FIELD: disproportionation reaction catalysts.
SUBSTANCE: invention relates to Fischer-Tropsch catalyst containing cobalt and zinc, to a method for preparation thereof, and to Fischer-Tropsch process. Catalyst according to invention containing co-precipitated cobalt and zinc particles, which are characterized by volume-average size below 150 μm and particle size distribution wherein at least 90% of the catalyst particle volume is occupied by particles having size between 0.4 and 2.5 times that of the average particle size and wherein zinc/cobalt atomic ratio within a range of 40 to 0.1. Catalyst is prepared by introducing acid solution containing zinc and cobalt ions at summary concentration 0.1 to 5 mole/L and alkali solution to reactor containing aqueous medium wherein acid solution and alkali solution come into contact with each other in aqueous medium at pH 4-9 (deviating by at most 0.2 pH units) at stirring with a speed determined by supplied power between 1 and 300 kW/L aqueous medium and temperature from 15 to 75°C. Resulting cobalt and zinc-including precipitate separated from aqueous medium, dried, and further treated to produce desired catalyst. Employment of catalyst in Fischer-Tropsch process is likewise described.
EFFECT: enhanced strength and separation properties suitable for Fischer-Tropsch process.
13 cl, 2 dwg, 1 tbl, 5 ex
The invention concerns a catalyst for Fischer-Tropsch containing cobalt and zinc, and a method of producing such a catalyst.
Containing cobalt oxide and zinc oxide catalyst used in the synthesis of C1-C3 aliphatic hydrocarbons, known from US-A-4,039,302.
USP 4,826,800 describes a method of obtaining containing cobalt and zinc oxide catalyst used, after reductive activation as a catalyst for the conversion of synthesis gas to hydrocarbons. The catalyst was prepared by mixing a solution of a soluble zinc salt and a soluble salt of cobalt with a precipitant such as ammonium hydroxide or ammonium carbonate, and recovering the precipitate. The ratio of carbonate and metal in a specified way high, that, as has been detrimental effect on the durability of the catalyst.
USP 5,345,005 concerns the Cu-Zn catalyst is aluminum oxide, which is used to obtain alcohols by hydrogenation, for example, ketone. In the example of the comparison described receiving Cu-Zn-Co-catalyst on aluminum oxide, where the receiving is performed with the use of soda ash. However, it was found that the use of soda ash potentially harm the durability of the catalyst. The area of distribution of particle size, within which lies 90% of the volume of Cu-Zn-Co-catalyst described in USP 5.345.005, not specified But it is assumed that the use of soda ash to obtain a catalyst leads to the expansion of the distribution of particle sizes.
US-A-5,945,458 and US-A-5,811,365 describe how the Fischer-Tropsch carried out in the presence of a catalytic composition consisting of a metal of group VIII, for example,cobalt deposited on the basis of zinc oxide. This catalyst was prepared first by making basis by adding a solution of zinc salts and other components to a solution of bicarbonate of an alkali metal. Then the precipitate is separated from the solution of bicarbonate by filtration, obtaining a dense precipitate on the filter, which is subsequently dried, calicivirus and specified sediment cause the metal of group VIII. The catalytic material is then formed into tablets, the tablets are crushed, receiving a particle size of 250-500 μm, which can be used in the method of Fischer-Tropsch. Additional subsequent processing, such as crushing, needed to obtain a powder catalyst with good strength characteristics. However, as indicated above, the average particle size is still relatively high. In addition, fragmentation leads to a wide distribution of particle sizes, and catalysts with such a large particle size and a wide distribution of particle sizes become less suitable for the method, provide iwaisako using bubble columns, reactor slurry phase or loop reactor.
WO-A-01/38269 describes a three-phase system for implementing the method of Fischer-Tropsch, where the suspension of catalyst in a liquid medium is mixed with the gaseous reagents in the zone of mixing at high shear force, after which the mixture is discharged into the zone of subsequent mixing. It is noted that thus increases massoperedacha. As suitable catalysts, among others, the above mentioned catalysts comprising cobalt on inorganic medium such as zinc oxide. The surface area of the carrier used for the receipt of such known catalysts is less than 100 g/m2. These are known from the prior art catalysts based on cobalt can be obtained by depositing cobalt on a suitable base, such as zinc oxide, using the technique of impregnation. Other common methods include obtaining ways deposition, usually involving the crushing of solid catalyst obtained by the catalytic method in the form of a thick sludge on the filter for small particles.
However, it was found that when used in the catalytic method such conventional catalysts do not always satisfy the requirements with respect to mass transfer and/or heat transfer.
In addition, Nai is prohibited, the ability to dispersion of such well - known catalysts for use in the method using a slurry phase is not good enough, because the catalyst particles have a tendency to form agglomerates.
Other problems associated with industrial applicable media based on zinc oxide, suitable for application of cobalt with the purpose of preparation of the catalyst, are: improper distribution of particles (in particular, in the case of carriers obtained by deposition), low surface area, typically complicate the treatment of these carriers, which causes the need to carry out several stages of impregnation to obtain a sufficient number of loading of cobalt on the media, and the low level of homogeneity of the distribution of cobalt after application of cobalt.
The present invention consists in obtaining a suitable for use in the Fischer-Tropsch synthesis of new catalysts that can be used as an alternative to known catalysts.
It was found that some catalysts comprising cobalt and zinc oxide, with a specific particle size and a specific distribution of particle sizes, have very favorable characteristics for use as catalysts for Fischer is-Tropsch.
