CN108014809A - The aluminium oxide formed body of metallic element containing group ivb and catalyst and preparation method and application and hydrotreating method - Google Patents

Abstract

The invention discloses an aluminum oxide molded body containing Group IVB metal elements and its preparation method and application. compounds of elements, and The molded product of the hydrated alumina composition having a value of 5 is optionally dried and then calcined in an oxygen-containing atmosphere in the presence of water vapor. The invention also discloses a catalyst with hydrogenation catalysis, a preparation method and a hydrogenation treatment method using the aluminum oxide molded body as a carrier. The present invention uses hydrated alumina wet gel as a starting material to prepare a molded body with relatively high strength, which simplifies the overall process flow, reduces overall operating energy consumption, and avoids the use of pseudo-boehmite dry rubber powder as a raw material. The resulting dust pollution improves the working environment. Catalysts prepared using the aluminum oxide shaped body as a support exhibit increased catalytic activity in the hydroprocessing of hydrocarbon oils.

Description

Alumina molded body and catalyst containing group IVB metal element, preparation method and application and hydroprocessing methods

technical field

The present invention relates to the technical field of alumina molding. Specifically, the present invention relates to an alumina molding containing Group IVB metal elements and its preparation method and application. The present invention also relates to an alumina molding containing Group IVB metal elements. A catalyst with an aluminum molded body as a carrier and a preparation method thereof, and the present invention further relates to a hydrogenation treatment method using the catalyst.

Background technique

In traditional methods, alumina shaped bodies, especially γ-alumina shaped bodies, are often used as adsorbents or supported catalysts because of their good pore structure, suitable specific surface area and high heat resistance stability. carrier used. This kind of alumina is usually obtained from dried hydrated alumina, such as pseudo-boehmite, which is shaped, dried, and then calcined at high temperature.

Based on the above understanding, as shown in Figure 1, the prepared hydrated alumina wet gel needs to be dried to obtain pseudo-boehmite dry rubber powder, and then the pseudo-boehmite dry rubber powder is used as a starting point to add extrusion aids And optional chemical peptizer (inorganic acid and/or organic acid) and auxiliary agent (such as the compound containing Group IVB metal elements), after kneading and molding, the molding is dried and optionally roasted as an adsorbent or carrier used. The main problems of this preparation method are relatively large dust pollution and high energy consumption.

In order to reduce dust pollution and improve the working environment, researchers realized that the raw materials used for molding should be changed, and began to try to use hydrated alumina wet gel or semi-dried pseudo-boehmite as raw materials to prepare alumina moldings.

US4613585 discloses a kind of method for preparing alumina catalyst carrier, and this method comprises the following steps:

(a) Pour the aluminum sulfate solution and sodium aluminate solution into a container with deionized water at the same time, so that the aluminum sulfate solution and sodium aluminate solution are reacted, the reaction conditions are pH6.0-8.5, and the temperature is 50-65 ° C, thereby preparing the 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 sodium aluminate solution used in step (a) and step (b) The total amount is equivalent to 0.95-1.05 of the chemical equivalent of _the amount of aluminum sulfate used in step (a), thereby preparing a second water slurry, the _Al2O3 concentration of the second water slurry is 7wt% or higher ;

(c) filtering out the amorphous aluminum hydroxide in the second aqueous slurry to obtain a filter cake, first washing the obtained filter cake with dilute ammonia water, then washing with dilute nitric acid solution, and finally washing with dilute ammonia water to obtain Remove sulfate anion and sodium cation impurities, while adjusting the pH of the filter cake in the range of 7.5-10.5;

(d) Then, without aging the filter cake, the filter cake is dehydrated on a filter press and its _Al2O3 content is increased to 28-35 _wt %, and at a pH in the range of 7.5-10.5, at a Kneading the filter cake in a self-cleaning mixer with a residence time of 10 s or longer, so that the pseudo-boehmite particles grow up in a short time, thereby obtaining a mass containing these particles;

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

According to the method disclosed in US4613585, although the method can form hydrated alumina wet gel, there are limitations from the preparation conditions of amorphous aluminum hydroxide to kneading equipment and kneading conditions, resulting in complicated process operations. Moreover, the carrier prepared by this method should not have very high strength, and it is difficult to meet the requirements of industrial applications. The reason is that the content of free water in the extrudate prepared by this method is high, and the extrudate obtained by drying and roasting The product is loose. At the same time, it is difficult to regulate the pore structure of the carrier by using this method to prepare the carrier, so it is difficult to meet the needs of various application occasions.

CN103769118A discloses a heavy oil hydrogenation catalyst, including a carrier and an active component, the carrier is alumina, and the active component is a metal of Group VIII and/or Group VIB, wherein the metal of Group VIII is Co or Ni, and the metal of Group VIB is Mo Or W, wherein the alumina carrier is prepared by molding pseudo-boehmite with a dry basis content of less than 50%. The preparation process of the pseudo-boehmite with a dry basis content of less than 50% includes: (1) neutralizing the aluminum salt solution and the precipitating agent to form a gel; (2) filtering and recovering the solid product of the gelation reaction; (3) ) The dry basis content of the solid product obtained after drying is 50% or less.

CN103769118A uses pseudo-boehmite with a dry basis content of less than 50% to prepare an alumina carrier, and the pseudo-boehmite with a dry basis content of less than 50% is the solid product separated from the mixture obtained from the gelling reaction. It is obtained by drying. In the actual operation process, this is a difficult method to implement. The main reasons are as follows:

(1) Pseudo-boehmite that has not been completely dried has strong viscosity, is difficult to transfer, and easily causes secondary dust pollution;

(2) Drying starts from the surface. The drying of the wet solid product separated from the mixture obtained from the gelling reaction is incomplete drying, so there is a sandwich biscuit phenomenon, that is, the surface of part of the pseudo-boehmite is dried (that is, the dried surface is substantially free of free water), while the interior is still wet (that is, for the non-dried interior, the content of free water is basically maintained at the level before drying), since the surface is dried, Therefore, hard particles are formed. When peptizing agent and/or binder are added to this incompletely dried pseudo-boehmite and kneaded, the hard particles formed during the drying process are in the process of extrusion. It is easy to cause blockage and affect production efficiency;

(3) It is difficult to stably control the dry base of pseudo-boehmite. The instability of the dry base will cause great interference to the molding process, making the molding process very unstable, resulting in an increase in the amount of unqualified products and low production efficiency;

(4) CN103769118A adopts a conventional molding process when molding, yet because the dry basis (35%-50%) of the pseudo-boehmite it adopts is far lower than the conventional dry basis content (about 70%), that is The water content is high, and there is basically no extrusion pressure during the extrusion molding process. Therefore, the carrier obtained after the extrudate is dried and roasted has basically no mechanical strength. As long as a little external force is applied, it will be pulverized, which is not suitable for industrial applications. Possibilities, this is the biggest problem facing the technology.

In summary, how to simplify the preparation process of alumina supports and reduce the energy consumption of the operation while ensuring that the alumina supports that meet the requirements of industrial use can be obtained is still an issue. A technical problem that needs to be solved.

Contents of the invention

The purpose of the present invention is to simplify the preparation process of the alumina carrier, reduce the dust pollution in the preparation process of the alumina carrier, and at the same time, the prepared carrier can meet the requirements of industrial use.

Aiming at the problems faced by US4613585 and CN103769118A in the preparation of alumina carriers, the inventors of the present invention developed a unique approach, combining a compound containing at least two proton acceptor sites in its molecular structure with alumina hydrate wet gel directly from the synthesis reaction Mixing, the formed mixture can not only be molded, but also the molded body obtained by drying and optional calcination can have the strength that meets the industrial requirements. The present invention has been accomplished on this basis.

According to a first aspect of the present invention, the present invention provides a method for preparing an aluminum oxide molded body containing the Group IVB metal element, the method comprising the following steps:

(1) A hydrated alumina composition is molded to obtain a molded product. The hydrated alumina composition contains hydrated alumina, a compound having at least two proton acceptor sites, and at least one compound containing a Group IVB metal compounds of elements,

of the composition value below 5, the The value is determined by the following method: 10 g of the composition is dried in an air atmosphere at 120° C. for 240 minutes, and the mass of the dried composition is recorded as w ₁ , and calculated by formula I value,

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

(3) In the presence of water vapor, calcining the molded product obtained in step (1) or the dried molded product obtained in step (2) in an oxygen-containing atmosphere.

According to the second aspect of the present invention, the present invention provides an alumina molded body containing Group IVB metal elements prepared by the method described in the first aspect of the present invention.

According to the third aspect of the present invention, the present invention provides an alumina molded body containing Group IVB metal elements prepared by the method described in the first aspect of the present invention, wherein the hydrated alumina composition The value is not lower than 1.8.

According to the fourth aspect of the present invention, the present invention provides an alumina molded body containing Group IVB metal elements prepared by the method described in the first aspect of the present invention, wherein the hydrated alumina composition The value is less than 1.8.

According to a fifth aspect of the present invention, the present invention provides a method for producing and forming alumina hydrate, the method comprising the following steps:

(1) A hydrated alumina gel solution is provided, and the hydrated alumina gel solution is washed and solid-liquid separated to obtain the first hydrated alumina wet gel, and the conditions of the solid-liquid separation make the first The i value of the alumina monohydrate wet gel is not lower than 60%, preferably not lower than 62%, more preferably not higher than 82%, further preferably not higher than 80%, still more preferably not higher than 78.5%,

The i value is determined by the following method: 10 g of alumina hydrate wet gel is dried in an air atmosphere at 120° C. for 240 minutes, the mass of the dried sample is recorded as w ₂ , and the i value is calculated using formula II,

(2) using the method described in the first aspect of the present invention to mix the first alumina hydrate wet gel with a compound having at least two proton acceptor sites, followed by shaping, optional drying, and calcination, Thereby preparing an aluminum oxide molded body containing the Group IVB metal element;

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

According to the sixth aspect of the present invention, the present invention provides a method for producing and forming hydrated alumina containing Group IVB metal elements, the method comprising the following steps:

(1) A hydrated alumina gel solution is provided, and the hydrated alumina gel solution is washed to obtain a first hydrated alumina wet gel;

(2) using (2-1) or (2-2) to treat the first alumina hydrate wet gel to obtain the second alumina hydrate wet gel,

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

(2-2) performing solid-liquid separation on the first alumina hydrate wet gel to obtain a second alumina hydrate wet gel,

In (2-1) and (2-2), the condition of the solid-liquid separation is such that the i value of the second alumina hydrate wet gel is not less than 60%, preferably not less than 62%, more preferably Preferably not higher than 82%, more preferably not higher than 80%, even more preferably not higher than 78.5%,

The i value is determined by the following method: 10 g of alumina hydrate wet gel is dried in an air atmosphere at 120° C. for 240 minutes, the mass of the dried sample is recorded as w ₂ , and the i value is calculated using formula II,

(3) using the method described in the first aspect of the present invention to mix the second alumina hydrate wet gel with a compound having at least two proton acceptor sites, followed by shaping, optional drying, and calcination, Thereby preparing an aluminum oxide molded body containing the Group IVB metal element;

Wherein, in step (1), step (2) and step (3), the operation of mixing the compound containing the metal element of Group IVB is carried out in one, both or three, so that the hydrated alumina composition Compounds containing Group IVB metal elements.

According to the seventh aspect of the present invention, the present invention provides an alumina molded body containing Group IVB metal elements prepared by the method described in the third aspect of the present invention.

According to the eighth aspect of the present invention, the present invention provides the aluminum oxide molded body containing Group IVB metal elements described in the second aspect, the third aspect, the fourth aspect or the seventh aspect of the present invention as a carrier or adsorption application of the agent.

According to the ninth aspect of the present invention, the present invention provides a catalyst with hydrogenation catalysis, the catalyst contains a carrier and a Group VIII metal element and a Group VIB metal element supported on the carrier, wherein the The carrier is the aluminum oxide molded body containing Group IVB metal elements described in the second aspect, the third aspect, the fourth aspect or the seventh aspect of the present invention.

