CN108014809B

CN108014809B - Alumina forming body containing IVB group metal element, catalyst, preparation method and application thereof, and hydrotreating method

Info

Publication number: CN108014809B
Application number: CN201610972007.9A
Authority: CN
Inventors: 胡大为; 杨清河; 聂红; 曾双亲; 刘滨; 孙淑玲; 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: CN108014809A

Abstract

The invention discloses an alumina forming body containing IVB group metal element, a preparation method and application thereof

The shaped hydrated alumina composition of value 5 is optionally dried and then calcined in the presence of steam in an oxygen-containing atmosphere. The invention also discloses a catalyst with hydrogenation catalysis function and a preparation method thereof, and a hydrotreating method, wherein the catalyst takes the alumina forming body as a carrier. The invention takes hydrated alumina wet gel as the initial raw material to prepare the formed body with higher strength, simplifies the overall process flow, reduces the overall operation energy consumption, avoids dust pollution caused by adopting the pseudo-boehmite dry glue powder as the raw material, and improves the operation environment. The catalyst prepared by using the alumina forming body as a carrier shows improved catalytic activity in hydrocarbon oil hydrotreating.

Description

Alumina forming body containing IVB group metal element, catalyst, preparation method and application thereof, and hydrotreating method

Technical Field

The invention relates to the technical field of alumina forming, in particular to an alumina forming body containing IVB group metal elements, a preparation method and application thereof, a catalyst taking the alumina forming body containing IVB group metal elements as a carrier and a preparation method thereof, and a hydrotreating method adopting the catalyst.

Background

In the conventional method, an alumina molded body, particularly a γ -alumina molded body, is often used as an adsorbent or a carrier of a supported catalyst because of its good pore structure, suitable specific surface area 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 the pseudo-boehmite dry gel powder is taken as a starting point, an extrusion aid, an optional chemical peptizing agent (inorganic acid and/or organic acid) and an auxiliary agent (such as a compound containing IVB group metal elements) are added, and the mixture is kneaded and formed, and the formed product is dried and optionally calcined to be used as an adsorbent or 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 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

The invention aims to simplify the preparation process flow of the alumina carrier, reduce the dust pollution in the preparation process of the alumina carrier and simultaneously ensure that the prepared carrier can meet the industrial use requirement.

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 method for producing an alumina formed body containing a group IVB metal element, the method comprising the steps of:

(1) forming 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 to obtain a formed product,

of said composition

A value of 5 or less, 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,

optionally, (2) drying the molded product obtained in the step (1) to obtain a dried molded product;

(3) and (2) roasting the formed product obtained in the step (1) or the dried formed product obtained in the step (2) in the presence of water vapor in an oxygen-containing atmosphere.

According to a second aspect of the present invention, there is provided a group IVB metal element-containing alumina formed body produced by the method according to the first aspect of the present invention.

According to a third aspect of the present invention, there is provided a group IVB metal element-containing alumina formed body produced by the method of the first aspect of the present invention, wherein the hydrated alumina composition is

The value is not less than 1.8.

According to a fourth aspect of the present invention, there is provided a group IVB metal element-containing alumina formed body produced by the method of the first aspect of the present invention, wherein the hydrated alumina composition is

The value is less than 1.8.

According to a fifth aspect of the present invention, there is provided a method for producing a hydrous alumina, comprising the steps of:

(1) providing a hydrated alumina gel solution, washing and carrying out solid-liquid separation on the hydrated alumina gel solution to obtain a first hydrated alumina wet gel, wherein the solid-liquid separation condition is that the i value of the first hydrated alumina wet gel is not less than 60%, preferably not less than 62%, more preferably not more than 82%, further preferably not more than 80%, further preferably not more than 78.5%,

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,

(2) mixing the first hydrated alumina wet gel with a compound having at least two proton acceptor sites by the method of the first aspect of the invention, and then shaping, optionally drying, and calcining to produce a group IVB metal element-containing alumina shaped body;

wherein the operation of mixing the group IVB metal element-containing compound is performed in step (1) and/or step (2) so that the hydrated alumina composition contains the group IVB metal element-containing compound.

According to a sixth aspect of the present invention, there is provided a method for producing a hydrated alumina containing a group IVB metal element, comprising the steps of:

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

(2) treating the first hydrated alumina wet gel by adopting (2-1) or (2-2) to obtain a second hydrated alumina wet gel,

(2-1) 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;

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

in (2-1) and (2-2), the solid-liquid separation is carried out under such conditions that the second hydrated alumina wet gel has an i value of not less than 60%, preferably not less than 62%, more preferably not more than 82%, further preferably not more than 80%, further preferably not more than 78.5%,

(3) mixing the second hydrated alumina wet gel with a compound having at least two proton acceptor sites by the method of the first aspect of the invention, and then shaping, optionally drying, and calcining to produce a group IVB metal element-containing alumina shaped body;

wherein the operation of mixing the group IVB metal element-containing compound is performed in one, two, or three of the step (1), the step (2), and the step (3) so that the hydrated alumina composition contains the group IVB metal element-containing compound.

According to a seventh aspect of the present invention, there is provided a group IVB metal element-containing alumina formed body produced by the method according to the third aspect of the present invention.

According to an eighth aspect of the present invention, there is provided a use of the alumina formed body containing a group IVB metal element according to the second, third, fourth or seventh aspect of the present invention as a carrier or an adsorbent.

According to a ninth aspect of the present invention, the present invention provides a catalyst with a hydrogenation catalytic effect, which comprises a carrier and a group VIII metal element and a group VIB metal element supported on the carrier, wherein the carrier is the alumina formed body containing the group IVB metal element according to the second, third, fourth or seventh aspect of the present invention.

According to a tenth aspect of the present invention, there is provided a method for preparing a catalyst with hydrogenation catalysis, the method comprising loading a group VIII metal element and a group VIB metal element on a carrier, wherein the method further comprises preparing an alumina carrier containing a group IVB metal element by the method of the first, fifth or sixth aspect of the present invention.

According to an eleventh aspect of the present invention, there is provided a hydrotreating process comprising contacting a hydrocarbon oil under hydrotreating conditions with a catalyst having a hydrocatalytic action, wherein the catalyst having a hydrocatalytic action is the catalyst according to the ninth aspect of the present invention or the catalyst prepared by the method according to the tenth aspect of the present invention.

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

(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 takes the hydrated alumina wet gel as the starting material to prepare the carrier, the process of the invention is simpler and has stronger operability, and can effectively improve the strength of the finally prepared formed body, and simultaneously can adjust the pore size distribution of the finally prepared formed body, thereby meeting the requirements of various use occasions. 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.

Also, the catalyst prepared with the alumina molded body according to the present invention as a support shows improved catalytic activity in hydrocarbon oil hydrotreating.

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 view for explaining a preferred embodiment of the alumina production molding method 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 method for producing an alumina formed body, comprising the steps of: (1) forming a hydrated alumina composition to obtain a formed product;

In the step (1), the hydrated alumina composition contains 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. The hydrated alumina composition according to this preferred embodiment is particularly suitable for the preparation of shaped bodies for use as catalyst supports.

The hydrated alumina is directly sourced from the hydrated alumina wet gel and is not sourced 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. The hydrated alumina composition according to the present invention can be used for molding (particularly extrusion molding) without using a dry rubber powder as a starting material, and the reason why the obtained molded article has a higher strength may be that: the compound with at least two proton acceptor sites and the free water in the hydrated alumina wet gel generate hydrogen bond interaction, so that the free water is adsorbed, and simultaneously, the compound and the hydroxyl in the molecular structure of the hydrated alumina generate interaction to play a role in peptization.

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. The substituted hydrocarbon group may be, for example, an alkyl group substituted with a hydroxyl group, a carboxyl group, a cyano group or an aryl group (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, carboxylMethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose. The polysaccharides and etherified polysaccharides may be provided in various forms. For example, the galactomannans may be provided in the form of 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. According to this more preferred embodiment, the molded body formed from the hydrated alumina composition has 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.%, based on the total amount of the compound having at least two proton acceptor sites; the cellulose ether may be present in an amount of 30 to 90 wt%, preferably 32 to 85 wt%, more preferably 35 to 80 wt%.

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 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, chlorine, bromine and iodine can be mentioned, preferably chlorine), and 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, 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-containing compound in terms of oxide may be 1.5 to 85 parts by weight, preferably 2 to 80 parts by weight, more preferably 3 to 75 parts by weight, relative to 100 parts by weight of the hydrated alumina.

Of the hydrated alumina composition

The value is 5 or less, preferably 4 or less, more preferably 3.5 or less, and further preferably 3.2 or less. Of the hydrated alumina composition

The value may be 1.2 or more, preferably 1.3 or more, and more preferably 1.4 or more. In particular, of the hydrated alumina composition

The value may be 1.2 to 5, preferably 4 to 1.2, more preferably 1.3 to 3.5, and further preferably 1.4 to 3.2.

In one embodiment, the hydrated alumina composition is

The value is not less than 1.8, for example, may be 1.8 to 5, preferably not less than 1.9, for example, may be 1.9 to 4, more preferably not less than 2, for example, may be 2 to 3.5. The hydrated alumina composition according to this embodiment can produce shaped bodies having a bimodal distribution of pore sizes.

In another embodiment, of the hydrated alumina composition

The value is less than 1.8, for example, may be from 1.2 to less than 1.8, preferably not higher than 1.7, and for example may be from 1.3 to 1.7. The hydrated alumina composition according to this embodiment can produce a shaped body having a monomodal distribution of pore diameters.

In the present invention,

the values were determined using the following method: 10g of the composition are placed in an air atmosphere at 120 DEG CDrying for 240 minutes, the mass of the dried composition being recorded as w₁Is calculated by formula I

The value of the one or more of,

the composition according to the invention, the compound having at least two proton acceptor sites being present in an amount such that the composition

The value meets the above requirements. 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, and still more preferably 3.5 to 17 parts by weight, relative to 100 parts by weight of the hydrated alumina.

The composition according to the invention 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.

According to the composition of the present invention, 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 content of the peptizing agent is 5 parts by weight or less, preferably 3 parts by weight or less, and more preferably 2 parts by weight or less, with respect to 100 parts by weight of the hydrated alumina.

In a particularly preferred embodiment of the invention, the composition according to the invention does not contain a peptizing agent.

