CN102161002B - Catalyst for hydrotreatment and application thereof - Google Patents

Abstract

A hydrotreating catalyst comprising an alumina support, at least one metal component selected from group VIII and at least one metal component selected from group VIB, characterized in that the alumina support is composed of at least two pseudoboehmite Stones P1 and P2 are obtained by mixing, molding, and roasting, wherein, P1 is pseudo-boehmite with 1.1≤n ₁ ≤2.5, and P2 is pseudo-boehmite with 0.8<n ₂ <1.1; n _{(1 or 2)} =D _{(1 or 2)} (031)/D _{(1 or 2)} (120), said D _{(1 or 2)} (031) represents the XRD spectrogram of P1 or P2 pseudo-boehmite crystal grains (031 ) The grain size of the crystal face represented by the peak, D _{(1 or 2)} (120) represents the crystal grain size of the (120) peak in the XRD spectrogram of P1 or P2 pseudoboehmite crystal grains, The 031 peak refers to the peak whose 2θ is 34-43° in the XRD spectrum, and the 120 peak refers to the peak whose 2θ is 23-33° in the XRD spectrum, D=Kλ/(Bcosθ), and λ is the target type The diffraction wavelength of the material, B is the half width of the corrected diffraction peak, and 2θ is the position of the diffraction peak. Compared with the prior art, the present invention provides significantly improved catalyst performance.

Description

A kind of hydrotreating catalyst and its application

technical field

The present invention relates to a hydrotreating catalyst and its application.

Background technique

With the increasing scarcity of petroleum resources, the contradiction between heavy crude oil and light products has become increasingly acute. Oil refining companies around the world are vigorously developing catalytic cracking (RFCC) technology and coking and other thermal cracking technologies for blending or fully refining residual oil. , of which the RFCC process has become the most effective process for lightening heavy oil. However, the high content of impurities in the residual oil, such as sulfur, nitrogen, metals and residual carbon, has a greater impact on the stable operation of the RFCC process unit. In order to increase the adaptability of residual oil feed to the RFCC unit, as the raw material pretreatment unit of the RFCC unit, the impurity removal rate of the catalyst bed of the residual oil fixed bed hydrotreating unit, especially the desulfurization rate, demetallization rate and residual carbon removal rate rate becomes more important.

Alumina carrier is the carrier for preparing such catalysts. The pore structure of the catalyst can be optimized through the selection of the alumina carrier, thereby improving the performance of the catalyst. For example:

Patent ZL97115112 discloses a residual oil hydrodemetallization catalyst, which uses Group VIII and/or Group VIB metal elements as active components and supports them on a large-pore alumina carrier. The carrier has a pore volume of 0.80-1.20ml/g (mercury porosimetry), a specific surface area of 110-200m ² /g, a programmable pore diameter of 15-20nm and a bulk density of 0.50-0.60g/ml. In the method of the present invention, during the kneading process of pseudo-boehmite, a physical pore-enlarging agent and a chemical pore-enlarging agent are added at the same time, kneaded into a plastic body, extruded, dried, and roasted to obtain a carrier, and then sprayed and impregnated. The active components are added to the carrier, dried and calcined to obtain the catalyst. The catalyst of the invention is suitable for the hydrodemetallization and/or hydrodesulfurization process of heavy oil, especially residual oil.

Patent ZL200310117322 discloses a residual oil hydrodemetallization catalyst and its preparation method. The catalyst contains a macroporous alumina carrier and molybdenum and/or tungsten and cobalt and/or nickel loaded on the carrier, with oxide Calculated and based on the catalyst, the catalyst contains 0.5-15% by weight of molybdenum and/or tungsten, 0.3-8% by weight of cobalt and/or nickel, and a balanced amount of carrier, characterized in that the carrier contains a Halogen, based on the total amount of the carrier, the carrier contains 95-99% by weight of alumina, calculated as elements, 0.1-5% by weight of halogen, and its acid content is less than 0.2 mmol/g. Because the amount of carrier acid in the catalyst provided by the invention is low, it maintains high hydrodemetallization activity and at the same time has low carbon deposition.

In the prior art, a hydrogenation catalyst meeting specific requirements can be obtained by selecting an alumina carrier. However, there is still much room for improvement in the performance of these catalysts when they are used in hydroprocessing reactions, especially in heavy oil hydroprocessing demetallization reactions.

Contents of the invention

The technical problem to be solved by the present invention is to provide a new hydroprocessing catalyst with better performance and the application of the catalyst based on the prior art.

The invention provides a hydrotreating catalyst, which contains an alumina support, at least one metal component selected from group VIII and at least one metal component selected from group VIB, characterized in that the alumina support is composed of P1 and P2 A composition of at least two kinds of pseudo-boehmite is obtained by mixing, molding, and roasting, wherein, P1 is pseudo-boehmite with 1.1≤n ₁ ≤2.5, and P2 is pseudo-boehmite with 0.8<n ₂ <1.1 ; n _{(1 or 2)} = D _{(1 or 2)} (031)/D _{(1 or 2)} (120), said D _{(1 or 2)} (031) represents P1 or P2 pseudo-boehmite crystal grains The crystal grain size of the crystal face represented by the (031) peak in the XRD spectrum of D _{(1 or 2)} (120) represents the location of the (120) peak in the XRD spectrum of the P1 or P2 pseudo-boehmite grain The grain size of the crystal plane, the 031 peak refers to the peak that 2θ is 34-43 ° in the XRD spectrum, and the 120 peak refers to the peak that 2θ is 23-33 ° in the XRD spectrum, D=Kλ/( Bcosθ), λ is the diffraction wavelength of the target material, B is the half-width of the corrected diffraction peak, and 2θ is the position of the diffraction peak.

The present invention provides a hydrocarbon oil hydrotreating method, comprising contacting and reacting hydrocarbon oil feedstock with a catalyst under hydrotreating reaction conditions, characterized in that the catalyst is the aforementioned catalyst provided by the present invention.

