CN107999099B

CN107999099B - Alumina forming body, preparation method and application thereof, catalyst, preparation method and hydrotreating method

Info

Publication number: CN107999099B
Application number: CN201610965926.3A
Authority: CN
Inventors: 胡大为; 杨清河; 聂红; 刘滨; 曾双亲; 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: 2016-10-28
Filing date: 2016-10-28
Publication date: 2020-06-16
Anticipated expiration: 2036-10-28
Also published as: CN107999099A

Abstract

The invention discloses an alumina forming body, a preparation method and application thereof, and a production forming system

The molded product of the phosphorus-containing hydrated alumina composition having a value of 5 or less is optionally dried and then calcined in the presence of water vapor 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 prepares the formed body with higher strength by taking the hydrated alumina wet gel as the initial raw material, omits the step of drying the hydrated alumina wet gel, does not need to additionally introduce water to prepare dry glue powder into a formable material when preparing the forming raw material, simplifies the overall process flow, reduces the overall operation energy consumption, avoids the dust pollution caused by adopting the pseudoboehmite dry glue powder as the raw material, and greatly improves the operation environment.

Description

Alumina forming body, preparation method and application thereof, catalyst, preparation method and hydrotreating method

Technical Field

The invention relates to the technical field of alumina forming, in particular to an alumina forming body, a preparation method and application thereof, and also relates to a catalyst taking the alumina forming body as a carrier, 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 alumina gel needs to be dried to obtain the pseudoboehmite dry gel powder, then the pseudoboehmite dry gel powder is taken as a starting point, the extrusion aid and the optional chemical peptizing agent (inorganic acid and/or organic acid) are added, and after kneading and forming, the formed product is dried and optionally calcined to be used as the adsorbent or the 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 use 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, comprising the steps of:

(1) forming a phosphorus-containing hydrated alumina composition containing hydrated alumina, a compound having at least two proton acceptor sites, and a phosphorus-containing compound to obtain a formed product,

the above-mentionedOf a 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 an alumina compact produced by the method of the first aspect of the present invention.

According to a third aspect of the present invention, there is provided an alumina molded body produced by the method of the first aspect of the present invention, wherein the phosphorus-containing hydrated alumina composition has

The value is not less than 1.8.

According to a fourth aspect of the present invention, there is provided an alumina molded body produced by the method of the first aspect of the present invention, wherein the phosphorus-containing hydrated alumina composition has

The value is less than 1.8.

According to a fifth aspect of the present invention, there is provided a use of the alumina compact according to the second, third or fourth aspect of the present invention as a carrier or adsorbent.

According to a sixth aspect of the present invention, there is provided a catalyst having hydrogenation catalysis, which comprises a carrier and a hydrogenation active component supported on the carrier, wherein the carrier is the alumina compact according to the second aspect of the present invention.

According to a seventh aspect of the present invention, there is provided a method for producing a catalyst having a hydrogenation catalytic action, which comprises supporting a hydrogenation active component on a carrier, wherein the carrier is the alumina compact according to the second aspect of the present invention.

According to an eighth aspect of the present invention, there is provided a hydroprocessing method, which comprises contacting a hydrocarbon oil with a catalyst having a hydroprocessing catalytic effect under hydroprocessing conditions, wherein the catalyst having a hydroprocessing catalytic effect is the catalyst according to the sixth aspect of the present invention or the catalyst prepared by the method according to the seventh 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.

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 schematic diagram illustrating a preferred embodiment of an alumina production molding system according to the present invention.

FIG. 3 is a process flow for preparing a phosphorus-containing hydrated alumina composition in the process of 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 phosphorus-containing hydrated alumina composition to obtain a formed product;

In step (1), the phosphorus-containing hydrated alumina composition contains hydrated alumina, a compound having at least two proton acceptor sites, and a phosphorus-containing compound.

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 phosphorus-containing hydrated alumina composition according to this preferred embodiment is particularly suitable for preparing 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 in 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 total amount of alumina trihydrate content in the composition before placement.

The phosphorus-containing hydrated alumina composition also contains a compound having at least two proton acceptor sites. The phosphorus-containing 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 resulting 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, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl celluloseCellulose, hydroxypropyl methylcellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose.

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 phosphorus-containing 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%.

In the phosphorus-containing hydrated alumina composition, the phosphorus-containing compound may be a phosphorus-containing compound conventional in the art, and for example, may be at least one of phosphoric acid, sodium phosphate, aluminum phosphate, ammonium phosphate and ammonium hydrogen phosphate, preferably phosphoric acid and/or aluminum phosphate.

Of the phosphorus-containing 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 phosphorus-containing hydrated alumina composition

The value may be 1.2 or more, preferably 1.3 or more, and more preferably 1.4 or more.

In one embodiment, the phosphorus-containing hydrated alumina composition

The value is not less than 1.8, for example, may be 1.8 to 5, preferably not less than 1.85, for example, may be 1.85 to 3.5, more preferably not less than 1.9, for example, may be 1.9 to 3.2. The phosphorus-containing hydrated alumina composition according to this embodiment can produce a shaped body having a bimodal distribution of pore sizes.

In another embodiment, of the phosphorus-containing 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 phosphorus-containing hydrated alumina composition according to this embodiment can produce a molded body having a monomodal distribution of pore diameters.

In the present invention,

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.

According to the composition of the invention, the phosphorus-containing compound is represented by P, relative to 100 parts by weight of the hydrated alumina₂O₅The content may be 1.5 to 45 parts by weight, preferably 2 to 35 parts by weight, more preferably 3 to 25 parts by weight.

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, 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 phosphorus-containing hydrated alumina composition can be prepared by mixing hydrated alumina, a compound having at least two proton acceptor sites, and a phosphorus-containing compound. As an example, the phosphorus-containing hydrated alumina composition is prepared using a process comprising the steps of: the phosphorus-containing hydrated alumina composition is obtained by mixing the components of a raw material composition, namely the mixture obtained by mixing is the phosphorus-containing hydrated alumina composition, and the raw material composition contains hydrated alumina wet gel, a compound with at least two proton acceptor sites and a phosphorus-containing compound.