According to the tenth aspect of the present invention, the present invention provides a method for preparing a catalyst with hydrogenation catalysis, the method comprising loading Group VIII metal elements and Group VIB metal elements on a carrier, wherein the method also It includes preparing the alumina carrier containing Group IVB metal element by adopting the method described in the first aspect, the fifth aspect or the sixth aspect of the present invention.

According to the eleventh aspect of the present invention, the present invention provides a method for hydroprocessing, the method comprising contacting hydrocarbon oil with a catalyst having a hydrocatalytic effect under hydrotreating conditions, wherein the The catalyst for hydrogen catalysis is the catalyst described in the ninth aspect of the present invention or the catalyst prepared by the method described in the tenth aspect of the present invention.

Compared with the existing process of preparing alumina carrier with pseudo-boehmite dry rubber powder as the starting material (the process shown in Figure 1), the present invention directly prepares the hydrated alumina wet coagulation with the synthesis reaction. As a starting material for molding, glue has the following advantages:

(1) The step used to dry the hydrated alumina wet gel in the existing process is omitted, and when preparing the molding raw material, it is not necessary to introduce additional water to adjust the pseudo-boehmite dry rubber powder into a moldable material, which simplifies The overall technological process reduces the overall operating energy consumption;

(2) The dust pollution caused by the use of pseudo-boehmite dry rubber powder as a raw material is avoided, and the working environment is greatly improved.

Compared with the existing technology, such as US4613585 and CN103769118A, which directly use hydrated alumina wet gel as the starting material to prepare the carrier, the process of the present invention is more concise, more operable, and can effectively improve the final preparation. The strength of the molded body can be adjusted at the same time, and the pore size distribution of the finally prepared molded body can be adjusted to meet the requirements of various application occasions. The reason why the present invention can use alumina hydrate wet gel as the starting material to prepare shaped bodies with higher strength may be that the compound with at least two proton acceptor sites interacts with the free water in the alumina hydrate wet gel. Form hydrogen bonds and absorb free water in the hydrated alumina wet gel. At the same time, compounds with at least two proton acceptor sites can also undergo hydrogen bond interactions with the hydroxyl groups in the molecular structure of hydrated alumina to act as a physical gel. Soluble, so that the hydrated alumina wet gel can not only be formed, but also can make the final prepared molded body have higher strength.

Furthermore, catalysts produced with the alumina shaped bodies according to the invention as supports exhibit increased catalytic activity in the hydroprocessing of hydrocarbon oils.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention.

Figure 1 is the molding process generally used in current industrial applications.

FIG. 2 is used to illustrate a preferred embodiment of the alumina production molding method according to the present invention.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention. Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

According to the first aspect of the present invention, the present invention provides a method for preparing an alumina molded body, the method comprising the following steps: (1) molding a hydrated alumina composition to obtain a molded body;

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

(3) In the presence of water vapor, calcining the molded product obtained in step (1) or the dried molded product obtained in step (2) in an oxygen-containing atmosphere.

In step (1), the hydrated alumina composition contains hydrated alumina, a compound having at least two proton acceptor sites and at least one compound containing a Group IVB metal element.

The alumina hydrate may be one or more selected from alumina trihydrate and alumina monohydrate. The hydrated alumina preferably contains 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 pseudoboehmite. In a preferred embodiment of the present invention, the hydrated alumina contains pseudo-boehmite, more preferably pseudo-boehmite. The alumina hydrate composition according to this preferred embodiment is particularly suitable for producing shaped bodies for use as catalyst supports.

The hydrated alumina is directly derived from hydrated alumina wet gel, not from hydrated alumina dry rubber powder. In the present invention, the term "alumina hydrate wet gel" refers to a hydrous alumina gel obtained through a synthesis reaction and not subjected to a dehydration process to reduce its i value below 60% (preferably below 62%). In the present invention, the value of i is determined by the following method: 10 g of alumina hydrate wet gel is dried in an air atmosphere at 120° C. for 240 minutes, and the mass of the dried sample is recorded as w ₂ , and the value of i is calculated by formula II,

The synthesis reaction refers to the reaction of preparing aluminum hydroxide gel, which can be the synthesis reaction of hydrated alumina gel commonly used in the art, specifically, precipitation method (including acid method and alkali method), hydrolysis method, species classification, etc. method and rapid dehydration method. The synthesized hydrated alumina gel can be hydrated alumina gel that has not undergone aging, and can also be hydrated alumina gel that has undergone aging. The specific operation methods and conditions of the precipitation method, hydrolysis method, seed separation method and rapid dehydration method can be conventionally selected, which will be explained below. The alumina hydrate wet gel can be obtained by optionally aging the alumina hydrate gel obtained in the synthesis reaction, washing, separating solid and liquid, and collecting the solid phase.

Different from the hydrated alumina derived from dry rubber powder, the phase of the hydrated alumina directly derived from hydrated alumina gel will change during storage. For example, if the composition is left at ambient temperature and under closed conditions for 72 hours, the phase of the aluminum oxide hydrate in the composition after standing will change. The ambient temperature depends on the storage environment, and generally can be 5-50°C, such as 20-40°C. The closed condition means that the composition is placed in a closed container, and the closed container can be a closed container (such as a tank, a bucket or a box), or a sealed flexible covering (such as a sealed bag), and the closed container can be closed. The flexible wrap may be paper and/or a polymeric material, preferably a polymeric material such as plastic.

In one example, when the hydrated alumina directly derived from the hydrated alumina gel contains pseudoboehmite (eg, the hydrated alumina directly derived from the hydrated alumina gel is pseudoboehmite), the combination The composition is placed at ambient temperature and under closed conditions for 72 hours, and the content of alumina trihydrate in the composition after placement is higher than that in the composition before placement. In this example, based on the content of alumina trihydrate in the composition before placement, the alumina trihydrate content in the composition after placement is generally increased by at least 0.5%, preferably by at least 1%, preferably by 1.1% to 2%.

The hydrated alumina composition also contains a compound having at least two proton accepting sites. According to the hydrated alumina composition of the present invention, it can be used for molding (especially extrusion molding) without using dry rubber powder as a starting material, and the reason why the obtained molded body has higher strength may be that: the The compound with at least two proton acceptor sites interacts with the free water in the hydrated alumina wet gel through hydrogen bond interaction, thereby adsorbing the free water, and at the same time interacts with the hydroxyl group in the molecular structure of the hydrated alumina to achieve peptization role.

In the compound having at least two proton acceptor sites, the proton acceptor site refers to the site in the molecular structure of the compound that can form hydrogen bonds with water and hydroxyl groups. Specific examples of the proton acceptor site include, but are not limited to, one 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, a molecular structure containing one selected from the group consisting of hydroxyl, carboxyl, amino, ether bond, aldehyde, carbonyl, amide and fluorine atoms. Or a compound of two or more groups, preferably a hydroxyl group and/or an ether bond.

The compound having at least two proton acceptor sites can be an organic compound, an inorganic compound, or a combination of an organic compound and an inorganic compound. Using an organic compound having at least two proton accepting sites, the organic compound can be removed by a roasting process. By using an inorganic compound with at least two proton accepting sites, part of the elements in the inorganic compound can be retained in the finally prepared molded body, thus the auxiliary element can be introduced into the molded body through the inorganic compound.

In a preferred embodiment of the present invention, the compound having at least two proton accepting sites is a polymer having multiple (eg, more than three) proton accepting sites in the molecular structure. According to this preferred embodiment, better physical peptization can be obtained, thereby further improving the strength of the finally prepared molded body, especially when the extrusion process is used for molding, the strength of the finally prepared molded body can be further improved. Preferably, the polymer is an organic polymer. According to this preferred embodiment, specific examples of the compound having at least two proton acceptor sites may include, but not limited to, one or two or more of polyols, polyethers and acrylic polymers.

The polyhydroxy compound may include, but is not limited to, polysaccharides, etherified polysaccharides, and polyols.

The polysaccharide can be a homopolysaccharide, a heteropolysaccharide, or a combination of a homopolysaccharide and a heteropolysaccharide. The polysaccharide and its etherified products specifically include, but are not limited to, dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and amino polysaccharide. The cellulose ether refers to an ether derivative formed after hydrogen atoms on some of the hydroxyl groups in the cellulose molecule are substituted by hydrocarbon groups, wherein a plurality of the hydrocarbon groups may be the same or different. The hydrocarbyl group is selected from substituted hydrocarbyl groups and unsubstituted hydrocarbyl groups. The unsubstituted hydrocarbon group is preferably an alkyl group (for example: a C ₁ -C ₅ alkyl group). In the present invention, specific examples of C ₁ -C ₅ alkyl groups include C ₁ -C ₅ straight chain alkyl groups and C ₃ -C ₅ branched chain alkyl groups, which may be but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and tert-amyl. The substituted hydrocarbon group can be, for example, an alkyl group substituted by a hydroxyl group, a carboxyl group, a cyano group or an aryl group (for example: a C ₁ -C ₅ alkyl group substituted by a hydroxyl group, a C ₁ -C ₅ alkyl group substituted by a carboxyl group , C ₁ -C ₅ alkyl substituted by aryl), the aryl may be phenyl or naphthyl. Specific examples of the substituted hydrocarbyl groups may include, but are not limited to: cyano, benzyl, phenethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, carboxymethyl, carboxyethyl, and carboxy Propyl. Specific examples of the cellulose ether may include, but are not limited to, methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose, hydroxypropylmethylcellulose, cyanoethylcellulose, benzylcyanoethylcellulose, carboxymethylhydroxyethylcellulose and phenylcellulose. The polysaccharides and etherified polysaccharides can be provided in various forms. For example, galactomannan may be provided in the form of scallop powder.

The polyhydric alcohols specifically include but are not limited to polyvinyl alcohol, partially acetalized polyvinyl alcohol (the degree of acetalization can be 95% or less, preferably 80% or less, more preferably 70% or less, further preferably 50% % or less), one or more of polyether polyols and polyester polyols.

The polyether specifically includes, but is not limited to, polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer, and polytetrahydrofuran.

The acrylic polymer refers to a polymer containing an acrylic monomer unit, and the acrylic monomer unit may specifically be, but not limited to, an acrylic acid monomer unit and an alkacrylic acid monomer unit (preferably C ₁ -C ₅ Alkacrylic acid monomer units, more preferably methacrylic acid monomer units). The acrylic polymer specifically can be enumerated 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 polysaccharides and/or etherified polysaccharides, further preferably polysaccharides and/or etherified polysaccharides.

In a more preferred embodiment of the present invention, the compound having at least two proton acceptor sites contains galactomannan and cellulose ether. According to this more preferred embodiment, the shaped body formed from the alumina hydrate composition has higher strength. Further preferably, the compound having at least two proton acceptor sites is preferably galactomannan and cellulose ether.

In this more preferred embodiment, based on the total amount of the compound having at least two proton acceptor sites, the content of the galactomannan may be 10-70% by weight, preferably 15% by weight. -68% by weight, more preferably 20-65% by weight; the content of the cellulose ether may be 30-90% by weight, preferably 32-85% by weight, more preferably 35-80% by weight.

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

The compound containing Group IVB metal element may be a compound containing Group IVB metal element in various molecular structures commonly used in the art. For example, when the Group IVB metal element is selected from titanium and zirconium, the compound containing the Group IVB metal element may be selected from zirconium oxychloride (such as ZrOCl ₂ ·8H ₂ O), zirconium acetate, zirconium sulfate, nitric acid Zirconium, zirconium carbonate, zirconium hydroxide, ammonium zirconium basic (such as (NH ₄ ) ₂ ZrO(CO ₃ ) ₂ nH ₂ O), zirconium dioxide, titanic acid, metatitanic acid (H ₂ TiO ₃ ), titanium dioxide , titanium sulfate and the compound shown in formula I,

TiX _n (OR) _4-n (Formula III),

In formula III, X is halogen (for example: can be chlorine, bromine and iodine, preferably chlorine), R is C ₁ -C ₅ alkyl, n is an integer of 0-4 (for example can be 0, 1, 2 , 3 or 4, preferably 0 or 4).

