CN108014813B

CN108014813B - Hydrogenation protection catalyst, preparation method and application thereof, and hydrocarbon oil hydrotreating method

Info

Publication number: CN108014813B
Application number: CN201610971471.6A
Authority: CN
Inventors: 杨清河; 孙淑玲; 胡大为; 曾双亲; 邓中活
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-10-31
Filing date: 2016-10-31
Publication date: 2020-08-18
Anticipated expiration: 2036-10-31
Also published as: CN108014813A

Abstract

The invention discloses a hydrogenation protection catalyst and a preparation method and application thereof, the catalyst comprises a carrier and a hydrogenation active component loaded on the carrier, wherein the carrier is prepared by mixing a compound containing hydrated alumina, at least two proton acceptor sites and a compound containing a metal element in group IVB, and

a hydrated alumina composition having a value of 1.8 to 5. The invention also discloses a hydrocarbon oil hydrotreating method adopting the catalyst. The catalyst of the invention takes hydrated alumina wet gel as a starting material to prepare the carrier with higher strength, omits the step of drying the hydrated alumina wet gel, simplifies the overall process flow, reduces the overall operation energy consumption, and avoids dust pollution caused by adopting the pseudo-boehmite dry gel powder as the raw material to prepare the carrier. The catalyst has higher catalytic activity, can more effectively reduce the content of metal impurities in hydrocarbon oil, and prolongs the service life of the main agent of the hydrogenation catalyst.

Description

Hydrogenation protection catalyst, preparation method and application thereof, and hydrocarbon oil hydrotreating method

Technical Field

The invention relates to the technical field of hydrocarbon oil hydrogenation, in particular to a hydrogenation protection catalyst, a preparation method and application thereof, and a hydrocarbon oil hydrotreating method adopting the hydrogenation protection catalyst.

Background

In the conventional catalyst preparation method, an alumina forming body, especially a gamma-alumina forming body, is often used as a carrier of a supported catalyst due to its good pore structure, suitable specific surface and high heat resistance stability. The alumina is usually prepared from dried hydrated alumina, such as pseudoboehmite, by molding, drying and high-temperature roasting.

Based on the above knowledge, as shown in fig. 1, the prepared wet hydrated alumina gel needs to be dried to obtain pseudo-boehmite dry gel powder, then an auxiliary agent (such as a compound containing a group IVB metal element), an extrusion aid and an optional chemical peptizing agent (inorganic acid and/or organic acid) are added with the pseudo-boehmite dry gel powder as a starting point, and the mixture is kneaded and then molded, and the molded product is dried and optionally calcined to be used as a carrier. The main problems of this preparation method are the high dust pollution and the high energy consumption.

In order to reduce dust pollution and improve working environment, researchers have realized that raw materials used for forming should be changed, and have begun to try to prepare alumina formed products using hydrated alumina wet gel or semi-dried pseudo-boehmite as raw materials.

US4613585 discloses a process for preparing an alumina catalyst support, which comprises the steps of:

(a) pouring an aluminum sulfate solution and a sodium aluminate solution simultaneously into a vessel containing deionized water to react the aluminum sulfate solution and the sodium aluminate solution under reaction conditions of pH6.0 to 8.5 and a temperature of 50 to 65 ℃, thereby preparing a first aqueous slurry containing amorphous aluminum hydroxide;

(b) adding an aqueous sodium aluminate solution to the first aqueous slurry in an amount sufficient to neutralize the first aqueous slurry, the total amount of sodium aluminate solution used in steps (a) and (b) corresponding to 0.95-1.05 of the stoichiometric amount of aluminum sulfate used in step (a), thereby preparing a second aqueous slurry having Al in the second aqueous slurry₂O₃A concentration of 7 wt% or more;

(c) filtering amorphous aluminum hydroxide in the second water slurry to obtain a filter cake, washing the obtained filter cake with dilute ammonia water, washing with dilute nitric acid solution, washing with dilute ammonia water to remove sulfate radical anions and sodium cation impurities, and adjusting the pH value of the filter cake to be within the range of 7.5-10.5;

(d) then, without aging the filter cake, the filter cake is dewatered on a filter press and Al is added thereto₂O₃Is increased to 28 to 35% by weight and the filter cake is kneaded in a self-cleaning type mixer at a pH in the range of 7.5 to 10.5 for a residence time of 10s or more to grow the pseudoboehmite particles in a short time, thereby obtaining agglomerates containing these particles;

(e) extruding the dough obtained in step (d) to form an extrudate, and then drying and roasting to obtain the extrudate.

From the method disclosed in US4613585, although the hydrated alumina wet gel can be shaped, there are limitations from the conditions for preparing amorphous aluminum hydroxide to kneading equipment and kneading conditions, resulting in complicated process operations. Also, the support prepared by the method should not have high strength and hardly meet the requirements for industrial applications because of high content of free water in the extrudate prepared by the method and the porosity of the extrudate obtained by drying and firing. Meanwhile, the carrier prepared by the method is difficult to regulate and control the pore structure of the carrier, so that the requirements of various use occasions are difficult to meet.

CN103769118A discloses a heavy oil hydrogenation catalyst, which comprises a carrier and an active component, wherein the carrier is alumina, the active component is metal of VIII group and/or VIB group, the VIII group metal is Co or Ni, the VIB group metal is Mo or W, and the alumina is prepared by molding pseudo-boehmite with a dry basis content of below 50%. The preparation process of the pseudo-boehmite with the dry basis content of less than 50 percent comprises the following steps: (1) carrying out neutralization gelling reaction on the aluminum salt solution and a precipitator; (2) filtering and recovering a solid product of the gelling reaction; (3) the solid product is dried to obtain the product with the dry content of below 50 percent.

CN103769118A adopts pseudoboehmite with a dry content of less than 50% to prepare an alumina carrier, and the pseudoboehmite with a dry content of less than 50% is obtained by drying a solid product separated from a mixture obtained by gelling reaction, which is a method difficult to implement in the actual operation process, mainly because:

(1) the incompletely dried pseudo-boehmite has strong viscosity and difficult transfer, and is easy to cause secondary dust pollution;

(2) drying is started from the surface, and the drying of a wet solid product separated from a mixture obtained by the gelling reaction belongs to incomplete drying, so that a sandwich biscuit phenomenon exists, namely, the surface of part of the pseudo-boehmite is dried (namely, the dried surface is basically free of free water), the inner part is still kept in a wet state (namely, the content of the free water in the non-dried inner part is basically kept at the level before drying), hard particles are formed because the surface is dried, and when the pseudo-boehmite which is not completely dried through is added with a peptizer and/or a binder and the like and is kneaded and formed, the hard particles formed in the drying process are easy to cause blockage in the extrusion process, so that the production efficiency is influenced;

(3) the dry basis of the pseudo-boehmite is difficult to be stably controlled, the instability of the dry basis can cause great interference to the forming, so that the forming process is also very unstable, the unqualified product quantity is increased, and the production efficiency is low;

(4) CN103769118A adopts a conventional forming process during forming, however, because the dry basis (35-50%) of the pseudo-boehmite adopted by the method is far lower than the conventional dry basis content (about 70%), namely the water content is high, extrusion pressure is not generated basically in the extrusion forming process, the carrier obtained after drying and roasting an extrudate has basically no mechanical strength, and the carrier can be pulverized only by applying a little external force, so that the possibility of industrial application is not provided, and the problem is the biggest problem faced by the technology.

In summary, how to simplify the preparation process of the alumina carrier and reduce the operation energy consumption, and at the same time, reduce the dust pollution in the preparation process of the alumina carrier is still an urgent technical problem to be solved on the premise of ensuring that the alumina carrier meeting the industrial use requirements can be obtained.

Disclosure of Invention

Aiming at the problems of the preparation of alumina carriers of US4613585 and CN103769118A, the inventor of the present invention has a new approach to mix a compound containing at least two proton acceptor sites in the molecular structure with hydrated alumina wet gel directly from the synthesis reaction, and the formed mixture can be shaped, and the shaped body obtained by drying and optional roasting can have the strength meeting the industrial requirements. The present invention has been completed based on this finding.

According to a first aspect of the present invention, there is provided a hydrogenation protection catalyst comprising a carrier and a hydrogenation active ingredient supported on the carrier, wherein the carrier is obtained by molding a hydrated alumina composition comprising hydrated alumina, a compound having at least two proton acceptor sites and at least one compound containing a group IVB metal element,

of said composition

A value of 1.8 to 5, said

The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was recorded as w₁Is calculated by formula I

The value of the one or more of,

according to a second aspect of the present invention, there is provided a process for preparing a hydrogenation protection catalyst, which comprises supporting a hydrogenation active ingredient on a carrier, wherein the carrier is prepared by a process comprising the steps of:

(1) mixing the components of a raw material composition containing a hydrated alumina wet gel having an i value of not less than 60%, a compound having at least two proton acceptor sites in an amount such that the hydrated alumina composition finally prepared has an i value of not less than 60%, and at least one compound containing a group IVB metal element to obtain a hydrated alumina composition

The value is 1.8 to 5,

the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w₂The value of i is calculated by adopting the formula II,

the above-mentioned

The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was designated as w₁Is calculated by formula I

The value of the one or more of,

(2) and forming the hydrated alumina composition, and drying and optionally roasting the formed product to obtain the carrier.

According to a third aspect of the invention there is provided a hydroprocessing protection catalyst prepared by the process of the second aspect of the invention.

According to a fourth aspect of the present invention, the present invention provides the use of the hydrogenation protection catalyst of the first or third aspect of the present invention in the hydrotreating of hydrocarbon oils.

According to a fifth aspect of the present invention, there is provided a method for hydrotreating a hydrocarbon oil, which comprises contacting a hydrocarbon oil under hydrotreating reaction conditions with a main hydrogenation catalyst after contacting the hydrocarbon oil with the hydrogenation protection catalyst according to the first or third aspect of the present invention.

Compared with the existing process method (such as the process shown in figure 1) for preparing the alumina carrier by taking the pseudo-boehmite dry glue powder as the starting material, the carrier in the hydrogenation protection catalyst directly takes the hydrated alumina wet gel prepared by the synthesis reaction as the formed starting material, and has the following advantages that:

(1) the step of drying the hydrated alumina wet gel in the prior art is omitted, and when the forming raw material is prepared, the pseudo-boehmite dry glue powder is prepared into a formable material without additionally introducing water, so that the overall process flow is simplified, and the overall operation energy consumption is reduced;

(2) avoids dust pollution caused by adopting the pseudo-boehmite dry glue powder as a raw material, and greatly improves the operation environment.

Compared with the prior art, such as US4613585 and CN103769118A, which directly uses the hydrated alumina wet gel as the starting material to prepare the carrier, the hydrogenation protection catalyst according to the present invention uses the carrier which has simpler preparation process, stronger operability and can effectively improve the strength of the finally prepared molded body. The reason why the present invention can produce a molded body having a higher strength from a hydrated alumina wet gel as a starting material may be that: the compound with at least two proton acceptor sites and the free water in the hydrated alumina wet gel interact to form hydrogen bonds to adsorb the free water in the hydrated alumina wet gel, and simultaneously, the compound with at least two proton acceptor sites and the hydroxyl in the molecular structure of the hydrated alumina can also perform hydrogen bond interaction to play a role of physical peptization, so that the hydrated alumina wet gel can be molded, and the finally prepared molded body has higher strength.

The hydrogenation protection catalyst has better catalytic performance, can more effectively reduce the content of metal impurities in hydrocarbon oil, and better prolongs the service life of a main agent of the hydrogenation catalyst.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.