Thus, the present invention concerns a catalyst comprising precipitated together particles of cobalt and zinc, having a volumetric average particle size less than 150 microns and a distribution of particle sizes in which at least 90% of the volume of catalyst particles has a size in the range 0.4 to 2.5-fold compared to the average size of the particles.
Used here, the volumetric average particle size and distribution of particle sizes using laser equipment for diffraction analysis, using the apparatus for classifying particles Malvern Master MS 20 (takes 3 minutes before measuring the distribution of particle sizes ultrasonic treatment 25% (maximum power); settlement model: model independent; display: 1907; see also the examples).
It was found that the catalyst according to the present invention has a very favorable characteristics for use in catalytic ways. Found that the catalyst according to the present invention has, in particular, good mass and/or heat transfer when used in catalytic methods.
It was found that the catalyst according to the present invention is particularly suitable for use in the reactor with a mixed suspension phase, the reactor bubble column loop reactor Il is the reactor with a fluidized bed.
The catalyst according to the present invention shows very good characteristics of fluidity in the dry form and/or when used in a reactor with a mixed suspension, and good dispersibility in the presence of the reagents of the reaction mixture. The catalyst according to the invention is very suitable distribution of particle sizes, which indicate a high fluidity of the dry catalyst was observed, for example, during curing catalyst in containers for storage.
The catalyst according to the invention has a very favorable characteristics for separation, and may be, for example, is very conveniently separated from the reaction mixture by filtration.
The catalyst according to the invention is extremely convenient ratio of activity and separation properties.
The catalysts according to the invention can be, in particular, obtained by joint precipitation of solutions containing Co - and Zn precursor. Joint precipitation (solids) can be subjected to subsequent processing and, finally, restored, resulting catalyst containing Co deposited on the zinc oxide. Very successful examples of co-deposition include joint precipitation containing oxide Co/Zn and carbonate Co/Zn, co precipitation containing hydroxide Co/Zn and hydroxycarbonate Co/Zn, and combinations thereof.
Preferably,the volumetric average particle size of the catalyst was less than 100 μm, more preferably, less than 50 microns. The lower limit is not particularly important. For practical purposes, it is preferable that the size was at least such that the particles can be separated from the liquid reaction mixture. Particularly useful, for example, a catalyst with an average particle size of 2 μm or more. Very good results can be achieved with a catalyst having a volumetric average particle size in the range of 5-50 microns.
With regard to the distribution of particle sizes, it is preferable that the number of particles with size less than 0.4-fold with respect to the average particle size was significantly smaller (for example, at least 5 times lower)than the number of particles with a size of more than 2.5-fold compared to the average size of the particles. More preferably, essentially no catalyst particles with a particle size of less than 0.4-fold with respect to the average particle size.
Very good results were obtained with a catalyst having a distribution of particle sizes in which at least 90% of the volume of catalyst particles has a size in the range from 0.5 to 2.2-fold compared to the average size of the particles, more preferably in the range from 0.6 to 2-fold compared to the average size of the particles.
Preferably the porosity of the catalyst is determined by adsorption of nitrogen (N2 -BET), measured on the apparatus Ankersmit Quantachrome Autosorb-6 after degassing the sample at 180°C to a pressure of 3.3 PA (25 mtorr) - at least, mostly created by pores having a diameter in the range 5-100 nm. Much preferable, when essentially no pores with a diameter less than 5 nm (in particular, less than 5% porosity is created by pores having a diameter of less than 5 nm). It was found that this catalyst has a particularly good ability to diffusion with respect to the reactant and product. Also found that this catalyst is highly selective in the reactions of Fischer-Tropsch.
Very good results were achieved with a catalyst having a porosity of less than 0.5 ml/g, Preferably, the porosity is equal to at least 0.05 ml/g, In particular, a convenient catalyst with porosity less than 0.45 ml/g
It was found that this catalyst is particularly good physical strength characteristics that are advantageous when using the catalyst in reactors of various types, including reactors with the suspension phase, loop reactors, the reactor bubble column and fluidized bed reactor.
Also the surface area, measured on the apparatus Ankersmit Quantachrome Autosorb-6 after degassing the sample at 180°C to a pressure of 3.3 PA (25 mtorr), can be selected within wide limits, dependent in the ti from the set goal. For the method of Fischer-Tropsch this parameter can be, for example, selected within 1-120 m2/, it is Preferable that the catalyst had a surface area in the range 5-100 m2/, Very good results were obtained with the catalyst having a surface area in the range 5-80 m2/year
The preferred catalyst according to the invention is a pulverulent material, where the particles are more or less spherical in shape. It was found that this catalyst has very good strength and separation characteristics and has a relatively high resistance to abrasion during use.
Very convenient is the catalyst having a more or less spherical shape, where at least the majority of the particles has mnogozhalcata spherical geometry. Example particles with megadeltas spherical geometry presented in figure 1. Particularly good results, for example,against heat transfer and/or mass transfer obtained with the catalyst, where at least the majority of the particles is mnogotochechnymi particles with surface area, which, at least, of 1.05-fold, preferably at least a 1.1-fold, more preferably at least 1.2-fold surface area of the so-called equivalent circle. The term "equivalent circle", as ispolzovanie, means circle with the largest circumference, which precisely fits the contour of a particle obtained by projecting particles (for example,by obtaining images using the microscope) on a plane with orientation in order to provide the maximum possible outer surface area within sight (see also figure 2, which represents the equivalent range for the particles shown in figure 1).
The composition of the catalyst can be widely varied by a qualified specialist is well known how to choose the composition depending on the task.