Preferably, the compound containing the metal element of Group IVB can be selected from zirconium acetate, zirconium carbonate, zirconium hydroxide, ammonium zirconium basic, zirconium dioxide, titanic acid, metatitanic acid, titanium dioxide, titanium sulfate, tetrachloride Titanium, tetra-n-butyl titanate, tetraisobutyl titanate and tetraisopropyl titanate.

The content of the group IVB metal element-containing compound in the hydrated alumina composition can be conventionally selected. Generally, relative to 100 parts by weight of hydrated alumina, the content of the compound containing Group IVB metal elements in terms of oxides can be 1.5-85 parts by weight, preferably 2-80 parts by weight, more preferably 3-75 parts by weight share.

The hydrated alumina composition of The value is 5 or less, preferably 4 or less, more preferably 3.5 or less, still more preferably 3.2 or less. The hydrated alumina composition of The value may be 1.2 or more, preferably 1.3 or more, more preferably 1.4 or more. Specifically, the hydrated alumina composition of The value may be 1.2-5, preferably 4-1.2, more preferably 1.3-3.5, further preferably 1.4-3.2.

In one embodiment, the hydrated alumina composition of The value is not lower than 1.8, such as 1.8-5, preferably not lower than 1.9, such as 1.9-4, more preferably not lower than 2, such as 2-3.5. The hydrated alumina composition according to this embodiment can produce a shaped body having a bimodal distribution of pore diameters.

In another embodiment, the hydrated alumina composition The value is less than 1.8, such as 1.2 to less than 1.8, preferably not higher than 1.7, such as 1.3-1.7. The hydrated alumina composition according to this embodiment can produce a molded body having a unimodal distribution of pore diameters.

In the present invention, The value is determined by the following method: 10 g of the composition is dried in an air atmosphere at 120° C. for 240 minutes, and the mass of the dried composition is recorded as w ₁ , and calculated by formula I value,

According to the composition of the present invention, the content of the compound having at least two proton acceptor sites is such that the composition Values that meet the above requirements shall prevail. Preferably, relative to 100 parts by weight of the hydrated alumina, the content of the compound having at least two proton acceptor sites may be 1-25% by weight, preferably 2-20 parts by weight, more preferably 3- 18 parts by weight, more preferably 3.5-17 parts by weight.

The composition according to the present invention may or may not contain a peptizing agent. The peptizing agent can be a reagent with a gelling effect commonly used in the technical field of alumina molding, and its specific examples can include but are not limited to aluminum 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, said compound having at least two proton accepting sites, in particular said compound having at least two proton accepting sites is a polymeric compound having at least two proton accepting sites When used as a compound, the compound having at least two proton acceptor sites can act as a physical peptizer, so that the amount of peptizer used can be reduced, or even no peptizer can be used.

In a preferred embodiment of the present invention, relative to 100 parts by weight of alumina hydrate, the content of the peptizer is less than 5 parts by weight, preferably less than 3 parts by weight, more preferably less than 2 parts by weight.

In a particularly preferred embodiment of the invention, the composition according to the invention contains no peptizers.

The hydrated alumina composition can be prepared by mixing hydrated alumina and a compound having at least two proton accepting sites. As an example, the hydrated alumina composition is prepared by a method comprising the following steps: mixing the components in a raw material composition to obtain the hydrated alumina composition, that is, the mixture obtained by mixing is the hydrated alumina composition. An alumina composition comprising a raw material mixture comprising a hydrated alumina wet gel, a compound having at least two proton accepting sites, and at least one Group IVB metal element-containing compound.

The hydrated alumina wet gel can be synthesized by conventional methods, such as one or more of precipitation method (including acid method and alkali method), hydrolysis method, seed separation method and rapid dehydration method. Generally, it is obtained by optionally aging the hydrated alumina gel solution, followed by washing and solid-liquid separation.

The precipitation method includes acid method and alkali method. The acid method is to carry out precipitation reaction of aluminum salt with basic compound. The alkali method is to carry out precipitation reaction of aluminate with acidic compound. In the precipitation method, the mixture obtained by the precipitation reaction is optionally aged (preferably aged), followed by solid-liquid separation, and the separated solid phase is washed to obtain the alumina hydrate wet gel.

The types of the aluminum salt and the aluminate can be conventionally selected. Specific examples of the aluminum salt may include, but are not limited to, one 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 basic compound may be various common compounds capable of making water alkaline, and may be selected from ammonia water, hydroxide and basic salts. 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 water alkaline, such as metaaluminate, carbonate and bicarbonate. Specific examples of the basic compound may include, but are not limited to, ammonia water, sodium hydroxide, potassium hydroxide, sodium metaaluminate, potassium metaaluminate, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate and one or more of potassium carbonate. The acidic compound may be various common compounds capable of making water acidic, and may be an inorganic acid and/or an 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 can be generated in situ by introducing carbon dioxide.

The precipitation reaction can be carried out under conventional conditions, which is not particularly limited in the present invention. Generally, the amount of the basic compound or the acidic compound is such that the pH of the aluminum salt solution or the aluminate solution is 6-10, preferably 7-9. The precipitation reaction can be carried out at a temperature of 30-90°C, preferably 40-80°C.

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

The aluminum-containing compound may be an aluminum-containing compound commonly used in the process of preparing hydrated alumina gel by hydrolysis. The aluminum-containing compound is preferably an organoaluminum compound that can undergo a hydrolysis reaction, more preferably 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-tert-butoxide, and aluminum isooctoxide.

In the present invention, the specific conditions for the hydrolysis reaction are not particularly limited, and can be carried out under conventional conditions. Generally, the hydrolysis reaction can be carried out at a pH of 3-11, preferably 6-10. The hydrolysis reaction can be carried out at a temperature of 30-90°C, preferably 40-80°C.

In the precipitation method and the hydrolysis method, the aging conditions are not particularly limited, and can be performed under normal conditions. Generally, the aging can be performed at a temperature of 35-98°C, preferably 40-80°C. The duration of aging may be 0.2-6 hours.

The method for preparing hydrated alumina wet gel by seed separation method may include: adding seed crystals to supersaturated aluminate solution, decomposing to produce aluminum hydroxide, performing solid-liquid separation on the decomposed mixture, and separating the separated solid phase Washing is performed 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 hydrated alumina wet gel by the rapid dehydration method may include: roasting the hydrated alumina at a temperature of 600-950° C., preferably 650-800° C., performing hydrothermal treatment on the roasted product, and performing hydrothermal treatment on the mixture obtained by the hydrothermal treatment. Solid-liquid separation to obtain hydrated alumina wet gel. The duration of the roasting may be 1-6 hours, preferably 2-4 hours. The hydrothermal treatment may be performed at a temperature of 120-200°C, preferably 140-160°C. The hydrothermal treatment is usually carried out in a closed container under autogenous pressure.

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

In the raw material mixture, the i value of the alumina hydrate wet gel is not lower than 60%, preferably not lower than 62%. The i value of the alumina hydrate wet gel is preferably not higher than 82%, more preferably not higher than 80%, even more preferably not higher than 78.5%. Specifically, the i value of the alumina hydrate wet gel is 60-82%, preferably 60-80%, more preferably 62-78.5%.

A hydrated alumina wet gel whose i value meets the above requirements can be obtained by controlling the solid-liquid separation conditions of the prepared alumina hydrate gel solution for solid-liquid separation. In one embodiment of the present invention, the solid-liquid separation is performed once or twice, and at least the last solid-liquid separation is pressure filtration and/or vacuum filtration. In this embodiment, the obtained i value of the alumina hydrate wet gel is controlled by adjusting the applied pressure and/or the degree of vacuum. Specific examples of the device used in the pressurized filtration may include, but are not limited to, a plate and frame filter press, a belt filter, or a combination of the two. In order to control the i value of the obtained alumina hydrate wet gel, natural wind or pressurized wind can also be used to sweep the separated solid phase, so as to improve the efficiency of moisture removal. The pressure of the pressurized air can be conventionally selected, generally 0.1-12MPa, preferably 0.5-10MPa.

In the raw material mixture, the alumina hydrate wet gel obtained by solid-liquid separation generally has not undergone dehydration treatment to reduce its i value to below 60% (preferably below 62%).

In the raw material mixture, the amount of the compound having at least two proton acceptor sites can make the final prepared hydrated alumina composition The value satisfies the requirements stated earlier.

The raw material mixture may or may not contain a peptizer. Preferably, relative to 100 parts by weight of alumina hydrate wet gel, the content of the peptizer is 5 parts by weight or less, preferably 3 parts by weight or less, more preferably 2 parts by weight or less, and the alumina hydrate wet gel Calculated as hydrated alumina. Further preferably, the raw material mixture does not contain peptizing agent.

Various mixing sequences may be used to mix the Group IVB metal element-containing compound, the compound having at least two proton accepting sites, and the alumina hydrate wet gel.

In one embodiment, as shown in Figure 2, the compound containing the metal element of Group IVB can be mixed in the process of preparing the hydrated alumina wet gel, or the compound containing the metal element of Group IVB can be added to the prepared In the hydrated alumina wet gel, it is also possible to mix part of the compound containing the IVB group metal element in the process of preparing the hydrated alumina wet gel, and the remaining part of the compound containing the IVB group metal element is added to the prepared hydrated oxide In the aluminum wet gel, the operation of mixing the compound containing the Group IVB metal element can be performed at one, two or three of the above-mentioned addition timings. When mixing the compound containing Group IVB metal elements in the process of preparing hydrated alumina wet gel, it can be used in one, two, three or four of the precipitation reaction process, aging process, solid-liquid separation process and washing process. Among them, the operation of mixing compounds containing Group IVB metal elements is carried out. Whether to mix the compound containing Group IVB metal elements during the preparation of the alumina hydrate wet gel, and the timing of mixing can be selected according to the type of precipitation reaction.

In another embodiment, as shown in FIG. 2 , the compound containing Group IVB metal elements is mixed after the alumina hydrate wet gel is prepared. In this embodiment, one of the following methods can be used: (1) firstly mix the compound containing the Group IVB metal element with the hydrated alumina wet gel, and then mix the compound with at least two proton acceptor sites; (2) first mix the compound with at least two proton acceptor sites with the alumina hydrate wet gel, and then mix the compound containing the IVB group metal element; (3) simultaneously mix the compound containing the IVB group metal element and A compound having at least two proton acceptor sites is mixed with a hydrated alumina wet gel.

Preferably, the compound containing the Group IVB metal element is mixed after the alumina hydrate wet gel is prepared.

Alumina hydrate wet gels can be mixed with compounds having at least two proton accepting sites using conventional methods. The alumina hydrate wet gel can be mixed with a compound having at least two proton accepting sites under shear. In one embodiment, the mixing method is stirring. The hydrated alumina composition can be obtained by putting the alumina hydrate wet gel and the compound having at least two proton acceptor sites in a container with a stirring device, and mixing them uniformly by stirring. The stirring can be carried out in a container with a stirring device, or in a beater. In another embodiment, the mixing method is kneading. The alumina hydrate composition may be obtained by kneading the alumina hydrate wet gel with a compound having at least two proton acceptor sites in a kneader. The type of the kneader is not particularly limited. A combination of agitation and mixing may be used to combine the alumina hydrate wet gel with the compound having at least two proton acceptor sites. At this time, it is preferable to first perform stirring and then perform kneading.

During the mixing process, water can be supplemented or not supplemented, as long as the prepared hydrated alumina composition can The value satisfies the above requirements. Generally, from the perspective of improving the uniformity of mixing, water can be supplemented during the mixing process. Generally, the weight ratio of supplementary added water to the compound having at least two proton acceptor sites may be 5-15:1, preferably 8-12:1, more preferably 9-10:1.

