CN108014825B

CN108014825B - Halogen-containing hydrated alumina composition, molded body and preparation method thereof, and catalyst and preparation method thereof

Info

Publication number: CN108014825B
Application number: CN201610975843.2A
Authority: CN
Inventors: 赵新强; 杨清河; 曾双亲; 贾燕子; 邵志才; 陈文斌
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-10-28
Filing date: 2016-10-28
Publication date: 2020-06-16
Anticipated expiration: 2036-10-28
Also published as: CN108014825A

Abstract

The invention discloses a halogen-containing hydrated alumina composition and a preparation method thereof, and a formed body and a preparation method and application thereof

The value is less than 1.8. 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 halogen-containing 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 and avoids the dust pollution caused by adopting the pseudoboehmite dry glue powder as the raw material. The catalyst prepared by using the molded body formed by the hydrated oxide composition as a carrier shows higher catalytic activity in the hydrotreatment of hydrocarbon oil.

Description

Halogen-containing hydrated alumina composition, molded body and preparation method thereof, and catalyst and preparation method thereof

Technical Field

The invention relates to the technical field of alumina forming, in particular to a halogen-containing hydrated alumina composition and a preparation method thereof, a hydrated alumina forming body and an alumina forming body which are formed by the halogen-containing 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 halogen-containing hydrated alumina composition as a carrier, and a hydrogenation treatment method adopting the catalyst.

Background

In the conventional method, an alumina molded body, particularly a γ -alumina molded body, is often used as an adsorbent or a carrier of a supported catalyst because of its good pore structure, suitable specific surface area and high heat resistance stability. The alumina can be modified by introducing an auxiliary halogen element into the molded body so as to meet the requirements of specific application occasions, such as: the hydrofining catalyst is prepared by adopting the halogen-containing alumina forming body as a carrier, and the hydrofining performance of the catalyst can be modulated. 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, an extrusion aid, an auxiliary agent (such as a halogen-containing compound shown in fig. 1) and an optional chemical peptizing agent (inorganic acid and/or organic acid) are added, and after kneading and molding, 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 28-35 wt% and the filter cake is kneaded in a self-cleaning type mixer at a pH in the range of 7.5-10.5 for a residence time of 10s or moreThe pseudoboehmite particles grow up in a short time, thereby obtaining agglomerates containing these particles;

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

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

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

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

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

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

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

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

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

Disclosure of Invention

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

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

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

of said composition

A value of less than 1.8, 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 the preparation of a halogen-containing hydrated alumina composition, which process comprises mixing the components of a feedstock composition comprising a hydrated alumina wet gel having an i value of not less than 60%, a halogen-containing compound, and a compound having at least two proton acceptor sites, to give the hydrated alumina composition, the compound having at least two proton acceptor sites being used in an amount such that the composition as finally prepared has an i value of not less than 60%

The value is less than 1.8 and,

the i value is determined using the following method: 10g of hydrated alumina wet gel was dried at 120 ℃ in an air atmosphere 2At 40 minutes, the mass of the dried sample is 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 halogen-containing 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 halogen-containing hydrated alumina molded body formed from the halogen-containing hydrated alumina composition of the first aspect of the present invention or the halogen-containing hydrated alumina composition of the third aspect of the present invention.

According to a fifth aspect of the present invention, there is provided a halogen-containing alumina hydrate formed body formed from the halogen-containing alumina hydrate composition according to the first aspect of the present invention or the halogen-containing alumina hydrate composition according to the third aspect of the present invention.

According to a sixth aspect of the present invention, there is provided a process for the preparation of a shaped body, which comprises shaping a halogen-containing hydrated alumina composition according to the first aspect of the present invention or a halogen-containing hydrated alumina composition according to the third aspect of the present invention, drying and optionally firing the obtained shaped body.

According to a seventh aspect of the present invention, there is provided a shaped article produced by the method of the sixth aspect of the present invention.

According to an eighth aspect of the present invention, there is provided a method for producing a halogen-containing hydrated 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 60%, preferably not less than 62%, more preferably not more than 80%, further preferably not more than 75%, and further preferably not more than 70%;

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

(2) mixing said 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 halogen-containing hydrated alumina composition;

(3) molding the halogen-containing hydrated alumina composition to obtain a halogen-containing hydrated alumina molding;

(4) drying the halogen-containing hydrated alumina forming product to obtain a halogen-containing hydrated alumina forming product;

(5) optionally, roasting at least part of the halogen-containing hydrated alumina forming body to obtain a halogen-containing alumina forming body,

wherein the method further comprises mixing a halogen-containing compound in step (1) and/or step (2) so that the hydrated alumina composition contains a halogen-containing compound.

According to a ninth aspect of the present invention, there is provided a method for producing and molding a hydrated alumina containing halogen, comprising the steps of:

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

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

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

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

in (2-1) and (2-2), the solid-liquid separation is carried out under such conditions that the second hydrated alumina wet gel has an i value of not less than 60%, preferably not less than 62%, more preferably not more than 80%, further preferably not more than 75%, further preferably not more than 70%,

(3) mixing a second 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 halogen-containing hydrated alumina composition;

(4) molding the hydrated alumina composition to obtain a halogen-containing hydrated alumina molding;

(5) drying the halogen-containing hydrated alumina forming product to obtain a halogen-containing hydrated alumina forming product;

(6) optionally, roasting at least part of the halogen-containing hydrated alumina forming body to obtain a halogen-containing alumina forming body;

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

According to an eleventh aspect of the present invention, there is provided a catalyst having a hydrogenation catalytic action, comprising a carrier and a hydrogenation-active component supported on the carrier, wherein the carrier is a halogen-containing hydrated alumina compact according to the present invention or a halogen-containing alumina compact according to the present invention.

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

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

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

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

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

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

The catalyst with hydrogenation catalysis prepared by using the formed body as a carrier shows higher catalyst 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 halogen-containing hydrated alumina composition comprising hydrated alumina, a halogen-containing compound 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. The hydrated alumina preferably comprises alumina monohydrate, more preferably alumina monohydrate. Specific examples of the hydrated alumina may include, but are not limited to, boehmite, alumina trihydrate, amorphous hydrated alumina, and pseudo-boehmite. In a preferred embodiment of the invention, the hydrated alumina contains pseudoboehmite, more preferably pseudoboehmite. The halogen-containing hydrated alumina composition according to this preferred embodiment is particularly suitable for preparing shaped bodies for use as catalyst supports.

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

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

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

In one example, where the hydrated alumina directly derived from the hydrated alumina gel comprises pseudo-boehmite (e.g., the hydrated alumina directly derived from the hydrated alumina gel is pseudo-boehmite), the composition is left at ambient temperature and under closed conditions for 72 hours, the alumina trihydrate content in the composition after being left to stand being higher than the alumina trihydrate content in the composition before being left to stand. In this example, the alumina trihydrate content in the composition after placement is generally increased by at least 0.5%, preferably by at least 0.8%, more preferably by from 1% to 2%, and even more preferably by from 1% to 1.8%, based on the total amount of alumina trihydrate content in the composition before placement.

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

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

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

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

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

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

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

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

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

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

In a more preferred embodiment of the invention, the compound having at least two proton acceptor sites comprises a galactomannan and a cellulose ether. 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 70 wt.%, preferably from 15 to 68 wt.%, more preferably from 20 to 65 wt.%, based on the total amount of the compound having at least two proton acceptor sites; the cellulose ether may be present in an amount of 30 to 90 wt%, preferably 32 to 85 wt%, more preferably 35 to 80 wt%.

The halogen-containing hydrated alumina composition according to the present invention contains a halogen-containing compound. The halogen element in the halogen-containing compound may be fluorine, chlorine, bromine or iodine, and is preferably fluorine, chlorine or iodine. The amount of halogen-containing compound may be selected depending on the end use application of the composition. In one embodiment, the composition may contain the halogen-containing compound in an amount of 0.1 to 12 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 1 to 8 parts by weight, in terms of halogen element, relative to 100 parts by weight of hydrated alumina. The composition according to this embodiment is particularly suitable for the preparation of a support for a catalyst having a hydrocatalytic effect. The content of halogen element in the halogen-containing hydrated alumina composition is determined by X-ray fluorescence spectroscopy (XRF). In addition, the content of the halogen element in the halogen-containing hydrated alumina composition can also be calculated by the material charging amount, and the material charging amount is used for calculating the content of the halogen element in the halogen-containing hydrated alumina composition in the embodiment of the invention.

