Method of production of blended metal composition based on additive, catalytic composition and method of catalytic hydraulic treatment of hydrocarbon material

FIELD: production of catalytic compositions.

SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.

EFFECT: enhanced efficiency.

29 cl, 8 ex

 

The invention relates to a method for producing a catalytic composition comprising at least one component made of base metal of group VIII and at least two of the component metals of group VIB, the components of metals of group VIII and group VIB comprise at least 50 wt.% the catalytic composition in terms of oxides. The invention also relates to the thus obtained catalysts and to their use in hydrobromide using these catalysts.

Catalysts containing at least one component made of base metal of group VIII and at least two of the component metals of group VIB, in which components of metals of group VIII and VIB groups constitute at least 50 wt.% the catalytic composition in terms of oxides, known from the prior art.

In U.S. patent 4596785 described catalytic composition containing disulfides at least one base metal of group VIII and at least one metal of group VIB. In U.S. patent 4820677 described catalyst containing amorphous sulfide comprising iron as the base metal of group VIII and a metal selected from molybdenum, tungsten or mixtures thereof as the metal of group VIB, and polydentate ligand such as Ethylenediamine. In both references the catalyst receive the coprecipitation is water-soluble sources of the same base metal of group VIII and the two metals of group VIB in the presence of sulfides. The precipitate produce, dried and calicivirus in an inert atmosphere, which means the need for complex technical equipment for carrying out these processes.

In U.S. patent 3678124 disclosed oxide catalysts for use in oxidative dehydrogenation of paraffin hydrocarbons. The catalysts obtained by coprecipitation of water-soluble components of metals of group VIB and base metals of group VIII.

In accordance with WO 9903578 catalysts obtained by coprecipitation of the corresponding quantities of the sources of Nickel, molybdenum and tungsten in the absence of sulphides.

In previously unpublished international patent application PCT/ER/00354 described getting sulfide catalytic compositions by co-precipitation of at least one component made of base metal of group VIII and at least two components of metals of group VIB with the formation of stable oxygen precipitate, which is then sulfidized. In previously unpublished international patent application PCT/ER/00355 describes how to obtain a catalytic composition by contacting at least one component made of base metal of group VIII and at least two components of metals of group VIB in the presence of proton liquid, where at least one of the component metals, at least partially located is designed in the solid state during contacting.

Although the catalysts of some of the above links, in particular from the previously unpublished international patent application PCT/ER/00354 and PCT/ER/00355, exhibit high activity, however, there is a need for improvements.

Presently discovered that the characteristics of catalysts containing at least one component made of base metal of group VIII and at least two of the component metals of group VIB, where the set of components of metals of group VIII and group VIB, in terms of oxides is at least 50 wt.% catalyst composition, calculated on dry basis, can be further improved by adding certain additives in an amount such that the molar ratio of the aggregate of all additives to the aggregate of VIB metals of the group and base metals of group VIII, used in the process was, at least 0.01.

It should be noted that the catalysts containing additives, and receipt of them known from the prior art. Links to EP 0601722, JP 04-166231, JP 04-166233, JP 06-339635, JP 06-210182 and WO 96/41848. However, these references refer to the usual catalysts hydrobromide on the media, which contain up to about 25 wt.% molybdenum, in terms of trioxide, and up to about 10 wt.% component metal of group VIII, in particular Nickel or kobal is the in terms of oxides on the catalyst carrier, which is typically alumina. The reason for increasing the activity obtained in the above reference, consider the effects of the additive on the interaction between the components of metals and aluminum oxide. In these references, there is nothing that would prove the influence of additives on the catalytic compositions based on a medium non-aluminum oxide. In addition, none of these links is not associated with catalysts containing two compounds VIB metal group.

This invention thus relates to a method for the catalytic composition, where at least one component made of base metal of group VIII and at least two of the component metals of group VIB combined and react in the presence of proton fluid, after which the resulting composition is isolated and dried, the set of components of metals of group VIII and group VIB, in terms of oxides is at least 50 wt.% catalyst composition, calculated on dry weight, characterized in that before, during or after integration and interaction of the components of metals add organic oxygen-containing additive in an amount such that the molar ratio of the total number of additives to the total amount of component metals of group VIII and group VIB was, hence, is her least 0,01.

The method of receiving according to the invention provides for two specific scenarios, namely, first, the currently favored option of execution, where the catalyst is dried under such conditions that at least part of the additive was maintained in the catalytic composition, and the second, less preferred in the present embodiment of where the catalytic composition is subjected to a stage of calcination under such conditions that the additive was removed from the catalyst.

Thus, the invention relates to a catalytic composition comprising at least one component made of base metal of group VIII and at least two of the component metals of group VIB, and a catalytic composition additionally contains at least 0.01 mole of supplements containing organic oxygen compound, per mole of combined metals of group VIB and base metals of group VIII present in the catalytic composition, and the combination of components of metals of group VIII and group VIB, in terms of oxides is at least 50 wt.% catalyst composition, calculated on dry basis.

In the context of this description, the wording "metal component" refers to a salt, oxide, sulfide or any intermediate form between oxide and metal sulfide. How about Eveno for professionals in this field, the wording "at least two component metals of group VIB" implies a reference to the components of at least two metals of group VIB, for example, a combination of molybdenum and tungsten.

Used in this specification, the definition of group VIB and group VIII correspond to the Periodic Table of Elements used Chemical Abstract Services (CAS system).

Suitable metals of group VIB are chromium, molybdenum, tungsten or their mixture, with the combination of molybdenum and tungsten are preferred. Suitable base metals of group VIII are iron, cobalt, Nickel or a mixture thereof, preferably cobalt and/or Nickel. Preferably, in the method of the invention uses a combination of components of metals containing Nickel, molybdenum and tungsten, or Nickel, cobalt, molybdenum and tungsten, or cobalt, molybdenum and tungsten.

Preferably, the Nickel and/or cobalt was at least 50 wt.% of the total number of all base metals of group VIII, more preferably at least 70 wt.%, even more preferably, at least 90 wt.%. Particularly preferably, the base metal of the VIII group consisted essentially of Nickel and/or cobalt.

Preferably, the molybdenum and tungsten were at least 50 wt.% of the total number of all metals, group VIB, Bo is her preferred at least 70 wt.%, even more preferably, at least 90 wt.%. Particularly preferably, the metal VIB group consisted essentially of molybdenum and tungsten.

The molar ratio of the metals of group VIB to base metals of group VIII in the catalyst of the invention is typically in the range from 10:1 to 1:10 and preferably from 3:1 to 1:3. The molar ratio of the various metals of group VIB, one to another, usually at the present time is not critical. If the VIB metals of groups use molybdenum and tungsten, the molar ratio of molybdenum:tungsten, preferably, is in the range of 9:1-1:19, more preferably 3:1-1:9, most preferably 3:1-1:6.

The catalytic composition comprises at least 50 wt.% collectively, the components of metals of group VIB and group VIII, in terms of oxides on the total weight of the catalytic composition, preferably at least 70 wt.%, more preferably at least 90 wt.%, in terms of oxides. The number of VIB metals of the group and base metals of group VIII can be determined by AAS or ICP.

The additive used in the catalyst and method according to the invention, is an organic oxygen-containing additive. In the context of this description, the term "oxygen-containing organic additive" refers to an additive that contains, what about the least one carbon atom, at least one hydrogen atom and at least one oxygen atom. Suitable additives are, for example, acids, esters of acids, alcohols, aldehydes, ketones and ethers.