Compared with the prior art, the present invention provides a catalyst prepared from a carrier obtained by mixing, molding and calcining compositions containing at least two pseudo-boehmites P1 and P2, so that the performance of the catalyst is improved. For example, a residue hydrodemetallization and desulfurization catalyst containing 14.5% by weight of molybdenum oxide and 3.4% by weight of cobalt oxide is prepared by using the alumina carrier obtained by roasting the pseudo-boehmite composition that meets the requirements of the present invention. Maoming Shaqing VRDS with a content of 15.6ppm, a vanadium content of 38.2ppm, a sulfur content of 3.3%, a nitrogen content of 0.24%, and a residual carbon content of 10.7% was used as a raw material for activity evaluation. The desulfurization rate was 88.7%, and the demetallization rate was 88.7%. is 67.2. And the residual oil hydrodemetallization and desulfurization catalyst containing 14.5% by weight of molybdenum oxide and 3.4% by weight of cobalt oxide prepared by the reference carrier, when evaluating with the same raw material oil and process conditions, the desulfurization rate and demetallization rate are respectively 87.8 % and 66.8%.

Detailed ways

According to the catalyst provided by the present invention, wherein the alumina support is prepared from a support obtained by mixing, molding and calcining a composition containing at least two pseudoboehmites P1 and P2, wherein P1 is 1.1≤n ₁ ≤ The pseudo-boehmite of 2.5, P2 is the pseudo-boehmite of 0.8<n ₂ <1.1; n _{(1 or 2)} = D _{(1 or 2)} (031)/D _{(1 or 2)} (120), The D _{(1 or 2)} (031) represents the grain size of the crystal face represented by (031) peak in the XRD spectrogram of P1 or P2 pseudo-boehmite grains, D _{(1 or 2)} (120) Represents the grain size of the crystal plane where the (120) peak is located in the XRD spectrum of the P1 or P2 pseudo-boehmite grain, D=Kλ/(Bcosθ), λ is the diffraction wavelength of the target material, and B is the corrected The half width of the diffraction peak, 2θ is the position of the diffraction peak. Preferably, P1 is pseudo-boehmite with 1.2≤n ₁ ≤2.2, and P2 is pseudo-boehmite with 0.85≤n ₂ ≤1.05.

The composition is obtained by mixing P1 and P2, and the mixing can be a simple stacking of the P1 and P2 in one place, or any existing technology can be used, for example, it can be directly mixed in a mixer or a grinder. Mixing P1 and P2 by stirring, may be mixing P1 and P2 and water under conditions sufficient for slurrying, followed by filtering, drying or non-drying. When using any of the existing techniques for mixing, those skilled in the art can control the uniformity of the mixing if necessary, and the present invention has no special limitation on this.

Wherein, the mixing ratio of P1 and P2 can be arbitrary if necessary, and there is no special limitation here. In a preferred embodiment, the mixing weight ratio of P1 and P2 is preferably P1:P2 in the range of 40:60-95:5, more preferably 45:55-80:20.

The pseudo-boehmite whose P2 is 0.8<n ₂ <1.1 can be selected from commercially available products or pseudo-boehmite prepared by any prior art.

The preparation method of the pseudo-boehmite whose P1 is 1.1≤n ₁ ≤2.5 comprises: contacting an aluminum-containing compound solution with an acid or an alkali for a precipitation reaction, or contacting an organic aluminum-containing compound with water for a hydrolysis reaction to obtain a hydrated Alumina: aging the hydrated alumina obtained above, wherein any one of the contacting of the aluminum-containing compound solution with acid or alkali or the contacting of the organic aluminum-containing compound with water and the aging of the hydrated alumina It is carried out in the presence of a grain growth regulator, which is a substance capable of regulating the growth rate of crystal grains on different crystal planes. According to the catalyst provided by the present invention, the pseudo-boehmite whose P2 is 0.8<n ₂ <1.1 can be the pseudo-boehmite prepared by any prior art.

Although the object of the present invention can be achieved as long as any one of the hydrolysis reaction or precipitation reaction and aging is carried out in the presence of a grain growth regulator, preferably, the hydrolysis reaction and aging process or the precipitation reaction and The aging process is all carried out in the presence of a grain growth regulator, so that n ₁ of the obtained P1 pseudo-boehmite can be preferably in the range of 1.2≤n ₁ ≤2.2.

Wherein, there is no particular limitation on the amount of the grain growth regulator, preferably the amount of the grain growth regulator in the hydrolysis reaction is 0.5-10% by weight of the weight of the organic aluminum-containing compound to be hydrolyzed, more preferably 1-8.5% by weight , more preferably 5-8.5% by weight; the amount of the grain growth regulator in the precipitation reaction is 0.5-10% by weight of the weight of the inorganic aluminum-containing reactant, more preferably 1-8.5% by weight, even more preferably 5- 8.5% by weight; during the aging process, the grain growth regulator can be used in an amount of 0.5-10% by weight of the alumina hydrate, preferably 1-8.5% by weight, and more preferably 5-8.5% by weight. Unless otherwise specified, in the present invention, the amount of the grain growth regulator is calculated based on the weight of the organic aluminum-containing compound, the inorganic aluminum-containing compound and the corresponding alumina in the hydrated alumina. That is, in terms of alumina, in the precipitation reaction, the amount of the grain growth regulator is 0.5-10% by weight of the weight of the inorganic aluminum-containing compound; in the hydrolysis reaction, the amount of the grain growth regulator is The amount used is 0.5-10% by weight of the weight of the organic aluminum-containing compound, and the amount of the grain growth regulator used during the aging process is 0.5-10% by weight of the weight of the hydrated alumina.

In the present invention, the grain growth regulator can be various substances capable of regulating the growth rate of grains on different crystal planes, especially substances capable of regulating the growth rates of grains on the 120 crystal plane and the 031 crystal plane, The preferred regulator is polyhydric sugar alcohol and carboxylate thereof, specifically one or more of sorbitol, glucose, gluconic acid, gluconate, ribitol, ribobic acid, and ribose salt. Each of the gluconate and ribose salt can be their soluble salts, for example, one or more of potassium salt, sodium salt and lithium salt.

In the preparation process of the P1 pseudoboehmite described in the present invention, there is no particular limitation on the addition method of the grain growth regulator, the grain growth regulator can be added separately, or the grain growth regulator can be added in advance It is mixed with one or several raw materials, and then the raw materials containing the grain growth regulator are reacted.

