CN107999117B

CN107999117B - Hydrated alumina composition containing Y-type molecular sieve, formed body, preparation method and application of hydrated alumina composition, catalyst and preparation method of catalyst

Info

Publication number: CN107999117B
Application number: CN201610930863.8A
Authority: CN
Inventors: 辛靖; 杨清河; 杨平; 李明丰; 聂红; 赵广乐; 王轶凡; 董松涛; 胡志海
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-10-31
Filing date: 2016-10-31
Publication date: 2020-07-28
Anticipated expiration: 2036-10-31
Also published as: CN107999117A

Abstract

The invention discloses a hydrated alumina composition and a preparation method thereof, a formed body and a preparation method and application thereof, wherein the composition contains hydrated alumina, a Y-type molecular sieve and a compound with at least two proton acceptor sites, and the composition

The value is 5 or less. The invention also discloses a catalyst with hydrogenation catalysis function and a preparation method thereof, and a hydrotreating method, wherein the catalyst takes a formed body formed by the hydrated alumina composition as a carrier. The invention prepares the forming 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, 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. And the catalyst prepared by using the formed body prepared from the hydrated alumina composition as a carrier shows higher catalytic activity in the hydrogenation treatment reaction of hydrocarbon oil.

Description

Hydrated alumina composition containing Y-type molecular sieve, formed body, preparation method and application of hydrated alumina composition, catalyst and preparation method of catalyst

Technical Field

The invention relates to the technical field of alumina forming, in particular to a hydrated alumina composition containing a Y-type molecular sieve and a preparation method thereof, a hydrated alumina forming body and an alumina forming body formed by the hydrated alumina composition, and further relates to a catalyst with hydrogenation catalysis effect and a preparation method thereof, wherein the catalyst takes the forming body formed by the hydrated alumina composition as a carrier, and a hydrogenation treatment method adopting the catalyst.

Background

In the conventional method, an alumina formed body containing a Y-type molecular sieve, particularly a γ -alumina formed body containing a Y-type molecular sieve, 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 pseudo-boehmite dry gel powder, then the pseudo-boehmite dry gel powder is taken as a starting point, a Y-type molecular sieve, an extrusion aid and an optional chemical peptizing agent (inorganic acid and/or organic acid) are added, and the mixture is kneaded and molded, and the molded product is dried and optionally calcined to be used as an adsorbent or a carrier. The main problems of this preparation method are the high dust pollution and the high energy consumption.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Disclosure of Invention

The invention aims to simplify the preparation process flow of the alumina carrier containing the Y-type molecular sieve, reduce the dust pollution in the preparation process of the alumina carrier containing the Y-type molecular sieve, and simultaneously, the prepared carrier can also 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 hydrated alumina composition containing a molecular sieve of type Y, which composition comprises hydrated alumina, a molecular sieve of type Y and a compound having at least two proton acceptor sites,

of said composition

A value of 5 or less, said

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

The value of the one or more of,

according to a second aspect of the present invention, there is provided a process for preparing a hydrated alumina composition containing a Y-type molecular sieve, which comprises mixing the components of a feedstock composition comprising a hydrated alumina wet gel having an i value of not less than 50%, a Y-type molecular sieve and a compound having at least two proton acceptor sites in an amount such that the composition finally prepared is a hydrated alumina composition, to obtain the hydrated alumina composition

The value of the amount of the organic acid is 5 or less,

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

the above-mentioned

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

The value of the one or more of,

according to a third aspect of the present invention there is provided a hydrated alumina composition prepared by the process of the second aspect of the present invention.

According to a fourth aspect of the present invention, there is provided a hydrated alumina molded body formed from the hydrated alumina composition of the first aspect of the present invention or the hydrated alumina composition of the third aspect of the present invention.

According to a fifth aspect of the present invention, there is provided a method for producing a hydrated alumina molded body, which comprises molding the hydrated alumina composition of the first aspect of the present invention or the hydrated alumina composition of the third aspect of the present invention, and drying the resulting molded body.

According to a sixth aspect of the present invention, there is provided a hydrated alumina molded body produced by the method of the fifth aspect of the present invention.

According to a seventh aspect of the present invention, there is provided an alumina molded body formed from the hydrated alumina composition of the first aspect of the present invention or the hydrated alumina composition of the third aspect of the present invention.

According to an eighth aspect of the present invention, there is provided a method for producing an alumina molded body, which comprises molding the hydrated alumina composition of the first aspect of the present invention or the hydrated alumina composition of the third aspect of the present invention, and drying and firing the resulting molded body.

According to a ninth aspect of the present invention, there is provided an alumina compact produced by the method of the eighth aspect of the present invention.

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

(1) providing a hydrated alumina gel solution, and washing and carrying out solid-liquid separation on the hydrated alumina gel solution to obtain a first hydrated alumina wet gel, wherein the solid-liquid separation condition is that the i value of the first hydrated alumina wet gel is not less than 50%;

(2) mixing the first hydrated alumina wet gel with a compound having at least two proton acceptor sites using the method of the second aspect of the invention to obtain a hydrated alumina composition;

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

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

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

wherein the method further comprises mixing the Y-type molecular sieve in the step (1) and/or the step (2), so that the hydrated alumina composition contains the Y-type molecular sieve.

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

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

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

(2-1) mixing the first hydrated alumina wet gel with water to form slurry, and carrying out solid-liquid separation on the slurry to obtain a second hydrated alumina wet gel;

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

(2-1) and (2-2), the solid-liquid separation conditions being such that the second hydrated alumina wet gel has an i value of not less than 50%,

(3) mixing a second wet hydrated alumina gel with a compound having at least two proton acceptor sites using the method of the second aspect of the invention to obtain a hydrated alumina composition;

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

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

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

wherein the method further comprises mixing Y-type molecular sieves in one, two or three of the steps (1), (2) and (3) so that the hydrated alumina composition contains Y-type molecular sieves.

According to a twelfth aspect of the present invention, there is provided a molded body produced by the method according to the tenth or eleventh aspect of the present invention.

According to a thirteenth aspect of the present invention, there are provided a hydrated alumina molded body according to the present invention and use of the alumina molded body as a carrier or an adsorbent.

According to a fourteenth aspect of the present invention, the present invention provides a catalyst having a hydrogenation catalytic action, which comprises a carrier and a group VIII metal element and a group VIB metal element supported on the carrier, wherein the carrier is a hydrated alumina formed body according to the present invention or an alumina formed body according to the present invention.

According to a fifteenth aspect of the present invention, there is provided a method for preparing a catalyst having a hydrocatalytic effect, which comprises supporting a group VIII metal element and a group VIB metal element on a carrier, wherein the method further comprises preparing a hydrated alumina compact or an alumina compact as a carrier by the method according to the fifth, seventh, tenth or eleventh aspect of the present invention.

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

Compared with the prior process method (shown as a process in figure 1) for preparing the alumina forming body by taking the pseudo-boehmite dry glue powder as the starting raw material, the invention directly takes the hydrated alumina wet gel prepared by the synthesis reaction as the starting raw material for forming to prepare the forming body containing the Y-shaped molecular sieve, and has the following advantages that:

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

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

Compared with the prior art, such as US4613585 and CN103769118A, which directly 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 prepare the Y-type molecular sieve-containing molded body having higher strength from the hydrated alumina wet gel as the starting material may be that: the compound with at least two proton acceptor sites and the free water in the hydrated alumina wet gel interact to form hydrogen bonds to adsorb the free water in the hydrated alumina wet gel, and simultaneously, the compound with at least two proton acceptor sites and the hydroxyl in the molecular structure of the hydrated alumina can also perform hydrogen bond interaction to play a role of physical peptization, so that the hydrated alumina wet gel can be molded, and the finally prepared molded body has higher strength.

The catalyst with hydrogenation catalysis, which takes the formed body prepared from the hydrated alumina composition as a carrier, shows higher catalytic activity in hydrocarbon oil hydrogenation treatment.

Drawings

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

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

FIG. 2 is a preferred embodiment of a method of making a hydrated alumina composition in accordance with the present invention.

Fig. 3 is a preferred embodiment of a molding process flow according to the present invention.

Detailed Description

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

According to a first aspect of the present invention there is provided a Y-type molecular sieve containing hydrated alumina composition comprising hydrated alumina, a Y-type molecular sieve and a compound having at least two proton acceptor sites.

The hydrated alumina may be one or more selected from alumina trihydrate and alumina monohydrate. Specific examples of the hydrated alumina may include, but are not limited to, boehmite, alumina trihydrate, amorphous hydrated alumina, and pseudo-boehmite. The hydrated alumina preferably comprises alumina monohydrate, more preferably alumina monohydrate. In a preferred embodiment of the invention, the hydrated alumina contains pseudoboehmite, more preferably pseudoboehmite. The hydrated alumina composition according to this preferred embodiment is particularly suitable for the preparation of shaped bodies for use as catalyst supports having a hydrocatalytic effect.

According to the hydrated alumina composition of the present invention, the hydrated alumina is directly derived from the hydrated alumina wet gel and not from the hydrated alumina dry gel powder. In the present invention, the term "hydrated alumina wet gel" refers to an aqueous hydrated alumina gel which is obtained by a synthesis reaction and has not undergone a dehydration process for reducing its i value to 50% or less (preferably 55% or less, more preferably 60% or less, further preferably 62% or less). In the present invention, the value of i is determined by the following method: 10g of hydrated alumina wet gel inDrying at 120 ℃ for 240 minutes in an air atmosphere, and recording the mass of the dried sample 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 wet gel undergoes a phase change during storage. For example, when the composition is left at ambient temperature and under closed conditions for 72 hours, the phase of the hydrated alumina in the composition after the standing is changed. 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 wet gel contains pseudoboehmite (e.g., is pseudoboehmite), the composition is left at ambient temperature and under closed conditions for 72 hours, the alumina trihydrate content in the composition after placement being greater than the alumina trihydrate content in the composition prior to placement. In this example, the alumina trihydrate content of the composition after placement is generally increased by at least 0.5%, preferably by at least 1%, more preferably by from 1.1 to 1.5%, based on the alumina trihydrate content of the composition before placement.