The halogen-containing compound may be a compound containing a halogen element in a molecular structure. When the compound having at least two proton acceptor sites contains a fluorine atom in its molecular structure, at least a part of the halogen-containing compound may be a compound having at least two proton acceptor sites. Preferably, at least a portion of the halogen-containing compound is different from the compound having at least two proton acceptor sites, such as a small molecule compound. More preferably, at least a part of the halogen-containing compound is ammonium halide, and specific examples thereof may include, but are not limited to, one or two or more of ammonium fluoride, ammonium chloride, ammonium bromide, and ammonium iodide. Further preferably, at least a part of the halogen-containing compound is one or two or more of ammonium fluoride, ammonium chloride and ammonium iodide.

Of the compositions according to the invention

The value is less than 1.8, for example, may be from 1.2 to less than 1.8, preferably not higher than 1.7, and for example may be from 1.3 to 1.7. From the composition, shaped bodies having a monomodal distribution of pore diameters can be produced.

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 20 parts by weight, preferably 2 to 15 parts by weight, more preferably 3 to 10 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 halogen-containing hydrated alumina composition, the process comprising mixing the components of a feedstock composition to obtain the halogen-containing hydrated alumina composition, i.e. the mixture obtained by mixing is the halogen-containing hydrated alumina composition.

According to the method for preparing a halogen-containing hydrated alumina composition of the present invention, the raw material mixture contains a hydrated alumina wet gel, a halogen-containing compound and a compound having at least two proton acceptor sites. The types of compounds having at least two proton acceptor sites and halogen-containing compounds are described in detail above and will not be described in detail here.

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

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

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

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

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

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

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

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

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

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

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

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

According to the method for preparing a halogen-containing hydrated alumina composition of the present invention, the i value of the hydrated alumina wet gel is not less than 60%, preferably not less than 62%. The i value of the hydrated alumina wet gel is preferably not higher than 80%, more preferably not higher than 75%, and further preferably not higher than 70%. Specifically, the i value of the hydrated alumina wet gel may be 60 to 80%, preferably 62 to 75%, more preferably 62 to 70%.

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

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

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

Generally, the compound having at least two proton acceptor sites may be used in an amount of 1 to 20 parts by weight, preferably 2 to 15 parts by weight, more preferably 3 to 10 parts by weight, based on the hydrated alumina, relative to 100 parts by weight of the hydrated alumina wet gel.

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

According to the method for producing a halogen-containing hydrated alumina composition of the present invention, when the compound having at least two proton acceptor sites contains a halogen element, at least a part of the halogen-containing compound is the compound having at least two proton acceptor sites. Preferably, at least a portion of the halogen-containing compound is different from the compound having at least two proton acceptor sites, such as a small molecule compound. More preferably, at least a part of the halogen-containing compound is ammonium halide, and specific examples thereof may include, but are not limited to, one or two or more of ammonium fluoride, ammonium chloride, ammonium bromide, and ammonium iodide. Further preferably, at least a part of the halogen-containing compound is one or two or more of ammonium fluoride, ammonium chloride and ammonium iodide.

The amount of halogen-containing compound in the feed mixture can be selected based on the amount of elemental halogen that is expected to be incorporated in the halogen-containing hydrated alumina composition. Generally, the content of the halogen-containing compound in the raw material mixture is such that the content of the halogen-containing compound in terms of halogen element may be 0.1 to 12 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, relative to 100 parts by weight of hydrated alumina in the finally prepared halogen-containing hydrated alumina composition.

According to the method for preparing the halogen-containing 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 halogen-containing 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 halogen-containing hydrated alumina composition of the present invention, the hydrated alumina wet gel may be mixed with the compound having at least two proton acceptor sites by a conventional method. The hydrated alumina wet gel may be mixed with a compound having at least two proton acceptor sites under shear. In one embodiment, the mixing is by stirring. The hydrated alumina wet gel and the compound having at least two proton acceptor sites may be mixed uniformly by stirring in a vessel having a stirring device to obtain the halogen-containing 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 compound having at least two proton acceptor sites in a kneader to obtain the halogen-containing hydrated alumina composition according to the present invention. The type of the kneader is not particularly limited. According to the method of preparing the halogen-containing 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 halogen-containing compound, the compound having at least two proton acceptor sites, and the hydrated alumina wet gel may be mixed in various mixing sequences.

In one embodiment, the halogen-containing compound may be mixed during the preparation of the hydrated alumina wet gel, or the halogen-containing compound may be added to the hydrated alumina wet gel obtained by the preparation, or a part of the halogen-containing compound may be mixed during the preparation of the hydrated alumina wet gel, and the remaining part of the halogen-containing compound may be added to the hydrated alumina wet gel obtained by the preparation, and the mixing of the halogen-containing compound may be performed at one, two, or three of the above-mentioned timings of addition. When the halogen-containing compound is mixed in the process of preparing the hydrated alumina wet gel, the operation of mixing the halogen-containing compound may be performed in one, two, three, or four of the precipitation reaction process, the aging process, the solid-liquid separation process, and the washing process. Whether the halogen-containing compound is mixed during the preparation of the hydrated alumina wet gel, and the timing of the mixing may be selected according to the type of precipitation reaction.

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

According to the method for preparing the hydrated alumina composition of the present invention, it is preferable to mix the halogen-containing compound after the preparation of the hydrated alumina wet gel is completed.

According to the method for producing a halogen-containing hydrated alumina composition of the present invention, water may or may not be added during the mixing process, as long as the halogen-containing 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. Generally, the weight ratio of the supplemental added water to the compound having at least two proton acceptor sites may be from 5 to 15: 1, preferably 8 to 12: 1.

The halogen-containing hydrated alumina composition according to the present invention can be shaped by a conventional method to obtain a halogen-containing hydrated alumina support or a halogen-containing alumina support.

The halogen-containing hydrated alumina composition according to the present invention may be molded, and the resulting molded article may be dried to obtain the halogen-containing 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 not more than 350 ℃, preferably 80 to 300 ℃, more preferably 110 ℃ or 260 ℃. 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 4 hours. The drying may be carried out in an oxygen-containing atmosphere (e.g., air atmosphere) or in an inert atmosphere (e.g., an atmosphere formed by nitrogen and/or a group-zero gas), preferably in an oxygen-containing atmosphere.

The halogen-containing hydrated alumina molded body according to the present invention may have various shapes according to specific use requirements, for example: spherical, strip, sheet, bird's nest, or honeycomb, and specific examples of the strip may include, but are not limited to: clover, disk, cylinder and raschig ring.

The halogen-containing hydrated alumina formed body according to the present invention has a rich pore structure. The halogen-containing hydrated alumina moldings have a monomodal distribution of pore diameters, as determined by mercury intrusion. Among them, the most probable pore diameter is 4 to 25nm, preferably 8 to 22nm, and more preferably 10 to 20 nm.

The halogen-containing hydrated alumina formed body according to the present invention has high strength. Generally, the halogen-containing hydrated alumina formed body according to the present invention has a radial crush strength of 12N/mm or more (for example, may be 12 to 55N/mm), preferably 15N/mm or more, and more preferably 15 to 50N/mm. In the present invention, the radial crush strength of the molded article was measured by the method specified in RIPP 25-90.

The halogen-containing hydrated alumina composition according to the present invention may be molded, and the obtained molded article may be dried and fired in sequence to obtain the halogen-containing alumina molded article.

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.

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 calcination may be 450-1500 ℃. In addition, the calcination temperature can be optimized according to the type of the hydrated alumina. In one embodiment, the hydrated alumina is hydrated alumina and the calcination temperature is preferably 450-. In another embodiment, the hydrated alumina is gibbsite and the calcination temperature is preferably 800-1500 ℃, more preferably 900-1400 ℃. The duration of the calcination may be 1 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 halogen-containing alumina molded body according to the present invention may have various shapes according to specific use requirements, for example: spherical, strip, sheet, bird's nest, or honeycomb, and specific examples of the strip may include, but are not limited to: clover, disk, cylinder and raschig ring.

The halogen-containing alumina moldings according to the invention have a rich pore structure. The pore diameter of the halogen-containing aluminum oxide shaped bodies is unimodal as determined by mercury intrusion. The pore size of the most probable pore is 4 to 25nm, preferably 10 to 20 nm.