The hydrated alumina composition can be prepared by mixing hydrated alumina and a compound having at least two proton acceptor sites. As an example, the hydrated alumina composition is prepared using a method comprising the steps of: mixing the components of a raw material composition to obtain the hydrated alumina composition, namely mixing the obtained mixture to obtain the hydrated alumina composition, wherein the raw material mixture contains hydrated alumina wet gel, a compound with at least two proton acceptor sites and at least one compound containing a group IVB metal element.

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 raw material mixture, the i value of the hydrated alumina wet gel is not less than 60%, and preferably not less than 62%. 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 is 60 to 82%, preferably 60 to 80%, more preferably 62 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 above-mentioned raw material mixture, the hydrated alumina wet 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).

The compound having at least two proton acceptor sites is used in the raw material mixture in an amount to provide a final hydrated alumina composition

The values meet the requirements described hereinbefore.

The raw material mixture may or may not contain a peptizing agent. Preferably, the peptizing agent is present in an amount of 5 parts by weight or less, preferably 3 parts by weight or less, more preferably 2 parts by weight or less, relative to 100 parts by weight of the hydrated alumina wet gel, based on the hydrated alumina. Further preferably, the raw material mixture does not contain a peptizing agent.

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 using 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.

The hydrated alumina wet gel can 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 a hydrated alumina wet gel with a compound having at least two proton acceptor sites in a vessel 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. Stirring and mixing can 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.

During the mixing, water may or may not be added so long as it enables the preparation of a hydrated alumina composition

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 (1), 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 step (1), the shaped article may have various shapes according to specific use requirements, for example: one or more than two of a sphere, a honeycomb, a bird nest, a sheet or a strip (such as a clover, a disc, a cylinder and a Raschig ring).

According to the preparation method of the present invention, the molded article obtained in step (1) may be fed to step (3) after being dried in step (2); the shaped product obtained in step (1) may be directly fed to step (3) and fired.

In the step (2), the temperature at which the shaped product is dried may be conventionally selected in the art. Generally, the temperature of the drying may be 60 ℃ or more and not more than 350 ℃, preferably 80 to 300 ℃, more preferably 110 ℃ or 260 ℃. 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 4 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 drying may be performed under normal pressure (i.e., 1 atm), or under reduced pressure.

In the step (3), the temperature of the calcination may be 400-. The duration of the calcination may be 1 to 20 hours, preferably 1.5 to 15 hours, more preferably 2 to 12 hours, and further preferably 2 to 6 hours.

In the step (3), the rate of raising the temperature to the calcination temperature at the time of the calcination may be conventionally selected. Preferably, the rate of temperature rise to raise the temperature within the container holding the shape to the firing temperature may be 10-400 deg.C/hr, preferably 30-350 deg.C/hr, more preferably 60-300 deg.C/hr, and still more preferably 100-. The temperature in the container for accommodating the molded object may be increased from the ambient temperature to the baking temperature, or the temperature in the container for accommodating the molded object may be increased from the drying temperature to the baking temperature, and is not particularly limited.

In the step (3), the calcination is carried out in an oxygen-containing atmosphere under water vapor, so that the prepared alumina carrier has higher pore volume and larger specific surface area, and the performance of the alumina forming body can be effectively improved.

Firing in the presence of steam may be accomplished by passing a stream of steam-containing gas into the container holding the shape during firing. The amount of water vapor (introduction amount) can be selected according to the amount of the molded article. In general, the amount of water vapour used may be in the range 0.01-0.8L/(min. g of mouldings), preferably 0.02-0.4L/(min. g of mouldings), calculated as hydrated alumina.

The gas stream containing water vapor may or may not contain a carrier gas. The carrier gas may be one or a combination of two or more of air, a group zero gas (e.g., argon and/or helium), and nitrogen.

The water vapor may be from a variety of sources. In a preferred embodiment, at least part of the water vapor in step (3) is water vapor generated during drying or firing of the shaped article obtained in step (1).

Specifically, when the shaped product obtained in step (1) is fed to be dried in step (2), the water vapor generated in the drying process may be collected, and at least part of the water vapor generated in the drying process may be fed to step (3). At this time, the amount of the steam generated in the drying process may or may not be supplemented with fresh steam. The term "fresh water vapor" is distinguished from water vapor generated during drying and calcination and refers to water vapor generated by water vapor generation processes other than the drying and calcination processes in the method of the present invention. All of the water vapor generated during the drying process may be fed to step (3). It is also possible to feed part of the water vapor produced in the process to step (3). Preferably, 10 to 90% by volume, preferably 20 to 88% by volume, more preferably 30 to 85% by volume, and further preferably 60 to 85% by volume of the gas generated in the drying process is fed to step (3).

When the molded article obtained in step (1) is directly fed to step (3) for calcination, water vapor generated during calcination (including a temperature raising process of raising the temperature to the calcination temperature) may be collected, and at least part of the water vapor generated during calcination may be recycled to step (3). In practice, the gas in the container containing the shaped article may be withdrawn during the heating and firing, and at least part of the withdrawn gas may be recycled into the container as recycle gas. The entire withdrawn gas may be recycled into the vessel as recycle gas, or part of the withdrawn gas may be recycled into the vessel as recycle gas. Preferably, part of the withdrawn gas is recycled as recycle gas into the vessel, in which case the vessel is preferably replenished with fresh water vapour. More preferably, 10 to 90% by volume, preferably 20 to 88% by volume, more preferably 30 to 85% by volume, and still more preferably 60 to 85% by volume of the withdrawn gas is recycled into the vessel.

The calcination in step (3) is carried out in an oxygen-containing atmosphere so that hydrated alumina is converted to alumina. In order to allow the hydrated alumina gel to be converted to alumina at a higher conversion rate, it is preferable to feed an oxygen-containing gas into the container holding the moldings during the calcination. The oxygen-containing atmosphere may be oxygen, air, or a mixture of oxygen and an inactive gas, and specific examples of the inactive gas may include, but are not limited to, nitrogen and/or a group zero gas (e.g., argon and/or helium). An oxygen-containing gas may be fed into the container holding the form along with water vapor.

The alumina forming body containing the IVB metal element prepared by the method has rich pore structure and adjustable pore size distribution, and is suitable for being used as an adsorbent or a carrier of a catalyst.

Thus, according to a second aspect of the present invention, there is provided a group IVB metal element-containing alumina formed body produced by the method of the present invention.

According to a third aspect of the present invention, there is provided a group IVB metal element-containing alumina formed body produced by the method of the present invention, wherein the hydrated alumina composition is

The value is not less than 1.8, for example, may be 1.8 to 5, preferably not less than 1.9, for example, may be 1.9 to 4, more preferably not less than 2, for example, may be 2 to 3.5.

The alumina formed body containing the IVB metal element according to the third aspect of the present invention has a bimodal distribution of pore sizes. Wherein, the most probable pore diameters are respectively 4-60nm and more than 60nm determined by mercury intrusion method; preferably, the most probable pore sizes are 5-40nm (e.g., 5-20nm) and 80-500nm (e.g., 100-400nm, preferably 200-300nm), respectively.

According to a fourth aspect of the present invention, there is providedAn alumina compact containing a group IVB metal element produced by the method of the first aspect of the present invention, wherein the hydrated alumina composition is

The value is less than 1.8, preferably not more than 1.7, more preferably 1.3 to 1.7.

The alumina formed body containing a group IVB metal element according to the fourth aspect of the present invention has a monomodal distribution of pore diameters. Wherein the largest possible pore diameter is 4-60nm, preferably 4.5-40nm, more preferably 4.5-20nm, as measured by mercury intrusion porosimetry.

The alumina formed body containing a group IVB metal element according to the second, third or fourth aspect of the present invention has a high strength. Generally, the radial crush strength of the alumina formed body containing a group IVB metal element according to the present invention is 10N/mm or more, usually 10 to 50N/mm, preferably 14 to 50N/mm. In one example, the group IVB metal element-containing alumina formed body is the group IVB metal element-containing alumina formed body according to the third aspect of the present invention, and the radial crush strength of the group IVB metal element-containing alumina formed body is 10 to 30N/mm. In another example, the group IVB metal element-containing alumina formed body is the group IVB metal element-containing alumina formed body according to the fourth aspect of the present invention, and the radial crush strength of the group IVB metal element-containing alumina formed body is 15 to 50N/mm. In the present invention, the radial crush strength of the molded article was measured by the method specified in RIPP 25-90.

According to a fifth aspect of the present invention, as shown in fig. 2, there is provided a method for producing a hydrous alumina, comprising the steps of:

optionally, (2) treating the first hydrated alumina wet gel with (2-1) or (2-2) to obtain a second hydrated alumina wet gel,

(3) mixing the first hydrated alumina wet gel or the second hydrated alumina wet gel with a compound having at least two proton acceptor sites by the method of the first aspect of the present invention, followed by shaping, optionally drying, and calcining, thereby preparing an alumina shaped body;

wherein the operation of mixing the group IVB metal element-containing compound is performed in one, two, or three of the step (1), the step (2), and the step (3) so that the hydrated alumina composition contains the group IVB metal element-containing compound. The method of mixing the group IVB metal element-containing compound is the same as the method and the sequence described above, and will not be described in detail here.

In the step (1), the hydrated alumina gel solution is a hydrated alumina gel-containing solution which is obtained by a hydrated alumina gel synthesis reaction and is aged or not 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 (1) to remove acidic substances and alkaline substances in the hydrated alumina wet gel, so that the adverse effect of the presence 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 (1) 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 (1), 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 value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites according to the first aspect of the present invention, or may be a value higher than the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites and the group IVB metal element-containing compound according to the first aspect of the present invention.

In one embodiment, the first hydrated alumina wet gel has an i value content which satisfies the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites according to the first aspect of the present invention, i.e., the i value of the first hydrated alumina wet gel is not less than 60%, preferably not less than 62%. 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%.

According to this embodiment, the first hydrated alumina wet gel may be directly fed to step (3) to be mixed with the compound having at least two proton acceptor sites and the group IVB metal element-containing compound. This applies in particular to situations in which the following requirements are satisfied: (A) 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; (B) 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 sent to step (2) for treatment with (2-1). This applies in particular to situations in which the following requirements are satisfied: (A) 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; (B) the washing device and the mixing device cannot be compactly arranged, so that the discharge of the washing device cannot directly enter the mixing device.

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 first 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 sent to step (2) and treated with either (2-1) or (2-2).

