Method of producing catalyst carrier from used catalyst
FIELD: process engineering.
SUBSTANCE: invention relates to method of producing, circulating or reusing catalyst material-carrier like that used in Fisher-Tropsch process. Method of producing catalyst material-carrier from used Fischer-Tropsch catalyst containing titanium dioxide and cobalt comprises: crushing of used catalyst on carrier, leaching of at least 50 wt % of cobalt from crushed used catalyst, and additional crushing of produced carrier material. Invention covers also catalyst carrier material produced by above described method, its application, catalyst containing said carrier material and method of producing hydrocarbons using catalyst containing said carrier material.
EFFECT: possibility to use used carrier materials, usually rejected, method of efficient circulation of active component.
12 cl, 2 ex
The present invention relates to a method of manufacture and, furthermore, to a method of recycling or reuse of the material carrier of the catalyst that is used in the Fischer-Tropsch process. Preferably the carrier material spent catalyst Fischer-Tropsch process is used to manufacture a new catalyst for the Fischer-Tropsch process.
the Fischer-Tropsch process can be used for the conversion of hydrocarbonaceous materials in liquid and/or solid hydrocarbons. Industrial raw materials (e.g. natural gas, associated gas and/or coal bed methane, biomass, residual oil and coal) is converted in the first stage, in a mixture of hydrogen and carbon monoxide (this mixture is often referred to as synthesis gas or syngas). Then the synthesis gas is fed into the reactor where it is converted with the participation of the appropriate catalyst at elevated temperature and pressure into paraffinic compounds from methane to high molecular weight compounds containing up to 200 carbon atoms, or under certain conditions even more.
The catalysts are usually active part, for example, metal or metal-containing component, is fixed on the base material, which may be in the form of a porous refractory oxide, such as titanium dioxide, silicon dioxide or aluminum oxide. The catalysts of detective is described with time, and so they must be periodically replaced to maintain acceptable product yield.
For example, fixed cobalt catalyst currently used as a catalyst for the reaction of the Fischer-Tropsch process, as well as in some other areas. Harmful effect on the catalyst to provide a catalyst poisons, including a number of different compounds, for example, sulphur-, sodium-, nitrogen - or carbon-containing compounds, all of which inactivate the catalyst. In addition, it may decrease the dispersion of metal or metal-containing component.
In addition, sintering and agglomeration of the particles of the medium reduces the surface area of the media and, as a consequence, the activity of the catalyst.
As soon as the economic costs of the shutdown of the reactor and replacement of the catalyst is lower than lose due to deactivation of the catalyst profit, the reactor is shut off and the catalyst is replaced. The deactivated catalyst can be processed, for example, nitric acid for leaching of some or preferably all of the amount of relatively expensive cobalt, which can be extracted and reused. However, the media traditionally thrown.
The aim of the present invention is to reuse materials carriers.
According to this izopet the tion is provided a method of manufacturing a material of the catalyst carrier, which includes:
- receiving waste material carrier of the catalyst by leaching of the catalytic components from spent catalyst on the carrier and
- fragmentation of the specified material-catalyst carrier so that a portion of the crushed material can be reused, it is preferable as a material of the catalyst carrier.
Because of this, the spent carrier material of the catalyst may be re-used.
Thus, the invention provides a way to re-use material-catalyst carrier, which includes:
- receiving waste material-catalyst carrier and
- fragmentation of the specified material carrier of the catalyst by leaching of the catalytic components from spent catalyst on the carrier so that a portion of the crushed material can be reused.
The invention also provides a method of manufacturing a material carrier of the catalyst, including the production of waste material-catalyst carrier and the crushing of the specified material-catalyst carrier.
Preferably the spent carrier material of the catalyst is a crystalline carrier material of the catalyst, respectively, the crystal is ical porous refractory oxides.
More preferably the carrier material of the catalyst is a material-catalyst carrier high crystallinity.
Suitable for the above purpose, the material carrier of the catalyst include refractory oxides, mainly of a porous refractory oxide, such as silicon dioxide, titanium dioxide (rutile and anatase), zirconium dioxide, α-quartz, aluminum oxide, for example, α-alumina, γ-alumina, θ-alumina, aluminosilicates (Al2SiO4), silicon dioxide/aluminum oxide (e.g., ASA) and their mixtures. Suitable are also CoTiO3, CoSiO3, MnTiO3, CoAl2O4, MnAl2O4or their mixtures, the formation of which may occur during the service life of the catalyst and which is suitable for use as a material carrier of the catalyst. Preferably the carrier material of the catalyst contains at least 90 wt.%. only one material carrier, calculated on the total weight of the material carrier; more preferably, at least 95% wt.; most preferably 98 wt.%. In the case of mixtures may occur some separation, resulting in a decrease in homogeneity of the material.
Preferably the method of the present invention also provides a stage of processing only a part or all of the spent catalyst is La deleting part of its active component(s). Suitable method for this purpose is a method of leaching with an acid or a base, in which the spent catalyst is in contact with the acid solution, which dissolves its active component. It is possible to use inorganic acids, for example hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and organic acids, for example formic acid, acetic acid, oxalic acid, benzoic acid and other Suitable bases are sodium hydroxide, potassium hydroxide and calcium hydroxide. Nitric acid (or, for example, a mixture of nitric acid with hydrochloric acid) is very suitable for the removal of certain active components, mainly iron, cobalt and Nickel. It can also remove contaminants, such as sodium, nitrogen and sulfur, which may be present in the catalyst.