In step (1), the molding method is not particularly limited, and various molding methods commonly used in the art can be used, such as extrusion, spraying, spheronizing, tableting or combinations thereof. In a preferred embodiment of the present invention, the shape is formed by extrusion.

In step (1), the molded object can have various shapes according to the specific requirements for use, such as: spherical, honeycomb, bird's nest, sheet or strip (such as clover, dish, cylinder and Raschig ring) One or more than two.

According to the preparation method of the present invention, the molding obtained in step (1) can be sent to step (2) for drying, and then sent to step (3); the molding obtained in step (1) can also be directly sent to Roasting is carried out in step (3).

In step (2), the temperature for drying the molded product can be a conventional choice in the art. Generally, the drying temperature may be above 60°C and not higher than 350°C, preferably 80-300°C, more preferably 110-260°C. The drying time can be properly selected according to the drying temperature. Generally, the duration of the drying may be 1-48 hours, preferably 2-24 hours, more preferably 2-12 hours, further preferably 2-4 hours. The drying can be carried out in an oxygen-containing atmosphere (such as an air atmosphere), or in an inert atmosphere (such as an atmosphere formed by nitrogen and/or zero-group gases), preferably in an oxygen-containing atmosphere. The drying may be performed under normal pressure (ie, 1 standard atmospheric pressure) or under reduced pressure.

In step (3), the calcination temperature may be 400-1200°C, preferably 450-1100°C, more preferably 500-1000°C. The duration of the calcination may be 1-20 hours, preferably 1.5-15 hours, more preferably 2-12 hours, further preferably 2-6 hours.

In step (3), when calcination is performed, the rate of temperature increase to the calcination temperature can be conventionally selected. Preferably, the temperature increase rate in the container containing the molding to the firing temperature can be 10-400°C/hour, preferably 30-350°C/hour, more preferably 60-300°C/hour, further preferably 100-200°C/hour. The temperature in the container containing the molded product may be raised from ambient temperature to the firing temperature, or the temperature in the container containing the molded product may be raised from the drying temperature to the firing temperature, and it is not particularly limited.

In step (3), the calcination is carried out under water vapor in an oxygen-containing atmosphere, and the alumina support thus prepared has a higher pore volume and a larger specific surface area, thereby effectively improving the strength of the alumina molded body. performance.

Roasting in the presence of water vapor can be achieved by passing an air stream containing water vapor into the container containing the molding during the roasting process. The amount of steam (introduction) can be selected according to the amount of molding. Generally, the amount of steam can be 0.01-0.8L/(min·g shaped product), preferably 0.02-0.4L/(min·g shaped product), the shaped product is calculated as alumina hydrate.

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

The water vapor may be water vapor from various sources. In a preferred embodiment, at least part of the water vapor in step (3) is the water vapor generated during the drying or roasting process of the molded product obtained in step (1).

Specifically, when the molded product obtained in step (1) is sent to step (2) for drying, the water vapor generated during the drying process can be collected, and at least part of the water vapor generated during the drying process can be sent to step (3 )middle. At this time, according to the amount of water vapor generated in the drying process, fresh water vapor can be added or not. The term "fresh water vapor" is different from the water vapor generated during the drying and roasting process, and refers to the water vapor generated by the water vapor generation process other than the drying and roasting process in the method of the present invention. All the water vapor generated by the drying process can be sent to step (3). It is also possible to feed part of the water vapor generated in the process into step (3). Preferably, 10-90% by volume, preferably 20-88% by volume, more preferably 30-85% by volume, further preferably 60-85% by volume of the gas generated during the drying process is fed into step (3).

When the molded object obtained in step (1) is directly sent to step (3) for roasting, the water vapor generated in the roasting process (including the heating process of raising the temperature to the roasting temperature) can be collected, and at least part of the water vapor in the roasting process can be collected. The water vapor produced in the process is recycled into step (3). During the actual operation, the gas in the container containing the molded product can be drawn out during the heating and sintering period, and at least part of the drawn out gas can be circulated into the container as circulating gas. All the extracted gas can be circulated into the container as cycle gas, or part of the extracted gas can be cycled into the container as cycle gas. Preferably, part of the extracted gas is circulated into the container as cycle gas, at which point fresh water vapor is preferably added to the container. More preferably, 10-90% by volume, preferably 20-88% by volume, more preferably 30-85% by volume, further preferably 60-85% by volume of the extracted gas is recycled into the container.

The calcination in step (3) is carried out in an oxygen-containing atmosphere, so that the hydrated alumina is transformed into alumina. In order to convert the hydrated alumina gel into alumina at a higher conversion rate, it is preferable to feed an oxygen-containing gas into the container containing the molded product during the firing process. The oxygen-containing atmosphere can be oxygen, air, or a mixture of oxygen and inert gas, and specific examples of the inert gas can include but are not limited to nitrogen and/or group zero element gases (such as argon and/or helium gas). Oxygen-containing gas can be fed together with water vapor into the container containing the moldings.

The aluminum oxide molded body containing Group IVB metal elements prepared by the method of the present invention has a rich pore structure and adjustable pore size distribution, and is suitable as an adsorbent or a catalyst carrier.

Thus, according to a second aspect of the invention, the invention provides a Group IVB metal element-containing alumina shaped body produced by the process of the invention.

According to a third aspect of the present invention, the present invention provides a Group IVB metal element-containing alumina formed body prepared by the method of the present invention, wherein the hydrated alumina composition The value is not lower than 1.8, such as 1.8-5, preferably not lower than 1.9, such as 1.9-4, more preferably not lower than 2, such as 2-3.5.

According to the third aspect of the present invention, the pore size distribution of the aluminum oxide molded body containing Group IVB metal elements is a bimodal distribution. Wherein, measured by mercury porosimetry, the most probable pore diameters are respectively 4-60nm and greater than 60nm; preferably, the most probable pore diameters are respectively 5-40nm (such as 5-20nm) and 80-500nm (such as 100-400nm, preferably 200-300nm).

According to the fourth aspect of the present invention, the present invention provides an alumina molded body containing Group IVB metal elements prepared by the method described in the first aspect of the present invention, wherein the hydrated alumina composition The value is less than 1.8, preferably not higher than 1.7, more preferably 1.3-1.7.

According to the fourth aspect of the present invention, the pore diameter of the aluminum oxide molded body containing Group IVB metal elements has a unimodal distribution. Wherein, the most probable pore diameter is 4-60 nm, preferably 4.5-40 nm, more preferably 4.5-20 nm, as determined by mercury intrusion porosimetry.

According to the second aspect, the third aspect or the fourth aspect of the present invention, the aluminum oxide molded body containing Group IVB metal elements has relatively high strength. Generally, the radial crushing strength of the aluminum oxide molded body containing Group IVB metal elements according to the present invention is above 10 N/mm, usually 10-50 N/mm, preferably 14-50 N/mm. In one example, the aluminum oxide formed body containing the Group IVB metal element is the aluminum oxide formed body containing the Group IVB metal element described in the third aspect of the present invention, the aluminum oxide formed body containing the Group IVB metal element The radial crushing strength is 10-30N/mm. In another example, the aluminum oxide formed body containing the Group IVB metal element is the aluminum oxide formed body containing the Group IVB metal element described in the fourth aspect of the present invention, the aluminum oxide formed body containing the Group IVB metal element The radial crushing strength is 15-50N/mm. In the present invention, the radial crushing strength of the molded body is measured by the method specified in RIPP 25-90.

According to a fifth aspect of the present invention, as shown in Figure 2, the present invention provides a method for producing and forming hydrated alumina, the method comprising the following steps:

(1) A hydrated alumina gel solution is provided, and the hydrated alumina gel solution is washed to obtain a first hydrated alumina wet gel;

Optionally, (2) using (2-1) or (2-2) to treat the first alumina hydrate wet gel to obtain a second alumina hydrate wet gel,

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

(2-2) performing solid-liquid separation on the first alumina hydrate wet gel to obtain a second alumina hydrate wet gel,

In (2-1) and (2-2), the condition of the solid-liquid separation is such that the i value of the second alumina hydrate wet gel is not less than 60%, preferably not less than 62%, more preferably Preferably not higher than 82%, more preferably not higher than 80%, even more preferably not higher than 78.5%,

The i value is determined by the following method: 10 g of alumina hydrate wet gel is dried in an air atmosphere at 120° C. for 240 minutes, the mass of the dried sample is recorded as w ₂ , and the i value is calculated using formula II,

(3) After mixing the first hydrated alumina wet gel or the second hydrated alumina wet gel with a compound having at least two proton acceptor sites using the method described in the first aspect of the present invention forming, optionally drying, and firing to produce an alumina shaped body;

Wherein, in step (1), step (2) and step (3), the operation of mixing the compound containing the metal element of Group IVB is carried out in one, both or three, so that the hydrated alumina composition Compounds containing Group IVB metal elements. The method of mixing the compound containing the Group IVB metal element is the same as the method and sequence described above, and will not be described in detail here.

In step (1), the hydrated alumina gel solution refers to a solution containing hydrated alumina gel that has been or has not been aged and obtained from the synthesis reaction of the hydrated alumina gel. The hydrated alumina gel solution may be prepared on site, or may be a hydrated alumina gel solution transported from other production sites. Preferably, the alumina hydrate gel solution is an alumina hydrate wet gel solution prepared on site. The synthesis method and conditions of the hydrated alumina gel have been described in detail above, and will not be repeated here.

Because the hydrated alumina gel solution obtained by the synthesis reaction has acidity and alkalinity, the hydrated alumina wet gel is washed in step (1), to remove acidic substances and alkaline substances therein, to avoid the formation of acidic substances and alkaline substances There is an adverse effect on the hydrated alumina gel while increasing the solid content of the hydrated alumina gel solution. The washing in step (1) can be carried out under normal conditions, as long as the amount of acidic substances and alkaline 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, so as to squeeze out the washing water to obtain the first hydrated alumina wet gel. The i value of the first alumina hydrate wet gel may be the i value of the alumina hydrate wet gel mixed with a compound having at least two proton acceptor sites as described in the first aspect of the present invention, or It may be higher than the i value of the alumina hydrate wet gel mixed with a compound having at least two proton accepting sites and a compound containing a Group IVB metal element according to the first aspect of the present invention.

In one embodiment, the i value content of the first hydrated alumina wet gel satisfies the moisture coagulation of hydrated alumina mixed with a compound having at least two proton acceptor sites described in the first aspect of the present invention. The i value of the gel, that is, the i value of the first alumina hydrate wet gel is not lower than 60%, preferably not lower than 62%. In this embodiment, the i value of the first alumina hydrate wet gel is preferably not higher than 82%, more preferably not higher than 80%, even more preferably not higher than 78.5%.

According to this embodiment, the first hydrated alumina wet gel can be directly sent to step (3), and mixed with the compound having at least two proton acceptor sites and the compound containing the Group IVB metal element. This is especially applicable to occasions that meet the following requirements: (A) the solid-liquid separation equipment in the washing device has a good separation ability, enough to control the i value of the first hydrated alumina wet gel to meet the above range; (B) The washing device and the mixing device can be arranged compactly, so that the output of the washing device can directly enter the mixing device.

According to this embodiment, the first hydrated alumina wet gel can also be sent to step (2) and treated by (2-1). This is especially applicable to occasions that meet the following requirements: (A) the solid-liquid separation equipment in the washing device has a good separation ability, enough to control the i value of the first hydrated alumina wet gel to meet the above range; (B) The washing device and the mixing device cannot be arranged compactly so that the discharge from the washing device cannot directly enter the mixing device.

In another embodiment, the i value of the first alumina hydrate wet gel is higher than 82%, which cannot meet the requirements of the first aspect of the present invention for mixing with compounds having at least two proton acceptor sites. Require. According to this embodiment, the first hydrated alumina wet gel is sent to step (2) and treated by (2-1) or (2-2).