Wherein, the inorganic aluminum-containing compound solution can be various aluminum salt solutions and/or aluminate solutions, and the aluminum salt solution can be various aluminum salt solutions, such as aluminum sulfate, aluminum chloride, aluminum nitrate One or several aqueous solutions. Because the price is low, aluminum sulfate and aluminum chloride solution are preferred. Aluminum salts can be used alone or in combination of two or more. The aluminate solution is any aluminate solution, such as sodium aluminate solution and/or potassium aluminate solution. Sodium aluminate solutions are preferred because of their availability and low cost. Aluminate solutions can also be used alone or in combination.

The concentration of the aluminum salt solution and/or aluminate solution is not particularly limited, and is preferably 0.2-1.1 mol/liter calculated as alumina.

The acid can be various protonic acids or acidic oxides in aqueous medium, for example, it can be one or more of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, oxalic acid, Preferred protic acid is selected from one or more of nitric acid, sulfuric acid, hydrochloric acid. The carbonic acid can be generated in situ by passing carbon dioxide into the aluminum salt solution and/or aluminate solution. The concentration of the acid solution is not particularly limited, preferably the concentration of H ⁺ is 0.2-2 mol/L.

The alkaline solution can be a hydroxide or a salt that is hydrolyzed in an aqueous medium to make the aqueous solution alkaline, and the preferred hydroxide is selected from one or more of ammonia, sodium hydroxide, and potassium hydroxide; preferred The salt is selected from one or more of sodium metaaluminate, potassium metaaluminate, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, and potassium carbonate. The concentration of the alkaline solution is not particularly limited, and the concentration of OH ^- is preferably 0.2-4 mol/liter. When sodium metaaluminate and/or potassium metaaluminate is used as the base, when calculating the dosage of the grain growth regulator, the corresponding amount of aluminum oxide in sodium metaaluminate and/or potassium metaaluminate is also considered.

The organic aluminum-containing compound can be one or more of various aluminum alkoxides that can undergo hydrolysis reactions with water to produce alumina hydrate precipitation, such as aluminum isopropoxide, aluminum isobutoxide, triisobutoxide One or more of aluminum propoxide, aluminum tri-tert-butoxide and aluminum isooctoxide. The ratio of the amount of the organic aluminum-containing compound to water is not particularly limited, and the amount of water is preferably greater than the stoichiometrically required amount.

In the preparation process of P1 pseudo-boehmite described in the present invention, the conditions for the precipitation reaction are not particularly limited, preferably the pH value is 3-11, more preferably 6-10; the temperature can be 30-90°C , preferably 40-80°C.

Among them, the method of precipitating aluminum by controlling the amount of alkali or acid used in the reactant is well known to those skilled in the art.

The conditions of the hydrolysis reaction are not particularly limited, as long as the water contacts with the aluminum alkoxide and undergoes a hydrolysis reaction to generate hydrated alumina, and the specific conditions for the hydrolysis to occur are known to those skilled in the art.

Among them, the compound that can regulate the grain growth can be added to the slurry of alumina hydrate obtained from the hydrolysis reaction or precipitation reaction or the slurry prepared by adding water to the filter cake after filtration, and the pH value can also be adjusted by adding an alkali solution or an acid solution. to 7-10, and then aged at an appropriate temperature. Then separate, wash and dry.

The acid solution or base solution may be the same as or different from that described above.

The aging temperature is preferably 35-98°C, and the aging time is preferably 0.2-6 hours.

According to the method provided by the present invention, the separation is a well-known technique in the art, such as filtration or centrifugation or evaporation.

In the P1 pseudo-boehmite preparation process of the present invention, after aging, the steps of washing and drying that are often included in the preparation of pseudo-boehmite process are also included, and the washing and drying method is to prepare pseudo-boehmite Stone idiomatic method. For example, drying, blast drying or spray drying can be used. Generally speaking, the drying temperature can be 100-350°C, preferably 120-300°C.

According to the preparation method of P1 pseudo-boehmite of the present invention, a preferred embodiment comprises the following steps:

(1) Add the aluminum-containing compound solution containing the grain growth regulator and the alkali solution or the acid solution in parallel or intermittently to the reaction vessel for precipitation reaction to obtain a hydrated alumina slurry; or add grain growth in deionized water The regulator and the aluminum alkoxide undergo a hydrolysis reaction to obtain a hydrated alumina slurry;

(2) Add water to the alumina slurry obtained after filtering the hydrated alumina slurry obtained in step (1), add a grain growth regulator, adjust the pH to 7-10, and heat the filter cake at 35-98°C Aging for 0.2-6 hours; the alumina hydrate slurry obtained in the above step (1) can also be aged at 35-98° C. for 0.2- 6 hours;

(3) filtering, washing the product obtained in step (2);

(4) drying the product obtained in step (3) to obtain the P1 pseudo-boehmite provided by the present invention.

The molding can be carried out by conventional methods, such as tableting, ball rolling, extrusion and other methods.

In a preferred embodiment, the preparation method of the alumina shaped carrier comprises:

(1) Mix the pseudo-boehmite P1 of 1.1≤n≤2.5 and the pseudo-boehmite P2 of n<1.1 with water under sufficient slurrying conditions, and then filter, dry or not dry to obtain the obtained said composition;

(2) extruding the composition obtained in step (1) on an extruder;

(3) drying and roasting the extruded product obtained in step (2).

Wherein, in order to guarantee the smooth carrying out of extruded molding, in step (2), include introducing appropriate amount of water, peptizing agent (such as being selected from one or more in nitric acid, acetic acid and citric acid), auxiliary Squeeze agent (such as can be one or more in the turnip powder, cellulose) and the step of mixing. The amount of water used and the types and amounts of the extrusion aid and peptizer are well known to those skilled in the art, and will not be repeated here. The drying is a conventional method, such as using an oven, a mesh belt kiln and a fluidized bed for drying. When using a heating method for drying, the preferred drying temperature is 50-200 ° C, and the drying time is 0.3-12 hours. More preferably, the drying temperature is The temperature is 60-150℃, and the drying time is 0.5-8 hours. The method and conditions of the calcination are the usual methods and conditions used in the preparation of the catalyst carrier, such as using a mesh belt kiln, a vertical test furnace and a converter for calcination, and the conditions of the calcination are preferably calcination at a temperature of 350-1200°C 1-12 hours, more preferably at a temperature of 500-950° C. for 2-8 hours.