According to the halogen-containing alumina molded body of the present invention, the halogen-containing alumina molded body has high strength. In general, the halogen-containing alumina shaped body according to the present invention has a radial crush strength of 12N/mm or more (for example, may be 12 to 55N/mm), preferably 15N/mm or more, and more preferably 15 to 50N/mm.

According to a sixth aspect of the present invention, there is provided a process for the preparation of a shaped body, which comprises shaping a halogen-containing hydrated alumina composition according to the first aspect of the present invention or a halogen-containing hydrated alumina composition according to the third aspect of the present invention, drying and optionally firing the obtained shaped body. The obtained molded product may be dried and then calcined to obtain a halogen-containing alumina hydrate molded product, or may be calcined to obtain a halogen-containing alumina hydrate molded product.

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

The pore diameter of the shaped bodies produced by the process for the production of shaped bodies according to the invention is unimodal. In particular, the halogen-containing aluminum oxide shaped bodies prepared according to this embodiment have a monomodal distribution of pore diameters, determined by mercury intrusion. The pore size of the most probable pore is 4 to 25nm, preferably 10 to 20 nm.

According to a seventh aspect of the present invention, there is provided a shaped article produced by the method of the sixth aspect of the present invention. The shaped bodies have a high strength. Generally, the radial crush strength of the shaped article produced by the method of the sixth aspect of the present invention is 12N/mm or more (for example, may be 12 to 55N/mm), preferably 15N/mm or more, and more preferably 15 to 50N/mm.

According to an eighth aspect of the present invention, there is provided a method for producing and molding a hydrated alumina containing halogen, 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 using the method of the second aspect of the invention to obtain a halogen-containing hydrated alumina composition, the hydrated alumina wet gel being either the first hydrated alumina wet gel or the second hydrated alumina wet gel;

(4) molding the halogen-containing hydrated alumina composition to obtain a halogen-containing hydrated alumina molding;

The method for mixing the halogen-containing compound according to the molding method 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, i.e., the i value of the first hydrated alumina wet gel is not less than 60%, preferably not less than 62%. In this embodiment, the first hydrated alumina wet gel preferably has an i value of not higher than 80%, more preferably not higher than 75%, and still more preferably not higher than 70%. In particular, the first hydrated alumina wet gel may have an i value of 60 to 80%, preferably 62 to 75%, more preferably 62 to 70%.

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 greater than 80% 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 to form a slurry, which can improve the transport properties of the hydrated alumina wet gel. In (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 60%, preferably not less than 62%. The second hydrated alumina wet gel preferably has an i value of not higher than 80%, more preferably not higher than 75%, and still more preferably not higher than 70%. In particular, the second hydrated alumina wet gel may have an i value of 60 to 80%, preferably 62 to 75%, more preferably 62 to 70%.

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

In step (3), the first hydrated alumina wet gel or the second hydrated alumina wet gel is mixed with a halogen-containing compound and a compound having at least two proton acceptor sites using the method according to the second aspect of the present invention to obtain a halogen-containing 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.

In the step (4), the halogen-containing hydrated alumina composition obtained in the step (3) is molded to obtain a halogen-containing hydrated alumina molded product. The forming method and the shape of the formed object can refer to the related description of the forming in the foregoing, and are not repeated herein.

In the step (5), the halogen-containing hydrated alumina molded product obtained in the step (3) is dried to obtain a halogen-containing hydrated alumina molded product. The drying conditions for drying the shaped hydrated alumina product to obtain the halogen-containing shaped hydrated alumina product have been described in detail in the method of the fifth aspect of the present invention, and will not be 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 of the halogen-containing hydrated alumina formed body obtained in step (5) may be fed to step (6) and calcined; it is also possible to feed part of the halogen-containing hydrated alumina formed body obtained in step (5) to step (6), so that the halogen-containing hydrated alumina formed body and the halogen-containing alumina formed body can be simultaneously produced. The conditions for the calcination have been described in detail in the method of the eighth aspect of the present invention, and are not described herein again.

According to a ninth aspect of the present invention, there is provided a halogen-containing hydrated alumina formed body or a halogen-containing alumina formed body produced by the method according to the eighth aspect of the present invention.

The halogen-containing hydrated alumina formed body and the halogen-containing alumina formed body produced by the method according to the eighth aspect of the present invention have high strength. In general, the halogen-containing hydrated alumina formed body and the halogen-containing alumina formed body may each have a radial crush strength of 12N/mm or more (for example, may be 12 to 55N/mm), preferably 15N/mm or more, and more preferably 15 to 50N/mm.

The method according to the eighth aspect of 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 and liquidThe 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, such that the solid-liquid separation is achievedOf solid-phase material obtained from separation and washing unit (i.e. hydrated alumina wet gel)

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

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

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

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

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

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

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

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

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

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

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

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

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

The production molding system is not provided with a dehydration unit which is enough to reduce the i value of the hydrated alumina wet gel to be less than 60 percent (preferably less than 62 percent) between the solid phase material outlet port of the solid-liquid separation and washing unit and the hydrated alumina wet gel inlet port of the mixing unit by taking the flow direction of the hydrated alumina gel as a reference.

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

When the hydrated alumina production forming system is used for producing a formed body, the method can comprise the following steps:

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

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

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

(4) molding the halogen-containing hydrated alumina composition in a molding unit to obtain a halogen-containing hydrated alumina molding;

(5) drying the halogen-containing hydrated alumina forming product in a drying unit to obtain a halogen-containing hydrated alumina forming product;

(6) roasting at least part of the halogen-containing hydrated alumina forming body in a roasting unit to obtain an alumina forming body;

wherein the addition of the halogen-containing compound is carried out in one, two or three of the steps (1), (2) and (3) so that the hydrated alumina composition contains the halogen-containing compound.

The method for preparing the hydrated alumina gel solution in the step (1) has been described in detail above and will not be described in detail herein.

In the step (2), the solid-liquid separation condition is that the obtained hydrated alumina wet gel is

The value satisfies the requirements set forth in the second aspect of the invention to enable mixing with a compound having at least two proton acceptor sites to obtain a halogen-containing hydrated alumina composition.

In step (3), the compound having at least two proton acceptor sites is added in an amount such that the halogen-containing hydrated alumina composition obtained is prepared

The values are such that they satisfy the requirements stated above. As mentioned above, the halogen-containing hydrated alumina composition may or may not contain a peptizing agent, i.e., in step (3), a peptizing agent may or may not be added to the hydrated alumina wet gel. In a preferred embodiment of the present invention, the peptizing agent is added in an amount of preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and more preferably 2 parts by weight or less, based on 100 parts by weight of the hydrated alumina wet gel. In a particularly preferred embodiment of the invention, no peptizing agent is added to the hydrated alumina wet gel.

The forming in the step (4), the drying in the step (5) and the baking in the step (6) can refer to the related descriptions above, and are not described herein again.

The halogen-containing hydrated alumina molded bodies and the halogen-containing 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 halogen-containing hydrated alumina molded body and/or a halogen-containing alumina molded body as a support. Preferably, the catalyst is a catalyst having a hydrogenation catalytic effect. That is, the halogen-containing hydrated alumina formed body and the halogen-containing alumina formed body according to the present invention are particularly suitable as a support of a catalyst having a hydrogenation catalytic action.

According to a tenth aspect of the present invention, there is provided a catalyst having hydrogenation catalysis, comprising a carrier and a hydrogenation-active component supported on the carrier, wherein the carrier is a halogen-containing hydrated alumina compact according to the present invention and/or a halogen-containing alumina compact according to the present invention.

The hydrogenation active component may be of conventional choice. Preferably, the hydrogenation active component is selected from at least one group VIB metal element and at least one group VIII metal element. The group VIII metal element and the group VIB metal element may be various elements having a hydrogenation catalytic action commonly used in the art. Preferably, the group VIII metal element is cobalt and/or nickel, and the group VIB metal element is molybdenum and/or tungsten. The contents of the group VIII metal elements and the group VIB metal elements may be appropriately selected according to the specific application of the catalyst. For example, when the catalyst according to the present invention is used for hydrotreating of hydrocarbon oil, the content of the carrier may be 55 to 94.5 wt%, preferably 65 to 92.5 wt%, more preferably 66 to 88 wt%, based on the total amount of the catalyst; the group VIII metal element may be contained in an amount of 0.5 to 10% by weight, preferably 1.5 to 5% by weight, more preferably 2 to 4% by weight, in terms of oxide; the group VIB metal element may be present in an amount of 5 to 35 wt.%, preferably 6 to 30 wt.%, more preferably 10 to 30 wt.%, calculated as oxide.