Preferably, the atomic ratio of zinc and cobalt were in the range from 40 to 0.1, more preferably in the range from 20 to 0.3.
The catalyst may essentially be composed of cobalt and zinc oxide. However, it is also possible that the catalyst contains one or more other components, such as components used in the catalysts of the Fischer-Tropsch process. For example, the catalyst may contain one or more promoters, such as ruthenium, hafnium, platinum, zirconium, palladium, rhenium, cerium, lanthanum, or combinations thereof. If present, such promoters are commonly used in the atomic ratio of cobalt and promoter to 10:1.
It was found that the catalyst according to the invention, comprising at least one element of group IIIa, pre is respectfully, at a concentration of 0.1-10 wt.% calculated on the total weight of the catalyst, has a very excellent structural stability. Preferred elements of the IIIa group include aluminum (Al), GA (Ga) and boron (B), from which aluminum is particularly preferred.
Very good results were obtained with the catalyst according to the invention essentially does not contain sodium. Found that a catalyst containing a relatively high amount of sodium, loses strength. In addition, it was found that the presence of sodium has a deleterious effect on the catalyst, reducing the activity of the specified catalyst in the method of Fischer-Tropsch. Therefore, the preferred catalyst with a sodium content less than 0.5 wt.%,in particular, from 0 to 0.15 wt.%, more preferably, from 0 to 0.1 wt.% based on the weight of the catalyst.
Very good results were obtained with the catalyst according to the invention, having a low content of copper or essentially not containing copper. Copper can promote side reactions such as the formation of alcohol in the hydrogenation of a ketone, aldehyde or carboxylic acid, which is usually desirable to avoid or want to suppress, especially in the way the Fischer-Tropsch process. The copper content is preferably less than 2 wt.%, more preferably, from 0 to 0.5 wt.%, more preferably, from 0 to 0.2 wt.%in the calculations of the e on the weight of the catalyst.
The present invention also relates to a method of obtaining a catalyst comprising cobalt and zinc oxide by co-deposition of cobalt ions and zinc, through which acid solution containing zinc ions and cobalt ions and the alkaline solution fed into the reactor containing the aqueous medium, preferably water or an aqueous solution, where the acid solution and alkaline solution are contacted in an aqueous medium and a precipitate comprising cobalt and zinc. The precipitate is then separated from the aqueous medium (which may form a suspension with sediment). The separated precipitate comprising cobalt and zinc, then dried and possibly using subsequent processing, for example, calcining, receive the specified catalyst.
Preferably the combination of the acidic solution and alkaline solution are chosen so that the components of the acidic solution and alkaline solution were soluble in water, but that cobalt and zinc to precipitate upon contact with an alkaline solution, whereas the counterions zinc and cobalt essentially remained in solution. Qualified know how to choose appropriate conditions, such as type and concentration of counterions each component.
Found that this method is particularly convenient for the above catalyst.
Found that the way out is retenu enables direct production, immediately after drying, fine sediment, which behaves like a free flowing the catalyst precursor, i.e. allows to obtain a residue, which it is not necessary to crush or otherwise mechanically processed in order to obtain pulverized material.
Also, the method according to the invention allows to obtain particles with more or less spherical, not necessarily many-lobed geometry.
Preferably, the deposition of particles perform essentially at constant pH, in particular at pH values deviating at most at ±0,2 pH units from the specified value. Thus the possibility of obtaining a catalytic precursor with excellent features free fluidity.
Preferably, the alkaline solution and acid solution to feeding into the reactor at the same time (from a separate pipelines).
Optional, cobalt is isolated and dried sludge or whether the product is reduced to cobalt metal.
Suitable sources of zinc ions, respectively, of cobalt ions include the salts of these metals, soluble in acid solution and water in sufficient concentration. Preferred examples of such salts include zinc nitrate, respectively, cobalt nitrate, and zinc acetate, respectively, cobalt acetate, and other neo is organic or organic salts of cobalt, accordingly, zinc, with similar solubility in the acid solution.
Suitable components for coprecipitation with the audience cobalt ions and zinc ions are inorganic salts and organic salts, are soluble in aqueous alkaline solution in sufficient concentration, such as hydroxides, carbonates, urea, isocyanate, and other salts that may be used as the source of the base and which can be dissolved by water and alkaline solution. Preferred examples of such salts include ammonium carbonate, ammonium bicarbonate and other inorganic or organic salt having at least a similar solubility in an alkaline solution.
Preferably the total concentration of cobalt ions and zinc ions in the aqueous medium is chosen in the range from 0.1 to 5 moles/liter. The concentration is preferably maintained within the specified limits during all stages of deposition.
the pH of the acidic solution is preferably in the range of 1-5; the pH of the alkaline solution is preferably in the range 6-14; pH of the water environment (where there is a joint deposition) is preferably in the range 4-9, depending on the preceding salts used as the source of cobalt, zinc and the alkaline component (components).
The frequency mixing select the corresponding the way, to obtain the input power in the range 1-300 kW/l aquatic environment. Very good results are achieved when the input power is within 10-100 kW/l aquatic environment.
Preferably the temperature during the process of co-precipitation to choose within 5-98°C, more preferably in the range of 15-75°C.
The present invention also relates to the use of the catalyst according to the invention in a suspension reactor, loop reactor, the reactor bubble column or reactor with a fluidized bed. The present invention also relates to the use of the catalyst according to the invention in the method of Fischer-Tropsch or the way hydrogenation of functional groups, such as the hydrogenation of NITRILES to amines.
