Method of hydrotreating catalyst activation

FIELD: chemistry.

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

 

The invention relates to a method for activating Hydrotreating catalyst. The Hydrotreating catalyst, which is subjected to activation can be either fresh Hydrotreating catalyst, or the catalyst for Hydrotreating, which has already been used and regenerated. The present invention relates to Hydrotreating catalyst obtained in the mentioned method, and its application for Hydrotreating.

Usually, the catalytic hydrotreatment of hydrocarbon raw material is the removal of impurities. The usual impurities are sulfur compounds and nitrogen compounds. Removing at least a portion of such impurities from raw materials ensures that the combustion of the final product will be less likely to stand out oxides of sulfur and/or nitrogen oxides that are harmful to the environment. In addition, sulfur compounds and nitrogen compounds are poisons for many of the catalysts used in industry for the conversion of raw materials into finished products.

Examples of such catalysts include catalytic cracking, catalytic hydrocracking, and catalytic reforming. Therefore, usually the raw material is subjected to catalytic hydrofining before processing, for example, in cracking unit.

Catalytic Hydrotreating process comprises contacting the feedstock with hydrogen at a selected temperature and pressure in the presence of a catalyst hydro is clean. In this process, compounds of sulfur and nitrogen compounds present in raw materials, turn them into easy to remove hydrogen sulfide and ammonia.

Generally, the Hydrotreating catalysts consist of a carrier coated with a component of a metal of group VI and a metal component of group VIII. The most commonly used VI group metals are molybdenum and tungsten, while cobalt and Nickel are typical metals of group VIII. The catalyst may also contain phosphorus. Known in the art methods of obtaining these catalysts are characterized by the fact that the material of the carrier injected components used for the hydrogenation metals, for example, by impregnation, after which the composite is calcined to convert the metal components in the oxides. Before applying for Hydrotreating catalysts are usually subjected to preliminary solifidian for the conversion used for the hydrogenation metal sulfides.

Since the requirements in respect of the legal contents of sulfur and nitrogen in fuels are becoming increasingly more stringent, there is a continuing need in the Hydrotreating catalysts with increased activity. In addition, in this final sulfur content of more active catalyst will be able to conduct the process in a more mild conditions (energy saving) or to increase the resource work rolled atora between regenerations (cycle length).

In the patent application WO 96/41848 described the way in which the Hydrotreating catalyst containing oxide used for the hydrogenation metal of group VIII and the oxide used for the hydrogenation of group VI metal on a carrier, activate as a result of its contact with the additive which is at least one compound selected from the group of compounds containing at least two hydroxyl groups and 2-10 carbon atoms and complex (poly)ethers of these compounds, after which the catalyst is dried under such conditions that the additive mainly remains in the catalyst. The additives described in this reference include sugar and various esters and polyesters. The catalyst may be either fresh (unused) catalyst or used catalyst which has been regenerated.

In the patent application WO 01/02092 describes how the regeneration and activation of the used catalyst containing the additive, by contact with oxygen-containing gas at a maximum temperature of 500°C with subsequent activation by contact with an organic additive, if necessary, followed by drying at a temperature at which at least 50% of the additive remains in the catalyst. Preferred additives described in this reference are additive selected from the group when joining, containing at least two oxygen-containing fragment and 2-10 carbon atoms and compounds constructed from these compounds. Cited examples include acids, aliphatic diatomic alcohols, their esters, sugars, N-containing compounds.

It was found, however, that the method described in these references can be improved if the catalyst is activated by a combination of acid and special additives. Accordingly, the present invention relates to a method for activating Hydrotreating catalyst containing an oxide of a metal of group VIB and a metal oxide of group VIII, which contains the contacting of the catalyst with an acid and an organic additive having a boiling point in the range of 80-500°C and a solubility in water of at least 5 grams per liter (20°C, atmospheric pressure), optionally followed by drying under such conditions, when at least 50 wt.% additives (relative to the total initial amount) is stored in the catalyst. The method of the present invention is suitable not only for activation of fresh Hydrotreating catalyst, but also for activation of the catalyst, which was already used for Hydrotreating of hydrocarbons.

The inventors have found that from the viewpoint of obtaining high activity of the reactivated catalyst, preferably, in the way that the image is etenia activated Hydrotreating catalyst contains crystalline fraction (defined as the weight of the crystalline compounds of the metals of group VIB and group VIII relative to the total weight of the catalyst) less 5 wt.%, more preferably less than 2.5 wt.%, even more preferably below 1 wt.% and most preferably below 0.5 wt.%. Best of all, if activated Hydrotreating catalyst contains almost no crystalline fraction. Crystalline compounds can be single crystalline compound or a mixture of various crystalline compounds. For example, in the case cobaltmolybdenum catalyst was found that the active metals for Hydrotreating can crystallize in alpha cobalt molybdate (α-CoMoO4). Depending on what metals are part of the Hydrotreating catalyst may be formed of various crystalline compounds, such as Nickel molybdate, tungstate, cobalt tungstate, Nickel, mixtures thereof, or can be found a mixture of crystals of metals. The crystalline fraction can be registered by x-ray diffraction.

It was found that the advantages of the method of the invention can be obtained not only in the case of the used regenerated catalyst, but also in the case of fresh Hydrotreating catalysts. In particular, for fresh Hydrotreating catalysts, which have been subjected to annealing, it is possible to achieve a significant increase in activity when using the activation method of the invention. In calcined St is the Polish Hydrotreating catalysts was found significant crystalline fraction, in particular during annealing at temperatures above 350°C, or even in this case, when progulivali at temperatures above 400°C, above 450°C or above 500°C. Very good increase in activity can be obtained when the method of the invention fresh Hydrotreating catalyst contains crystalline fraction in the amount of at least 0.5 wt.%, preferably at least 1 wt.%, more preferably at least 2.5 wt.% and most preferably at least 5 wt.%.

The invention also relates to Hydrotreating catalysts obtained using the methods described above, in particular to the Hydrotreating catalyst containing the oxides of metals of group VIII and group VI, which further comprises an acid and an organic additive having a boiling point in the range of 80-500°C and a solubility in water of at least 5 grams per liter (20°C, atmospheric pressure). Preferably, the catalyst was regenerated used catalyst or fresh calcined catalyst, which is preferably contained crystalline fraction in the amount less than 5 wt.%, more preferably less than 2.5 wt.%, most preferably less than 1 wt.% (expressed as a weight fraction of crystalline compounds of metals of group VIB and metals of group VIII relative to the total weight of the catalyst).

In PA entei application EP-A-0601722 described a method of producing the catalyst by impregnation substance carrier, alumina, a solution containing components of the metals used for Hydrotreating, phosphoric acid and organic additives, followed by drying at a temperature below 200°C to prevent decomposition or evaporation of the additives. This method does not apply to activate fresh or used and regenerated Hydrotreating catalyst. In this way active when the Hydrotreating metals caused by the presence in the solution for impregnation with phosphoric acid, with which they form a complex, and organic additives. Surprisingly, used and regenerated or fresh catalyst Hydrotreating, in which the metals used for Hydrotreating, has already been done, can be activated by acid and organic additives with specific values of the boiling point and solubility.

The starting material for the method of the invention is a Hydrotreating catalyst containing the oxides used for the hydrogenation of VIII group metals and oxides used for the hydrogenation of metals of group VI, hereinafter referred to as oxide catalyst.

Typically, at least 80% of all used for the hydrogenation metals of group VIII and group VI present in the catalyst are in the oxide form, preferably at least 90%, more preferably at least 95%, and even more pre is respectfully, at least 98%. The percentage of metals present in the catalyst in the oxide form, can be determined by the method of x-ray fluorescence analysis (RFSA) or spectroscopy with inductively coupled plasma (ISPS). The percentage is the ratio of the weight content to the total weight of the metals.

The oxide catalyst Hydrotreating, used as starting material in the method of the invention can thus be oxidic Hydrotreating catalyst obtained by the method in which the components used for the hydrogenation metals add to the media, after which the composite material is subjected to a stage of annealing to convert the components used for the hydrogenation metals into their oxides. However, it can be used Hydrotreating catalyst which has been regenerated by removal of coke. In this case, the catalyst prior to its first use could contain or may not contain additives.