May vary for different groups of additives. First, preferred at the moment the group of additives selected from the group of compounds containing at least two atoms of oxygen and 2-20 carbon atoms, preferably 2-10 carbon atoms, and compounds constructed from these compounds. Preferably, the organic compounds of this group essentially saturated, that is, have iodine number less than 60, preferably less than 20. Preferred organic compounds selected from the group of compounds containing at least two oxygen-containing structural element, such as carboxyl, carbonyl or hydroxyl, and 2-10 carbon atoms, and compounds constructed from these compounds. Examples of suitable compounds are citric acid, tartaric acid, oxalic acid, malonic acid, malic acid, butanediol, provincy aldehyde, glycol aldehyde and acetaldol. In the currently preferred within this group additive that is selected from the group of compounds containing at least two hydroxyl groups and 2-10 atoms of plastics technology : turning & the Yes in the molecule, and simple (poly)ethers of these compounds. Suitable compounds of this group are aliphatic alcohols, such as ethylene glycol, propylene glycol, glycerin, trimethylacetyl, trimethylolpropane etc. ethers of these compounds include diethylene glycol, dipropyleneglycol, triethyleneglycol, triethylene glycol, tributylamine, tetraethylene glycol, tetraethyleneglycol. This number can be extrapolated with the inclusion of polyethers such as polyethylene glycol. Other ethers that are suitable for use in this invention are simple monobutyl ether of ethylene glycol, simple onomatology ether of diethylene glycol, a simple monotropy ether of diethylene glycol, simple monopropylene ether of diethylene glycol and simple monobutyl ether of diethylene glycol. Of them preferred glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropyleneglycol and polyethylene glycol with a molecular weight between 200 and 600. Another group of compounds containing at least two hydroxyl groups and 2-10 carbon atoms in the molecule, are sugars. Preferred saccharides are monosaccharides, such as glucose and fructose. Their simple esters are disaccharides, such as lactose, maltose and sucrose. Simple is the polyesters of the above compounds are polysaccharides.

The second group of oxygen-containing additives suitable for use in this invention are compounds containing at least one covalently linked to the nitrogen atom and at least one carbonyl structural element. This type of organic compounds preferably contains at least two carbonyl structural element. Preferably, at least one carbonyl structural element was present in the carboxyl group. Further, it is preferable that at least one atom of nitrogen was covalently linked to at least two carbon atoms. Preferred organic compound satisfies the formula (I) or (II)

where R1, R2, R1' and R2' are independently selected from alkyl, alkenyl and allyl with up to 10 carbon atoms optionally substituted by one or more groups selected from carbonyl, carboxyl, ester, simple, ether, amino or aminogroup. R3 means alkylenes group with up to 10 carbon atoms which may be interrupted by-O - or-NR4. R4 is selected from the same groups as listed above for R1. Allenova group R3 may be substituted by one or more groups selected from carbonyl, carboxyl, ester, simple, ether, amino or aminogroup. As mentioned above, it is essential that the PR is anicescu compound of formula (I) or (II) contain, at least one carbonyl structural element.

Preferably, at least two of R1, R2, R1' and R2' (formula (I)and at least two of R1, R2 and R1' (formula (II)) had the formula-R5-COOX, where R5 means alkylenes group containing 1-4 carbon atoms, and X denotes hydrogen or another cation, such as ammonium cation, sodium, potassium and/or lithium. If X means a multivalent cation, one X may be attached to two or more groups R5-COO. Typical examples of compounds of formula (I) are Ethylenediamine(Tetra)acetic acid (EDTA), hydroxyethylenediaminetriacetate acid and diethylenetriaminepentaacetic acid. A typical example of the compounds of formula (II) is nitrilotriacetic acid (NTA).

An additional group of organic oxygen-containing compounds that are suitable as additives in this invention are described in WO 9425157. Unsaturated compounds which have an iodine value of at least 60 preferred.

Oxygen-containing hydrocarbons of the specified group include, for example, higher alcohols containing at least 12, preferably at least 16, more preferably at least 20 carbon atoms, such as dodecanol, hexadecanol, alerby alcohol, cetyl alcohol, hexacosanol, triacontanol and octacosanol; higher ethers, containing the s, at least 12, preferably at least 16, more preferably at least 20 carbon atoms, such as deatroy ether; higher ketones containing at least 12 carbon atoms, preferably at least 16 carbon atoms, more preferably at least 20 carbon atoms, such as palmitin, 10-hydroxyvalerate and 3-octadecanol; higher aldehydes containing at least 12 carbon atoms, preferably at least 16, more preferably, at least 20 carbon atoms, such as palmitic aldehyde and oleic aldehyde; higher acid containing at least 12, preferably at least 16, more preferably at least 20 carbon atoms, such as saturated acids, such as, for example, lauric, myristic, palmitic, stearic and docosanoate acid, or unsaturated higher acids such as palmitoleic, oleic, linoleic, linolenic, aleocharinae, ricinoleate, Aksenova, docosanoate, eicosatetraenoate, eicosapentaenoic acid, docosapentaenoic and docosahexaenoic; esters of higher acids containing at least 12, preferably at least 16, more preferably at least 20 carbon atoms, including esters of mono-, di-, tri - and poly-fatty acids, including alkalemia and arilo the haunted esters of the above acids (for example, bansilalpet and butylurea) and esters of the above acids monoglycerides, diglycerides and triglycerides, and mixtures thereof. Preferred these esters of glycerides of fatty acids containing from 16 to 100, more preferably from 18 to 90, most preferably from 20 to 80 carbon atoms. Suitable glycerides of fatty acids commercially available as described in WO 9425157.

As additives can be used as individual compounds, and combinations thereof.

The amount of additive used in the method according to the invention, and the amount of additive present in the catalyst according to the invention is at least 0.01, preferably at least to 0.05, more preferably at least of 0.1 mole of additive per mole of combined metals of group VIB and group VIII. Typically, the molar ratio can be at most 3, preferably at most 2. However, the upper limit, suitable for a particular situation may depend on various parameters such as the number of functional groups present in organic oxygen-containing compound, or from the pore volume of the catalytic composition. The competence of a specialist to determine the amount of additive that should be used in specific situations.

From the point of view of the environment it is preferable to use the additive which are essentially free from sulfur. In addition, sulfur-containing additives are usually unstable with respect to oxygen. Therefore, if the use of sulfur-containing additives, all the successive stages of the process should be conducted in an inert atmosphere. Thus, for the above reasons it is preferable to use free of sulfur additives.

The catalytic composition according to the invention may also contain appropriate components of the catalyst, such binders or carriers, craterous components, conventional catalysts hydrobromide etc. in Detail these connections are described in the previously unpublished international patent applications PCT/ER/00354 and PCT/ER/00355.

Examples of suitable binders and carriers are silica, silica-alumina, alumina, titanium dioxide, titanium dioxide-aluminum oxide, zirconium dioxide, boron oxide, cationic clays or anionic clays such as saponite, bentonite, kaolin, thick or hydrotalcite, and mixtures thereof. Preferred components are silica, silica-alumina, alumina, titanium dioxide, titanium dioxide-aluminum oxide, zirconium dioxide, bentonite, boron oxide and mixtures thereof, are particularly preferred, silicon dioxide, silicon dioxide-aluminum oxide, and aluminum oxide.

Examples for the walking kekirawa components are crystalline kekirawa components, such as zeolites, for example ZSM-5, (ultra-stable zeolite Y, zeolite X, ALPOs, SAPOs, MCM-41, amorphous kekirawa components such as silica-alumina, and mixtures thereof. It is clear that some materials, such as silica-alumina, can simultaneously act as a binder and krakeroy component.

If desired, the catalytic composition may contain any additional substances, such as phosphorus-containing compounds, boron compounds, silicon compounds, fluorine-containing compounds, additional transition metals, rare earth metals or mixtures thereof.

According to the invention, preferably, the number of other components other than the components of metals of group VIB, the components of metals of group VIII and additives should be less than 30 wt.%, preferably less than 20 wt.%. Preferred may be a number of other components less than 10 wt.%. Preferred may be a catalytic composition comprising 1-50 wt.%, preferably 1-30 wt.%, more preferably 1-10 wt.% binder or carrier, aluminium oxide in particular. In the above cases, the number of other components other than the components of metals of group VIB, of the component metals of group VIII and additives, determined after calcination at 500°C.

Typically, the catalytic composition invented the I has a mechanical strength, expressed as resistance to lateral crushing of at least 1 lb/mm and, preferably, at least 3 lb/mm (measured on the extrudates with a diameter of 1-2 mm).