The hydrated alumina composition according to the present invention further contains a compound having at least two proton acceptor sites. The hydrated alumina composition according to the present invention can be used for molding (particularly extrusion molding) without using a dry rubber powder as a starting material, and the reason why the obtained molded article has a higher strength may be that: the compound with at least two proton acceptor sites and the free water in the hydrated alumina wet gel generate hydrogen bond interaction, so that the free water is adsorbed, and simultaneously, the compound and the hydroxyl in the molecular structure of the hydrated alumina generate interaction to play a role in peptization.

In the compound having at least two proton acceptor sites, the proton acceptor sites are sites capable of forming hydrogen bonds with water and hydroxyl groups 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 one or more 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, C₁-C₅Aryl-substituted alkyl) which may be phenyl or naphthyl. Specific examples of the substituted hydrocarbon group may include, but are not limited to: cyano, benzyl, benzeneEthyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, carboxymethyl, carboxyethyl and carboxypropyl. Specific examples of the cellulose ether may include, but are not limited to, methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose. The polysaccharide may be of various origins, for example: the galactomannan may be derived from sesbania powder.

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

Specific examples of the polyether include, but are not limited to, polyethylene oxide, polypropylene oxide, an ethylene oxide-propylene oxide block 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 moulded body formed from the composition according to the invention has a higher strength. Further preferably, the compound having at least two proton acceptor sites is preferably a galactomannan and a cellulose ether.

In this more preferred embodiment, the galactomannan may be present in an amount of from 10 to 80 wt.%, preferably from 15 to 70 wt.%, more preferably from 20 to 60 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 20 to 90 wt%, preferably 30 to 85 wt%, more preferably 40 to 80 wt%.

The composition according to the invention also contains a molecular sieve of type Y, particularly suitable for preparing a support for catalysts having a hydrocatalytic effect.

The amount of Y-type molecular sieve in the composition may be selected according to the particular application of the composition. In a preferred embodiment, the Y-type molecular sieve may be present in an amount of from 0.5 to 90 wt%, preferably from 1 to 80 wt%, more preferably from 5 to 70 wt%, and even more preferably from 10 to 60 wt%, based on the total weight of the calcined composition; the content of alumina may be 10 to 99.5% by weight, preferably 20 to 99% by weight, more preferably 30 to 95% by weight, and further preferably 40 to 90% by weight, and the calcination is carried out at a temperature of 600 ℃ and the duration of the calcination is 3 hours. The composition according to this preferred embodiment is particularly suitable for the preparation of a support for a catalyst having a hydrocatalytic effect.

The Y-type molecular sieve can be one or more of hydrogen-type Y-type molecular sieve, hydrogen-type Y-type molecular sieve containing rare earth, Y-type molecular sieve containing IVB group metal (such as titanium), phosphorus-containing Y-type molecular sieve and dealuminated Y-type molecular sieve.

Of the compositions according to the invention

The value is 5 or less, preferably 4 or less, and more preferably 3.5 or less.

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

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

In the present invention,

The value of the one or more of,

the compound having at least two proton acceptor sites is contained in an amount enabling the composition according to the invention

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 22 parts by weight, more preferably 4 to 20 parts by weight, relative to 100 parts by weight of the hydrated alumina.

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

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

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

In a particularly preferred embodiment of the invention, the composition according to the invention does not contain a peptizing agent. According to the composition of this particularly preferred embodiment, when used for the production of a shaped body, the produced hydrated alumina shaped body can be used as an adsorbent or a carrier even if it is converted into an alumina shaped body without calcination, because when the unfired hydrated alumina shaped body contains a peptizing agent, the peptizing agent is dissolved during adsorption and impregnation, and is lost in a large amount, so that the shaped body is dissolved, pulverized, and collapsed in the channels, and finally loses its shape, and thus cannot be used as an adsorbent or a carrier.

According to a second aspect of the present invention, there is provided a process for preparing a hydrated alumina composition containing a Y-type molecular sieve, which comprises mixing the components of a feedstock composition to obtain the hydrated alumina composition, i.e. the mixture obtained by mixing is the hydrated alumina composition.

According to the method for preparing a hydrated alumina composition of the present invention, the raw material mixture contains a hydrated alumina wet gel, a Y-type molecular sieve, and a compound having at least two proton acceptor sites. The compound having at least two proton acceptor sites and the Y-type molecular sieve have been described in detail above and will not be described herein again.

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

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

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

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 under conventional conditions. The hydrothermal treatment may be carried out at a temperature of 100-200 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.

According to the method for producing a hydrated alumina composition of the present invention, the i value of the hydrated alumina wet gel is not less than 50%, preferably not less than 55%, more preferably not less than 60%, and further preferably not less than 62%. The i value of the hydrated alumina wet gel is preferably not higher than 95%, more preferably not higher than 90%, further preferably not higher than 85%, and further preferably not higher than 82%. In one embodiment, the hydrated alumina wet gel has an i value of 50 to 95%, such as 50 to 90%. In a more preferred embodiment, the hydrated alumina wet gel has an i value of 60 to 90%, more preferably 60 to 85%, and still more preferably 62 to 82%. The composition prepared according to this more preferred embodiment, when used for molding, gives a molded article having higher strength.

The hydrated alumina wet gel with the value i meeting the requirement can be obtained by controlling the solid-liquid separation conditions when the prepared hydrated alumina gel-containing solution is subjected to solid-liquid separation. In one embodiment of the present invention, the solid-liquid separation is performed once or twice or more, and at least the last solid-liquid separation is performed by pressure filtration and/or vacuum filtration. In this embodiment, the value of the hydrated alumina wet gel i obtained is controlled by adjusting the magnitude of the applied pressure and/or vacuum. Specific examples of the pressure filtration apparatus 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.

According to the method for producing a hydrated alumina composition of the present invention, the hydrated alumina wet gel obtained by solid-liquid separation is generally not subjected to dehydration treatment for reducing the i value thereof to 50% or less (preferably 55% or less, more preferably 60% or less, further preferably 62% or less).

According to the method for preparing a hydrated alumina composition of the present invention, the compound having at least two proton acceptor sites is used in an amount such that the hydrated alumina composition finally prepared

The value is 5 or less, preferably 4 or less, and more preferably 3.5 or less. The compound having at least two proton acceptor sites is preferably used in an amount such that the final prepared hydrated alumina composition is

The value is 1.2 or more. The amount of the compound having at least two proton acceptor sites is more preferably such that the final hydrated alumina composition is prepared

The value is 1.3 or more, and more preferably 1.4 or more. In particular, the compound having at least two proton acceptor sites is more preferably used in an amount such that the final hydrated alumina composition is prepared

The value is 1.2 to 5, preferably 1.3 to 4, more preferably 1.4 to 3.5.

Generally, the compound having at least two proton acceptor sites may be used in an amount of 1 to 25 parts by weight, preferably 2 to 22 parts by weight, more preferably 4 to 20 parts by weight, based on the hydrated alumina, relative to 100 parts by weight of the hydrated alumina wet gel.

According to the method for preparing the hydrated alumina composition, the content of the Y-type molecular sieve in the raw material mixture is 0.5 to 90 wt%, preferably 1 to 80 wt%, more preferably 5 to 70 wt%, and further preferably 10 to 60 wt% based on the total amount of the calcined hydrated alumina composition; the content of alumina may be 10 to 99.5% by weight, preferably 20 to 99% by weight, more preferably 30 to 95% by weight, and further preferably 40 to 90% by weight, and the calcination is carried out at a temperature of 600 ℃ and the duration of the calcination is 3 hours.

According to the method for preparing the hydrated alumina composition of the present invention, the raw material mixture may or may not contain a peptizing agent. Preferably, the peptizing agent is present in an amount of 5 parts by weight or less, preferably 3 parts by weight or less, more preferably 2 parts by weight or less, relative to 100 parts by weight of the hydrated alumina wet gel, based on the hydrated alumina. More preferably, the raw material mixture does not contain a peptizing agent. That is, the method for producing a hydrated alumina composition according to the present invention more preferably does not include a step of adding a peptizing agent to the raw material mixture.

According to the method for preparing the hydrated alumina composition of the present invention, the hydrated alumina wet gel may be mixed with the Y-type molecular sieve and the compound having at least two proton acceptor sites by a conventional method. The hydrated alumina wet gel may be mixed with a Y-type molecular sieve and a compound having at least two proton acceptor sites under shear. In one embodiment, the mixing is by stirring. The hydrated alumina wet gel may be mixed with the Y-type molecular sieve and the compound having at least two proton acceptor sites uniformly by stirring in a vessel having a stirring device to obtain the hydrated alumina composition according to the present invention. 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 Y-type molecular sieve and a compound having at least two proton acceptor sites in a kneader to obtain the hydrated alumina composition according to the present invention. The type of the kneader is not particularly limited. According to the method for preparing the hydrated alumina composition of the present invention, stirring and mixing may be used in combination to mix the hydrated alumina wet gel with a compound having at least two proton acceptor sites. In this case, it is preferable to perform stirring and kneading.