According to an eleventh aspect of the present invention, there is provided a method for producing a catalyst having a hydrogenation catalytic action, which comprises supporting a hydrogenation-active component on a carrier, wherein the carrier is a halogen-containing hydrated alumina compact and/or a halogen-containing alumina compact 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 halogen-containing hydrated alumina molded body and/or a halogen-containing alumina molded body. In this step, a molded body is produced by the method according to the sixth aspect or the eighth aspect of the present invention.

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

According to the preparation method of the catalyst having hydrogenation catalysis of the present invention, the hydrogenation active component can be supported on the carrier by various methods commonly used in the art, such as: and (4) dipping. The impregnation may be a saturated impregnation or an excess impregnation.

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

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

According to a twelfth aspect of the present invention, there is provided a hydrotreating process comprising contacting a hydrocarbon oil under hydrotreating conditions with a catalyst having a hydrocatalytic action, wherein the catalyst having a hydrocatalytic action is the catalyst according to the tenth aspect of the present invention or the catalyst prepared by the method according to the eleventh 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. Preferably, the hydrocarbon oil may be one or more of various heavy mineral oils or heavy mineral oils, such as heavy deasphalted oil, atmospheric residue, and vacuum residue. The hydrotreating conditions include: the temperature can be 300-380 ℃; the hydrogen partial pressure may be 4-15MPa in gauge pressure; the liquid hourly space velocity of the hydrocarbon oil can be 0.5-3h^-1。

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

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

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

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

The value of the one or more of,

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

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

in the following examples and comparative examples, the mode pore size was determined using the Congta Poremaster33 instrument, USA, with reference to the mercury intrusion method specified in GB/T21650.1-2008. The 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 dry basis is determined by firing the sample at a temperature of 600 ℃ for 4 hours, as the ratio of the mass of the sample after firing to the mass of the sample before firing.

Examples 1 to 12 are intended to illustrate the halogen-containing hydrated alumina composition, the molded body and the method of 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 numbered as SLB-1) obtained by washing and filtering a hydrated alumina gel solution prepared by an acid method (sodium metaaluminate-aluminum sulfate method, taken from the tommy division, petrochemical, china), and the i value of the wet cake was determined to be 78.2%.

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

(2) 300g of wet cake LB-1, reference number, was placed in a beaker and 8g of NH were added₄Cl、4.5g of hydroxyethyl methylcellulose (available from Shanghai Hui Guang Fine chemical Co., Ltd., the same below) and 1.5g of sesbania powder (having a galactomannan content of 85% by weight, available from Beijing chemical Co., Ltd.) were stirred with a mechanical stirrer for 10 minutes to obtain a halogen-containing hydrated alumina composition of the present invention, the properties of which are shown in Table 1.

(3) And (3) extruding the halogen-containing hydrated alumina composition prepared in the step (2) into strips by using a circular orifice plate with the diameter of 2.0mm on an F-26 type double-screw extruder (manufactured by general scientific and technical industries of southern China university, the same shall apply hereinafter). Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.

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

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

Example 2

A shaped body was produced in the same manner as in example 1, except that sesbania powder was not used in step (2) and hydroxyethyl methylcellulose was used in an amount of 5.8g, and the properties of the halogen-containing hydrated alumina composition, halogen-containing hydrated alumina dry strip HT-2 and halogen-containing alumina dry strip OT-2 thus produced are shown in Table 1.

Example 3

A shaped body was produced in the same manner as in example 1, except that hydroxyethyl methylcellulose was not used in step (2) and that sesbania powder was used in an amount of 6.8g, and the properties of the halogen-containing hydrated alumina composition, halogen-containing hydrated alumina dry strip HT-3 and halogen-containing alumina dry strip OT-3 thus produced are shown in Table 1.

Example 4

A molded body was produced in the same manner as in example 1, except that 3g of nitric acid (HNO) was further added in the step (2) when the hydroxyethylmethylcellulose and the sesbania powder were added₃Content of 65 wt.%), prepared halogen-containing hydrated alumina compositionThe properties of the halogen-containing hydrated alumina dry strip HT-4 and halogen-containing alumina dry strip OT-4 are set forth in Table 1.

Comparative example 1

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

(2) 228g of pseudo-boehmite powder prepared in the step (1) and 8g of NH₄After mixing with Cl, the strands were extruded on a twin-screw extruder of type F-26 using a circular orifice plate of 2.0 mm. The extruder has large heat productivity during extrusion (the extruder body is hot and a large amount of hot air is emitted), and the extruder frequently trips during extrusion, so that burrs are formed on the surface of an extruded material.

(3) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 ℃ for 2 hours in an air atmosphere to give halogen-containing alumina hydrate dry strips DHT-1, the property parameters of which are listed in Table 1.

(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 480 ℃ for 8 hours in an air atmosphere to obtain a halogen-containing alumina dry strip DOT-1, wherein the property parameters are listed in Table 1.

Comparative example 2

(1) 500g of wet filter cake No. LB-1 was dried at 90 ℃ for 3 hours in an air atmosphere to obtain pseudo-boehmite powder having an i value of 40%. The pseudo-boehmite powder was left at ambient temperature (25-30 ℃) for 72 hours under closed conditions (in a sealed plastic bag), and no formation of alumina trihydrate was detected after the left standing.

(2) 190g of pseudo-boehmite powder prepared in the step (1) is put in a beaker, and 8g of NH is added₄Cl, 4.5g of hydroxyethyl methylcellulose (same as in example 3) and 1.5g of sesbania powder (same as in example 3) were stirred for 10 minutes by a mechanical stirrer to obtain a pseudo-boehmite composition.

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

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

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

Comparative example 3

(1) 190g of pseudo boehmite powder prepared by the same method as in step (1) of comparative example 2 was put in a beaker, and 8g of NH was added₄Cl, 4.5g hydroxyethyl methylcellulose (same as example 3), 1.5g sesbania powder (same as example 3) and 6g nitric acid (HNO)₃65 wt.%) was stirred with a mechanical stirrer for 10 minutes to obtain a pseudo-boehmite composition.

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

(3) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 ℃ for 2 hours in an air atmosphere to give halogen-containing alumina hydrate dry strips DHT-3, the property parameters of which are listed in Table 1.

(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 480 ℃ for 8 hours in an air atmosphere to obtain the halogen-containing alumina dry strip DOT-3, wherein the property parameters are listed in Table 1.

Comparative example 4

A halogen-containing hydrated alumina composition was prepared by the same method as in example 1, except that hydroxyethylmethylcellulose and sesbania powder were not used, but 6.0g of paraffin was used. As a result, the halogen-containing hydrated alumina composition prepared cannot be extrusion molded.

Comparative example 5

A halogen-containing hydrated alumina composition was prepared by the same method as in example 1, except that hydroxyethyl methyl cellulose and sesbania powder were not used, and 6.0g of wood flour was used. As a result, the halogen-containing hydrated alumina composition prepared cannot be extrusion molded.

Comparative example 6

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

Comparative example 7

(1) 162g of dry powder of pseudoboehmite (purchased from Chang Ling, China petrochemical Co., Ltd., dry basis of 0.70) was left for 72 hours at ambient temperature (25-30 ℃) under closed conditions (in a sealed plastic bag) and no formation of alumina trihydrate was detected after the left standing), and 8g of NH was added₄Cl, 4.5g hydroxyethyl methyl cellulose (same as in example 1), 1.5g sesbania powder (same as in example 1) and a solution containing 6g nitric acid (HNO)₃65 wt%) was added to the reaction solution, and stirred for 10 minutes using a mechanical stirrer to obtain a pseudo-boehmite composition.

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

(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 480 ℃ for 8 hours in an air atmosphere to obtain a halogen-containing alumina dry strip DOT-4, wherein the property parameters are listed in Table 1.