This embodiment is particularly suitable for occasions where the separation capacity or operating conditions of the solid-liquid separation equipment in the washing device are not sufficient to control the i value of the first alumina hydrate wet gel to meet the requirements described in the first aspect of the present invention, And when the washing device and the mixing device cannot be installed compactly.

In step (2), (2-1) or (2-2) is used to treat the first alumina hydrate wet gel to obtain a second alumina hydrate wet gel.

In (2-1), the first hydrated alumina wet gel is mixed with water to form a slurry, which can improve the transport performance of the hydrated alumina wet gel.

In (2-1), the amount of water added is subject to the formed slurry meeting the transportation requirements, which can be selected according to the specific transportation equipment.

The i value of the second alumina hydrate wet gel obtained in step (2) meets the requirements of the alumina hydrate wet gel mixed with a compound having at least two proton acceptor sites described in the first aspect of the present invention. The i value, that is, the i value of the alumina hydrate wet gel is not lower than 60%, preferably not lower than 62%. The i value of the second alumina hydrate wet gel is preferably not higher than 82%, more preferably not higher than 80%, even more preferably not higher than 78.5%.

The second alumina hydrate wet gel whose i value meets the above requirements can be obtained by controlling the conditions of solid-liquid separation in step (2). The method of adjusting the i value of the alumina hydrate wet gel by selecting the solid-liquid separation method and its conditions has been described in detail above, and will not be described in detail here.

In step (3), use the method described in the first aspect of the present invention to combine the first hydrated alumina wet gel or the second hydrated alumina wet gel with a compound having at least two proton acceptor sites and a compound containing the second Compounds of Group IVB metal elements are mixed and then molded, optionally dried, and calcined to prepare an alumina molded body. The i value of the first hydrated alumina wet gel and the second hydrated alumina wet gel sent into step (3) satisfies the compound with at least two proton acceptor sites described in the first aspect of the present invention and Values of i for alumina hydrate wet gels mixed with compounds containing group IVB metal elements.

The method according to the fifth aspect of the present invention can be implemented in an alumina production molding system, which includes a hydrated alumina gel production unit, a solid-liquid separation and washing unit, a mixing unit, a molding unit, and an optional Drying unit, and roasting unit.

The output port of the hydrated alumina gel solution of the hydrated alumina gel production unit is connected with the input port of the to-be-separated washing material of the solid-liquid separation and washing unit, and the solid-phase material output of the solid-liquid separation and washing unit is The port is connected with the solid phase material input port of the mixing unit, the mixed material output port of the mixing unit is connected with the raw material input port of the molding unit, and the material input port of the drying unit is connected with the molding unit. The output port of the molded product is connected, and the input port of the material to be roasted of the roasting unit is connected with the output port of the dried material of the drying unit or the output port of the molded product of the molding unit,

The roasting unit includes a container for accommodating materials to be roasted, and a water vapor delivery subunit for inputting water vapor into the container during the roasting process.

The hydrated alumina gel production unit is used to generate hydrated alumina gel solution through synthesis reaction. The method for synthesizing the hydrated alumina gel can be a conventional method, such as the above-mentioned precipitation method, hydrolysis method, seed separation method and rapid dehydration method, which will not be described in detail here.

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

The solid-liquid separation and washing unit is used to separate and wash the aqueous alumina hydrate gel solution output from the hydrated alumina gel production unit to obtain a hydrated alumina wet gel, and the hydrated alumina wet gel Glue The value satisfies the requirement of being able to mix with compounds having at least two proton accepting sites according to the first aspect of the invention.

The solid-liquid separation and washing unit can adopt various commonly used methods for solid-liquid separation and washing, so as to obtain Alumina hydrate gels that meet the requirements for mixing with compounds having at least two proton acceptor sites. The solid-liquid separation and washing unit can use a conventional solid-liquid separation device, such as a filter device, a centrifugal device or a combination of both. When the solid-liquid separation and washing unit includes a filter device, the filter device can be one or a combination of two or more of a gravity filter device, a pressure filter device and a vacuum filter device. Preferably, the filtering device comprises at least a pressurized filtering device. Specific examples of the pressurized filtration device may include, but are not limited to, a plate-and-frame filter press, a belt filter, or a combination of the two. In order to control the obtained hydrated alumina wet gel value, the solid-liquid separation and washing unit may also include a purging device, which uses natural wind or pressurized wind to purge the separated solid phase, thereby improving the efficiency of moisture removal. The pressure of the pressurized air can be conventionally selected, generally 0.1-12MPa, preferably 0.5-10MPa.

The solid-liquid separation and washing unit may include one or more solid-liquid separation subunits, preferably at least one solid-liquid separation subunit and the last solid-liquid separation subunit is a pressure filter and/or a vacuum filter, to Make the solid-phase material (that is, hydrated alumina wet gel) obtained by solid-liquid separation and washing unit The value satisfies the requirement of mixing with a compound having at least two proton accepting sites according to the first aspect of the invention. By adjusting the applied pressure or the size of the vacuum degree, the final obtained hydrated alumina wet gel can be adjusted value is adjusted. When the solid-liquid separation and washing unit includes more than two solid-liquid separation subunits, except that the last solid-liquid separation subunit preferably adopts the solid-liquid separation method with pressure as the driving force, the remaining solid-liquid separation subunits can be Use pressure filter device and/or vacuum filter device, also can not use pressure filter device and vacuum filter device, preferably adopt pressure filter device and/or vacuum filter device.

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

Based on the trend of the hydrated alumina gel material flow, the solid-liquid separation and washing unit is arranged between the hydrated alumina gel production unit and the mixing unit, and is used to clean the gel solution output from the hydrated alumina gel production unit. separate, get Alumina hydrate wet gel whose value meets the mixing requirements, provides the raw material for the mixing unit.

On the premise of being able to provide the mixing unit with alumina hydrate gel that meets the requirements, from the perspective of facilitating the transportation of materials, in a preferred embodiment, the solid-liquid separation and washing unit may include washing subunits, Dilution subunit, transport subunit and solid-liquid separation subunit,

The washing subunit is used to collect and wash the solid phase in the hydrated alumina gel solution output from the hydrated alumina gel production unit;

The dilution subunit is used to dilute the solid phase output by the washing subunit with water to obtain a slurry;

The delivery subunit is used to send the slurry output from the dilution subunit into the solid-liquid separation subunit;

The solid-liquid separation subunit is used for solid-liquid separation of the slurry to obtain a hydrated alumina wet gel.

The conveying subunit can adopt various conventional conveying devices, such as a conveyor belt. The conveying subunit and the washing subunit can be integrated together, for example, integrated into one device, so as to perform washing during conveying and improve production efficiency. For example: a conveyor belt with solid-liquid separation function is used, and a spray device is installed above the solid-phase material on the conveyor belt, so as to perform washing and solid-liquid separation during transportation.

The mixing unit includes an auxiliary agent adding device for adding auxiliary agents to the hydrated alumina wet gel. When the production system is running, the auxiliary agent adding device at least adds at least two protons to the hydrated alumina wet gel. A compound for the acceptor site and optionally a Group IVB metal element-containing compound.

The mixing unit can use conventional mixing devices, such as various common mixers, kneaders or a combination of the two. The molding unit can adopt a conventional molding device, such as an extrusion device, a spray device, a spheronizing device, a tablet pressing device or a combination of two or more. The drying unit may adopt a conventional drying device, which is not particularly limited in the present invention. The calcination unit may adopt a conventional calcination device, which is not particularly limited in the present invention.

Based on the flow direction of the hydrated alumina gel, the production molding system does not set enough water between the solid-liquid separation and washing unit’s solid-phase material outlet port and the mixing unit’s hydrated alumina wet gel input port. A dehydration unit where the i-value of the wet gel is reduced below 60%, preferably below 62%.

The water vapor conveying subunit is used to input water vapor into the container containing the material to be roasted during the roasting process. The water vapor conveying subunit may be connected with a water vapor storage tank, so as to input water vapor into the container during the roasting process. The water vapor input through the water vapor conveying sub-unit may be fresh water vapor, water vapor generated during a drying process or a roasting process, or a combination of fresh water vapor and water vapor generated during a drying or roasting process.

The production molding system preferably also includes a water vapor collection unit, the water vapor input port of the water vapor collection unit is connected with the water vapor output port of the drying unit for outputting the water vapor generated in the drying process and/or the steam output port of the roasting unit for The water vapor output port of the water vapor produced in the output roasting process is connected, and the water vapor output port of the water vapor collection unit is connected with the water vapor inlet port of the water vapor delivery sub-unit for collecting the drying unit during the drying process. or the water vapor generated by the roasting unit during the roasting process, and at least part of the steam is circulated into the roasting unit. In one embodiment, the production molding system includes a drying unit, and when the input port of the material to be roasted of the roasting unit is connected with the output port of the drying material of the drying unit, the output port of the drying unit used to output the drying process The water vapor output port of the generated water vapor communicates with the water vapor input port of the water vapor collection unit to receive the water vapor generated by the drying unit during the drying process. In another embodiment, the input port of the material to be roasted of the roasting unit communicates with the output port of the molded product of the molding unit (that is, the production molding system does not include a drying unit), and the roasting unit is used for The steam output port for outputting the steam generated during the roasting process communicates with the steam input port of the steam collecting unit to receive the steam generated during the roasting process.

In the actual production process, on the basis of the existing hydrated alumina gel production equipment, additional mixing units, molding units, drying units and roasting units can be added, so as to realize the integration of production and molding of hydrated alumina gels.

According to the sixth aspect of the present invention, the present invention provides an alumina carrier containing Group IVB metal elements prepared by the method described in the fifth aspect of the present invention.

According to the sixth aspect of the present invention, the aluminum oxide molded body containing Group IVB metal elements has a rich pore structure and is suitable for use as an adsorbent or a catalyst carrier.

According to the alumina carrier containing Group IVB metal elements described in the sixth aspect of the present invention, through the hydrated alumina composition Carriers with different pore distributions can be obtained by adjusting the value.

In one embodiment, the hydrated alumina composition of The value is not less than 1.8, such as 1.8-5, preferably not less than 1.9, such as 1.9-4, more preferably not less than 2, such as 2-3.5, and the prepared IVB-containing metal The pore size distribution of the elemental alumina shaped body is bimodal. Wherein, measured by mercury porosimetry, the most probable pore diameters are respectively 4-60nm and greater than 60nm; preferably, the most probable pore diameters are respectively 5-40nm (such as 5-20nm) and 80-500nm (such as 100-400nm, preferably 200-300nm).

In another embodiment, the hydrated alumina composition The value is less than 1.8, preferably not higher than 1.7, more preferably 1.3-1.7, and the pore size distribution of the prepared aluminum oxide molded body containing Group IVB metal elements shows a unimodal distribution. Wherein, the most probable pore diameter is 4-60 nm, preferably 4.5-40 nm, more preferably 4.5-20 nm, as determined by mercury intrusion porosimetry.

According to the sixth aspect of the present invention, the aluminum oxide molded body containing Group IVB metal elements has relatively high strength. Generally, according to the sixth aspect of the present invention, the radial crushing strength of the aluminum oxide molded body containing Group IVB metal elements is above 10N/mm, usually 10-50N/mm, preferably 14-50N/mm .

According to the seventh aspect of the present invention, the present invention provides the aluminum oxide molded body containing Group IVB metal element according to the second aspect, the third aspect, the fourth aspect or the sixth aspect of the present invention as a carrier or Adsorbent application.

The aluminum oxide shaped bodies containing group IVB metal elements according to the invention are particularly suitable as supports for supported catalysts. The supported catalyst can be various catalysts commonly used in the art that can be supported by an alumina shaped body containing Group IVB metal elements. Preferably, the catalyst is a catalyst with hydrogenation catalysis. That is, the Group IVB metal element-containing alumina shaped body according to the invention is particularly suitable as a support for a catalyst having a hydrogenation catalytic effect.