According to the method of preparing the hydrated alumina composition of the present invention, the Y-type molecular sieve, 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, the Y-type molecular sieve may be mixed during the preparation of the hydrated alumina wet gel, or the Y-type molecular sieve may be added to the hydrated alumina wet gel obtained by the preparation, or a part of the Y-type molecular sieve may be mixed during the preparation of the hydrated alumina wet gel, and the remaining part of the Y-type molecular sieve may be added to the hydrated alumina wet gel obtained by the preparation, and the operation of mixing the Y-type molecular sieve may be performed at one, two, or three of the above-mentioned addition timings. When the Y-type molecular sieve is mixed in the process of preparing the hydrated alumina wet gel, the operation of mixing the Y-type molecular sieve may be performed in one, two, three or four of the precipitation reaction process, the aging process, the solid-liquid separation process and the washing process. Whether the Y-type molecular sieve is mixed in the process of preparing the hydrated alumina wet gel, and the timing of mixing may be selected according to the type of the precipitation reaction, so that the structure of the Y-type molecular sieve is not or substantially not damaged. Preferably, the mixing of the Y-type molecular sieve is performed in a solid-liquid separation process.

In another embodiment, the Y-type molecular sieve is mixed after the hydrated alumina wet gel preparation is complete. In this embodiment, the Y-type molecular sieve may be first mixed with the wet gel of hydrated alumina, followed by mixing of the compound having at least two proton acceptor sites; or mixing a compound with at least two proton acceptor sites with the hydrated alumina wet gel, and then mixing the Y-type molecular sieve; the Y-type molecular sieve and the compound having at least two proton acceptor sites can also be mixed with the hydrated alumina wet gel simultaneously.

According to the method of preparing the hydrated alumina composition of the present invention, the Y-type molecular sieve is preferably mixed after the preparation of the hydrated alumina wet gel is completed.

According to the method for producing a hydrated alumina composition of the present invention, water may or may not be added during the mixing process, as long as the hydrated alumina composition can be produced

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. The weight ratio of the additionally added water to the compound having at least two proton acceptor sites may be 5 to 15: 1, preferably 8 to 12: 1.

The hydrated alumina composition according to the present invention can be shaped by a conventional method to obtain a hydrated alumina compact or an alumina compact.

The hydrated alumina composition according to the present invention may be molded, and the resulting molded article may be dried to obtain a hydrated alumina molded article according to the present invention.

The molding method is not particularly limited, and various molding methods commonly used in the art may be employed, 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.

The temperature at which the shaped article is dried may be a conventional choice in the art. Generally, the temperature of the drying may be 60 ℃ or more and less than 350 ℃, preferably 65 to 300 ℃, more preferably 70 to 250 ℃. The drying time can be properly selected according to the drying temperature, so that the volatile content in the finally obtained hydrated alumina forming body can meet the use requirement. Generally, the duration of the drying may be 1 to 48 hours, preferably 2 to 24 hours, more preferably 2 to 12 hours, and further preferably 2 to 6 hours. The drying may be carried out in an oxygen-containing atmosphere (e.g., air atmosphere) or in an inert atmosphere (e.g., an atmosphere formed by nitrogen and/or a group-zero gas), preferably in an oxygen-containing atmosphere.

The hydrated alumina molded body according to the present invention may have various shapes according to specific use requirements, for example: spherical, bar, annular, clover, honeycomb, bird's nest, cylindrical, raschig ring, or butterfly.

The hydrated alumina formed body has abundant pore structure and adjustable pore size distribution.

In one embodiment, the hydrated alumina shaped bodies have a bimodal pore size distribution as measured by mercury intrusion. Wherein the most probable pore size is 4-20nm (preferably 5-15nm, more preferably 6-10nm) and more than 20nm (e.g. 20.5-35nm), respectively.

In another embodiment, the hydrated alumina shaped body has a unimodal pore size distribution as determined by mercury intrusion. Among them, the most probable pore diameter is 4 to 30nm, preferably 10 to 25nm, and more preferably 12 to 23 nm.

According to the hydrated alumina molded body of the present invention, the hydrated alumina molded body has high strength. In general, the hydrated alumina molded body according to the present invention has a radial crush strength of 10N/mm or more, preferably 12N/mm or more, and more preferably 15N/mm or more. Specifically, the hydrated alumina compact may have a radial crush strength of 10 to 50N/mm, preferably 15 to 35N/mm. In the present invention, the radial crush strength of the molded article was measured by the method specified in RIPP 25-90.

According to a fifth aspect of the present invention, there is provided a method for producing a hydrated alumina molded body, which comprises molding the hydrated alumina composition of the first aspect of the present invention or the hydrated alumina composition of the third aspect of the present invention, and drying the obtained molded body to obtain the hydrated alumina molded body.

The methods and conditions for the shaping and drying are the same as those described for the fourth aspect of the present invention and will not be described in detail here.

According to the method for producing a hydrated alumina molded body of the present invention, the hydrated alumina composition can be changed

Values to obtain hydrated alumina shaped bodies with different pore size distributions.

In one embodiment of the invention, the hydrated alumina composition is

The value is not less than 1.85, and may be, for example, 1.8 to 5, preferably 1.85 to 4, and more preferably 1.9 to 3.5. The pore size distribution of the hydrated alumina formed bodies prepared according to this embodiment is bimodal as measured by mercury intrusion. The mode pore size is 4-20nm (preferably 5-15nm, more preferably 6-10nm) and greater than 20nm (e.g., 20.5-35nm), respectively.

In another embodiment of the present invention, the hydrated alumina composition is

The value is less than 1.8, and may be, for example, from 1.2 to less than 1.8, preferably from 1.3 to 1.78, and more preferably from 1.4 to 1.75. The pore diameter of the hydrated alumina molded body prepared according to this embodiment is unimodal as measured by mercury intrusion method. The mode pore size is 4 to 30nm, preferably 10 to 25nm, more preferably 12 to 23 nm.

The hydrated alumina formed body prepared by the method of the invention has higher strength. Generally, the hydrated alumina compact produced by the method of the present invention has a radial crush strength of 10N/mm or more, preferably 12N/mm or more, and more preferably 15N/mm or more. Specifically, the hydrated alumina compact produced by the method of the present invention may have a radial crush strength of 10 to 50N/mm, preferably 15 to 35N/mm.

The hydrated alumina composition according to the present invention may be molded, and the obtained molded article may be dried and calcined in sequence to obtain the alumina molded body.

The conditions for calcination in the present invention are not particularly limited, and may be selected conventionally in the art. Specifically, the temperature of the roasting may be 400-950 ℃, preferably 450-900 ℃, and more preferably 460-650 ℃; the duration of the calcination may be 2 to 10 hours, preferably 3 to 8 hours. The calcination may be carried out in an oxygen-containing atmosphere (e.g., air atmosphere) or in an inert atmosphere (e.g., an atmosphere formed of nitrogen and/or a group-zero gas), preferably in an oxygen-containing atmosphere.

The alumina molded body according to the present invention may have various shapes according to specific use requirements, for example: spherical, bar, annular, clover, honeycomb, bird's nest, cylindrical, raschig ring, or butterfly.

The alumina formed body has abundant pore structure and adjustable pore size distribution.

In one embodiment, the pore size distribution of the alumina compact is bimodal as determined by mercury intrusion. The mode pore size is 4-20nm (preferably 5-15nm, more preferably 6-10nm) and greater than 20nm (e.g., 20.5-35nm), respectively.

In another embodiment, the pore size of the aluminum oxide shaped body is unimodal as determined by mercury intrusion. The mode pore size is 4 to 30nm, preferably 10 to 25nm, more preferably 12 to 23 nm.

According to the alumina formed body of the present invention, the alumina formed body has high strength. In general, the alumina molded body according to the present invention has a radial crush strength of 10N/mm or more, preferably 12N/mm or more, and more preferably 15N/mm or more. Specifically, the hydrated alumina compact produced by the method of the present invention may have a radial crush strength of 10 to 50N/mm, preferably 15 to 35N/mm.

The methods and conditions for forming, drying and firing are the same as those described in the seventh aspect of the present invention and will not be described in detail herein.

According to the method for producing the alumina formed body of the present invention, the alumina composition can be changed

To obtain alumina shaped bodies with different pore size distributions.

In one embodiment of the invention, the hydrated alumina composition is

The value is not less than 1.8, and may be, for example, 1.8 to 5, preferably 1.85 to 4, and more preferably 1.9 to 3.5. The pore diameters of the alumina moldings produced according to this embodiment are bimodal, as determined by mercury intrusion. The mode pore size is 4-20nm (preferably 5-15nm, more preferably 6-10nm) and greater than 20nm (e.g., 20.5-35nm), respectively.

Value of less than 18, for example, may be 1.2 to less than 1.8, preferably 1.3 to 1.78, more preferably 1.4 to 1.75. The pore diameter of the aluminum oxide shaped bodies produced according to this embodiment is unimodal as determined by mercury intrusion. The mode pore size is 4 to 30nm, preferably 10 to 25nm, more preferably 12 to 23 nm.

The alumina formed body prepared by the method has higher strength. In general, the alumina molded product produced by the method of the present invention has a radial crush strength of 10N/mm or more, preferably 12N/mm or more, and more preferably 15N/mm or more. In particular, the radial crush strength of the alumina compact produced by the process of the present invention may be in the range of 10 to 50N/mm, preferably 15 to 35N/mm.

According to a tenth aspect of the present invention, there is provided a method for producing and molding hydrated alumina, as shown in fig. 2 and 3, comprising the steps of:

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

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

(3) mixing a hydrated alumina wet gel with a compound having at least two proton acceptor sites by using the method of the second aspect of the present invention to obtain a hydrated alumina composition, wherein the hydrated alumina wet gel is the first hydrated alumina wet gel or the second hydrated alumina wet gel;

wherein the method further comprises mixing Y-type molecular sieve in one, two or three of the steps (1), (2) and (3), so that the hydrated alumina composition contains Y-type molecular sieve.

The method of mixing the Y-type molecular sieve according to the method for producing the shaped article of the present invention is the same as the method and the sequence described in the second aspect of the present invention, and will not be described in detail herein.