FIG. 1 is a flow chart of a molding process commonly used in current industrial applications.

FIG. 2 is a preferred process flow for the preparation of a support according to the present invention.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

According to a first aspect of the present invention, there is provided a hydrogenation protection catalyst comprising a support and a hydrogenation active ingredient supported on the support.

According to the hydrogenation protection catalyst of the present invention, the carrier is obtained by molding a hydrated alumina composition containing hydrated alumina, a compound having at least two proton acceptor sites, and at least one compound containing a group IVB metal element.

The hydrated alumina may be one or more selected from alumina trihydrate and alumina monohydrate. The hydrated alumina preferably comprises alumina monohydrate, more preferably alumina monohydrate. Specific examples of the hydrated alumina may include, but are not limited to, boehmite, alumina trihydrate, amorphous hydrated alumina, and pseudo-boehmite. In a preferred embodiment of the invention, the hydrated alumina contains pseudoboehmite, more preferably pseudoboehmite.

According to the hydrated alumina composition of the present invention, the hydrated alumina is directly derived from the hydrated alumina wet gel and not from the hydrated alumina dry gel powder. In the present invention, the term "hydrated alumina wet gel" means an aqueous hydrated alumina gel which is obtained by a synthesis reaction and has not undergone a dehydration process for lowering its i value to 60% or less (preferably 62% or less). In the present invention, the value of i is determined by the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w₂The value of i is calculated by adopting the formula II,

the synthesis reaction refers to a reaction for preparing an aluminum hydroxide gel, and may be a synthesis reaction of a hydrated alumina gel commonly used in the art, and specifically, a precipitation method (including an acid method and an alkaline method), a hydrolysis method, an seeded precipitation method, and a rapid dehydration method may be mentioned. The synthesized hydrated alumina gel may be either a hydrated alumina gel that has not undergone aging or a hydrated alumina gel that has undergone aging. The specific operating methods and conditions for the precipitation, hydrolysis, seeding and flash dehydration processes may be routinely selected and will be described hereinafter. The hydrated alumina wet gel can be obtained by optionally aging the hydrated alumina gel obtained by the synthesis reaction, washing and performing solid-liquid separation, and collecting the solid phase.

Unlike hydrated alumina derived from dry gelatine powder, the hydrated alumina directly derived from hydrated alumina gel undergoes a phase change during storage. For example, the phase of the hydrated alumina in the composition after exposure to ambient temperature and under closed conditions may change for 72 hours. The ambient temperature depends on the environment in which it is placed and may typically be in the range of 5-50 deg.C, such as 20-40 deg.C. The closed condition means that the composition is placed in a closed container, which may be a closed container (such as a can, pail or box) or a closed flexible wrap (such as a lidded bag), which may be paper and/or a polymeric material, preferably a polymeric material such as plastic.

In one example, where the hydrated alumina directly derived from the hydrated alumina gel comprises pseudo-boehmite (e.g., the hydrated alumina directly derived from the hydrated alumina gel is pseudo-boehmite), the composition is left at ambient temperature and under closed conditions for 72 hours, the alumina trihydrate content in the composition after being left to stand being higher than the alumina trihydrate content in the composition before being left to stand. In this example, the alumina trihydrate content of the composition after placement is generally increased by at least 0.5%, preferably by at least 1%, preferably by from 1.1% to 2%, based on the alumina trihydrate content of the composition before placement.

The hydrated alumina composition also contains a compound having at least two proton acceptor sites. In the compound having at least two proton acceptor sites, the proton acceptor site refers to a site capable of forming a hydrogen bond with water and a hydroxyl group in the molecular structure of the compound. Specific examples of the proton acceptor site include, but are not limited to, one or two or more of fluorine (F), oxygen (O), and nitrogen (N). Specific examples of the compound having at least two proton acceptor sites may include, but are not limited to, compounds having one or more groups selected from hydroxyl groups, carboxyl groups, amino groups, ether linkages, aldehyde groups, carbonyl groups, amide groups, and fluorine atoms in the molecular structure, preferably hydroxyl groups and/or ether linkages.

The compound having at least two proton acceptor sites may be an organic compound, an inorganic compound, or a combination of an organic compound and an inorganic compound. An organic compound having at least two proton acceptor sites is employed, which can be removed by a calcination process. By using an inorganic compound having at least two proton acceptor sites, part of the elements in the inorganic compound can remain in the finally produced shaped body, whereby auxiliary elements can be introduced into the shaped body by means of the inorganic compound.

In a preferred embodiment of the present invention, the compound having at least two proton acceptor sites is a polymer having a plurality of (e.g., three or more) proton acceptor sites in a molecular structure. According to this preferred embodiment, a better physical peptization effect is obtained, which further increases the strength of the finally produced shaped body, in particular when shaping is carried out by an extrusion process. Preferably, the polymer is an organic polymer. According to the preferred embodiment, specific examples of the compound having at least two proton acceptor sites may include, but are not limited to, one or more of polyhydroxy compounds, polyethers, and acrylic-type polymers.

The polyol compound may be exemplified by, but not limited to, polysaccharides, etherified polysaccharides and polyols.

The polysaccharide can be a homopolysaccharide, a heteropolysaccharide or a combination of the homopolysaccharide and the heteropolysaccharide. Specific examples of the polysaccharide and its etherified product include, but are not limited to, dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide. The cellulose ether is an ether derivative in which hydrogen atoms of partial hydroxyl groups in a cellulose molecule are substituted with hydrocarbon groups, and the hydrocarbon groups may be the same or different. The hydrocarbyl group is selected from substituted hydrocarbyl and unsubstituted hydrocarbyl. The unsubstituted hydrocarbon group is preferably an alkyl group (e.g., C)₁-C₅Alkyl groups of (ii). In the present invention, C₁-C₅Specific examples of the alkyl group of (1) include C₁-C₅Straight chain alkyl of (2) and C₃-C₅The branched alkyl group of (a), may be, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and tert-pentyl. Examples of the substituted hydrocarbon groupsSuch as alkyl which may be substituted by hydroxy, carboxy, cyano or aryl (e.g. C)₁-C₅Alkyl substituted by hydroxy, C₁-C₅Alkyl substituted by carboxyl, C substituted by aryl₁-C₅Alkyl) which may be phenyl or naphthyl. Specific examples of the substituted hydrocarbon group may include, but are not limited to: cyano, benzyl, phenethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, carboxymethyl, carboxyethyl and carboxypropyl. Specific examples of the cellulose ether may include, but are not limited to, methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose. The polysaccharide may be of various origins, for example: the galactomannan may be derived from sesbania powder.

Specific examples of the polyol include, but are not limited to, one or more of polyvinyl alcohol, partially acetalized polyvinyl alcohol (the acetalization degree may be 95% or less, preferably 80% or less, more preferably 70% or less, and further preferably 50% or less), polyether polyol, and polyester polyol.

Specific examples of the polyether include, but are not limited to, polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer, and polytetrahydrofuran.

The acrylic acid-type polymer refers to a polymer containing acrylic acid-type monomer units, which may be specifically, but not limited to, acrylic acid monomer units and alkyl acrylic acid monomer units (preferably, C)₁-C₅More preferably a methacrylic acid monomer unit). Specific examples of the acrylic polymer include polyacrylic acid, polymethacrylic acid, acrylic acid-methyl acrylate copolymer, acrylic acid-methyl methacrylate copolymer, methacrylic acid-methyl acrylate copolymer, and methacrylic acid-methyl methacrylate copolymer.

In this preferred embodiment, the compound having at least two proton acceptor sites more preferably contains a polysaccharide and/or an etherified polysaccharide, and still more preferably a polysaccharide and/or an etherified polysaccharide.

In a more preferred embodiment of the invention, the compound having at least two proton acceptor sites comprises a galactomannan and a cellulose ether. The support according to this more preferred embodiment has a higher strength. Further preferably, the compound having at least two proton acceptor sites is preferably a galactomannan and a cellulose ether.

In this more preferred embodiment, the galactomannan may be present in an amount of from 10 to 70 wt.%, preferably from 15 to 68 wt.%, more preferably from 20 to 65 wt.%, even more preferably from 25 to 60 wt.%, even more preferably from 30 to 55 wt.%, based on the total amount of the compound having at least two proton acceptor sites; the content of the cellulose ether may be 30 to 90% by weight, preferably 32 to 85% by weight, more preferably 35 to 80% by weight, still more preferably 40 to 75% by weight, and still more preferably 45 to 70% by weight.

The group IVB metal element in the group IVB metal element-containing compound may be various group IVB metal elements commonly used in the art, and for example, may be selected from titanium, zirconium and hafnium, preferably from titanium and zirconium, and more preferably titanium.

The group IVB metal element-containing compound may be a compound containing a group IVB metal element in various molecular structures commonly used in the art. For example, where the group IVB metal element is selected from titanium and zirconium, the group IVB metal element-containing compound may be selected from zirconium oxychloride (e.g., ZrOCl)₂·8H₂O), zirconium tetrachloride, zirconium acetate, zirconium sulfate, zirconium nitrate, zirconium carbonate, zirconium hydroxide, basic ammonium zirconium (e.g., (NH)₄)₂ZrO(CO₃)₂·nH₂O), zirconium dioxide, titanic acid, metatitanic acid (H)₂TiO₃) Titanium dioxide, titanium sulfate and a compound shown in a formula I,

TiX_n(OR)_4-n(in the formula III),

in formula III, X is halogen (for example)Such as: can be chlorine, bromine and iodine, preferably chlorine), R is C₁-C₅N is an integer of 0 to 4 (for example, 0, 1, 2, 3 or 4, preferably 0 or 4).

Preferably, the group IVB metal element-containing compound may be selected from zirconium acetate, zirconium carbonate, zirconium hydroxide, basic zirconium ammonium, zirconium dioxide, zirconium tetrachloride, titanic acid, metatitanic acid, titanic oxide, titanium sulfate, titanium tetrachloride, tetra-n-butyl titanate, tetra-isobutyl titanate, and tetra-isopropyl titanate.

The content of the group IVB metal element-containing compound in the hydrated alumina composition may be conventionally selected. Generally, the content of the group IVB metal element in terms of oxide is from 0.1 to 6% by weight, preferably from 0.3 to 4% by weight, more preferably from 0.5 to 2% by weight, based on the total amount of the catalyst.

Of the hydrated alumina composition

The value is 1.8 to 5, preferably not less than 1.85, for example, 1.85 to 4, more preferably not less than 1.9, for example, 1.9 to 3.5.

In the present invention,

The value of the one or more of,

the hydrated alumina composition is such that the compound having at least two proton acceptor sites is present in the composition

Value satisfiesThe above requirements are met. Preferably, the compound having at least two proton acceptor sites may be contained in an amount of 1 to 25 parts by weight, preferably 2 to 20 parts by weight, more preferably 3 to 18 parts by weight, relative to 100 parts by weight of the hydrated alumina.

The hydrated alumina composition may or may not contain a peptizing agent. The peptizing agent may be an agent having a gelling effect, which is generally used in the technical field of preparation of alumina moldings, and specific examples thereof may include, but are not limited to, alumina sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid, and trichloroacetic acid.

The compound having at least two proton acceptor sites can perform a physical peptization effect, particularly when the compound having at least two proton acceptor sites is a polymer containing at least two proton acceptor sites, so that the amount of a peptizing agent can be reduced, and even the peptizing agent can be omitted.

In a preferred embodiment of the present invention, the peptizing agent is contained in an amount of 5 parts by weight or less with respect to 100 parts by weight of hydrated alumina.