Various methods (for example: impregnation) commonly used in the art can be used to load the active component with hydrogenation catalysis on the aluminum oxide molded body containing the Group IVB metal element according to the present invention, for example: by using the An aqueous solution of the active component is impregnated into the shaped body according to the invention, and then the shaped body loaded with the active component is dried and optionally calcined, so that a catalyst having a hydrogenation catalytic effect is obtained.

According to the eighth aspect of the present invention, the present invention provides a catalyst with hydrogenation catalysis, the catalyst contains a carrier and a hydrogenation active component loaded on the carrier, wherein the carrier is The aluminum oxide molded body containing Group IVB metal elements according to the second aspect, the third aspect, the fourth aspect or the sixth aspect.

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

According to the ninth aspect of the present invention, the present invention provides a method for preparing a catalyst with hydrogenation catalysis, the method includes loading hydrogenation active components on a carrier, wherein the method also includes using the first method of the present invention The method described in one aspect prepares an alumina carrier containing Group IVB metal elements.

According to the preparation method of the catalyst having hydrogenation catalytic function of the present invention, the hydrogenation active component can be conventionally selected. Preferably, the hydrogenation active components are Group VIB metal elements and Group VIII metal elements. The Group VIII metal element is preferably cobalt and/or nickel, and the Group VIB 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 the hydrotreating of hydrocarbon oil, based on the total amount of the prepared catalyst, the loading of the Group VIII metal element and the Group VIB metal element on the carrier is such that the final preparation The contents of Group VIII metal elements and Group VIB metal elements in the catalyst can meet the requirements described in the eighth aspect of the present invention.

According to the preparation method of the catalyst with 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 impregnation. The impregnation may be saturated or excessive impregnation. The compound containing the metal element of Group VIII and the compound containing the metal element of Group VIB can be dissolved in a solvent (usually water) to form an impregnation solution, and the support can be described with the impregnation solution. The compound containing the Group VIII metal element can be a conventional choice in the technical field of catalyst preparation, and can be selected from nitrates of the Group VIII metal elements, chlorides of the Group VIII metal elements, sulfates of the Group VIII metal elements, Formate of group VIII metal elements, acetate of group VIII metal elements, phosphate of group VIII metal elements, citrate of group VIII metal elements, oxalate of group VIII metal elements, Carbonates of Group VIII metal elements, basic carbonates of Group VIII metal elements, hydroxides of Group VIII metal elements, phosphates of Group VIII metal elements, phosphides of Group VIII metal elements, Sulfides of Group VIII metal elements, aluminates of Group VIII metal elements, molybdates of Group VIII metal elements, tungstates of Group VIII metal elements and water-soluble oxides of Group VIII metal elements. Specifically, specific examples of the compound containing a Group VIII metal element may include, but are not limited to, nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, basic cobalt carbonate, chlorine cobalt and nickel chloride. Specific examples of compounds containing Group VIB metal elements may include, but are not limited to, ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide, and tungsten oxide.

According to the preparation method of the catalyst with hydrogenation catalysis of the present invention, the hydrogenation active components can be loaded on the carrier at the same time, or the hydrogenation active components can be loaded on the carrier in stages.

According to the preparation method of the catalyst with hydrogenation catalysis of the present invention, the impregnated support can be dried and optionally calcined under the conditions commonly used in the art. Generally, the drying conditions include: the temperature may be 100-200°C, preferably 120-150°C; the duration may be 1-15 hours, preferably 1.5-10 hours, more preferably 2-4 hours. The calcination conditions include: the temperature may be 350-550°C, preferably 400-500°C; the duration may be 1-8 hours, preferably 1.5-6 hours, more preferably 1.5-3 hours.

According to the tenth aspect of the present invention, the present invention provides a method for hydroprocessing, the method comprising contacting hydrocarbon oil with a catalyst having a hydrogenation catalytic effect under hydrotreating conditions, wherein the hydrogenation The catalytic catalyst is the catalyst described in the eighth aspect of the present invention or the catalyst prepared by the method described in the ninth aspect of the present invention.

The hydrotreating method of the present invention has no special limitation on the type of hydrocarbon oil and hydrotreating conditions, which can be conventional choices in the field. Specifically, the hydrocarbon oil can be various heavy mineral oils, synthetic oils or mixed distillates of heavy mineral oil and synthetic oil, for example: the hydrocarbon oil can be selected from crude oil, distillate oil, solvent refined oil, One or more of wax paste, waxy oil, Fischer-Tropsch synthetic oil, coal liquefied oil, light deasphalted oil and heavy deasphalted oil. Preferably, the hydrocarbon oil is hydrocarbon oil containing heavy mineral oil, such as various inferior heavy oils, such as atmospheric residue, vacuum residue, vacuum gas oil, coker wax oil and coal tar. The conditions of the hydrogenation treatment include: the temperature can be 300-380° C.; the hydrogen partial pressure can be 4-15 MPa in gauge pressure; the liquid hourly volume space velocity of the hydrocarbon oil can be 0.5-3 h ⁻¹ .

According to the hydroprocessing method of the present invention, before carrying out the hydrogenation reaction, preferably under conventional conditions in the art, in the presence of hydrogen, the catalyst is presulfurized, and the presulfurization can be carried out in a hydrogenation reactor or It can be performed outside the hydrogenation reactor and is not particularly limited. The pre-vulcanization can generally be carried out at a temperature of 140-370°C.

The present invention will be described in detail below in conjunction with the examples, but the scope of the present invention is not limited thereby.

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

In the following examples and comparative examples, adopt the following method to determine Value: Dry 10g of the hydrated alumina composition at 120°C in an air atmosphere for 240 minutes, record the mass of the dried composition as w ₁ , and calculate using formula I value,

In the following examples and comparative examples, the value of i was determined by the following method: 10 g of alumina hydrate wet gel was dried in an air atmosphere at 120 ° C for 240 minutes, and the mass of the dried sample was recorded as w ₂ , calculated using formula II i value,

In the following examples and comparative examples, the following method was used to measure the water absorption of the prepared molded body: the molded body to be tested was dried at 120°C for 4 hours, and then sieved with a 40-mesh standard sieve, and 20 g of the sieved material was weighed as the sample to be tested. To measure the sample (marked as w ₃ ), soak the sample to be tested with 50g deionized water for 30 minutes, after filtering, drain the solid phase for 5 minutes, then weigh the weight of the drained solid phase (marked as w ₄ ), Calculate water absorption with the following formula:

In the following examples and comparative examples, the most probable pore diameter was determined by using the Poremaster 33 instrument from Quanta Corporation of the United States, referring to the mercury porosimetry specified in GB/T21650.1-2008. Referring to the method stipulated in the petrochemical analysis method RIPP133-90, the composition of the catalyst was determined on a 3271 X-ray fluorescence spectrometer from Rigaku Electric Industries, Ltd. of Japan.

Examples 1-16 are used to illustrate the alumina shaped body of the present invention and its preparation method.

Example 1

The alumina hydrate wet gel used in this example is a quasi-alumina hydrogel solution prepared by the acid method (sodium metaaluminate-aluminum sulfate method, obtained from Sinopec Changling Branch) after washing and filtering. The wet filter cake of boehmite (the wet filter cake is coded as SLB-1), after measurement, the i value of the wet filter cake is 78.2%.

(1) Put 200g of wet filter cake numbered SLB-1 in a beaker, then add 5g of TiO ₂ , 5g of methyl cellulose (purchased from Zhejiang Haishen Chemical Co. The content of lactomannan is 80% by weight, purchased from Beijing Chemical Reagent Company, the same below), and after being stirred by a mechanical stirrer for 10 minutes, the obtained mixture is the hydrated alumina composition of the present invention, and its property parameters are listed in Table 1 listed in .

(2) Extrude the hydrated alumina composition prepared in step (1) on a F-26 twin-screw extruder (manufactured by the General Factory of Science and Technology Industry of South China University of Technology, the same below) using a disc-shaped orifice plate of Ф1.5mm. strip. Among them, the extrusion process is smooth, and the surface of the extrudate is smooth and burr-free.

(3) Cut the extrudate into a wet strip with a length of about 6mm, send the wet strip into a tube furnace, and raise the temperature from ambient temperature (25°C) to 580°C at a heating rate of 150°C/hour, And keep the temperature at this temperature for 6 hours, after the wet strip is sent into the tube furnace, air is supplied from the entrance of the tube furnace to the inner space of the tube furnace at 15L/min, wherein, the air volume of 12L/min is from the tube furnace The circulating air output from the outlet (the amount of water vapor is 6L/min, which is 0.13L/(min·g molded product)), and the remaining 3L/min air volume is air. After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Comparative example 1

Adopt the same method as in Example 1 to prepare the alumina molded body, the difference is that in step (3), after the wet strip is sent into the tube furnace, the airflow output from the outlet of the tube furnace is not sent into the tube furnace in a circular manner However, air is sent from the inlet of the tube furnace to the inner space of the tube furnace at 15 L/min. The property parameters of the prepared alumina supports are listed in Table 1.

Example 2

(1) Mix 5 kg of wet filter cake numbered SLB-1 with 500 g of deionized water for beating for 1 minute, then send the obtained slurry into a plate and frame filter press, adjust the pressure of the plate and frame to 0.7 MPa and maintain After 15 minutes, a wet filter cake (coded as LB-1) was obtained. It has been determined that the i value of the wet filter cake numbered LB-1 is 62%.

(2) Put 300g of wet filter cake numbered LB-1 in a beaker, add 8g of TiO ₂ , 4.5g of hydroxyethyl methylcellulose (purchased from Shanghai Huiguang Fine Chemical Co., Ltd., the same below) and 1.5g Scallop powder (the content of galactomannan is 85% by weight, purchased from Beijing Chemical Reagent Company), after being stirred by a mechanical stirrer for 10 minutes, the hydrated alumina composition of the present invention is obtained, and its properties are listed in Table 1 out.

(3) Extrude the hydrated alumina composition prepared in step (2) on an F-26 twin-screw extruder with a circular orifice plate of Ф2.0 mm. Among them, the extrusion process is smooth, and the surface of the extrudate is smooth and burr-free.

(4) Cut the extrudate into a wet strip with a length of about 6mm, send the wet strip into a tube furnace, and raise the temperature from ambient temperature (25°C) to 500°C at a heating rate of 100°C/hour, And keep the temperature at this temperature for 4 hours, after the wet strip is sent into the tube furnace, air is supplied from the inlet of the tube furnace to the inner space of the tube furnace at 14L/min, wherein, the air volume of 11L/min is from the tube furnace The circulating air output from the outlet (the amount of water vapor is 6L/min, 0.05L/(min·g molded product)), and the remaining 3L/min air volume is air. After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Example 3

The aluminum oxide molded body was prepared by the same method as in Example 2, except that, in the step (2), no scallop powder was used, and the amount of hydroxyethyl methylcellulose was 5.8 g. The property parameters of the prepared alumina shaped bodies are listed in Table 1.

Example 4

The aluminum oxide molded body was prepared by the same method as in Example 2, except that hydroxyethyl methylcellulose was not used in step (2), and the amount of scallop powder was 6.8 g. The property parameters of the prepared alumina shaped bodies are listed in Table 1.

Example 5

Adopt the method identical with embodiment 2 to prepare molded body and catalyst, difference is, in step (2), when adding hydroxyethyl methylcellulose and turnip powder, also add 3g nitric acid (HNO _The content is 65% by weight %). The property parameters of the prepared alumina shaped bodies are listed in Table 1.

Comparative example 2

(1) Dry 500 g of the wet filter cake numbered LB-1 at 80° C. in an air atmosphere for 2 hours to obtain pseudo-boehmite powder whose i value is 50%. The pseudo-boehmite powder was placed at ambient temperature (25-30°C) under closed conditions (placed in a sealed plastic bag) for 72 hours, and the formation of alumina trihydrate was not detected after the placement.