The analysis of a sample of titanium dioxide after leaching. A sample of titanium dioxide was previously used as a material carrier of the catalyst, together with cobalt as the active component and the manganese as a promoter. It contained, it was found that 0.1% by weight. cobalt and 0.1% wt. manganese and had an average crystal size of 40-50 nm.
You can remove at least 50% wt. the active ingredient; preferably is, at least 80% wt.; more preferably, at least 90% wt. The active component is mainly cobalt.
Preferably the spent carrier material of the catalyst is crushed before removing the active component, more preferably a partially crushed in order to facilitate the removal process of the active component. It is a partial or preliminary crushing preferably reduces the particle size to a value of from 10 to 15 microns.
Optional exhaust catalyst calcined in order to remove some of the deactivated connection, such as gray - and/or carbon compounds. Typically, the calcination is carried out after removal of the active component. Typically, the calcination is carried out after the initial crushing stage. The calcination is usually carried out in air at temperatures from 200 to 800°C, mainly from 300 to 650°C., for from 0.5 to 18 hours.
The spent carrier material of the catalyst is preferably crushed to the desired average particle size. The crushing is preferably carried out after calcination. Preferably the average particle size after crushing is less than 1 micron.
Crushing can be done so that rather destroyed agglomerated particles on a single part of the s, than individual particles, because the fragmentation of particles requires a disproportionately higher amount of energy than for crushing of agglomerates of individual particles.
Preferably the method of the present invention also includes a stage of mixing the crushed waste material-catalyst carrier with a new material-the carrier of the catalyst before its next use.
The term "new material-catalyst carrier" in the context of the present description includes a material carrier of the catalyst, which are fresh, not used and has not been used previously as a material carrier of the catalyst.
Usually fragmented exhaust carrier material of the catalyst has an average particle size of 1000 nm, which was formed of agglomerated primary particles size of about 40-50 nm. Preferably a new carrier material of the catalyst has an average primary particle size 30 nm, which allows to obtain a combined (exhaust + new) carrier material of the catalyst with an average size of crystals of the third, of a given size, for example, about 35 nm.
Primary particles are those particles that can be seen under transmission electron microscope (THEMES), or the average size of which is calculated from the area of the surface of the I.
In the case of crystalline materials, the primary particles are crystals.
Preferably, at least 5% of the combined catalyst is used, the catalyst, more preferably at least 10% of the combined catalyst is the spent catalyst. In certain embodiments of the invention a new and waste materials carriers and catalyst are mixed in a ratio of 1:1.
Usually exhaust the carrier material of the catalyst can be recycled, preferably as a material carrier of the catalyst.
Reusable carrier material of the catalyst can be combined with the active component by pre-mixing and extrusion, spray drying, impregnation or any other traditional method.
Preferably the active component, which remains on used material-catalyst carrier (or the part of the active component remaining after removing some of its quantity), determine before adding additional active component to the combined material is the carrier of the catalyst prior to its re-use. Typical active components are cobalt, iron or ruthenium, or combinations thereof.
Preferably, the mod is offered by the content of any promoter on used material of the catalyst was determined before adding additional promoter to the combined material of the catalyst carrier. Typical promoters include manganese, ruthenium, platinum, rhenium, zirconium, vanadium, etc. In practice, about 80% wt. promoter (from mass only metal) may remain as residual content in the base material of the catalyst. Preferably, at least 40% wt. the initial promoter (from mass only metal) remains on the carrier, more preferably 60 wt.%, most preferably 80 wt.%. It should be borne in mind that the term "catalytic component" refers to a catalytically active metal-containing components (e.g., cobalt, iron, Nickel and others) and does not include connection-promoters (for example, rhenium, platinum, manganese, vanadium, and others).
The ratio of the crystalline forms of the material of the carrier, for example, titanium dioxide, can also be balanced to determine if the content of the crystalline forms in the catalyst and to consider it in combination with the new catalyst. For example, in the case of repeated use of titanium dioxide set proportional to the ratio of the anatase:rutile can be 80%:20%. If the number of anatase in the used material of the catalyst below, for example, 70%, and the amount of rutile above, for example, 30%, mixing with the new titanium dioxide can be carried out at a proportionally higher number of anatase, for example, 90% and more is a low amount of rutile, for example, 10%. This will ensure that the total content of anatase/rutile in combination of exhaust and a new titanium dioxide, corresponding to the above specified ratio of 80% anatase and 20% rutile.
The share of such crystalline forms of titanium dioxide, as brookite, also can be increased in this way. Some of the material carrier of the catalyst can contain, for example, 70% of brookite and 30% rutile. In this case, there is no need to mix the exhaust carrier material of the catalyst with the new material-the carrier of the catalyst for achieving the fraction of material or crystalline phase, which was used previously, because you can apply different proportions or mixture. For example, the new brookite can be added to the worked material is the carrier of the catalyst, which was previously prepared, mainly of anatase and rutile without brookite.
In the case of recycling of aluminum oxide ratio of the crystalline form of aluminium oxide (alpha, gamma and theta) can also be adjusted by appropriate selection of the proportional amounts of different crystalline forms in the new material of the catalyst, so that a desired ratio of different crystalline forms in the composite material of catalyst.