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 requirements described in the first aspect of the present invention, and the case where the washing apparatus and the mixing apparatus cannot be compactly arranged.

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

In (2-1), 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 (2-1), 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 (2) 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 according to the first aspect of the present invention, that is, the i value of the hydrated alumina wet gel is not less than 60%, preferably not less than 62%. 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%.

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 (2). 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 the step (3), the first hydrated alumina wet gel or the second hydrated alumina wet gel is mixed with the compound having at least two proton acceptor sites and the compound containing the group IVB metal element by the method according to the first aspect of the present invention, followed by molding, optionally drying, and baking, thereby preparing an alumina molded body. The i values of the first hydrated alumina wet gel and the second hydrated alumina wet gel fed to the step (3) satisfy 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 according to the first aspect of the present invention.

The method according to the fifth aspect of the present invention may be carried out in an alumina production molding system comprising a hydrated alumina gel production unit, a solid-liquid separation and washing unit, a mixing unit, a molding unit, an optional drying unit, and a calcining unit.

The hydrated alumina gel solution output port of the hydrated alumina gel production unit is communicated with the washing material input port to be separated of the solid-liquid separation and washing unit, the solid-phase material output port of the solid-liquid separation and washing unit is communicated with the solid-phase material input port of the mixing unit, the mixed material output port of the mixing unit is communicated with the raw material input port of the forming unit, the material input port to be dried of the drying unit is communicated with the formed product output port of the forming unit, the material input port to be calcined of the calcining unit is communicated with the dried material output port of the drying unit or the formed product output port of the forming unit,

the roasting unit comprises a container for containing materials to be roasted and a water vapor conveying subunit, wherein the water vapor conveying subunit is used for inputting water vapor into the container in the roasting process.

The hydrated alumina gel production unit is used for generating 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 unit to obtain hydrated alumina wet gel

The value satisfies the requirement of being able to be mixed with a compound having at least two proton acceptor sites according to the first aspect of the present invention.

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 requirements with a compound having at least two proton acceptor sites. 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 apparatusMention may be made, but not limited to, of plate and frame filters, belt filters or a combination of both. For controlling the hydrated alumina wet gel obtained

The solid-liquid separation and washing unit can also comprise a purging device, and natural air or pressurized air is adopted to purge 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 values are such as to satisfy the requirements of the first aspect of the invention for admixture with a compound having at least two proton acceptor sites. 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 adopt a conventional washing device to wash the separated solid phase. 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.

In a preferred embodiment, the solid-liquid separation and washing unit may comprise a washing subunit, a diluting subunit, a conveying subunit and a solid-liquid separation subunit, from the viewpoint of facilitating the transportation of the material, on the premise that the mixing unit is provided with the hydrated alumina gel satisfying the requirements,

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 the solid-liquid separation subunit;

and the 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 and an optional compound containing a group IVB metal element 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 firing unit may employ a conventional firing 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 be less than 60 percent (preferably less than 62 percent) 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 by taking the flow direction of the hydrated alumina gel as a reference.

The water vapor conveying subunit is used for inputting water vapor into a container containing materials to be roasted in the roasting process. The steam delivery sub-unit may be in communication with a steam storage tank to deliver steam to the vessel during the firing process. The water vapor input by the water vapor transmission subunit can be fresh water vapor, water vapor generated in a drying process or a roasting process, and a combination of the fresh water vapor and the water vapor generated in the drying process or the roasting process.

The production molding system preferably further comprises a water vapor collecting unit, wherein a water vapor input port of the water vapor collecting unit is communicated with a water vapor output port of the drying unit for outputting water vapor generated in the drying process and/or a water vapor output port of the roasting unit for outputting water vapor generated in the roasting process, and a water vapor output port of the water vapor collecting unit is communicated with a water vapor introduction port of the water vapor conveying subunit, and is used for collecting water vapor generated in the drying process of the drying unit or the roasting process of the roasting unit and circularly conveying at least part of the water vapor into the roasting unit. In one embodiment, the production molding system comprises a drying unit, wherein when a material input port of the roasting unit to be roasted is communicated with a dried material output port of the drying unit, a water vapor output port of the drying unit for outputting water vapor generated in the drying process is communicated with a water vapor input port of the water vapor collecting unit so as to receive the water vapor generated in the drying process by the drying unit. In another embodiment, the material to be fired input port of the firing unit is communicated with the molded product output port of the molding unit (i.e., the production molding system does not include a drying unit), and the water vapor output port of the firing unit for outputting water vapor generated during the firing process is communicated with the water vapor input port of the water vapor collection unit to receive the water vapor generated during the firing process.

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 a sixth aspect of the present invention there is provided an alumina support containing a group IVB metal element produced by the method of the fifth aspect of the present invention.

The alumina formed body containing the group IVB metal element according to the sixth aspect of the present invention has a rich pore structure and is suitable as an adsorbent or a carrier of a catalyst.

The alumina carrier containing the IVB metal element according to the sixth aspect of the invention is prepared by mixing the alumina hydrate composition

The value is adjusted, and the carriers with different pore distributions can be obtained.

In one embodiment, the hydrated alumina composition is

The value is not less than 1.8, for example, may be 1.8 to 5, preferably not less than 1.9, for example, may be 1.9 to 4, more preferably not less than 2, for example, may be 2 to 3.5, and the pore size distribution of the group IVB metal element-containing alumina formed body produced is in a bimodal distribution. Wherein, the most probable pore diameters are respectively 4-60nm and more than 60nm determined by mercury intrusion method; preferably, the most probable pore sizes are 5-40nm (e.g., 5-20nm) and 80-500nm (e.g., 100-400nm, preferably 200-300nm), respectively.

In another embodiment, of the hydrated alumina composition

A value of less than 1.8, preferably not more than 1.7, more preferably 1.3 to 1.7, and the pore diameter of the alumina formed body containing a group IVB metal element produced is in a monomodal distribution. Wherein the largest possible pore diameter is 4-60nm, preferably 4.5-40nm, more preferably 4.5-20nm, as measured by mercury intrusion porosimetry.

The alumina formed body containing the IVB metal element according to the sixth aspect of the present invention has a high strength. In general, the alumina formed body containing a group IVB metal element according to the sixth aspect of the present invention has a radial crush strength of 10N/mm or more, usually 10 to 50N/mm, preferably 14 to 50N/mm.

According to a seventh aspect of the present invention, there is provided the use of the alumina formed body containing a group IVB metal element according to the second, third, fourth or sixth aspect of the present invention as a carrier or adsorbent.

The alumina shaped bodies according to the invention containing a metal element of group IVB are particularly suitable as supports for supported catalysts. The supported catalyst may be any of various catalysts commonly used in the art that can support an alumina molded body containing a group IVB metal element. Preferably, the catalyst is a catalyst having a hydrogenation catalytic effect. That is, the alumina formed body containing a group IVB metal element according to the present invention is particularly suitable as a carrier of a catalyst having a hydrogenation catalytic action.

The active component having a hydrogenation catalytic action may be supported on the alumina compact containing a group IVB metal element according to the present invention by various methods commonly used in the art (e.g., impregnation), for example: the catalyst having a hydrogenation catalytic action can be obtained by impregnating the shaped body of the invention with an aqueous solution containing the active component and then drying and optionally calcining the shaped body loaded with the active component.

According to an eighth aspect of the present invention, there is provided a catalyst having hydrogenation catalytic action, comprising a carrier and a hydrogenation-active component supported on the carrier, wherein the carrier is the group IVB metal element-containing alumina compact according to the second, third, fourth or sixth aspect of the present invention.

The hydrogenation active component may be of conventional choice. Preferably, the hydrogenation active components are VIB group metal elements and VIII group metal elements. The group VIII metal element and the group VIB metal element may be various elements having a hydrogenation catalytic action commonly used in the art. Preferably, the group VIII metal element is cobalt and/or nickel, and the group VIB metal element is molybdenum and/or tungsten. The contents of the group VIII metal elements and the group VIB metal elements may be appropriately selected according to the specific application of the catalyst. For example, when the catalyst according to the present invention is used for hydrotreating a heavy hydrocarbon oil, the content of the carrier may be 67 to 94.9 wt%, preferably 75 to 88 wt%, based on the total amount of the catalyst; the content of the group VIII metal element may be 0.1 to 8% by weight, preferably 2 to 5% by weight, in terms of oxide; the group VIB metal element may be present in an amount of 5 to 25 wt.%, preferably 10 to 20 wt.%, calculated as oxide.

According to a ninth aspect of the present invention, there is provided a method for preparing a catalyst having hydrogenation catalysis, the method comprising loading a hydrogenation active component on a carrier, wherein the method further comprises preparing an alumina carrier containing a group IVB metal element by the method of the first aspect of the present invention.

According to the preparation method of the catalyst with hydrogenation catalysis, the hydrogenation active component can be selected conventionally. Preferably, the hydrogenation active components are VIB group metal elements and VIII group metal elements. The VIII group metal element is preferably cobalt and/or nickel, and the VIB group metal element is preferably molybdenum and/or tungsten. The loading amount of the hydrogenation active component on the carrier can be properly selected according to the specific application of the catalyst. For example, when the prepared catalyst is used for hydrotreating hydrocarbon oil, the loading amounts of the group VIII metal element and the group VIB metal element on the carrier are such that the contents of the group VIII metal element and the group VIB metal element in the finally prepared catalyst can satisfy the requirements of the eighth aspect of the present invention, based on the total amount of the prepared catalyst.

According to the preparation method of the catalyst having hydrogenation catalysis of the present invention, the hydrogenation active component can be supported on the carrier by various methods commonly used in the art, such as: and (4) dipping. The impregnation may be a saturated impregnation or an excess impregnation. The carrier may be used as an impregnating solution formed by dissolving a group VIII metal element-containing compound and a group VIB metal element-containing compound in a solvent, typically water. The group VIII metal element-containing compound may be a conventional choice in the art of catalyst preparation, may be selected from the group consisting of nitrates of group VIII metal elements, chlorides of group VIII metal elements, sulfates of group VIII metal elements, formates of group VIII metal elements, acetates of group VIII metal elements, phosphates of group VIII metal elements, citrates of group VIII metal elements, oxalates of group VIII metal elements, carbonates of group VIII metal elements, basic carbonates of group VIII metal elements, hydroxides of group VIII metal elements, phosphates of group VIII metal elements, phosphides of group VIII metal elements, sulfides of group VIII metal elements, aluminates of group VIII metal elements, molybdates of group VIII metal elements, tungstates of group VIII metal elements and water-soluble oxides of group VIII metal elements. 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. Specific examples of the group VIB metal element-containing compound may include, but are not limited to, ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide, and tungsten oxide.