Preferably, the catalytic composition in its oxide state, i.e. prior to any stage of sulfatirovnie has a surface area according to the BET equation, at least 10 m2/g, more preferably at least 50 m2/g and most preferably at least 80 m2/g, as measured according to the method of the BET. The average diameter of pores (50% of the volume of pores less than the specified diameter, the other 50% more) of the oxide catalyst composition, preferably, equal 3-25 nm, more preferably 5-15 nm (determined by absorption of N2). The total volume of the pores of the oxide catalyst composition is usually at least 0.05 ml/g, preferably 0.05 to 5 ml/g, more preferably 0.1 to 4 ml/g, even more preferably 0.1 to 3 ml/g and, most preferably, 0.1 to 2 ml/g as determined by nitrogen adsorption. To further increase the mechanical strength of the oxide catalyst composition of the invention preferably have a low macroporosity. Preferably, less than 30%, more preferably less than 20% of the pore volume of the catalytic compositions have a pore diameter of 100 nm (determined by mercury intrusion, contact angle: 130°).

Catalytics the second composition can have many different forms. Appropriate forms are powders, spheres, cylinders, rings and symmetric or asymmetric megapoli, for example, three - and quadropole. Particles obtained by extrusion, pelletizing or granulating, typically have a diameter in the range from 0.2 to 10 mm and their length in the same manner is in the range from 0.5 to 20 mm, Such particles are usually preferred. Powders, incl. those obtained, for example, by spray drying, typically have an average particle diameter in the range of 1 μm-100 μm, but it is possible deviations from normal ranges.

In its oxide state of the catalyst according to the invention has a structure of the diffraction of X-rays, which is mainly amorphous, crystalline peaks at d=2,53and d=1,70

This invention also relates to catalytic compositions according to the invention, where the components of the metal is partially or completely converted into their sulfides. In this case, it is preferable that the catalyst was largely free from disulfide base metals of group VIII. Base metals of group VIII are preferably present as (base metal of group VIII)ySxc x/y in the range of 0.5-1.5, which can be determined by, for example, XRD. Molybdenum and tungsten, if present, is preferably at least partially is present in about solifidianism the catalyst in the form disulfides, what can be determined by, for example, XRD. Chromium, if present, is preferably at least partially present in the form of sulfide (CrS or Cr2S3), which can be determined by, for example, XRD.

As defined above, the invention also relates to a method for the catalytic composition, where at least one component made of base metal of group VIII and at least two of the component metals of group VIB are combined and injected into the reaction in the presence of proton fluid, after which the resulting composition is isolated and dried, the set of components of metals of group VIII and group VIB, in terms of oxides is at least 50 wt.% catalyst composition, calculated on dry weight, wherein the organic oxygen-containing additive is added before, during or after integration and interaction of the components of the metals in such a quantity that the molar ratio of the total amount of additives to the total amount of component metals of group VIII and group VIB is at least 0.01.

Detailed description for the catalytic compositions containing at least one component made of base metal of group VIII, at least two of the component metals of group VIB, where the components of metals of group VIII and VIB groups constitute at least 50 wt.% cat the political composition, in terms of oxides presented in references: previously unpublished international patent applications PCT/ER/00354 and PCT/ER/00355.

Regardless of the addition of additives, the decisive point of the method according to the invention is that the metal components react in the presence of proton fluid. Can be used any proton liquid which does not interfere with the reaction. Suitable liquids are water, carboxylic acids, lower alcohols, such as ethanol and propanol, and mixtures thereof. The use of water is preferable.

At least three of the component metals used in the method according to the invention, namely, at least one component of a metal of group VIII and at least two of the component metals of group VIB, may be in the solid state or at least partly in the solid state during the process according to the invention. Thus, the reaction may include three of the dissolved component, two of the dissolved component and one at least partially solid component, one dissolved component and two at least partially solid component, and three at least partially solid component. The reaction involves the deposition and possibly, depending on the status of the various components, the dissolution and re-precipitation.

Usually there are two possible ways of contacting components of the metals with each other, namely, by combining and interaction components of the metals in the solution with the precipitate (hereinafter designated as "the way of solution") or by Association and interaction of the components of metals in the presence of proton fluid with at least one of the metal components remaining at least partly in the solid state (hereinafter designated as "the way of solid").

By way of solution components are completely dissolved metals, when they are combined and/or interact with the sediment. You can, for example, to combine the components of metals when they are already dissolved, and then give them to react with sediment. However, you can combine one or more components of the metals, which are partly or fully in the solid state, with other components of the metals. However, in this case care should be taken that the components of the metals, which are partly or fully in the solid state, dissolved, being in the reaction mixture. In other words, during the process path with a solution of all the components of the metal must be completely dissolved.

The deposition can be carried out by, for example,

(a) the change of pH during or after combining the solutions of the component metals to a value that causes the precipitation

(b) adding complexing agents during or after combining the solutions of the component metals and complexing agents form complexes with one or more metals to prevent deposition of metals, and then changing the reaction conditions such as temperature or pH, so that the complexing agents releases metals for deposition;

(C) raising the temperature during or after combining the solutions of the component metals to a value that causes the deposition;

(d) reducing the amount of solvent during or after combining the solutions of metal components in such a way as to cause precipitation;

(e) adding herstories during or after combining the solutions of the component metals to call their deposition under nerastvorim understand that practically insoluble precipitate in the indicated solvent;

(f) adding an excess of one of the components to such an extent as to cause precipitation.

Bringing the pH, for example, in the variant (a) or (b)may be carried out by adding to the reaction mixture a base or acid. However, you can add the connection that when the temperature can decompose with the formation of hydroxide ions or ions of N+which, respectively, increase or decrease the pH. Examples of compounds that mo is ut to decompose when the temperature rises, raising or lowering at this pH, are urea, nitrite, ammonium cyanate, ammonium hydroxide and ammonium carbonate.

Version of the way of solid provides for the integration and interaction of components of metal with at least one of the metal components remaining at least partly in the solid state. More specifically, it provides for the addition of the components of the metals to the other (component) and the simultaneous and/or subsequent interaction. Therefore in variant ways with a solid substance, at least one metal component is added in at least a partially solid state, and the specified component metal remains at least partly in the solid state during the reaction. The term "at least partly in the solid state" in this context means that at least part of the metal component is present in the form of a solid metal component and, optionally, another portion of the metal component is present in the form of a solution in the proton fluid. A typical example of this is the suspension component metal in the proton fluid, where the metal is at least partially present in the solid state and, optionally, partially dissolved in the surrounding liquid.

You can first prepare a suspension of a metal component in the proton fluid and to which awiti, simultaneously or sequentially, the solution(s) and/or other(s) suspension(s)that contain(s) component(s) of metal(s), dissolved(s) and/or suspended(s) in the proton fluid. You can combine the solutions simultaneously or sequentially, and subsequently added to the suspension(s) and, optionally, a solution of(s) simultaneously or sequentially.

Since at least one component of the metal at least partially located in the solid state during the path with the solid substance, the number of components of metals, which are at least partially located in the solid state, is not critical. Thus, there is an opportunity for all components of the metals to be United in the way using a path with a solid substance, at least partly in the solid state. Alternatively, the metal component, which at least partially is in the solid state, can be combined with a component of the metal in the dissolved state. For example, one of the metal components add in at least a partially solid state, for example, at least two and, preferably, two component metals added in a dissolved state. In another embodiment, for example, two component metals add in at least a partially solid state, and at least one and, preferably, one component metals added in a dissolved state.

Thus, the metal component is added in a dissolved state" means that the whole amount of the specified component metal is added in the form of a solution in the proton fluid.

As is clear from the above, you can add the base metal of group VIII component and the metal of group VIB of different ways, at different temperatures and pH values in solution, in suspension, wetted or as such, simultaneously or sequentially. It should be noted that it is preferable not to use sulfur-containing metal components, as these components and the resulting products are unstable with respect to oxygen, which means that all the stages of the method, following the addition of the specified component of the metal, even flowing at a lower temperature, should be carried out in an inert atmosphere.

Suitable water-soluble components of the base metals of the VIII group for use in the method of the invention are salts such as nitrates, hydrated nitrates, chlorides, hydrated chlorides, sulfates, hydrated sulfates, formate, acetate or hypophosphite. Suitable water-soluble Nickel and cobalt components are nitrates, who ulfate, the acetate, chloride, formate, or mixtures thereof, as well as hypophosphite Nickel. Suitable water-soluble components based on iron are the acetate, chloride, formate, nitrate, ferric sulfate, or a mixture thereof.