In the step (1), the hydrated alumina gel solution is a hydrated alumina gel-containing solution which is obtained by a hydrated alumina gel synthesis reaction and is aged or not aged. The hydrated alumina gel solution can be prepared on site or transported from other production sites. Preferably, the hydrated alumina gel solution is a hydrated alumina wet gel solution prepared in situ. The synthesis method and conditions of the hydrated alumina gel have been described in detail above and will not be described herein.

Because the hydrated alumina gel solution obtained by the synthesis reaction has acidity and alkalinity, the hydrated alumina wet gel is washed in the step (1) to remove acidic substances and alkaline substances in the hydrated alumina wet gel, so that the adverse effect of the presence of the acidic substances and the alkaline substances on the hydrated alumina gel is avoided, and meanwhile, the solid content of the hydrated alumina gel solution is increased. The washing in step (1) may be carried out under conventional conditions as long as the amounts of acidic substances and basic substances in the hydrated alumina gel solution can be reduced to meet the usual requirements.

In step (1), solid-liquid separation is also involved in the washing process to squeeze out the wash water to give a first hydrated alumina wet gel. The i value of the first hydrated alumina wet gel may be a value satisfying the i value of the hydrated alumina wet gel mixed with a compound having at least two proton acceptor sites according to the second aspect of the present invention, or may be higher than the i value of the hydrated alumina wet gel mixed with a compound having at least two proton acceptor sites according to the second aspect of the present invention.

In one embodiment, the first hydrated alumina wet gel has an i value which satisfies the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites according to the second aspect of the present invention, that is, the i value of the first hydrated alumina wet gel is not less than 50%, preferably not less than 55%, more preferably not less than 60%, and still more preferably not less than 62%. In this embodiment, the first hydrated alumina wet gel preferably has an i value of not higher than 95%, more preferably not higher than 90%, still more preferably not higher than 85%, and still more preferably not higher than 82%. In one example, the first hydrated alumina wet gel has an i value of 50 to 95%, such as 50 to 90%. In a more preferred embodiment, the first hydrated alumina wet gel has an i value of 60 to 90%, more preferably 60 to 85%, still more preferably 62 to 82%.

According to this embodiment, the first hydrated alumina wet gel may be fed directly to step (3) to be mixed with a compound having at least two proton acceptor sites. This applies in particular to situations in which the following requirements are satisfied: (A) the solid-liquid separation equipment in the washing device has better separation capacity, and the value i of the first hydrated alumina wet gel is controlled to meet the range; (B) the washing device and the mixing device can be compactly arranged, so that the discharge of the washing device can directly enter the mixing device.

According to this embodiment, the first hydrated alumina wet gel may also be sent to step (2) for treatment with (2-1). This applies in particular to situations in which the following requirements are satisfied: (A) the solid-liquid separation equipment in the washing device has better separation capacity, and the value i of the first hydrated alumina wet gel is controlled to meet the range; (B) the washing device and the mixing device cannot be compactly arranged, so that the discharge of the washing device cannot directly enter the mixing device.

In another embodiment, the first hydrated alumina wet gel has an i value of 95% or greater and fails to meet the requirements of the second aspect of the invention for mixing with a compound having at least two proton acceptor sites. According to this embodiment, the first hydrated alumina wet gel is sent to step (2) and treated with either (2-1) or (2-2).

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

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

In (2-1), the first hydrated alumina wet gel is mixed with water and diluted to form a slurry, which can improve the transport properties of the hydrated alumina wet gel. In the step (2-1), the amount of water added is selected according to the specific transportation equipment, so that the formed slurry can meet the transportation requirement.

The second hydrated alumina wet gel obtained in the step (2) has an i value satisfying the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites according to the second aspect of the present invention, that is, the i value of the hydrated alumina wet gel is not less than 50%, preferably not less than 60%, and more preferably not less than 62%. The second hydrated alumina wet gel preferably has an i value of not higher than 95%, more preferably not higher than 90%, further preferably not higher than 85%, further preferably not higher than 82%. In one embodiment, the second hydrated alumina wet gel has an i value of 50 to 95%, such as 50 to 90%. In a more preferred embodiment, the second hydrated alumina wet gel has an i value of 60 to 90%, more preferably 60 to 85%, still more preferably 62 to 82%.

The second hydrated alumina wet gel having an i value satisfying the above requirements can be obtained by controlling the conditions of the solid-liquid separation in the step (2). The method for adjusting the i value of the hydrated alumina wet gel by selecting the solid-liquid separation method and the conditions thereof has been described in detail above and will not be described in detail herein.

As shown in fig. 2 and 3, at least a portion of the Y-type molecular sieve may be mixed in step (2). When the method described in (2-1) is employed, the Y-type molecular sieve may be mixed in a dilution operation and/or a solid-liquid separation operation, as shown in FIGS. 2 and 3.

In step (3), the first hydrated alumina wet gel or the second hydrated alumina wet gel is mixed with a compound having at least two proton acceptor sites by the method according to the second aspect of the present invention to obtain a hydrated alumina composition. The i values of the first hydrated alumina wet gel and the second hydrated alumina wet gel fed to the step (3) satisfy the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites according to the second aspect of the present invention. As shown in fig. 3, at least a portion of the Y-type molecular sieve may be mixed in step (3).

In the step (3), the hydrated alumina composition can be determined based on the intended pore size distribution of the hydrated alumina molded body or the alumina molded body

This is illustrated in the method according to the fifth aspect of the invention and in the method according to the eighth aspect of the invention and will not be described in detail here.

In the step (4), the hydrated alumina composition obtained in the step (3) is molded to obtain a hydrated alumina molded product. The forming method and the shape of the formed object can refer to the description related to the forming in the fourth aspect of the present invention, and are not described herein again.

In the step (5), the hydrated alumina molded product obtained in the step (3) is dried to obtain a hydrated alumina molded product. The drying conditions for drying the shaped hydrated alumina product to obtain the shaped hydrated alumina product have been described in detail in the method of the fifth aspect of the present invention, and are not described herein again.

Depending on the type of shaped body to be expected, step (6) may or may not be carried out. In the case of performing step (6), the whole hydrated alumina compact obtained in step (5) may be fed to step (6) and calcined; the partially hydrated alumina formed body obtained in the step (5) may also be fed to the step (6), so that the hydrated alumina formed body and the alumina formed body can be simultaneously produced. The conditions for the calcination have been described in detail in the method of the seventh aspect of the present invention, and are not described herein again.

According to an eleventh aspect of the present invention, there is provided a hydrated alumina compact or an alumina compact produced by the method of the tenth aspect of the present invention.

The hydrated alumina formed body and the alumina formed body produced by the method according to the tenth aspect of the present invention have high strength. In general, the radial crush strength of the hydrated alumina compact and the alumina compact may be 10N/mm or more, preferably 12N/mm or more, and more preferably 15N/mm or more, respectively. In one example, the hydrated alumina compact and the alumina compact each have a radial crush strength of 10 to 50N/mm. In a more preferred example, the hydrated alumina compact and the alumina compact each have a radial crush strength of 15 to 35N/mm.

The tenth aspect according to the present invention may be carried out in a hydrated alumina production molding system comprising a hydrated alumina gel production unit, a solid-liquid separation and washing unit, a mixing unit, a molding unit, a drying unit and optionally a calcining unit,

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

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

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

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

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

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

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

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

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

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

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

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

The solid-liquid separation and washing unit is arranged between the hydrated alumina gel production unit and the mixing unit in terms of 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 second 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 a second solid-liquid separation subunit;

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

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

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

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

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 50% or less (preferably 55% or less, more preferably 60% or less, further 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.

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

According to a twelfth aspect of the present invention, the present invention provides the use of the hydrated alumina formed body or the alumina formed body according to the present invention as a carrier or an adsorbent.

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

According to a thirteenth aspect of the present invention, there is provided a catalyst with a hydrogenation catalytic action, the catalyst comprising a carrier, and a group VIII metal element and a group VIB metal element supported on the carrier, wherein the method further comprises preparing a hydrated alumina compact or an alumina compact as the carrier by the method according to the fifth, seventh, or tenth aspect of the present invention.

The group VIII metal element and the group VIB metal element may be various elements having a hydrogenation catalytic action commonly used in the art. Preferably, the group VIII metal element is cobalt and/or nickel, and the group VIB metal element is molybdenum and/or tungsten. The contents of the group VIII metal elements and the group VIB metal elements may be appropriately selected according to the specific application of the catalyst. For example, when the catalyst according to the present invention is used for hydrotreating a hydrocarbon oil, the content of the group VIII metal element may be 1 to 10% by weight, preferably 1.5 to 8% by weight, more preferably 2 to 6% by weight, in terms of oxide, based on the total amount of the catalyst; the group VIB metal element may be present in an amount of 5 to 50 wt.%, preferably 10 to 35 wt.%, more preferably 20 to 30 wt.%, calculated as oxide.

The catalyst having a hydrogenation catalytic action according to the invention preferably contains an organic additive which is an oxygen-containing organic compound and/or a nitrogen-containing organic compound. The oxygen-containing organic compound is preferably selected from alcohols and carboxylic acids. The nitrogen-containing organic compound is preferably selected from amines. Specific examples of the organic additive may include, but are not limited to, one or more of ethylene glycol, glycerol, polyethylene glycol (preferably having an average molecular weight of 200-.

The molar ratio of the organic additive to the sum of the group VIII and group VIB metal elements, calculated as oxides, may be from 0.03 to 2: 1, preferably 0.08 to 1.5: 1, more preferably 0.1 to 1: 1, more preferably 0.2 to 0.8: 1, more preferably 0.3 to 0.6: 1.

according to a fourteenth aspect of the present invention, the present invention provides a method for preparing a catalyst having a hydrogenation catalytic action, the method comprising loading a group VIII metal element and a group VIB metal element on a carrier, wherein the carrier is a hydrated alumina formed body and/or an alumina formed 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, which is a hydrated alumina molded body and/or an alumina molded body. In this step, the shaped bodies are produced by the process according to the invention described above.