Another advantage of certain embodiments of the invention for luchetta in proportions between the new rutile and anatase, required to achieve a given relationship when mixed with waste titanium dioxide: this new ratio is easier to achieve on an industrial scale than the specified ratio, and thus re-use of waste titanium dioxide and mixing it with a new titanium dioxide may allow use of less expensive new titanium dioxide.
Embodiments of the invention provide the advantage that they require less promoter and/or active component, because the spent catalyst carrier may have a residual content of this material. This is especially true in the case of manganese, which is used in catalysts, mainly in combination with cobalt. Apparently, on a porous refractory oxides, mainly titanium dioxide, such mn containing layer is formed on the surface. This means that if you re-use of spent catalyst carrier can be used significantly fewer promoter, because not all of, and only a small proportion of manganese as a promoter washed out from the media.
Embodiments of the invention provide the advantage that the recirculated carrier material of the catalyst does not seek to absorb some of the newly added sports the component, rather, the active ingredient remains on its surface, making it easier, for the reaction that it catalyzes. This can be explained by the fact that the recirculated carrier material of the catalyst still contains a residual amount of absorbed on the active component, even if the majority of the primary active component has been removed, for example, by leaching.
Therefore, in the case of repeated application of the material-catalyst carrier may require a lower amount of the active component.
Embodiments of the invention provide the advantage that the combined carrier material of the catalyst, including waste and new materials-media catalyst may contain some fraction of particles larger than a new carrier material. The combination of particles of different sizes adds to the strength of the catalyst. For example, with repeated use of the titanium dioxide particles used rutile will be larger than new particles of rutile, resulting in combined media from the new and spent media) greater strength in comparison with a completely new media traditional manufacturing.
For embodiments of the present invention also found that the aging of the material-wear the El catalyst is slower in the case of using recycled material.
The traditional method of removing the active component of the material of the carrier is very hard due to the high cost of the active component. In certain embodiments implementing the present invention method of removing the active component may be less stringent and less costly, because the active ingredient can remain on the base material of the catalyst, and thus reused.
Another advantage of this alternative embodiment of the invention is that trace amounts of impurities, usually found in new materials-carriers, for example, TiOCl2, which is an impurity in some types of titanium dioxide, is much lower in recycled material, because they are leached from the titanium dioxide with the help of HCl in the process of the prior application. These impurities reduce the activity of the catalyst, can damage equipment and can be combined with the hydrocarbons with the formation of undesirable chloro-hydrocarbon impurities, and due to the recirculation of the material carrier the number is preferably minimized.
Thus, embodiments of the present invention provide the advantage that the quantity of these impurities have to be removed, much less.
Recycled material is ial group can be reused and then recycled many more times.
Therefore, the invention also provides the use of the catalyst carrier made, at least partially, by crushing waste material-catalyst carrier.
In a preferred embodiment, the spent catalyst carrier may be silicon dioxide, titanium dioxide or aluminum oxide, preferably titanium dioxide or aluminum oxide, and metal-containing component may be iron - or cobalt containing component, preferably cobalt containing component; at the same time may be a second metal-containing component selected from rhenium, platinum, zirconium, vanadium or manganese, preferably manganese.
In the following a preferred embodiment, the spent carrier material of the catalyst is obtained by leaching at least 50% wt. metal components from spent catalyst; preferably 80 wt.%. metal-containing component; more preferably 90 wt.%, moreover, the metal-containing components are preferably metals of group VIII, more preferably iron, cobalt or Nickel components, most preferably cobalt containing components.
The invention also provides a carrier material of the catalyst, made JV which means according to the first aspect of the invention.
The invention also provides a catalyst containing a carrier material of the catalyst produced by the method according to the first aspect of the invention, the catalytically active material.
To manufacture a new material-catalyst carrier does not necessarily take to re-use material from spent catalyst, and it is possible to use other waste materials, for example, the materials used in nanotechnology, solar, medicine and other
Therefore, the invention also provides a method of preparation of the catalyst, including:
obtaining spent a crystalline material;
- add an active component to the specified crystalline material with the formation of the catalyst;
mainly including specific and preferred options described above.
Commonly used crystalline material is crushed before adding to it the active component.
Usually spent crystalline material can be also other stages similar to the stages performed with waste material carrier of the catalyst.
The present invention is suitable in particular for use for recycling of titanium dioxide, irrespective of its use or as a catalyst carrier and is in a different as, more preferably for recycling of titanium dioxide used in reactors for Fischer-Tropsch, mainly in accordance with the specific and preferred options for implementation described above.
The products of synthesis in Fishery-Tropsch may vary from methane to heavy paraffin waxes. Preferably the methane formation is minimized, and a significant part of the produced hydrocarbons contain carbon chain of at least 5 carbon atoms. Preferably the number With5+hydrocarbon is at least 60% wt. total product; more preferably, at least 70% wt.; even more preferably, at least 80% wt.; most preferably, at least 85% wt. The reaction products which are liquid under the reaction conditions, can be separated and disposed of by appropriate means, such as one or more filters. You can use internal or external filters or a combination of both. Products in the gas phase, such as light hydrocarbons and water, can be removed by appropriate means known to the skilled in the art specialist.
The catalysts of the Fischer-Tropsch process known from the prior art and typically include a component containing a metal of group VIII, site is preferably cobalt, iron and/or ruthenium, more preferably cobalt. Typically, the catalysts contain a catalyst carrier.