The original catalyst contains an oxide of a metal of group VIII and a metal oxide of a group VI, usually on the media. Of the metals of group VI may be mentioned molybdenum, tungsten and chromium, and preferred are molybdenum and tungsten. Molybdenum is particularly preferred. The metals of group VIII include Nickel, cobalt and iron. PR is doctitle are Nickel and cobalt, and combinations thereof. The catalyst typically contains a metal in the range of from 0.1 to 50 wt.%, considering the ratio of the weight of the oxide to the total weight of the catalyst. Component of group VI metal is usually present in amounts of 5-40 wt.%, per trioxide, preferably 10-35 wt.%, more preferably 15-30 wt.%. Component metal of group VIII is usually present in the amount of 1-10 wt.%, preferably 2-8 wt.%, in the calculation of the oxide. If necessary, the catalyst may contain other components such as phosphorus, halogen and boron. Especially, it may be preferable to the presence of phosphorus in the amount of 1-10 wt.%, in the calculation of the P2O5to improve the activity of the catalyst in the Hydrotreating from nitrogen-containing compounds.

The catalyst carrier can contain conventional oxides such as aluminum oxide, silicon oxide, aluminium silicate, aluminium oxide with dispersed therein aluminum silicate, aluminum oxide coated with silicon oxide, magnesium oxide, zirconium oxide, boron oxide and titanium oxide as well as mixtures of these oxides. Generally, the preferred carrier based on alumina, aluminosilicate, aluminum oxide with dispersed therein aluminum silicate or alumina-coated silica.

Particular preference is given to aluminum oxide and the aluminum oxide containing up to 10 wt.% silicon oxide. The media content is a broad transition alumina, for example, this-, theta-, or gamma-aluminum oxide, is preferred in this group, and the media on the basis of gamma-alumina is the most preferred.

The pore volume of the catalyst (as measured by the mercury penetration, the contact angle of 140°and a surface tension of 480 Dyne/cm) is not determinative for the method of the invention and is typically a value from 0.2 to 2 ml/g, preferably 0.4 to 1 ml/g, the specific surface is not critical to the method of the invention and typically has a value of from 50 to 400 m2/g (measured by the method of Brunker, Emmett and teller, BET-method). Preferably, the catalyst had an average diameter of pores in the range of 7-15 nm, determined by the method of mercury porosimetry, and at least 60% of the total pore volume was the deviation from the average diameter in the range of 2 nm.

Usually the catalyst is used in the form of spheres or extrudates. Examples of suitable types of extrudates are disclosed in the literature (see, among others, U.S. Patent 4028227). Very easy to use particles of cylindrical shape (which may be hollow or solid), as well as symmetric and asymmetric particles in the form of multiple lobes (2, 3 or 4 petals).

In the method of the invention the oxidized catalyst for Hydrotreating in contact with the acid and an organic additive of temperaturas boiling in the range of 80-500°C and a solubility in water, at least 5 grams per liter.

Acid and the additive is introduced into the catalyst in liquid form as a result of impregnation. For acid, this usually means that it is dissolved. For supplements, the presence or absence of solvent will depend on its properties. If the additive has sufficient fluidity to penetrate into the pores of the catalyst without the presence of a solvent, it is possible to do without solvent. However, typically, the solvent will be used. The solvent is typically water, although other compounds such as methanol, ethanol and other alcohols, can also be employed for this purpose depending on the nature of the additive and acid.

In the preferred implementation of the method of the invention, the catalyst is subjected to the aging stage after the introduction of the acid. Stage aging is carried out until the catalyst is still wet, that is, before removing the solvent from the catalyst. It was found that the stage of aging especially gives a positive effect when the catalyst has been used for Hydrotreating of hydrocarbons, subject to reactivation. The aging time used at the stage of aging, is a function of temperature. Usually the ageing time decreases with increasing temperature aging. Stage of aging usually requires at least 15 minutes. After opredelennosti, for example, after 48 hours, no additional increase in activity is observed. If the stage of aging is carried out at a temperature from 0 to 50°C, the aging time is usually at least 1 hour, preferably at least 2 hours, more preferably at least 6 hours. If the stage of aging is carried out at temperatures above 50°C, the aging time is usually at least 0.5 hours, preferably at least 1 hour, more preferably at least 2 hours. It is also possible to carry out the stage of aging at temperatures above 100°C under hydrothermal conditions for 15 minutes. Stage of aging can also be carried out by heating the catalyst currents of ultra-high frequency or induction heating. Preferably, the catalytic composition was subjected to aging in a period of time sufficient to reduce the content of the crystalline fraction below 5 weight percent, more preferably less than 2.5 wt.%. In addition, it was found that the ageing time can be significantly reduced and/or can be achieved much better results, if the method of the invention the concentration of the acid is at least 5 wt.%, preferably at least 7 wt.%, most preferably at least 10 wt.% (relative to the total weight of the catalyst is).

If for supplementation and/or acid catalyst was used, the solvent, the catalyst can be dried after impregnation stage to remove at least part of the solvent, usually at least 50%, preferably at least 70%, more preferably at least 80% (in weight percent relative to the original weight compounds). For the method of the invention it is important that any stage of drying was carried out so that at least part of the additive remained in the catalyst. Therefore, the catalyst is not calcined. So that the drying conditions depend strongly on the temperature at which the specific additive boils or decomposes. In the context of the present invention stage of drying should be carried out under such conditions that at least 50%, preferably 70%, more preferably 90% of the additive introduced into the catalyst by impregnation stage, is still present in the catalyst after the stage of drying. Of course, it is preferable to maintain the catalyst as much as possible the amount of additive on the stage of drying, but for the more volatile compounds is not always possible to avoid evaporation. Stage of drying may, for example, be carried out in air, under vacuum or in an atmosphere of inert gas. It is usually better to maintain the temperature below 220°C, although, depending on the nature of the additive, can onover the beat use of a higher or lower temperature.

Acid and the additive can be introduced into the catalyst simultaneously or sequentially and in any order.

In one embodiment, the initial material in contact with the acid solution, not necessarily followed by drying. Then introduced into the catalyst organic additive, not necessarily with the subsequent stage of drying under such conditions that at least 50% of the additive remains in the catalyst (in weight percent relative to the original weight compounds). If this embodiment, conducting stage of aging, it may be held before or after the organic additive is introduced into the catalytic composition.

In another embodiment, the first stage organic additive is introduced into the source material, optionally followed by a stage of drying under such conditions, when at least 50% of the additive remains in the catalyst. Then, the resulting material is in contact with the acid solution, optionally followed by a stage of aging and/or drying under such conditions that at least 50% of the additive remains in the catalyst.

The advantage of introducing acid and additives in the catalyst at various stages is that the properties of the impregnating solutions can be chosen based on the properties of acids and additives. However, for reasons of effective the particular preferably contacting the initial catalyst with a single impregnating solution, containing and acid, and an additive, optionally with a further stage of aging and/or drying under such conditions that at least 50% of the additive remains in the catalyst.

The acid may be inorganic or organic acid. To inorganic acids include acid components that do not contain a carbon atom. Examples of inorganic acids include HCl, H2SO4, HNO3H3PO4, (NH4)H2PO4, (NH4)2HPO4H2PHO3H2P2H2O5and H(n+2)PnO(3n+1). Within the group of inorganic acids are preferred phosphorus-containing acid as the phosphorus itself can have a positive effect on the activity of the Hydrotreating catalyst. H3PO4it is especially preferred.

One disadvantage of using inorganic acids is that in the catalytic composition is introduced counterion such as chloride, sulfate or nitrate. If the activation method of the present invention to be repeated several times, it can lead to undesirable accumulation of counterions in the catalytic composition. However, depending on the nature of the counterion and the number envisaged stages of regeneration, this might not be a problem. Organic acids are preferred, the AK as they do not have the above disadvantage.

In the context of the present description of the invention under understand organic acid compound containing at least one carboxyl group (COOH). Organic acid usually is a carboxylic acid containing at least one carboxyl group and 1 to 20 carbon atoms (including the carbon atoms in the carboxyl group). Suitable acids include acetic acid, citric acid, malic acid, maleic acid, formic acid, glycolic acid, hydroxypropionic acid, hydroxybutiric acid, hydroxycitronellal acid, tartaric acid, glyceric acid, gluconic acid, oxalic acid, malonic acid, polyacrylic acid, ascorbic acid and N-containing acids, such as EDTU, CDU (1,2,-cyclohexanedicarboxylate acid) and so on. Within this group, compounds containing at least two carboxyl groups, are preferred. Considerations of cost and activity preferred are citric acid, malic acid, maleic acid, malonic acid and tartaric acid. Citric acid is particularly preferred.