According to the preparation method of the catalyst with hydrogenation catalysis, the hydrogenation active components can be loaded on the carrier at the same time, and the hydrogenation active components can also be loaded on the carrier in a plurality of times.

According to the process for the preparation of the catalyst having a hydrocatalytic effect according to the present invention, the impregnated support may be dried and optionally calcined under conditions commonly used in the art. Generally, the drying conditions include: the temperature can be 100-200 ℃, and preferably 120-150 ℃; the duration may be 1 to 15 hours, preferably 1.5 to 10 hours, more preferably 2 to 4 hours. The roasting conditions comprise: the temperature can be 350-550 ℃, and preferably 400-500 ℃; the duration may be 1 to 8 hours, preferably 1.5 to 6 hours, more preferably 1.5 to 3 hours.

According to a tenth aspect of the present invention, there is provided a hydroprocessing method comprising contacting, under hydroprocessing conditions, a hydrocarbon oil with a catalyst having a hydrocatalytic effect, wherein the catalyst having a hydrocatalytic effect is the catalyst according to the eighth aspect of the present invention or the catalyst prepared by the method according to the ninth aspect of the present invention.

The hydrotreating method of the present invention is not particularly limited with respect to the kind of hydrocarbon oil and the hydrotreating conditions, and may be a routine choice in the art. Specifically, the hydrocarbon oil may be various heavy mineral oils, synthetic oils, or mixed distillates of heavy mineral oils and synthetic oils, such as: the hydrocarbon oil may be one or more selected from crude oil, distillate oil, solvent refined oil, cerate, under-wax oil, fischer-tropsch synthetic oil, coal liquefied oil, light deasphalted oil and heavy deasphalted oil. Preferably, the hydrocarbon oil is a hydrocarbon oil containing heavy mineral oil, such as various heavy oils of inferior qualityOils such as atmospheric residue, vacuum gas oil, coker gas oil, coal tar, and the like. The hydrotreating conditions include: the temperature can be 300-380 ℃; the hydrogen partial pressure may be 4-15MPa in gauge pressure; the liquid hourly space velocity of the hydrocarbon oil can be 0.5-3 hours^-1。

According to the hydrotreating process of the present invention, before the hydrogenation reaction, the catalyst is presulfided, preferably under conventional conditions in the art, in the presence of hydrogen, and the presulfiding may be performed inside the hydrogenation reactor or outside the hydrogenation reactor, without particular limitation. The presulfiding may generally be carried out at a temperature of 140 ℃ and 370 ℃.

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,

the following examples andin the comparative example, the water absorption of the molded article prepared was 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 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.

Examples 1 to 16 are intended to illustrate the alumina moldings of the invention and the process for their production.

Example 1

The hydrated alumina wet gel used in this example was a pseudoboehmite wet cake (the wet cake was numbered as SLB-1) obtained by washing and filtering a hydrated alumina gel solution prepared by an acid method (sodium metaaluminate-aluminum sulfate method, taken from the tommy division, petrochemical, china), and the i value of the wet cake was determined to be 78.2%.

(1) 200g of SLB-1 numbered wet cake was placed in a beaker, followed by the addition of 5g TiO₂5g 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 stirred with a mechanical stirrer for 10 minutes to obtain a mixture of the hydrated alumina composition of the present invention, the property parameters of which are shown 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, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 580 ℃ at a temperature rise rate of 150 ℃/hr, and the temperature was maintained at that temperature for 6 hours, and after the wet strips were fed into the tube furnace, air was blown into the internal space of the tube furnace from the inlet of the tube furnace at 15L/min, wherein the air volume of 12L/min was the circulating air (the amount of water vapor was 6L/min, 0.13L/(min · g molded product)) which was discharged from the outlet of the tube furnace, and the remaining air volume of 3L/min was air. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Comparative example 1

An alumina molded body was produced in the same manner as in example 1, except that, in the step (3), after the wet bar was fed into the tube furnace, air was fed from the inlet of the tube furnace to the inner space of the tube furnace at 15L/min instead of circulating the gas flow discharged from the outlet of the tube furnace into the tube furnace. The properties of the prepared alumina carrier are listed in table 1.

Example 2

(1) 5kg of the wet cake numbered SLB-1 was mixed with 500g of deionized water and beaten for 1 minute, and the resulting slurry was fed to a plate and frame filter press, and the pressure of the plate and frame was adjusted to 0.7MPa and held for 15 minutes to obtain a wet cake (numbered LB-1). The wet cake numbered LB-1 was determined to have an i value of 62%.

(2) 300g of wet cake LB-1, reference number, was placed in a beaker and 8g of TiO was added₂4.5g of hydroxyethyl methylcellulose (available from Shanghai Huikang Fine chemical Co., Ltd., the same below) and 1.5g of sesbania powder (having a galactomannan content of 85% by weight, available from Beijing chemical Co., Ltd.) were stirred with a mechanical stirrer for 10 minutes to obtain a hydrated alumina composition of the present invention, the properties of which are shown 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 2.0 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, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 500 ℃ at a temperature rise rate of 100 ℃/hr, and the temperature was maintained at that temperature for 4 hours, and after the wet strips were fed into the tube furnace, air was blown into the internal space of the tube furnace from the inlet of the tube furnace at 14L/min, wherein the air volume of 11L/min was the circulating air (the amount of water vapor was 6L/min, 0.05L/(min · g molded product)) which was discharged from the outlet of the tube furnace, and the remaining air volume of 3L/min was air. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Example 3

An alumina molded body was produced in the same manner as in example 2, except that sesbania powder was not used in the step (2) and the amount of hydroxyethyl methylcellulose was 5.8 g. The properties of the alumina shaped bodies produced are listed in table 1.

Example 4

An alumina molded body was produced in the same manner as in example 2, except that hydroxyethylmethylcellulose was not used in the step (2) and that sesbania powder was used in an amount of 6.8 g. The properties of the alumina shaped bodies produced are listed in table 1.

Example 5

A molded body and a catalyst were produced in the same manner as in example 2, except that 3g of nitric acid (HNO) was further added in the step (2) while adding hydroxyethyl methylcellulose and sesbania powder₃Content of 65 wt%). The properties of the alumina shaped bodies produced are listed in table 1.

Comparative example 2

(1) 500g of wet filter cake No. LB-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) Extruding the pseudo-boehmite powder prepared in the step (1) on an F-26 type double-screw extruder by using a circular orifice plate with the diameter of 2.0 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 strands having a length of about 6mm and shaped into alumina bodies having the property parameters shown in Table 1 by the same method as in step (4) of example 2.

Comparative example 3

(1) 500g of wet filter cake No. LB-1 was dried at 90 ℃ for 3 hours in an air atmosphere to obtain pseudo-boehmite powder having an i value of 40%. 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) 190g of the pseudo-boehmite powder prepared in the step (1) was put in a beaker, 4.5g of hydroxyethyl methyl cellulose (same as in example 2) and 1.5g of sesbania powder (same as in example 2) were added, and after stirring for 10 minutes with a mechanical stirrer, a pseudo-boehmite composition was obtained.

(3) And (3) extruding the pseudo-boehmite composition prepared in the step (2) into strips on an F-26 type double-screw extruder by using a circular orifice plate with the phi of 2.0 mm. Wherein, the extruder frequently trips in the extrusion process, and the surface of the extruded material is smooth.

(4) The extrudate was cut into wet strands having a length of about 6mm and shaped into alumina bodies having the property parameters shown in Table 1 by the same method as in step (4) of example 2.

Comparative example 4

(1) 190g of pseudo-boehmite powder prepared in the same manner as in step (1) of comparative example 3 was put in a beaker, and 4.5g of hydroxyethyl methyl cellulose (same as in example 2), 1.5g of sesbania powder (same as in example 2) and 6g of nitric acid (HNO)₃65 wt.%) was stirred with a mechanical stirrer for 10 minutes to obtain a pseudo-boehmite composition.

(2) Extruding the pseudoboehmite composition prepared in the step (1) on an F-26 type double-screw extruder by using a circular orifice plate with the phi of 2.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth.

Comparative example 5

A hydrated alumina composition was prepared in the same manner as in example 2, except that hydroxyethyl methylcellulose 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.

Comparative example 6

A hydrated alumina composition was prepared in the same manner as in example 2, except that hydroxyethyl methylcellulose and sesbania powder were not used, but 6.0g of wood flour was used. As a result, the prepared hydrated alumina composition cannot be subjected to extrusion molding.

Comparative example 7

The wet cake with the LB-1 designation was fed directly into an F-26 type twin-screw extruder and extruded into a rod using a circular orifice plate with a 2.0mm Φ diameter, with the result that extrusion molding could not be carried out.

Example 6

(1) 300g of wet cake LB-1 was placed in a beaker, 10mL of tetraethyl titanate, 2.6g of hydroxypropyl methylcellulose (available from Hakken chemical Co., Ltd., Zhejiang, the same below), and 3.5g of sesbania powder (galactomannan content 85% by weight) were added and stirred with a mechanical stirrer for 10 minutes to obtain a hydrated alumina composition of the present invention, the properties of which are listed in Table 1.

(2) The alumina hydrate composition prepared in the step (1) was extruded on a single screw extruder of SK132S/4 type (manufactured by BONNT, USA) using an orifice plate composed of a circular shape having an outer diameter of phi 4.5mm and a cylinder having a diameter of 1.5mm in the middle. Wherein, the extrusion process is smooth, and the surface of the extrusion material (Raschig ring) is smooth and has no burrs.

(3) The extrudate was cut into wet strips having a length of about 6mm, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 850 ℃ at a temperature rise rate of 200 ℃/hr, and the temperature was maintained constant at that temperature for 3 hours, and after the wet strips were fed into the tube furnace, 16L/min of circulating air (the amount of water vapor was 6L/min, 0.05L/(min · g molded product)) was blown into the internal space of the tube furnace from the inlet of the tube furnace, wherein the air volume at 12L/min was air output from the outlet of the tube furnace, and the remaining air volume at 4L/min was air. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Example 7

(1) 300g of the wet cake numbered LB-1 were placed in a beaker and 12g ZrO added₂2g of methylcellulose, 1.1g of hydroxypropylmethylcellulose and 4g of sesbania powder (galactomannan content 85% by weight) were stirred with a mechanical stirrer for 10 minutes, giving the hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(2) Extruding the hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a clover-shaped 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.