The catalyst carrier is preferably porous, such as a porous inorganic refractory oxide, more preferably such as aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide or mixtures thereof. The optimal number of catalytically active metal present on the media, depends, inter alia, on the specific activity of the catalytically active metal. Generally, the amount of cobalt present in the catalyst can vary from 1 to 100 wt. parts per 100 wt. parts of the material carrier; preferably from 10 to 50 wt. parts per 100 wt. parts of the material of the carrier.
The catalytically active metal may be present in the catalyst together with one or more metal promoters or co-catalysts. The promoters may be present in the form of metals or metal oxides, depending on the specific type of promoter. Suitable for this purpose, the promoters include oxides of metals of groups IIA, IIIB, IVB, VB, VIB and/or VIIB of the Periodic table; the oxides of the lanthanides and/or actinides. Preferably the catalyst contains at least one element of group IVB, VB and/or VIIB of the Periodic table, in particular, titanium, zirconium, manganese and/or vanadium. As alternative or in addition to the promoter in the form of a metal oxide catalyst may contain metal-promoter, selected from groups VIIB and/or VIII of the Periodic table. Preferred metals promoters include rhenium, platinum and palladium.
The most suitable catalyst contains cobalt as the catalytically active metal and zirconium as a promoter. Another most suitable catalyst contains cobalt as the catalytically active metal and manganese and/or vanadium as a promoter. Preferably the catalyst is extruded catalyst suitable for use in Novotrubny reactor with a fixed catalyst bed.
The promoter, if present in the catalyst that is typically contained in an amount of from 0.1 to 60 wt. parts per 100 wt. parts of the material carrier. However, it is desirable that the optimal number of promoter could change if each of the corresponding elements, acting as a promoter. If the catalyst contains cobalt as the catalytically active metal and manganese and/or vanadium as a promoter, the atomic ratio of cobalt (manganese+vanadium) preferably will be at least 12:1.
Synthesis by the Fischer-Tropsch preferably carried out at a temperature of from 125 to 350°C., more preferably from 175 to 275°C., most preferably from 200 to 260°C. the Pressure preferably ranges from 5 to 150 abs. bar., Bo is her preferably from 5 to 80 abs. bar.
Hydrogen and carbon monoxide (synthesis gas) usually arrives in three-phase slurry reactor in a molar ratio of from 0.4 to 2.5. Preferably the molar ratio of hydrogen to carbon monoxide is from 1.0 to 2.5.
Hourly average volumetric feed rate of the gaseous phase can vary within wide limits: usually from 1500 to 10000 nl/l/h, preferably from 2500 to 7500 nl/l/h
Needless to say that the skilled in the art specialist can select the most suitable conditions depending on the specific configuration and mode of operation of the reactor. It is clear that the preferred conditions may depend on the preferred mode of operation.
Possible improvements and modifications without deviating from the scope of the present invention.
The invention also includes a method of producing hydrocarbons from synthesis gas using recycled material carrier, as described earlier, as the material of the carrier for the manufacture of catalysts for the Fischer-Tropsch process, as described above. The invention also concerns the hydrocarbons obtained in the specified process, optionally after hydroconversion. These products include the fraction of oil - naphtha, kerosene, gas oil and base oil.
The spent catalyst Fischer-Tropsch (extraditability-manganese-titanium dioxide (P25)) was treated with (after crushing) nitric acid to leach the contained cobalt. The resulting carrier material contains about 0.1 wt.%. cobalt and 0.1% wt. manganese (calculated on the total weight of the carrier). After further crushing part of the material of the carrier, the average size of the crystals was approximately 45 nm. The carrier material used for the manufacture of a new catalyst having the same composition as the original (new) catalyst. After activation, the catalyst showed the same activity in the Fischer-Tropsch process, the original (new) catalyst. Thus, the regenerated carrier on the basis of titanium dioxide can be used instead of new (i.e. not previously used) media based on titanium dioxide.
Get the spent catalyst Fischer-Tropsch (cobalt-manganese titanium dioxide in the form of extrudate P25). The amount of cobalt in the catalyst (before leaching) is about 20 wt.% calculated on the total weight of the catalyst. The ratio of the anatase:rutile in titanium dioxide waste material is 75:25 (first attitude).
The spent catalyst Fischer-Tropsch crushed to an average particle size of about 1000 nm and videlacele nitric acid to remove cobalt from the catalyst.
Received carrier material, containing about 0.1 wt.% cobalt and 0.1 wt.% manganese calculated on the total weight of the carrier So more than 50 wt.% cobalt was leached.
After further crushing of the material carrier average particle size was 45 nm (first average size). This material was used to obtain a new catalyst having the same composition as that of the original fresh catalyst.
Leached and crushed material spent catalyst combined with fresh titanium dioxide (P25) in equivalent amounts. The average particle size of titanium dioxide was about 30 nm (the second average size). The ratio of the anatase:rutile was 84:16 (second ratio).
The result of combining the received composite material having an average particle size of about 40 nm (the third average size). The ratio of the anatase:rutile in the combined material was 80:20 (the third).
The catalyst was added cobalt to a new catalyst contained about 20 wt.% cobalt calculated on the total weight of the catalyst.
The material was extrudible and illnerova, i.e. progulivali at 550°C.
After activation, the catalyst showed the same activity as the fresh catalyst Fischer-Tropsch process.
Thus, it is possible to reuse the carrier of titanium dioxide instead of the new, i.e. not previously used, titanium dioxide.