In another preferred embodiment, the preparation method of the alumina shaped carrier comprises:

(1) Mixing the pseudo-boehmite P1 of 1.1≤n≤2.5 and the pseudo-boehmite P2 of n<1.1 on a kneader to obtain the composition;

(2) extruding the composition obtained in step (1) on an extruder;

(3) drying and roasting the extruded product obtained in step (2).

Wherein, in order to ensure the smooth progress of extrusion molding, step (1) includes introducing an appropriate amount of water, peptizer (such as one or more selected from nitric acid, acetic acid and citric acid), extrusion aid (such as can be one or more of safflower powder and cellulose). The amount of water used and the types and amounts of the extrusion aid and peptizer are well known to those skilled in the art, and will not be repeated here. The drying is a conventional method, such as using an oven, a mesh belt kiln and a fluidized bed for drying. When using a heating method for drying, the preferred drying temperature is 50-200 ° C, and the drying time is 0.3-12 hours. More preferably, the drying temperature is The temperature is 60-150℃, and the drying time is 0.5-8 hours. The method and conditions of the calcination are the usual methods and conditions used in the preparation of the catalyst carrier, such as using a mesh belt kiln, a vertical test furnace and a converter for calcination, and the conditions of the calcination are preferably calcination at a temperature of 350-1200°C 1-12 hours, more preferably at a temperature of 500-950° C. for 2-8 hours.

According to the catalyst provided by the present invention, the content of at least one metal component selected from group VIII and at least one metal component selected from group VIB is the usual content of heavy oil hydrotreating catalysts. In a preferred embodiment, the preferred VIII group metal component is cobalt and/or nickel, the VIB group metal component is molybdenum and/or tungsten, calculated as an oxide and based on the catalyst, the VIII group metal component The content of the VIB metal component is preferably 0.5-10% by weight, more preferably 1.5-5% by weight, and the content of the VIB group metal component is preferably 5-35% by weight, more preferably 6-30% by weight.

On the premise that the metal components selected from at least one Group VIB and at least one Group VIII are sufficiently supported on the support, the present invention supports the metal components of Group VIB and Group VIII The method of loading on the carrier is not particularly limited. For example, the support may be mixed with an effective amount of a metal component selected from Group VIII under conditions sufficient to deposit an effective amount of a nickel and/or cobalt metal component selected from Group VIII on the support. Contact with the solution of the compound of nickel and/or cobalt metal components of the group, such as by impregnation, co-precipitation, etc., preferably impregnation, followed by drying, calcination or no calcination. The drying conditions are common conditions for preparing such catalysts, for example, the drying temperature is 80-350°C, preferably 100-300°C, and the drying time is 1-24 hours, preferably 2-12 hours. When the catalyst needs to be calcined, the temperature is preferably 100-700° C., and the calcination time is 1-6 hours. More preferably, the temperature is 200-500° C., and the calcination time is 2-4 hours.

The Group VIII metal compound is selected from one or more of Group VIII metal soluble compounds, such as nitrates, acetates, soluble carbonates, chlorides, and soluble complexes of cobalt and/or nickel metals one or more of them.

The VIB group metal compound is selected from one or more of the VIB group metal soluble compounds, such as one or more of molybdate, tungstate, metatungstate, ethyl metatungstate .

According to the catalyst provided by the present invention, it can also contain any material that does not affect the catalytic performance of the catalyst provided by the present invention or can improve the catalytic performance of the catalyst provided by the present invention. For example, one or both of the components such as phosphorus or silicon can be introduced, calculated as elements and based on the catalyst, the introduction amount of the above additives is 0-10% by weight, preferably 0.5-5% by weight.

When the catalyst contains one or two components selected from components such as phosphorus or silicon, the introduction method can be to directly mix the compound containing the auxiliary agent with pseudo-boehmite, shape and roast ; It can be that the compound containing the auxiliary agent and the compound containing the hydrogenation active metal component are formulated into a mixed solution and then contacted with the alumina carrier; it can also be that the compound containing the auxiliary agent is prepared separately. The alumina support is contacted and fired. When the auxiliary agent and the first hydrogenation active metal are respectively introduced into the alumina support, it is preferable to contact and roast the alumina support with a solution containing the auxiliary agent compound first, and then with a solution containing the compound of the hydrogenation active metal component For contacting, for example, ion exchange, impregnation, co-precipitation and other methods, preferably impregnation method, the calcination temperature is 250-600°C, preferably 350-500°C, and the calcination time is 2-8 hours, preferably 3-6 hours.

According to the method provided by the present invention, the hydrotreating reaction conditions are the usual reaction conditions for the hydrotreating of heavy feedstock oil, and in a preferred embodiment, the hydrotreating reaction conditions are: reaction temperature 300-550°C , more preferably 330-480°C, hydrogen partial pressure 4-20 MPa, more preferably 6-18 MPa, volume space velocity 0.1-3 hours ^-1 , more preferably 0.15-2 hours ^-1 , hydrogen-oil volume ratio 200- 2500, more preferably 300-2000.

The device for the hydroprocessing reaction can be carried out in any reaction device sufficient to allow the feed oil to contact the catalyst under the hydroprocessing reaction conditions, for example, in the fixed bed reactor, moving bed reaction in reactors or ebullating bed reactors.

According to conventional methods in this field, before use, the hydrotreating catalyst can be presulfurized with sulfur, hydrogen sulfide or sulfur-containing raw materials at a temperature of 140-370° C. in the presence of hydrogen, and this presulfurization It can be vulcanized outside or in-situ, and the active metal components supported by it can be converted into metal sulfide components.

The catalyst provided by the invention is suitable for hydrogenation treatment of hydrocarbon oil, especially heavy oil, so as to remove sulfur, nitrogen and metals therein. In order to provide qualified raw material oil for subsequent processes (such as catalytic cracking process).

The invention will be illustrated below by way of examples. The reagents used in the examples are chemically pure reagents unless otherwise specified.