(3) The extrudate was cut into wet strips having a length of about 8mm, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 900 ℃ at a temperature rise rate of 150 ℃/hr, and the temperature was maintained at that temperature for 2 hours, and after the wet strips were fed into the tube furnace, air was blown into the internal space of the tube furnace from the inlet of the tube furnace at 10L/min, wherein the air volume of 8L/min was the circulating air (the amount of water vapor was 5L/min, 0.04L/(min · g molded product)) which was discharged from the outlet of the tube furnace, and the air volume of the remaining 2L/min was air. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Example 8

(1) 300g of wet cake No. LB-1 was placed in a beaker and 30g of metatitanic acid (H) was added₂TiO₃) 2.2g hydroxyethyl methylcellulose and 2.1g hydroxypropylMethylcellulose, after 10 minutes of agitation with a mechanical stirrer, gave 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 1.8 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, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 800 ℃ at a temperature rise rate of 200 ℃/hr, and the temperature was maintained at that temperature for 2 hours, and after the wet strips were fed into the tube furnace, air was blown into the internal space of the tube furnace from the inlet of the tube furnace at 15L/min, wherein the air volume of 10L/min was the circulating air (the amount of water vapor was 6L/min, 0.05L/(min · g molded product)) which was discharged from the outlet of the tube furnace, and the remaining air volume of 5L/min was air. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Example 9

(1) 5kg of the wet cake numbered SLB-1 was fed into a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.5MPa and maintained for 20 minutes, then the cake in the plate and frame was swept with pressurized air at 0.5MPa for 10 minutes, and the plate and frame was depressurized to obtain a wet cake (numbered LB-2). The i value of the wet cake was 64.9%.

(2) 1000g of wet cake LB-2, reference number, was placed in a beaker and 100g of metatitanic acid (H) was added₂TiO₃) 16g of hydroxypropylmethylcellulose and 20g of sesbania powder (galactomannan content 85% by weight, available from Beijing Chemicals) were stirred for 10 minutes using a mechanical stirrer to give the hydrated alumina composition of the present invention having the property parameters listed in Table 1.

(3) 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 2.4 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, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 700 ℃ at a temperature rise rate of 150 ℃/hr, and the temperature was maintained constant at that temperature for 3 hours, and after the wet strips were fed into the tube furnace, the air was blown into the internal space of the tube furnace from the inlet of the tube furnace at 18L/min, wherein the air volume of 14L/min was the circulating air (the amount of water vapor was 8L/min, 0.07L/(min · g molded product)) which was discharged from the outlet of the tube furnace, and the remaining air volume of 4L/min was air. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Example 10

(1) 5kg of SLB-1 wet cake was mixed with 500g of deionized water and 30g of TiO₂33g of methylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd.) and 20g of sesbania powder (with a galactomannan content of 80 wt%, purchased from Beijing chemical reagents Co., Ltd.) were mixed and beaten for 1 minute, and the resulting slurry was fed into a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.7MPa and maintained for 15 minutes, and the plate and frame was depressurized to obtain a hydrated alumina composition containing a group IVB metal element of the present invention, the property parameters of which are listed in Table 1.

(2) The extrudate was cut into wet strips having a length of about 6mm, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 600 ℃ at a temperature rise rate of 100 ℃/hr, and the temperature was maintained constant at that temperature for 3 hours, and after the wet strips were fed into the tube furnace, 16L/min of circulating air (amount of water vapor 5L/min, 0.1L/(min · g molded product)) was blown into the internal space of the tube furnace from the inlet of the tube furnace, wherein the air volume of 11L/min was air output from the outlet of the tube furnace, and the remaining air volume of 5L/min was air. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Example 11

The hydrated alumina wet gel used in this example was prepared by mixing CO₂Method (sodium aluminate-CO)₂The method is from Shanxi province, Shaanxi county, Xinghao catalysisNew chemicals co) was washed and filtered to obtain a pseudo-boehmite wet cake (the wet cake was numbered SLB-2), and the i value of the wet cake was measured to be 65.3%.

(1) 1000g of SLB-2 numbered wet cake was placed in a beaker, followed by the addition of 50g of metatitanic acid (H)₂TiO₃) 16g of methylcellulose and 20g of sesbania powder (galactomannan content 80% by weight), the mixture obtained after stirring for 10 minutes with a mechanical stirrer is a hydrated alumina composition according to the invention, the properties of which are given 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, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 550 ℃ at a temperature rise rate of 100 ℃/hr, and the temperature was maintained constant at that temperature for 3 hours, and after the wet strips were fed into the tube furnace, air was blown into the internal space of the tube furnace from the inlet of the tube furnace at 16 mL/min, wherein the air volume of 12L/min was the circulating air (the amount of water vapor was 6L/min, 0.2L/(min · g molded product)) which was discharged from the outlet of the tube furnace, and the remaining air volume of 4L/min was air. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Example 12

The hydrated alumina wet gel used in this example was an alumina trihydrate wet cake (the wet cake was designated as SLB-3) obtained by washing and filtering a hydrated alumina gel solution prepared by a sodium aluminate fractionation method (obtained from Shandong division of aluminum industries, China), and the i value of the wet cake was determined to be 70%.

(1) 5000g of SLB-3 with the number of the code number is mixed with 1000g of water for pulping, the obtained slurry is pressed into a plate and frame filter press, the pressure of a plate and frame filter press is adjusted to 0.9MPa and kept for 3 minutes, then filter cakes in the plate and frame are blown by 0.6MPa of pressurized air for 5 minutes, the plate and frame are decompressed to obtain an alumina trihydrate wet filter cake, and the i value of the wet filter cake is 60.8 percent by weight.

(2) Placing 1000g of the wet cake obtained in step (1) in a beaker, and adding 30g of metatitanic acid (H)₂TiO₃) 10g of methylcellulose and 20g of sesbania powder (galactomannan content 80% by weight), the mixture obtained after stirring for 10 minutes with a mechanical stirrer is a hydrated alumina composition according to the invention, the properties of which are given in Table 1.

(4) The extrudate was cut into wet strips having a length of about 6mm, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 1000 ℃ at a temperature rise rate of 200 ℃/hr, and the temperature was maintained at that temperature for 2 hours, and after the wet strips were fed into the tube furnace, air was blown into the internal space of the tube furnace from the inlet of the tube furnace at 15L/min, wherein the air volume of 12L/min was the circulating air (the amount of water vapor was 8L/min, 0.02L/(min · g molded product)) which was discharged from the outlet of the tube furnace, and the remaining air volume of 3L/min was air. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Example 13

The hydrated alumina wet gel used in this example was obtained from Shandong Zibozimao catalyst Co., Ltd, and was prepared by calcining 1000g of dry pseudoboehmite powder (70% by weight on a dry basis) prepared by an acid process (sodium aluminate-aluminum sulfate process) at 700 ℃ in an air atmosphere for 3 hours, 700g of alumina is obtained, 700g of alumina is put into a 10L high-pressure reaction kettle and is evenly stirred with 5L of deionized water, the high-pressure reaction kettle is sealed, reacting for 6h at 150 ℃ under autogenous pressure, after the reaction is finished, cooling the temperature of the high-pressure reaction kettle to room temperature (25 ℃), sending the slurry obtained by the reaction into a plate-and-frame filter press, the plate frame pressure of the plate frame type filter is adjusted to 0.5MPa and kept for 10 minutes, then blowing the filter cake in the plate frame for 3 minutes by 10MPa pressurized air, and decompressing the plate frame to obtain the hydrated alumina wet filter cake LB-3. The phase of the wet cake was determined to be boehmite and the i value of the wet cake was 63%.

(1) 300g of wet cake numbered LB-3 was placed in a beaker and then 20g of metatitanic acid (H) was added₂TiO₃) 3.8g of methylcellulose and 6g of sesbania powder (galactomannan content 85% by weight), the mixture obtained after stirring for 10 minutes with a mechanical stirrer is a hydrated alumina composition according to the invention, the properties of which are given 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 2.4 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, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 600 ℃ at a temperature rise rate of 120 ℃/hr, and the temperature was maintained constant at that temperature for 4 hours, and after the wet strips were fed into the tube furnace, air was blown into the internal space of the tube furnace from the inlet of the tube furnace at a rate of 12L/min, wherein the air flow rate at 10L/min was the circulating air (the amount of water vapor was 6L/min, 0.05L/(min · g moldings)) which was output from the outlet of the tube furnace, and the air flow rate at the remaining 2L/min was air. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Example 14

The hydrated alumina wet gel used in this example was prepared by the method described in section "new method for preparing alumina by hydrolyzing low-carbon alkoxy aluminum", test method ", in article" new method for preparing alumina by hydrolyzing low-carbon alkoxy aluminum ", published in" Petroleum institute (Petroleum processing) ", volume 10, 4, wherein the aging time was 12 hours, after the aging was completed and isopropanol and water were evaporated, 500g of water was added, the mixture was stirred for 1 minute by a mechanical stirrer, the slurry was pressed into a plate and frame filter, the pressure of the plate and frame was adjusted to 0.7MPa, the pressing time was 8 minutes, and then the filter cake in the plate and frame was blown with 7MPa of pressurized air for 4 minutes to obtain 200g of wet filter cake (numbered LB-4). The phase of the wet cake was determined to be pseudo-boehmite, and the i value of the wet cake was 65.2%.

(1) 200g of wet cake numbered LB-4 were placed in a beaker and then 20g of metatitanic acid (H) were added₂TiO₃) 2.8g of methylcellulose and 4.5g of sesbania powder (galactomannan content 80% by weight), after stirring for 10 minutes with a mechanical stirrer, the mixture obtained is a hydrated alumina composition according to the invention, the parameters of which are listed in Table 1.