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 thirteenth aspect of the present invention, based on the total amount of the prepared catalyst.

According to the preparation method of the catalyst with hydrogenation catalysis of the present invention, various methods commonly used in the art can be adopted to load the group VIII metal element and the group VIB metal element on the carrier, 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 VIII group metal element and the VIB group metal element can be loaded on the carrier at the same time, and the VIII group metal element and the VIB group metal element can also be loaded on the carrier in times.

The method for preparing the catalyst with hydrocatalysis according to the present invention preferably further comprises a step of loading at least one organic additive on the carrier before, during or after loading the group VIII metal element and the group VIB metal element on the carrier, wherein the organic additive and the type and loading amount thereof are described in detail in the thirteenth aspect of the present invention and are not further detailed herein. The organic additive may be supported on the carrier by a conventional method, and preferably, the organic additive is supported on the carrier by impregnation. More preferably, the carrier is contacted with an impregnation solution containing the group VIII metal element, the group VIB metal element and the organic additive, so that the group VIII metal element, the group VIB metal element and the organic additive are simultaneously loaded on the carrier.

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 100-300 ℃, preferably 100-280 ℃, and more preferably 120-250 ℃; the duration may be from 1 to 12 hours, preferably from 2 to 8 hours, more preferably from 3 to 6 hours. The roasting conditions comprise: the temperature can be 350-550 ℃, and preferably 400-500 ℃; the duration may be from 1 to 10 hours, preferably from 2 to 8 hours.

According to a fifteenth aspect of the present invention, there is provided a hydrotreating process comprising contacting, under hydrotreating conditions, a hydrocarbon oil with a catalyst having hydrocatalytic action, wherein the catalyst having hydrocatalytic action is the catalyst of the thirteenth aspect of the present invention or the catalyst prepared by the method of the fourteenth aspect of the present invention.

The hydrotreating method of the present invention is not particularly limited with respect to the kind of hydrocarbon oil and the hydrotreating conditions, and may be a routine choice in the art. Specifically, the hydrocarbon oil may be one or more selected from the group consisting of crude oil, distillate oil, solvent refined oil, cerate, under-wax oil, fischer-tropsch synthetic oil, coal liquefied oil, light deasphalted oil, and heavy deasphalted oil. Preferably, the hydrocarbon oil is diesel oil. The hydrotreating method of the invention is particularly suitable for hydrocracking hydrocarbon oil or hydro-upgrading poor diesel oil.

According to the hydrotreating process of the invention, the catalyst may be presulfided under conditions conventional in the art before use. The presulfiding conditions can be, for example, presulfiding with sulfur, hydrogen sulfide or a sulfur-containing feedstock in the presence of hydrogen at a temperature of 140 ℃ and 370 ℃, either outside the reactor or in situ within the reactor.

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

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

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

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

The value of the one or more of,

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

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

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

Examples 1 to 11 are intended to illustrate the hydrated alumina composition, the shaped body and the process for producing the same of the present invention.

Example 1

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

(1) To 50kg of the wet cake S L B-1 was added 5.48kg of Y type molecular sieve (available from China petrochemical catalyst Chang Ling division, Inc., having a unit cell constant of

Dry basis is 0.75, and sodium oxide content is less than0.8 percent BY weight), then 10kg of water is added for mixing and pulping for 5 minutes, then the slurry is filtered BY a belt filter to obtain a wet filter cake S L BY-1, the i value of the wet filter cake S L BY-1 is determined to be 80.2 percent, and the weight ratio of the alumina to the Y-type molecular sieve is determined to be 65: 35 after the wet filter cake S L BY-1 is roasted at 600 ℃ for 3 hours.

(2) 200g of the wet cake numbered S L BY-1 was placed in a beaker, then 5g of methylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd., the same applies hereinafter) and 3g of sesbania powder (having a galactomannan content of 80% BY weight, purchased from Beijing chemical Co., Ltd.) were added and stirred for 10 minutes using a mechanical stirrer, and the resulting mixture was the hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(3) And (3) extruding the hydrated alumina composition prepared in the step (2) into strips on an F-26 type double-screw extruder (general factory of science and technology industry of southern China university, the same below) by using a disc-shaped orifice plate with the diameter of 1.6 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 strands having a length of about 6mm, and the wet strands were dried at 120 ℃ for 3 hours in an air atmosphere to give hydrated alumina moldings HT-1, the property parameters of which are shown in Table 1.

(5) And (3) roasting the alumina hydrate formed body prepared in the step (4) at 580 ℃ for 4 hours in an air atmosphere to obtain an alumina formed body OT-1, wherein the property parameters are listed in Table 1.

Comparative example 1

(1) 100kg of wet filter cake with the serial number of S L B-1 is subjected to spray drying to obtain pseudo-boehmite dry glue powder, the dry basis of the pseudo-boehmite dry glue powder is 0.7, the pseudo-boehmite powder is placed for 72 hours at the ambient temperature (25-30 ℃) under a closed condition (placed in a sealed plastic bag), and alumina trihydrate is not detected to be formed after the placement.

(2) 300g of the pseudo-boehmite dry glue powder prepared in the step (1), 150g Y type molecular sieve (same as in example 1) (the weight ratio of alumina to Y type molecular sieve is 65: 35), 5.4g of methylcellulose (same as in example 1), 3.3g of sesbania powder (same as in example 1), and 400m L of an aqueous solution containing 11m L concentration of 65 wt% concentrated nitric acid were stirred for 10 minutes by a mechanical stirrer to obtain a mixture.

(3) The mixture prepared in step (2) was extruded in the same manner as in example 1 to prepare a hydrated alumina formed body DHT-1 and an alumina formed body DOT-1, respectively, the properties of which are shown in Table 1.

Example 2

(1) 5kg of the wet filter cake numbered S L BY-1 was mixed with 500g of deionized water and beaten for 1 minute, and then 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 to obtain a wet filter cake numbered L BY-1. the i value of the wet filter cake numbered L BY-1 was determined to be 64%.

(2) 300g of the wet cake numbered L BY-1 was placed in a beaker, 4.3g of hydroxyethyl methylcellulose (purchased from Shanghai Huikang Fine chemical Co., Ltd., the same below) and 1.7g of sesbania powder (having a galactomannan content of 85% BY weight, purchased from Beijing chemical Co., Ltd.) were added, and after stirring for 10 minutes with a mechanical stirrer, the hydrated alumina composition of the present invention was obtained, the properties of which are shown in Table 1.

(3) And (3) extruding the hydrated alumina composition prepared in the step (2) on an F-26 type double-screw extruder by using a round orifice plate with the phi of 2.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.

(4) The extrudate was cut into wet strands having a length of about 6mm, and the wet strands were dried at 150 ℃ for 2 hours in an air atmosphere to give hydrated alumina moldings HT-2, the property parameters of which are shown in Table 1.

(5) And (3) roasting the hydrated alumina forming body prepared in the step (4) at 480 ℃ for 8 hours in an air atmosphere to obtain an alumina forming body OT-2, wherein the property parameters are listed in Table 1.

Example 3

A molded body was produced in the same manner as in example 2, except that sesbania powder was not used in the step (2) and the amount of hydroxyethyl methylcellulose was 5.8g, and properties of the produced hydrated alumina composition, the hydrated alumina molded body HT-3 and the alumina molded body OT-3 were as shown in Table 1.

Example 4

A molded body was produced in the same manner as in example 2, except that hydroxyethyl methylcellulose was not used in step (2) and that sesbania powder was used in an amount of 6.8g, and properties of the produced hydrated alumina composition, the hydrated alumina molded body HT-4 and the alumina molded body OT-4 were as shown in Table 1.

Example 5

A molded body was produced in the same manner as in example 2, except that in the step (2), 2.8g of nitric acid (HNO) was further added to the mixture of hydroxyethyl methylcellulose and sesbania powder₃Content of 65 wt%), properties of the prepared hydrated alumina composition, hydrated alumina molded body HT-5 and alumina molded body OT-5 are listed in Table 1.

Comparative example 2

(1) 300g of the wet filter cake numbered L BY-1 was dried at 95 ℃ for 2 hours in an air atmosphere to obtain pseudo-boehmite powder having an i value of 40%, which was left to stand at ambient temperature (25-30 ℃) under a closed condition (in a sealed plastic bag) for 72 hours, and no formation of alumina trihydrate was detected after standing.

(2) 180g of the pseudo-boehmite powder prepared in the step (1) was put in a beaker, 4.3g of hydroxyethyl methyl cellulose (same as in example 2) and 1.7g of sesbania powder (same as in example 2) were added, and after stirring for 10 minutes with a mechanical stirrer, a pseudo-boehmite composition was obtained.

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

(4) The extrudate was cut into wet strands having a length of about 6mm, and the wet strands were dried at 150 ℃ for 2 hours in an air atmosphere to give DHT-2 as a hydrated alumina molded body, the property parameters of which are shown in Table 1.

(5) And (3) roasting the hydrated alumina forming body prepared in the step (4) at 480 ℃ for 8 hours in an air atmosphere to obtain an alumina forming body DOT-2, wherein the property parameters of the alumina forming body DOT-2 are listed in Table 1.

Comparative example 3

The molding was carried out in the same manner as in comparative example 2, except that the pseudo boehmite powder prepared in step (1) was directly fed to the step (3) for bar extrusion without carrying out the step (2). 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. The prepared hydrated alumina forming body is marked as DHT-3, the prepared alumina forming body is marked as DOT-3, and the property parameters are respectively listed in Table 1.