The pseudo-boehmite P1 with 1.1≤n≤2.5 and the pseudo-boehmite P2 with n<1.1 used in the embodiments of the present invention have the following preparation methods and sources:

P1-1, prepared by the following method:

In a 2-liter reaction tank, 1000 milliliters of aluminum chloride solution containing 48 grams of alumina per liter and 300 milliliters of 200 grams of alumina per liter with a caustic coefficient of 1.58 and a sorbitol content of 1.82 grams were added in parallel. The sodium metaaluminate solution per liter carries out precipitation reaction, and the reaction temperature is 80 ℃, and the reactant flow rate is adjusted so that the neutralization pH value is 4.0, and the reaction residence time is 15 minutes; in the obtained slurry, adding a concentration of 5% by weight dilute ammonia to adjust The pH of the slurry is 10.0, and the temperature is raised to 80°C, aged for 3 hours, and then filtered with a vacuum filter. After the filter is finished, 20 liters of deionized water (temperature 80°C) is added to the filter cake to rinse the filter cake for about 30 minutes . Add the washed filter cake to 1.5 liters of deionized water and stir to form a slurry. The slurry is pumped into the spray dryer for drying. The outlet temperature of the spray dryer is controlled in the range of 100-110°C. The drying time of the material is about 2 minutes. Alumina hydrate P1-1 was obtained. Characterized by XRD, P1-1 has a pseudo-boehmite structure.

XRD was measured on a SIMENS D5005 X-ray diffractometer, CuKα radiation, 44 kV, 40 mA, and a scanning speed of 2°/min. According to the Scherrer formula: D=Kλ/(Bcosθ) (D is the grain size, λ is the diffraction wavelength of the target material, B is the half-maximum width of the corrected diffraction peak, and 2θ is the position of the diffraction peak) with 2θ as The parameters of the 23-33 ° peak calculate the grain size of (120) to be D (120), and the parameters of the 34-43 ° peak calculate the grain size of (031) to be D (031) with 2θ, and calculate n=D(031)/D(120), the n value of P1-1 obtained through XRD characterization and calculation is listed in Table 1.

P1-2 (including P1-2a and P1-2b), prepared by the following method:

In a 2-liter reaction tank, add 600 milliliters of concentration and be 96 grams of alumina/liter, aluminum sulfate solution containing 3.6 grams of ribitol and ammonia solution of 8% by weight to carry out precipitation reaction in parallel, and the reaction temperature is 40 ℃ , the reaction time is 10 minutes, the flow rate of the ammonia solution is controlled so that the pH of the reaction system is 7, after the precipitation reaction is completed, an appropriate amount of ammonia water is added to the slurry to make the pH of the slurry 8.5, and the slurry is aged at 55°C for 60 minutes and then filtered. The filter cake was beaten and washed twice with deionized water, without drying to obtain hydrated alumina P1-2a; dried at 120°C for 24 hours to obtain hydrated alumina P1-2b, which was characterized by XRD (characterized P1-2a was also tested at 120°C Drying for 24 hours), P1-2a and P1-2b have pseudo-boehmite structure.

The XRD characterization was carried out according to the same method as the aforementioned P1-1, and the calculated n values of P1-2a and P1-2b are listed in Table 1.

P2-1, prepared by the following method:

Prepare pseudo-boehmite according to the method of P1-1. The difference is that the aluminum sulfate solution is changed into an aluminum chloride solution with a concentration of 48 grams of alumina/liter, and the sodium metaaluminate solution does not contain sorbitol. Alumina hydrate P2-1 was obtained. XRD was used to characterize according to the method of Example 1. P2-1 had a pseudo-boehmite structure. XRD was characterized and calculated by the same method as P1-1, and the n value of P2-1 was listed in Table 1.

P2-2 (including P2-2a and P2-2b), prepared by the following method:

Prepare pseudo-boehmite according to the method of P1-2. The difference is that the aluminum sulfate solution containing ribitol is replaced by the aluminum sulfate solution with a concentration of 96 grams of alumina/liter, that is, ribitol is not contained in the aluminum sulfate solution. Alumina hydrate P2-2a was obtained without drying; and alumina hydrate P2-2b was obtained by drying at 120°C for 24 hours. According to the method of Example 1, XRD is used for characterization (P2-2a is also dried at 120°C for 24 hours for characterization), P2-2a and P2-2b have a pseudo-boehmite structure, and XRD characterization is carried out according to the same method as the aforementioned P1-1 , The calculated n values of P2-2a and P2-2b are listed in Table 1.

P2-3 is commercial pseudo-boehmite (SD powder) produced by Shandong Aluminum Works. XRD characterization was carried out according to the same method as P1-1 above, and the calculated n value of P2-3 is listed in Table 1.

P2-4 is the commercial pseudo-boehmite (Yantai powder) produced by Yantai Henghui Chemical Co., Ltd., XRD characterization is carried out according to the same method as the aforementioned P1-1, and the calculated n value of P2-4 is listed in Table 1 .

Table 1

*The crystallinity of each sample was measured based on Condea's commercial SB powder.

Examples 1-5 illustrate pseudo-boehmite, supports and preparation methods suitable for preparing catalysts provided by the present invention.

Example 1

(1) Pseudoboehmite composition:

Two kinds of pseudo-boehmite P1-1 and P2-3 were fed in a dry basis weight ratio of 60:40 and mixed on a kneader for 20 minutes to obtain the composition ZP-1 provided by the present invention.

(2) Alumina carrier:

First take the composition ZP-1600 grams, add 20 grams of scallop powder and mix, and mix the mixture with 520 milliliters of 1% nitric acid aqueous solution at room temperature, and then continue kneading on a twin-screw extruder to form a plastic body , and extruded into a butterfly-shaped strip with a diameter of 1.1 mm. The wet strip was dried at 120°C for 4 hours, and then fired at 600°C for 3 hours to obtain the carrier Z1. The properties of the carrier Z1 are shown in Table 2.

Reference examples 1 to 5 illustrate the reference pseudo-boehmite, the alumina forming carrier and the preparation method thereof.

Reference example 1

(1) Pseudoboehmite composition:

Two kinds of pseudo-boehmite P2-1 and P2-3 were fed in a weight ratio of 60:40 on a dry basis and mixed on a kneader for 20 minutes to obtain a comparative composition DZP-1.

(2) Alumina carrier:

First take the composition DZP-1600 grams, add 20 grams of turnip powder and mix, then mix the mixture with 520 milliliters of 1% nitric acid aqueous solution at room temperature, and then continue kneading on the twin-screw extruder to form a plastic body , and extruded into a butterfly strip with a diameter of 1.1 mm, the wet strip was dried at 120°C for 4 hours, and then baked at 600°C for 3 hours to obtain the carrier DZ1. The properties of the carrier DZ1 are shown in Table 2.