(3) The extrudate was cut into wet strips having a length of about 6mm, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 550 ℃ at a temperature rise rate of 100 ℃/hr, and the temperature was maintained constant at that temperature for 3 hours, and after the wet strips were fed into the tube furnace, air was blown into the internal space of the tube furnace from the inlet of the tube furnace at 14L/min, wherein the air volume of 10L/min was the circulating air (the amount of water vapor was 6L/min, 0.08L/(min · g molded product)) which was discharged from the outlet of the tube furnace, and the remaining air volume of 4L/min was air. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Example 15

(1) 5kg of the wet cake numbered SLB-1 was mixed with 700g of deionized water and beaten for 1 minute, the resulting slurry was fed into a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.5MPa and held for 3 minutes, and after the cake in the plate and frame was swept with pressurized air of 0.5MPa for 3 minutes, the plate and frame was depressurized to obtain a wet cake (numbered LB-5). The wet cake numbered LB-5 was determined to have an i value of 75 wt%.

(2) 1000g of wet cake LB-5, reference number, was placed in a beaker and 50g of metatitanic acid (H) was added₂TiO₃) 16g of hydroxypropylmethylcellulose and 20g of sesbania powder (galactomannan content 85% by weight)%) was stirred with a mechanical stirrer for 10 minutes, to obtain a hydrated alumina composition of the present invention, the property parameters of which are shown 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, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃) to 900 ℃ at a temperature rise rate of 200 ℃/hr, and the temperature was maintained at that temperature for 2.5 hours, and after the wet strips were fed into the tube furnace, 16L/min of circulating air (amount of water vapor of 5L/min, 0.2L/(min · g molding)) was blown from the inlet of the tube furnace to the inner space of the tube furnace, wherein the amount of air of 11L/min was the amount of circulating air (amount of water vapor of 5L/min, 0.2L/(min · g molding)) discharged from the outlet of the tube furnace. After the completion of the constant temperature, the supply of air was stopped, the temperature of the tube furnace was naturally lowered to ambient temperature, and the solid matter was taken out to obtain an alumina compact according to the present invention, the property parameters of which are listed in table 1.

Example 16

An alumina support was produced in the same manner as in example 15, except that, in the step (4), instead of feeding the circulating air discharged from the outlet of the tube furnace into the interior of the tube furnace, a mixed gas of fresh water vapor generated by a water vapor generator and air was fed into the tube furnace, wherein the feeding amount of water vapor was 10L/min. The properties of the alumina shaped bodies produced are listed in table 1.

TABLE 1

¹: standing at ambient temperature (25-30 deg.C) and under sealed condition (in sealed plastic bag) for 72 hr to obtain a composition with aluminum oxide trihydrate content

Rate of increase before placement.

The results of examples 1-16 demonstrate that the hydrated alumina wet gel is not dried into dry gel powder or semi-dry gel powder, but is directly mixed with a compound having 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 bad working environment, high energy consumption and low strength of the prepared molded body when the conventional molded body is prepared by taking the dry gel powder or the semi-dry gel powder as a starting material. And, according to the method of the invention, by adjusting the hydrated alumina composition

The pore diameter of the alumina formed body can be adjusted, and the formed body with the pore diameter distribution in a bimodal distribution or a monomodal distribution is respectively prepared.

Experimental examples 1 to 10 are provided to illustrate catalysts having hydrogenation catalysis according to the present invention and a method for preparing the same.

Experimental example 1

Dispersing molybdenum oxide and basic cobalt carbonate in water to form an impregnation liquid, wherein MoO₃Has a concentration of 197.4g/L and a concentration of basic cobalt carbonate calculated as CoO of 47.6 g/L. The alumina molded body prepared in example 1 was impregnated with the impregnation solution at ambient temperature (25 ℃ C.) for 1 hour. The impregnated alumina dry strands were dried at 120 ℃ under normal pressure in an air atmosphere for 2 hours, followed by calcination at 400 ℃ under normal pressure in an air atmosphere for 3 hours, to thereby obtain catalyst C-1 having a hydrogenation catalytic action according to the present invention, the composition of which is shown in Table 2.

Experimental comparative example 1

A catalyst DC-1 was prepared in the same manner as in Experimental example 1, except that the alumina compact prepared in example 1 was not used, but the alumina compact prepared in comparative example 1 was used, and the composition thereof is shown in Table 2.

Experimental example 2

Dispersing molybdenum oxide and basic cobalt carbonate in water to form a leaching solutionImpregnating liquid of, among them, MoO₃Has a concentration of 141.2g/L and a concentration of basic cobalt carbonate, calculated as CoO, of 33.6 g/L. The alumina compact prepared in example 2 was impregnated with this impregnation solution at ambient temperature (25 ℃ C.) for 1 hour. The impregnated alumina dry strands were dried at 120 ℃ under normal pressure in an air atmosphere for 2 hours, followed by calcination at 400 ℃ under normal pressure in an air atmosphere for 3 hours, to thereby obtain catalyst C-2 having a hydrogenation catalytic action according to the present invention, the composition of which is shown in Table 2.

Experimental example 3

A catalyst was prepared in the same manner as in Experimental example 2, except that the alumina formed body prepared in example 3 was used, and the composition of the catalyst C-3 prepared was as shown in Table 2.

Experimental example 4

A catalyst was prepared in the same manner as in Experimental example 2, except that the alumina formed body prepared in example 4 was used, and the composition of the catalyst C-4 prepared was as shown in Table 2.

Experimental example 5

A catalyst was prepared in the same manner as in Experimental example 2, except that the alumina formed body prepared in example 5 was used, and the composition of the catalyst C-5 prepared was as shown in Table 2.

Experimental comparative example 2

A catalyst was prepared in the same manner as in Experimental example 2, except that the alumina formed body prepared in comparative example 2 was used, and the composition of the prepared catalyst DC-2 was as shown in Table 2.

Experimental comparative example 3

A catalyst was prepared in the same manner as in Experimental example 2, except that the alumina formed body prepared in comparative example 3 was used, and the composition of the prepared catalyst DC-3 was as shown in Table 2.

Experimental comparative example 4

A catalyst was prepared in the same manner as in Experimental example 2, except that the alumina formed body prepared in comparative example 4 was used, and the composition of the prepared catalyst DC-4 was as shown in Table 2.

Experimental example 6

Molybdenum oxide and basic nickel carbonate are dispersed in water to form a steeping liquor, wherein MoO is used₃The concentration of the molybdenum oxide is 40g/L, and the concentration of the basic nickel carbonate is 170g/L in terms of NiO. The alumina compact prepared in example 7 was prepared by impregnating the impregnated solution with the solution at ambient temperature (25 ℃ C.) for 1 hour. The impregnated alumina dry strands were dried at 150 ℃ under normal pressure in an air atmosphere for 1.5 hours, followed by calcination at 420 ℃ under normal pressure in an air atmosphere for 2 hours, to thereby obtain catalyst C-6 having a hydrogenation catalytic action according to the present invention, the composition of which is shown in Table 2.

Experimental example 7

Molybdenum oxide and basic nickel carbonate are dispersed in water to form a steeping liquor, wherein MoO is used₃The concentration of the molybdenum oxide is 40g/L, and the concentration of the basic nickel carbonate is 170g/L in terms of NiO. The alumina compact prepared in example 11 was impregnated with the impregnation solution at ambient temperature (25 ℃ C.) for 1 hour. The impregnated alumina dry strips were dried at 160 ℃ under normal pressure for 1 hour in an air atmosphere, followed by calcination at 460 ℃ under normal pressure for 1.5 hours in an air atmosphere, to thereby obtain catalyst C-7 having a hydrogenation catalytic action according to the present invention, the composition of which is listed in table 2.

Experimental example 8

Molybdenum oxide and basic nickel carbonate are dispersed in water to form a steeping liquor, wherein MoO is used₃The concentration of (B) was 238.4g/L, and the concentration of basic nickel carbonate (calculated as NiO) was 57.5 g/L. The alumina compact prepared in example 14 was prepared by impregnating the impregnated solution with saturated water at ambient temperature (25 ℃ C.) for 1 hour. The impregnated alumina dry strands were dried at 120 ℃ under normal pressure in an air atmosphere for 2 hours, followed by calcination at 400 ℃ under normal pressure in an air atmosphere for 3 hours, to thereby obtain catalyst C-8 having a hydrogenation catalytic action according to the present invention, the composition of which is shown in Table 2.

Experimental example 9

Molybdenum oxide and basic nickel carbonate are dispersed in water to form a steeping liquor, wherein MoO is used₃The concentration of the molybdenum oxide is 150g/L, and the concentration of the basic nickel carbonate is 37g/L in terms of NiO. By the immersionThe alumina molded bodies prepared in preparation example 15 were impregnated with the impregnation solution at ambient temperature (25 ℃ C.) for 1 hour. The impregnated alumina dry strands were dried at 120 ℃ under normal pressure in an air atmosphere for 3 hours, and then calcined at 480 ℃ under normal pressure in an air atmosphere for 2 hours, thereby obtaining catalyst C-9 having a hydrogenation catalytic action according to the present invention, the composition of which is shown in table 2.

Experimental example 10

A catalyst was prepared in the same manner as in Experimental example 10, except that the alumina formed body prepared in example 16 was used. Catalyst C-10 was prepared having the composition set forth in Table 2.

TABLE 2

Numbering	Source of vector	Catalyst numbering	NiO(wt％)	CoO(wt％)	MoO₃(wt％)
						Experimental example 1	Example 1	C-1	/	4.1	19.5
Experimental comparative example 1	Comparative example 1	DC-1	/	4.1	19.5
						Experimental example 2	Example 2	C-2	/	3.0	13.5
Experimental example 3	Example 3	C-3	/	3.0	13.5
						Experimental example 4	Example 4	C-4	/	3.0	13.5
Experimental example 5	Example 5	C-5	/	3.0	13.5
						Experimental comparative example 2	Comparative example 2	DC-2	/	3.0	13.5
Experimental comparative example 3	Comparative example 3	DC-3	/	3.0	13.5
						Experimental comparative example 4	Comparative example 4	DC-4	/	3.0	13.5
Experimental example 6	Example 7	C-6	3.2	/	14.1
						Experimental example 7	Example 11	C-7	2.4	/	11.2
Experimental example 8	Example 14	C-8	3.5	/	14.5
						Experimental example 9	Example 15	C-9	4.2	/	17.0
Experimental example 10	Example 16	C-10	4.3	/	17.8

Test examples 1 to 10

The catalysts prepared in experimental examples 1 to 10 were evaluated for their catalytic performance by the following methods, and the results are shown in Table 3.

The raw oil used was atmospheric residue oil, the mass content of nickel was 13.7ppm, the mass content of vanadium was 34.7ppm, the sulfur content was 3.6 wt%, the nitrogen content was 0.22 wt%, and the carbon residue was 12.7 wt%.