The organic additive used in combination with the acid in the method of the invention, is an organic compound, namely a compound containing at least one carbon atom and at least one hydrogen atom, with a boiling point in the range of 80-500°C and a solubility in water of at least 5 grams per liter at room temperature (20°C) (atmospheric pressure). Preferably, the additive was oxygen - or nitrogen-containing compound.

Preferably, the boiling point of the additive was in the range of 100-400°C, more preferably 150-350°C. the boiling point of the additive must satisfy, on the one hand, the desire to Supplement remained on the catalyst during its preparation, including the stage of drying, and on the other hand, the necessity of removing the additive from the catalyst when the catalyst or sulfatirovaniu. If the organic additives no boiling point, and she instead decomposes at a certain temperature range, the term boiling point means the same as the temperature of the composition.

The solubility of the additive is at least 5 grams per liter at room temperature, preferably at least 10 grams. It should be noted that the requirements for the solubility of the additives have a double meaning. First of all compounds that satisfy this requirement solubility, suitable for use in impregnating solutions.

In addition, it is obvious that compounds that satisfy oraut these requirements solubility, one way or another interact with components of the metals present in the catalyst, leading to increased activity of the final product.

Under this definition can be considered different groups of additives.

First, preferred at the present time, the group of additives is a group of organic compounds containing at least two oxygen atoms and 2 to 20 carbon atoms, preferably 2-10 carbon atoms, and compounds constructed from these compounds. Organic compounds selected from the group of compounds containing at least two oxygen-containing fragment, such as carboxyl, carbonyl or hydroxyl fragments, and 2-10 carbon atoms, and compounds constructed from these compounds, are preferred. Examples of suitable compounds include butanediol, pyruvic aldehyde, glycol aldehyde and 3-hydroxybutanal. In the currently preferred within this group is given additive, which is selected from the group of compounds containing at least two hydroxyl groups and 2-10 carbon atoms in the molecule, and a complex (poly)ethers of these compounds. Suitable compounds of this group include aliphatic alcohols, such as ethylene glycol, propylene glycol, glycerin, trimethylacetyl, trimethylolpropane and so on. Clonality these compounds include diethylene glycol, dipropyleneglycol, triethyleneglycol, triethylene glycol, tributylamine, tetraethylene glycol, tetraethyleneglycol. This group can be extended to include polyesters, such as polyethylene glycol. Other esters which are suitable for use in the present invention include monobutyl ether of ethylene glycol, onomatology ether of diethylene glycol, monotropy ether of diethylene glycol, monopropylene ether of diethylene glycol and monobutyl ether of diethylene glycol. Preferred are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropyleneglycol and polyethylene glycol with a molecular weight of from 200 to 600.

Another group of compounds containing at least two hydroxyl groups and 2-10 carbon atoms in the molecule, are sugars. Preferred saccharides include monosaccharides such as glucose and fructose. Their esters include disaccharides, such as lactose, maltose and sucrose. Polyesters of these compounds include polysaccharides. Preferably, organic compounds of this group were mainly saturated, which is characterized by the value of iodine number less than 60, preferably less than 20.

The second group of organic additives suitable for use in the present invention, the two who are those compounds which contain at least one covalently linked to the nitrogen atom and at least one carbonyl fragment. Preferably, this type of organic compounds containing at least two carbonyl fragment. Preferably, at least one carbonyl fragment contained in the carboxyl group. In addition, it is preferable that at least one atom of nitrogen was covalently linked to at least two carbon atoms. Preferred organic compound corresponds to the formula (I) or (II)

(R1R2)N-R3-N(R1'R2')(I)
N(R1R2R1')(II)

Where R1, R2, R1' and R2' are independently selected from alkyl, alkenyl and allyl, with the number of carbon atoms up to 10, optionally substituted by one or more groups selected from carbonyl, carboxyl, ester, ether, amino or amido. R3 is alkalinous group with the number of carbon atoms up to 10, which may alternate with-O - or-NR4-. R4 are selected from the same groups as the above R1. Allenova group R3 may be substituted by one or more groups selected from carbonyl, carboxyl, ester, ether, amino or amido. As it was already fitted the but higher it is important that the organic compound of the formula (I) or (II) contain at least one carbonyl fragment.

Preferably, at least two of R1, R2, R1' and R2' groups of formula (I)and at least two of R1, R2 and R1' groups (formula (II)) had the formula-R5-COOX, where R5 is alkalinous group having 1-4 carbon atoms, and X is a hydrogen or another cation, such as ammonium cation, sodium, potassium and/or lithium. If X is a multivalent cation, one X can connect to two or more R5-COO-groups. Typical examples of the compounds of formula (I) are Ethylenediamine(Tetra)acetic acid (EDTU), hydroxyethylnitrosamine acid and diethylenetriaminepentaacetic acid. A typical example of the compounds of formula (II) is nitrilotriacetate acid (NTU). Based on the requirements of the preferred solubility can be salts of these compounds.

It should be noted that the above description of organic additives include various acidic components. Where in the context of the present invention discussed the combination of acid and an organic additive, this means that (at least) use two different compounds, of which one is an acid and the second meets the requirements of solubility and boiling point, applicable to organic additive. Deuteronomy is the fifth connection can be acid, and it might not be.

From the point of view of environmental protection, it is preferable to use supplements that contain virtually no sulfur. In addition, sulfur-containing additives are usually not stable with respect to oxygen. So if you had used a sulfur-containing additives, all subsequent stages of the method would have to carry out in an inert atmosphere. For this reason, it is also preferable to use additives that do not contain sulfur. This applies to both acid and an organic additive.

As an additive can be used as a single compound or combination of compounds.

The total amount of acid and additives used in the method of the invention, and the total amount of acid and additives present in the catalyst of the invention is at least 0.01, preferably at least to 0.05, more preferably at least 0.1 mol of the sum of the acid and the additive per mole of the sum of the metals of group VIB and group VIII. Typically, the molar ratio is not more than 3, preferably no more than 2.

If you are using an inorganic acid, the acid number is usually from 0.01 to 1 mole per mole of the sum of the metals of group VIB and group VIII, preferably from 0.05 to 0.5 mole per mole of the sum of the metals of group VIB and group VIII.

If you are using an organic acid, the amount of acid obychnoystali from 0.01 to 1 mole per mole of the sum of the metals of group VIB and group VIII, preferably from 0.05 to 0.5 mole per mole of the sum of the metals of group VIB and group VIII.

The amount of organic additives is generally from 0.1 to 2.5 mole per mole of the sum of the metals of group VIB and group VIII, preferably from 0.15 to 1 mole per mole of the sum of the metals of group VIB and group VIII, more preferably from 0.2 to 1 mole per mole of the sum of the metals of group VIB and group VIII.

The molar ratio of acid to Supplement is usually 0.01-10:1, preferably 0.1 to 5:1, more preferably 0.15 to 3:1.

Usually, if you add the total amount of acid and the additive is too low, the positive effect of the invention will not be achieved. On the other hand, adding too much of the total amount of acid and supplements will not improve the effect of the present invention. For the specialist in this area it is obvious that the exact amount of acid used and the additive in a particular situation will depend on various parameters, including the metal content in the catalyst pore volume of the catalyst and the distribution of their size, the nature of the acid and additives used solvent for impregnating solutions, the conditions of impregnation, and so forth. For the specialist in this area it is obvious that you should take into account the above variables when determining the optimal amounts used acid and additives in each specific lyrics by the tea.

The present invention also relates to a Hydrotreating catalyst that contains a metal oxide of group VIII and a metal oxide VI group on the carrier and which further comprises an acid and an organic additive, as described above.

Dried containing the additive of the Hydrotreating catalyst of the present invention may be subjected under sulfatirovnie before it will be used for Hydrotreating of hydrocarbons, but, as has been explained previously, this is not necessary. If you decide to sulphydrate the catalyst prior to its use, it can be done in one of known in the art by the way. For example, you can contact the catalyst with an inorganic or organic sulfur compounds such as hydrogen sulfide, elemental sulfur or organic polysulfides, or sulfidizing the catalyst as a result of its contact with hydrocarbons, to which was added sulfur compound. All these methods are known to the expert as sulfatirovnie or preliminary sulfatirovnie catalyst.