Comparative example 4

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

Comparative example 5

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

Example 6

(1) 300g of the wet cake numbered L BY-1 was placed in a beaker, and 2.8g of hydroxypropylmethylcellulose (available from Haishi chemical Co., Zhejiang, the same applies hereinafter) and 3.7g 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 hydrated alumina composition of the present invention, the properties of which are shown in Table 1.

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

(3) The extrudate was cut into wet strands having a length of about 5mm, and the wet strands were dried at 70 ℃ for 3 hours in an air atmosphere and then at 100 ℃ for 2 hours in an air atmosphere to obtain a hydrated alumina molded article HT-6, the property parameters of which are shown in Table 1.

(4) And (3) roasting the alumina hydrate formed body prepared in the step (4) at 650 ℃ for 3 hours in an air atmosphere to obtain an alumina formed body OT-6, wherein the property parameters are listed in Table 1.

Example 7

(1) 300g of the wet cake numbered L BY-1 were placed in a beaker and 2.5g of methylcellulose, 1.2g of hydroxypropyl methylcellulose and 4g of sesbania powder (galactomannan content 85% BY weight) were added and after stirring for 10 minutes with a mechanical stirrer, the hydrated alumina composition of the present invention was obtained with the property parameters listed in Table 1.

(2) Extruding the hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a clover-shaped orifice plate with the phi of 3.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.

(3) The extrudate was cut into wet strands having a length of about 8mm, and the wet strands were dried at 120 ℃ for 3 hours in an air atmosphere to give hydrated alumina moldings HT-7, the property parameters of which are shown in Table 1.

(4) And (3) roasting the alumina hydrate formed body prepared in the step (4) at 600 ℃ for 4 hours in an air atmosphere to obtain an alumina formed body OT-7, wherein the property parameters are listed in Table 1.

Example 8

(1) 300g of the wet cake numbered L BY-1 were placed in a beaker, 2.4g of hydroxyethyl methylcellulose and 1.8g of hydroxypropyl methylcellulose were added and after stirring for 10 minutes with a mechanical stirrer, a hydrated alumina composition according to the invention was obtained, the properties of which are given in Table 1.

(2) And (2) extruding the hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 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 strands having a length of about 6mm, and the wet strands were dried at 250 ℃ for 2 hours in an air atmosphere to give hydrated alumina moldings HT-8, the property parameters of which are shown in Table 1.

(4) And (3) roasting the alumina hydrate formed body prepared in the step (4) at 650 ℃ for 3 hours in an air atmosphere to obtain an alumina formed body OT-8, wherein the property parameters are listed in Table 1.

Example 9

(1) A hydrated alumina composition, a hydrated alumina molded body and an alumina molded body were prepared in the same manner as in example 2, except that in the step (1), 5kg of the wet cake numbered S L BY-1 was mixed with 650g of deionized water, 30g of methyl cellulose and 23g of sesbania powder (the content of galactomannan was 80% BY weight) and beaten for 1 minute, followed BY filter pressing to obtain a hydrated alumina composition according to the present invention.

(2) And (2) extruding the hydrated alumina composition obtained in the step (1) on an F-26 type double-screw extruder by using a butterfly-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 strands having a length of about 6mm, and the wet strands were dried at 150 ℃ for 2 hours in an air atmosphere to give hydrated alumina moldings HT-9, the property parameters of which are shown in Table 1.

(4) And (3) roasting the alumina hydrate formed body prepared in the step (3) at 600 ℃ for 3 hours in an air atmosphere to obtain an alumina formed body OT-9, wherein the property parameters are listed in Table 1.

Example 10

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

(1) To 1kg of the wet cake S L B-2 was added 0.054kg of Y type molecular sieve (purchased from Changling division of petrochemical catalyst, China, having a unit cell constant of

Dry basis 0.50, sodium oxide content less than 0.8 wt%), then 0.5kg of water was added, mixed and beaten for 10 minutes, and the slurry was filtered with a belt filter to give 1.12kg of wet cake S L BY-2The i value of the filter cake S L BY-2 was 62.6%, and the weight ratio of alumina to Y-type molecular sieve was determined to be 90: 10 after calcining the wet filter cake S L BY-2 at 600 ℃ for 3 hours.

(2) 1.10kg of the wet cake numbered S L BY-2 was placed in a beaker, followed BY the addition of 16g of methylcellulose and 20g of sesbania powder (galactomannan content 80% BY weight), and after stirring for 10 minutes using a mechanical stirrer, the resulting mixture was a hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(2) And (2) extruding the hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the 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 strands having a length of about 6mm, and the wet strands were dried at 130 ℃ for 2 hours in an air atmosphere to give hydrated alumina moldings HT-10, the property parameters of which are shown in Table 1.

(4) And (3) roasting the alumina hydrate formed body prepared in the step (3) at 550 ℃ for 3 hours in an air atmosphere to obtain an alumina formed body OT-10, wherein the property parameters are listed in Table 1.

Example 11

The hydrated alumina wet gel used in this example is obtained from Shandong Zibo zimao catalyst Co., Ltd, 1000g of a dry pseudo-boehmite powder (dry basis is 70 wt%) prepared by an acid process (sodium aluminate-aluminum sulfate process) is calcined at 700 ℃ for 3 hours in an air atmosphere to obtain 700g of alumina, 700g of alumina is placed in a 10L high-pressure reaction vessel, and is uniformly stirred with 5L deionized water, the high-pressure reaction vessel is sealed, and is reacted at 150 ℃ under the self-pressure for 6 hours, after the reaction is finished, the temperature of the high-pressure reaction vessel is reduced to room temperature (25 ℃), the slurry obtained by the reaction is sent to a plate and frame filter press, the plate and frame pressure of the plate and frame filter is adjusted to 0.5MPa and kept for 10 minutes, then, a filter cake in the plate and frame is blown by 10MPa of compressed air for 3 minutes, the plate and frame is decompressed to obtain a hydrated alumina wet filter cake L B-3.

(1) To 825g of wet cake L B-3 was added 0.43kg of Y-type molecular sieve (available from China)Long ridge division of petrochemical catalyst having a unit cell constant of

Dry basis is 0.75), then 0.5kg of water is added to mix and pulp for 10 minutes, then the slurry is filtered BY a belt filter to obtain 1.12kg of wet filter cake S L BY-3, the i value of the wet filter cake S L BY-3 is determined to be 66.8%, and the weight ratio of alumina to the Y-type molecular sieve is determined to be 40: 60 after the wet filter cake S L BY-3 is roasted at 600 ℃ for 3 hours.

(2) 300g of the wet cake numbered S L BY-3 were placed in a beaker, and then 3.2g of methylcellulose and 5g of sesbania powder (85% BY weight content of galactomannan) were added and after stirring for 10 minutes with a mechanical stirrer, the resulting mixture was a hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

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

(4) The extrudate was cut into wet strands having a length of about 6mm, and the wet strands were dried at 150 ℃ for 2 hours in an air atmosphere to give hydrated alumina moldings HT-11, the property parameters of which are shown in Table 1.

(5) And (3) roasting the alumina hydrate formed body prepared in the step (3) at 600 ℃ for 4 hours in an air atmosphere to obtain an alumina formed body OT-11, wherein the property parameters are listed in Table 1.

Comparative example 6

The wet alumina hydrate cake L B-3 prepared in example 11 was spray dried to give a powder of pseudoboehmite dry glue (dry basis 0.7). The powder was allowed to stand at ambient temperature (25-30 ℃ C.) in a closed condition (in a sealed plastic bag) for 72 hours, after which no formation of alumina trihydrate was detected.

300g of the dry powder of the pseudo-boehmite and the 420g Y type molecular sieve (same as example 11) (the weight ratio of the alumina to the Y type molecular sieve is 40: 60), 3.6g of the methylcellulose (same as example 11), 5.7g of the sesbania powder (same as example 11), and 400m L of an aqueous solution containing 11m L concentration of 65 wt% of concentrated nitric acid were stirred for 10 minutes by a mechanical stirrer to obtain a mixture.

The prepared mixture was extruded in the same manner as in example 11 to prepare a hydrated alumina molded body DHT-4 and an alumina molded body DOT-4, respectively, having the property parameters shown in Table 1.

Comparative example 7

The wet cake S L BY-3 prepared in the same manner as in step (1) of example 11 was extruded in the same manner as in steps (3) and (4) of example 11, and as a result, extrusion molding could not be performed.

TABLE 1

¹: the composition after standing at ambient temperature (25-30 ℃) and under closed conditions (in a sealed plastic bag) for 72 hours had an alumina trihydrate content and an increase in the alumina trihydrate content over that before standing.

The results of examples 1-11 demonstrate that the present invention mixes wet hydrated alumina gel directly with a compound having at least two proton acceptor sites without drying the wet hydrated alumina gel to form dry gel powder, the resulting mixture can be used directly for molding, and the resulting molded article has high strength, thereby avoiding the problems of harsh working environment and high energy consumption of the conventional process for preparing molded articles from dry gel powder as a starting material. And, according to the hydrated alumina composition of the present invention, by adjusting it

The pore diameter can be prepared into a bimodal distribution or a unimodal distribution, thereby meeting the requirements of different application occasions.

Experimental examples 1 to 8 are intended to illustrate the catalyst having a hydrogenation catalytic action according to the present invention, the preparation method thereof and the hydrotreating method.

Experimental example 1

Ammonium metatungstate, nickel nitrate and citric acid were dissolved in deionized water at a temperature of 25 ℃ to form an impregnation solution, 100g of the alumina compact prepared in example 1 was impregnated by a saturation impregnation method for 1 hour, and the impregnated mixture was dried at 120 ℃ for 2 hours, followed by drying at 150 ℃ for 3 hours to obtain catalyst OC-1. Wherein, in the impregnation liquid, the molar ratio of the citric acid to the tungsten and the nickel calculated by oxides is 0.3. The composition of the prepared catalyst OC-1 was measured after calcination at 600 ℃ for 4 hours, and the results are shown in Table 2.