Crushing a catalyst into particles with the diameter of 2-3mm, loading the particles into a reactor, and introducing raw oil for reaction, wherein the reaction temperature is 380 ℃, the hydrogen partial pressure is 14MPa, and the volume space velocity of the raw oil is 0.6h^-1。

Measuring the sulfur content in the oil by adopting an electric method according to a method specified in a petrochemical analysis method RIPP 62-90; determining carbon residue in oil by the method specified in GB/T17144, wherein the adopted instrument is an MCRT-160 micro carbon residue determinator of ALCOR company in America; measuring the content of metal nickel and vanadium in the oil sample by an inductively coupled plasma emission spectrometer (ICP-AES) (the used instrument is a PE-5300 type plasma photometer of PE company in America, and the specific method is shown in petrochemical engineering analysis method RIPP 124-90); the nitrogen content of the oil was determined by an electrometric method, according to the method specified in petrochemical analysis method RIPP 63-90. And calculating the removal rate of the impurities according to the following formula according to the measurement result, wherein the demetallization rate refers to the removal rate of nickel and vanadium:

testing of comparative examples 1-4

The catalysts prepared in experimental comparative examples 1 to 4 were evaluated for their catalytic performance in the same manner as in test examples 1 to 11, and the results are shown in Table 3.

TABLE 3

Numbering	Source of vector	Catalyst numbering	Desulfurization rate/%)	Denitrification rate/%)	Demetallization rate/%)	Percent carbon removal /)
							Experimental example 1	Example 1	C-1	80.7	43.3	82.2	53.4
Experimental comparative example 1	Comparative example 1	DC-1	73.2	36.7	71.8	46.7
							Experimental example 2	Example 2	C-2	79.0	42.6	81.6	52.3
Experimental example 3	Example 3	C-3	76.4	40.9	78.6	50.9
							Experimental example 4	Example 4	C-4	77.9	39.6	79.9	50.1
Experimental example 5	Example 5	C-5	77.8	42.2	78.9	51.4
							Experimental comparative example 2	Comparative example 2	DC-2	62.9	30.1	68.0	41.0
Experimental comparative example 3	Comparative example 3	DC-3	70.1	35.9	73.3	43.9
							Experimental comparative example 4	Comparative example 4	DC-4	73.9	37.6	73.1	44.0
Experimental example 6	Example 7	C-6	77.4	40.9	80.0	50.8
							Experimental example 7	Example 11	C-7	78.1	42.4	81.1	51.3
Experimental example 8	Example 14	C-8	77.5	41.0	80.7	51.9
							Experimental example 9	Example 15	C-9	77.1	40.1	82.1	50.1
Experimental example 10	Example 16	C-10	77.3	40.6	82.0	49.8

The results of test examples 1 to 10 confirm that the catalyst according to the present invention has high catalytic activity and can effectively reduce the impurity content of heavy hydrocarbon oil.

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 production and forming method of hydrated alumina comprises the following steps:

(1) providing a hydrated alumina gel solution, washing and carrying out solid-liquid separation on the hydrated alumina gel solution to obtain a first hydrated alumina wet gel, wherein the solid-liquid separation condition is that the i value of the first hydrated alumina wet gel is not less than 60 percent, the hydrated alumina gel solution is a reaction mixture which is aged or not aged and is prepared by one or more than two methods of a precipitation method, a hydrolysis method, a seed precipitation method and a rapid dehydration method,

(2) will be described inMixing the first wet gel of hydrated alumina with a compound having at least two proton acceptor sites, wherein the compound having at least two proton acceptor sites is one or more selected from the group consisting of dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, and the compound having at least two proton acceptor sites is used in an amount such that the composition is finally prepared

A value of 1.2 or more and 5 or less

The value of the one or more of,

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

optionally, (4) drying the molded object obtained in the step (3) to obtain a dried molded object;

(5) roasting the formed product obtained in the step (3) or the dried formed product obtained in the step (4) in the presence of water vapor in an oxygen-containing atmosphere to prepare an alumina formed body containing the IVB group metal element;

2. The method of claim 1 wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not less than 62%.

3. The method of claim 1, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of no greater than 82%.

4. The method of claim 3, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not greater than 80%.

5. The method of claim 4, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of no more than 78.5%.

6. The method according to any one of claims 1-5, wherein the solid-liquid separation is performed one or more times, at least the last solid-liquid separation being pressure filtration and/or vacuum filtration.

7. The method of any one of claims 1-5, wherein the hydrated alumina wet gel is a hydrated alumina wet gel that has not been subjected to a dehydration treatment such that its i value is 60% or less.

8. The method of claim 1, wherein the hydrated alumina composition is free of peptizing agents.

9. The method according to claim 1, wherein the temperature of the drying in the step (4) is 60 ℃ or more and not more than 350 ℃.

10. The method of claim 9, wherein the drying temperature of step (4) is 80-300 ℃.

11. The method as claimed in claim 10, wherein the drying temperature in step (4) is 110-260 ℃.

12. The method according to claim 1, wherein in the step (5), the amount of the water vapor is 0.01 to 0.8L/(min-g molding), and the molding is based on the hydrated alumina.

13. The method according to claim 1, wherein the method comprises a step (5) of generating at least part of the water vapor as the water vapor generated during the drying in step (4).

14. The method according to claim 1, wherein the molded product obtained in step (3) is directly fed into step (5), and at least part of the water vapor is the water vapor generated in the roasting process in step (5).

15. The method according to claim 14, wherein in the step (5), during the baking, the gas inside the container that contains the molded article is taken out, and at least part of the taken-out gas is circulated as a circulating gas into the container.

16. A process according to claim 15, wherein from 10 to 90% by volume of the withdrawn gas is recycled into the vessel.

17. A method according to claim 16, wherein 20-88% by volume of the withdrawn gas is recycled into the vessel.

18. A process according to claim 17, wherein 30-85% by volume of the withdrawn gas is recycled into the vessel.

19. A process according to claim 18, wherein 60-85% by volume of the withdrawn gas is recycled into the vessel.

20. The method as claimed in any one of claims 1 and 12 to 19, wherein the temperature of the calcination in step (5) is 400-1200 ℃.

21. The method as claimed in claim 20, wherein the temperature of the calcination in step (5) is 450-1100 ℃.

22. The method as claimed in claim 21, wherein the temperature of the calcination in the step (5) is 500-1000 ℃.

23. The method of any one of claims 1 and 12-19, wherein the duration of the roasting in step (5) is 1-20 hours.

24. The method of claim 23, wherein the duration of the firing in step (5) is 1.5-15 hours.

25. The method of claim 24, wherein the duration of the firing in step (5) is 2-12 hours.

26. The method according to any one of claims 1 and 12 to 19, wherein in the step (5), the temperature inside the container containing the molded object is raised to the firing temperature at a temperature raising rate of 10 to 400 ℃/hr.

27. The method as claimed in claim 26, wherein, in the step (5), the temperature inside the container containing the molding is raised to the firing temperature at a temperature raising rate of 30-350 ℃/hr.

28. The method as claimed in claim 27, wherein, in the step (5), the temperature inside the container containing the molding is raised to the firing temperature at a temperature raising rate of 60-300 ℃/hr.

29. The method as claimed in claim 28, wherein the temperature raising rate for raising the temperature in the container for receiving the molding to the baking temperature in step (5) is 100-.

30. The method of any one of claims 1-5 and 8-19, wherein in step (2), the method further comprises

The value is 4 or less.

31. The method of claim 30, wherein in step (2), the step (c) is performed by

The value is 3.5 or less.

32. The method of claim 31, wherein in step (2), the step (c) is performed by

The value is 3.2 or less.

33. The method of any one of claims 1-5 and 8-19, wherein in step (2), the method further comprises

The value is 1.3 or more.

34. The method of claim 33, wherein in step (2), the step (c) is performed by

The value is 1.4 or more.

35. The method of any of claims 1-5 and 8-19, wherein in step (2), the hydrated alumina composition is

The value is not less than 1.8.

36. The method of claim 35, wherein in step (2), the hydrated alumina composition is

The value is 1.9-4.

37. The method of claim 36, wherein in step (2), the hydrated alumina composition is

The value is 2-3.5.

38. The method of any of claims 1-5 and 8-19, wherein in step (2), the hydrated alumina composition is

The value is less than 1.8.

39. The method of claim 38, wherein in step (2), the hydrated alumina composition is

The value is not higher than 1.7.

40. The method of any of claims 1-5 and 8-19, wherein in step (2), the hydrated alumina composition is

The value is 1.3-1.7.

41. 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, in step (2).

42. The method according to claim 41, wherein the compound having at least two proton acceptor sites is contained in an amount of 2 to 20 parts by weight, relative to 100 parts by weight of the hydrated alumina, in step (2).

43. The method according to claim 42, wherein the compound having at least two proton acceptor sites is contained in an amount of 3 to 18 parts by weight, relative to 100 parts by weight of the hydrated alumina, in step (2).

44. The method according to claim 43, wherein the compound having at least two proton acceptor sites is contained in the amount of 3.5 to 17 parts by weight, relative to 100 parts by weight of the hydrated alumina, in step (2).

45. The method of any one of claims 1 and 41-44, wherein the compound having at least two proton acceptor sites is one or more of a galactan, mannan, galactomannan, and cellulose ether.

46. The method of claim 45, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.

47. The method of any one of claims 1 and 41-44, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.

48. The method of claim 47, 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.

49. The method of claim 48, 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.

50. The method of claim 49, 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.

51. The method of any one of claims 1-8, wherein the hydrated alumina comprises pseudoboehmite.

52. The method of claim 51, wherein the hydrated alumina is pseudoboehmite.

53. A method according to claim 52, wherein the hydrated alumina composition is allowed to stand at ambient temperature and under closed conditions for 72 hours, the alumina trihydrate content of the composition after standing being higher than the alumina trihydrate content of the composition before standing.

54. A process as claimed in claim 53, in which the alumina trihydrate content of the composition after standing is increased by at least 0.5% based on the alumina trihydrate content of the hydrated alumina composition before standing.

55. A process as claimed in claim 54, in which the alumina trihydrate content of the composition after standing is increased by at least 1%, based on the alumina trihydrate content of the hydrated alumina composition before standing.

