: petrochemical process catalyst.

SUBSTANCE: invention, in particular, relates to precursors of catalysts used in production of hydrocarbons from synthesis gas. Preparation of catalyst precursor involves contacting crude catalyst carrier, which is partly soluble in aqueous acid solution and/or in neutral aqueous solution, with modifying component of general formula Me(OR)x, wherein Me is selected from Si, Zr, Ti, Cu, Zn, Mn, Ba, Co, Ni, Na, K, Ca, Sn, Cr, Fe, Li, Ti, Mg, Sr, Ga, Sb, V, Hf, Th, Ce, Ge, U, Nb, Ta, and W; R represents alkyl or alkoxy group; and x is integer from 1 to 5. Therefore, modifying component is introduced into catalyst carrier or deposited onto surface thereof to form protected modified catalyst carrier, which is less soluble and more inert in aqueous acid solution and/or in neutral aqueous solution than crude carrier. Resulting catalyst carrier is then subjected to heat treatment at temperature lower than 100° C so that calcination of the carrier does not take place. Non-calcined protected modified catalyst carrier is mixed with aqueous solution of cobalt, which is active component of catalyst or its precursor, to form slurry. Which is exposed to subatmospheric pressure to facilitate impregnation of the catalyst carrier with cobalt or its precursor. Impregnated carrier is then dried at subatmospheric pressure and finally calcined.

EFFECT: enhanced selectivity and activity of catalyst in Fischer-Tropsch synthesis and eliminated need to perform calcination step after contact of crude Carrier with modifying component and drying.

16 cl, 5 dwg, 1 tbl, 6 ex

FIELD: catalyst production, in particular Fischer-Tropsch synthesis of C5-C10-hydrocarbons from CO and H2.

SUBSTANCE: claimed method includes two-stage impregnation of zeolite carrier with cobalt nitrate aqueous solution with intermediate annealing in air flow at 350-450°C and drying.

EFFECT: catalyst of increased selectivity and activity in respect of isoparafinic hydrocarbons.

2 tbl, 9 ex

FIELD: preparation of cerium-containing catalysts modified by palladium on granulated and monolithic carriers.

SUBSTANCE: proposed method of preparation of Pd-CeO2 applied catalysts is performed by self-spreading thermosynthesis in layer of high surface granulated or block carrier from precursors, for example cerium-ammonium nitrate or mixture of cerium nitrate with fuel additives; palladium is introduced into catalyst in form of palladium nitrate by application on cerium-treated carrier or by joint application of cerium and palladium precursors followed by self-spreading thermosynthesis. Used as carriers are granulated carriers, ceramic blocks or blocks with high specific surface of Al2O3.

EFFECT: enhanced rapidness of catalyst preparation process.

2 cl, 1 tbl, 8 ex

FIELD: alternate fuel production.

SUBSTANCE: invention relates to synthesis of hydrocarbons from CO and H2, in particular to catalysts and methods for preparation thereof in order to carrying out synthesis of hydrocarbons C5 and higher according to Fischer-Tropsch reaction. Method resides in that non-calcined zeolite ZSM-12 in tetraethylammonium-sodium form is subjected to decationation at pH 5-9, after which decationized zeolite (30-70 wt %) is mixed with alumina binder while simultaneously adding cobalt (7.5-11.5 wt %) as active component and modifier, in particular boron oxide (3-5 wt %). Proposed method allows catalyst preparation time to be significantly reduced owing to combining support preparation and deposition of active component and modifier in one stage with required catalytic characteristics preserved. In addition, method is environmentally safe because of lack of waste waters, which are commonly present when active components are deposited using impregnation, coprecipitation, and ion exchange techniques.

EFFECT: reduced catalyst preparation time and improved environmental condition.

1 tbl, 10 ex

FIELD: petrochemical processes.

SUBSTANCE: catalyst, containing high-silica zeolite of the H-ZSM-5 type having silica modulus SiO2/Al2O3 = 20 to 160 in amount 60.0-90.0%, contains (i) as modifying component at least one oxide of element selected from group: boron, phosphorus, magnesium, calcium, or combination thereof in amount 0.1-10.0 wt %; and (ii) binding agent: alumina. Catalyst is formed in the course of mechanochemical and high-temperature treatments. Described is also a catalyst preparation process comprising impregnation of decationized high-silica zeolite with compounds of modifying elements, dry mixing with binder (aluminum compound), followed by mechanochemical treatment of catalyst paste, shaping, drying, and h-temperature calcination. Conversion of methanol into olefin hydrocarbons is carried out in presence of above-defined catalyst at 300-550°C, methanol supply space velocity 1.0-5.0 h-1, and pressure 0.1-1.5 mPa.

EFFECT: increased yield of olefin hydrocarbons.

3 cl, 1 tbl, 15 ex

FIELD: petroleum processing and catalysts.

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

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

21 cl, 4 tbl, 14 cl

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