Experimental comparative example 1

A catalyst was prepared in the same manner as in experimental example 1, except that the alumina formed body was the alumina formed body prepared in comparative example 1. The catalyst prepared was designated DOC-1 and its composition is set forth in Table 2.

Experimental example 2

Ammonium metatungstate, nickel nitrate and ethylenediamine were dissolved in deionized water at a temperature of 30 ℃ to form an impregnation solution, 100g of the alumina molded body prepared in example 2 was impregnated by a saturation impregnation method for 1 hour, and the impregnated mixture was dried at 120 ℃ for 2 hours and then at 180 ℃ for 3 hours to obtain catalyst OC-2. Wherein, in the impregnating solution, the molar ratio of the ethylenediamine to the tungsten and the nickel calculated by the oxide is 0.48. The composition of the prepared catalyst OC-2 was measured after calcination at 600 ℃ for 4 hours, and the results are 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 was the alumina formed body prepared in example 3. The catalyst prepared was designated as OC-3 and its composition is listed 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 was the alumina formed body prepared in example 4. The catalyst prepared was designated as OC-4 and its composition is listed in table 2.

Experimental example 5

A catalyst was prepared in the same manner as in experimental example 2, except that the alumina formed body was the alumina formed body prepared in example 5. The catalyst prepared was designated as OC-5 and its composition is listed in table 2.

Experimental example 6

Ammonium metatungstate, ammonium molybdate, nickel nitrate and citric acid were dissolved in deionized water at a temperature of 35 ℃ to form an impregnation solution, 100g of the alumina compact prepared in example 11 was impregnated by a saturation impregnation method for 1 hour, and the impregnated mixture was dried at 120 ℃ for 2 hours and then at 180 ℃ for 3 hours to obtain catalyst OC-6. Wherein, in the impregnation liquid, the molar ratio of citric acid to molybdenum, nickel and tungsten calculated by oxides is 0.36. The composition of the prepared catalyst OC-6 was measured after calcination at 600 ℃ for 4 hours, and the results are shown in Table 2.

Experimental comparative example 2

A catalyst was prepared in the same manner as in experimental example 6, except that the alumina formed body was the alumina formed body prepared in comparative example 6. The catalyst prepared was designated DOC-2 and its composition is set forth in Table 2.

Experimental example 7

A catalyst was prepared in the same manner as in experimental example 1, except that the alumina molded body was replaced with the hydrated alumina molded body prepared in example 1. The catalyst prepared was designated HC-1 and its composition is given in Table 2.

Experimental comparative example 3

The catalyst was prepared in the same manner as in experimental comparative example 1 except that the alumina molded body was replaced with the hydrated alumina molded body prepared in comparative example 1. As a result, the structure of the hydrated alumina molded body collapses during impregnation, and a molded catalyst cannot be produced.

Experimental example 8

A catalyst was prepared in the same manner as in experimental example 6, except that the alumina molded body was replaced with the hydrated alumina molded body prepared in example 11. The catalyst prepared was designated HC-2 and its composition is given in Table 2.

Experimental comparative example 4

The catalyst was prepared in the same manner as in experimental comparative example 2 except that the alumina molded body was replaced with the hydrated alumina molded body prepared in comparative example 6. As a result, the structure of the hydrated alumina molded body collapses during impregnation, and a molded catalyst cannot be produced.

TABLE 2

Test examples 1-8 are intended to illustrate the hydrotreating process according to the invention.

Test examples 1 to 8

The catalysts prepared in experimental examples 1 to 8 were evaluated for their catalytic performance by the following methods, and the results are shown in Table 3.

The catalytic performance of the catalysts prepared in experimental examples 1-8 in the reaction of tetrahydronaphthalene was respectively determined on a miniature fixed bed reactor using tetrahydronaphthalene with a purity of 99 wt% as a raw material (analytical purity), wherein the loading of the catalyst was 1.4g, the pressure was 4.0MPa (gauge pressure), and the space velocity was 4.5h^-1。

Wherein the conversion rate is the conversion rate of tetrahydronaphthalene when the reaction is carried out at the temperature of 370 ℃, and is calculated by adopting a formula IV:

in the formula IV, C is the conversion rate of tetrahydronaphthalene,

m₁is the mass fraction of tetrahydronaphthalene in the raw material,

m₂is the mass fraction of tetrahydronaphthalene in the product;

the ring-opening product selectivity is calculated by adopting a formula V that the reaction is carried out under the condition that the conversion rate of tetrahydronaphthalene is 35 percent:

in the formula V, m₃Is C of one ring in the product₁₀Hydrocarbons and C₁₀The total mass fraction of paraffins is,

c is the conversion rate of tetrahydronaphthalene;

relative ring-opened product selectivity was calculated based on the catalyst prepared in experimental comparative example 2.

Testing of comparative examples 1-2

The catalysts prepared in experimental comparative examples 1-2 were evaluated for their catalytic performance in the same manner as in test examples 1-8, respectively, and the results of the experiments are shown in Table 3.

TABLE 3

Numbering	Catalyst numbering	Relative conversion (%)	Relative selectivity (%)
				Test example 1	OC-1	37	143
Test comparative example 1	DOC-1	29	128
				Test example 2	OC-2	35	148
Test example 3	OC-3	33	139
				Test example 4	OC-4	32	140
Test example 5	OC-5	32	138
				Test example 6	OC-6	48	112
Test comparative example 2	DOC-2	41	100
				Test example 7	HC-1	39	146
Test example 8	HC-2	50	113

The results of test examples 1 to 8 confirmed that the catalysts prepared with the hydrated alumina molded bodies and the alumina molded bodies according to the present invention as a carrier exhibited higher catalytic activity in hydrotreating of hydrocarbon oil.

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

Claims

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

(1) providing a hydrated alumina gel solution, and washing and carrying out solid-liquid separation on the hydrated alumina gel solution to obtain a first hydrated alumina wet gel, wherein the solid-liquid separation condition is that the i value of the first hydrated alumina wet gel is not less than 50%, and the hydrated alumina gel solution is prepared by one or more than two methods of a precipitation method, a hydrolysis method, a seed precipitation method and a rapid dehydration method, and is aged or not aged;

(2) mixing the first hydrated alumina wet gel with a compound having at least two proton acceptor sites selected from dextran to obtain a hydrated alumina compositionOne or more of galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, said compound having at least two proton acceptor sites being used in an amount to provide a composition which is ultimately prepared

A value of 1.2 or more and 5 or less,

the above-mentioned

The value of the one or more of,

wherein the method comprises mixing Y-type molecular sieve in step (1) and/or step (2) so that the hydrated alumina composition contains Y-type molecular sieve.

2. The process of claim 1, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not less than 55%.

3. The method of claim 2, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not less than 60%.

4. The method of claim 3, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not less than 62%.

5. The method of claim 1, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not greater than 95%.

6. The method of claim 5, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of no more than 90%.

7. The method of claim 6, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not greater than 85%.

8. The method of claim 7, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of no greater than 82%.

9. The method of claim 1, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of 50-95%.

10. The method of claim 9, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of 50-90%.

11. The method of claim 10, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of 60-90%.

12. The method of claim 11, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of 60-85%.

13. The method of claim 12, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of 62-82%.

14. The method of any of claims 1-13, wherein the first 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 50% or less.

15. The method of claim 14, wherein the first 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 55% or less.

16. The method of claim 15, wherein the first 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.

17. The method of claim 16, wherein the first 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 62% or less.

18. The method according to any one of claims 1-13, 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.

19. The method of claim 1, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 4 or less.

20. The method of claim 19, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 3.5 or less.

21. The method of claim 1, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.3 or more.

22. The method of claim 21, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.4 or more.

23. The method of claim 1, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.2-4.

24. The method of claim 23, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.3-4.

25. According to claim24, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.4-3.5.

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

27. The process of claim 1, wherein the amount of Y-type molecular sieve in the raw material mixture is such that the total amount of Y-type molecular sieve is 0.5 to 90 wt% and the amount of alumina is 10 to 99.5 wt% based on the total amount of the calcined hydrated alumina composition, the calcination is carried out at a temperature of 600 ℃ and the duration of the calcination is 3 hours.

28. The process of claim 27, wherein the amount of Y-type molecular sieve in the feed mixture is such that the total amount of Y-type molecular sieve is from 1 to 80 wt% and the amount of alumina is from 20 to 99 wt% based on the total amount of calcined hydrated alumina composition, and the calcination is carried out at a temperature of 600 ℃ and the duration of calcination is 3 hours.

29. The process of claim 28, wherein the amount of Y-type molecular sieve in the feed mixture is such that the total amount of Y-type molecular sieve is 5 to 70 wt% and the amount of alumina is 30 to 95 wt% based on the total amount of calcined hydrated alumina composition, and the calcination is carried out at a temperature of 600 ℃ and the duration of calcination is 3 hours.

30. The process of claim 29, wherein the amount of Y-type molecular sieve in the feed mixture is such that the total amount of Y-type molecular sieve is 10 to 60 wt% and the amount of alumina is 40 to 90 wt% based on the total amount of calcined hydrated alumina composition, and the calcination is carried out at a temperature of 600 ℃ and the duration of calcination is 3 hours.

31. The method according to claim 1, wherein the compound having at least two proton acceptor sites is contained in the raw material mixture in an amount of 1 to 25 parts by weight relative to 100 parts by weight of a first hydrated alumina wet gel calculated on the basis of hydrated alumina.