Example 5

(1) 300g of wet cake LB-1, reference number, was placed in a beaker and 10g of NH were added₄I. 2.6g of hydroxypropylmethylcellulose (available from Hakka chemical Co., Ltd., Zhejiang, the same applies hereinafter) and 3.5g of sesbania powder (having a galactomannan content of 85% by weight) were stirred with a mechanical stirrer for 10 minutes to obtain a halogen-containing hydrated alumina composition of the present invention, the properties of which are shown in Table 1.

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

(3) The extrudate was cut into wet strips having a length of about 6mm, and the wet strips were dried at 60 ℃ for 2 hours in an air atmosphere, followed by drying at 110 ℃ for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-5, the property parameters of which are listed in Table 1.

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

Example 6

(1) 300g of wet cake LB-1, reference number, was placed in a beaker and 15g of NH were added₄F. 2g of methylcellulose, 1.1g of hydroxypropylmethylcellulose and 4g of sesbania powder (galactomannan content 85% by weight) gave, after stirring for 10 minutes with a mechanical stirrer, a halogen-containing hydrated alumina composition according to the invention, the property parameters of which are listed in Table 1.

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

(3) The extrudate was cut into wet strips having a length of about 8mm, and the wet strips were dried at 110 ℃ for 4 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-6, the property parameters of which are listed in Table 1.

(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (4) at 1050 ℃ for 1.5 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-6, wherein the property parameters are listed in Table 1.

Example 7

(1) 300g of wet cake LB-1, reference number, was placed in a beaker and 10g of NH were added₄Cl, 2.2g hydroxyethyl methyl cellulose and 2.1g hydroxypropyl methyl celluloseThe vitamins, after 10 minutes of stirring with a mechanical stirrer, give the halogen-containing hydrated alumina composition of the present invention, the property parameters of which are listed in table 1.

(2) And (2) extruding the halogen-containing hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 1.8 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.

(3) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 260 c for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-7, the property parameters of which are listed in table 1.

(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (4) at 850 ℃ for 3 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-7, wherein the property parameters are listed in Table 1.

Example 8

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

(2) 1000g of wet cake LB-2, reference number, was placed in a beaker and 30g of NH were added₄F. After stirring for 10 minutes with a mechanical stirrer, 16g of hydroxypropylmethylcellulose and 20g of sesbania powder (galactomannan content 85% by weight, available from Beijing Chemicals) gave the halogen-containing hydrated alumina composition of the present invention having the property parameters listed in Table 1.

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

(4) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-8, the property parameters of which are listed in table 1.

(5) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (4) at 700 ℃ for 2 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-8, wherein the property parameters are listed in Table 1.

Example 9

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 SLB-2) obtained by washing and filtering a hydrated alumina gel solution prepared by Xinghao catalyst new material Co., Shanxi province) is measured to be 65.3%.

(1) 1000g of SLB-2 numbered wet cake was placed in a beaker, then 30g NH was added₄Cl, 16g of methylcellulose and 20g of sesbania powder (galactomannan content 80% by weight), the mixture obtained after stirring for 10 minutes with a mechanical stirrer is a halogen-containing hydrated alumina composition according to the invention, the property parameters of which are listed in Table 1.

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

(3) The extrudate was cut into wet strips having a length of about 5mm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-9, the property parameters of which are listed in table 1.

(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 550 ℃ for 3 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-9, wherein the property parameters are listed in Table 1.

Example 10

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

(1) 5000g of SLB-3 with the number of the SLB-3 and 1000g of water are mixed and pulped, the obtained slurry is pressed into a plate and frame filter press, the plate and frame pressure of the plate and frame filter press is adjusted to 0.9MPa and kept for 3 minutes, then filter cakes in the plate and frame are blown by 0.6MPa of compressed air for 5 minutes, the plate and frame are decompressed, 2.5kg of alumina trihydrate wet filter cakes are obtained, and the i value of the wet filter cakes is 60.8 percent by weight.

(2) Placing 1000g of the wet cake obtained in step (1) in a beaker, and adding 20g of NH₄F. 10g of methylcellulose and 20g of sesbania powder (galactomannan content 80% by weight) were stirred for 10 minutes using a mechanical stirrer, and the resulting mixture was a halogen-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.

(4) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-10, the property parameters of which are listed in table 1.

(5) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 1400 ℃ for 2 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-10, wherein the property parameters are listed in Table 1.

Example 11

The hydrated alumina wet gel used in the embodiment is obtained from Shandong Zibo zimao catalyst Co., Ltd, 1000g of pseudo-boehmite dry powder (dry basis is 0.70) prepared by an acid method (sodium aluminate-aluminum sulfate method) is calcined in 700 ℃ and air atmosphere for 3 hours to obtain 700g of alumina, 700g of alumina is put in a 10L high-pressure reaction kettle and is uniformly stirred with 5L of deionized water, the high-pressure reaction kettle is sealed and reacts at 150 ℃ under the autogenous pressure for 6 hours, after the reaction is finished, the temperature of the high-pressure reaction kettle is reduced to room temperature (25 ℃), slurry obtained by the reaction is sent into a plate and frame filter press, the plate and frame pressure of the plate and frame filter is adjusted to 0.5MPa and is kept for 10 minutes, then filter cakes in the plate and frame are blown by 10MPa of pressurized air for 3 minutes, and the plate and frame is decompressed to obtain the hydrated alumina wet filter cake LB-3. The phase of the wet cake was determined to be boehmite and the i value of the wet cake was 63%.

(1) 300g of wet cake No. LB-3 was placed in a beaker, then 9g of NH were added₄I. After stirring 3.8g of methylcellulose and 6g of sesbania powder (galactomannan content 85% by weight) for 10 minutes using a mechanical stirrer, the mixture obtained was a halogen-containing hydrated alumina composition according to the invention, the property parameters of which are listed in table 1.

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

(3) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-11 having the property parameters listed in table 1.

(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 600 ℃ for 4 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-11, wherein the property parameters are listed in Table 1.

Comparative example 8

(1) 158g of dry powder of pseudo-boehmite (obtained from Zibozimao catalysts Co., Ltd., prepared by the sodium aluminate-aluminium sulfate process, dry basis 0.70, placed at ambient temperature (25-30 ℃) for 72 hours in a closed condition (in a sealed plastic bag), no formation of alumina trihydrate being detected after placement), 9g of NH are added₄I. After 3.8g of methylcellulose (same as example 11) and 6g of sesbania powder (same as example 11) and 300mL of deionized water have been stirred for 10 minutes with a mechanical stirrer, the resulting mixture is a halogen-containing hydrated alumina composition of the present invention, the property parameters of which are listed in table 1.

(3) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 ℃ for 2 hours in an air atmosphere to give halogen-containing alumina hydrate dry strips DHT-5, the property parameters of which are listed in Table 1.

(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 600 ℃ for 4 hours in an air atmosphere to obtain the halogen-containing alumina dry strip DOT-5, wherein the property parameters are listed in Table 1.

Example 12

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

(1) 200g of wet cake numbered LB-4 were placed in a beaker and 5g of NH were added₄Cl, 2.8g of methylcellulose and 4.5g of sesbania powder (galactomannan content 80% by weight), the mixture obtained after stirring for 10 minutes with a mechanical stirrer is a halogen-containing hydrated alumina composition according to the invention, the property parameters of which are listed in Table 1.

(3) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-12, the property parameters of which are listed in table 1.

(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 580 ℃ for 6 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-12, wherein the property parameters are listed in Table 1.

TABLE 1

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

The results of examples 1-12 demonstrate that the hydrated alumina wet gel is not dried to dry gel powder or semi-dry gel powder, but is directly mixed with a halogen-containing compound and a compound having at least two proton acceptor sites, the obtained mixture can be directly used for molding, and the obtained molded body has higher strength, thereby avoiding the problems of severe working environment, high energy consumption and low strength of the prepared molded body when the conventional molded body is prepared by taking the dry gel powder or the semi-dry gel powder as a starting material.

Experimental examples 1 to 7 are provided to illustrate catalysts having hydrogenation catalysis according to the present invention and a method for preparing the same.

Experimental example 1

(1) Dispersing ammonium metatungstate and nickel nitrate in deionized water to prepare an impregnation liquid, wherein WO is added₃The concentration of ammonium metatungstate was 430.1g/L, and the concentration of basic nickel carbonate was 43.8g/L as NiO. The obtained impregnation liquid was impregnated into the halogen-containing hydrated alumina dry strip prepared in example 1 as a carrier by a saturated impregnation method for 2 hours. The impregnated mixture was dried at 120 ℃ for 3 hours and then calcined at 450 ℃ for 4 hours to obtain the catalyst CH-1 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 2.