The catalysts of the present invention can be used for Hydrotreating of various kinds of raw materials to implement one or more operations hydrodesulfurised, gidrogenizirovanii and hydrodearomatization. Examples of suitable materials include the with middle distillates, kerosene, naphtha, vacuum gas oils and heavy gas oils. The catalyst is particularly suitable for very deep hydrodesulfurised, such as hydrodesulfurised with sulfur content in the final product below 200 ppm, most often with a sulfur content in the final product below 50 ppm. This can be used in normal conditions of implementation of this method, such as a temperature in the range of 250-450°C, a pressure in the range of 5-250 bar, a space velocity in the range of 0.1 to 10 h-1and the relation of H2/oil in the range of 50-2000 nl/L.

As mentioned above, the catalyst in the method of the invention are activated, or is fresh Hydrotreating catalyst or regenerated catalyst Hydrotreating.

Fresh oxide catalysts for Hydrotreating, suitable for use as starting material in the method of the invention known in the art. They can be obtained, for example, as follows. The predecessor of the media receive, for example, in the case of aluminum oxide in the form of Almohades (boehmite). After it is dried or not, for example, by spray drying, it is formed into particles, for example, by extrusion.

These particles are calcined at a temperature in the range from 400 to 850°C, receiving in the case of aluminum oxide carrier containing transition of the aluminum led, for example, in the form of gamma, theta - or ETA-alumina. Then put on a catalyst, for example, in the form of aqueous solutions of the appropriate number of precursors used for the hydrogenation metals and other optional components, such as phosphorus. In the case of group VI metals and metals of group VIII of the predecessors can be ammonium molybdate, tungstate ammonium, nitrate of cobalt and/or Nickel nitrate. Respective predecessors phosphate component include phosphoric acid and various substituted ammonium phosphate. After an optional stage of drying at a temperature in the range of 25-200°C, the resulting material is calcined at a temperature in the range of 350-750°C, more specifically from 425 to 600°C, to convert all predecessors of the component metals and precursors optional other components in the oxide form component.

For professionals it is obvious that there are many variants of this method. For example, you can apply multiple impregnation used impregnating solutions containing one or more of the applied precursor component or part. Instead of the methods of impregnation may apply methods of dipping, spraying methods, and so forth. When multiple impregnation, immersion, and so on drying and/or calcination may be conducted in which Romareda between stages of impregnation. Alternatively, precursors of one or more components can be mixed in whole or in part with the carrier to stage molding. In this embodiment, the material of the precursor component or part thereof may be deposited on another neoformans material media, such as a powder, for example, by impregnation, followed by a stage of forming. As a variant, it is possible to mix one or more precursor components are fully or partially with material media, better at the stage of formation than before. Methods that are suitable for this method are joint briquetting and joint extrusion. This method is recommended as a precursor component of a metal of group VIB of the molybdenum trioxide.

Oxidized Hydrotreating catalysts and methods for their preparation, in principle, known to the expert and are described, for example, in U.S. Patent 4738767, U.S. Patent 4062809, U.S. Patent 4500424, the United Kingdom Patent 1504586, U.S. Patent 4212729, U.S. Patent 4326995, U.S. Patent 4051021, U.S. Patent 4066574, European patent A 0469675.

The activation method of the present invention is also applicable to the catalyst, which was already used for Hydrotreating of hydrocarbons and then regenerated.

The present invention also relates to the United way of regeneration is activated used Hydrotreating catalyst, used in which the Hydrotreating catalyst containing a metal oxide of group VIB and a metal oxide of group VIII, is first subjected to a stage of regeneration to remove carbonaceous and sulphurous deposits and subsequent activation of the thus obtained material in the contacting it with an acid and an organic additive, which has a boiling point in the range of 80-500°C and a solubility in water of at least 5 grams per liter (20°C, atmospheric pressure).

Stage regeneration method of the invention is carried out by contacting the used catalyst containing the additive, with the oxygen-containing gas under such conditions, in which after regeneration of the carbon content in the catalyst is usually less than 3 wt.%, preferably less than 2 wt.%, more preferably less than 1 wt.%. After regeneration of the sulfur content in the catalyst is typically less than 2 wt.%, preferably below 1 wt.%. To the stage of regeneration of the carbon content in the catalyst is more than 5 wt.%, usually from 5 to 25 wt.%. The sulfur content in the catalyst to the stage of regeneration is usually more than 5 wt.%, usually from 5 to 20 wt.%.

The maximum temperature of the catalyst at the stage of regeneration is determined by the properties of the regenerated catalyst and limitations of the method, and in principle before occhialino use the highest possible temperature, since this reduces the regeneration time. However, the use of high temperature regeneration contains the risk of damage to the catalyst. Catalysts with higher metal content generally require a lower maximum temperature of the catalyst than the catalyst with a lower metal content. Normally, the maximum temperature of the catalyst during regeneration is not more than 650°C, preferably not more than 575°C, more preferably not more than 550°C and even more preferably not more than 525°C.

The maximum temperature of the catalyst in the regeneration process is usually at least 300°C, preferably at least 350°C, more preferably at least 400°C and even more preferably at least 450°C.

It should be noted that in this description of the invention any given temperature refers to the temperature of the catalyst, if not explicitly stated otherwise. The temperature of the catalyst may be measured by any known specialist method, for example by placing appropriately thermocouples.

Preferably, the stage of regeneration in the presence of oxygen was carried out in two stages, namely the first stage at a lower temperature and a second stage at a higher temperature. In the first stage at a lower temperature kata is isator contact with oxygen-containing gas at a temperature of 100 to 370°C, preferably from 175 to 370°C. In the second stage of regeneration at a higher temperature, the catalyst is contacted with oxygen-containing gas at a temperature of from 300 to 650°C, preferably from 320 to 550°C, even more preferably from 350 to 525°C. Preferably, the temperature in the second stage was higher than in the first stage, discussed above, of at least 10°C, more preferably at least 20°C. Taking into account the above guidance for specialist obvious how to determine the appropriate temperature interval.

Preferably, the catalyst is subjected to regeneration in the process of moving bed, preferably, if possible, when the layer thickness of 1-15 see In the context of describing the present invention it is assumed that the term "moving layer" refers to all processes in which the catalyst is in motion with respect to the installation, including processes in pseudocyesis layer processes in the fluidized bed, the processes in which the catalyst is rotated in the installation, and all other processes in which the catalyst is in motion. The duration of the regeneration process, including washing, depends on the properties of the catalyst and how exactly is the process, but it typically ranges from 0.25 to 24 hours, preferably from 2 to 16 hours.

Regenerated the initial catalyst in contact with the acid and the additive according to the method of the invention, as has been described above.

The invention will be illustrated in the following examples, but not to limit in any way.

Example 1: Activation of the used catalyst with citric acid and polyethylene glycol

The Hydrotreating catalyst used in the past 12 months for Hydrotreating raw materials, light gas oil, was regenerated as follows. The catalyst contained 23.2 wt.% carbon, 9 wt.% sulfur and 22.4 wt.% the hydrocarbon.

In the first stage leaching was removed from the catalyst, the hydrocarbon. Then regenerates the catalyst by contact with air at a temperature of 490-500°C for 24 hours. Thus obtained regenerated starting material contained molybdenum, cobalt and phosphorus on the media, aluminum oxide.

The regenerated catalyst was impregnated by impregnation of the pore volume impregnation with a solution containing citric acid and polyethylene glycol in an amount of 0.1 mol of acid per mol used for the hydrogenation metals and 0.5 mole of glycol per mole used for the hydrogenation metals, respectively, and then dried overnight at a temperature of 120°C.

The catalyst was tested for raw materials, light gas oil, with the following properties:

S (wt.%) 1,4837
N (the weight. ppm)170
Density (15°C, g/ml)0,8609
Viscosity (50°C, cSt)4,11
H (wt.%)12,90
Data distillation (ASTM D-86, °C)
Initial boiling point182
10 vol.%288
50%vol.325
90 vol.%364
Final boiling point375

The catalyst was tested with an hourly volumetric fluid velocity (LHSV) of 1.5 h-1and the ratio of hydrogen to oil of 200 nl/l under various conditions with changing temperature and pressure. Each condition was maintained for two days. The catalyst was tested in parallel with a fresh catalyst. Test conditions and activity of these two catalysts are given below.