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%.

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 invention, the solid-liquid separation is one or more times (i.e. two or more times), at least the last solid-liquid separation being a pressure filtration device and/or a vacuum filtration device. 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 pressure filtration device 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 that results in the final preparation of a phosphorus-containing hydrated alumina composition

The values meet the requirements described hereinbefore.

The raw material mixture may or may not contain a peptizing agent. Preferably, the content of the peptizing agent is 5 parts by weight or less, preferably 3 parts by weight or less, with respect to 100 parts by weight of hydrated alumina. More preferably, the raw material mixture does not contain a peptizing agent.

In the process of the present invention, the phosphorus-containing compound, the compound having at least two proton acceptor sites, and the hydrated alumina wet gel may be mixed in various mixing sequences.

In one embodiment, as shown in fig. 3, the phosphorus-containing compound may be mixed during the preparation of the hydrated alumina wet gel, or the phosphorus-containing compound may be added to the hydrated alumina wet gel obtained by the preparation, or a part of the phosphorus-containing compound may be mixed during the preparation of the hydrated alumina wet gel, and the remaining part of the phosphorus-containing compound may be added to the hydrated alumina wet gel obtained by the preparation, and the phosphorus-containing compound may be mixed at one, two, or three of the above-mentioned addition timings. When the phosphorus-containing compound is mixed in the process of preparing the hydrated alumina wet gel, the operation of mixing the phosphorus-containing compound 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. Preferably, the operation of mixing the phosphorus-containing compounds is performed in a solid-liquid separation process.

In another embodiment, as shown in FIG. 3, the phosphorous-containing compound is mixed after the hydrated alumina wet gel is prepared. In this embodiment, the phosphorus-containing compound may be mixed with the wet gel of hydrated alumina prior to mixing the compound having at least two proton acceptor sites; alternatively, the compound having at least two proton acceptor sites can be mixed with the hydrated alumina wet gel first, followed by the phosphorus-containing compound; it is also possible to first mix a portion of the phosphorus-containing compound with the wet gel of hydrated alumina and then mix the remaining portion of the phosphorus-containing compound with a compound having at least two proton acceptor sites.

The operation of mixing the individual components of the raw material mixture can be carried out by conventional methods. The mixing may be carried out under shear. In one embodiment, the mixing is by stirring. The hydrated alumina wet gel, the compound with at least two proton acceptor sites and the phosphorus-containing compound can be uniformly mixed by stirring in a container with a stirring device, so as to obtain the phosphorus-containing hydrated alumina composition. 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 and a phosphorus-containing compound in a kneader to obtain the phosphorus-containing 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 and a phosphorous-containing compound. 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 phosphorus-containing 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 and the phosphorus-containing compound 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 2 to 15 hours, more preferably 3 to 12 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 increase to raise the temperature within the container holding the form to the firing temperature may be from 10 to 400 deg.C/hr, preferably from 15 to 350 deg.C/hr, more preferably from 20 to 300 deg.C/hr. 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 vapor used may be 0.01 to 0.8L/(min. g shaped article) of Al₂O₃And (6) counting.

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 85% by volume, more preferably 30 to 80% by volume of the gas produced in the drying process is fed into step (3).

When the formed product obtained in the step (1) is directly fed into the step (3) for roasting, water vapor generated in the roasting process can be collected, and at least part of the water vapor generated in the roasting process can be circularly fed into the step (3). In practice, the gas in the container containing the shaped product can be withdrawn and at least part of the withdrawn gas can 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, from 10 to 90% by volume, preferably from 20 to 85% by volume, more preferably from 30 to 80% 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 formed body prepared by the method has rich pore structures 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, the present invention provides an alumina compact prepared by the method of the present invention.

According to a third aspect of the present invention, there is provided an alumina formed body produced by the method of the present invention, wherein the phosphorus-containing hydrated alumina composition has

The value is not less than 1.8, preferably not less than 1.85, more preferably 1.9 to 3.2.

The pore size distribution of the alumina molded body according to the third aspect of the present invention is bimodal. Wherein, the most probable pore diameters are respectively 4-60nm and more than 60nm determined by mercury intrusion method; preferably, the mode pore size is 5-40nm and 80-500nm, respectively.

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

The pore diameter of the alumina molded body according to the fourth aspect of the present invention is unimodal distribution. Wherein the largest possible pore diameter is 4-60nm, preferably 5-40nm, as determined by mercury intrusion porosimetry.

The alumina formed body according to the second, third or fourth aspect of the present invention has a high strength. In general, the alumina molded body according to the present invention has a radial crush strength of 10N/mm or more, usually 10 to 30N/mm, preferably 12 to 30N/mm. In one example, the alumina compact is the alumina compact according to the third aspect of the present invention, and the radial crush strength of the alumina compact is 10 to 30N/mm, preferably 12 to 30N/mm. In another example, the alumina compact is the alumina compact according to the fourth aspect of the present invention, and the alumina compact has a radial crush strength of 18 to 30N/mm. In the present invention, the radial crush strength of the molded article was measured by the method specified in RIPP 25-90.