Further, the invention is illustrated by the following examples.
EXAMPLE 1. Obtaining catalyst
The solution of the metal (1000 ml)containing 10.0 g/l of cobalt and 72.3 g/l zinc, obtained by dissolution of 329 g of Zn(NO3)2.9H2O, 49.4 g of Co(NO3)2.6H2O in 1000 ml of demineralized water. The solution obtained by dissolution of the base 154 g (NH4)2CO3in 1000 ml of demineralized water. The solution of the metal and substrate are injected simultaneously at equal flow rates (1000 ml/hour) mix well in a precipitation vessel to regulate the direction of flow dividers containing 1750 ml on the saline water. The temperature during the deposition of the support 60°C. power Input (N), equal to 0.5 watts per litre; is calculated applying the following formula:
whereN - input power turbine stirrer (watts);
k - factor of 6 for turbine stirrers;
p is the density of the mixed fluid (kg/m3);
n is the rotation speed stirring (with-1);
d - diameter of the mixer (m);
V is the volume of the precipitation vessel (3.5 liters).
The pH maintain a constant at pH 5.8, feeding the acidic solution and the alkaline solution with equal velocities add.
The precipitate is washed with demineralized water and dried over night at 110°C. the Dried catalyst was heated from room temperature at 150°C/h to 500°C and calicivirus for 5 hours at 500°C. the characteristics of the calcined catalyst shown in the table.
EXAMPLE 2 (comparison) (for example, described in USP 4,826,800)
The solution of the metal containing 20,0 g/l Co and 64,3 g/l Zn is obtained by dissolution of 292 g of Zn(NO3)2.6H2O and by 98.7 grams of Co(NO3)2.6H2O 2.6 l of demineralized water, which gives an acidic solution. In a precipitation vessel solution obtained by dissolution of the base 675 g (NH4)2CO35.2 l of demineralized water. Acid rest the R inject at 12 ml/min in a precipitation vessel, containing a solution of the base, by stirring at room temperature (300 rpm). When adding pH drops from 9.2 (initial) to 8.4 (final).
The precipitate is washed with demineralized water and dried over night at 110°C. Require some machining to extract the dried filter residue in the form of a powder. This powder is not free flowing. The dried powder of the catalyst calicivirus at 500°C for 5 hours (the rate of increase of 150°C/h).
EXAMPLE 3 - characterizing the catalyst data and comparison with conventional catalyst
The table presents characteristics of the catalyst according to the invention and comparison with the corresponding conventional catalyst.
|The catalyst according to example 1||The catalyst of comparison example 2)|
|The content of cobalt||wt.%||7,1||26,3|
|The distribution of particles sizes|
|D(v.0,5)1||mcm||to 25.3||the 5.7|
|Interval1||0,6 (very narrow)||16,5 (very wide)|
|The size of the crystallite2||E||154||143|
Note 1. The interval calculated from the measured on Malvern'the distribution of particle size and lead data width of the interval distribution of particle size, defined as follows:
D[v,0,9] = particle size (μm)below which is 90% of the particles (volume distribution of particle sizes Malvern').
D[v,0.5] would = particle size (μm)below which is 50% of the particles (volume distribution of particle sizes Malvern').
D[v,0,1] = particle size (μm)below which is 10% of the particles (volume distribution of particle sizes Malvern').
Note 2. The size of the crystallite Co3O4when is entered in the table, calculated from the spectrum of x-ray diffraction analysis, in particular of d=2,03 line spectrograms x-ray diffraction analysis (CuK□-radiation).
The content of cobalt measured here by x-ray fluorescence.
EXAMPLE 4. Measuring the distribution of particle sizes
The distribution of particle size for the catalyst according to the invention is measured on Malvern Mastersizer MS 20.
The sampler apparatus is filled with demineralised water and determine the diffraction measuring cell filled with water (to amendment on background). Then in the sampler contribute the appropriate amount of powder catalyst treated before measurement by ultrasonic bath for 3 minutes (25% of maximum output us. capacity) under stirring (50% of maximum speed mixing). After this treatment the sample is measured and modifies the measured diffraction signal to 'background'.
The calculation of the distribution of particle sizes is produced, using the following parameters: model: model independent; display: 1907; the distribution of particle sizes: three-dimensional distribution).
EXAMPLE 5 Catalytic efficiency of the catalyst in the reaction of the Fischer-Tropsch
Get the catalyst with a binder content of 20 wt.%. And with the exception of differences in the content of cobalt conditions for obtaining t the same that in example 1.
A sample of catalyst (20 g) recover in a tubular reactor with an OD of 3.5, see the Reactor is rinsed with nitrogen at flow rate (GHSV) of 1000 l/h and the atmospheric pressure. The temperature was raised at a speed of 2°C/min up to 60°C. Gazoprovod then switch on the air at 1000 GHSV. Then the temperature is raised at a speed of 1°C/min to 250°C and incubated for 3 hours. The gas stream is then replaced with nitrogen at 1000 GHSV for 6 minutes and then the gas flow is changed to carbon monoxide at 1000 GHSV and incubated for 3.5 hours.
Then the gas flow is returned back to nitrogen and the temperature change with a speed of 4°C/min to 280°C. Upon reaching 280°C gas flow again switch to hydrogen at a GHSV of 2500 and incubated for 10 hours. Then the reactor is cooled to room temperature and rinsed with nitrogen before pumping content into the reactor.