(2) The catalyst was prepared by the same method as in step (1) except that the impregnation solution was WO₃The concentration of ammonium metatungstate was 415.9g/L, the concentration of basic nickel carbonate was 42.4g/L as NiO, and the support was the halogen-containing alumina dry strip prepared in example 1, thereby obtaining catalyst CO-1 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.

Experimental example 2

Prepared by the same method as Experimental example 1A catalyst, except that: (1) in the immersion liquid, WO₃The concentration of ammonium metatungstate was 275.2g/L, the concentration of basic nickel carbonate was 28.0g/L as NiO, and the support was the halogen-containing hydrated alumina dry strip prepared in example 2, to obtain catalyst CH-2 of the present invention. The composition of the catalyst was determined using XRF, with the results shown in table 2;

(2) in the immersion liquid, WO₃The concentration of ammonium metatungstate was calculated to be 366.9g/L, the concentration of basic nickel carbonate was calculated to be 37.4g/L in terms of NiO, and the support was the halogen-containing alumina dry strip prepared in example 2, to obtain the catalyst CO-2 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.

Experimental example 3

A catalyst was prepared in the same manner as in experimental example 1, except that: (1) in the immersion liquid, WO₃The concentration of ammonium metatungstate was 246.3g/L, the concentration of basic nickel carbonate as NiO was 25.1g/L, and the support was the halogen-containing hydrated alumina dry strip prepared in example 3, to obtain catalyst CH-3 of the present invention. The composition of the catalyst was determined using XRF, with the results shown in table 2;

(2) in the immersion liquid, WO₃The concentration of ammonium metatungstate was 304.3g/L, the concentration of basic nickel carbonate was 31.0g/L as NiO, and the support was the halogen-containing alumina dry strip prepared in example 3, to obtain catalyst CO-3 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.

Experimental example 4

A catalyst was prepared in the same manner as in experimental example 1, except that: (1) in example 4, the carrier was the halogen-containing hydrated alumina dry strip, and as a result, the phenomena of structural collapse and pulverization occurred during the impregnation process;

(2) in the immersion liquid, WO₃The concentration of ammonium metatungstate was 363.4g/L, the concentration of basic nickel carbonate was 37.0g/L as NiO, and the support was the halogen-containing alumina dry strip prepared in example 4, to obtain the catalyst CO-4 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.

Experimental comparative example 1

A catalyst was prepared in the same manner as in experimental example 1, except that: (1) in the above, the carrier was the halogen-containing hydrated alumina dry strip prepared in comparative example 7, so that the phenomena of structural collapse and pulverization occurred during the impregnation process;

(2) in the immersion liquid, WO₃The concentration of ammonium metatungstate was calculated to be 411.3g/L, the concentration of basic nickel carbonate was calculated to be 41.9g/L in terms of NiO, and the support was the halogen-containing alumina dry strip prepared in comparative example 7, to obtain catalyst DCO-1. The composition of the catalyst was determined by XRF and the results are shown in table 3.

Experimental example 5

(1) Dispersing basic nickel carbonate and molybdenum oxide in deionized water to prepare a steeping fluid, wherein MoO₃The concentration of (2) was 282.4g/L, and the concentration of basic nickel carbonate (calculated as NiO) was 68.2 g/L. The obtained impregnation liquid was impregnated into the halogen-containing hydrated alumina dry strip prepared in example 11 as a carrier by a saturated impregnation method for 2 hours. The impregnated mixture was dried at 130 ℃ for 2 hours and then calcined at 480 ℃ for 3 hours to obtain the catalyst CH-5 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 2.

(2) The catalyst was prepared by the same method as in step (1) except that MoO₃286.8g/L, the concentration of basic nickel carbonate calculated as NiO was 69.2g/L, and the support was the halogen-containing alumina dry strip prepared in example 11, thereby obtaining catalyst CO-5 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.

Experimental comparative example 2

A catalyst was prepared in the same manner as in experimental example 5, except that: (1) in the above, the carrier was the halogen-containing hydrated alumina dry strip prepared in comparative example 8, so that the phenomena of structural collapse and pulverization occurred during the impregnation process;

(2) medium, MoO₃Was 221.1g/L, the concentration of basic nickel carbonate calculated as NiO was 53.4g/L, and the support was the halogen-containing alumina dry strip prepared in comparative example 8, to obtain catalyst DCO-2. The composition of the catalyst was determined by XRF and the results are shown in table 3.

Experimental example 6

(1) Dispersing basic nickel carbonate and molybdenum oxide in deionized water to prepare a steeping fluid, wherein MoO₃The concentration of (B) was 185.5g/L, and the concentration of basic nickel carbonate (calculated as NiO) was 44.2 g/L. The obtained impregnation liquid was impregnated into the halogen-containing hydrated alumina dry strip prepared in example 12 as a carrier by a saturated impregnation method for 2 hours. The impregnated mixture was dried at 150 ℃ for 2 hours and then calcined at 400 ℃ for 2 hours to obtain the catalyst CH-6 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 2.

(2) The catalyst was prepared by the same method as in step (1) except that MoO₃Was 194.2g/L, the concentration of basic nickel carbonate, calculated as NiO, was 46.2g/L, and the support was the halogen-containing alumina dry strip prepared in example 12, thereby obtaining catalyst CO-6 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.

TABLE 2

Numbering	Source of vector	Catalyst numbering	NiO(wt％)	MoO₃(wt％)	WO₃(wt％)
						Experimental example 1	Example 1 (hydrated alumina Dry strip)	CH-1	2.7	/	26.5
Experimental example 2	Example 2 (hydrated alumina Dry strip)	CH-2	2.7	/	26.5
						Experimental example 3	Example 3 (hydrated alumina Dry strip)	CH-3	2.7	/	26.5
Experimental example 5	Example 11 (hydrated alumina Dry strip)	CH-5	3.5	14.5	/
						Experimental example 6	Example 12 (hydrated alumina Dry strip)	CH-6	2.5	10.5	/

TABLE 3

Numbering	Source of vector	Catalyst numbering	NiO(wt％)	MoO₃(wt％)	WO₃(wt％)
						Experimental example 1	Example 1 (alumina dry strip)	CO-1	2.7	/	26.5
Experimental comparative example 1	COMPARATIVE EXAMPLE 7 (Dry alumina strip)	DCO-1	2.7	/	26.5
						Experimental example 2	Example 2 (alumina dry strip)	CO-2	2.7	/	26.5
Experimental example 3	Example 3 (alumina dry strip)	CO-3	2.7	/	26.5
						Experimental example 4	Example 4 (alumina dry strip)	CO-4	2.7	/	26.5
Experimental example 5	Example 11 (alumina dry strip)	CO-5	3.5	14.5	/
						Experimental comparative example 2	COMPARATIVE EXAMPLE 8 (Dry alumina strip)	DCO-2	3.5	14.5	/
Experimental example 6	Example 12 (alumina dry strip)	CO-6	2.5	10.5	/

Test examples 1-6 are intended to illustrate the hydrotreating process according to the invention.

Test examples 1 to 6

The catalysts prepared in experimental examples 1 to 6 were evaluated for their catalytic performance by the following methods, and the results are shown in Table 4.

The adopted raw oil is light and normal pressure sieroze residual oil, the mass content of nickel is 11.7ppm, the mass content of vanadium is 31.7ppm, the sulfur content is 3.5 weight percent, the nitrogen content is 0.21 weight percent, and the carbon residue is 11.7 weight percent.

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

The removal rate of impurities was calculated according to the following formula:

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 1-6, respectively, and the results of the experiments are shown in Table 4.

TABLE 4

The results of test examples 1 to 6 confirm that the catalysts prepared with the halogen-containing hydrated alumina molded body and the alumina molded body according to the present invention as a support show 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 halogen-containing hydrated alumina composition comprising hydrated alumina, a halogen-containing compound and a compound having at least two proton acceptor sites, the compound having at least two proton acceptor sites being one or more of dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide,

of said composition

A value of less than 1.8, said

The value of the one or more of,

the preparation method of the halogen-containing hydrated alumina composition comprises the step of mixing the components in a raw material composition to obtain the hydrated alumina composition, wherein the raw material composition contains hydrated oxidationAn aluminum wet gel, a halogen-containing compound, and a compound having at least two proton acceptor sites, the hydrated alumina wet gel having an i value of not less than 60%, the compound having at least two proton acceptor sites being used in an amount such that the composition finally prepared is of

The value is less than 1.8 and,

2. the composition of claim 1, wherein the composition is

Values of 1.2 to less than 1.8.