Suitable water-soluble components on the basis of VIB metals of the group are salts of metals of group VIB, such as monopolarity and wolframite ammonium or alkali metals, as well as water-soluble isopoliteia molybdenum and tungsten, such as methanolmaria acid, or water soluble heteropolysaccharide molybdenum or tungsten, optionally containing, for example, P, Si, Ni or Co, or combinations thereof. Suitable water-soluble versions, displacements contour plots and heteropolysaccharide presented in Molybdenum Chemicals, Chemical data series, Bulletin Cdb-14 February 1969 and Molybdenum Chemicals, Chemical data series, Bulletin Cdb-12a-revised November 1969. Suitable water-soluble chromium compounds are chromium, isoprinosine and sulfate ammonium.

If proton liquid is water, suitable components of the base metals of group VIII, which at least partially located in the solid state during the process according to the invention, are components of the base metals of group VIII of low solubility in water, such as citrates, oxalates, carbonates, hydroxycarbonate, hydroxides, phosphates, phosphides, sulfides is, aluminates, molybdates, wolframates, oxides or mixtures thereof. Preferred oxalates, citrates, carbonates, hydroxycarbonate, hydroxides, phosphates, molybdates, wolframates, oxides or mixtures thereof, most preferred hydroxycarbonate and carbonates. Typically, the molar ratio between the hydroxyl groups and carbonate groups in hydroxycarbonate is in the range of 0-4, preferably 0-2, more preferably 0-1 and, most preferably, from 0.1 to 0.8.

If proton liquid is water, suitable components of metals of group VIB, which at least partially located in the solid state during contacting, are components of metals of group VIB of low solubility in water, such as di - and trioxide, carbides, nitrides, aluminum salts, acids, sulfides or mixtures thereof. Preferred components of metals of group VIB, which at least partially located in the solid state during contacting, are di - and trioxide, acid and mixtures thereof. Suitable molybdenum components are di - and trioxide molybdenum, molybdenum sulfide, molybdenum carbide, molybdenum nitride, aluminum molybdate, molybdenum acid (e.g., H2MoO4), phosphomolybdate ammonium or mixtures thereof, and molybdenum acid and di - and trioxide molybdenum are preferred. Appropriate ultramobile components are di - and trioxide tungsten, sulfides of tungsten (WS2and WS3), tungsten carbide, orthovalerate acid (H2WO4·H2O), a nitride of tungsten, aluminum tungstate (also meta - or polivalente), phospholipase ammonium or mixtures thereof, and orthovalerate acid and di - and trioxide tungsten is preferred.

If proton fluid is water, the solubility of the components of the base metals of group VIII and components of metals of group VIB, which during the method of the invention, at least partially situated in the solid state, is typically less than 0.05 mol/(100 ml water at 18°).

As stated above, if desired, before, during and/or after merging and interaction of the components of metals and/or immediately after this can be added a binder, conventional catalysts hydrobromide, kekirawa components or mixtures thereof. These substances are identified below as "carriers".

Media can be added to the contacting of the metal components, for example, by combining with one or more, but not all components of metals or vice versa and by then combining the mixture with yet an added metal components simultaneously or sequentially. Media can be added during the contacting of the metal components by, for example, simultaneous joint is through the media and components of metals of the first or join metal components simultaneously or sequentially with the subsequent addition of the medium during the reaction of the combined metal components. Media can be added simultaneously with the contacting of the metal components, for example, by adding it directly in the reaction mixture obtained after the interaction of the components of the metals, or by adding it after any further stage of the process that will be discussed in detail below. Preferably the media type after contacting of the metal components. Perhaps the catalytic composition obtained after merging and interaction of the components of metals, can be subjected to separation into solid and liquid phase before combining with a carrier, for example, by filtration. After separation of the solid phase and the liquid can be carried out stage washing. Optionally heat treated catalyst composition prior to its Association with the carrier. Media can be added in the dry state, treated or not treated thermally in moist and/or suspended state, in the form of filtration of sediment and/or in the form of a solution.

The additive may be added before, during or after integration and interaction of the components of metals. The additive may be added during the contacting of the metal components by, for example, simultaneous associations additives and components of metals or first combining component metal is simultaneously or sequentially, and then the addition of additives during the reaction of the combined metal components. Alternatively, the media or any other material that is combined with the additive, may be added to the components of the metals during their connection and/or communication. The additive may also be added after contacting components of metals, for example, by adding it to the catalytic composition obtained after the interaction of the component metals. It is generally preferable to introduce the additive into the catalytic composition after merging and interaction of metal compounds. You can add the additive is used or regenerated catalyst.

If added, the media, the sequence in which the gain medium and the additive is not critical. You can combine media with addition and combine combination with components of metal. Thus, it is possible to combine the components of the metal additive and the carrier in any order.

Optionally, the method of the present invention may include additional stages of the drying process spray, quick drying, grinding, plastilinovaya, mixing suspensions, dry or wet mixing, molding and/or calcination. Dry mixing means mixing the catalytic composition in the dry state with any above-mentioned material in a dry condition. Wet the e mixing, for example, allow for the blending of wet filtration of the precipitate, containing the catalytic composition and, optionally, any of the above materials in the form of powders or filtration of the precipitate with the formation of a homogeneous paste. Molding provides, for example, extrusion, granulation, tableting and/or spray drying. A detailed description of these additional process steps described with reference to previously unpublished international patent application PCT/NR/00354 (head "Catalyst preparation process" under "Further optional process steps") and PCT/ER/00355 (Chapter Process of the invention" under "(C) Subsequent process steps").

Usually for the method according to the invention preferably include the stage of molding. Stage molding is preferably carried out after the Association and interaction between the components of metals. If in the method according to the invention to add the carrier, it is preferably added before the stage of molding. The additive may be added before or after the stage of forming, although the addition of additives stage after molding may be preferable.

The method of receiving according to the invention provides for two specific scenarios, namely, first, presently preferred embodiment of where the catalyst is dried under such conditions that at least cha is th additive is retained in the catalytic composition, and second, presently less preferred method of execution, where the catalyst composition is subjected to a stage of calcination under such conditions that the additive is removed from the catalyst. The specified stage of calcination, if present, is usually carried out at a temperature of 100 to 600°more specifically, inlet 150 up to 450°more specifically, 250-450°C. the calcination Time is usually varies from 0.5 to 48 hours. The calcination can be carried out in an inert gas, such as nitrogen, or oxygen-containing gas such as air or pure oxygen, possibly in the presence of water vapor. Preferably the calcination is carried out in oxygen-containing atmosphere. The exact temperature of the stage calcination depends on the temperature required to remove the additive from the catalyst. If you intend to dry the catalyst under such conditions that at least part of the additive remained in the catalyst used, the temperature of drying is to a large extent depends on the temperature at which the additive is present in the catalyst, boil or decompose. Of course, it is preferable to maintain the catalyst so many additives as possible during any such treatment, but in the case of more volatile additives evaporation during the specified treatment is usually unavoidable. Usually, preferably, they shall be temperature during any such treatment below 300° With and preferably below 220°C, although it may be necessary to lower the temperature depending on the nature of the additive present in the catalyst.

The method according to the invention may also include the intermediate stage of calcination carried out before the introduction of additives in catalytic composition. In the case of such an intermediate stage of calcination, which can be carried out under the conditions specified above, it is usually applied after the stage of forming, if it is present. It can be, among other things, used to convert the precursor medium, for example, the precursor of aluminium oxide, such as bohemic, in the media, similar to gamma alumina.

If desired, the catalytic composition containing the additive, or, if used, the calcination, the calcined catalyst composition may be subjected to solifidian. Sulfatirovnie may, for example, be carried out in the gas or liquid phase. It is usually carried out by contacting the precipitate with a sulfur-containing compound, such as elemental sulfur, hydrogen sulfide, DMDS, or polysulfides. Sulfatirovnie usually carried out in situ and/or ex situ. Preferably sulfatirovnie carried out ex situ, i.e. sulfatirovnie are in a separate reactor to download solifidians catalytic composition on a hundred is the Oia hydrobromide. Moreover, preferably, the catalytic composition was sliderule, both ex situ and in situ.

Two preferred options for performing the method of receiving according to the invention will be explained below.