In a particularly preferred embodiment of the invention, the hydrated alumina composition does not contain a peptizing agent. According to the composition of this particularly preferred embodiment, the produced hydrated alumina compact can be used as a carrier even if it is converted into an alumina compact without calcination, because when the unfired hydrated alumina compact contains a peptizing agent, the peptizing agent is dissolved during adsorption and impregnation, and is lost in a large amount, so that the compact is dissolved, pulverized, and collapsed in the channels, and finally loses its shape, and thus cannot be used as an adsorbent or a carrier. Thus, according to the hydrogenation protection catalyst of the present invention, the support is a molded body obtained by drying and optionally calcining the molded body of the hydrated alumina composition, and may be a calcined alumina molded body, or may be an uncalcined hydrated alumina molded body when the hydrated alumina composition does not contain a peptizing agent. The calcination means heat treatment at a temperature of not less than 355 ℃, and generally, the calcination is carried out at a temperature of 355 ℃ to 1800 ℃, preferably at a temperature of 500 ℃ to 1200 ℃, more preferably at a temperature of 550 ℃ to 1000 ℃, and the duration of the calcination may be 0.1 to 20 hours, preferably 0.5 to 10 hours, more preferably 2 to 6 hours. The calcination may be carried out in an oxygen-containing atmosphere (e.g., air atmosphere) or in an inert atmosphere (e.g., an atmosphere formed of nitrogen and/or a group-zero gas), preferably in an oxygen-containing atmosphere.

According to the hydrogenation protection catalyst of the present invention, the support may have various shapes, for example: spherical, sheet, strip, honeycomb or bird's nest shapes. Specific examples of the sheet-shaped and strip-shaped may include, but are not limited to, clover-shaped, butterfly-shaped, cylindrical, and raschig rings.

The hydrogenation protection catalyst according to the present invention may be obtained by shaping the hydrated alumina composition by a method conventional in the art, and drying and optionally calcining the shaped product. The specific methods and conditions for the forming, drying and firing will be described in detail in the second aspect of the invention, for reasons of brevity and will not be described in any further detail herein.

According to the hydrogenation protection catalyst, the carrier has higher strength and meets the use requirement of serving as a catalyst carrier. Generally, the radial crush strength of the carrier is 8N/mm or more, preferably 10N/mm or more, and may be, for example, 10 to 20N/mm. In the present invention, the radial crush strength of the carrier was measured by the method specified in RIPP 25-90.

According to the hydrogenation protection catalyst, the carrier is a porous substance, and the pore diameter of the carrier is in bimodal distribution. Wherein the most probable pore diameters are 4-20nm and more than 20nm (such as 21-35 nm).

According to the hydrogenation protection catalyst provided by the invention, the hydrogenation active component can be a component which has a catalytic action on hydrogenation of hydrocarbon oil. Preferably, the hydrogenation active components are VIB group metal elements and VIII group metal elements. The group VIB metal element is preferably molybdenum and/or tungsten. The group VIII metal element is preferably cobalt and/or nickel.

The loading amount of the hydrogenation active component on the carrier depends on the specific type of the hydrogenation active component. As an example, when the hydrogenation active components are a group VIB metal element and a group VIII metal element, the content of the group VIII metal element in terms of oxide is not higher than 0.8 wt%, preferably 0.2 to 0.6 wt%, and the content of the group VIB metal element in terms of oxide is not higher than 4 wt%, preferably 1.5 to 3.5 wt%, based on the total amount of the catalyst.

The hydrogenation active component can be loaded on the carrier in the form of oxide, or can be loaded on the carrier in the form of non-oxide (such as salt and/or simple substance), or can be a combination of oxide and non-oxide.

According to the hydrogenation protection catalyst of the present invention, when the hydrogenation active component is supported on the carrier in an inactive state, the hydrogenation active component may be activated by a conventional method in the art before use to convert the hydrogenation active component in the inactive state into an active state.

According to a second aspect of the present invention, there is provided a process for producing a hydrogenation protection catalyst, which comprises supporting a hydrogenation active ingredient on a carrier.

According to the preparation method of the invention, the carrier is prepared by adopting a method comprising the following steps:

The value is 1.8 to 5,

the i value is determined using the following method: 10g of the hydrated alumina wet gel was dried at 120 ℃ for 240 minutes in an air atmosphere,the mass of the dried sample is recorded as w₂The value of i is calculated by adopting the formula II,

the above-mentioned

The value of the one or more of,

The kind of the compound having at least two proton acceptor sites and the kind of the compound containing the group IVB metal element are described in detail above and will not be described herein again.

The hydrated alumina wet gel can be synthesized by a conventional method, for example, by one or more of precipitation (including acid and alkaline methods), hydrolysis, seed separation, and flash dehydration. Generally, the hydrated alumina gel solution is obtained by optionally aging, washing and solid-liquid separation.

The precipitation method comprises an acid method and an alkali method. The acid method is to precipitate aluminum salt with alkaline compound. The alkaline method is to carry out precipitation reaction on aluminate by using an acidic compound. In the precipitation method, after the mixture obtained by the precipitation reaction is optionally aged (preferably, aged), solid-liquid separation is performed, and the separated solid phase is washed to obtain the hydrated alumina wet gel.

The kind of the aluminum salt and the aluminate may be conventionally selected. Specific examples of the aluminum salt may include, but are not limited to, one or two or more of aluminum sulfate, aluminum chloride, and aluminum nitrate. Specific examples of the aluminate may include, but are not limited to, one or more of sodium metaaluminate, potassium metaaluminate, and magnesium metaaluminate.

The basic compound and the acidic compound may be conventionally selected. The alkaline compound can be various common compounds capable of making water alkaline, and can be selected from ammonia, hydroxide and alkaline salt. The hydroxide may be a common water-soluble hydroxide such as an alkali metal hydroxide. The basic salt may be a common salt that decomposes in water to make the water basic, such as meta-aluminates, carbonates and bicarbonates. Specific examples of the basic compound may include, but are not limited to, one or more of ammonia, sodium hydroxide, potassium hydroxide, sodium metaaluminate, potassium metaaluminate, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, and potassium carbonate. The acidic compound can be various common compounds capable of making water acidic, and can be inorganic acid and/or organic acid. Specific examples of the acidic compound may include, but are not limited to, one or more of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, and oxalic acid. The carbonic acid may be generated in situ by the introduction of carbon dioxide.

The precipitation reaction may be carried out under conventional conditions, and the present invention is not particularly limited thereto. Generally, the alkaline compound or the acidic compound is used in such an amount that the pH of the aluminium salt solution or the aluminate solution is 6-10, preferably 7-9. The precipitation reaction may be carried out at a temperature of 30 to 90 deg.C, preferably 40 to 80 deg.C.

The method for preparing the hydrated alumina wet gel by the hydrolysis method may include: subjecting an aluminum-containing compound to hydrolysis reaction, optionally aging (preferably aging) the mixture obtained by the hydrolysis reaction, then performing solid-liquid separation, and washing the separated solid phase to obtain the hydrated alumina wet gel.

The aluminum-containing compound may be an aluminum-containing compound generally used in a process for preparing a hydrated alumina gel by a hydrolysis method. The aluminum-containing compound is preferably an organoaluminum compound which can undergo hydrolysis reaction, and more preferably an aluminum alkoxide. Specific examples of the aluminum-containing compound may include, but are not limited to, one or more of aluminum isopropoxide, aluminum isobutoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, and aluminum isooctanolate.

The hydrolysis reaction of the present invention is not particularly limited, and may be carried out under conventional conditions. Generally, the hydrolysis reaction may be carried out at a pH of 3 to 11, preferably 6 to 10. The hydrolysis reaction may be carried out at a temperature of 30 to 90 deg.C, preferably 40 to 80 deg.C.

In the precipitation method and the hydrolysis method, the aging conditions are not particularly limited and may be carried out under conventional conditions. In general, the ageing can be carried out at temperatures of from 35 to 98 deg.C, preferably from 40 to 80 deg.C. The duration of the aging may be 0.2 to 6 hours.

The method for preparing the hydrated alumina wet gel by the seed precipitation method can comprise the following steps: adding seed crystals into the supersaturated aluminate solution, decomposing to generate aluminum hydroxide, carrying out solid-liquid separation on a mixture obtained by decomposition, and washing a separated solid phase to obtain the hydrated alumina wet gel. Specific examples of the aluminate may include, but are not limited to, one or more of sodium metaaluminate, potassium metaaluminate, and magnesium metaaluminate.

The method for preparing the hydrated alumina wet gel by the rapid dehydration method may include: roasting the hydrated alumina at the temperature of 600-950 ℃, preferably 650-800 ℃, carrying out hydrothermal treatment on the roasted product, and carrying out solid-liquid separation on the mixture obtained by the hydrothermal treatment, thereby obtaining the hydrated alumina wet gel. The duration of the calcination may be 1 to 6 hours, preferably 2 to 4 hours. The hydrothermal treatment may be carried out at a temperature of 120-200 deg.C, preferably 140-160 deg.C. The hydrothermal treatment is usually carried out under autogenous pressure in a closed vessel.

In the precipitation method, the hydrolysis method, the seed precipitation method and the rapid dehydration method, the solid-liquid separation can be performed by a conventional method, and specifically, the solid-liquid separation can be performed by filtration, centrifugation or a combination of the two.

In the step (1), the i value of the hydrated alumina wet gel is not less than 60%, preferably not less than 62%, more preferably not less than 64%. The i value of the hydrated alumina wet gel is preferably not higher than 82%, more preferably not higher than 80%, and further preferably not higher than 78.5%. Specifically, the i value of the hydrated alumina wet gel may be 60 to 82%, preferably 62 to 80%, more preferably 64 to 78.5%.

The hydrated alumina wet gel with the value i meeting the requirement can be obtained by controlling the solid-liquid separation conditions when the prepared hydrated alumina gel-containing solution is subjected to solid-liquid separation. In one embodiment of the present invention, the solid-liquid separation is performed once or twice or more, and at least the last solid-liquid separation is performed by pressure filtration and/or vacuum filtration. In this embodiment, the value of the hydrated alumina wet gel i obtained is controlled by adjusting the magnitude of the applied pressure and/or vacuum. Specific examples of the apparatus used for the pressure filtration include, but are not limited to, a plate and frame filter press, a belt filter, or a combination of both. In order to control the i value of the obtained hydrated alumina wet gel, natural wind or pressurized wind can be adopted to blow the separated solid phase, so that the efficiency of water removal is improved. The pressure of the pressurized air can be selected conventionally, and generally can be 0.1-12MPa, and preferably 0.5-10 MPa.

In the step (1), the wet hydrated alumina gel obtained by the solid-liquid separation is generally not subjected to a dehydration treatment for reducing the i value thereof to 60% or less (preferably 62% or less, more preferably 64% or less).

In step (1), the compound having at least two proton acceptor sites is used in an amount sufficient to produce a final hydrated alumina composition

Generally, the compound having at least two proton acceptor sites may be used in an amount of 1 to 25 parts by weight, preferably 2 to 20 parts by weight, more preferably 3 to 18 parts by weight, based on the hydrated alumina, relative to 100 parts by weight of the hydrated alumina wet gel.

In step (1), in a more preferred embodiment, the compound having at least two proton acceptor sites comprises a galactomannan and a cellulose ether. The carrier formed from the composition according to this more preferred embodiment has a higher strength. Further preferably, the compound having at least two proton acceptor sites is preferably a galactomannan and a cellulose ether.

The content of the group IVB metal element-containing compound in the raw material mixture may be selected according to the content of the group IVB metal element expected to be introduced in the finally prepared catalyst. Generally, the content of the compound containing the group IVB metal element in the raw material mixture is such that the content of the group IVB metal element in terms of oxide is from 0.1 to 6% by weight, preferably from 0.3 to 4% by weight, more preferably from 0.5 to 2% by weight, based on the total amount of the finally produced catalyst.