1. A method of manufacturing a material carrier of the catalyst of the exhaust was pushing the congestion Fischer-Tropsch process on the media,
contains titanium dioxide and cobalt, which includes:
crushing the spent catalyst on the carrier;
leaching at least 50 wt.% cobalt from crushed spent catalyst and
additional crushing of the material obtained carrier.
2. The method according to claim 1, further comprising a stage of mixing a part or all of the optional crushed material carrier with a new titanium dioxide, is used as the material of the catalyst carrier.
3. The method according to claim 2, which further crushed carrier material has a first average particle size, a new carrier material has a second average particle size and a combined carrier material has a third particle size.
4. The method according to claim 2, which further crushed carrier material has a first ratio of the anatase:rutile in titanium dioxide, a new carrier material has a second ratio of the anatase:rutile in titanium dioxide, and a combined carrier material has a third ratio of the anatase:rutile in titanium dioxide.
5. The method according to any one of claims 1 to 4, in which the spent catalyst Fischer-Tropsch process on the media further comprises manganese.
6. The method according to any one of claims 1 to 4, in which the carrier material of the catalyst obtained after the leaching step, calicivirus.
7. The method according to any one of claims 1 to 4, in which the material carrier spent catalyst re-use as a material carrier of the catalyst.
8. The method according to any one of claims 1 to 4, in which at least 80 wt.% cobalt leached from the crushed spent catalyst.
9. The carrier material of the catalyst produced by the method according to any of the preceding claims 1 to 8.
10. The use of the material carrier of the catalyst according to claim 9 in the Fischer-Tropsch process.
11. The catalyst containing carrier material of the catalyst according to claim 9 and cobalt.
12. A method of producing hydrocarbons using the catalyst according to claim 11.
SUBSTANCE: invention relates to a method of producing aromatic hydrocarbons from synthetic gas containing carbon monoxide and hydrogen, involving bringing the gas into contact with an effective amount of catalyst which contains 30% cobalt and promoted 4% magnesium (II) oxide and 3% zirconium (II) oxide, in which the carrier used is decationated zeolite, characterised by that the method is carried out in molar ratio of carbon monoxide to hydrogen equal to 1:(0.5-2), contact temperature of gases equal to 250-300°C, bulk speed of supplying gas equal to 300-2000 h-1 and pressure of 0.5-3 MPa, and molar ratio SiO2/Al2O3=38 in the carrier.
EFFECT: use of pressure and high bulk speed of feeding synthetic gas increases synthesis efficiency and considerably lowers output of carbon dioxide.
4 cl, 1 tbl, 13 ex
SUBSTANCE: bifunctional cobalt-containing zeolite catalyst for synthesis of aromatic hydrocarbons (mixture of benzene, toluene, xylols and ethyl benzene) from synthetic gas contains a structural promoter - magnesium (II) oxide and an energy promoter - titanium oxide or hafnium oxide, in which the zeolite component used is zeolite ZVM in Ga form with molar ratio SiO2/Al2O3=30, and ratio of components in pts. wt: cobalt 50-150, magnesium (II) oxide 2-8, hafnium oxide or titanium oxide 2-5, zeolite (Ga form) 100-300, a method of preparing said catalyst and a method for synthesis of aromatic hydrocarbons from synthetic gas using said catalyst. The catalyst is characterised by low formation carbon dioxide - main by-product whose output is over 100 g/m3, and optimum ratio of components reaches 50 g/m3. Disclosed catalyst is characterised by high stability and enables synthesis of aromatic hydrocarbons without loss of selectivity for desired synthesis products for a long period of time (over 30 hours).
EFFECT: possibility of selective synthesis of aromatic hydrocarbons with output of desired products.
8 cl, 15 ex, 1 tbl
SUBSTANCE: invention relates to petrochemistry, gas chemistry, coal chemistry and a catalyst for synthesis of hydrocarbons from CO and H2 and a method of preparing said catalyst. The catalyst for synthesis of hydrocarbons from CO and H2 contains Raney cobalt as one of the active components, aluminium metal and a binding component and is in form of granules. The method of preparing the catalyst for synthesis of hydrocarbons from CO and H2 involves mixing powdered Raney cobalt, aluminium metal, binding component with a liquid phase, obtaining granules through extrusion of the obtained paste, drying and calcination of the obtained granules.
EFFECT: higher resistance of the catalyst to overheating and high output of C5-C100 hydrocarbons during synthesis of hydrocarbons from CO and H2.
18 cl, 1 tbl, 19 ex
SUBSTANCE: carbon dioxide is extracted from initial gas mixture and concentrated in absorber by means of 9 liquid amine-based absorbents, which are regenerated with dry water vapours with temperature 170…190°C in desorber 12. Desorbed carbon dioxide is dried by wateer vapour condensation. Obtained water in liquid phase is supplied to electrolyser 20 in order to obtain oxygen on anode and hydrogen on cathode. After drying carbon dioxide is mixed with obtained hydrogen in mole ratio H2:CO2=(2.1…3.2) and carbon dioxide is reduced with hydrogen at temperature from 600°C to 800 °C in apparatus 27 until synthesis-gas consisting of H2:CO=2…2.3 and water vapours is obtained. Obtained synthesis-gas is dried by water vapour condensation and subjected to absorption purification from residual carbon dioxide in apparatus 29, hydrogen is added to it and exothermal reaction of catalytic conversion, such as of Fischer-Tropsch type is carried out at temperature from 170 to 190°C in apparatus 31 in order to obtain gaseous carbon dioxide products and liquid motor fuel. Heat of synthesis-gas conversion is removed and utilised for water evaporation and generation of dry vapours which are directed for absorbent regeneration in process of carbon dioxide concentration from initial gas mixture. Obtained trade products - gaseous carbon dioxide products, liquid motor fuel and electrolysis oxygen are directed to consumer.