The first option is the implementation of a method comprising the successive stages of Association and interaction between the components of the metals in the surrounding liquid, the optional selection of the reaction products, optional washing, drying and/or heat treatment of the obtained material, an optional mixing the resulting catalytic composition with a carrier, forming the resulting composition, for example, by spray drying or extrusion, optional calcining the resulting composition, the introduction of additives to the formed particles, optional aging containing the additive composition with subsequent optional drying, calcining and/or solifidianism catalyst particles. The preferred option is specified execution stage provides the Association and interaction between the components of the metals in the surrounding liquid, the reaction product, optionally mixing the resulting catalytic composition with a carrier, forming the resulting composition, for example, by spray drying or extrusion, calcining the resulting composition, BB is Denia additive to the formed particles, followed by drying, optional calcining and/or solifidianism catalyst particles.

The second option is the implementation of a method comprising the successive stages of Association and interaction between the components of the metals in the surrounding liquid, the optional selection of the products obtained, for example, by filtration, optional washing, drying and/or heat treatment of the obtained catalytic composition, mixing the resulting catalytic composition with the additive and, optionally, a carrier, forming the resulting composition, for example, by spray drying or extrusion with subsequent optional drying, calcining and/or solifidianism catalytic composition. The preferred option is specified execution stage provides the Association and interaction between the components of the metals in the proton fluid, separation of the resulting product, for example, filtration, mixing the resulting catalytic composition with the additive and, optionally, a carrier, forming the resulting composition, for example, by spray drying or extrusion, followed by drying and optional calcination and/or solifidianism catalytic composition.

The use according to the invention

The catalytic composition according to the invention can be used factors is automatic in all ways hydrobromide for processing raw materials in a wide range of reaction conditions, for example, at temperatures in the range from 200° up to 450°C, the hydrogen pressure in the range from 5 to 300 bar and volume velocity (LHSV) in the range from 0.05 to 10 h-1. The term "hydrobromide" in this context encompasses all processes in which the hydrocarbon feedstock is reacted with hydrogen at elevated temperature and elevated pressure, including hydrogenation, hydrodesulfurization, hydrogencitrate, hydrodemetallization, hydrodearomatization, hydroisomerization, hydrodehalogenation, hydrocracking, and hydrocracking under mild conditions, which is usually designated as shallow hydrocracking. The catalytic composition of the invention particularly suitable for hydrobromide hydrocarbons. These methods of hydrobromide include, for example, hydrodesulfurization, hydrogencitrate and hydrodearomatization hydrocarbons. Suitable raw material is, for example, middle distillate, kerosene, naphtha (naphtha), vacuum gas oil and heavy gas oil. Usually can be used in process conditions, such as temperature in the range 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 ratio of N2/oil in the range of 50-2000 nl/L.

Research methods

(a) resistance to lateral crushing (SCS)

First measure the length, for example, particles of the extrudate and ZAT is part of the extrudate is subjected to compression (25 pounds during 8,6 sec.) with the help of the rolling piston. Measure the force required for crushing the particles. The procedure is repeated with at least 40 extrudate particles and calculate the average value as the force (in pounds) per unit length (mm). This method is used for the molded particle length of not more than 7 mm

(b) pore Volume (adsorption of N2)

Determination of pore volume by adsorption of N2produced, as described in the PhD thesis J.C.P.Broekhoff (University of Technology Delft 1969)at. t

Examples

Comparative example a

The catalytic composition was prepared by combining and interaction hydroxycarbonate Nickel Moo3and H2WO4in the aquatic environment. The resulting suspension was filtered. The wet filter cake was mixed with moist filter residue of aluminum oxide. During mixing the temperature is slightly increased. In this way, the water content in the mixture was reduced with formation of a mixture suitable for extrusion. The mixture was then extrudible, dried at 120°and illnerova at 300°C. the Obtained catalyst composition contained 18 wt.% Moo3, 32 wt.% WO3, 31 wt.% NiO and 17 wt.% Al2O3.

Example 1

The extrudates obtained from comparative example a, was soaked 0.12 moles of diethylene glycol (ex. Merck) per mole of Nickel, molybdenum and tungsten contained in the catalytic composition. Diethylene glycol probabl is whether in the form of aqueous solution, adjusting the volume for proper impregnation of the pore volume. Impregnated extrudates were dried in air at 140°C.

Example 2

The catalytic composition was obtained by merging and interaction of hydroxycarbonate Nickel Moo3and H2WO4in the aquatic environment. The resulting suspension was filtered. The wet filter cake was mixed with moist filter residue of aluminum oxide. The resulting mixture contained 20 wt.% Moo3, 33 wt.% WO3, 31 wt.% NiO and 16 wt.% Al2O3(measured on a dry basis). To the mixture was added 0.12 moles of diethylene glycol (ex. Merck) per mole of Nickel, molybdenum and tungsten contained in the mixture. During mixing the temperature of the mixture was increased. In this way, the water content in the mixture was reduced with obtaining suitable for extruding the mixture. The mixture containing the additive was extrudible and the resulting extrudates were dried overnight at 120°C.

Example 3

The catalysts of comparative example a, example 1 and example 2 were tested on hydrodesulfurization, using waste diesel fuel having the following characteristics:

contents S: 217 nm;

the N content: 29 CNM;

the number of monoaromatic hydrocarbons: 31,3 wt.%;

the number of di-aromatic hydrocarbons: 5.8 wt.%;

the number triaromatic hydrocarbon is in: 0.6 wt.%;

initial boiling point: 161°C;

end boiling point: 423°C.

During the test, we used the following process conditions:

LHSV (volumetric rate): 1.8 h-1;

the relation of H2/oil raw material: 300 nl/l;

pressure: 30 bar;

temperature: 325°C.

The relative activity of hydrodesulfurization (on a weight basis, based on the weight of the catalyst minus the weight of the additive, if it is present) of the catalysts of examples 1 and 2 was 124 and 147, respectively, when the activity of the catalyst of comparative example A, taken as 100. Adding organic compounds clearly improves catalyst.

Comparative example

The catalytic composition prepared by the Association and interaction of hydroxycarbonate Nickel Moo3and H2WO4in the aquatic environment. The resulting suspension was filtered. The obtained wet filter cake was dried at 140°C. the Dried substance was crushed and granulated. The resulting pellets contained 24 wt.% Moo3, 39 wt.% WO3and 37 wt.% NiO.

Example 4

The catalytic composition was prepared as described in comparative example B, except that the wet filter cake obtained after filtration of the suspension was mixed with 0.12 moles of diethylene glycol per mole of Nickel, molybdenum and tungsten contained in the Phil the traditional draught.

Example 5

The catalytic composition of comparative example b and example 4 was tested for the removal of polynuclear aromatic compounds from the exhaust of diesel fuel. Characteristics of raw materials and process conditions were as described in example 3. Relative activity (on a weight basis, based on the weight of the catalyst minus the weight of the additive, if it was present) of the catalyst of example 4 was measured and amounted to 118, compared to the activity of the catalyst of the comparative example, taken as 100. Supplement organic compounds clearly improves catalyst.

The dried substance was crushed and granulated. The resulting pellets contained 24 wt.% Moo3, 39 wt.% WO3and 37 wt.% NiO.

Example 4

The catalytic composition was prepared as described in comparative example B, except that the wet filter cake obtained after filtration of the suspension was mixed with 0.12 moles of diethylene glycol per mole of Nickel, molybdenum and tungsten contained in the filtration lees.

Example 5

The catalytic composition of comparative example b and example 4 was tested for the removal of polynuclear aromatic compounds from the exhaust of diesel fuel. Characteristics of raw materials and process conditions were as described in example 3. Relative activity (on a weight basis, based on the weight of the cat who lyst minus the weight of the additive, if it was present) of the catalyst of example 4 was measured and amounted to 118, compared to the activity of the catalyst of the comparative example, taken as 100. Supplement organic compounds clearly improves catalyst.

Comparative example

The catalytic composition was prepared by combining and interaction hydroxycarbonate Nickel Moo3and H2WO4in the aquatic environment at 90°C for 16 hours (in the continuation of the night) with continuous stirring. The resulting suspension was filtered. Received moist filter residue was mixed in the wet state with 7.5% wt. binder (where wt.% Dan calculated on the total weight of the catalytic composition). The water content of the mixture was regulated to obtain suitable for extruding the mixture, and the mixture was then extrudible. The obtained solid material was dried at 120°C for 16 hours (in the continuation of the night) and was caliciviral at 300°C for 1 hour. The obtained extrudates contained in 25.2 wt.% Moo3, of 41.5 wt.% WO3, and 26.5 wt.% NiO.