3. The composition of claim 2, wherein the composition is

The value is not higher than 1.7.

4. The composition of claim 3, wherein the composition is

The value is 1.3-1.7.

5. The composition according to any one of claims 1 to 4, wherein the compound having at least two proton acceptor sites is contained in an amount of 1 to 20 parts by weight relative to 100 parts by weight of the hydrated alumina.

6. The composition according to claim 5, wherein the compound having at least two proton acceptor sites is contained in an amount of 2 to 15 parts by weight relative to 100 parts by weight of the hydrated alumina.

7. The composition according to claim 6, wherein the compound having at least two proton acceptor sites is contained in an amount of 3 to 10 parts by weight with respect to 100 parts by weight of the hydrated alumina.

8. The composition of any one of claims 1-4, wherein the compound having at least two proton acceptor sites is one or more of a galactan, a mannan, a galactomannan, and a cellulose ether.

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

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

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

12. The composition of claim 11, wherein the galactomannan is present in an amount of 15 to 68 wt% and the cellulose ether is present in an amount of 32 to 85 wt%, based on the total amount of the compound having at least two proton acceptor sites.

13. The composition of claim 12, wherein the galactomannan is present in an amount of 20 to 65 wt% and the cellulose ether is present in an amount of 35 to 80 wt%, based on the total amount of the compound having at least two proton acceptor sites.

14. The composition as claimed in any one of claims 1 to 4, wherein the content of the halogen-containing compound is 0.1 to 12 parts by weight in terms of halogen element, relative to 100 parts by weight of hydrated alumina.

15. The composition as claimed in claim 14, wherein the content of the halogen-containing compound is 0.5 to 10 parts by weight in terms of halogen element, relative to 100 parts by weight of hydrated alumina.

16. The composition as claimed in claim 15, wherein the content of the halogen-containing compound is 1 to 8 parts by weight based on the halogen element with respect to 100 parts by weight of hydrated alumina.

17. The composition according to any one of claims 1 to 4, wherein the halogen element in the halogen-containing compound is fluorine, chlorine or iodine.

18. The composition of claim 17, wherein the halogen-containing compound is selected from ammonium halides.

19. The composition according to claim 18, wherein the halogen-containing compound is one or more selected from the group consisting of ammonium fluoride, ammonium chloride and ammonium iodide.

20. The composition of any one of claims 1-4, wherein the hydrated alumina comprises pseudoboehmite.

21. The composition of claim 20, wherein the hydrated alumina is pseudoboehmite.

22. The composition of claim 20, wherein the composition is allowed to stand at ambient temperature and under closed conditions for 72 hours, the amount of alumina trihydrate in the composition after standing being higher than the amount of alumina trihydrate in the composition before standing.

23. The composition of claim 22, wherein the alumina trihydrate content in the composition after placement is increased by at least 0.5% based on the total amount of alumina trihydrate content in the composition before placement.

24. The composition of claim 23, wherein the alumina trihydrate content of the composition after placement is increased by at least 0.8% based on the total alumina trihydrate content of the composition prior to placement.

25. The composition of claim 24, wherein the alumina trihydrate content in the composition after placement is increased by 1% to 2% based on the total alumina trihydrate content in the composition before placement.

26. The composition of any of claims 1-4, wherein the hydrated alumina is derived directly from a hydrated alumina wet gel.

27. The composition of any one of claims 1-4, wherein the composition is free of a peptizing agent.

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

Values of 1.2 to less than 1.8.

29. The composition 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 not higher than 1.7.

30. The composition of claim 29, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.3-1.7.

31. The composition of any of claims 1 and 28-30, wherein the hydrated alumina wet gel has an i value of not less than 62%.

32. The composition of claim 31, wherein the hydrated alumina wet gel has an i value of not greater than 80%.

33. The composition of claim 32, wherein the hydrated alumina wet gel has an i value of not greater than 75%.

34. The composition of claim 33, wherein the hydrated alumina wet gel has an i value of not greater than 70%.

35. The composition of any of claims 1 and 28-30, wherein the hydrated alumina wet gel has an i value of 60-80%.

36. The composition of claim 35, wherein the hydrated alumina wet gel has an i value of 62-75%.

37. The composition of claim 36, wherein the hydrated alumina wet gel has an i value of 62-70%.

38. The composition of any of claims 1 and 28-30, wherein the hydrated alumina wet gel is a hydrated alumina wet gel that has not been subjected to a dehydration treatment such that its i value is 60% or less.

39. The composition of any of claims 1 and 28-30, wherein the hydrated alumina wet gel is obtained by washing and solid-liquid separation of at least one hydrated alumina gel solution after optional aging.

40. The composition of claim 39, wherein the hydrated alumina gel solution is prepared by one or more of precipitation, hydrolysis, seeded precipitation, and flash dehydration.

41. The composition of any of claims 1 and 28-30, wherein the feedstock composition is free of a peptizing agent.

42. The composition of any of claims 1 and 28-30, wherein the compound having at least two proton acceptor sites is used in an amount of 1-20 parts by weight relative to 100 parts by weight of the hydrated alumina wet gel, based on the hydrated alumina.

43. A composition according to claim 42, wherein the compound having at least two proton acceptor sites is used in an amount of 2 to 15 parts by weight per 100 parts by weight of the hydrated alumina wet gel calculated as hydrated alumina.

44. The composition of claim 43, wherein the compound having at least two proton acceptor sites is used in an amount of 3 to 10 parts by weight relative to 100 parts by weight of a hydrated alumina wet gel, based on hydrated alumina.

45. A composition as set forth in any one of claims 1 and 28-30 wherein said feedstock mixture comprises a halogen-containing compound in an amount such that the hydrated alumina composition produced has a content of from 0.1 to 12 parts by weight halogen-containing compound, calculated as elemental halogen, per 100 parts by weight hydrated alumina.

46. A composition as set forth in claim 45 wherein the halogen-containing compound is present in the feed mixture in an amount of from 0.5 to 10 parts by weight based on elemental halogen per 100 parts by weight of hydrated alumina in the produced hydrated alumina composition.

47. A composition as set forth in claim 46 wherein the halogen-containing compound is present in the feed mixture in an amount of from 1 to 8 parts by weight based on elemental halogen per 100 parts by weight of hydrated alumina in the produced hydrated alumina composition.

48. The composition of any of claims 1 and 28-30, wherein the halogen element of the halogen-containing compound is fluorine, chlorine, or iodine.

49. The composition of claim 48, wherein the halogen-containing compound is selected from ammonium halides.

50. The composition as claimed in claim 49, wherein the halogen-containing compound is one or more selected from ammonium fluoride, ammonium chloride and ammonium iodide.

51. The composition of any of claims 1 and 28-30, wherein the method of mixing is stirring and/or kneading.

52. A halogen-containing hydrated alumina molded body formed from the halogen-containing hydrated alumina composition of any one of claims 1 to 51.

53. The halogen containing hydrated alumina forming body of claim 52, wherein the halogen containing hydrated alumina forming body has a unimodal distribution of pore sizes as measured by mercury intrusion porosimetry, and a mode pore size of from 4 to 25 nm.

54. The halogen containing hydrated alumina forming body of any one of claims 52 and 53, wherein the halogen containing hydrated alumina forming body has a radial crush strength of 12 to 55N/mm.

55. A halogen-containing alumina compact formed from the halogen-containing hydrated alumina composition of any one of claims 1 to 51.

56. The halogen containing alumina shaped body according to claim 55 having a unimodal distribution of pore diameters as determined by mercury intrusion porosimetry, the mode pore diameter being from 4 to 25 nm.

57. The halogen containing alumina forming body according to any one of claims 55 and 56, wherein the halogen containing alumina forming body has a radial crush strength of from 12 to 55N/mm.

58. A process for the preparation of shaped bodies, which process comprises shaping a halogen-containing hydrated alumina composition as claimed in any of claims 1 to 51, drying and optionally calcining the obtained shaped bodies.