(2) Extrude the pseudo-boehmite powder prepared in step (1) on an F-26 twin-screw extruder with a circular orifice plate of Ф2.0 mm. Among them, the heat generated by the extruder is relatively large during extruding (expressed as the body of the extruder is hot and a large amount of hot air comes out), and the extruder frequently trips during the extruding process, and there are burrs on the surface of the extruded product.

(3) The extrudate was cut into a wet strip with a length of about 6mm, and the alumina molded body was prepared by the same method as in step (4) of Example 2, and its property parameters are listed in Table 1.

Comparative example 3

(1) Dry 500 g of the wet filter cake numbered LB-1 at a temperature of 90° C. in an air atmosphere for 3 hours to obtain pseudo-boehmite powder whose i value is 40%. The pseudo-boehmite powder was placed at ambient temperature (25-30°C) under closed conditions (placed in a sealed plastic bag) for 72 hours, and the formation of alumina trihydrate was not detected after the placement.

(2) the pseudo-boehmite powder prepared by 190g step (1) is placed in a beaker, add 4.5g hydroxyethyl methylcellulose (same as Example 2) and 1.5g scallop powder (same as Example 2), After stirring with a mechanical stirrer for 10 minutes, a pseudo-boehmite composition was obtained.

(3) Extrude the pseudo-boehmite composition prepared in step (2) on an F-26 twin-screw extruder using a circular orifice plate with a diameter of 2.0 mm. Among them, the extruder tripped frequently during the extruding process, and the surface of the extruded product was smooth.

(4) The extrudate was cut into a wet strip with a length of about 6mm, and the alumina molded body was prepared by the same method as in step (4) of Example 2, and its property parameters are listed in Table 1.

Comparative example 4

(1) 190g of pseudo-boehmite powder prepared by the same method as Comparative Example 3 step (1) is placed in a beaker, and 4.5g of hydroxyethyl methylcellulose (same as in Example 2), 1.5g of Sinensis powder (same as Example 2) and 6g of nitric acid (the concentration of _HNO3 is 65% by weight), and after stirring for 10 minutes with a mechanical stirrer, a pseudo-boehmite composition was obtained.

(2) The pseudo-boehmite composition prepared in step (1) was extruded on an F-26 twin-screw extruder with a circular orifice plate of Φ2.0 mm. Among them, the extrusion process is smooth, and the surface of the extrudate is smooth.

(3) The extrudate was cut into a wet strip with a length of about 6mm, and the alumina molded body was prepared by the same method as in step (4) of Example 2, and its property parameters are listed in Table 1.

Comparative example 5

A hydrated alumina composition was prepared by the same method as in Example 2, except that 6.0 g of paraffin wax was used instead of hydroxyethyl methylcellulose and safflower powder. As a result, the prepared alumina hydrate composition could not be extruded.

Comparative example 6

A hydrated alumina composition was prepared by the same method as in Example 2, except that 6.0 g of wood powder was used instead of hydroxyethyl methylcellulose and scallop powder. As a result, the prepared alumina hydrate composition could not be extruded.

Comparative example 7

The wet filter cake numbered LB-1 was directly fed into the F-26 twin-screw extruder for extruding with a circular orifice plate of Ф2.0mm, but extrusion molding could not be performed.

Example 6

(1) Put 300g of wet filter cake numbered LB-1 in a beaker, add 10mL of tetraethyl titanate, 2.6g of hydroxypropyl methylcellulose (purchased from Zhejiang Haishen Chemical Co., Ltd., the same below) and After stirring 3.5g of squat powder (the content of galactomannan is 85% by weight) with a mechanical stirrer for 10 minutes, the hydrated alumina composition of the present invention was obtained, and its properties are listed in Table 1.

(2) The hydrated alumina composition prepared in step (1) is used in a SK132S/4 single-screw extruder (manufactured by BONNT Corporation of the United States) using a circular shape with an outer diameter of Ф4.5mm and a 1.5mm in the middle. The orifice plate composed of cylinders is extruded. Among them, the extruding process is smooth, and the extrudate (Raschig ring) has a smooth surface without burrs.

(3) Cut the extrudate into a wet strip with a length of about 6mm, send the wet strip into a tube furnace, and raise the temperature from ambient temperature (25°C) to 850°C at a heating rate of 200°C/hour, And keep the temperature at this temperature for 3 hours, after the wet strip is sent into the tube furnace, air is supplied from the entrance of the tube furnace to the inner space of the tube furnace with 16L/min, wherein, the air volume of 12L/min is from the tube furnace The circulating air output from the outlet (the amount of water vapor is 6L/min, which is 0.05L/(min·g molded product)), and the remaining 4L/min of air volume is air. After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Example 7

(1) 300g of wet filter cake numbered LB-1 is placed in a beaker, and 12g of ZrO ₂ , 2g of methylcellulose, 1.1g of hydroxypropylmethylcellulose and 4g of turnip powder (galactomannan The content is 85% by weight), and after being stirred by a mechanical stirrer for 10 minutes, the hydrated alumina composition of the present invention is obtained, and its property parameters are listed in Table 1.

(2) Extrude the hydrated alumina composition prepared in step (1) on an F-26 twin-screw extruder using a clover-shaped orifice plate with a diameter of Ф3.0 mm. Among them, the extrusion process is smooth, and the surface of the extrudate is smooth and burr-free.

(3) Cut the extrudate into a wet strip with a length of about 8mm, send the wet strip into a tube furnace, and raise the temperature from ambient temperature (25°C) to 900°C at a heating rate of 150°C/hour, And keep the temperature at this temperature for 2 hours, after the wet strip is sent into the tube furnace, air is supplied from the entrance of the tube furnace to the inner space of the tube furnace at 10L/min, wherein, the air volume of 8L/min is the air volume from the tube furnace The circulating air output from the outlet (the amount of water vapor is 5L/min, which is 0.04L/(min·g molded product)), and the remaining 2L/min air volume is air. After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Example 8

(1) Put 300g of wet filter cake numbered LB-1 in a beaker, add 30g of metatitanic acid (H ₂ TiO ₃ ), 2.2g of hydroxyethylmethylcellulose and 2.1g of hydroxypropylmethylcellulose , after stirring for 10 minutes with a mechanical stirrer, the hydrated alumina composition of the present invention was obtained, and its property parameters are listed in Table 1.

(2) The hydrated alumina composition prepared in step (1) was extruded on a F-26 twin-screw extruder using a disc-shaped orifice plate with a diameter of 1.8 mm. Among them, the extrusion process is smooth, and the surface of the extrudate is smooth and burr-free.

(3) Cut the extrudate into a wet strip with a length of about 6mm, send the wet strip into a tube furnace, and raise the temperature from ambient temperature (25°C) to 800°C at a heating rate of 200°C/hour, And keep the temperature at this temperature for 2 hours, after the wet strip is sent into the tube furnace, air is supplied from the entrance of the tube furnace to the inner space of the tube furnace at 15L/min, wherein, the air volume of 10L/min is from the tube furnace The circulating air output from the outlet (the amount of water vapor is 6L/min, which is 0.05L/(min·g molded product)), and the remaining 5L/min of air volume is air. After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Example 9

(1) Send 5kg of wet filter cake numbered SLB-1 into the plate and frame filter press, adjust the pressure of the plate and frame to 0.5MPa and keep it for 20 minutes, and then blow the plate and frame with 0.5MPa pressurized air The filter cake in the medium was depressurized for 10 minutes to obtain a wet filter cake (coded as LB-2). The i value of the wet cake was 64.9%.

(2) Put 1000g of the wet filter cake numbered LB-2 in a beaker, add 100g of metatitanic acid (H ₂ TiO ₃ ), 16g of hydroxypropyl methylcellulose and 20g of squash powder (galactomannan The content is 85% by weight, purchased from Beijing Chemical Reagent Company), and after stirring for 10 minutes with a mechanical stirrer, the hydrated alumina composition of the present invention is obtained, and its property parameters are listed in Table 1.

(3) The hydrated alumina composition prepared in step (1) was extruded on a F-26 twin-screw extruder using a disc-shaped orifice plate with a diameter of 2.4 mm. Among them, the extrusion process is smooth, and the surface of the extrudate is smooth and burr-free.

(4) Cut the extrudate into a wet strip with a length of about 6mm, send the wet strip into a tube furnace, and raise the temperature from ambient temperature (25°C) to 700°C at a heating rate of 150°C/hour, And keep the temperature at this temperature for 3 hours, after the wet strip is sent into the tube furnace, air is supplied from the entrance of the tube furnace to the inner space of the tube furnace with 18L/min, wherein, the air volume of 14L/min is from the tube furnace The circulating air output from the outlet (the amount of water vapor is 8L/min, which is 0.07L/(min·g molded product)), and the remaining 4L/min of air volume is air. After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Example 10

(1) Combine 5kg of wet filter cake numbered SLB-1 with 500g of deionized water, 30g of TiO ₂ , 33g of methylcellulose (purchased from Zhejiang Haishen Chemical Co., Ltd.) content of 80% by weight, purchased from Beijing Chemical Reagent Company) mixed and beaten for 1 minute, then the obtained slurry was sent into a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.7MPa and kept for 15 minutes, and the plate and frame The pressure was released to obtain the hydrated alumina composition containing Group IVB metal elements of the present invention, and its property parameters are listed in Table 1.

(2) Cut the extrudate into a wet strip with a length of about 6mm, send the wet strip into a tube furnace, and raise the temperature from ambient temperature (25°C) to 600°C at a heating rate of 100°C/hour, And keep the temperature at this temperature for 3 hours, after the wet strip is sent into the tube furnace, air is supplied from the entrance of the tube furnace to the inner space of the tube furnace at 16L/min, wherein, the air volume of 11L/min is from the tube furnace The circulating air output from the outlet (the amount of water vapor is 5L/min, which is 0.1L/(min·g molded product)), and the remaining 5L/min of air volume is air. After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Example 11

The hydrated alumina wet gel used in this example is to wash the hydrated alumina gel solution prepared by the _CO2 method (sodium aluminate- _CO2 method, taken from Shanxian Xinghao Catalyst New Material Co., Ltd., Shanxi Province) And the pseudo-boehmite wet filter cake obtained by filtering (the wet filter cake is numbered as SLB-2), after determination, the i value of this wet filter cake is 65.3%.

(1) Put 1000g of wet filter cake numbered SLB-2 in a beaker, then add 50g of metatitanic acid (H ₂ TiO ₃ ), 16g of methylcellulose and 20g of scallop powder (the content of galactomannan is 80% by weight), and after stirring for 10 minutes with a mechanical stirrer, the obtained mixture is the hydrated alumina composition of the present invention, and its property parameters are listed in Table 1.

(2) Extrude the hydrated alumina composition prepared in step (1) on the F-26 twin-screw extruder using a disc-shaped orifice plate of Ф2.4mm. The extrusion process is smooth, and the surface of the extrudate is smooth and burr-free .

(3) Cut the extrudate into a wet strip with a length of about 5mm, send the wet strip into a tube furnace, and raise the temperature from ambient temperature (25°C) to 550°C at a heating rate of 100°C/hour, And keep the temperature at this temperature for 3 hours, after the wet strip is sent into the tube furnace, air is supplied from the inlet of the tube furnace to the inner space of the tube furnace at 16mL/min, wherein, the air volume of 12L/min is from the tube furnace The circulating air output from the outlet (the amount of water vapor is 6L/min, which is 0.2L/(min·g molded product)), and the remaining 4L/min of air volume is air. After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Example 12

The hydrated alumina wet gel used in this example is obtained by washing and filtering the hydrated alumina gel solution prepared by the sodium aluminate seed separation method (taken from Aluminum Corporation of China Shandong Branch). Cake (this wet filter cake is coded as SLB-3), after determination, the i value of this wet filter cake is 70%.