The preparation method of the alumina forming body provided by the invention can be implemented by adopting an alumina production forming system, as shown in figure 2, the production forming system comprises a hydrated alumina gel production unit, a solid-liquid separation and washing unit, a mixing unit, a forming unit, an optional drying unit and a roasting 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 and a phosphorus-containing compound as described in 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 requirement for mixing with a compound having at least two proton acceptor sites and a phosphorus-containing compound. The solid-liquid separation and washing unit may employ conventional solid-liquid separation devices, such as: a filtration device, a centrifugation device, or a combination of both. When the solid-liquid separation and washing unit includes a filtering device, the filtering device may be one or a combination of two or more of a gravity filtering device, a pressure filtering device, and a vacuum filtering device. Preferably, the filtration means comprises at least a pressure filtration means. Specific examples of the pressure filtration device include, but are not limited to, a plate and frame filter press, a belt filter, or a combination of both. For controlling the hydrated alumina wet gel obtained

The solid-liquid separation and washing unit can 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 can be generally 0.1-12MPa, preferablyIs selected to be 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 that the requirements set forth in the first aspect of the invention for mixing with the compound having at least two proton acceptor sites and the phosphorus-containing compound are met. By adjusting the magnitude of the applied pressure or vacuum, the final hydrated alumina wet gel can be treated

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

The solid-liquid separation and washing unit can 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, and the auxiliary agent adding device at least adds a compound with at least two proton acceptor sites and a phosphorus-containing compound 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.

According to the production molding system of the present invention, the production molding system is not provided with a dehydration unit sufficient to reduce the i value of the hydrated alumina wet gel to 60% or less (preferably 62% or less) between the solid phase material discharge port of the solid-liquid separation and washing unit and the hydrated alumina wet gel input port of the mixing unit, based on the flow direction of the hydrated alumina gel.

According to the production molding system of the invention, 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 according to the present invention 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 in the roasting process of the roasting unit and recycling 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.

When the production molding system is used for preparing the alumina carrier, the following steps can be included:

(1) feeding raw materials for producing the hydrated alumina gel solution into a hydrated alumina gel production unit for reaction to obtain the hydrated alumina gel solution;

(2) sending the hydrated alumina gel solution into a solid-liquid separation and washing unit for solid-liquid separation to obtain hydrated alumina wet gel;

(3) mixing the hydrated alumina wet gel with a compound having at least two proton acceptor sites and a phosphorus-containing compound in a mixing unit to obtain a phosphorus-containing hydrated alumina composition;

(4) forming the phosphorus-containing hydrated alumina composition in a forming unit to obtain a hydrated alumina forming product;

optionally, (5) drying the hydrated alumina forming product in a drying unit to obtain a hydrated alumina forming product;

(6) and roasting the hydrated alumina forming product or the hydrated alumina forming product in a roasting unit to obtain an alumina forming product.

According to a fifth aspect of the invention, the invention provides the use of the alumina molding according to the invention as a support or adsorbent.

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

The active component having a hydrocatalytic effect can be supported on the alumina shaped body according to the invention by various methods customary 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.

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 of hydrocarbon oil, the content of the support may be 30 to 93 wt%, preferably 50 to 91 wt%, more preferably 72 to 89 wt%, based on the total amount of the catalyst; the content of the group VIII metal element may be 2 to 15% by weight, preferably 3 to 10% by weight, more preferably 3 to 8% by weight, in terms of oxide; the group VIB metal element may be present in an amount of 5 to 55 wt.%, preferably 6 to 40 wt.%, more preferably 8 to 20 wt.%, calculated as oxide.

According to a seventh aspect of the present invention, there is provided a method for producing a catalyst having a hydrogenation catalytic action, which comprises supporting a hydrogenation active component on a support, wherein the support is an alumina molded body according to the present invention.

The method for producing a catalyst having a hydrogenation catalytic action according to the present invention preferably further comprises a step of producing a molded body. In this step, a molded body is produced by the method according to the second 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 sixth 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.

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 2 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 2 to 6 hours, more preferably 2 to 3 hours.

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. The hydrotreating conditions include: the temperature can be 300-380 ℃; the pressure may be 4-15MPa in gauge pressure; the liquid hourly space velocity of the hydrocarbon oil can be 1-3 hours^-1(ii) a The hydrogen-oil volume ratio may be 200-1000.

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 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,

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

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

in the following examples and comparative examples, the pore size distribution of the molded articles prepared was measured by mercury intrusion method.

In the following examples and comparative examples, the dry content was determined by baking a sample to be tested at 600 ℃ for 4 hours.

In the following examples and comparative examples, the composition of the catalyst was measured on a 3271X-ray fluorescence spectrometer, manufactured by Nippon Denshi electric mechanical Co., 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 phosphorus-containing pseudo-boehmite wet cake (the wet cake was numbered as SLB-1) prepared by adding sodium phosphate to a hydrated alumina gel solution prepared by an acid process (sodium metaaluminate-aluminum sulfate process, available from Changling division, petrochemical, China) during aging and washing the hydrated alumina gel solution with a belt filter, and the i value of the wet cake was 77.6% as measured by the P value₂O₅The calculated phosphorus content was 3 wt.%.

(1) 240g of the wet cake numbered SLB-1 was placed in a beaker, followed by addition of 6g of methylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd., the same below) and 3.6g of sesbania powder (having a galactomannan content of 80% by weight, purchased from Beijing chemical reagents Co., Ltd., the same below), and after stirring for 10 minutes with a mechanical stirrer, the resulting mixture was the phosphorus-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(2) And (2) extruding the phosphorus-containing hydrated alumina composition prepared in the step (1) into strips on an F-26 type double-screw extruder (manufactured by general scientific and technical industries of southern China university, the same shall apply hereinafter) 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 6cm, 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, while 15L/min of circulating air (amount of water vapor 8L/min) was blown from the inlet of the tube furnace to the inner space of the tube furnace, and the air volume at 12L/min was air at the outlet of the tube furnace, and the remaining 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 compact was produced in the same manner as in example 1, except that in the step (3), during the constant temperature period, the gas flow outputted from the outlet of the tube furnace was not circulated into the tube furnace, but air was fed from the inlet of the tube furnace to the inner space of the tube furnace at 50 mL/min during the constant temperature period. The properties of the prepared alumina carrier are listed in table 2.

Example 2

(1) 4kg of the wet cake numbered SLB-1 was mixed with 400g 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 65%.