T (°C)PPH2(MPa)Fresh catalystReactivated catalyst
OOA-SDS(ppm S)OOA-SDS(ppm S)
13455,1100 (42)93 (50)
23505,1100 (28)93 (33)
33503,0100 (159)98 (165)
43505,1100 (55)103 (52)

The table above shows that the activity of waste and reactivated catalyst was restored to activity, which is almost the same high as that of the fresh catalyst. For comparison, the activity of the spent catalyst after regeneration was 70% compared with its initial activity.

Example 2: Activation of the used catalyst is phosphoric acid and polyethylene glycol

the Hydrotreating Catalyst, used within 24 months for Hydrotreating raw materials, light gas oil, was regenerated as follows. The catalyst consisted of 25.4 wt.% carbon, of 8.8 wt.% sulfur and 18.3 wt.% the hydrocarbon. In the first stage leaching was removed from the catalyst, the hydrocarbon. Then regenerates the catalyst by contact with air at a temperature of 450°C for 24 hours. Thus obtained regenerated starting material contained molybdenum, cobalt and phosphorus on the media, aluminum oxide.

The regenerated catalyst was impregnated by impregnation of the pore volume impregnation with a solution containing phosphoric acid and a glycol in an amount of 0.2 mole of glycol per mole used for hydrogenation metal, and then dried overnight at a temperature of 120°C. the Final catalyst contained 4.8 wt.% phosphorus, considering P2O5, while the original catalyst contained 1.6 wt.%.

The catalyst was tested for raw materials, light gas oil, with the following properties:

Data distillation (ASTM D-86, °C)
S (wt.%)1,323
N (the weight. ppm)110
Density (15°C, g/ml)0,8574
Initial boiling point183
10 vol.%253
50%vol.298
90 vol.%360
Final boiling point380

The catalyst was tested at a partial pressure of hydrogen to 3.92 MPa, with an hourly volumetric fluid velocity (LHSV) of 1.5 h-1and the ratio of hydrogen to oil of 200 nl/l under various conditions with temperature changes. Each condition was maintained for two days. The catalyst was tested in parallel with a fresh catalyst. Test conditions and activity of these two catalysts are given below.

T (°C)Fresh catalystReactivated catalyst
OOA-SDS(ppm S)OOA-SDS(ppm S)
1340100 (114)98 (120)
2 350100 (39)99 (41)
3330100 (406)101 (398)

The table above shows that the activity of waste and reactivated catalyst was restored to activity, which is almost the same high as that of the fresh catalyst. For comparison, the relative volumetric activity on SDS spent catalyst used within 24 months for Hydrotreating hydrocarbon oils decreased to 53% in comparison with the initial relative volume activity.

Example 3: Activation of the used catalyst with citric acid and polyethylene glycol

The Hydrotreating catalyst used for Hydrotreating of hydrocarbons, was regenerated as follows. The catalyst contained 17,9% wt. carbon and 10.7 wt.% sulfur. Were regenerating the catalyst by contacting with air at a temperature of 500-530°C. thus Obtained regenerated starting material contained molybdenum, cobalt and phosphorus on the media, aluminum oxide.

The regenerated catalyst was impregnated by impregnation of the pore volume impregnation with a solution containing citric acid and polyethylene glycol in Koli is estwe of 0.09 mole of acid per mole used for the hydrogenation metals and 0.22 mole of glycol per mole used for the hydrogenation metals, respectively, and then subjected to wet aging for 24 hours and dried overnight at 90°C.

The catalyst was tested for raw materials, oil coking, with the following properties:

S (wt.%)2,44
N (the weight. ppm)3546
Density (15°C, g/ml)0,9173
H (wt.%)11,7
Data distillation (ASTM D 1160 °C)
Initial boiling point176
10 vol.%250
50%vol.332
90 vol.%412
Final boiling point503

The catalyst was tested at a temperature of 387° C, a pressure of 100 bar, with an hourly volumetric fluid velocity (LHSV) of 2.1 h-1and the ratio of hydrogen to oil of 1000 nl/l, the Activity of the regenerated and reactivated catalyst for gidrogenizirovanii was 90% of the activity on gidrogenizirovannogo catalyst. For comparison, the activity of the spent catalyst after regeneration, but to reactivate accounted for about 60% of the activity of fresh catalyst.

Comparative experiments 1-3 and examples 4-8:

In comparative experiments 1-3 and examples 4-8 were prepared various catalysts, as described below. The catalysts were tested for liquid gas oil IGO) at a temperature of 340°C, a pressure of 45 bar, time bulk fluid velocity (LHSV) of 2.5 h-1and the ratio of hydrogen to oil of 200 nl/l was Measured activity at hydrodesulfurised. Measured relative volumetric activity (AOA) shown in the table below.

The crystalline fraction (CHRIS) of cobalt molybdate was measured by x-ray diffraction. The crystalline fraction (expressed as weight percent relative to the weight of catalyst) was evaluated by x-ray diffraction pattern by estimating the peak area of the reflections of the crystal of α-cobalt molybdate on the calibration curve obtained for one hundred percent crystalline α-cobalt molybdate.

All reactivation carried out by impregnation of the pore volume of the solution containing the organic additive and/or acid, followed by aging for 2 hours at 60°C followed by drying at 120°C.

Comparative experiment 1 (SA) refers to the regenerated catalyst described in the example . In comparative experiment 2 (KE2) catalyst SA reactivit using only citric acid (SA) in an amount of 5 wt.% (relative to the weight of catalyst). In comparative experiment 3 (KE3) catalyst SA activate using only polyethylene glycol (PEG) in an amount of 10 wt.% (relative to the weight of catalyst). In example 4 according to the invention (PR) catalyst SA activate using 4 wt.% Luke and 10 wt.% The PEG. Example 5 (WP5) of the catalyst SA activate using 10 wt.% Luke and 10 wt.% The PEG. Example 6 (PR) catalyst SA activate using 3.75 wt.% acetic acid (CA) and 10 wt.% The PEG. In example 7 (PR) catalyst SA activate using 4 wt.% LK and 5 wt.% glycerin (GLI).

We can conclude that the method of the invention allows to almost completely restore the catalytic activity of the used and regenerated catalyst, in particular, at higher concentrations of citric acid. The examples demonstrate the synergistic action of acid and an organic additive.

Comparative experiment 4 (SA) refers to the fresh catalyst containing cobalt and molybdenum on the media, the silicon oxide/aluminum oxide, calcined at 500°C. Example 8 of the invention (PR) refers to the catalyst CA, reactivated using 4 wt.% Luke and 10 wt.% The PEG. PR is measures 8 shows that may be also received a significant increase in activity as a result of reactivation of fresh catalyst.

ExperimentAcidAdditiveAAACHRIS
SA--428,4
KE2LC-46
KE3-PEG50
PRLCPEG612,4
WP5Luke 10%PEG97<0,5
PRMCPEG55
PRLK GLI54
SA--702,1
PRLCPEG76

1. The activation method of Hydrotreating catalyst containing a metal oxide of group VIB and a metal oxide of group VIII containing the contacting of the catalyst with an acid and an organic additive, which has a boiling point in the range of 80-500°C and a solubility in water of at least 5 grams per liter (20°C, atmospheric pressure), optionally followed by drying under such conditions that at least 50 wt.% the additive remains in the catalyst.

2. The method according to claim 1, in which activated the Hydrotreating catalyst contains crystalline fraction, expressed as a weight fraction of crystalline compounds of metals of group VIB and group VIII relative to the total weight of the catalyst, in the amount of less than 5 wt.%.

3. The method according to claim 1, wherein the activated catalyst Hydrotreating contains almost no crystalline fraction.

4. The method according to claim 1, wherein the Hydrotreating catalyst is a catalyst used is ω Hydrotreating, which were regenerating.

5. The method according to claim 1, wherein the Hydrotreating catalyst is fresh Hydrotreating catalyst.

6. The method according to claim 5, in which fresh Hydrotreating catalyst contains crystalline fraction in the amount of at least 0.5 wt.%.

7. The method according to claim 5, in which fresh Hydrotreating catalyst is calcined.

8. The method according to claim 7, in which fresh Hydrotreating catalyst contains crystalline fraction in the amount of at least 0.5 wt.%.