EFFECT: invention allows to increase process productivity, reduce process cost, extent field of application due to utilisation of carbon dioxide from industrial gas emissions and from surrounding atmosphere.
3 cl, 7 dwg
SUBSTANCE: invention relates to a method of producing hydrocarbon compounds, which is characterised by that it includes the following: a) feeding water vapour with external supply of hydrogen gas and carbon dioxide gas into a first reverse conversion reactor, where the molar ratio of hydrogen gas to carbon dioxide gas is greater than one, in order to produce a first stream of synthetic gas which contains a mixture of at least carbon monoxide gas and hydrogen gas, water vapour and residual carbon dioxide gas; b) production of a second stream of synthetic gas from the first stream of synthetic gas through condensation and removal of at least a portion of water vapour from the first stream of synthetic gas; c) feeding the second stream of synthetic gas into a second water vapour reverse conversion reactor to produce a third stream of synthetic gas which contains a mixture of at least carbon monoxide gas and hydrogen gas, water vapour and residual carbon dioxide; d) production of a fourth stream of synthetic gas from a third stream of synthetic gas through condensation and removal of at least a portion of water vapour from the third stream of synthetic gas; and e) preparation of a mixture of at least hydrocarbon compounds from at least carbon monoxide gas and hydrogen gas from the fourth stream of synthetic gas. The invention also relates to a system for realising the said method.
EFFECT: use of the invention reduces power consumption on producing hydrocarbons from synthetic gas.
20 cl, 1 tbl, 32 dwg
SUBSTANCE: invention concerns application of chrome source as catalyst activator in combination with precipitated iron catalyst in high-temperature Fischer-Tropsch process for transformation of CO and H2 reagents into reaction products in the form of hydrocarbons and possible hydrocarbon oxygenates by contacting CO and H2 with chrome source combined with precipitated iron catalyst in the course of two-phase high-temperature Fischer-Tropsch reaction. Reaction is performed in reactor with fluidised layer, reactants and reaction products are in gas phase, and catalyst is in solid phase. Chrome source concentration in precipitated iron catalyst comprises 0.3-1 g of chrome per 100 g of iron. Beside chrome source, precipitated iron catalyst includes at least one additional catalyst activator. Also invention claims two-phase high-temperature Fischer-Tropsch process.
EFFECT: enhanced catalyst activity, reduced organic acid formation and methane concentration.
12 cl, 1 tbl
SUBSTANCE: present invention relates to a Fischer-Tropsch synthesis catalyst, a method of preparing the said catalyst and a hydrocarbon synthesis method. Described is a supported Fischer-Tropsch synthesis catalyst which contains catalytic material, a promoter and support material; where the catalytic material contains cobalt in amount of at least 4% of the mass of the catalyst and at least part of the cobalt has catalytic activity in Fischer-Tropsch synthesis; the promoter contains nickel in an amount less than the amount of cobalt; and the support material contains an oxide of a metal selected from aluminium, titanium or zirconium. A method is described for preparing the catalyst, where the support is impregnated with cobalt and nickel compounds, the impregnated composition is dried, annealed and activated. Also described is a hydrocarbon synthesis method in which synthetic gas is brought into contact with the catalyst described above.
EFFECT: increased activity, stability and selectivity of the catalyst.
34 cl, 2 tbl, 3 dwg
SUBSTANCE: method of obtaining synthetic liquid hydrocarbons from hydrocarbon gases involves catalytic vapour-carbon dioxide conversion of the starting material and recycled products with supply of high-grade heat and obtaining synthetic gas, catalytic processing of the synthetic gas using a Fischer-Tropsch method while tapping low-grade heat through evaporation cooling, division of products obtained from processing synthetic gas into three streams: a mixture of liquid hydrocarbons, water and exhaust gases, and subsequent division of the obtained mixture of liquid hydrocarbons into a fraction of commercial grade hydrocarbons (petrol, kerosene, diesel fuel) and C21+ hydrocarbons, distinguished by that starting gaseous material fed at constant pressure of 0.8-3.0 MPa after purification from sulphur compounds is divided into two streams, one of which together with a portion of waste gases from the Fischer-Tropsch synthesis reactor, carbon dioxide, extracted from exhaust flue gases, and water vapour, are fed into a radial-spiral catalytic reactor for vapour-carbon dioxide conversion, which is carried out at temperature 950-1050°C; the obtained synthetic gas is fed into a steam boiler as heating medium, after partial cooling in which the synthetic gas is further cooled to 20-40°C by an external coolant for moisture removal and is separated from moisture in a surface cooler - drier for synthetic gas, after which it is fed into a Fischer-Tropsch synthesis reactor, and the second stream of starting gaseous material is mixed with another portion of exhaust gases from the Fischer-Tropsch synthesis reactor and fed into the burner of the catalytic reactor as fuel, where before feeding into the burner, the said mixture and air necessary for combustion are heated in a heat recovery unit through partial cooling of flue gases coming out of the catalytic reactor, after which the flue gases are further cooled by an external coolant for moisture removal in the surface cooler-drier for flue gases, further carbon dioxide is removed from the flue gases and fed into the catalytic reactor for vapour-carbon dioxide conversion, flue gases cooled and purified from carbon dioxide are removed from the installation, and the condensate extracted in cooler-driers for synthetic gas and flue gases, and water obtained after separation of Fischer-Tropsch reaction products are purified in a water treatment unit and taken for steam generation, necessary for vapour-carbon dioxide conversion of the starting gaseous material, into a boiler in which the condensate is heated and evaporated using heat of the synthetic gas.