(2) 600g of wet cake LB-1 was placed in a beaker, 9g of hydroxyethyl methylcellulose (obtained from Shanghai Hui Guang Fine chemical Co., Ltd., the same below) and 3g of sesbania powder (galactomannan content 85% by weight, obtained from Beijing chemical Co., Ltd.) were added and stirred with a mechanical stirrer for 10 minutes to obtain a phosphorus-containing hydrated alumina composition of the present invention, the properties of which are shown in Table 1.

(3) And (3) extruding the phosphorus-containing hydrated alumina composition prepared in the step (2) on an F-26 type double-screw extruder by using a round orifice plate with the diameter 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 6cm, 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 constant at that temperature for 4 hours, while blowing air from the inlet of the tube furnace to the inner space of the tube furnace at a rate of 12L/min, wherein the air volume of 10L/min was the circulating air (the amount of water vapor was 8L/min) discharged from the outlet of the tube furnace, and the remaining air volume of 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 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 11.6 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 the amount of sesbania powder used was 13.6 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) 600g of wet filter cake with the number of LB-1 is dried for 2 hours at 80 ℃ in the air atmosphere to obtain the pseudo-boehmite powder, and the i value of the pseudo-boehmite powder is 50 percent. 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 6cm and shaped into alumina bodies having the properties shown in Table 1 by the same method as in step (4) of example 2.

Comparative example 3

(1) 600g of wet filter cake with the number of LB-1 is dried for 3 hours at the temperature of 90 ℃ in the air atmosphere to obtain the pseudo-boehmite powder, and the i value of the pseudo-boehmite powder is 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) 300g of the pseudo-boehmite powder prepared in the step (1) is placed in a beaker, 3g of hydroxyethyl methyl cellulose and 3g of sesbania powder (the content of galactomannan is 85 wt%) are added, and the mixture is stirred for 10 minutes by a mechanical stirrer to obtain the pseudo-boehmite composition.

(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 6cm and shaped into alumina bodies having the properties shown in Table 1 by the same method as in step (4) of example 2.

Comparative example 4

(1) 300g of pseudo-boehmite powder prepared in the same manner as in step (1) of comparative example 3 was put in a beaker, and 3g of hydroxyethyl methyl cellulose, 3g of sesbania powder (galactomannan content 85% by weight) and 6g of nitric acid (HNO) were added₃65 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 phosphorus-containing hydrated alumina composition was prepared in the same manner as in example 2, except that hydroxyethylmethylcellulose and sesbania powder were not used, but 6.0g of paraffin was used. Of the resulting phosphorus-containing hydrated alumina composition

The value was 63, and the phosphorus-containing hydrated alumina composition could not be extrusion molded.

Comparative example 6

A phosphorus-containing hydrated alumina composition was prepared in the same manner as in example 2, except that hydroxyethyl methyl cellulose and sesbania powder were not used, and 6.0g of wood flour was used. The resulting phosphorusOf hydrated alumina compositions

The value is 50, and the phosphorus-containing hydrated alumina composition cannot be extrusion molded.

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) 600g of the wet cake numbered LB-1 was placed in a beaker, and 5.2g of hydroxypropylmethylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd., the same applies hereinafter) and 7g of sesbania powder (having a galactomannan content of 85% by weight) were added and stirred with a mechanical stirrer for 10 minutes to obtain a phosphorus-containing hydrated alumina composition of the present invention, the properties of which are shown in Table 1.

(2) The phosphorus-containing hydrated alumina composition prepared in the step (1) was extruded on a single-screw extruder of SK132S/4 type (BONNT, USA) using an orifice plate composed of a circular shape having an outer diameter of φ 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 6cm, 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, while blowing air from the inlet of the tube furnace to the inner space of the tube furnace at 16L/min, wherein the air volume of 13L/min was circulating air (the amount of water vapor was 9L/min) 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 7

(1) 600g of the wet cake numbered LB-1 were placed in a beaker and after addition of 4g of methylcellulose, 2.2g of hydroxypropylmethylcellulose and 8g of sesbania powder (galactomannan content 85% by weight) and stirring for 10 minutes with a mechanical stirrer, a phosphorus-containing hydrated alumina composition according to the invention was obtained, the properties of which are given in Table 1.

(2) Extruding the phosphorus-containing hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a clover-shaped pore 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 8cm, the wet strips were fed into a tube furnace, the temperature was raised from ambient temperature (25 ℃ C.) to 900 ℃ at a temperature rise rate of 150 ℃ per hour, and the temperature was maintained at that temperature for 2 hours, while blowing air from the inlet of the tube furnace to the inner space of the tube furnace at 15L/min, wherein the air volume of 13L/min was circulating air (the amount of water vapor was 10L/min) output from the outlet of the tube furnace, and the remaining air volume of 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) 600g of the wet cake numbered LB-1 were placed in a beaker, 4.4g of hydroxyethyl methylcellulose and 4.2g of hydroxypropyl methylcellulose were added and, after stirring for 10 minutes with a mechanical stirrer, the phosphorus-containing hydrated alumina composition of the invention was obtained, the properties of which are given in Table 1.

(2) And (2) extruding the phosphorus-containing 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 6cm, 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 constant at that temperature for 3 hours, while blowing air from the inlet of the tube furnace to the inner space of the tube furnace at 17L/min, wherein the air volume of 15L/min was circulating air (the amount of water vapor was 12L/min) which was discharged from the outlet of the tube furnace, and the remaining air volume of 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 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 63.9%.