The catalyst is transferred in a stream of nitrogen in a flow reactor with a stirrer, capacity 600 ml (CSTR), which is filled with squalane (300 ml; Aldrich). The reactor is sealed and heated to 125°C under a stream of nitrogen, 250 ml/min and Then fed to the reactor gas is replaced by synthesis gas at 8000 GHSV, the speed of the stirrer was raised to 700 rpm and the temperature raised at a speed of 2°C/min to 130°C. After which the reactor to raise the pressure up to 20 bar I.D. at 30 bar/hour. Then the temperature odnim the Ute at 60° C/h to 160°C, 5°C/hour up to 175, 1°C/hour up to 185, 0,5°C/hour up to 205 and 0.3°C/h to 212°C. and then use the automatic temperature control to maintain the % conversion of CO at 60%.
After 40 hours of operation receive C5+ productivity 608 g/liter of catalyst/hour at a temperature of 226°C.
By power of attorney
1. The catalyst for the Fischer-Tropsch containing precipitated together particles of cobalt and zinc, and these particles have a volumetric average particle size less than 150 microns and a distribution of particle sizes in which at least 90% of the volume of catalyst particles has a size between 0.4 and 2.5-fold compared to the average size of the particles and where the atomic ratio of zinc and cobalt is in the range from 40 to 0.1.
2. The catalyst according to claim 1, where the volumetric average particle size of less than or equal to 100 μm, preferably from 2 to 50 microns.
3. The catalyst according to claim 1 or 2, where the pore volume is basically formed by pores with a diameter in the range 5-100 nm.
4. The catalyst according to claim 1, where the pore volume is less than 0.5 ml/g, preferably less than 0.45 ml/g
5. The catalyst according to claim 1, where the surface area is less than 120 m2/g, preferably 5-100 m2/year
6. The catalyst according to claim 1, mainly includes particles with megadeltas spherical geometry.
7. The catalyst according to claim 6, where Mnogotochie particles have positiverate, which, at least, of 1.05-fold, preferably at least 1,1 times the surface area of the so-called equivalent circle, where the equivalent circle is defined as a circle with the largest circumference, which precisely fits the contour of a particle obtained by projecting the particles onto a plane with orientation in order to provide the maximum possible outer surface area within sight.
8. The catalyst according to claim 1, where the copper content is less than 2% calculated on the total weight of the catalyst, preferably less than 0.5%, based on the total weight of the catalyst.
9. The method of producing catalyst according to one of the preceding paragraphs, in which acid solution containing zinc ions and cobalt ions at a total concentration of from 0.1 to 5 mol/l, and alkaline and acid solutions are fed into the reactor containing the aqueous environment, where the acid solution and alkaline solution are contacted in an aqueous medium at pH 4-9, deviating at most ±0,2 pH units from the specified value, with stirring, the frequency of which is due to the input power in the range 1-300 kW/l aqueous medium, at a temperature of 15-75°in which a precipitate comprising cobalt and zinc, after which the precipitate was separated from the aqueous medium, dried, and, putting further processing, receive a specified cat is the lyst.
10. The method according to claim 9, where the acid solution containing one or more anions selected from the group including nitrate and acetate.
11. The method according to claim 9 or 10, where the alkaline solution includes ammonium.
12. The use of the catalyst according to one of claims 1 to 8 in the method of Fischer-Tropsch.
13. The use of the catalyst according to one of claims 1 to 8 in a suspension reactor.
FIELD: production of pigments and catalysts based on titanium dioxide, in particular, process for treatment of titanium dioxide for removal of sulfur, in particular sulfates.
SUBSTANCE: method involves treating calcined titanium dioxide at elevated temperatures using aqueous solution containing one or more ammonium compounds; separating titanium dioxide from aqueous solution and drying titanium dioxide. Ammonium compounds preferably used in treatment process are ammonium acetate or ammonium chloride.
EFFECT: increased efficiency in cleaning of titanium dioxide from sulfur, in particular sulfates.
9 cl, 5 tbl, 5 ex
FIELD: petrochemical process catalyst.
SUBSTANCE: invention relates to a method of preparing catalyst for use in Fischer-Tropsch process and to catalyst obtained according present invention. Preparation of catalyst suitable for conversion at least one synthesis gas component comprises: providing aqueous solution of organic acid; adding iron metal to acid solution; passing oxidant through the solution until iron metal is consumed and iron-containing slurry formed; grinding resulting slurry to achieve average particle size less than about 2 μm; adding at least one promoter to ground iron-containing slurry to form product suspension, concentration of said promoter being such as to obtain said product suspension containing solid phase constituting from about 10 to about 40% of the weight of suspension, including said promoter; performing spray drying of suspension to obtain particles; and calcining these particles to obtain desired catalyst.
EFFECT: optimized catalyst preparation procedure.
23 cl, 2 dwg, 1 tbl, 12 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: synthesis gas is subjected to conversion to produce liquid hydrocarbons in sequentially connected reactors containing catalytic slurry of at least one solid catalyst in a liquid phase. Reactors are triphase bubble column-type reactors provided with virtually full stirring characterized by liquid Peclet number below 8, gas Peclet number below 0.2, and diameter larger than 6 m. Last reactor at least partially receives at least part of at least one of the gas fractions collected at the outlet of at least one of other reactors. At least one reactor is supplied with stream of catalytic slurry coming directly out of another reactor, and at least one stream of catalytic slurry coming out of reactor is at least partially separated so as to receive liquid product substantially free of catalyst and catalyst-rich catalytic slurry, which is then recycled.
EFFECT: improved process technology.