9. The method according to any one of claims 1 to 8, in which the catalytic composition containing the acid, in the wet state is subjected to the aging stage.

10. The method according to claim 9, in which the catalytic composition is subjected to aging in a period of time sufficient to reduce the content of the crystalline fraction below 5 wt.%.

11. The method according to any one of claims 1 to 8, in which the concentration of the acid is at least 5 wt.%, preferably at least 7 wt.%, most preferably at least 10 wt.% relative to the total weight of the catalyst.

12. The method according to any one of claims 1 to 8, in which the acid is an inorganic acid, preferably phosphorus-containing inorganic acid.

13. The method according to any one of claims 1 to 8, in which the acid is a carboxylic acid containing at least one carboxyl group and 1-20 carbon is s atoms.

14. The method according to item 13, in which the acid is citric acid.

15. The method according to any one of claims 1 to 8, in which the additive is an organic oxygen - or nitrogen-containing compound with a boiling point in the range of 100-400°C. and a solubility in water of at least 5 g per liter at room temperature (20°C, atmospheric pressure).

16. The method according to item 15, in which the additive is selected from the group of compounds containing at least two hydroxyl groups and 2-10 carbon atoms in the molecule, and a complex (poly)ethers of these compounds.

17. The Hydrotreating catalyst obtained by the method according to claims 1 to 16.

18. The Hydrotreating catalyst containing a metal oxide of group VIII and a metal oxide of a group VI, which further comprises an acid and an organic additive, which has a boiling point in the range of 80-500°C and a solubility in water of at least 5 grams per liter (20°C, atmospheric pressure).

19. The Hydrotreating catalyst at 17, which is regenerated used catalyst or fresh calcined catalyst which contains a crystalline fraction in the amount less than 5 wt.%, expressed as a weight fraction of crystalline compounds of metals of group VIB and group VIII relative to the total weight of the catalyst.

20. The method of Hydrotreating of hydrocarbons, which hydrocarbons contact irout in the Hydrotreating conditions with a catalyst according to claim 11, which was not necessarily pre-sulfidation prior to its contact with the hydrocarbon feedstock.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention describes method of obtaining aggregated catalyst for hydrogen treatment of oil fractions. The catalyst is a composition of components in the form of compounds of one VIII group metal and two VIB group metals. Method involves mixing and chemical interaction of components, producing active complex by mechanic and chemical activation of components, which remain in solid state during the whole process performed in aggregates of mechanic and/or hydrodynamic effect, preferably in planetary centrifugal mill, at room temperature for 5-30 minutes, with free pass distance of milling bodies equal to 4.0-5.0 cm, relative collision speed of milling bodies equal to 17-34 m/s, reaction layer thickness for component mix on the surface of milling bodies equal to (0.4-2.6)·10-2 cm, with further drying, tempering and sulfidation. Active complex is dried for 10-15 minutes.

EFFECT: high-grade purification of oil products from sulfur.

1 cl, 1 tbl, 2 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: invention refers to high metal catalyst compositions, production and application thereof in hydrotreating, specifically in hydrodesulfurisation and hydrodenitrogenating. Described is carrier-free catalyst composition containing one or more metals of VIb group, one or more metals of VIII group and refractory oxide material which contains at least 50 wt % of oxide-based titanium dioxide. Described is production method of catalyst compositions implying that one or more compounds of metal of VIb group is combined with one or more compounds of metal of VIII group and with refractory oxide material containing titanium dioxide with proton liquid and optionally alkaline compound; and catalyst composition is recovered by following precipitation. Described is application of composition described above or produced by method described above, moulded and sulphided if necessary, in hydrotreating of hydrocarbon raw materials.

EFFECT: higher activity of catalyst composition.

15 cl, 8 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: stable composition for application for catalyst carrier impregnation in order to obtain catalytically active solid substance includes: (A) water; (B) catalytically active metals, which are in form of and containing: (1) at least, one component, ensuring, at least, one metal of group VIB of Periodic system; and (2) at least, one component, ensuring, at least, one metal of group VIII of Periodic system, selected from group consisting of Fe, Co and Ni; and (i) said metal of group VIII is supplied with, in fact, insoluble in water component; (ii) molar ratio of said metal of group VIII and metal of group VIB constitutes approximately from 0.05 to approximately 0.45, on condition that amount of said metal of group VIII is sufficient for promoting catalytic impact of said metal of group VIB; (iii) concentration of said metal of group VIB, expressed as oxide, constitutes, at least, from approximately 3 to approximately 50 wt % of said composition weight; and (C) at least, one, in fact, water-soluble phosphorus-containing acid component in amount, insufficient for dissolving said metal of group VIII at room temperature, and sufficient for ensuring molar ratio of phosphorus and metal of group VIB from approximately 0.05 to less than approximately 0.25. Described is method of obtaining described above composition, including addition to suitable water amount of: (A) at least, one in fact water-insoluble component based on metal of group VIII, selected from group consisting of Fe, Co and Ni; and (B) at least, one in fact water-soluble phosphorus-containing acid component in amount insufficient for causing dissolution of said component based on metal of group VIII, with obtaining suspension, and combining suspension with: (C) at least, one component based on metal of VIB group; and (D) mixing of combinations (A), (B) and (C), and heating mixture during time and to temperature sufficient for formation of solution by (A), (B) and (C); and (E) adding supplementary amount of water, if necessary, in order to obtaining concentrations of solution of, at least, one said metal of group VIII, at least, one said metal of group VIB and phosphorus, suitable for impregnation of said carriers; group VIB and VIII refer to groups of periodic system of elements. Described is catalyst obtained by carrier impregnation with stable composition, suitable for hydrocarbon raw material processing.

EFFECT: increase of conversion degree of sulphur, microcarbon residue.

23 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: catalysts are intended for deep hydropurification of Diesel fractions from sulphureous compounds and can be used in oil-refining and oil-chemical industry. Catalyst for process of Diesel fraction hydrodesulphurisation has following composition, wt %: molybdenum oxide MoO3 16.0-29.0, cobalt oxide CoO and/or nickel oxide - 3-8, and phosphorus - 0.1-0.5, uranium oxide 1-15, carrier - the remaining part, atomic ratio Mo/Co(Ni) and P/Mo within 1.8-2.6 and 0.08-0.15, respectively. Method of obtaining catalyst (versions) includes successive or simultaneous impregnation of oxide carrier with solution of uranyl nitrate or acetate and complex solution of salts of metals of VIII and VI groups of periodic system with further thermal processing in flow of air or nitrogen at temperature not higher than 240°C. Process of Diesel fraction hydrodesulphurization is carried out under the following conditions: partial hydrogen pressure 3.5 MPa, temperature 300-370°C, weight liquid consumption 2 hour-1, volume ratio hydrogen/fuel 300-500 in presence of catalyst of said composition or obtained by invention methods.

EFFECT: deep purification of Diesel fractions, catalyst stability, its resistance to deactivation.

9 cl, 17 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: description is given of a catalytic composition with general formula, in consideration of oxides: (X)b(M)c(Z)d(O)e (I), in which X represents at least one group VIII base metal, M represents at least one group VIB metal, Z represents one or more elements, chosen from aluminium, silicon, magnesium, titanium, zirconium, boron and zinc, O represents oxygen, one of b and c represents an integer 1, and d, e and one of b and c represents each a number bigger than 0, such that the molar ratio b:c ranges from 0.5:1 to 5:1, molar ratio d:c ranges from 0.1:1 to 50:1, and molar ratio e:c ranges from 3.6:1 to 108:1. The method of obtaining the composition involves heating a composition with general formula (NH4)a(X)b(M)c(Z)d(O)e (II), in which a represents a number bigger than 0, and X, M, Z, O, b, c, d and e are such that, they are bigger, at temperature ranging from 100 to 600°C, where the composition with formula II is in suspension form or is extracted from a suspension, optionally after maturing at temperature ranging from 20 to 95°C for a period of not less than 10 min. The above mentioned suspension is obtained by precipitation at temperature and within a period of time, sufficient for obtaining formula II composition, of at least one compound of a group VIII base metal at least one compound of a group VIB metal at least one refractory oxide material and alkaline compound in protonic liquid. At least one of the metal compounds is partially in solid state and partially in dissolved state. Description is given of volumetric metal oxide catalytic composition, obtained using the method given above, and a composition with general formula I, which can be obtained using a precipitation method, in which a refractory oxide material in quantity ranging from 15 to 40 wt % is precipitated at least with one compound of a group VIII base metal, and at least with one compound of a group VIB metal, as well as the method of obtaining it. Description is also given of the use of compositions, moulded or sulphided when necessary, in hydro-processing.