(2) 500g of wet cake LB-2, reference numeral LB-2, was placed in a beaker, to which 8g of hydroxypropylmethylcellulose and 10g of sesbania powder (galactomannan content 85% by weight, available from Beijing Chemicals) were added and stirred for 10 minutes using a mechanical stirrer to obtain a phosphorus-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(3) And (2) extruding the phosphorus-containing 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 6cm, 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, while blowing air from the inlet of the tube furnace to the inner space of the tube furnace at a rate of 12L/min, wherein the air volume of 10L/min was the circulating air (the amount of water vapor was 8L/min) discharged from the outlet of the tube furnace, and the remaining air volume of 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 10

(1) 4kg of the wet cake numbered SLB-1 was mixed with 400g of deionized water, 26.4g of methylcellulose and 16g of sesbania powder (galactomannan content 80% by weight) and beaten for 1 minute, and the resulting slurry was fed to a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.7MPa and held for 15 minutes, and the wet cake obtained by pressure relief of the plate and frame was the phosphorus-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

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

(3) The extrudate was cut into wet strips having a length of about 6cm, 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, while 15L/min of circulating air (10L/min of water vapor) was blown from the inlet of the tube furnace to the inner space of the tube furnace, wherein the air volume of 12L/min was air, 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 11

The hydrated alumina wet gel used in this example was prepared by mixing CO₂Method (sodium aluminate-CO)₂The method is that hydrated alumina gel solution prepared from the new material of the catalyst of Haohao of Shaanxi county, Henan province) is taken, sodium phosphate is added into the sodium aluminate solution, and the phosphate-containing pseudo-boehmite wet filter cake (the number of the wet filter cake is LB-3) is prepared after washing by a plate-and-frame filter press, and the i value of the wet filter cake is determined to be 64.6 percent, and the P is used as the P₂O₅The phosphorus content was 7% by weight.

(1) 500g of the wet cake numbered LB-3 were placed in a beaker, followed by the addition of 8g of methylcellulose and 10g of sesbania powder (galactomannan content 80% by weight), and after stirring for 10 minutes with a mechanical stirrer, the resulting mixture was a phosphorus-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(2) And (2) extruding the phosphorus-containing 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 5cm, 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, while blowing air from the inlet of the tube furnace to the inner space of the tube furnace at 10L/min, wherein the air volume of 8L/min was circulating air (the amount of water vapor was 6L/min) which was discharged from the outlet of the tube furnace, and the remaining air volume of 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 12

The hydrated alumina wet gel used in this example was a hydrated alumina gel solution prepared by sodium aluminate seeded precipitation (from Shandong division of Alumina, China), and 5kg of a phosphorus-containing alumina trihydrate wet cake was prepared by adding sodium phosphate to the sodium aluminate solution and washing the solution with a leaf filter, and the wet cake was adjusted to P₂O₅The calculated phosphorus content was 15% by weight, 1000g of water was added to mix and pulp, the resulting slurry was pressed into a plate and frame filter press, the plate and frame pressure of the plate and frame filter was adjusted to 0.9MPa and held for 3 minutes, and then the cake in the plate and frame was swept with pressurized air of 0.6MPa for 5 minutes to give 2.5kg of a wet cake of phosphorus-containing alumina trihydrate (this wet cake was designated as LB-4), the wet cake having an i value of 61.5% by weight.

(1) 500g of wet cake LB-4 were placed in a beaker, then 5g of methylcellulose and 10g of sesbania powder (galactomannan content 80% by weight) were added and, after stirring for 10 minutes with a mechanical stirrer, the mixture obtained was a phosphorus-containing hydrated alumina composition according to the invention, the parameters of which are given in Table 1.

(2) And (2) extruding the phosphorus-containing 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 6cm, 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, while blowing air from the inlet of the tube furnace to the inner space of the tube furnace at a rate of 12L/min, wherein the air volume of 10L/min was the circulating air (the amount of water vapor was 8L/min) discharged from the outlet of the tube furnace, and the remaining air volume of 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 13

The hydrated alumina wet gel used in the embodiment is obtained from Shandong Zibozimao catalyst Co., Ltd, 1000g of pseudo-boehmite dry powder (dry basis is 70 wt%) prepared by an acid method (sodium aluminate-aluminum sulfate method) is roasted at 700 ℃ for 3 hours in an air atmosphere to obtain 697g of alumina, 697g of alumina is put in a 10L high-pressure reaction kettle and is uniformly stirred with 5L of deionized water, the high-pressure reaction kettle is sealed and reacts for 6 hours at 150 ℃ under the self pressure, after the reaction is finished, the temperature of the high-pressure reaction kettle is reduced to room temperature (25 ℃), aluminum phosphate is added, and P is used as aluminum phosphate₂O₅The calculated phosphorus content is 10 weight percent, slurry obtained by the reaction is sent into a plate-and-frame filter press, the plate-and-frame pressure of the plate-and-frame filter press is adjusted to 0.5MPa and kept for 10 minutes, then filter cakes in the plate-and-frame filter press are blown and swept by 10MPa pressurized air for 3 minutes, and the plate-and-frame filter press is decompressed to obtain the hydrated alumina wet filter cake LB-5. The phase of the wet cake was determined to be phosphoboehmite and the i value of the wet cake was 63.5%.

(1) 500g of the wet cake numbered LB-5 were placed in a beaker, then 6.3g of methylcellulose and 10g of sesbania powder (galactomannan content 85% by weight) were added and after stirring for 10 minutes with a mechanical stirrer, the resulting mixture was a phosphorus-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(3) The extrudate was cut into wet strips having a length of about 6cm, 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, while blowing air from the inlet of the tube furnace to the inner space of the tube furnace at 10L/min, wherein the air volume of 8L/min was the circulating air (the amount of water vapor was 6L/min) which was discharged from the outlet of the tube furnace, and the remaining air volume of 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 "New Process for alumina preparation by hydrolysis of Low-carbon alkoxy aluminum", test method ", in" Petroleum institute "(Petroleum processing), Vol.10, No. 4, wherein the aging time was 12 hours, after aging was completed and isopropanol and water were evaporated, 500g of water was added, aluminum phosphate was added, and P was used as P₂O₅The calculated phosphorus content was 15% by weight, and the slurry was stirred with a mechanical stirrer for 1 minute, pressed into a plate and frame filter, and the pressure of the plate and frame was adjusted to 0.7MPa for 8 minutes, and then the cake in the plate and frame was blown with 7MPa of pressurized air for 4 minutes to obtain 200g of a wet cake (No. LB-6). The phase of the wet cake was determined to be pseudo-boehmite containing phosphorus and the i value of the wet cake was 65.3%.