32. The method of claim 31, wherein the compound having at least two proton acceptor sites is present in the feed mixture in an amount of 2 to 22 parts by weight relative to 100 parts by weight of the first hydrated alumina wet gel, the first hydrated alumina wet gel being based on hydrated alumina.

33. The method of claim 32, wherein the compound having at least two proton acceptor sites is present in the feed mixture in an amount of 4 to 20 parts by weight per 100 parts by weight of the first hydrated alumina wet gel, the first hydrated alumina wet gel being based on hydrated alumina.

34. The method of any one of claims 1, 19-25, and 31-33, 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.

35. The method of claim 34, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.

36. The method of any one of claims 1, 19-25, and 31-33, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.

37. The method of claim 36, wherein the galactomannan is present in an amount of 10 to 80 wt% and the cellulose ether is present in an amount of 20 to 90 wt%, based on the total amount of the compound having at least two proton acceptor sites.

38. The method of claim 37, wherein the galactomannan is present in an amount of 15 to 70 wt% and the cellulose ether is present in an amount of 30 to 85 wt%, based on the total amount of the compound having at least two proton acceptor sites.

39. The method of claim 38, wherein the galactomannan is present in an amount of 20 to 60 wt% and the cellulose ether is present in an amount of 40 to 80 wt%, based on the total amount of the compound having at least two proton acceptor sites.

40. The method according to claim 1, wherein in the step (2), the mixing is performed by stirring and/or kneading.

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

(1) providing a hydrated alumina gel solution, washing the hydrated alumina gel solution to obtain a first hydrated alumina wet gel, wherein the hydrated alumina gel solution is prepared by one or more methods of a precipitation method, a hydrolysis method, a seed precipitation method and a rapid dehydration method after aging or not aging;

(3) mixing a second hydrated alumina wet gel with a compound having at least two proton acceptor sites, wherein the compound having at least two proton acceptor sites is one or more selected from the group consisting of glucan, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, the i value of the hydrated alumina wet gel is not less than 50%, and the compound having at least two proton acceptor sites is used in an amount such that the composition finally prepared is

A value of 1.2 or more and 5 or less,

the above-mentioned

The value of the one or more of,

wherein the method comprises mixing Y-type molecular sieves in one, two or three of step (1), step (2) and step (3) such that the hydrated alumina composition contains Y-type molecular sieves.

42. A process as claimed in claim 41, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not less than 55%.

43. A process as claimed in claim 42, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not less than 60%.

44. The process according to claim 43, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not less than 62%.

45. The process of claim 41, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not more than 95%.

46. The process of claim 45, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not more than 90%.

47. The process of claim 46, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not more than 85%.

48. The process of claim 47, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not higher than 82%.

49. The method of claim 41, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 50-95%.

50. The method of claim 49, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 50-90%.

51. The method of claim 50, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 60-90%.

52. The method of claim 51, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 60-85%.

53. The method of claim 52, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 62-82%.

54. The method of any of claims 41-53, wherein the second 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 50% or less.

55. The method of claim 54, wherein the second 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 55% or less.

56. The method of claim 55, wherein the second 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.

57. The method of claim 56, wherein the second 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 62% or less.

58. The process according to any one of claims 41 to 53, wherein the solid-liquid separation is carried out one or more times, at least the last solid-liquid separation being pressure filtration and/or vacuum filtration.

59. The method of claim 41, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 4 or less.

60. The method of claim 59, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 3.5 or less.

61. The method of claim 41, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.3 or more.

62. The method of claim 61, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.4 or more.

63. The method of claim 41, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.2-4.

64. The method of claim 63, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.3-4.

65. The method of claim 64, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.4-3.5.

66. The method of claim 41, wherein the hydrated alumina composition is free of peptizing agents.

67. The process of claim 41, wherein the amount of Y-type molecular sieve in the feed mixture is such that the total amount of Y-type molecular sieve is from 0.5 to 90 wt% and the amount of alumina is from 10 to 99.5 wt% based on the total amount of calcined hydrated alumina composition, and the calcination is carried out at a temperature of 600 ℃ and the duration of calcination is 3 hours.

68. The process of claim 67, wherein the amount of Y-type molecular sieve in the feed mixture is such that the total amount of Y-type molecular sieve is from 1 to 80 wt.% and the amount of alumina is from 20 to 99 wt.% based on the total amount of calcined hydrated alumina composition, and wherein the calcination is carried out at a temperature of 600 ℃ and the duration of calcination is 3 hours.

69. The process of claim 68, wherein the amount of Y-type molecular sieve in the feed mixture is such that the total amount of Y-type molecular sieve is 5-70 wt% and the amount of alumina is 30-95 wt% based on the total amount of calcined hydrated alumina composition, and wherein the calcination is carried out at a temperature of 600 ℃ and the duration of calcination is 3 hours.

70. The process of claim 69, wherein the amount of Y-type molecular sieve in the feed mixture is such that the total amount of Y-type molecular sieve is 10-60 wt.% and the amount of alumina is 40-90 wt.% based on the total amount of calcined hydrated alumina composition, and wherein the calcination is carried out at a temperature of 600 ℃ and the duration of calcination is 3 hours.

71. A process as claimed in claim 41, in which the compound having at least two proton acceptor sites is present in the feed mixture in an amount of 1 to 25 parts by weight per 100 parts by weight of the wet gel of second hydrated alumina calculated as hydrated alumina.

72. A process as claimed in claim 71, in which the compound having at least two proton acceptor sites is present in the feed mixture in an amount of from 2 to 22 parts by weight per 100 parts by weight of the wet gel of second hydrated alumina calculated as hydrated alumina.

73. A process as claimed in claim 72, in which the compound having at least two proton acceptor sites is present in the feed mixture in an amount of from 4 to 20 parts by weight per 100 parts by weight of the wet gel of second hydrated alumina calculated as hydrated alumina.

74. The method of any one of claims 41, 59-65, and 71-73, wherein the compound having at least two proton acceptor sites is one or more of a galactan, mannan, galactomannan, and cellulose ether.

75. The method of claim 74, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.

76. The method of any one of claims 41, 59-65, and 71-73, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.

77. The method of claim 76, wherein the galactomannan is present in an amount of 10 to 80 wt.% and the cellulose ether is present in an amount of 20 to 90 wt.%, based on the total amount of the compound having at least two proton acceptor sites.

78. The method of claim 77, wherein the galactomannan is present in an amount of 15 to 70 wt.% and the cellulose ether is present in an amount of 30 to 85 wt.%, based on the total amount of the compound having at least two proton acceptor sites.

79. The method of claim 78, wherein the galactomannan is present in an amount of 20 to 60 wt.% and the cellulose ether is present in an amount of 40 to 80 wt.%, based on the total amount of the compound having at least two proton acceptor sites.

80. The method according to claim 41, wherein in the step (3), the mixing is performed by stirring and/or kneading.

81. A shaped body produced by the method of any one of claims 1 to 80.

82. The shaped body of claim 81, wherein the shaped body has a radial crush strength of from 10 to 50N/mm.

83. The shaped body of claim 82, wherein the shaped body has a radial crush strength of 15-35N/mm.

84. Use of the shaped bodies according to any of claims 81 to 83 as supports or adsorbents.

85. The use according to claim 84, wherein the support is a support for a supported catalyst.

86. The use according to claim 85, wherein the support is a support for a supported hydrogenation catalyst.

87. A catalyst with hydrogenation catalysis effect, which comprises a carrier and a VIII group metal element and a VIB group metal element loaded on the carrier, wherein the carrier is the formed body of any one of claims 81-83.

88. The catalyst of claim 87, wherein the group VIII metal element is present in an amount ranging from 1 to 10 wt.% in terms of oxides and the group VIB metal element is present in an amount ranging from 5 to 50 wt.% in terms of oxides, based on the total amount of the catalyst.

89. The catalyst of claim 88, wherein the group VIII metal element is present in an amount of from 1.5 to 8 wt.% on an oxide basis and the group VIB metal element is present in an amount of from 10 to 35 wt.% on an oxide basis, based on the total amount of the catalyst.

90. The catalyst of claim 89, wherein the group VIII metal element is present in an amount of 2 to 6 wt.% as oxide and the group VIB metal element is present in an amount of 20 to 30 wt.% as oxide, based on the total amount of the catalyst.

91. A method for preparing a catalyst having a hydrocatalytic effect, which comprises loading a group VIII metal element and a group VIB metal element on a carrier, wherein the method further comprises preparing a hydrated alumina compact or an alumina compact as a carrier by the method of any one of claims 1 to 80.

92. The preparation method of claim 91, wherein the loading amounts of the group VIII metal element-containing compound and the group VIB metal element-containing compound on the carrier are such that the group VIII metal element content is 1-10 wt% in terms of oxide and the group VIB metal element content is 5-50 wt% in terms of oxide, based on the total amount of the finally prepared catalyst.

93. The preparation method of claim 92, wherein the loading amounts of the group VIII metal element-containing compound and the group VIB metal element-containing compound on the carrier are such that the group VIII metal element content is 1.5-8 wt% in terms of oxide and the group VIB metal element content is 10-35 wt% in terms of oxide, based on the total amount of the finally prepared catalyst.

94. The preparation method of claim 93, wherein the loading amounts of the group VIII metal element-containing compound and the group VIB metal element-containing compound on the carrier are such that the group VIII metal element content is 2 to 6 wt% in terms of oxide and the group VIB metal element content is 20 to 30 wt% in terms of oxide, based on the total amount of the finally prepared catalyst.

95. A hydroprocessing method comprising contacting, under hydroprocessing conditions, a hydrocarbon oil with a catalyst having a hydrocatalytic effect, wherein the catalyst having a hydrocatalytic effect is a catalyst according to any of claims 87-90 or a catalyst prepared by a method according to any of claims 91-94.