Example 2

(1) Pseudoboehmite composition:

Feed 500 grams of P1-1 and P2-3 pseudo-boehmite in a dry basis weight ratio of 60:40, add 1500 milliliters of deionized water respectively, stir until slurry and continue stirring for 15 minutes, then filter, Obtain composition ZP-2 provided by the invention

(2) Alumina carrier:

Take the composition ZP-2600g, continue to knead it into a plastic body on a twin-screw extruder, extrude it into a butterfly-shaped strip with a diameter of 1.1mm, dry the wet strip at 120°C for 4 hours, and then bake it at 600°C for 3 hours to obtain Carrier Z2, the properties of carrier Z2 are shown in Table 2.

Reference example 2

(1) Pseudoboehmite composition:

The P2-3 and P2-1 two kinds of pseudo-boehmite were fed a total of 500 grams according to the weight ratio of 40:60 on a dry basis, respectively added to 1500 milliliters of deionized water, stirred until slurry and continued to stir for 15 minutes, and then filtered. Obtain comparative composition DZP-2

(2) Alumina:

Take the composition DZP-2600g, continue to knead it into a plastic body on a twin-screw extruder, extrude it into a butterfly-shaped strip with a diameter of 1.1mm, dry the wet strip at 120°C for 4 hours, and then roast it at 600°C for 3 hours to obtain Carrier DZ2, the properties of carrier DZ2 are shown in Table 2.

Example 3

(1) Pseudoboehmite:

Two kinds of pseudo-boehmite P1-2 and P2-4 were fed in a dry basis weight ratio of 50:50 and mixed on a kneader for 20 minutes to obtain the composition ZP-3 provided by the present invention.

(2) Alumina

First take 600 grams of the composition ZP-3, add 20 grams of kale powder and mix, then mix the mixture with 660 milliliters of 1% nitric acid aqueous solution at room temperature, and then continue kneading on a twin-screw extruder to form a plastic body , and extruded into a butterfly-shaped strip with a diameter of 1.1 mm. The wet strip was dried at 120°C for 4 hours, and then fired at 900°C for 3 hours to obtain carrier Z3. The properties of carrier Z3 are shown in Table 2.

Comparative example 3

(1) Pseudoboehmite:

Two kinds of pseudo-boehmite P2-2 and P2-4 were fed in a weight ratio of 50:50 on a dry basis and mixed on a kneader for 20 minutes to obtain a comparative composition DZP-3.

(2) Alumina:

First take the composition DZP-3600 grams, add 20 grams of turnip powder and mix, then mix the mixture with 660 milliliters of 1% nitric acid aqueous solution at room temperature, and then continue to knead it into a plastic body on a twin-screw extruder , and extruded into butterfly strips with a diameter of 1.1mm. The wet strips were dried at 120°C for 4 hours, and then calcined at 900°C for 3 hours to obtain the carrier DZ3. The properties of the carrier DZ3 are shown in Table 2.

Example 4

(1) Pseudoboehmite:

Two kinds of pseudo-boehmite P1-1 and P2-3 were fed in a weight ratio of 70:30 on a dry basis and mixed on a kneader for 20 minutes to obtain the composition ZP-4 provided by the present invention.

(2) Alumina:

First take the composition ZP-4600 grams, add 20 grams of kale powder and mix, then mix the mixture with 520 milliliters of 1% nitric acid aqueous solution at room temperature, and then continue to knead it into a plastic body on a twin-screw extruder , and extruded into butterfly strips with a diameter of 1.1 mm. The wet strips were dried at 120°C for 4 hours, and then calcined at 600°C for 3 hours to obtain carrier Z4. The properties of carrier Z4 are shown in Table 2.

Comparative example 4

(1) Pseudoboehmite:

Two kinds of pseudo-boehmite P2-1 and P2-3 were fed in a weight ratio of 70:30 on a dry basis and mixed on a kneader for 20 minutes to obtain a comparative composition DZP-4.

(2) Alumina:

First take the composition DZP-4600 grams, add 20 grams of turnip powder and mix, and then mix the mixture with 520 milliliters of 1% nitric acid aqueous solution at room temperature, and then continue kneading on the twin-screw extruder to form a plastic body , and extruded into butterfly strips with a diameter of 1.1mm. The wet strips were dried at 120°C for 4 hours, and then calcined at 600°C for 3 hours to obtain carrier DZ4. The properties of carrier DZ4 are shown in Table 2.

Example 5

(1) Pseudoboehmite:

Two kinds of pseudo-boehmite P1-1 and P2-3 were fed in a weight ratio of 60:40 on a dry basis and mixed on a kneader for 20 minutes to obtain the composition ZP-5 provided by the present invention.

(2) Alumina:

First take the composition ZP-5600 grams, add 20 grams of kale powder and mix, then mix the mixture with 520 milliliters of 1% nitric acid aqueous solution at room temperature, and then continue kneading on the twin-screw extruder to form a plastic body , and extruded into a butterfly-shaped strip with a diameter of 1.3 mm. The wet strip was dried at 120°C for 4 hours, and then fired at 600°C for 3 hours to obtain carrier Z5. The properties of carrier Z5 are shown in Table 2.

Comparative example 5

(1) Pseudoboehmite:

Two kinds of pseudo-boehmite P2-1 and P2-3 were fed in a weight ratio of 60:40 on a dry basis and mixed on a kneader for 20 minutes to obtain a comparative composition DZP-5.

(2) Alumina:

First take the composition DZP-5600 grams, add 20 grams of turnip powder and mix, then mix the mixture with 520 milliliters of 1% nitric acid aqueous solution at room temperature, and then continue to knead it into a plastic body on a twin-screw extruder , and extruded into butterfly strips with a diameter of φ1.3mm. After the wet strips were dried at 120°C for 4 hours, they were calcined at 600°C for 3 hours to obtain the carrier DZ5. The properties of the carrier DZ5 are shown in Table 2.

Table 2

Embodiment 6～11 illustrate catalyst provided by the present invention and preparation thereof

Example 6

Take 1200 grams of carrier Z, impregnate it with 170 ml of mixed solution of ammonium molybdate and cobalt nitrate containing MoO ₃ 208 g/L, CoO 48.7 g/L for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours to obtain the catalyst C1. Based on the total weight of the catalyst, the content of molybdenum oxide and cobalt oxide in the catalyst C1 was measured by X-ray fluorescence method (see the petrochemical analysis method RIPP133-90 for the specific method), and the measurement results are shown in Table 3.