According to the method for preparing the hydrated alumina composition of the present invention, the group IVB metal element-containing compound, the compound having at least two proton acceptor sites, and the hydrated alumina wet gel may be mixed in various mixing sequences.

In one embodiment, as shown in fig. 2, the compound containing the group IVB metal element may be mixed during the preparation of the hydrated alumina wet gel, the compound containing the group IVB metal element may be added to the hydrated alumina wet gel obtained, a part of the compound containing the group IVB metal element may be mixed during the preparation of the hydrated alumina wet gel, the remaining part of the compound containing the group IVB metal element may be added to the hydrated alumina wet gel obtained, and the operation of mixing the compound containing the group IVB metal element may be performed at one, two, or three of the above-mentioned addition timings. When the compound containing the group IVB metal element is mixed in the process of preparing the hydrated alumina wet gel, the operation of mixing the compound containing the group IVB metal element may be performed in one, two, three, or four of the precipitation reaction process, the aging process, the solid-liquid separation process, and the washing process. Whether or not the compound containing the group IVB metal element is mixed in the process of preparing the hydrated alumina wet gel, and the timing of mixing may be selected according to the type of the precipitation reaction.

In another embodiment, as shown in FIG. 2, the group IVB metal element-containing compound is mixed after the hydrated alumina wet gel is prepared. In this embodiment, this can be done in one of the following ways: (1) mixing a compound containing a group IVB metal element with a hydrated alumina wet gel, and then mixing a compound having at least two proton acceptor sites; (2) mixing a compound having at least two proton acceptor sites with a hydrated alumina wet gel, and then mixing a compound containing a group IVB metal element; (3) simultaneously mixing a group IVB metal element-containing compound and a compound having at least two proton acceptor sites with the hydrated alumina wet gel.

Preferably, the compound containing the group IVB metal element is mixed after the preparation of the hydrated alumina wet gel is completed.

In the step (1), the raw material mixture may or may not contain a peptizing agent. Preferably, the peptizing agent is contained in an amount of 5 parts by weight or less with respect to 100 parts by weight of hydrated alumina. More preferably, the raw material mixture does not contain a peptizing agent. That is, in step (1), it is more preferable that the addition of a peptizing agent to the raw material mixture is not included.

In step (1), the hydrated alumina wet gel may be mixed with a compound having at least two proton acceptor sites using conventional methods. The hydrated alumina wet gel may be mixed with a compound having at least two proton acceptor sites under shear. In one embodiment, the mixing is by stirring. The hydrated alumina composition can be obtained by uniformly mixing the hydrated alumina wet gel and a compound having at least two proton acceptor sites in a container having a stirring device by stirring. The stirring can be carried out in a vessel with a stirring device or in a beater. In another embodiment, the mixing is by kneading. The hydrated alumina wet gel may be kneaded with a compound having at least two proton acceptor sites in a kneader to obtain the hydrated alumina composition. The type of the kneader is not particularly limited. In step (1), stirring and mixing may be used in combination to mix the hydrated alumina wet gel with a compound having at least two proton acceptor sites. In this case, it is preferable to perform stirring and kneading.

In the step (1), water may or may not be added during the mixing process, as long as the hydrated alumina composition prepared therefrom can be made to contain water

The value satisfies the above requirements. In general, water may be additionally added during the mixing process from the viewpoint of improving the homogeneity of the mixing. Generally, the weight ratio of the supplemental added water to the compound having at least two proton acceptor sites may be from 5 to 15: 1, preferably 8 to 12: 1, more preferably 9 to 10: 1.

in the step (2), the forming method is not particularly limited, and various forming methods commonly used in the art may be adopted, for example: extrusion, spraying, spheronization, tableting or a combination thereof. In a preferred embodiment of the invention, the shaping is carried out by means of extrusion.

In the step (2), the temperature at which the shaped product is dried may be conventionally selected in the art. Generally, the drying temperature may be 60 ℃ or higher and not higher than 350 ℃, preferably 80 to 300 ℃, more preferably 110-. The drying time may be appropriately selected depending on the drying temperature. Generally, the duration of the drying may be 1 to 48 hours, preferably 2 to 24 hours, more preferably 2 to 12 hours, and further preferably 2 to 6 hours. The drying may be carried out in an oxygen-containing atmosphere (e.g., air atmosphere) or in an inert atmosphere (e.g., an atmosphere formed by nitrogen and/or a group-zero gas), preferably in an oxygen-containing atmosphere.

The conditions for calcination in the present invention are not particularly limited, and may be selected conventionally in the art. Specifically, the calcination means a heat treatment at a temperature of not less than 355 ℃ in an air atmosphere, and generally, the calcination is carried out at a temperature of 355 ℃ to 1800 ℃, preferably at a temperature of 500-1200 ℃, more preferably at a temperature of 550-1000 ℃, and the duration of the calcination may be 0.1 to 20 hours, preferably 0.5 to 10 hours, more preferably 2 to 6 hours. The calcination may be carried out in an oxygen-containing atmosphere (e.g., air atmosphere) or in an inert atmosphere (e.g., an atmosphere formed of nitrogen and/or a group-zero gas), preferably in an oxygen-containing atmosphere.

In the step (2), the roasting is an optional operation. In general, when the hydrated alumina composition does not contain a peptizing agent, the dried molded product may be used as it is as a carrier, but may be calcined; when the hydrated alumina composition contains a peptizing agent, the dried shaped article is then calcined to obtain the support.

According to the preparation method, the carrier has higher strength and meets the use requirement of serving as a catalyst carrier. In general, the support produced in step (2) has a radial crush strength of 8N/mm or more, preferably 10N/mm or more, and for example, may be 10 to 20N/mm.

According to the preparation method of the invention, the carrier is a porous substance, and the pore diameter of the porous substance is in bimodal distribution. Wherein the most probable pore diameters are 4-20nm and more than 20nm (such as 21-35 nm).

According to the preparation method of the present invention, the support may have various shapes, for example: spherical, sheet, strip, honeycomb or bird's nest shapes. Specific examples of the sheet-shaped and strip-shaped may include, but are not limited to, clover-shaped, butterfly-shaped, cylindrical, and raschig rings.

Fig. 2 shows a preferred embodiment of the preparation of the carrier, which, as shown in fig. 2, comprises the following steps:

(A) providing a hydrated alumina gel solution, and washing the hydrated alumina gel solution to obtain a first hydrated alumina wet gel;

optionally (B), treating the first hydrated alumina wet gel with (B-1) or (B-2),

(B-1) mixing the first hydrated alumina wet gel with water to form slurry, and carrying out solid-liquid separation on the slurry to obtain a second hydrated alumina wet gel;

(B-2) carrying out solid-liquid separation on the first hydrated alumina wet gel to obtain a second hydrated alumina wet gel;

(C) mixing a hydrated alumina wet gel with a compound having at least two proton acceptor sites to obtain a hydrated alumina composition, the hydrated alumina wet gel being the first hydrated alumina wet gel or the second hydrated alumina wet gel;

(D) forming the hydrated alumina composition to obtain a hydrated alumina forming product;

(E) drying the hydrated alumina forming product to obtain a hydrated alumina forming body;

(F) optionally, roasting at least part of the hydrated alumina forming body to obtain an alumina forming body;

wherein the mixing of the group IVB metal element-containing compound is performed in one, two or three of the step (A), the step (B) and the step (C) so that the hydrated alumina composition contains the group IVB metal element. The method of mixing the group IVB metal element-containing compound is the same as the method and the sequence described in the second aspect of the present invention, and will not be described in detail here.

In the step (a), the hydrated alumina gel solution is a hydrated alumina gel-containing solution obtained by a hydrated alumina gel synthesis reaction, which may or may not be aged. The hydrated alumina gel solution can be prepared on site or transported from other production sites. Preferably, the hydrated alumina gel solution is a hydrated alumina wet gel solution prepared in situ. The synthesis method and conditions of the hydrated alumina gel have been described in detail above and will not be described herein.

Because the hydrated alumina gel solution obtained by the synthesis reaction has acidity and alkalinity, the hydrated alumina wet gel is washed in the step (A) to remove acidic substances and alkaline substances in the hydrated alumina wet gel, so that the adverse effect of the existence of the acidic substances and the alkaline substances on the hydrated alumina gel is avoided, and meanwhile, the solid content of the hydrated alumina gel solution is increased. The washing in step (a) may be carried out under conventional conditions as long as the amounts of acidic substances and basic substances in the hydrated alumina gel solution can be reduced to meet the usual requirements.

In step (a), solid-liquid separation is also involved in the washing process to squeeze out the wash water to give a first hydrated alumina wet gel. The i value of the first hydrated alumina wet gel may be a value satisfying the i values of the hydrated alumina wet gels mixed with the compound having at least two proton acceptor sites and the compound containing the group IVB metal element described above, or may be a value higher than the i value of the hydrated alumina wet gels mixed with the compound having at least two proton acceptor sites and the compound containing the group IVB metal element described above.

In one embodiment, the first hydrated alumina wet gel has an i value content satisfying the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites and the compound containing the group IVB metal element as described above, i.e., the i value of the first hydrated alumina wet gel is not less than 60%, preferably not less than 62%, more preferably not less than 64%. In this embodiment, the first hydrated alumina wet gel preferably has an i value of not higher than 82%, more preferably not higher than 80%, and still more preferably not higher than 78.5%. Specifically, the i value of the hydrated alumina wet gel may be 60 to 82%, preferably 62 to 80%, more preferably 64 to 78.5%.

According to this embodiment, the first hydrated alumina wet gel may be fed directly to step (C) to be mixed with a compound having at least two proton acceptor sites. This applies in particular to situations in which the following requirements are satisfied: (I) the solid-liquid separation equipment in the washing device has better separation capacity, and the value i of the first hydrated alumina wet gel is controlled to meet the range; (II) the washing device and the mixing device can be compactly arranged, so that the discharge of the washing device can directly enter the mixing device.

According to this embodiment, the first hydrated alumina wet gel may also be fed to step (B) and treated with (B-1). This applies in particular to situations in which the following requirements are satisfied: (I) the solid-liquid separation equipment in the washing device has better separation capacity, and the value i of the first hydrated alumina wet gel is controlled to meet the range; (II) the washing apparatus and the mixing apparatus cannot be arranged compactly, so that the discharge from the washing apparatus cannot enter the mixing apparatus directly.

In another embodiment, the first hydrated alumina wet gel has an i value of greater than 82% and fails to meet the requirements of the second aspect of the invention for mixing with a compound having at least two proton acceptor sites. According to this embodiment, the first hydrated alumina wet gel is fed to step (B) and treated with (B-1) or (B-2).

This embodiment is particularly suitable for the case where the separation capacity or the operating conditions of the solid-liquid separation device in the washing apparatus are insufficient to control the i value of the first hydrated alumina wet gel to satisfy the aforementioned requirements, and the case where the washing apparatus and the mixing apparatus cannot be compactly arranged.

In the step (B), the first hydrated alumina wet gel is treated by the method (B-1) or (B-2) to obtain a second hydrated alumina wet gel.

In (B-1), the first hydrated alumina wet gel is mixed with water to form a slurry, which can improve the transport properties of the hydrated alumina wet gel. In the step (B-1), the amount of water added is selected according to the specific transportation equipment, so that the formed slurry can meet the transportation requirement.