EFFECT: increased activity of catalytic compositions.

14 cl, 10 tbl, 24 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for deep processing of hydrocarbon stock and can be employed in petroleum processing and petrochemical industries. Particularly, invention provides catalyst for diesel fraction hydrodesulfurization process, which contains, as active component, oxygen-containing molybdenum and cobalt and/or nickel complex compound at Mo/(Co+Ni) atomic ratio 1.5-2.5 and is characterized by specific surface 100-190 m2/g, pore volume 0.3-0.5 cm3/g, prevailing pore radius 80-120 Å. Catalyst support is constituted by alumina or alumina supplemented with silica or montmorillonite. Described are also catalyst preparation procedure and diesel fraction hydrodesulfurization process.

EFFECT: increased catalytic activity and resistance of catalyst against deactivation in presence of diesel fuel hydrocarbon components and sulfur compound of thiophene and its derivatives series.

8 cl, 1 tbl, 7 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for production of low-sulfur motor fuels and methods for preparing such catalysts. Hydrodesulfurization catalyst according to invention is characterized by pore volume 0.3-0.7 mL/g, specific surface 200-350 m2/g, and average pore diameter 9-13 nm and containing following components, wt %: cobalt compounds (calculated as CoO) 2.5-7.5, molybdenum compounds (as MoO3), citric acid 15-35, boron compounds (as B2O3) 0.5-3.0, aluminum oxide - the rest, cobalt, molybdenum, citric acid, and boron optionally being part of complex compound having different stoichiometry. Catalyst is prepared by impregnating catalyst support with impregnation solution obtained by dissolving, in water or aqueous solution, following compounds: citric acid, ammonium paramolybdate (NH4)6Mo7O24·4H2O, at least one cobalt compound, and at least boron compound, addition order and component dissolution conditions being such as to provide formation of complex compounds, whereas concentration of components in solution is selected such that catalyst obtained after drying would contain components in above-indicated concentrations.

EFFECT: maximized activity of desired reactions ensuring production of diesel fuels with sulfur level below 50 ppm.

9 cl, 8 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: proposed catalyst is composed of 12.0-25.0% MoO3, 3.3-6.5% CoO, 0.5-1.0% P2O5, and Al2O3 to the balance. Catalyst preparation comprises one- or two-step impregnation of support with solution obtained by mixing solutions of ammonium paramolybdate, cobalt nitrate, phosphoric and citric acids taken at ratios P/Mo = 0.06-0.15 and citric acid monohydrate/Co = 1±0.1, or mixing solutions of ammonium paramolybdate and phosphoric acid at ratio P/Mo 0.06-0.15 and cobalt acetate followed by drying and calcination stages. Diesel fraction hydrodesulfurization process is carried out in presence of above-defined catalyst at 340-360°C and H2-to-feedstock ratio = 500.

EFFECT: intensified diesel fraction desulfurization.

7 cl, 2 tbl, 13 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for extensive hydrofining of hydrocarbon stock, in particular diesel fractions, to remove sulfur compounds. Catalyst of invention, intended for diesel fraction desulfurization processes, comprises active component, selected from oxides of group VIII and VIB metals and phosphorus, dispersed on alumina support, said alumina support containing 5-15% of montmorillonite, so that total composition of catalyst is as follows, wt %: molybdenum oxide MoO3 14.0-29.0, cobalt oxide CoO and/or nickel oxide 3-8, phosphorus 0.1-0.5, and support - the balance, molar ratio Mo/Co and/or Mo/Ni being 1.3-2.6 and P/Mo 0.08-0.1. Preparation of catalyst support consists in precipitation of aluminum hydroxide and addition of montmorillonite with moisture content 55-70% to water dispersion of aluminum hydroxide in amount such as to ensure 5-15% of montmorillonite in finished product, after which resulting mixture is extruded and extrudate is calcined at 500-600°C to give support characterized by specific surface 200-300 m2/g, pore volume 0.5-0.9 cm3/g, and prevailing pore radius 80-120 Å. Catalyst preparation comprises impregnation of calcined support with complex solution of group VIII and VIB metal salts and phosphorus followed by heat treatment in air or nitrogen flow at temperature not exceeding 200°C, impregnation solution notably containing molybdenum oxide and cobalt and/or nickel carbonate at Mo/Co and/or Mo/Ni molar ratio 1.3-2.6 stabilized with orthophosphoric acid and citric acid to P/Mo molar ratio between 0.008 and 0.1 at medium pH between 1.3 and 3.5. Described is also diesel fraction hydrodesulfurization process involving passage of diesel fraction through bed of above-defined catalyst.

EFFECT: intensified diesel fraction desulfurization.

9 cl, 3 tbl, 19 ex

FIELD: petroleum processing.

SUBSTANCE: object of invention is production of low-sulfur diesel fuels from high sulfur-level hydrocarbon feedstock. Proposed process consists in conversion of straight-run diesel fuel having high sulfur level in presence of preliminarily sulfidized heterogeneous catalyst containing group VIII metal and group VIB metal deposited on alumina characterized by pore volume 0.3-0.7 mL/g, specific surface area 200-350 m2/g, and average pore diameter 9-13 nm. Prior to be sulfidized, catalyst has following components: cobalt compounds in concentration 2.5-7.5% calculated as CoO; molybdenum compounds, 12-25% as MoO3; citric acid derivatives, 15-35% as citric acid; boron compounds, 0.5-3% as B2O3; and alumina, the balance. Process is conducted at 320-370°C, pressure 0.5-10 MPa, feedstock weight rate 0.5-5 h-1, and hydrogen-to-feedstock volume ratio 100-1000.

EFFECT: reduced sulfur level in diesel fuel to less than 50 ppm.

3 cl, 1 tbl, 8 ex

The invention relates to the chemical industry, in particular to methods of regeneration of silver catalysts for the preparation of formaldehyde from methanol
The invention relates to the field of inorganic chemistry, more specifically to methods of regeneration of spent catalyst in the hydrogenation of 1,4-butynediol 1,4-butanediol

FIELD: chemistry.

SUBSTANCE: group of inventions refers to supports (alumina support), to methods for making supports of catalysts activated in aerated layer and chrome-alumina catalyst for dehydrogenation of C3-C5 paraffin hydrocarbons to related olefines being monomers used for manufacturing of chemical rubbers, polymers, blending fuels. There is disclosed alumina support of boehmite morphology, specific surface 80 to 250 m2/g, pore size at least 0.2 cm3/g, microcrystallite size by coherent scattering region 500 to 3000 A. It contains interlayer water in amount corresponding to mole ratio aluminium oxide to water 0.8 to 1.2. There is described method for making support by high-temperature processing of hydrargillite in inert gas and/or ammonia, and/or carbon oxide medium at temperature 100 to 300°C and pressure 0.1 to 150 kgs/cm2 and following drying. Besides, there is disclosed method for making dehydrogenation catalyst of C3-C5 paraffin hydrocarbons by impregnation of support produced as described above with precursor solutions of chrome oxide, potassium oxide and activating agent representing, at least, one oxide chosen from the group: copper oxide, zinc oxide, manganous oxide, tin oxide, boron oxide, zirconium oxide, there after dried and baked at temperature 600 to 900°C.

EFFECT: production of alumina support, development of production methods and methods for making dehydrogenation catalyst on this support of high mechanical strength, low abrasiveness and high activity and selectivity in dehydrogenation of propane, isobutane and isopentane.

7 cl, 2 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: there is disclosed selective oxidation catalyst of gas hydrogen sulphide to element sulphur on carbon carrier containing natural ferric oxide. Herewith catalyst is additionally introduced with ferric oxide in amount 0.5-2.0 wt % and magnesium oxide in amount 0.1-0.5 wt % on metal basis. Substrate is high-ash microcellular carbon carrier made of low-caking fossil coal by crushing, water granulation, drying, carbonisation in inert medium, and gas-vapour activation. Besides, there are described method of catalyst production and method of gas desulphurisation.