10 cl, 8 dwg, 7 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: invention provides fischer-tropsch process catalyst comprising at least one metal suitably absorbing carbon monoxide and at least one promoter, said metal and said promoter being dispersed on a substrate to form catalytic particle having BET surface area between 100 and 250 m2/g so that size of metal oxide crystallites ranges from 40 to 200 while said metal and said promoter are different compound and said particle has predominantly smooth and uniform morphology of surface. substrate is characterized by particle size between 60 and 150 μm, surface area 90 to 210 m2/g, pore volume 0.35 to 0.50 mL/g, and pore diameter 8 to 20 nm. Described are also catalyst and a method of preparing catalyst including cobalt dispersed onto substrate to form catalyst particle.
EFFECT: increased surface of catalyst, improved uniformity in distribution of metal, and reduced size of metal crystallites.
33 cl, 9 dwg, 1 tbl, 10 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of alcohol comprising synthesis of olefins by the Fischer-Tropsch process followed by the hydroformylation reaction and isolation of mixture of alcohols. Hydrocarbon fraction with the content of linear olefins 10-45 wt-% is separated from products reaction synthesized by the Fischer-Tropsch process with using cobalt catalyst by distillation followed by its hydroformylation with carbon monoxide and hydrogen taken in the molar ratio hydrogen to carbon monoxide = 1.0-5.0. The reaction of synthesis is carried out in the presence of cobalt-base catalyst and a substituted or unsubstituted monophosphocycloalkane ligand followed by steps of hydrogenation and distillation. Invention provides preparing a composition with the content of linear (C7-C12)-alcohols 60 wt.-%, not less, high rate of reaction and high selectivity of the process.
EFFECT: improved method of synthesis.
8 cl, 3 tbl, 4 ex
FIELD: method for separating at least a fraction of non-acidic chemical products from at least a fraction of raw gaseous product received in Fischer-Tropsch reaction, or from condensate of said product.
SUBSTANCE: in accordance to method at least a fraction of raw gaseous product or its condensate is fed into feeding plate of distillation column, liquid flow is drained from aforementioned column from plate, positioned above feeding plate of the column. Received liquid flow is divided on water phase and saturated non-acidic chemical product phase and water phase is returned to distillation column onto plate positioned below plate from which liquid flow is drained.
EFFECT: increased efficiency of cleaning method.
23 cl, 1 dwg
FIELD: petroleum chemistry.
SUBSTANCE: method involves preparing synthesis gas, catalytic conversion of synthesis gas in reactor for synthesis of dimethyl ether (DME) at enhanced temperature and pressure wherein synthesis gas is contacted with catalyst followed by cooling the gaseous mixture and its separation for liquid and gaseous phases. Dimethyl ether is isolated from the liquid phase that is fed into catalytic reactor for synthesis of gasoline and the gaseous phase containing unreacted components of synthesis gas is fed to repeated catalytic conversion into additional reactor for synthesis of DME being without the parent synthesis gas. Residue of gaseous phase containing components of synthesis gas not reacted to DME after repeated catalytic conversion in additional reactor for synthesis of DME are oxidized in reactor for synthesis of carbon dioxide. Then carbon dioxide is separated and mixed its with natural gas at increased temperature and pressure that results to preparing synthesis gas that is fed to the catalytic conversion into reactor for synthesis of DME. Invention provides increasing yield of gasoline fraction and decrease of carbon dioxide waste in atmosphere.
EFFECT: improved method of synthesis.
4 cl, 1 tbl, 1 dwg, 1 ex
FIELD: chemical industry; petrochemical industry; methods of production of the catalysts and hydrocarbons with their use.
SUBSTANCE: the invention is pertaining to the method of production of the catalyst for production of hydrocarbons and to the method for production of hydrocarbons at the presence of the catalyst on the basis of the metal of VIII group on the carrier - the refractory oxide. The presented method of production of the catalyst for production of hydrocarbons on the basis of the metal of VIII group on the carrier - the refractory oxide provides for mixing of the refractory oxide with the surface area of no less than 0.5 m2 /g with the solution of the precursor of this refractory oxide and with the metal or with the precursor of this metal till production of the suspension, drying of the suspension and its calcination. The invention also presents the method of production of the hydrocarbons providing for contacting of the mixture of the hydrocarbon monoxide with hydrogen at the heightened temperature and pressure at presence of the catalyst produced by the method described above. The technical result is production of the catalyst with higher activity in the synthesis of the hydrocarbons at conservation of high selectivity.
EFFECT: the invention ensures production of the catalyst with the higher activity in the synthesis of the hydrocarbons at conservation of the high selectivity.
8 cl, 1 tbl, 1 ex
FIELD: alternate fuel production and catalysts.
SUBSTANCE: synthesis gas containing H2, CO, and CO2 is brought into contact, in first reaction zone, with bifunctional catalyst consisting of (i) metal oxide component containing 65-70% ZnO, 29-34%, Cr2O3, and up to 1% W2O5 and (ii) acid component comprised of zeolite ZSM-5 or ZSM-11, beta-type zeolite or crystalline silica-alumino-phosphate having structure SAPO-5 at silica-to-alumina molar ratio no higher than 200, whereas, in second reaction zone, multifunctional acid catalyst is used containing zeolite ZSM-5 or ZSM-11 and having silica-to-alumina molar ratio no higher than 200.
EFFECT: increased selectivity with regard to C5+-hydrocarbons and increased yield of C5+-hydrocarbons based on synthesis gas supplied.