EFFECT: use of said method enable efficient realisation of the proposed method.
4 cl, 2 dwg
SUBSTANCE: invention relates to a reaction system with a bubble column type suspended layer in a Fischer-Tropsch synthesis reaction system for synthesis of liquid hydrocarbons by bringing synthetic gas consisting of hydrogen and carbon oxide into contact with catalyst particles, involving the following: (1) a Fischer-Tropsch synthesis reaction in a bubble column with a suspended layer, in which synthetic gas continuously supplied from the bottom of the reactor and suspended catalyst particles are brought into contact to obtain liquid hydrocarbons, gaseous hydrocarbons and water, (2) a process where the suspension of suspended liquid products formed during Fischer-Tropsch synthesis and catalyst particles move from the reactor to the bottom part of the container for separation through a moving pipe inclined downward for separating catalyst particles and liquid products, (3) a process where gaseous products formed during Fischer-Tropsch synthesis are directed to the top part of the container for separation through a connecting pipe fitted on top of the moving pipe which is inclined downwards, and comes out of from the top, (4) a process where liquid products are extracted from the container for separation, and (5) a process where the suspension in which catalyst particles are concentrated is extracted from the bottom of the container for separation and circulated to the bottom of the reactor, moved by the moving force (gaslift) of the synthetic gas fed from the bottom of the reactor, and rises upwards through the reactor with the suspended layer without using an external source of moving force for circulation, and the formed liquid hydrocarbon products, gaseous hydrocarbon products and water are separated and extracted without using an external source of moving force for separation, where in the container for separation, which is connected to the reactor by the moving pipe inclined downwards and has a line for circulating the suspension which circulates the suspension with the concentrated catalyst in form of particles into the reactor, the speed of the rising liquid inside the container for separating is controlled so that it is 0.4 or less of the rate of sedimentation of the catalyst in form of particles with particle diametre of 20 mcm using a control valve for outlet of the suspension with the concentrated catalyst, fitted on the line for circulating the suspension between the container for separation and the reactor, a control valve for outlet of liquid reaction products coming from the container for separation, and a differential pressure valve in the upper space of the gas phase between the container for separation and the reactor, where concentration of the catalyst ranges from 10 to 40 wt % and speed of movement of the suspension ranges from 0.4 to 1.6 m/s. The invention also relates to a Fischer-Tropsch synthesis installation.
EFFECT: use of the invention simplifies the operating system used for synthesis of liquid hydrocarbons through Fischer-Tropsch synthesis.
11 cl, 2 ex, 1 tbl, 1 dwg
SUBSTANCE: described is a catalyst used in a synthetic gas conversion process, where the said catalyst contains: a) a substrate formed from a composite spinel structure with formula MxM'(1-x)Al2O4/Al2O3●SiO2, where x varies from 0 to 1 exclusively, or with a simple spinel structure with formula MAl2O4/Al2O3●SiO2 in which M and M' are different metals selected from a group consisting of: magnesium, copper, cobalt, nickel, tin, zinc, lithium, calcium, caesium and sodium, and Al2O3●SiO2 is the chemical formula of aluminium silicate, where the said substrate is burnt in at least a partially oxidative atmosphere at temperature ranging from 850°C to 900°C, b) an active phase deposited on the said substrate containing one or more group VIII metals selected from cobalt, nickel, ruthenium or iron. The said catalyst is used in a fixed bed or in a suspension in a three-phase reactor for synthesis of hydrocarbons from a mixture containing carbon monoxide and hydrogen.
EFFECT: increased activity of the catalyst, its hydrothermal stability and resistance to mechanical wearing.
10 cl, 9 ex, 3 tbl
SUBSTANCE: invention relates to a method of recycling wastes from catalytic epoxidation of olefins using organic hydroperoxides, which involves extraction and treatment of the heavy epoxidate fraction with an alkali solution and treatment of the resultant spent alkaline stream with an extractant. The invention proposes addition of a ligand which forms a molybdenum organometallic complex to the spent alkaline stream and extraction from the spent alkaline stream of a fraction containing propylene glycol, acetophenone, ethylbenzene, phenol, methyl phenyl carbinol and the molybdenum organometallic complex formed, treatment with an extractant at T≥Tcr and P≥Pcr with subsequent splitting of the extract into fractions through stepped reduction of pressure from Pextr to P<Pcr with number of pressure reduction steps equal to the number of fractions of the components which should be obtained, taking into account the molybdenum organometallic complex, where Tcr, Pcr are critical temperature and pressure values of the extractant and Pextr is extraction pressure.
EFFECT: maintaining high degree of extracting molybdenum from the spent alkaline stream regardless of its composition and possibility of extracting fractions of components contained in the spent alkaline stream.