Comparative Examples 6-11 illustrate reference catalysts and their preparation.

Comparative example 6

Take carrier DZ1200g, impregnate it with 170ml mixed solution of ammonium molybdate and cobalt nitrate containing MoO ₃ 208 g/L, CoO 48.7 g/L for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours to obtain the catalyst DC1. The contents of molybdenum oxide and cobalt oxide in the catalyst DC1 were measured in the same manner as in Example 6, and the results are shown in Table 3.

Example 7

Take 200 grams of carrier Z2, impregnate with 170 ml of mixed solution of ammonium molybdate and nickel nitrate containing MoO ₃ 206 g/L, NiO 45 g/L for 1 hour, dry at 120°C for 2 hours, and roast at 420°C for 3 hours to obtain the catalyst C2. The contents of molybdenum oxide and nickel oxide in catalyst C2 were determined in the same manner as in Example 6, and the results are shown in Table 3.

Comparative example 7

Take 200 grams of carrier DZ2, impregnate with 170 ml of ammonium molybdate and nickel nitrate mixed solution containing MoO ₃ 206 g/L, NiO 45 g/L for 1 hour, dry at 120°C for 2 hours, and roast at 420°C for 3 hours to obtain the catalyst DC2. The contents of molybdenum oxide and nickel oxide in the catalyst DC2 were determined in the same manner as in Example 6, and the results are shown in Table 3.

Example 8

Take 200 grams of carrier Z3, impregnate with 200 ml of mixed solution of ammonium molybdate and nickel nitrate containing MoO ₃ 85 g/L, NiO 26 g/L for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours to obtain the catalyst C3. The contents of molybdenum oxide and nickel oxide in catalyst C3 were determined in the same manner as in Example 6, and the results are shown in Table 3.

Comparative example 8

Take 200 grams of carrier DZ3, impregnate it with 200 ml of mixed solution of ammonium molybdate and nickel nitrate containing MoO ₃ 85 g/L, NiO 26 g/L for 1 hour, dry at 120°C for 2 hours, and roast at 420°C for 3 hours to obtain the catalyst DC3. The contents of molybdenum oxide and nickel oxide in the catalyst DC3 were determined in the same manner as in Example 6, and the results are shown in Table 3.

Example 9

Take 200 grams of carrier Z4, impregnate it with 170 ml of mixed solution of ammonium molybdate and cobalt nitrate containing MoO ₃ 154 g/L, CoO 37 g/L for 1 hour, dry at 120°C for 2 hours, and roast at 420°C for 3 hours to obtain the catalyst C4. The contents of molybdenum oxide and cobalt oxide in catalyst C4 were determined in the same manner as in Example 6, and the results are shown in Table 3.

Comparative example 9

Take 200 grams of carrier DZ4, impregnate with 170 ml of ammonium molybdate and cobalt nitrate mixed solution containing MoO ₃ 154 g/L, CoO 37 g/L for 1 hour, dry at 120°C for 2 hours, and roast at 420°C for 3 hours to obtain the catalyst DC4. The contents of molybdenum oxide and cobalt oxide in the catalyst DC4 were determined in the same manner as in Example 6, and the results are shown in Table 3.

Example 10

Take 200 grams of carrier Z5, impregnate it with 170 ml of ammonium metatungstate and nickel nitrate mixed solution containing WO ₃ 477 g/L, NiO 49.4 g/L for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours to obtain Catalyst C5. The contents of tungsten oxide and nickel oxide in the catalyst C5 were determined in the same manner as in Example 6, and the results are shown in Table 3.

Comparative example 10

Take 200 grams of carrier DZ5, impregnate it with 170 ml mixed solution of ammonium metatungstate and nickel nitrate containing WO ₃ 477 g/L, NiO 49.4 g/L for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours to obtain Catalyst DC5. The contents of tungsten oxide and nickel oxide in the catalyst DC5 were determined in the same manner as in Example 6, and the results are shown in Table 3.

Example 11

Take carrier Z5, impregnate it with 170 ml of ammonium fluoride solution containing 72 g/L fluorine for 1 hour, dry at 120°C for 2 hours, and bake at 450°C for 3 hours to obtain catalyst fluorine strip F6.

Take 200 grams of catalyst fluorine bar F6, impregnate it with 160 ml mixed solution of ammonium metatungstate and nickel nitrate containing WO ₃ 507 g/L, NiO 52 g/L for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours , to obtain catalyst C6. The contents of tungsten oxide and nickel oxide in catalyst C6 were determined in the same manner as in Example 6, and the results are shown in Table 3.

Comparative example 11

Take carrier DZ5, impregnate it with 170 ml of ammonium fluoride solution containing 72 g/L fluorine for 1 hour, dry at 120°C for 2 hours, and bake at 450°C for 3 hours to obtain catalyst fluorine strip DF6.

Take 200 grams of catalyst fluorine bar DF6, impregnate it with 160 ml mixed solution of ammonium metatungstate and nickel nitrate containing WO ₃ 507 g/L, NiO 52 g/L for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours , to obtain catalyst DC6. The contents of tungsten oxide and nickel oxide in the catalyst DC6 were measured in the same manner as in Example 6, and the results are shown in Table 3.

table 3

Examples 12-17 illustrate the application and effect of the catalyst provided by the present invention.

Example 12-13

The desulfurization performance of catalysts C1 and C4 were evaluated in a fixed-bed reactor.

Raw oil: The raw oil is Maoming Shaqing VRDS with a nickel content of 15.6ppm, a vanadium content of 38.2ppm, a sulfur content of 3.3%, a nitrogen content of 0.24%, and a residual carbon content of 10.7%.

Reaction conditions: Catalysts C1 and C4 are respectively broken into particles with a diameter of 2-3 mm and loaded into the reactor. The reaction temperature is 380°C, the hydrogen partial pressure is 14 MPa, the space velocity is 0.5h ^-1 , and the hydrogen-oil ratio is 700 (volume).