The second hydrated alumina wet gel obtained in the step (B) has an i value satisfying the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites as described above, i.e., the i value of the hydrated alumina wet gel is not less than 60%, preferably not less than 62%, more preferably not less than 64%. The second hydrated alumina wet gel preferably has an i value of not higher than 82%, more preferably not higher than 80%, and further preferably not higher than 78.5%. Specifically, the i value of the hydrated alumina wet gel may be 60 to 82%, preferably 62 to 80%, more preferably 64 to 78.5%.

The second hydrated alumina wet gel having an i value satisfying the above requirements can be obtained by controlling the conditions of the solid-liquid separation in the step (B). The method for adjusting the i value of the hydrated alumina wet gel by selecting the solid-liquid separation method and the conditions thereof has been described in detail above and will not be described in detail herein.

In step (C), the first hydrated alumina wet gel or the second hydrated alumina wet gel is mixed with a compound having at least two proton acceptor sites to obtain a hydrated alumina composition. The i values of the first hydrated alumina wet gel and the second hydrated alumina wet gel fed to step (C) satisfy the i values of the hydrated alumina wet gels mixed with the compound having at least two proton acceptor sites as described hereinbefore.

In the step (D), the hydrated alumina composition obtained in the step (C) is molded to obtain a hydrated alumina molded product.

In the step (E), the hydrated alumina molded product obtained in the step (C) is dried, and when the hydrated alumina composition does not contain a peptizing agent, the obtained hydrated alumina molded product can be used as a carrier.

Depending on the type of shaped body desired, step (F) may or may not be carried out. In carrying out step (F), the whole hydrated alumina formed body obtained in step (E) may be fed to step (F) and calcined; the partially hydrated alumina formed body obtained in the step (E) may also be fed to the step (F), so that the hydrated alumina formed body and the alumina formed body can be simultaneously produced. When the hydrated alumina composition contains a peptizing agent, the whole hydrated alumina formed body obtained in the step (E) is sent to the step (F). When the hydrated alumina composition does not contain a peptizing agent, step (F) may be performed or may not be performed.

The preferred embodiment shown in fig. 2 may be implemented in a hydrated alumina production molding system comprising a hydrated alumina gel production unit, a solid-liquid separation and washing unit, a mixing unit, a molding unit, a drying unit, and optionally a calcining unit,

the hydrated alumina gel production unit is characterized in that an output port of a hydrated alumina gel solution of the hydrated alumina gel production unit is communicated with an input port of a washing material to be separated of the solid-liquid separation and washing unit, an output port of a solid-phase material of the solid-liquid separation and washing unit is communicated with an input port of a solid-phase material of the mixing unit, an output port of a mixed material of the mixing unit is communicated with an input port of a raw material of the forming unit, an input port of a material to be dried of the drying unit is communicated with an output port of a formed product of the forming unit, and an input port of a material to be calcined of the.

The hydrated alumina gel production unit is used for producing a hydrated alumina gel solution through a synthesis reaction. The method for synthesizing the hydrated alumina gel may be a conventional method such as the precipitation method, the hydrolysis method, the seed precipitation method, and the rapid dehydration method described above, and will not be described in detail herein.

The hydrated alumina gel production unit may perform a synthesis reaction using a conventional reactor to obtain a hydrated alumina gel solution, which is not particularly limited in the present invention.

The solid-liquid separation and washing unit is used for carrying out solid-liquid separation and washing on the hydrated alumina gel aqueous solution output by the hydrated alumina gel production unitTo obtain

A hydrated alumina wet gel having a value satisfying the requirements as described hereinbefore.

The solid-liquid separation and washing unit can adopt various common methods to carry out solid-liquid separation and washing, thereby obtaining

A hydrated alumina gel having a value that satisfies the mixing requirement with a compound having at least two proton acceptor sites and at least one compound containing a group IVB metal element. The solid-liquid separation and washing unit may employ conventional solid-liquid separation devices, such as: a filtration device, a centrifugation device, or a combination of both. When the solid-liquid separation and washing unit includes a filtering device, the filtering device may be one or a combination of two or more of a gravity filtering device, a pressure filtering device, and a vacuum filtering device. Preferably, the filtration means comprises at least a pressure filtration means. Specific examples of the pressure filtration device include, but are not limited to, a plate and frame filter press, a belt filter, or a combination of both. For controlling the hydrated alumina wet gel obtained

The solid-liquid separation and washing unit can further comprise a blowing device, and natural wind or pressurized wind is adopted to blow the separated solid phase, so that the efficiency of water removal is improved. The pressure of the pressurized air can be selected conventionally, and generally can be 0.1-12MPa, and preferably 0.5-10 MPa.

The solid-liquid separation and washing unit may comprise one or more solid-liquid separation subunits, preferably at least one solid-liquid separation subunit and the last solid-liquid separation subunit being a pressure filtration device and/or a vacuum filtration device, so that the solid-phase material (i.e. hydrated alumina wet gel) obtained by the solid-liquid separation and washing unit is

The value is such that the requirements for mixing with a compound having at least two proton acceptor sites according to the second aspect of the invention are met. By adjusting the magnitude of the applied pressure or vacuum, the final hydrated alumina wet gel can be treated

The value is adjusted. When the solid-liquid separation and washing unit comprises more than two solid-liquid separation subunits, except that the last solid-liquid separation subunit preferably adopts a solid-liquid separation mode taking pressure as a driving force, the other solid-liquid separation subunits can adopt a pressurizing and filtering device and/or a vacuum filtering device, or do not adopt the pressurizing and filtering device and the vacuum filtering device, and preferably adopt the pressurizing and filtering device and/or the vacuum filtering device.

The solid-liquid separation and washing unit can wash the separated solid phase by adopting a conventional washing device. For example, a spray device may be used to spray wash water onto the surface of the separated solid phase. In order to improve the washing effect and the washing efficiency, shearing and/or oscillation may be applied to the solid phase during or after the spraying, and the spray water and the solid phase may be mixed uniformly with the shearing, such as stirring.

The solid-liquid separation and washing unit is arranged between the hydrated alumina gel production unit and the mixing unit based on the material flow direction of the hydrated alumina gel, and is used for separating the gel solution output by the hydrated alumina gel production unit to obtain

The hydrated alumina wet gel, which has a value that meets the mixing requirements, provides the raw materials for the mixing unit.

On the premise that the mixing unit can be provided with the hydrated alumina gel meeting the requirements, from the viewpoint of facilitating the transportation of materials, in a preferred embodiment, the solid-liquid separation and washing unit can comprise a washing subunit, a diluting subunit, a conveying subunit and a second solid-liquid separation subunit,

the washing subunit is used for collecting and washing a solid phase in the hydrated alumina gel solution output by the hydrated alumina gel production unit;

the diluting subunit is used for diluting the solid phase output by the washing subunit with water to obtain slurry;

the conveying subunit is used for conveying the slurry output by the diluting subunit into a second solid-liquid separation subunit;

and the second solid-liquid separation subunit is used for carrying out solid-liquid separation on the slurry to obtain hydrated alumina wet gel.

The conveying subunit may employ any of a variety of conventional conveying devices, such as a conveyor belt. The delivery sub-unit and the washing sub-unit may be integrated together, for example in one device, so that washing is performed during delivery, improving production efficiency. For example: a conveying belt with a solid-liquid separation function is adopted, and a spraying device is arranged above solid-phase materials of the conveying belt, so that washing and solid-liquid separation are carried out in the conveying process.

The mixing unit comprises an auxiliary agent adding device for adding an auxiliary agent to the hydrated alumina wet gel, wherein the auxiliary agent adding device at least adds a compound with at least two proton acceptor sites to the hydrated alumina wet gel when the production system is in operation.

The mixing unit may employ conventional mixing devices such as various conventional mixers, kneaders, or a combination of both. The forming unit may employ conventional forming devices, such as: an extrusion device, a spraying device, a rounding device, a tabletting device or a combination of more than two. The drying unit may employ a conventional drying device, and the present invention is not particularly limited thereto. The baking unit may employ a conventional baking apparatus, and the present invention is not particularly limited thereto.

The production molding system is not provided with a dehydration unit which is enough to reduce the i value of the hydrated alumina wet gel to below 60% (preferably below 62%, more preferably below 64%) between the solid phase material outlet port of the solid-liquid separation and washing unit and the hydrated alumina wet gel inlet port of the mixing unit based on the flow direction of the hydrated alumina gel.

In the actual production process, a mixing unit, a forming unit, a drying unit and a roasting unit can be additionally arranged on the basis of the existing hydrated alumina gel production device, so that the production and the forming of the hydrated alumina gel are integrated.

According to the preparation method of the invention, the hydrogenation active component can be a component which has a catalytic action on hydrogenation of hydrocarbon oil. Preferably, the hydrogenation active component is at least one group VIB metal element and at least one group VIII metal element. The group VIB metal element is preferably molybdenum and/or tungsten. The group VIII metal element is preferably cobalt and/or nickel.

The loading amount of the hydrogenation active component on the carrier depends on the specific type of the hydrogenation active component. As an example, when the hydrogenation active components are a group VIB metal element and a group VIII metal element, the loading amount of the hydrogenation active components on the carrier is such that the content of the group VIII metal element in terms of oxide is not higher than 0.8 wt%, preferably 0.2 to 0.6 wt%, and the content of the group VIB metal element in terms of oxide is not higher than 4 wt%, preferably 1.5 to 3.5 wt%, based on the total amount of the finally prepared catalyst.

The hydrogenation active component can be loaded on the carrier in the form of oxide, or can be loaded on the carrier in the form of non-oxide (such as salt and/or simple substance), or can be a combination of oxide and non-oxide. According to the preparation method of the present invention, when the hydrogenation active ingredient is supported on the carrier in an inactive state, before use, activation may be performed using a conventional method in the art to convert the hydrogenation active ingredient in an inactive state into an active state.

The hydrogenation active ingredient may be supported on the carrier using conventional methods. As a preferred example, the hydrogenation active ingredient is supported on the carrier by means of impregnation. In particular, the hydrogenation protection catalyst according to the invention can be obtained by impregnating the support with an impregnation solution containing the hydrogenation active ingredient, drying the impregnated support and optionally calcining the dried support.

The impregnation fluid may be formulated using conventional methods, for example: the compound containing the hydrogenation active ingredient may be dispersed in a solvent to form an impregnation solution. When the hydrogenation active components are a group VIB metal element and a group VIII metal element, specific examples of the compound containing the group VIB metal element may include, but are not limited to, ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide, and tungsten oxide. The group VIII metal element-containing compound may be selected from the group consisting of a nitrate of a group VIII metal element, a chloride of a group VIII metal element, a sulfate of a group VIII metal element, a formate of a group VIII metal element, an acetate of a group VIII metal element, a phosphate of a group VIII metal element, a citrate of a group VIII metal element, an oxalate of a group VIII metal element, a carbonate of a group VIII metal element, a basic carbonate of a group VIII metal element, a hydroxide of a group VIII metal element, a phosphate of a group VIII metal element, a phosphide of a group VIII metal element, a sulfide of a group VIII metal element, an aluminate of a group VIII metal element, a molybdate of a group VIII metal element, a tungstate of a group VIII metal element, and a water-soluble oxide of a group VIII metal element. Specifically, specific examples of the group VIII metal element-containing compound may include, but are not limited to, nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, basic cobalt carbonate, cobalt chloride, and nickel chloride.

The solvent of the impregnation solution may be water and/or alcohol. Preferably, the solvent of the impregnation liquid is water.

The impregnation may be a saturated impregnation or an excess impregnation.

When the hydrogenation active components are two or more, the hydrogenation active components may be simultaneously supported on the carrier, or the hydrogenation active components may be supported on the carrier in divided portions.