59. A shaped body produced by the method of claim 58.

60. The shaped body according to claim 59, wherein the shaped body has a radial crush strength of from 12 to 55N/mm.

61. A method for producing and molding hydrated alumina containing halogen 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 60%;

(2) mixing the first 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 than two of glucan, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, and the compound having at least two proton acceptor sites is used in an amount that enables the final prepared composition to have a high degree of hydration

A value of less than 1.8, said

The value of the one or more of,

(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;

62. The method of claim 61, wherein the solid-liquid separation conditions are such that the i value of the first hydrated alumina wet gel is not less than 62%.

63. The method of claim 61, wherein the solid-liquid separation conditions are such that the i value of the first hydrated alumina wet gel is not greater than 80%.

64. The method of claim 63, wherein the conditions of solid-liquid separation are such that the i value of the first hydrated alumina wet gel is not greater than 75%.

65. The method of claim 64 wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of no more than 70%.

66. The method according to claim 61, wherein in the step (2), the mixing is performed by stirring and/or kneading.

67. A method for producing and molding hydrated alumina containing halogen comprises the following steps:

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

(3) mixing the second hydrated alumina wet gel with a compound having at least two proton acceptor sites, wherein the compound having at least two proton acceptor sites is one or more of glucan, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, and the compound having at least two proton acceptor sites is used in an amount to obtain the final composition

A value of less than 1.8, said

The value of the one or more of,

(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;

68. The process of claim 67, 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%.

69. The method of claim 67 wherein in (2-1) and (2-2) the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not greater than 80%.

70. The process of claim 69, 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 75%.

71. The process of claim 70, 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 70%.

72. The process of claim 67, wherein in step (3), the mixing is by stirring and/or kneading.

73. The process of any one of claims 61 to 72, 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.

74. The method of any one of claims 61-72, wherein the hydrated alumina gel solution is aged or unaged and is prepared by one or more of precipitation, hydrolysis, seeded precipitation, and flash dehydration.

75. A process according to any one of claims 61 to 72, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

Values of 1.2 to less than 1.8.

76. A process according to any one of claims 61 to 72, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is not higher than 1.7.

77. The method of claim 76, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition

The value is 1.3-1.7.

78. The method of any of claims 61-72, wherein the hydrated alumina wet gel has an i value of not less than 62%.

79. The method of claim 78, wherein the hydrated alumina wet gel has an i value of not greater than 80%.

80. The method of claim 79, wherein the hydrated alumina wet gel has an i value of not greater than 75%.

81. The method of claim 80, wherein the hydrated alumina wet gel has an i value of not greater than 70%.

82. The method of any one of claims 61-72, wherein the hydrated alumina wet gel has an i value of 60-80%.

83. The method of claim 82, wherein the hydrated alumina wet gel has an i value of 62-75%.

84. The method of claim 83, wherein the hydrated alumina wet gel has an i value of 62-70%.

85. The method of any one of claims 61-72, 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.

86. The method of claim 85, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.

87. The method of any one of claims 61-72, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.

88. The method of claim 87, wherein the galactomannan is present in an amount of 10 to 70 wt.% and the cellulose ether is present in an amount of 30 to 90 wt.%, based on the total amount of the compound having at least two proton acceptor sites.

89. The method of claim 88, wherein the galactomannan is present in an amount of 15 to 68 wt.% and the cellulose ether is present in an amount of 32 to 85 wt.%, based on the total amount of the compound having at least two proton acceptor sites.

90. The method of claim 89, wherein the galactomannan is present in an amount of 20 to 65 wt.% and the cellulose ether is present in an amount of 35 to 80 wt.%, based on the total amount of the compound having at least two proton acceptor sites.

91. A process as claimed in any one of claims 61 to 72, in which the compound having at least two proton acceptor sites is used in an amount of from 1 to 20 parts by weight per 100 parts by weight of hydrated alumina wet gel, based on hydrated alumina.

92. The method of claim 91, wherein the compound having at least two proton acceptor sites is used in an amount of 2 to 15 parts by weight relative to 100 parts by weight of a hydrated alumina wet gel based on hydrated alumina.

93. The method of claim 92, wherein the compound having at least two proton acceptor sites is used in an amount of 3-10 parts by weight relative to 100 parts by weight of the hydrated alumina wet gel, based on hydrated alumina.

94. A process as claimed in any one of claims 61 to 72, in which the halogen-containing compound is present in an amount such that the hydrated alumina composition produced has a content of 0.1 to 12 parts by weight of the halogen-containing compound calculated as elemental halogen, relative to 100 parts by weight of the hydrated alumina.

95. A process as set forth in claim 94 wherein said halogen-containing compound is present in an amount of from 0.5 to 10 parts by weight calculated as elemental halogen, based on 100 parts by weight of hydrated alumina in the produced hydrated alumina composition.

96. A process as set forth in claim 95 wherein said halogen-containing compound is present in an amount of from 1 to 8 parts by weight calculated as elemental halogen, based on 100 parts by weight hydrated alumina in the produced hydrated alumina composition.

97. The method of any one of claims 61-72, wherein the elemental halogen of the halogen-containing compound is fluorine, chlorine, or iodine.

98. The method of claim 97 wherein the halogen containing compound is selected from ammonium halides.

99. The method of claim 98, wherein the halogen containing compound is one or more selected from ammonium fluoride, ammonium chloride, and ammonium iodide.

100. A shaped body prepared by the method of any one of claims 61-99.

101. The shaped body of claim 100, wherein the shaped body has a radial crush strength of from 12 to 55N/mm.

102. A catalyst having a hydrogenation catalytic action, comprising a carrier and a hydrogenation-active component supported on the carrier, wherein the carrier is the halogen-containing hydrated alumina compact of any one of claims 52 to 54, the halogen-containing alumina compact of any one of claims 55 to 57, the compact of any one of claims 59 and 60, or the compact of any one of claims 100 and 101.

103. The catalyst of claim 102, wherein the hydrogenation active component is selected from at least one group VIII metal element and at least one group VIB metal element.

104. The catalyst of claim 103, wherein the group VIII metal element is present in an amount of 0.5 to 10 wt.% on an oxide basis and the group VIB metal element is present in an amount of 5 to 35 wt.% on an oxide basis, based on the total amount of the catalyst.

105. The catalyst of claim 104, wherein the group VIII metal element is present in an amount of 1.5 to 5 wt.% on an oxide basis and the group VIB metal element is present in an amount of 6 to 30 wt.% on an oxide basis, based on the total amount of the catalyst.

106. The catalyst of claim 105, wherein the group VIII metal element is present in an amount of 2 to 4 wt.% on an oxide basis and the group VIB metal element is present in an amount of 10 to 30 wt.% on an oxide basis, based on the total amount of the catalyst.

107. A process for preparing a catalyst having a hydrogenation catalytic action, which comprises supporting a hydrogenation-active component on a carrier, wherein the carrier is the halogen-containing hydrated alumina compact of any one of claims 52 to 54, the halogen-containing alumina compact of any one of claims 55 to 57, the compact of any one of claims 59 and 60, or the compact of any one of claims 100 and 101.

108. The process of claim 107, wherein said hydrogenation active component is selected from at least one group VIII metal element and at least one group VIB metal element.

109. The process of claim 108, wherein the group VIII metal element is present in an amount of from 0.5 to 10 wt.% on an oxide basis and the group VIB metal element is present in an amount of from 5 to 35 wt.% on an oxide basis, based on the total amount of the catalyst.

110. The process of claim 109, wherein the group VIII metal element is present in an amount of from 1.5 to 5 wt.% on an oxide basis and the group VIB metal element is present in an amount of from 6 to 30 wt.% on an oxide basis, based on the total amount of the catalyst.

111. The process of claim 110, wherein the group VIII metal element is present in an amount of 2 to 4 wt.% on an oxide basis, based on the total amount of the catalyst; the content of group VIB metal elements calculated as oxides is 10-30 wt.%.

112. A hydrotreating process comprising contacting a hydrocarbon oil with a catalyst having a hydrogenation catalytic action under hydrotreating conditions, wherein the catalyst having a hydrogenation catalytic action is the catalyst as defined in any one of claims 102-106 or the catalyst prepared by the method as defined in any one of claims 107-111.