(1) 200g of the wet cake numbered LB-6 were placed in a beaker, then 2.8g of methylcellulose and 4.5g of sesbania powder (galactomannan content 80% by weight) were added and, after stirring for 10 minutes with a mechanical stirrer, the resulting mixture was a phosphorus-containing hydrated alumina composition according to the invention, the properties of which are given in Table 1.

(3) The extrudate was cut into wet strips having a length of about 6cm, 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, while air was blown from the inlet of the tube furnace to the inner space of the tube furnace at 9L/min, wherein the air volume of 7L/min was the circulating air (the amount of water vapor was 5L/min) which was output from the outlet of the tube furnace, and the remaining air volume of 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 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-7). The wet cake numbered LB-5 was determined to have an i value of 75 wt%.

(2) 500g of the wet cake numbered LB-7 were placed in a beaker and 8g of hydroxypropylmethylcellulose and 10g of sesbania powder (galactomannan content 85% by weight) were added and stirred for 10 minutes using a mechanical stirrer to obtain a phosphorus-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(3) And (3) extruding the phosphorus-containing hydrated alumina composition prepared in the step (2) on an F-26 type double-screw extruder by using a round orifice plate with the diameter 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 6cm, and the wet strips were fed into a tube furnace, elevated from ambient temperature (25 ℃) to 900 ℃ at a temperature rise rate of 200 ℃/hr, and kept at the same temperature for 2.5 hours while blowing air from the inlet of the tube furnace to the inner space of the tube furnace at a rate of 12L/min, wherein the air flow rate of 10L/min was circulating air (the amount of water vapor was 8L/min) which was 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 8L/min. The properties of the alumina shaped bodies produced are listed in table 1.

TABLE 1

¹: the composition after standing was allowed to stand at ambient temperature (25-30 ℃) in a closed condition (in a sealed plastic bag) for 72 hours, and the content of alumina trihydrate in the composition after standing was increased more than before standing.

The results of examples 1-16 demonstrate that the present invention mixes the hydrated alumina wet gel directly with the compound having at least two proton acceptor sites and the phosphorus-containing compound without drying the hydrated alumina wet gel into dry or semi-dry gel powder, and the resulting mixture can be used directly for molding, and the resulting molded article has higher strength, thereby avoiding the problems of the prior art that the working environment is poor, the energy consumption is high and the strength of the prepared molded article is not high when the dry or semi-dry gel powder is used as the starting material for preparing the molded article.

Experimental examples 1 to 16 are provided to illustrate a catalyst having a hydrogenation catalytic action according to the present invention, a preparation method thereof, and a hydrotreating method thereof.

Experimental example 1

Dispersing molybdenum oxide and basic cobalt carbonate in water to form an impregnation liquid, wherein MoO₃The concentration of (b) was 95g/L, and the concentration of basic cobalt carbonate (CoO) was 15 g/L. The alumina compact prepared in example 1 was impregnated with the impregnation solution at ambient temperature (25 ℃ C.) for 1 hour. The impregnated hydrated alumina dry strips were dried at 120 ℃ under normal pressure for 2 hours in an air atmosphere, and then calcined at 400 ℃ under normal pressure for 3 hours in an air atmosphere, to thereby obtain the catalyst C-1 having a hydrogenation catalytic action according to the present invention,the compositions are listed in table 2.

Experimental example 2

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 35g/L in terms of NiO. The alumina compact prepared in example 2 was impregnated with this impregnation solution at ambient temperature (25 ℃ C.) for 1 hour. The impregnated hydrated alumina dry strands were dried at 130 ℃ under normal pressure for 2.5 hours in an air atmosphere, and then calcined at 450 ℃ under normal pressure for 2 hours in an air atmosphere, 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 5 was used, and the composition of the catalyst C-5 prepared was as shown in Table 2.

Experimental example 5

Experimental comparative example 1

A catalyst was prepared in the same manner as in Experimental example 1, except that the alumina formed body prepared in comparative example 1 was used, and the composition of the prepared catalyst DC-1 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

Dispersing molybdenum oxide and basic nickel carbonate in water to form an impregnating solution, wherein MoO₃The concentration of (2) was 85g/L, and the concentration of basic nickel carbonate (calculated as NiO) was 22 g/L. The alumina compact prepared in example 6 was prepared by impregnating the impregnated solution with the impregnation solution at ambient temperature (25 ℃ C.) for 1 hour. The impregnated hydrated 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-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 (2) was 60g/L, and the concentration of basic nickel carbonate (calculated as NiO) was 10 g/L. 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 hydrated 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-7 having a hydrogenation catalytic action according to the present invention, the composition of which is shown in Table 2.

Experimental examples 8 to 16

A catalyst was produced in the same manner as in example 7, except that the alumina formed bodies prepared in examples 8 to 16 were used as the alumina formed bodies, respectively. The compositions of the catalysts C-8 to C-16 prepared are listed in Table 2.

TABLE 2

Test examples 1 to 16

The catalysts prepared in experimental examples 1 to 16 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, with a nickel mass content of 27.8ppm, a vanadium mass content of 81.2ppm, a sulfur content of 4.5 wt.%, and a carbon residue of 11.7 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 referring to the method specified in GB/T17144, wherein the adopted instrument is MCRT-160 model micro carbon residue determinator of ALCOR company in America; the content of metallic nickel and vanadium in the oil sample is determined by inductively coupled plasma emission spectrometry (ICP-AES) (the instrument is PE-5300 plasma photometer of PE company in USA, and the specific method is shown in petrochemical industry analysis method RIPP 124-90). According to the measurement result, the removal rate of the impurities is calculated according to the following formula:

testing of comparative examples 1-4

The catalysts prepared in experimental examples 1 to 4 were evaluated for their catalytic performance in the same manner as in test examples 1 to 16, and the results are shown in Table 3.