Example 6

The catalytic composition was prepared as described in comparative example C, except that the obtained extrudates were subjected to volume impregnation of the pores of ethylenediaminetetraacetic acid (AGTC; was added in the form of a 20% (wt.) aqueous solution diammonium salt add in number to 0.055 mol per mol of Nickel, contained in the material. The obtained solid material was dried at 120°C for 1 hour.

Example 7

The catalytic composition was prepared as described in comparative example C, except that the obtained extrudates were subjected to volume impregnation of the pores of nitrilotriacetic acid (NTA; was added in the form of a 20% (wt.) aqueous solution diammonium salt NTA) in the number of 0.085 mol per mol of the Nickel contained in the material. The obtained solid material was dried at 120°C for 1 hour.

Example 8

The catalysts were tested in a flow tube reactor with downward flow. Each tube reactor was filled with 10 ml of catalyst mixed with an equal amount of SiC particles and placed in a layer between layers of SiC particles. Before testing the pre-catalyst was sliderule by liquid phase prior sulfatirovnie using the raw materials described below, which was reinforced by the addition of dimethyl sulfide and total sulfur concentration in 3.7% of the mass.

During the preliminary sulfatirovnie used the following process conditions:

LHSV (vhsv): 3.0 hours-1;

the relation of H2/oil raw material: 200 nl/l;

pressure: 45 bar;

temperature: 320°C.

Pre sulforophane catalytic composition of comparative example C, example 6 the example 7 was tested on gidrogenizirovanii (hydrogencitrate), using waste diesel fuel having the following characteristics:

contents S: 1.2 wt.%;

the content of N: 106 h/m;

the number of monoaromatic hydrocarbons: 16.5 wt.%;

the number of di-aromatic hydrocarbons: 11,0 wt.%;

the number triaromatic hydrocarbons: 0.8 wt.%;

initial boiling point: to 178.4°C;

end boiling point: 372,0°C.

During the tests used the following process conditions:

LHSV (volume velocity): 2.0 hours-1;

the relation of H2/oil raw material: 300 nl/l;

pressure: 45 bar;

temperature: 320°C.

The relative activity of gidrogenizirovanii (on a weight basis, based on the weight of the catalyst minus the weight of the additive, if it is present) of the catalysts of examples 6 and 7 was $ 108 for both catalysts, the activity of the catalyst of the comparative example, taken as 100. Adding organic compounds, thus, clearly improves the performance of the catalyst.

1. The method for the catalytic composition, where at least one component made of base metal of group VIII and at least two of the component metals of group VIB are combined and injected into the interaction in the presence of proton fluid, after which the resulting composition is isolated and dried, and the total amount of component metals of the VIII g is uppy and VIB groups in terms of oxides is at least 50 wt.% the catalytic composition based on dry weight, and where the molar ratio of the metals of group VIB to base metals of group VIII is in the range from 10:1 to 1:10, characterized in that before, during or after integration and interaction of the components of metals add organic oxygen-containing additive containing at least one carbon atom, at least one hydrogen atom and at least one oxygen atom, in such manner and in such quantities that the molar ratio of the total amount of additives added to the total amount of component metals of group VIII and VIB group was, at least 0.01.

2. The method according to claim 1, where the catalyst is dried under such conditions that at least part of the additive is retained in the catalytic composition.

3. The method according to claim 1, where the catalyst composition additionally subjected to a stage of calcination.

4. The method according to any of the preceding paragraphs, where the components of metals combine and interact in solution with precipitate formation.

5. The method according to any one of claims 1 to 3, where at least one of the components of metals remains at least partly in the solid state during the entire process.

6. The method according to any of the preceding paragraphs, where the additive is selected from the group of compounds containing, less is th least two groups with oxygen atoms and from 2 to 20 carbon atoms, and compounds built from these compounds.

7. The method according to claim 6, where the organic additive selected from the group of compounds containing at least two hydroxy-group and 2-20 carbon atoms, and compounds built from these compounds.

8. The method according to claim 7, where the additive is at least one compound selected from ethylene glycol, diethylene glycol, polyethylene glycol, saccharide or polysaccharide.

9. The method according to any one of claims 1 to 8, wherein the additive satisfies the formula (I) (R1R2)N-R3-N(R1'R2') or formula (II) N(R1R2R1'), 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, simple, ether, amino or aminogroup, and R3 means alkylenes group with the number of carbon atoms up to 10, which can be interrupted by a group-O - or-NR4-, and R4 is selected from the same group defined above for R1, and where Allenova group R3 may be substituted by one or more groups selected from carbonyl, carboxyl, ester, simple, ether, amino or aminogroup; and the organic compound of the formula (I) or (II) contains at least one carbonyl structural element.

10. The method according to claim 9, where EXT is the WHC selected from Ethylenediamine(Tetra)acetic acid (EDTA), hydroxyethylenediaminetriacetate acid, diethylenetriaminepentaacetic acid and nitrilotriacetic acid (NTA).

11. The method according to any one of claims 1 to 10, where the additive is an ester of fatty(s) acid(acid), contains (), at least 12, preferably at least 16, more preferably at least 20 carbon atoms.

12. The method according to claim 11, where the acid ester is an ester of fatty(s) acid(acid) with a monoglyceride, diglyceride or triglyceride.

13. The method according to any of the preceding paragraphs, which additionally includes a step sulfatirovnie.

14. Catalytic composition comprising at least one component made of base metal of group VIII and at least two of the component metals of group VIB, where the catalytic composition further comprises at least 0.01 mol of organic oxygen-containing additive on 1 mol of the total number of VIB metals of the group and base metals of group VIII present in the catalytic composition, and this oxygen-containing organic additive contains at least one carbon atom, at least one hydrogen atom and at least one oxygen atom, and the total amount of component metals of the VIII group and VIB group in terms of oxides is at least 50 wt.% catalytic HDMI is tion per dry weight, where the molar ratio of the metals of group VIB to base metals of group VIII is in the range from 10:1 to 1:10.

15. The catalytic composition according to 14, where the components of metals of group VIII and VIB groups comprise at least 70 wt.% the catalytic composition in terms of oxides, preferably at least 90 wt.%.

16. The catalytic composition according to 14 or 15, where the component base metal of group VIII contains cobalt, Nickel, iron or mixtures thereof.

17. The catalytic composition according to item 16, where Nickel and cobalt are at least 50 wt.% of the total number of components of the base metals of group VIII, preferably at least 70 wt.%, more preferably at least 90 wt.%, most preferably, essentially all the components of the base metals of group VIII.

18. The catalytic composition according to any one of p-17, where the component metals of group VIB contains at least two of molybdenum, tungsten and chromium.

19. Catalytic composition for p, where molybdenum and tungsten are at least 50 wt.% of the total number of components of metals of group VIB, preferably at least 70 wt.%, more preferably at least 90 wt.%, most preferably, essentially all the components of metals of group VIB.

20. The catalytic composition according to any and the previous p-19, where the additive is selected from the group of compounds containing at least two oxygen atoms and from 2 to 20 carbon atoms, and compounds built from these compounds.

21. The catalytic composition according to claim 20, where the organic additive selected from the group of compounds containing at least two hydroxy-group and 2-20 carbon atoms, and compounds built from these compounds.

22. The catalytic composition according to item 21, where the additive is at least one compound selected from ethylene glycol, diethylene glycol, polyethylene glycol, saccharide or polysaccharide.

23. The catalytic composition according to any one of p-22, where the additive satisfies the formula (I) (R1R2)N-R3-N(R1'R2') or formula (II) N(R1R2R1'), 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, simple, ether, amino or aminogroup, and R3 means alkylenes group containing up to 10 atoms carbon, which can be interrupted by a group-O - or-NR4-, where R4 is selected from the same group defined above for R1, and Allenova group R3 may be substituted by one or more groups selected from carbonyl, carboxyl, ester, simple, ether, amino or aminogroup; moreover, the organic compound of the formula (I) or (II) contains, at least one carbonyl structural element.