The impregnated support may be dried under conventional conditions to devolatilize it. Generally, the drying can be carried out at a temperature of 80-250 deg.C, preferably 100-200 deg.C, more preferably 120-180 deg.C. The drying may be performed under normal pressure (i.e., 1 atm), or under reduced pressure. The duration of the drying may be selected according to the temperature at which the drying is carried out and the pressure at which the drying is carried out. In general, the duration of the drying may be from 1 to 10 hours, preferably from 1 to 6 hours.

The dried support can be used directly as a catalyst. The catalyst may be used after further calcination. The conditions for the calcination in the present invention are not particularly limited, and the calcination may be carried out under conventional conditions. Generally, the calcination may be carried out at a temperature of 360-500 deg.C, preferably at a temperature of 360-450 deg.C. The duration of the firing may be selected according to the temperature of firing. In general, the duration of the calcination may be from 1 to 10 hours, preferably from 2 to 6 hours.

According to a fourth aspect of the present invention, there is provided the use of the hydrogenation protection catalyst of the first and third aspects of the present invention in the hydroprocessing of hydrocarbon oils. The hydrogenation protection catalyst can effectively reduce the content of metal impurities in hydrocarbon oil, effectively prolong the service life of the main catalyst, prevent the rapid rise of the pressure drop of a reactor bed layer, and keep an industrial device to operate for a long time.

The hydrocarbon oil may be any of various conventional feedstocks to be hydrotreated, preferably a heavy hydrocarbon oil of various origins, and specific examples thereof may include, but are not limited to, one or more of atmospheric residue, vacuum wax oil and coker wax oil.

The hydrotreating conditions include: the temperature can be 330-410 ℃; the hydrogen partial pressure may be in the range of 10 to 18MPa in gauge pressure; the liquid hourly volume space velocity of the heavy oil can be 0.2-1 hour^-1。

The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.

In the following examples and comparative examples, the radial crush strength of the molded articles prepared was measured by the method specified in RIPP 25-90.

In the following examples and comparative examples, the following methods were used to measure

The value: 10g of the hydrated alumina composition are dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition is recorded as w₁Is calculated by formula I

The value of the one or more of,

in the following examples and comparative examples, the value of i was determined by the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w₂The value of i is calculated by adopting the formula II,

in the following examples and comparative examples, the water absorption of the molded articles prepared were measured by the following method: drying the molded body to be tested at 120 ℃ for 4 hours, then sieving by using a 40-mesh standard sieve, and weighing 20g of oversize as a sample to be tested (marked as w)₃) The sample to be tested is soaked in 50g of deionized water for 30 minutes, after filtration, the solid phase is drained for 5 minutes, and the weight of the drained solid phase is then weighed (denoted as w)₄) The water absorption was calculated using the following formula:

in the following examples and comparative examples, the mode pore size was determined using the Congta Poremaster33 instrument, USA, with reference to the mercury intrusion method specified in GB/T21650.1-2008. The dry basis is determined by roasting the sample to be tested at 600 ℃ for 4 hours, and is the percentage of the mass of the sample after roasting to the mass of the sample before roasting. The composition of the catalyst was measured on a 3271X-ray fluorescence spectrometer, manufactured by Nippon Denshi electric and mechanical industries, Ltd., according to the method specified in the petrochemical analysis method RIPP 133-90.

Preparation examples 1 to 10 were used to prepare the supports.

Preparation of example 1

The hydrated alumina wet gel used in the preparation example was a pseudo-boehmite wet cake (the wet cake was numbered as SLB-1) obtained by adding titanium tetrachloride to a hydrated alumina gel solution prepared by an acid method (sodium metaaluminate-aluminum sulfate method, available from Changling division, petrochemical, China) during aging, washing, and filtering, and the i value of the wet cake was 77.7% as measured with TiO₂The titanium content was 1 wt%.

(1) 200g of the wet cake numbered SLB-1 was placed in a beaker, then 5g of methylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd., the same below) and 3g of sesbania powder (having a galactomannan content of 80% by weight, purchased from Beijing chemical Co., Ltd., the same below) were added and stirred for 10 minutes using a mechanical stirrer, and the resulting mixture was the hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(2) And (2) extruding the hydrated alumina composition prepared in the step (1) into strips on an F-26 type double-screw extruder (general factory of scientific and technological industry of southern China university, the same below) by using a disc-shaped orifice plate with the diameter of 1.5 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.

(3) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 120 c for 3 hours in an air atmosphere to give dry alumina hydrate strips HT-1, the property parameters of which are listed in table 1.

(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) at 580 ℃ for 6 hours in an air atmosphere to obtain an alumina dry strip OT-1, wherein the property parameters of the alumina dry strip OT-1 are listed in Table 1.

Preparation of example 2

A carrier was prepared in the same manner as in preparation example 1, except that, in step (4), the alumina hydrate dry strip prepared in step (3) was calcined at 980 ℃ for 3 hours in an air atmosphere to obtain an alumina dry strip OT-2, the property parameters of which are shown in Table 1.

Preparation of example 3

A carrier was prepared in the same manner as in preparation example 1, except that sesbania powder was not used in step (2) and methylcellulose was used in an amount of 7.4g, and properties of the prepared hydrated alumina composition, hydrated alumina dry strip HT-3 and alumina dry strip OT-3 were as shown in Table 1.

Preparation of example 4

A carrier was prepared in the same manner as in preparation example 1, except that no methylcellulose was used in step (2) and sesbania powder was used in an amount of 9.3g, and properties of the prepared hydrated alumina composition, hydrated alumina dry strip HT-4 and alumina dry strip OT-4 were as shown in Table 1.

Preparation of example 5

A carrier was prepared in the same manner as in example 1, except that 3g of nitric acid (HNO) was further added in the step (2) while adding methylcellulose and sesbania powder₃In an amount of 65 wt.%), the properties of the prepared hydrated alumina composition, hydrated alumina dry strip HT-5 and alumina dry strip OT-5 are listed in table 1.

Preparation of comparative example 1

(1) 500g of the wet cake numbered SLB-1 was dried at 80 ℃ for 2 hours in an air atmosphere to obtain pseudo-boehmite powder having an i value of 50%. The pseudo-boehmite powder was left at ambient temperature (25-30 ℃) for 72 hours under closed conditions (in a sealed plastic bag), and no formation of alumina trihydrate was detected after the left standing.

(2) And (2) extruding the pseudo-boehmite powder prepared in the step (1) into strips on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 1.5 mm. The extruder has large heat productivity during extrusion (the extruder body is hot and a large amount of hot air is emitted), and the extruder frequently trips during extrusion, so that burrs are formed on the surface of an extruded material.

(3) The extrudate was cut into wet strips having a length of about 6mm, and the wet strips were dried at 120 ℃ for 3 hours in an air atmosphere to give DHT-1, which is a dry alumina hydrate strip having the property parameters listed in Table 1.

(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) for 6 hours at 580 ℃ in an air atmosphere to obtain alumina dry strip DOT-1, wherein the property parameters of the alumina dry strip are listed in Table 1.

Preparation of comparative example 2

A carrier was prepared in the same manner as in preparation example 1, except that in step (1), not the wet cake SLB-1 was used, but the pseudo-boehmite powder prepared in preparation example 1 was used in an equal weight (on a dry basis) in which the extruder frequently tripped during extrusion and burrs were formed on the surface of the extrudate. Alumina dry strip DHT-2 and alumina dry strip DOT-2 are prepared respectively, and the property parameters are listed in Table 1.

Preparation of comparative example 3

A carrier was prepared in the same manner as in preparation example 1, except that the wet cake SLB-1 was not used in step (1), but the wet cake SLB-1 was dried at 100 ℃ for 4 hours in an air atmosphere to obtain pseudo-boehmite powder having an i value of 30%, which was allowed to stand at ambient temperature (25-30 ℃) under a closed condition (placed in a sealed plastic bag) for 72 hours, and no formation of alumina trihydrate was detected after standing. Wherein, the extruder frequently trips in the extrusion process, and the surface of the extruded material is smooth. Alumina dry strip DHT-3 and alumina dry strip DOT-3 are respectively prepared, and the property parameters are listed in Table 1.

Preparation of comparative example 4

The carrier was prepared in the same manner as in preparation example 1, except that in step (1), instead of using the wet cake SLB-1, an equal weight (on a dry basis) of a dry powder of pseudoboehmite (purchased from the chinese petrochemical long-distance division, having an i value of 32%) was used, which was left to stand at ambient temperature (25-30 ℃) for 72 hours under closed conditions (placed in a sealed plastic bag), and no formation of alumina trihydrate was detected after standing, wherein the extruder was frequently tripped during the strip extrusion process, and the surface of the extrudate was smooth. DHT-4 and DOT-4 are prepared separately, and the property parameters are listed in Table 1.

Preparation of comparative example 5

The carrier was prepared in the same manner as in preparation of comparative example 4, except that in the step (1), 6g of nitric acid (HNO) was further added at the time of mixing₃Concentration of 65 wt%), wherein the extrusion process was smooth and the extrudate surface was smooth. DHT-5 and DOT-5 are prepared separately, and the property parameters are listed in Table 1.

Preparation of comparative example 6

A carrier was prepared in the same manner as in preparation example 1, except that methyl cellulose and sesbania powder were not used, and 6.0g of paraffin was used. As a result, the prepared hydrated alumina composition cannot be subjected to extrusion molding.

Preparation of comparative example 7

A carrier was prepared in the same manner as in preparation example 1, except that hydroxyethyl methyl cellulose and sesbania powder were not used, but 6.0g of wood powder was used. As a result, the prepared hydrated alumina composition cannot be subjected to extrusion molding.

Preparation of comparative example 8

The wet cake numbered SLB-1 was directly fed into an F-26 type twin-screw extruder and extruded through a circular orifice plate having a diameter of 2.0mm, with the result that extrusion molding was not possible.

Preparation of example 6

(1) 5kg of the wet cake numbered SLB-1 was mixed with 500g of deionized water, 33g of methylcellulose and 20g of sesbania powder (galactomannan content: 80% by weight) and beaten for 1 minute, and the resulting slurry was fed to a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.7MPa and held for 15 minutes, and the wet cake obtained by pressure relief of the plate and frame was the hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(2) And (2) extruding the hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 1.5 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.

(3) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry alumina hydrate strips HT-6 having the property parameters listed in table 1.

(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) at 600 ℃ for 3 hours in an air atmosphere to obtain an alumina dry strip OT-6, wherein the property parameters of the alumina dry strip OT-6 are listed in Table 1.

Preparation of example 7

(1) The hydrated alumina wet gel used in the preparation example was a pseudo-boehmite wet cake (the wet cake was numbered as SLB-1) obtained by adding titanium tetrachloride to a hydrated alumina gel solution prepared by an acid method (sodium metaaluminate-aluminum sulfate method, available from Changling division, petrochemical, China) during aging, washing, and filtering, and the i value of the wet cake was 77.5% as measured with TiO₂The titanium content was 2% by weight.

(2) 1000g of the wet cake numbered LB-1 were placed in a beaker, and 16g of hydroxypropylmethylcellulose and 20g of sesbania powder (galactomannan content 85% by weight) were added and stirred for 10 minutes using a mechanical stirrer to obtain the hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(3) And (3) extruding the hydrated alumina composition prepared in the step (2) on an F-26 type double-screw extruder by using a round orifice plate with the phi of 3.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.

(4) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry alumina hydrate strips HT-7, the property parameters of which are listed in table 1.