TABLE 3

Numbering	Source of vector	Catalyst numbering	Demetallization Rate (%)	Desulfurization degree (%)	Carbon residue removal ratio (%)
						Experimental example 1	Example 1	C-1	80.4	84.6	51.3
Experimental comparative example 1	Comparative example 1	DC-1	78.9	81.3	49.8
						Experimental example 2	Example 2	C-2	80.1	83.9	50.8
Experimental example 3	Example 3	C-3	79.9	83.5	51.0
						Experimental example 4	Example 4	C-4	80.3	83.0	50.6
Experimental example 5	Example 5	C-5	80.2	82.6	51.2
						Experimental comparative example 2	Comparative example 2	DC-2	74.2	76.3	46.1
Experimental comparative example 3	Comparative example 3	DC-3	73.9	76.0	46.4
						Experimental comparative example 4	Comparative example 4	DC-4	74.5	76.8	46.0
Experimental example 6	Example 6	C-6	78.8	82.1	49.6
						Experimental example 7	Example 7	C-7	79.4	81.6	49.8
Experimental example 8	Example 8	C-8	79.9	80.8	50.1
						Experimental example 9	Example 9	C-9	80.0	80.6	49.9
Experimental example 10	Example 10	C-10	78.1	79.9	50.4
						Experiment ofExample 11	Example 11	C-11	78.9	80.5	50.1
Experimental example 12	Example 12	C-12	77.9	81.1	49.6
						Experimental example 13	Example 13	C-13	79.2	80.4	49.9
Experimental example 14	Example 14	C-14	79.5	79.8	49.5
						Experimental example 15	Example 15	C-15	78.0	80.1	48.9
Experimental example 16	Example 16	C-16	78.9	80.3	49.3

The results of test examples 1 to 16 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 method for producing an alumina molding, comprising the steps of:

(1) forming a phosphorus-containing hydrated alumina composition to obtain a formed product, wherein the phosphorus-containing hydrated alumina composition contains hydrated alumina, a compound with at least two proton acceptor sites and a phosphorus-containing compound, the compound with at least two proton acceptor sites is one or more than two of glucan, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and amino polysaccharide,

the phi value of the composition is from 1.2 to 5,the phi value is determined by 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 w₁The value phi is calculated by adopting the formula I,

(formula I) is shown in the specification,

the phosphorus-containing hydrated alumina composition is prepared by a method comprising the following steps: mixing the components of a raw material composition containing a hydrated alumina wet gel having an i value of not less than 60% and not more than 78.5%, a compound having at least two proton acceptor sites in an amount such that the finally prepared composition has a phi value of 1.2 to 5,

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

(formula II);

2. 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, and the phosphorus-containing compound is represented by P, relative to 100 parts by weight of the hydrated alumina₂O₅The content is 1.5-45 weight portions.

3. The method according to claim 2, wherein the compound having at least two proton acceptor sites is contained in an amount of 2 to 20 parts by weight with respect to 100 parts by weight of the hydrated alumina.

4. The method according to claim 1, wherein the compound having at least two proton acceptor sites is contained in an amount of 3 to 18 parts by weight with respect to 100 parts by weight of the hydrated alumina.

5. The method according to claim 1, wherein the compound having at least two proton acceptor sites is contained in an amount of 3.5 to 17 parts by weight with respect to 100 parts by weight of the hydrated alumina.

6. The method of claim 2, wherein the phosphorus-containing compound is represented by P, relative to 100 parts by weight of the hydrated alumina₂O₅The content is 2-35 weight portions.

7. The method of claim 6, wherein the phosphorus-containing compound is represented by P, relative to 100 parts by weight of the hydrated alumina₂O₅The content is 3-25 weight portions.

8. The method of claim 1, wherein the compound having at least two proton acceptor sites is one or more of a galactan, a mannan, a galactomannan, and a cellulose ether.

9. The method of claim 8, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.

10. The method of claim 8, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.

11. The method of claim 10, 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.

12. The method of claim 11, 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.

13. The method of claim 12, 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.

14. The method of any one of claims 1-7, wherein the hydrated alumina comprises pseudoboehmite.

15. The method of claim 14, wherein the hydrated alumina is pseudoboehmite.

16. The method of claim 14, wherein the composition is allowed to stand at ambient temperature and under closed conditions for 72 hours, the amount of alumina trihydrate in the composition after standing being higher than the amount of alumina trihydrate in the composition before standing.

17. The method of claim 16, wherein the alumina trihydrate content of the composition after placement is increased by at least 0.5% based on the total amount of alumina trihydrate content of the composition before placement.

18. The method of claim 17, wherein the alumina trihydrate content of the composition after placement is increased by at least 1%, based on the total alumina trihydrate content of the composition before placement.

19. The method of claim 18, wherein the alumina trihydrate content in the composition after placement is increased by 1.1% to 2% based on the total alumina trihydrate content in the composition before placement.

20. The method of any one of claims 1-7, wherein the hydrated alumina is derived directly from a hydrated alumina wet gel.

21. The method of any one of claims 1-7, wherein the composition is free of a peptizing agent.

22. The method of claim 1, wherein the hydrated alumina wet gel has an i value of not less than 62%.

23. The method of claim 1, 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.

24. The method of claim 1, wherein the wet hydrated alumina gel is obtained by washing and solid-liquid separation of at least one hydrated alumina gel solution after optional aging.

25. The method of claim 24, wherein the hydrated alumina gel solution is prepared using a precipitation method, a hydrolysis method, a seed precipitation method, and a flash dehydration method.