24. The catalytic composition according to item 23, where the additive is selected from Ethylenediamine(Tetra)acetic acid (EDTA), hydroxyethylenediaminetriacetate acid and diethylenetriaminepentaacetic acid and nitrilotriacetic acid (NTA).

25. The catalytic composition according to any one of p-24, where the additive is an ester of fatty(s) acid(acid), contains (), at least 12, preferably at least 16, more preferably at least 20 carbon atoms.

26. The catalyst A.25, where the acid ester is an ester of fatty(s) acid(acid) with a monoglyceride, diglyceride or triglyceride.

27. The catalytic composition according to any one of the preceding p-26, which further comprises one or more compounds selected from the group of binder, conventional catalysts hydrobromide, kekirawa components or mixtures thereof.

28. The catalytic composition according to item 27, which contains 1-50, preferably 1-30, more preferably 1-10 wt.% binder or carrier, in particular of aluminum oxide.

29. Way catalytic hydrobromide hydrocarbon, optionally after sulfatirovnie, characterized in that the catalyst used for catalytic composition according to any one of p-28.



 

Same patents:

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides petroleum fraction hydrofining catalyst with following chemical analysis, wt %: CoO 2.5-4.0, MoO3 8.0-12.0, Na20.01-0.08, La2O3 1.5-4.0, P2O5 2.0-5.0, B2O3 0.5-3.0, Al2O3 - the balance.

EFFECT: enhanced hydrofining efficiency in cases of feedstock containing elevated amount of unsaturated hydrocarbons.

2 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic system of hydrocarbon feedstock hydrofining is activated by circulating hydrogen-containing gas or mixture thereof with starting feedstock through layer-by-layer loaded catalysts in presulfided or in presulfided and oxide form at elevated temperature and pressure. Hydrogen is injected into circulating hydrogen-containing gas or mixture thereof with starting feedstock portionwise, starting concentration of hydrogen in circulating hydrogen-containing gas not exceeding 50 vol %. Starting feedstock consumption is effected stepwise: from no more than 40% of the working temperature to completely moistening catalytic system and then gradually raising feedstock consumption to working value at a hourly rate of 15-20% of the working value. Simultaneously, process temperature is raised gradually from ambient value to 300-340°C. Circulating factor of hydrogen-containing gas achieves 200-600 nm3/m3. Addition of each portion of hydrogen is performed after concentration of hydrogen in circulating hydrogen-containing gas drops to level of 2-10 vol % and circulation of hydrogen-containing gas through catalysts loaded into reactor begins at ambient temperature and further temperature is stepwise raised. Starting feedstock, which is straight-run gasoline or middle distillate fractions, begins being fed onto catalytic system at 80-120°C.

EFFECT: enabled prevention and/or suppression of overheating in catalyst bed.

5 cl, 6 tbl, 12 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic system is prepared by consecutively charging into reactor alumino-cobalt and alumino-nickel-molybdenum catalysts containing 12.0-25.0% molybdenum oxide, 3,0-6.0% nickel oxide, and 3.0-6.9% cobalt oxide provided that alumino-cobalt and alumino-nickel-molybdenum catalysts are charged at ratio between 1.0:0.1 and 0.1:1.0, preparation of catalysts employs mixture of aluminum hydroxide and/or oxide powders, to which acids are added to pH 1-5. More specifically, aluminum hydroxide powder mixture utilized is a product of thermochemical activation of gibbsite and pseudoboehmite AlOOH and content of pseudoboehmite in mixture is at least 70%, and aluminum oxide powder mixture utilized comprises powders of γ-Al2O3 with particle size up to 50 μm and up to 50-200 μm taken at ratio from 5:1 to 2:5, or γ-Al2O3 powders with particle size up to 50 μm, 50-200 μm, and up to 200-400 μm taken at ratio between 1:8:1 and 3:6:1.

EFFECT: method of preparing catalytic systems for large-scale high-sulfur hydrocarbon feedstock hydrofining processes is provided allowing production of products with desired levels of residual sulfur and polycyclic aromatic hydrocarbons.

4 tbl, 3 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention provides catalyst for hydrofining of petroleum fractions, which catalyst shows elevated strength and stability upon regeneration. This is achieved supplementing alumina-based carrier with texturing additives selected from alumina and gibbsite thermochemical activation product in amount 5 to 30 wt %. Alumina additive is used with particle size not larger than 15 μm and gibbsite thermochemical activation product with that not larger than 45 μm. As binding agent in catalyst, nitric acid is used at molar ratio to alumina (0.01-0.03):1 and/or aluminum nitrate/ aluminum metal reaction product in amounts 1 to 5% based on alumina. Prior to be impregnated, catalyst is steamed at elevated temperature and impregnation is carried out from aqueous solution of nickel-cobalt-molybdenum-containing complex at pH 1-3.

EFFECT: improved performance characteristics of catalyst.

2 cl, 3 tbl, 10 ex

FIELD: petroleum refining industry.

SUBSTANCE: the invention is pertaining to the field of petroleum refining industry, in particular, to the methods of production of an ecologically pure diesel fuel. Substance: carry out hydraulic purification of a mixture of a virgin diesel fraction and distillate of carbonization and a catalytic cracking. The layers of the catalysts are located in the following way. The first on a course of traffic of a gas-raw material stream protective layer of wide-porous low-percentageNi-Co-Mo/Al2O3 catalyst is made in the form of the hollow cylinders. The second layer - the catalyst with a diameter of granules of 4.5-5.0 mm. The third - the basic catalyst made in the form of granules with a diameter of 2.0-2.8 mm. The basic catalyst has a surface of 250-290 m2 /g, a pore volume - 0.45-0.6 cm3 / g, in which - no less than 80 % of poremetric volume is formed by the through internal pores predominary of a cylindrical shape with a diameter of 4.0-14.0 nanometers. The last layer on a course of raw material traffic layer is organized analogously to the second layer. Loading of 2-4 layers is performed by a method of a tight packing. The technical result - production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm from the mixture of the virgin run fraction and distillates of a carbonization and a catalytic cracking containing up to 1.3 % mass of sulfur, at a low hardness of the process and a long time interrecovery cycle.

EFFECT: the invention ensures production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm.

7 cl, 2 tbl, 2 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of catalyst comprises two-step impregnation of preliminarily calcined carrier with first ammonium heptamolybdate solution and then, after intermediate heat treatment at 100-200°C, with cobalt and/or nickel nitrate solution followed by final heat treatment including drying at 100-200°C and calcination at 400-650°C. Catalyst contains 3.0-25.0% MoO3, 1.0-8.0% CoO and/or NiO on carrier: alumina, silica, or titanium oxide.

EFFECT: enhanced hydrodesulfurization and hydrogenation activities allowing involvement of feedstock with high contents of sulfur and unsaturated hydrocarbons, in particular in production of environmentally acceptable motor fuels.

3 cl, 4 tbl, 13 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention related to hydrofining of hydrocarbon mixtures with boiling range 35 to 250оС and containing no sulfur impurities provides catalytic composition containing β-zeolite, group VIII metal, group VI metal, and possibly one or more oxides as carrier. Catalyst is prepared either by impregnation of β-zeolite, simultaneously or consecutively, with groups VIII and VI metal salt solutions, or by mixing, or by using sol-gel technology.

EFFECT: increased isomerization activity of catalytic system at high degree of hydrocarbon conversion performed in a single stage.

40 cl, 2 tbl, 19 ex

FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

10 cl, 8 ex, 4 dwg

The invention relates to the refining and can be used when cleaning the cracking of gasoline from sulfur and unsaturated compounds

FIELD: chemical industry; materials and the methods for the catalyst carrier manufacture.