(5) And (3) roasting the hydrated alumina dry strip prepared in the step (4) at 950 ℃ for 2.5 hours in an air atmosphere to obtain an alumina dry strip OT-7, wherein the property parameters are listed in Table 1.

Preparation of example 8

A carrier was prepared in the same manner as in preparation example 7, except that, in step (2), hydroxypropylmethylcellulose was not used, but 39g of sesbania powder was used. Dry alumina hydrate strips HT-8 and dry alumina oxide strips OT-8 were prepared separately and the property parameters are listed in Table 1.

Preparation of example 9

A carrier was prepared in the same manner as in preparation example 7, except that in step (2), sesbania powder was not used, but 33g of hydroxypropylmethylcellulose was used. Dry alumina hydrate strips HT-9 and dry alumina oxide strips OT-9 were prepared separately and the property parameters are listed in Table 1.

Preparation of example 10

The hydrated alumina wet gel used in the preparation example is prepared by mixing CO₂Method (sodium aluminate-CO)₂The method is that the i value of the pseudo-boehmite wet filter cake (the wet filter cake is numbered as SLB-2) obtained by washing and filtering a hydrated alumina gel solution prepared by Xinghao catalyst new material Co., Shanxi province) is measured to be 65.3%.

(1) 1000g of SLB-2 wet cake was placed in a beaker, and then 15g of methylcellulose (available from Zhejiang Haishi chemical Co., Ltd.), 20g of sesbania powder (having a galactomannan content of 80 wt.% and available from Beijing chemical Co., Ltd.) and 13.8g of zirconium tetrachloride as a compound containing a metal element of group IVB were added, and after stirring with a mechanical stirrer for 10 minutes, the resulting mixture was a hydrous alumina composition of the present invention (ZrO based on the dry basis of the composition)₂The content of zirconium element was 2% by weight), the properties of which are listed in table 1.

(2) And (2) extruding the hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the diameter of 2.4mm, wherein the strip extruding process is smooth, and the surface of an extruded product is smooth and has no burrs.

(3) The extrudate was cut into wet strips having a length of about 5mm and the wet strips were dried at 140 c for 3 hours in an air atmosphere to give dry alumina hydrate strips HT-10, the property parameters of which are listed in table 1.

(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) for 4 hours at 560 ℃ in an air atmosphere to obtain an alumina dry strip OT-10, wherein the property parameters of the alumina dry strip OT-10 are listed in Table 1.

Preparation of comparative example 9

500g of dried rubber powder P1 (pore volume 0.9mL/g, specific surface area 280 m) produced by Zhongshimei Changling Kong²A pore diameter of 8.5nm and 500g of dried rubber powder P2 (pore volume of 1.2mL/g, specific surface area of 280 m) from China petrochemical ChangLing division²(15.8 nm in the largest possible pore diameter), 1300mL of an aqueous solution containing 10mL of nitric acid (65 wt% in concentration) and 18g of titanium tetrachloride was added and mixed, and the mixture was molded in the same manner as in steps (2) to (4) of production example 1 to obtain a hydrated alumina compact designated DHT-6 and a alumina compact designated DOT-6, the properties of which are shown in Table 2.

Preparation of comparative example 10

400g of dry rubber powder P2 (pore volume 0.9mL/g, specific surface area 290 m) from Zibozimao catalyst Co., Ltd²Per g, the most probable pore diameter is 8.3nm) and 600g of dry glue powder P2 (pore volume is 1.1mL/g, specific surface area is 260m, produced by Nicotiana constant-glow chemical Co., Ltd.)²(ii)/g, the most probable pore diameter was 12nm), 1300mL of an aqueous solution containing 10mL of nitric acid (65% by weight in concentration) and 22g of titanium tetrachloride was added and mixed, and the mixture was molded in the same manner as in steps (2) to (4) of production example 7 to obtain a hydrated alumina compact designated as DHT-7 and a alumina compact designated as DOT-7, the properties of which are shown in Table 2.

TABLE 1

¹: standing at ambient temperature (25-30 deg.C) under sealed condition (in sealed plastic bag) for 72 hr, and collecting the compositionThe content of alumina is improved compared with that before the storage.

²: the pore diameter is unimodal distribution.

The results of preparation examples 1 to 10 confirm that the hydrated alumina wet gel is not dried into dry rubber powder or semi-dry rubber powder, but is directly mixed with a compound with at least two proton acceptor sites, the obtained mixture can be directly used for molding, and the obtained molded body has higher strength, thereby avoiding the problems of severe working environment, high energy consumption and low strength of the prepared molded body when the conventional molded body is prepared by taking the dry rubber powder or the semi-dry rubber powder as a starting material. The results of preparation examples 1 to 10 also demonstrate that the hydrated alumina composition according to the invention does not require the formulation of two dry glue powders, but rather the use of only one hydrated alumina allows the preparation of shaped bodies with a bimodal distribution of pore sizes.

TABLE 2

Examples 1-10 are provided to illustrate a hydrogenation protection catalyst and a method of making the same according to the present invention.

Example 1

(1) Dispersing ammonium molybdate and nickel nitrate in water to form an impregnating solution, wherein MoO is used₃The concentration of ammonium molybdate was 37.01g/L and the concentration of nickel nitrate was 6.47g/L as NiO. The alumina hydrate dry strip prepared in example 1 was impregnated with the impregnation solution saturated at ambient temperature (25 ℃ C.) for HT-11 hours. The impregnated hydrated alumina dry strands were dried at 120 ℃ under normal pressure in an air atmosphere for 4 hours, and then calcined at 400 ℃ under normal pressure in an air atmosphere for 3 hours, thereby obtaining a hydrogenation protection catalyst CH-1 according to the present invention, the composition of which is shown in Table 3.

(2) A catalyst was prepared in the same manner as in (1) except that the carrier was alumina dry strip OT-1 prepared in preparation example 1, to obtain catalyst CO-1 of the present invention, the composition of which is shown in Table 3.

Example 2

A catalyst was prepared in the same manner as in (1) in example 1, except that the support was the alumina dry strip OT-2 prepared in preparation example 2, and the impregnated support was not calcined after drying, to thereby obtain the catalyst CO-2 of the present invention, the composition of which is shown in table 3.

Example 3

(1) A catalyst was prepared in the same manner as in (1) in example 1, except that the carrier was the hydrated alumina dry strip HT-3 prepared in preparation example 3, to give catalyst CH-3, the composition of which is shown in Table 3.

(2) A catalyst was prepared in the same manner as in (2) in example 1, except that the carrier was alumina dry strip OT-3 prepared in preparation example 3, to obtain catalyst CO-3, the composition of which is shown in Table 3.

Example 4

(1) A catalyst was prepared in the same manner as in (1) in example 1, except that the carrier was the hydrated alumina dry strip HT-4 prepared in preparation example 4, to give catalyst CH-4, the composition of which is shown in Table 3.

(2) A catalyst was prepared in the same manner as in (2) in example 1, except that the carrier was alumina dry strip OT-4 prepared in preparation example 4, to obtain catalyst CO-4, the composition of which is shown in Table 3.

Example 5

(1) A catalyst was prepared in the same manner as in (1) in example 1, except that the carrier was the hydrated alumina rod HT-5 prepared in preparation example 5, and as a result, the hydrated alumina rod was pulverized during impregnation, and a shaped catalyst could not be prepared.

(2) A catalyst was prepared in the same manner as in (2) in example 1, except that the carrier was alumina dry strip OT-5 prepared in preparation example 5, to obtain catalyst CO-5, the composition of which is shown in Table 3.

Comparative example 1

(1) A catalyst was prepared in the same manner as in (1) in example 1, except that the carrier was DHT-3, which was a hydrated alumina dry strip prepared in comparative example 3, to give catalyst DCH-1, the composition of which is shown in Table 3.

(2) A catalyst was prepared in the same manner as in (2) in example 1, except that the carrier was DOT-3 which was an alumina dry strip prepared in comparative example 3, to obtain a catalyst DCO-1 whose composition is shown in Table 3.

Comparative example 2

(1) A catalyst was prepared in the same manner as in (1) in example 1, except that the carrier was DHT-4 as a hydrated alumina dry strip prepared in comparative example 4, to give catalyst DCH-2, the composition of which is shown in Table 3.

(2) A catalyst was prepared in the same manner as in (2) in example 1, except that the carrier was DOT-4 which was an alumina dry strip prepared in comparative example 4, to obtain a catalyst DCO-2 whose composition is shown in Table 3.

Comparative example 3

(1) A catalyst was prepared in the same manner as in (1) in example 1, except that the carrier was DHT-5, which was prepared in the hydrated alumina dry strip prepared in comparative example 5, and as a result, the hydrated alumina dry strip was pulverized during impregnation, and a shaped catalyst could not be prepared.

(2) A catalyst was prepared in the same manner as in (2) in example 1, except that the carrier was DOT-5 which was an alumina dry strip prepared in comparative example 5, to obtain a catalyst DCO-3 whose composition is shown in Table 3.

Comparative example 4

(1) A catalyst was prepared in the same manner as in (1) in example 1, except that the carrier was DHT-6, which was prepared in the hydrated alumina dry strip prepared in comparative example 9, and as a result, the hydrated alumina dry strip was pulverized during impregnation, and a shaped catalyst could not be prepared.

(2) A catalyst was prepared in the same manner as in (2) in example 1, except that the carrier was DOT-6, which was an alumina dry strip prepared in comparative example 9, to obtain a catalyst DCO-4, the composition of which is shown in Table 3.

Example 6

(1) Dispersing ammonium molybdate and cobalt nitrate in water to form an impregnation solution, wherein MoO is used₃The concentration of ammonium molybdate was 33.13g/L and the concentration of cobalt nitrate as CoO was 3.98 g/L.The dry alumina hydrate strips prepared in example 6 were impregnated with the impregnation solution at ambient temperature (35 ℃) for HT-61 hours. The impregnated hydrated alumina dry strands were dried at 120 ℃ under normal pressure in an air atmosphere for 2 hours, and then calcined at 420 ℃ under normal pressure in an air atmosphere for 3 hours, thereby obtaining a hydrogenation protection catalyst CH-6 according to the present invention, the composition of which is shown in Table 3.

(2) A catalyst was prepared in the same manner as in (1) except that the carrier was alumina dry strip OT-6 prepared in preparation example 6, to obtain catalyst CO-6 of the present invention, the composition of which is shown in Table 3.

Example 7

(1) Dispersing ammonium metatungstate and nickel nitrate in water to form an impregnation solution, wherein WO is added₃The concentration of the ammonium metatungstate is 21.77g/L, and the concentration of NiO is 2.29 g/L. The dry alumina hydrate strips prepared in example 7 were impregnated with the impregnation solution at ambient temperature (30 ℃) for HT-72 hours. The impregnated hydrated alumina dry strands were dried at 120 ℃ under normal pressure in an air atmosphere for 2 hours, and then calcined at 420 ℃ under normal pressure in an air atmosphere for 3 hours, thereby obtaining a hydrogenation protection catalyst CH-7 according to the present invention, the composition of which is shown in Table 3.

(2) A catalyst was prepared in the same manner as in (1) except that the carrier was alumina dry strip OT-7 prepared in preparation example 7, to obtain catalyst CO-7 of the present invention, the composition of which is shown in Table 3.

Comparative example 5

(1) A catalyst was prepared in the same manner as in (1) in example 7, except that the carrier was DHT-7 as the hydrated alumina dry strip prepared in comparative example 10, and as a result, the hydrated alumina dry strip was pulverized during impregnation, and a shaped catalyst could not be prepared.