26. The method according to claim 25, 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.

27. The method of claim 1, wherein the feedstock composition is free of peptizing agents.

28. The method of claim 1, wherein the method of mixing is stirring and/or kneading.

29. The method according to any one of claims 1 to 7, wherein the drying temperature in step (2) is 60 ℃ or higher and not higher than 350 ℃.

30. The method of claim 29, wherein the drying of step (2) is at a temperature of 80-300 ℃.

31. The method as claimed in claim 30, wherein the drying temperature in step (2) is 110-260 ℃.

32. The method according to any one of claims 1 to 7, wherein in the step (3), the amount of water vapor is 0.01 to 0.8L/(min-g shaped article) and the shaped article is Al₂O₃And (6) counting.

33. The method according to any one of claims 1-7, wherein the method comprises step (2), and at least part of the water vapor is water vapor generated during the drying in step (2).

34. The method according to any one of claims 1 to 7, wherein the shaped article obtained in step (1) is fed directly into step (3), and at least part of the water vapor is the water vapor generated during the calcination in step (3).

35. The method according to claim 34, wherein in step (3), during the baking, 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.

36. A process according to claim 35, wherein from 10 to 90% by volume of the withdrawn gas is recycled into the vessel.

37. A process as claimed in claim 36, in which from 20 to 85% by volume of the withdrawn gas is recycled into the vessel.

38. A process as claimed in claim 37, in which from 30 to 80% by volume of the withdrawn gas is recycled into the vessel.

39. The method as claimed in any one of claims 1 to 7, wherein the temperature of the calcination in step (3) is 400-1200 ℃.

40. The method as claimed in claim 39, wherein the temperature of the calcination in step (3) is 450-1100 ℃.

41. The method as claimed in claim 40, wherein the temperature of the calcination in the step (3) is 500-1000 ℃.

42. The method according to any one of claims 1 to 7, wherein the duration of the calcination in step (3) is 1 to 20 hours.

43. The process of claim 42, wherein the duration of the calcination in step (3) is 2-15 hours.

44. The method of claim 43, wherein the duration of the firing in step (3) is 3-12 hours.

45. The method according to any one of claims 1 to 7, wherein in the step (3), the temperature inside the container containing the molded object is raised to the baking temperature at a temperature raising rate of 10 to 400 ℃/hr.

46. The method as claimed in claim 45, wherein, in the step (3), the temperature in the container for receiving the molding is raised to the baking temperature at a temperature raising rate of 15-350 ℃/hr.

47. The method as claimed in claim 46, wherein, in the step (3), the temperature in the container for receiving the molding is raised to the baking temperature at a temperature raising rate of 20-300 ℃/hr.

48. The method of any of claims 1-7, wherein the phosphorus-containing compound is selected from at least one of phosphoric acid, sodium phosphate, aluminum phosphate, ammonium phosphate, and ammonium hydrogen phosphate.

49. The method of any of claims 1-7, wherein the value of Φ is 4 or less.

50. The method of claim 49, wherein the value of φ is 3.5 or less.

51. The method of claim 50 wherein the value of φ is 3.2 or less.

52. The method of any of claims 1-7, wherein the value of Φ is 1.3 or greater.

53. The method of claim 52, wherein said value of φ is 1.4 or greater.

54. The method of any of claims 1-7, wherein the phosphorus-containing hydrated alumina composition has a value of Φ of not less than 1.8.

55. The method of claim 54, wherein the phosphorus-containing hydrated alumina composition has a φ value of not less than 1.85.

56. The method of claim 55 wherein the phosphorus-containing hydrated alumina composition has a φ value of 1.9 to 3.2.

57. The method of any of claims 1-7, wherein the phosphorus-containing hydrated alumina composition has a φ value of less than 1.8.

58. The method of claim 57, wherein the phosphorus-containing hydrated alumina composition has a φ value of not greater than 1.7.

59. The method of claim 58, wherein the phosphorus-containing hydrated alumina composition has a φ value of 1.3 to 1.7.

60. An alumina shaped body prepared by the method of any one of claims 1 to 59.

61. An alumina shaped body prepared by the method of any one of claims 54-56.

62. The shaped body according to claim 61, wherein the alumina shaped body has a bimodal distribution of pore sizes, the mode pore sizes being 4-60nm and greater than 60nm, respectively, as determined by mercury intrusion.

63. The shaped body according to claim 62, wherein the mode pore size is from 5 to 40nm and from 80 to 500nm, respectively.

64. An alumina shaped body prepared by the method of any one of claims 57-59.

65. Shaped body according to claim 64, wherein the pore size of the shaped alumina body is unimodal as determined by mercury intrusion, the mode pore size being from 4 to 60 nm.

66. The shaped body according to claim 65, wherein the mode pore size is from 5 to 40 nm.

67. Shaped body according to any one of claims 60, 61 and 64, wherein the radial crush strength of the alumina shaped body is from 10 to 30N/mm.

68. The shaped body according to claim 67, wherein the alumina shaped body has a radial crush strength of from 12 to 30N/mm.

69. Use of the alumina molding according to any one of claims 60 to 68 as a support or adsorbent.

70. The use according to claim 69, wherein the support is a support for a supported catalyst.

71. The use according to claim 70, wherein the support is a support for a supported hydrogenation catalyst.

72. A catalyst having a hydrogenation catalytic action, which comprises a carrier and a hydrogenation active component supported on the carrier, wherein the carrier is the alumina compact according to any one of claims 60 to 68.

73. A process for producing a catalyst having a hydrogenation catalytic action, which comprises supporting a hydrogenation-active component on a carrier, wherein the carrier is the alumina compact according to any one of claims 60 to 68.

74. A hydroprocessing method comprising contacting, under hydroprocessing conditions, a hydrocarbon oil with a hydrocatalytically effective catalyst, wherein said hydrocatalytically effective catalyst is the catalyst of claim 72 or the catalyst produced by the process of claim 73.