SUBSTANCE: the invention is pertaining to the new mixed oxides produced from ceric oxide and zirconium oxide, which can used as the catalyzers or the catalyzers carriers for purification of the combustion engine exhaust gases. The mixed oxide possesses the polyphase cubical form of the crystallization and oxygenous capacity of at least 260/ micromoles of O2 /g of the sample and the speed of the oxygen extraction of more than 1.0 mg-O2/m2-minute, which are measured after combustion within 4 hours at the temperature of 1000°C. The invention also presents the substrate with the cover containing the indicated mixed oxide. The method of production of the polycrystallic particles of the indicated mixed ceric-zirconium oxide includes the following stages: i) production of the solution of the mixed salt which are containing, at least, one salt of cerium and, at least, one salt of zirconium in the concentration, sufficient for formation of the polycrystallic particles of the corresponding dry product on the basis of the mixed oxide. At that the indicated particles have the cerium-oxide component and zirconium-oxide component, in which these components are distributed inside the subcrystalline structure of the particles in such a manner, that each crystallite in the particle consists of a set of the adjacent one to another domains, in which the atomic ratios of Ce:Zr which are inherited by the adjacent to each other domains, are characterized by the degree of the non-uniformity with respect to each other and determined by means of the method of the X-ray dissipation the small angles and expressed by the normalized intensity of the dissipation I(Q) within the limits from approximately 47 up to approximately 119 at vector of dissipation Q, equal to 0.10 A-1; ii) treatment of the solution of the mixed salt produced in compliance with the stage (i),with the help of the base with formation of sediment; iii) treatment of the sediment produced in compliance with the stage (ii),using the oxidative agent in amount, sufficient for oxidizing Ce+3 up to Ce+4; iv) washing and drying of the residue produced in compliance with the stage (iii); and v) calcination of the dry sediment produced in compliance with the stage (iv),as the result there are produced polycrystallic particles of the oxide of ceric and zirconium in the form of the mixed oxide with the above indicated characteristics. The technical result is the produced mixed oxide possesses both the high oxygenous capacitance, and the heightened speed of the oxygen return in the conditions of the high temperatures.

EFFECT: the invention ensures production of the mixed oxide manufactured from ceric oxide and zirconium oxide and possessing the high oxygenous capacitance and the heightened speed of the oxygen return in the conditions of the high temperatures.

68 cl, 21 ex, 2 dwg

FIELD: catalyst preparation methods.

SUBSTANCE: invention provides Fischer-Tropsch catalyst, which consists essentially of cobalt oxide deposited on inert carrier essentially composed of alumina, said cobalt oxide being consisted essentially of crystals with average particle size between 20 and 80 Å. Catalyst preparation procedure comprises following stages: (i) preparing alumina-supported intermediate compound having general formula I: [Co2+1-xAl+3x(OH)2]x+[An-x/n]·mH2O (I), wherein x ranges from 0.2 to 0.4, preferably from 0.25 to 0.35; A represents anion; x/n number of anions required to neutralize positive charge; and m ranges from 0 to 6 and preferably is equal to 4; (ii) calcining intermediate compound I to form crystalline cobalt oxide. Invention also described a Fischer-Tropsch process for production of paraffin hydrocarbons in presence of above-defined catalyst.

EFFECT: optimized catalyst composition.

16 cl, 12 tbl, 2 ex

FIELD: chemical industry; methods of production of zirconium oxides

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of obtaining of zirconium oxide for production of the catalytic agents used, for example, in the reactions of the organic synthesis. The invention presents the method of obtaining of zirconium oxide for production of the catalytic agents, which includes the operations of dissolution of the zirconium salt in water, treatment of the solution with the alkaline reactant, settling of the metals hydroxides, filtration, separation of the mother-liquor from the settlings, the settlings water flushing, its drying, calcination and granulation and-or granulation by molding. At that dissolution of the source zirconium chloride and-or zirconium oxychloride is conducted in the sodium chloride solution with concentration of 200-250 g/dc3 till reaching of the concentration of zirconium of 20-120 g/dc3. Settling of zirconium oxyhydrate is conducted by the adding the initial chloride solution in the solution of the sodium hydroxide with concentration of 20-80 g/dm3 up to reaching the suspension pH equilibrium value - 5-8. Then the suspension is filtered up to the zirconium oxyhydrate pasta residual humidity of 40-80 %. The mother chloride solution is separated from the settlings of zirconium oxyhydrate and again use it for dissolution of the next batch of zirconium chloride and-or zirconium oxychloride. The settlings of zirconium oxyhydrate are subjected to drying at 80-100°C within 2-6 hours, then the dry settlings are suspended in the water at the ratio of liquid to solid L:S = (5-10 :1, the suspension is filtered, the sediment on the filter is flushed by water, the chlorides are wash off up to the residual concentration of ions of chlorine in the flush waters of 0.1-0.5 g/dm3, divided into 2 parts, one of which in amount of 60-80 % is subjected to drying and calcinations at the temperatures of 300-600°C, and other part in amount of 20-40 % is mixed with the calcined part of the settlings and subjected to granulation by extrusion at simultaneous heating and dehydration of the damp mixture of zirconium oxide and zirconium oxyhydrate with production of the target product. The technical result of the invention is improvement of quality of the produced zirconium oxide for production of the catalytic agents due to provision of the opportunity to use ZrO2 for the subsequent production of the various catalytic agents of the wide range of application and thereby improving the consumer properties of the produced production.

EFFECT: the invention ensures improvement of the quality of the produced zirconium oxide for production of the catalytic agents with improved consumer properties.

1 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention, in particular, relates to catalyst based on synthetic mesoporous crystalline materials and provides hydrocarbon conversion catalyst composed of: group VIII metal/SO42-/ZrO2-EOx, where E represents element of the group III or IV of Mendeleev's periodic table, x = 1.5 or 2, content of SO42- is 0.1 to 10% by weight, ZrO2/EOx molar ratio is 1:(0.1-1.0), which has porous crystalline structure with specific surface 300-800 m2/g and summary pore volume 0.3-0.8 cm3/g. Preparation method comprises precipitation of zirconium compounds, in particular zirconium hydroxide or zirconyl, under hydrothermal conditions in presence of surfactant to form mesoporous phase, which is stabilized with stabilizing agents: group III and IV elements. When stabilization is achieved, if necessary, acidity is adjusted and group VIII metal is added.

EFFECT: increased specific surface area and heat resistance at simplified technology.

9 cl, 2 dwg, 2 tbl, 6 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention relates to methods for preparing carbon monoxide-conversion catalysts used in production of hydrogen, nitrogen-hydrogen mixture, and other hydrogen-containing gases. According to first option, active catalyst component, i.e. iron compound, is precipitated from solution with precipitation reagent, whereupon precipitate is separated from mother liquor and washed to form catalyst mass, which is molded and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. According to second option, iron compound is first mixed with promoting additives and cations of promoting additives are precipitated jointly with iron cations, resulting precipitate is separated from mother liquor, washed and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. As iron compound in the first and second options, ferrous and ferric sulfates and, as precipitation reagent, carbonate salts or corresponding hydroxides are utilized. Promoting additives are selected from Cu, Mn, and Al or, in the second option, their mixture.

EFFECT: reduced content of sulfur in finished catalyst at the same catalyst activity.

3 cl, 1 tbl, 12 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to environmentally friendly processes for production of isoalkanes via gas-phase skeletal isomerization of linear alkanes in presence of catalyst. Invention provides catalyst for production of hexane isomers through skeletal isomerization of n-hexane, which catalyst contains sulfurized zirconium-aluminum dioxide supplemented by platinum and has concentration of Lewis acid sites on its surface 220-250 μmole/g. Catalyst is prepared by precipitation of combined zirconium-aluminum hydroxide from zirconium and aluminum nitrates followed by deposition of sulfate and calcination in air flow before further treatment with platinum salts. Hexane isomer production process in presence of above-defined cat is also described.

EFFECT: increased catalyst activity.

5 cl, 2 tbl, 6 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.

EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.

1 dwg, 1 tbl, 12 ex

FIELD: heterogeneous catalysts.

SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.

55 cl, 4 dwg

The invention relates to a method for producing a catalyst hydrobromide, to a catalytic composition obtained by the above method, and to use this catalytic composition in hydrobromide

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to composition suitable for use in reaction zone wherein aniline is brought into contact with nitrobenzene to produce 4-aminodiphenylamine synthesis intermediates, which composition contains zeolite having internal channels with a base introduced therein to take part in above reaction. Dimensions of cross-section of channels is such that a limited reaction transition state is ensured thereby improving selectivity of reaction with regard to desired intermediates. Invention also related to the title process using above defined composition.

EFFECT: improved selectivity of 4-aminodiphenylamine intermediates production.

9 cl, 12 dwg, 7 tbl, 8 ex

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