7 cl, 2 tbl, 15 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: invention relates to catalyst for aromatization of alkanes, to a method of preparation thereof, and to aromatization of alkanes having from two to six carbon atoms in the molecule. Hydrocarbon aromatization method consists in that (a) C2-C6-alkane is brought into contact with at least one catalyst containing platinum supported by aluminum/silicon/germanium zeolite; and (b) aromatization product is isolated. Synthesis of above catalyst comprises following steps: (a) providing aluminum/silicon/germanium zeolite; (b) depositing platinum onto zeolite; (c) calcining zeolite. Hydrocarbon aromatization catalyst contains microporous aluminum/silicon/germanium zeolite and platinum deposited thereon. Invention further describes a method for preliminary treatment of hydrocarbon aromatization catalyst comprising following steps: (a) providing aluminum/silicon/germanium zeolite whereon platinum is deposited; (b) treating zeolite with hydrogen; (c) treating zeolite with sulfur compound; and (d) retreating zeolite with hydrogen.
EFFECT: increased and stabilized catalyst activity.
26 cl, 1 dwg, 5 tbl, 4 cl
FIELD: redox reaction catalysts.
SUBSTANCE: invention relates to methods for preparing vanadium-titanium oxide catalysts for redox reactions, e.g. for industrial processes of production of phthalic anhydride via oxidation of o-xylene, selective reduction nitrogen oxides, and detoxification of organochlorine compounds. Method of invention comprises following stages: providing titanyl sulfate solution; adding ammonia and then vanadium peroxide solution to titanyl sulfate solution or adding to the same vanadyl sulfate or oxalate and then ammonia solution; optionally ageing suspension resulting after mixing of solutions; filtration; and calcinations at 450°C.
EFFECT: increased heat resistance of active chlorobenzene oxidation catalyst and reduced catalyst preparation time (10-12 h instead 72 h as in a known method).
1 tbl, 3 ex
FIELD: production of catalytic compositions.
SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.
EFFECT: enhanced efficiency.
29 cl, 8 ex
FIELD: chemical industry; materials and the methods for the catalyst carrier manufacture.
SUBSTANCE: the invention is pertaining to the new mixed oxides produced from ceric oxide and zirconium oxide, which can used as the catalyzers or the catalyzers carriers for purification of the combustion engine exhaust gases. The mixed oxide possesses the polyphase cubical form of the crystallization and oxygenous capacity of at least 260/ micromoles of O2 /g of the sample and the speed of the oxygen extraction of more than 1.0 mg-O2/m2-minute, which are measured after combustion within 4 hours at the temperature of 1000°C. The invention also presents the substrate with the cover containing the indicated mixed oxide. The method of production of the polycrystallic particles of the indicated mixed ceric-zirconium oxide includes the following stages: i) production of the solution of the mixed salt which are containing, at least, one salt of cerium and, at least, one salt of zirconium in the concentration, sufficient for formation of the polycrystallic particles of the corresponding dry product on the basis of the mixed oxide. At that the indicated particles have the cerium-oxide component and zirconium-oxide component, in which these components are distributed inside the subcrystalline structure of the particles in such a manner, that each crystallite in the particle consists of a set of the adjacent one to another domains, in which the atomic ratios of Ce:Zr which are inherited by the adjacent to each other domains, are characterized by the degree of the non-uniformity with respect to each other and determined by means of the method of the X-ray dissipation the small angles and expressed by the normalized intensity of the dissipation I(Q) within the limits from approximately 47 up to approximately 119 at vector of dissipation Q, equal to 0.10 A-1; ii) treatment of the solution of the mixed salt produced in compliance with the stage (i),with the help of the base with formation of sediment; iii) treatment of the sediment produced in compliance with the stage (ii),using the oxidative agent in amount, sufficient for oxidizing Ce+3 up to Ce+4; iv) washing and drying of the residue produced in compliance with the stage (iii); and v) calcination of the dry sediment produced in compliance with the stage (iv),as the result there are produced polycrystallic particles of the oxide of ceric and zirconium in the form of the mixed oxide with the above indicated characteristics. The technical result is the produced mixed oxide possesses both the high oxygenous capacitance, and the heightened speed of the oxygen return in the conditions of the high temperatures.
EFFECT: the invention ensures production of the mixed oxide manufactured from ceric oxide and zirconium oxide and possessing the high oxygenous capacitance and the heightened speed of the oxygen return in the conditions of the high temperatures.
68 cl, 21 ex, 2 dwg
FIELD: catalyst preparation methods.
SUBSTANCE: invention provides Fischer-Tropsch catalyst, which consists essentially of cobalt oxide deposited on inert carrier essentially composed of alumina, said cobalt oxide being consisted essentially of crystals with average particle size between 20 and 80 Å. Catalyst preparation procedure comprises following stages: (i) preparing alumina-supported intermediate compound having general formula I: [Co2+ 1-xAl+3 x(OH)2]x+[An- x/n]·mH2O (I), wherein x ranges from 0.2 to 0.4, preferably from 0.25 to 0.35; A represents anion; x/n number of anions required to neutralize positive charge; and m ranges from 0 to 6 and preferably is equal to 4; (ii) calcining intermediate compound I to form crystalline cobalt oxide. Invention also described a Fischer-Tropsch process for production of paraffin hydrocarbons in presence of above-defined catalyst.
EFFECT: optimized catalyst composition.