1 dwg, 3 tbl, 8 ex
SUBSTANCE: method involves treatment of heavy olefin fraction by an alkali solution, processing of obtained discharge alkali flow by extragent, and further precipitation of molybdenum trisulfide by precipitator. According to invention, sodium hydrosulfide is applied as molybdenum trisulfide precipitator. The method allows regulation of molybdenum trisulfide precipitator feed, reduction of precipitation reactor dimensions and energy consumption of heating and stirring, significant reduction waste and hydrogen sulfide discharge at high molybdenum extraction degree of 90.5-97.6%.
EFFECT: improved method of molybdenum extraction from products of catalytic olefin epoxidation by organic hydroperoxides.
FIELD: industrial organic synthesis.
SUBSTANCE: molybdenum is recovered from catalytic olefin epoxidation products using organic hydroperoxides. Method comprises treating heavy epoxidate fraction with alkali solution, treating resultant spent alkali stream with extractant, and subsequent precipitation of molybdenum trisulfide using sulfur-alkali effluents formed in production of olefins by pyrolysis of hydrocarbon feedstock.
EFFECT: increased molybdenum recovery degree and simplified operation.
FIELD: oil-and-gas production.
SUBSTANCE: invention related to oil-and-gas production, particularly to crude oil refinery with low temperature initiated cracking, and can be use for distilled motor fuel production increase. The method includes of oil residue processing into distillate fraction by adding catalyst followed by thermal-cracking, as a catalyst use ashes micro sphere magnetic fractions d from heat and power plants in a quantity 2.0-20.0% wt, containing 40.0-95.0% wt, iron oxide (III), with micro sphere diametres 0.01-0.60 mm, tempered at 600-800°C, process itself to be executed at temperature 400-500°C.
EFFECT: increase in distilled fractions total outcome up to 58,0% wt with the temperature up to 350°C, outcome of gasoline fractions up to 18,0% wt (with the temperature up to 200°C).
1 cl, 1 tbl, 7 ex
SUBSTANCE: invention refers to the field of organic synthesis, namely to the preparation of butyraldehyde from synthesis gas and propylene by the method of oxo process (called also propylene hydroformylation process), particularly to the cobalt regeneration of cobalt sludge. The described method involves the regeneration of the cobalt from cobalt-containing sludge forming in oxo process with usage of cobalt dicarbonyl as catalyst by the way of sludge treatment by the high-boiling organic acid with stirring at elevated temperatures, preferably 190-220°C at the ratio acid: sludge equal 10-20 during no less than 4 hrs.
EFFECT: simplifying of the technology of cobalt sludge regeneration and implementation of the regeneration stage directly on the hydroformylation plant.
3 cl, 3 tbl, 1 ex
SUBSTANCE: invention refers to the method of the reduction of hydrogenisation catalyst by the way of serial operations of 1) hydrocarbon desorption from the surface of the spent catalyst located in the stationary layer in the media of hydrogen-containing gas at temperature 200-400°C; 2) passivation of the catalyst surface by its treatment with oxygen-containing gas (oxygen content is 0.02-0.5 vol. %) in the stationary layer at temperature 100-120°C; 3) burn-off of the hydrocarbon condensation products in the oxygen-containing gas flow at temperature 400-550°C; 4) catalyst conversion from oxide to presulphide form by their contacting with elemental sulphur in the air or inert gas flow. The burn-off of the hydrocarbon condensation products and catalyst transforming are implemented in the moving-bed catalyst with burn-off temperature being regulated with the oxygen-containing gas temperature and volume ratio oxygen-containing gas :catalyst in the range (15-30):1.
EFFECT: reduction of the hydrogenisation catalyst with minimal destruction losses of the catalyst.
3 cl, 5 tbl, 2 ex, 2 dwg
SUBSTANCE: invention concerns method of hydrotreating catalyst activation containing metal oxide of group VIB and metal oxide of group VIII containing contacting catalyst, acid and organic additive with boiling point within 80-500°C and water solubility, at least, 5 gram per litre (20°C, atmospheric pressure), optionally with following drying in the environment providing at least, 50% of the additive remains in the catalyst. There are disclosed hydrotreating catalyst produced by the method described above, and method of hydrotreating raw hydrocarbons there after applied.
EFFECT: higher activity of both raw hydrotreating catalyst, and utilized hydrotreating catalyst being regenerated.
20 cl, 8 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention, in particular, relates to catalysts based on nickel, cobalt, molybdenum, aluminum oxides. Regeneration of exhausted catalyst is carried out through heat treatment in air atmosphere at 550-600°C for 1-1.5 h followed by: mechanical activation at energy concentration at least 6.6 W/g on vibrational mill; grinding into powder; adding at stirring a mixture containing nitric acid solution (concentration 3,5-7%), cobalt or nickel nitrate and ammonium paramolybdate; molding; drying; and calcination.
EFFECT: simplified regeneration procedure and enabled restoration of catalyst strength.
1 tbl, 12 ex
FIELD: oxidation catalysts.
SUBSTANCE: invention relates to manufacture of heterogeneous catalysts for the processes of liquid-phase oxidation of inorganic and/or organic compounds, including sulfur-containing ones, with air oxygen. Invention provides heterogeneous catalyst containing (i) active component (15-50%) on polymer carrier, namely polyethylene, polypropylene, polystyrene or another polymer, said active component being variable-valence metal oxides and/or hydroxides, or spinels, and additionally (ii) modifying additive (0.5-20%), namely organic bases and/or heteropolyacids, and/or carbon-containing material.
EFFECT: increased catalytic activity.
2 cl, 5 tbl, 6 ex