(2) A catalyst was prepared in the same manner as in (2) in example 7, except that the carrier was DOT-7 which was an alumina dry strip prepared in comparative example 10, to obtain catalyst DCO-5 whose composition is shown in Table 3.

Example 8

(1) A catalyst was prepared in the same manner as in (1) in example 7 except that the carrier was the hydrated alumina dry strip HT-8 prepared in preparation example 8, to obtain the catalyst CH-8 of the present invention, the composition of which is shown in Table 3.

(2) A catalyst was prepared in the same manner as in (2) in example 7, except that the carrier was the alumina dry strip OT-8 prepared in preparation example 8, to obtain the catalyst CO-8 of the present invention, the composition of which is shown in Table 3.

Example 9

(1) A catalyst was prepared in the same manner as in (1) in example 7 except that the carrier was the hydrated alumina dry strip HT-9 prepared in preparation example 9, to obtain the catalyst CH-9 of the present invention, the composition of which is shown in Table 3.

(2) A catalyst was prepared in the same manner as in (2) in example 7, except that the carrier was alumina dry strip OT-9 prepared in preparation example 9, to obtain catalyst CO-9 of the present invention, the composition of which is shown in Table 3.

Example 10

(1) Dispersing ammonium metatungstate and nickel nitrate in water to form an impregnation solution, wherein WO₃The concentration of (2) was 21.77g/L, and the concentration of NiO was 3.98 g/L. . The alumina hydrate dry strip prepared in example 10 was impregnated with the impregnation solution saturated at ambient temperature (30 ℃ C.) for HT-102 hours. The impregnated hydrated alumina dry strips were dried at 140 ℃ under normal pressure in an air atmosphere for 2 hours, and then dried at 180 ℃ under normal pressure in an air atmosphere for 3 hours, thereby obtaining a hydrogenation protection catalyst CH-10 according to the present invention, the composition of which is shown in Table 3.

(2) A catalyst was prepared in the same manner as in (1) except that the carrier was alumina dry strip OT-10 prepared in preparation example 10, to obtain catalyst CO-10 of the present invention, the composition of which is shown in Table 3.

TABLE 3

¹: m is a group IVB metal element.

Experimental examples 1 to 10

Experimental examples 1-10 are provided to illustrate the heavy oil hydrodeasphaltene removal process according to the present invention.

The catalytic performance of the catalysts prepared in examples 1 to 10 was evaluated by the following method.

The catalysts prepared in the above examples were each crushed into particles having a diameter of 2 to 3mm and charged into a 100mL mini-fixed bed reactor. The feed oil was heavy atmospheric residuum, the properties of which are listed in table 4. The reaction conditions are as follows: the reaction temperature is 380 ℃, the hydrogen partial pressure is 14MPa, and the liquid hourly space velocity of the raw oil is 0.6h^-1. The total Ni and V content of the oil before and after the hydrotreatment was measured by an inductively coupled plasma emission spectrometer (PE-5300 plasma spectrometer by PE company, usa) with reference to the method specified in the petrochemical analysis method RIPP124-90, and the metal removal rate was calculated according to the following formula, and the results are listed in table 5:

experimental comparative examples 1 to 5

The catalytic performances of the catalysts prepared in comparative examples 1 to 5 were evaluated in the same manner as in experimental examples 1 to 10, respectively, and the results of the experiments are shown in Table 5.

TABLE 4

Raw oil name	Slag of illite gravity
		Density (20 ℃), kg/m³	0.966
Average molecular weight	452
		Ni，μg/g	47.7
V，μg/g	133
		Fe，μg/g	8.4
Ca，μg/g	29.5

TABLE 5

The results of experimental examples 1-10 confirm that the hydrogenation protection catalyst according to the present invention has high catalytic activity, can more effectively reduce the content of metal impurities in hydrocarbon oil, and can better prolong the service life of the hydrogenation catalyst main agent.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A preparation method of a hydrogenation protection catalyst, which comprises the step of loading a hydrogenation active component on a carrier, and is characterized in that the carrier is prepared by adopting the method comprising the following steps:

(A) providing a hydrated alumina gel solution, washing the hydrated alumina gel solution to obtain a first hydrated alumina wet gel, wherein the hydrated alumina gel solution is prepared by adopting one or more than two methods of a precipitation method, a hydrolysis method, a seed precipitation method and a rapid dehydration method;

(C) mixing a hydrated alumina wet gel with a compound having at least two proton acceptor sites to obtain a hydrated alumina composition, wherein the hydrated alumina wet gel is the first hydrated alumina wet gel or the second hydrated alumina wet gel, the compound having at least two proton acceptor sites is one or more selected from dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, the i value of the hydrated alumina wet gel is not less than 60%, and the compound having at least two proton acceptor sites is used in an amount such that the hydrated alumina composition finally prepared has an i value of not less than 60%

The value is 1.8 to 5,

the above-mentioned

The value of the one or more of,

wherein the mixing of the group IVB metal element-containing compound is performed in one, two or three of the step (A), the step (B) and the step (C) so that the hydrated alumina composition contains the group IVB metal element.

2. The process of claim 1, wherein in step (C), the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.85-4.

3. The method of claim 2, whereinIn step (C), the compound having at least two proton acceptor sites is used in an amount such that the hydrated alumina composition is prepared

The value is 1.9-3.5.

4. The method according to any one of claims 1 to 3, wherein in step (C), the i value of the hydrated alumina wet gel is not less than 62%.

5. The method according to claim 4, wherein in the step (C), the i value of the hydrated alumina wet gel is not less than 64%.

6. The method according to any one of claims 1 to 3, wherein in step (C), the i value of the hydrated alumina wet gel is not higher than 82%.

7. The method of claim 6, wherein in step (C), the hydrated alumina wet gel has an i value of not higher than 80%.

8. The method of claim 7, wherein in step (C), the hydrated alumina wet gel has an i value of not higher than 78.5%.

9. The method according to any one of claims 1 to 3, wherein in step (C), the hydrated alumina wet gel is a hydrated alumina wet gel which has not been subjected to a dehydration treatment so that the i value thereof is 60% or less.

10. The process according to claim 1, wherein the content of the group IVB metal element-containing compound is such that the content of the group IVB metal element in terms of oxide is from 0.1 to 6% by weight based on the total amount of the finally produced catalyst.

11. The process according to claim 10, wherein the content of the group IVB metal element-containing compound in the hydrated alumina composition is such that the content of the group IVB metal element in terms of oxide is 0.3 to 4% by weight based on the total amount of the finally prepared catalyst.

12. The method of any one of claims 1, 10 and 11, wherein the group IVB metal element is selected from titanium and zirconium.

13. The method according to any one of claims 1, 10 and 11, wherein the group IVB metal element-containing compound is selected from the group consisting of zirconium oxychloride, zirconium acetate, zirconium sulfate, zirconium tetrachloride, zirconium nitrate, zirconium carbonate, zirconium hydroxide, zirconium ammonium hydroxide, zirconium dioxide, titanic acid, metatitanic acid, titanium dioxide, titanium sulfate, and a compound represented by formula III,

TiX_n(OR)_4-n(in the formula III),

in the formula III, X is halogen and R is C₁-C₅N is an integer of 0 to 4.

14. The process of claim 1, wherein in step (C), the hydrated alumina composition is free of peptizing agent.

15. The method according to claim 1, wherein the compound having at least two proton acceptor sites is contained in an amount of 1 to 25 parts by weight relative to 100 parts by weight of the hydrated alumina wet gel, the hydrated alumina wet gel being based on hydrated alumina.

16. The method of claim 15, wherein the compound having at least two proton acceptor sites is present in an amount of 2 to 20 parts by weight relative to 100 parts by weight of the hydrated alumina wet gel, based on the hydrated alumina.

17. The method of claim 16, wherein the compound having at least two proton acceptor sites is present in an amount of 3 to 18 parts by weight relative to 100 parts by weight of the hydrated alumina wet gel, based on hydrated alumina.

18. The method of any one of claims 1-3 and 15-17, wherein the compound having at least two proton acceptor sites is one or more of a galactan, mannan, galactomannan, and cellulose ether.

19. The method of claim 18, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.

20. The method of any one of claims 1-3 and 15-17, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.

21. The method of claim 20, wherein the galactomannan is present in an amount of 10 to 70 wt% and the cellulose ether is present in an amount of 30 to 90 wt%, based on the total amount of the compound having at least two proton acceptor sites.

22. The method of claim 21, wherein the galactomannan is present in an amount of 15 to 68 wt% and the cellulose ether is present in an amount of 32 to 85 wt%, based on the total amount of the compound having at least two proton acceptor sites.

23. The method of claim 22, wherein the galactomannan is present in an amount of 20 to 65 wt% and the cellulose ether is present in an amount of 35 to 80 wt%, based on the total amount of the compound having at least two proton acceptor sites.

24. The method of claim 23, wherein the galactomannan is present in an amount of 25 to 60 wt% and the cellulose ether is present in an amount of 40 to 75 wt%, based on the total amount of the compound having at least two proton acceptor sites.

25. The method of claim 24, wherein the galactomannan is present in an amount of 30 to 55 wt% and the cellulose ether is present in an amount of 45 to 70 wt%, based on the total amount of the compound having at least two proton acceptor sites.

26. The process according to claim 1, wherein in step (E), the drying is carried out at a temperature of from 60 ℃ to less than 350 ℃, the duration of the drying being from 2 to 6 hours; in the step (F), the roasting is carried out at the temperature of 550-1000 ℃, and the roasting duration is 2-6 hours.

27. The method as claimed in claim 26, wherein, in step (E), the drying is carried out at a temperature of 120-180 ℃, and the duration of the drying is 2-6 hours; in the step (F), the roasting is carried out at the temperature of 550-1000 ℃, and the roasting duration is 2-6 hours.

28. The process of claim 1, wherein the hydrogenation active components are at least one group VIB metal element and at least one group VIII metal element.

29. The process according to claim 28, wherein the group VIB metal element is molybdenum and/or tungsten.

30. The method of claim 29, wherein the group VIII metal element is cobalt and/or nickel.

31. The process of any of claims 1 and 28-30, wherein the amount of the hydrogenation active component supported on the support is such that the content of group VIII metal elements, calculated as oxides, is not higher than 0.8 wt% and the content of group VIB metal elements, calculated as oxides, is not higher than 4 wt%, based on the total amount of the finally prepared catalyst.

32. The process according to claim 31, wherein the loading of the hydrogenation active components on the support is such that the content of group VIII metal elements, calculated as oxides, is from 0.2 to 0.6% by weight and the content of group VIB metal elements, calculated as oxides, is from 1.5 to 3.5% by weight, based on the total amount of the finally prepared catalyst.

33. The method of any one of claims 1 and 28-30, wherein loading a hydrogenation active ingredient on the support comprises: impregnating the carrier with an impregnation solution containing the hydrogenation active ingredient, drying the impregnated carrier, and optionally calcining the dried carrier.

34. The process of claim 33, wherein the impregnated support is dried at a temperature of 80-250 ℃; the dried support is calcined at a temperature of 360-500 ℃.

35. The method as claimed in claim 34, wherein the impregnated support is dried at a temperature of 100-200 ℃; the dried support was calcined at a temperature of 360-450 ℃.

36. A hydroprocessing catalyst prepared by the process of any one of claims 1-35.

37. Use of the catalyst of claim 36 in the hydroprocessing of hydrocarbon oils.

38. A method for hydrotreating a hydrocarbon oil, which comprises contacting a hydrocarbon oil-containing hydrocarbon oil with the hydrogenation protection catalyst of claim 36 under hydrotreating reaction conditions, and then contacting the hydrocarbon oil-containing hydrocarbon oil with a main hydrogenation catalyst.