56. A process as claimed in claim 55, in which the alumina trihydrate content of the composition after standing is increased by from 1.1% to 2% based on the alumina trihydrate content of the hydrated alumina composition before standing.

57. The method according to claim 1, wherein the content of the compound containing the group IVB metal element in terms of oxide is 1.5 to 85 parts by weight relative to 100 parts by weight of the hydrated alumina.

58. A process as claimed in claim 57, in which the content of the compound containing an element of a group IVB metal in terms of oxide is from 2 to 80 parts by weight relative to 100 parts by weight of the hydrated alumina.

59. A process as claimed in claim 58, in which the content of the compound containing an element of a group IVB metal in terms of oxide is from 3 to 75 parts by weight relative to 100 parts by weight of the hydrated alumina.

60. The method of any one of claims 1 and 57-59, wherein the group IVB metal element is selected from titanium and zirconium.

61. The method of any one of claims 1 and 57-59, wherein the group IVB metal element-containing compound is selected from the group consisting of zirconium oxychloride, zirconium acetate, zirconium sulfate, zirconium nitrate, zirconium carbonate, zirconium hydroxide, zirconium ammonium hydroxide, zirconium dioxide, titanic acid, metatitanic acid, titanium dioxide, titanium sulfate, and a compound of 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.

62. A production and forming method of hydrated alumina comprises the following steps:

(1) 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 an aged or unaged reaction mixture prepared by one or more methods of a precipitation method, a hydrolysis method, a seed precipitation method and a rapid dehydration method;

(2-1) and (2-2), the solid-liquid separation conditions being such that the second hydrated alumina wet gel has an i value of not less than 60%,

(3) mixing the second hydrated alumina wet gel with a compound having at least two proton acceptor sites, the compound having at least two proton acceptor sites being one or more than two selected from the group consisting of dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, the compound having at least two proton acceptor sites being used in an amount such that the composition finally prepared is

A value of 1.2 or more and 5 or less

The value of the one or more of,

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

63. The process of claim 62, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not less than 62%.

64. The process of claim 63, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not higher than 82%.

65. The method of claim 64 wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not greater than 80%.

66. The process of claim 65, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not more than 78.5%.

67. The method of any one of claims 62-66, wherein the solid-liquid separation is performed one or more times, at least the last solid-liquid separation being pressure filtration and/or vacuum filtration.

68. The method of any of claims 62-66, wherein the hydrated alumina wet gel is a hydrated alumina wet gel that has not been subjected to a dehydration treatment such that its i value is 60% or less.

69. The method of claim 62, wherein the hydrated alumina composition is free of peptizing agents.

70. The method as claimed in claim 62, wherein the temperature of the drying in the step (4) is 60 ℃ or more and not more than 350 ℃.

71. The method of claim 70, wherein the drying of step (4) is at a temperature of 80-300 ℃.

72. The method as claimed in claim 71, wherein the drying temperature in step (4) is 110-260 ℃.

73. The method according to claim 62, wherein in step (5), the amount of water vapor is 0.01-0.8L/(min-g form), and the form is based on hydrated alumina.

74. The method according to claim 62, wherein the method comprises a step (5) of generating at least part of the water vapor as the water vapor generated during the drying in the step (4).

75. The method according to claim 62, wherein the shaped product obtained in step (3) is fed directly into step (5), and at least part of the water vapor is the water vapor generated in the roasting process in step (5).

76. The method as claimed in claim 75, wherein, in the step (5), during the baking, gas in the container accommodating the molded article is taken out, and at least part of the taken-out gas is circulated as a circulating gas into the container.

77. The process of claim 76, wherein 10-90% by volume of the withdrawn gas is recycled into the vessel.

78. A process as claimed in claim 77, in which from 20 to 88% by volume of the withdrawn gas is recycled into the vessel.

79. The process of claim 78, wherein 30-85% by volume of the withdrawn gas is recycled into the vessel.

80. The process of claim 79, wherein 60-85% by volume of the withdrawn gas is recycled into the vessel.

81. The method as claimed in any one of claims 62 and 73-80, wherein the temperature of the roasting in step (5) is 400-1200 ℃.

82. The method as claimed in claim 81, wherein the temperature of the roasting in step (5) is 450-1100 ℃.

83. The method as claimed in claim 82, wherein the temperature of the roasting in step (5) is 500-1000 ℃.

84. The method of any one of claims 62 and 73-80, wherein the duration of the roasting in step (5) is 1-20 hours.

85. The process as claimed in claim 84, wherein the duration of the calcination in step (5) is 1.5-15 hours.

86. The process of claim 85, wherein the duration of the calcination in step (5) is 2-12 hours.

87. The method of any of claims 62 and 73-80, wherein in step (5), the temperature inside the container containing the shape is raised to the firing temperature at a ramp rate of 10-400 ℃/hr.

88. The method of claim 87, wherein in step (5), the temperature in the container holding the shape is raised to the firing temperature at a ramp rate of 30-350 ℃/hr.

89. The method of claim 88, wherein in step (5), the temperature inside the container containing the shape is raised to the firing temperature at a ramp rate of 60-300 ℃/hr.

90. The method as claimed in claim 89, wherein in the step (5), the temperature in the container for accommodating the molding is raised to the baking temperature at a temperature raising rate of 100 ℃ to 200 ℃/hr.

91. The method of any of claims 62-66 and 73-80, wherein in step (2), the method further comprises performing a post-treatment on the sample to obtain the sample

The value is 4 or less.

92. The method of claim 91, wherein in step (2), the

The value is 3.5 or less.

93. The method according to claim 92, wherein in step (2), the

The value is 3.2 or less.

94. The method of any of claims 62-66 and 73-80, wherein in step (2), the method further comprises performing a post-treatment on the sample to obtain the sample

The value is 1.3 or more.

95. The method of claim 94, wherein in step (2), the

The value is 1.4 or more.

96. The method of any of claims 62-66 and 73-80, wherein in step (2), the hydrated alumina composition is

The value is not less than 1.8.

97. The method of claim 96 wherein in step (2), the hydrated alumina composition is

The value is 1.9-4.

98. The method of claim 97, wherein in step (2), the hydrated alumina composition is

The value is 2-3.5.

99. The method of any of claims 62-66 and 73-80, wherein step(s) (ii) are performed2) Of the hydrated alumina composition

The value is less than 1.8.

100. The method of claim 99, wherein in step (2), the hydrated alumina composition is

The value is not higher than 1.7.

101. The method of any of claims 62-66 and 73-80, wherein in step (2), the hydrated alumina composition is

The value is 1.3-1.7.

102. The method according to claim 62, 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, in step (2).

103. The method as claimed in claim 102, wherein the compound having at least two proton acceptor sites is contained in the range of 2 to 20 parts by weight with respect to 100 parts by weight of the hydrated alumina in the step (2).

104. The method according to claim 103, wherein the compound having at least two proton acceptor sites is contained in an amount of 3 to 18 parts by weight, relative to 100 parts by weight of the hydrated alumina, in step (2).

105. The method as claimed in claim 104, wherein the compound having at least two proton acceptor sites is contained in the range of 3.5 to 17 parts by weight with respect to 100 parts by weight of the hydrated alumina in the step (2).

106. The method as claimed in any one of claims 62 and 102, 105, wherein the compound having at least two proton acceptor sites is one or more of galactan, mannan, galactomannan, and cellulose ether.

107. The method of claim 106, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.

108. The method of any one of claims 62 and 102-105 wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.

109. The method of claim 108, 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.

110. The method of claim 109, 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.

111. The method of claim 110, 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.

112. The method of any one of claims 62-69, wherein the hydrated alumina comprises pseudoboehmite.

113. The method of claim 112, wherein the hydrated alumina is pseudoboehmite.

114. The method of claim 113, wherein the hydrated alumina composition is allowed to stand at ambient temperature and under closed conditions for 72 hours, and wherein the alumina trihydrate content of the composition after standing is higher than the alumina trihydrate content of the composition prior to standing.

115. The method of claim 114 wherein the alumina trihydrate content of the composition after placement is increased by at least 0.5% based on the alumina trihydrate content of the hydrated alumina composition prior to placement.

116. The method of claim 115 wherein the alumina trihydrate content of the composition after placement is increased by at least 1% based on the alumina trihydrate content of the hydrated alumina composition prior to placement.

117. The method of claim 116 wherein the alumina trihydrate content in the composition after placement is increased by 1.1% to 2% based on the alumina trihydrate content in the hydrated alumina composition prior to placement.

118. The method according to claim 62, wherein the content of the compound containing the group IVB metal element in terms of oxide is 1.5 to 85 parts by weight relative to 100 parts by weight of the hydrated alumina.

119. A process as set forth in claim 118 wherein the group IVB metal element-containing compound is present in an amount of from 2 to 80 parts by weight in terms of oxide relative to 100 parts by weight of the hydrated alumina.

120. A process as set forth in claim 119 wherein the group IVB metal element-containing compound is present in an amount of from 3 to 75 parts by weight in terms of oxide, relative to 100 parts by weight of the hydrated alumina.

121. The method as set forth in any one of claims 62 and 118-120, wherein the group IVB metal element is selected from titanium and zirconium.

122. The method as claimed in any one of claims 62 and 118-120, wherein the compound containing the group IVB metal element is selected from the group consisting of zirconium oxychloride, zirconium acetate, zirconium sulfate, 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.

123. A group IVB metal element-containing alumina formed body prepared by the method of any one of claims 1-122.

124. Use of the group IVB metal element-containing alumina shaped body of claim 123 as a support or adsorbent.

125. The use according to claim 124, wherein the support is a support for a supported catalyst.

126. The use according to claim 125, wherein the support is a support for a supported hydrogenation catalyst.

127. A catalyst with hydrogenation catalysis effect, which comprises a carrier and a group VIII metal element and a group VIB metal element loaded on the carrier, wherein the carrier is the alumina forming body containing the group IVB metal element in claim 123.

128. A method for preparing a catalyst having a hydrocatalytic effect, which method comprises loading a group VIII metal element and a group VIB metal element on a carrier, wherein the method further comprises preparing an alumina carrier containing a group IVB metal element by the method of any one of claims 1-122.

129. A hydroprocessing method comprising contacting, under hydroprocessing conditions, a hydrocarbon oil with a hydrocatalytic catalyst, wherein said hydrocatalytic catalyst is the catalyst of claim 127 or the catalyst prepared by the process of claim 128.