Product analysis: use the inductively coupled plasma emission spectrometer (ICP-AES) to measure the content of nickel and vanadium in the treated oil (the instrument used is the PE-5300 plasma light meter of the American PE company, and the specific method is shown in the petrochemical analysis method RIPP124 -90). The content of sulfur and nitrogen was determined by the coulometric method (see the petrochemical analysis method RIPP62-90 for specific methods).

Calculate the total removal rate of impurities (sulfur or metal) according to the following formula:

The results are listed in Table 4.

Example 14

The carbon removal performance of catalyst C2 was evaluated in a fixed-bed reactor.

Raw oil: The raw oil is Maoming Shaqing VRDS with a nickel content of 15.6ppm, a vanadium content of 38.2ppm, a sulfur content of 3.3%, a nitrogen content of 0.24%, and a residual carbon content of 10.7%.

Reaction conditions: Catalyst C2 is broken into particles with a diameter of 2-3 mm and loaded into the reactor. The reaction temperature is 380°C, the hydrogen partial pressure is 14 MPa, the space velocity is 0.5h ^-1 , and the hydrogen-oil ratio is 700.

Product analysis: Determination of residual carbon content in the treated oil by the carbon residual determination method of petroleum products (the instrument used is the MCRT-160 trace carbon residual tester of the American ALCOR company, and the specific method is shown in GB/T17144).

Calculate the total removal rate of impurities (char residue) according to the following formula:

The results are listed in Table 4.

Example 15

Catalyst C3 was evaluated for demetallization performance in a fixed bed reactor.

Raw material oil: The raw material oil is Kuwaiti normal slag with a nickel content of 29.3ppm, a vanadium content of 83ppm, a sulfur content of 4.7%, a nitrogen content of 0.3%, and a residual carbon content of 15.1%.

Reaction conditions: Catalyst C3 is broken into particles with a diameter of 2-3 mm and loaded into the reactor. The reaction temperature is 380°C, the hydrogen partial pressure is 14 MPa, the space velocity is 0.6h ^-1 , and the hydrogen-oil ratio is 700 (volume).

Product analysis: use the inductively coupled plasma emission spectrometer (ICP-AES) to measure the content of nickel and vanadium in the treated oil (the instrument used is the PE-5300 plasma light meter of the American PE company, and the specific method is shown in the petrochemical analysis method RIPP124 -90)

Calculate the total removal rate of impurities (metal) according to the following formula:

The results are listed in Table 4.

Examples 16-17

The desulfurization and denitrogenation performances of catalysts C5 and C6 were evaluated in a fixed-bed reactor.

Raw material oil: The raw material oil is Maoming Zhichai with a sulfur content of 9700ppm and a nitrogen content of 97ppm.

Reaction conditions: Catalysts C5 and C6 are respectively broken into particles with a diameter of 2-3 mm and loaded into the reactor. The reaction conditions are: reaction temperature 325°C, hydrogen partial pressure 6.4 MPa, space velocity 2h ^-1 , hydrogen-oil ratio 300.

Product analysis: Determination of sulfur content in treated oil by ultraviolet fluorescence method (the instrument used is TS-3000 ultraviolet fluorescence sulfur determination instrument of THERMO company, see industry standard SH-T0689 for specific methods); Nitrogen content (the instrument used is the EA3100 chemiluminescent azotometer from Jena Company, see industry standard SH-T0657 for specific methods).

Calculate the total removal rate of impurities (sulfur, nitrogen) according to the following formula:

The results are listed in Table 4.

Comparative Examples 12-17

Describe the performance of the catalyst prepared with reference to the alumina shaped carrier.

The impurity removal performance of the catalysts DC1-DC6 was evaluated according to the methods of Examples 12-17, and the results are shown in Table 4.

Table 4

As can be seen from the results in Table 4, the desulfurization activity, demetallization activity, and carbon residue removal of the catalyst prepared by alumina provided by the present invention are significantly better than that of the reference catalyst in the hydrotreating process of inferior residual oil. Among them, the desulfurization and denitrogenation activities of the catalyst provided by the invention are also higher than those of the reference catalyst.

Claims (6)

1. A hydrotreating catalyst, containing an alumina support, at least one metal component selected from Group VIII and at least one metal component selected from Group VIB, characterized in that, the alumina support is composed of P1 and P2 at least The composition of two pseudo-boehmite is obtained by mixing, molding and roasting, wherein the weight ratio of P1 and P2 in the composition is 40:60-95:5, and P1 is a pseudo-boehmite of 1.1≤n ₁ ≤2.5. Boehmite, P2 is the pseudo-boehmite of 0.8<n ₂ <1.1; n _{(1 or 2)} = D _{(1 or 2)} (031)/D _{(1 or 2)} (120), the D _{(1 or 2)} (031) represents the grain size of the crystal plane represented by (031) peak in the XRD spectrogram of P1 or P2 pseudoboehmite crystal grains, and D _{(1 or 2)} (120) represents P1 or P2 in the XRD spectrogram of pseudo-boehmite crystal grain (120) the grain size of the place crystal face of peak, described 031 peak refers to the peak that 2θ is 34-43 ° in XRD spectrogram, and described 120 peak is Refers to the peak with 2θ of 23-33° in the XRD spectrum, D=Kλ/(Bcos θ), λ is the diffraction wavelength of the target material, B is the half-maximum width of the corrected diffraction peak, and 2θ is the position of the diffraction peak . 2 . The catalyst according to claim 1 , wherein P1 is pseudo-boehmite with 1.2≤n ₁ ≤2.2, and P2 is pseudo-boehmite with 0.85≤n ₂ ≤1.05. 3. The pseudo-boehmite composition according to claim 1, characterized in that the weight ratio of P1 and P2 in the composition is 45:55˜80:20. 4. The catalyst according to claim 1, characterized in that, the VIII group metal components are cobalt and/or nickel, and the VIB group metal components are molybdenum and/or tungsten, based on oxides and catalysts , the content of the Group VIII metal component is 0.5-10% by weight, and the content of the VIB Group metal component is 5-35% by weight. 5. The catalyst according to claim 4, characterized in that the content of the Group VIII metal component is 1.5-5% by weight, and the content of the Group VIB metal component is 6-30% by weight. 6. A hydrocarbon oil hydrotreating method, comprising under hydrotreating reaction conditions, the hydrocarbon oil raw material oil and catalyst contact reaction, it is characterized in that, described catalyst is the catalyst described in any one of claim 1-5 .