EFFECT: production of new catalyst ensuring comprehensive adsorption catalytic removal of hydrogen sulphide in gas, improved engineering-and-economical performance ensured with temperature reduction, higher sulphur content and catalyst service life.

5 cl, 2 tbl, 31 ex

FIELD: chemistry.

SUBSTANCE: catalyst contains active components based on nickel and uranium compounds applied on the carrier. Nickel content in final catalyst is 7-12 wt % on metal nickel basis, while uranium content is 1-50 wt % on metal uranium basis, the rest is the carrier. Disclosed methods of catalyst preparation involve solid-phase synthesis from catalyst component precursors, or moisture capillary impregnation. Disclosed methods cover production of synthetic gas within vapour reforming of methane or natural gas, or within oxygen or air partial oxidations of methane or natural gas, or within carbon dioxide reforming of methane or natural gas.

EFFECT: higher hydrogen yield, simplified technology of catalyst production and reduced reagent sink, decreased coke formation in synthetic gas production.

15 cl, 12 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: present invention pertains to the method of depositing a suspension coating onto a carrier. The invention particularly relates to the method and device for coating catalyst carriers, for example, carriers of automobile catalytic converters. Description is given of a device which implements the method of coating a carrier with open pores with at least, one suspension coating. The coating contains solid substances and substances dissolved in a liquid medium, the amount of which, in wet conditions, always exceeds the required amount of coating and fluctuates from one carrier to another. Excess suspension is removed from carrier channels by pre-extraction. The difference between the actual amount of suspension deposited on the carrier and the given required amount of coating is then determined and that difference is reduced through repeated extraction of wet suspension. After stages (a) and (b), the coating deposited on the carrier is dried and burned.

EFFECT: perfection of the method of coating a carrier and design of the coating device.

8 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention concerns neutralisation catalysts for exhaust gas (EG) of internal combustion engines (ICE) and industrial effluent gas. Catalyst is obtained due to: 1) adding orthophosphoric acid to coating suspension to obtain alumophosphate, a binding substance, the total composition of which serves for coating reinforcement and thermal stabilisation of porous coating structure; 2) energy heterogeneity increase by adding zyrconyl dihydrophosphate to coating suspension, so that the total composition serves to enhance heat resistance of both modified aluminium oxide and catalytic contacts, i.e. of the whole catalyst. Invention claims method of catalyst preparation, involving preliminary processing of inert Al-containing foil block carrier by baking at 850-920°C in air flow for 12-15 hours, followed by carrier application onto intermediary modified aluminium oxide coating surface from suspension at room temperature, thermal processing of block with intermediary coating in air flow and further applying one or more active catalytic metals of platinum group. Intermediary coating is applied from suspension containing additionally orthophosphoric acid and zyrconyl dihydrophosphate at the following component ratio, wt %: aluminium hydroxide (pseudobemite) - 22-32, aluminium nitrite - 2-4, cerium nitrite - 2-5, orthophosphoric acid - 1-2, zyrconyl dihydrophosphate - 1-3, water - up to 100; thermal processing of block with intermediary coating is performed at 620-650°C with maturing for 1.8-2 hours. Invention also claims catalyst including metal block carrier, intermediary coating of modified aluminium oxide and active phase of noble metals of platinum group applied onto porous surface of intermediary coating. Catalyst includes 7-14 wt % of modified Al2O3 with specific surface area of 120-130 m2/g, which includes additionally aluminium phosphate and zyrconyl phosphate at the following weight ratio of coating components (%): aluminium oxide (89.7-71.4), cerium oxide - (3.5-9.7), aluminium phosphate - (3.6-8.1), zyrconyl dihydrophosphate - (3.2-10.9).

EFFECT: significant enhancement of mechanical and heat resistance of catalytic coating at high efficiency in waste gas treatment process, prolonged lifetime.

2 cl, 2 tbl, 26 ex

FIELD: chemistry.

SUBSTANCE: invention refers to oil refining and petrochemical industry, specifically to methods of effective low-polymeric hydrocarbon pyrolysis catalysts. Described is low-polymeric paraffin fraction pyrolysis catalyst containing pentacyl family zeolite with silica ratio SiO2/Al2O3=20-80, modifiers chromium and fluorine, and binding agent aluminium oxide specific for the fact that simultaneously chromium and fluorine modified pentacyl family zeolite is used as catalyst base in ratio as follows, wt %: zeolite 55 - 80; chrome oxide 1 - 6.75; hydrogen fluoride 1 - 5.8; binding agent (γ-Al2O3) - the rest.

EFFECT: lowered number of technological operations for production of effective pentacyl containing catalyst for pyrolysis of low-polymeric hydrocarbons, reducted hard-to-dispose catalyst sewage, higher running time of regeneration-free pentacyl containing the catalyst.

1 cl, 3 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: described are solid Lewis adducts, containing MgCl2, Lewis base (LB), belonging to simple ethers, complex alkyl esters of C1-C10 aliphatic carboxylic acids, ketones, silanes or amines, and alcohol ROH, where R represents C1-C15 carbon group, optionally substituted with heteroatom-containing groups, said compounds being in molar ratio with each other, which is determined by the following formula MgCl2(ROH)m(LB)n(H2O)p, in which m lies in interval from 0.05 to 6, n lies in interval from 0.08 to 6 and p lies in interval from 0.01 to 0.6. Also described is method of obtaining said solid Lewis adduct, including (i) contacting of MgCl2, alcohol ROH and Lewis base LB optionally in presence of inert liquid thinner; (ii) heating of system to temperature of mixture melting and sustaining said conditions in order to obtain fully melted adduct; and (iii) quick cooling of melted adduct and obtaining as a result its hardening; also described are catalytic components obtained during contacting of described above adducts with compounds of titanium of formula Ti(OR)nXy-n, where n equals from 0 to y, y represents titanium valency, X represents halogen and R represents alkyl radical, which has 1-10 carbon atoms, or COR group, and containing electron donor, selected from complex esters, simple ethers, amines and ketones; described is catalytic system for alpha-olefin polymerisation and method of olefin polymerisation.

EFFECT: good morphological stability of catalyst and high polymerisation activity.

24 cl, 2 tbl, 38 ex

FIELD: chemistry.

SUBSTANCE: stable composition for application for catalyst carrier impregnation in order to obtain catalytically active solid substance includes: (A) water; (B) catalytically active metals, which are in form of and containing: (1) at least, one component, ensuring, at least, one metal of group VIB of Periodic system; and (2) at least, one component, ensuring, at least, one metal of group VIII of Periodic system, selected from group consisting of Fe, Co and Ni; and (i) said metal of group VIII is supplied with, in fact, insoluble in water component; (ii) molar ratio of said metal of group VIII and metal of group VIB constitutes approximately from 0.05 to approximately 0.45, on condition that amount of said metal of group VIII is sufficient for promoting catalytic impact of said metal of group VIB; (iii) concentration of said metal of group VIB, expressed as oxide, constitutes, at least, from approximately 3 to approximately 50 wt % of said composition weight; and (C) at least, one, in fact, water-soluble phosphorus-containing acid component in amount, insufficient for dissolving said metal of group VIII at room temperature, and sufficient for ensuring molar ratio of phosphorus and metal of group VIB from approximately 0.05 to less than approximately 0.25. Described is method of obtaining described above composition, including addition to suitable water amount of: (A) at least, one in fact water-insoluble component based on metal of group VIII, selected from group consisting of Fe, Co and Ni; and (B) at least, one in fact water-soluble phosphorus-containing acid component in amount insufficient for causing dissolution of said component based on metal of group VIII, with obtaining suspension, and combining suspension with: (C) at least, one component based on metal of VIB group; and (D) mixing of combinations (A), (B) and (C), and heating mixture during time and to temperature sufficient for formation of solution by (A), (B) and (C); and (E) adding supplementary amount of water, if necessary, in order to obtaining concentrations of solution of, at least, one said metal of group VIII, at least, one said metal of group VIB and phosphorus, suitable for impregnation of said carriers; group VIB and VIII refer to groups of periodic system of elements. Described is catalyst obtained by carrier impregnation with stable composition, suitable for hydrocarbon raw material processing.

EFFECT: increase of conversion degree of sulphur, microcarbon residue.

23 cl, 3 ex

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