16 cl, 12 tbl, 2 ex
FIELD: chemical industry; methods of production of zirconium oxides
SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of obtaining of zirconium oxide for production of the catalytic agents used, for example, in the reactions of the organic synthesis. The invention presents the method of obtaining of zirconium oxide for production of the catalytic agents, which includes the operations of dissolution of the zirconium salt in water, treatment of the solution with the alkaline reactant, settling of the metals hydroxides, filtration, separation of the mother-liquor from the settlings, the settlings water flushing, its drying, calcination and granulation and-or granulation by molding. At that dissolution of the source zirconium chloride and-or zirconium oxychloride is conducted in the sodium chloride solution with concentration of 200-250 g/dc3 till reaching of the concentration of zirconium of 20-120 g/dc3. Settling of zirconium oxyhydrate is conducted by the adding the initial chloride solution in the solution of the sodium hydroxide with concentration of 20-80 g/dm3 up to reaching the suspension pH equilibrium value - 5-8. Then the suspension is filtered up to the zirconium oxyhydrate pasta residual humidity of 40-80 %. The mother chloride solution is separated from the settlings of zirconium oxyhydrate and again use it for dissolution of the next batch of zirconium chloride and-or zirconium oxychloride. The settlings of zirconium oxyhydrate are subjected to drying at 80-100°C within 2-6 hours, then the dry settlings are suspended in the water at the ratio of liquid to solid L:S = (5-10 :1, the suspension is filtered, the sediment on the filter is flushed by water, the chlorides are wash off up to the residual concentration of ions of chlorine in the flush waters of 0.1-0.5 g/dm3, divided into 2 parts, one of which in amount of 60-80 % is subjected to drying and calcinations at the temperatures of 300-600°C, and other part in amount of 20-40 % is mixed with the calcined part of the settlings and subjected to granulation by extrusion at simultaneous heating and dehydration of the damp mixture of zirconium oxide and zirconium oxyhydrate with production of the target product. The technical result of the invention is improvement of quality of the produced zirconium oxide for production of the catalytic agents due to provision of the opportunity to use ZrO2 for the subsequent production of the various catalytic agents of the wide range of application and thereby improving the consumer properties of the produced production.
EFFECT: the invention ensures improvement of the quality of the produced zirconium oxide for production of the catalytic agents with improved consumer properties.
FIELD: catalyst preparation methods.
SUBSTANCE: invention, in particular, relates to catalyst based on synthetic mesoporous crystalline materials and provides hydrocarbon conversion catalyst composed of: group VIII metal/SO4 2-/ZrO2-EOx, where E represents element of the group III or IV of Mendeleev's periodic table, x = 1.5 or 2, content of SO4 2- is 0.1 to 10% by weight, ZrO2/EOx molar ratio is 1:(0.1-1.0), which has porous crystalline structure with specific surface 300-800 m2/g and summary pore volume 0.3-0.8 cm3/g. Preparation method comprises precipitation of zirconium compounds, in particular zirconium hydroxide or zirconyl, under hydrothermal conditions in presence of surfactant to form mesoporous phase, which is stabilized with stabilizing agents: group III and IV elements. When stabilization is achieved, if necessary, acidity is adjusted and group VIII metal is added.
EFFECT: increased specific surface area and heat resistance at simplified technology.
9 cl, 2 dwg, 2 tbl, 6 ex
FIELD: catalyst preparation methods.
SUBSTANCE: invention relates to methods for preparing carbon monoxide-conversion catalysts used in production of hydrogen, nitrogen-hydrogen mixture, and other hydrogen-containing gases. According to first option, active catalyst component, i.e. iron compound, is precipitated from solution with precipitation reagent, whereupon precipitate is separated from mother liquor and washed to form catalyst mass, which is molded and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. According to second option, iron compound is first mixed with promoting additives and cations of promoting additives are precipitated jointly with iron cations, resulting precipitate is separated from mother liquor, washed and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. As iron compound in the first and second options, ferrous and ferric sulfates and, as precipitation reagent, carbonate salts or corresponding hydroxides are utilized. Promoting additives are selected from Cu, Mn, and Al or, in the second option, their mixture.
EFFECT: reduced content of sulfur in finished catalyst at the same catalyst activity.
3 cl, 1 tbl, 12 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: invention relates to environmentally friendly processes for production of isoalkanes via gas-phase skeletal isomerization of linear alkanes in presence of catalyst. Invention provides catalyst for production of hexane isomers through skeletal isomerization of n-hexane, which catalyst contains sulfurized zirconium-aluminum dioxide supplemented by platinum and has concentration of Lewis acid sites on its surface 220-250 μmole/g. Catalyst is prepared by precipitation of combined zirconium-aluminum hydroxide from zirconium and aluminum nitrates followed by deposition of sulfate and calcination in air flow before further treatment with platinum salts. Hexane isomer production process in presence of above-defined cat is also described.
EFFECT: increased catalyst activity.
5 cl, 2 tbl, 6 ex
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.
EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.
1 dwg, 1 tbl, 12 ex
FIELD: exhaust gas afterburning means.
SUBSTANCE: invention relates to catalytic neutralizer for treating internal combustion engine exhausted gases. Proposed catalyst is composed of catalytically active coating on inert ceramic or metallic honeycomb structure, wherein coating contains at least one platinum group metal selected from series including platinum, palladium, rhodium, and iridium on fine-grain supporting oxide material, said supporting oxide material representing essentially nonporous silica-based material including aggregates of essentially spherical primary particles 7 to 60 nm in diameter, while pH of 4% water dispersion of indicated material is below 6.
EFFECT: increased catalyst activity and imparted sufficient resistance to aggressive sulfur-containing components.
27 cl, 2 dwg, 7 tbl, 6 ex