(1) 5000g is numbered as SLB-3 and 1000g water mixing beating, the obtained slurry is pressed into the plate and frame filter press, the plate and frame pressure of the plate and frame filter is adjusted to 0.9MPa and kept for 3 minutes, then Blow the filter cake in the plate frame with 0.6 MPa pressurized air for 5 minutes, release the pressure of the plate frame to obtain a wet filter cake of alumina trihydrate, the i value of the wet filter cake is 60.8% by weight.

(2) Place 1000g of the wet filter cake obtained in step (1) into a beaker, then add 30g of metatitanic acid (H ₂ TiO ₃ ), 10g of methylcellulose and 20g of squash powder (the content of galactomannan is 80% by weight), and after stirring for 10 minutes with a mechanical stirrer, the obtained mixture is the hydrated alumina composition of the present invention, and its property parameters are listed in Table 1.

(3) The hydrated alumina composition prepared in step (1) was extruded on a F-26 twin-screw extruder using a disc-shaped orifice plate with a diameter of 2.4 mm. Among them, the extrusion process is smooth, and the surface of the extrudate is smooth and burr-free.

(4) Cut the extrudate into a wet strip with a length of about 6mm, send the wet strip into a tube furnace, and raise the temperature from ambient temperature (25°C) to 1000°C at a heating rate of 200°C/hour, And keep the temperature at this temperature for 2 hours, after the wet strip is sent into the tube furnace, air is supplied from the inlet of the tube furnace to the inner space of the tube furnace at 15L/min, wherein, the air volume of 12L/min is from the tube furnace The circulating air output from the outlet (the amount of water vapor is 8L/min, 0.02L/(min·g molded product)), and the remaining 3L/min air volume is air. After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Example 13

The hydrated alumina wet gel used in this example is taken from Shandong Zibo Qimao Catalyst Co., Ltd., which is pseudoboehmite dry powder (70 wt. %) was roasted at 700°C for 3 hours in an air atmosphere to obtain 700g of alumina, and 700g of alumina was placed in a 10L autoclave, stirred evenly with 5L of deionized water, and then the autoclave was sealed and heated at 150°C under autogenous pressure After the reaction was completed, the temperature of the autoclave was lowered to room temperature (25° C.), and the slurry obtained by the reaction was sent into a plate and frame filter press, and the plate and frame pressure of the plate and frame filter was adjusted. 0.5MPa and keep it for 10 minutes, then use 10MPa pressurized air to blow the filter cake in the plate frame for 3 minutes, and release the pressure of the plate frame to obtain the hydrated alumina wet filter cake LB-3 of the present invention. It was determined that the phase of the wet filter cake was boehmite, and the i value of the wet filter cake was 63%.

(1) Put 300g of wet filter cake numbered LB-3 in a beaker, then add 20g of metatitanic acid (H ₂ TiO ₃ ), 3.8g of methyl cellulose and 6g of turmeric powder (galactomannan content is 85% by weight), and after being stirred by a mechanical stirrer for 10 minutes, the obtained mixture is the hydrated alumina composition of the present invention, and its property parameters are listed in Table 1.

(2) The hydrated alumina composition prepared in step (1) was extruded on a F-26 twin-screw extruder using a disc-shaped orifice plate with a diameter of 2.4 mm. Among them, the extrusion process is smooth, and the surface of the extrudate is smooth and burr-free.

(3) Cut the extrudate into a wet strip with a length of about 6mm, send the wet strip into a tube furnace, and raise the temperature from ambient temperature (25°C) to 600°C at a heating rate of 120°C/hour, And keep the temperature at this temperature for 4 hours, after the wet strip is sent into the tube furnace, air is supplied from the inlet of the tube furnace to the inner space of the tube furnace at 12L/min, wherein, the air volume of 10L/min is from the tube furnace The circulating air output from the outlet (the amount of water vapor is 6L/min, 0.05L/(min·g molded product)), and the remaining 2L/min air volume is air. After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Example 14

The hydrated alumina wet gel used in this example is adopted in "Acta Petroleum Sinica (Petroleum Processing)", the article "A new method for preparing alumina by hydrolysis of low-carbon alkoxy aluminum" published in the 10th issue of "Acta Petroleum Sinica (Petroleum Processing)". , Test method" section, wherein the aging time is 12 hours, after the aging is completed and the isopropanol and water are evaporated, add 500g of water, stir with a mechanical stirrer for 1 minute, and press the slurry into the plate and frame In the filter machine, the pressure of the plate frame is adjusted to 0.7MPa, and the extrusion time is 8 minutes, and then the filter cake in the plate frame is blown with the pressurized wind of 7MPa for 4 minutes to obtain a 200g wet filter cake (the number is LB- 4). It was determined that the phase of the wet filter cake was pseudo-boehmite, and the i value of the wet filter cake was 65.2%.

(1) Put 200g of wet filter cake numbered LB-4 in a beaker, then add 20g of metatitanic acid (H ₂ TiO ₃ ), 2.8g of methylcellulose and 4.5g of scallop powder (galactomannan The content is 80% by weight), and after being stirred by a mechanical stirrer for 10 minutes, the obtained mixture is the hydrated alumina composition of the present invention, and its property parameters are listed in Table 1.

(2) The hydrated alumina composition prepared in step (1) was extruded on a F-26 twin-screw extruder using a disc-shaped orifice plate with a diameter of 2.4 mm. Among them, the extrusion process is smooth, and the surface of the extrudate is smooth and burr-free.

(3) Cut the extrudate into wet strips with a length of about 6mm, send the wet strips into a tube furnace, and raise the temperature from ambient temperature (25°C) to 550°C at a heating rate of 100°C/hour, And keep the temperature at this temperature for 3 hours, after the wet strip is sent into the tube furnace, air is supplied from the entrance of the tube furnace to the inner space of the tube furnace with 14L/min, wherein, the air volume of 10L/min is from the tube furnace The circulating air output from the outlet (the amount of water vapor is 6L/min, which is 0.08L/(min·g molded product)), and the remaining 4L/min of air volume is air. After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Example 15

(1) Mix 5kg of wet filter cake numbered SLB-1 with 700g of deionized water for beating for 1 minute, then send the obtained slurry into a plate and frame filter press, adjust the pressure of the plate and frame to 0.5MPa and keep After 3 minutes, blow the filter cake in the plate frame with 0.5MPa pressurized air for 3 minutes, and then release the pressure of the plate frame to obtain a wet filter cake (code LB-5). After determination, the i value of the wet filter cake numbered LB-5 is 75% by weight.

(2) Put 1000g of wet filter cake numbered LB-5 in a beaker, add 50g of metatitanic acid (H ₂ TiO ₃ ), 16g of hydroxypropyl methylcellulose and 20g of scallop powder (galactomannan The content is 85% by weight), and after being stirred by a mechanical stirrer for 10 minutes, the hydrated alumina composition of the present invention is obtained, and its property parameters are listed in Table 1.

(3) Extrude the hydrated alumina composition prepared in step (2) on an F-26 twin-screw extruder with a circular orifice plate of Ф3.0 mm. Among them, the extrusion process is smooth, and the surface of the extrudate is smooth and burr-free.

(4) Cut the extrudate into a wet strip with a length of about 6mm, send the wet strip into a tube furnace, and raise the temperature from ambient temperature (25°C) to 900°C at a heating rate of 200°C/hour, And keep the temperature at this temperature for 2.5 hours, after the wet strip is sent into the tube furnace, air is supplied from the entrance of the tube furnace to the inner space of the tube furnace at 16L/min, wherein, the air volume of 11L/min is from the tube furnace The circulating air output from the outlet of the outlet (the amount of water vapor is 5L/min, which is 0.2L/(min·g molded product)). After the constant temperature is completed, the air supply is stopped, and the temperature of the tube furnace is naturally lowered to the ambient temperature, and the solid matter is taken out to obtain the alumina molded body according to the present invention, and its property parameters are listed in Table 1.

Example 16

Adopt the same method as in Example 15 to prepare the alumina carrier, the difference is that in step (4), instead of sending the circulating air output from the outlet of the tube furnace into the inside of the tube furnace, the air generated by the steam generator will be The mixture of fresh water vapor and air is fed into the tube furnace, wherein the feed rate of water vapor is 10L/min. The property parameters of the prepared alumina shaped bodies are listed in Table 1.

Table 1

¹ : ambient temperature (25-30 ℃) and place 72 hours under closed conditions (placed in a sealed plastic bag), the content of aluminum oxide trihydrate in the composition after placing is relatively

Ratio before placement.

The results of Examples 1-16 confirm that the present invention does not dry the alumina hydrate wet gel into dry rubber powder or semi-dried rubber powder, but directly mixes it with a compound having at least two proton acceptor sites to obtain The mixture can be directly used for molding, and the obtained molded body has higher strength, thereby avoiding the existing harsh working environment and energy consumption when dry rubber powder or semi-dried rubber powder is used as the starting material to prepare molded bodies. High and the strength of the prepared molded body is not high. And, according to the method of the present invention by adjusting the The value can adjust the pore diameter of the prepared alumina molded body, and respectively prepare a molded body with a bimodal distribution or a unimodal distribution of the pore diameter.

Experimental Examples 1-10 are used to illustrate the catalyst having hydrogenation catalysis and the preparation method thereof according to the present invention.

Experimental Example 1

Disperse molybdenum oxide and basic cobalt carbonate in water to form an impregnation solution, in which the concentration of _MoO3 is 197.4g/L, and the concentration of basic cobalt carbonate calculated as CoO is 47.6g/L. The alumina shaped body produced in Example 1 was impregnated with this impregnation solution to saturation at ambient temperature (25° C.) for 1 hour. After the impregnated alumina dry strips were dried in an air atmosphere at 120° C. under normal pressure for 2 hours, they were then calcined at 400° C. and under normal pressure in an air atmosphere for 3 hours, thereby obtaining the hydrogenation catalyst according to the present invention. Catalyst C-1, whose composition is listed in Table 2.

Experimental Comparative Example 1

The catalyst was prepared by the same method as in Experimental Example 1, except that instead of the alumina molded body prepared in Example 1, the alumina molded body prepared in Comparative Example 1 was used to prepare catalyst DC-1, which The composition is listed in Table 2.

Experimental Example 2

Disperse molybdenum oxide and basic cobalt carbonate in water to form an impregnation solution, in which the concentration of _MoO3 is 141.2g/L, and the concentration of basic cobalt carbonate calculated as CoO is 33.6g/L. The alumina shaped body prepared in Production Example 2 was saturately impregnated with this impregnating solution at ambient temperature (25° C.) for 1 hour. After the impregnated alumina dry strips were dried in an air atmosphere at 120° C. under normal pressure for 2 hours, they were then calcined at 400° C. and under normal pressure in an air atmosphere for 3 hours, thereby obtaining the hydrogenation catalyst according to the present invention. Catalyst C-2, whose composition is listed in Table 2.

Experimental Example 3

The catalyst was prepared by the same method as in Experimental Example 2, except that the alumina molded body prepared in Example 3 was used, and the composition of the prepared catalyst C-3 was listed in Table 2.

Experimental Example 4

The catalyst was prepared by the same method as in Experimental Example 2, except that the alumina molded body prepared in Example 4 was used, and the composition of the prepared catalyst C-4 was listed in Table 2.

Experimental Example 5

The catalyst was prepared by the same method as in Experimental Example 2, except that the alumina molded body prepared in Example 5 was used, and the composition of the prepared catalyst C-5 was listed in Table 2.

Experimental comparative example 2

The catalyst was prepared by the same method as in Experimental Example 2, except that the alumina molded body prepared in Comparative Example 2 was used, and the composition of the prepared catalyst DC-2 was listed in Table 2.

Experimental comparative example 3

The catalyst was prepared by the same method as in Experimental Example 2, except that the alumina molded body prepared in Comparative Example 3 was used, and the composition of the prepared catalyst DC-3 was listed in Table 2.

Experimental comparative example 4

The catalyst was prepared by the same method as in Experimental Example 2, except that the alumina molded body prepared in Comparative Example 4 was used, and the composition of the prepared catalyst DC-4 was listed in Table 2.

Experimental Example 6

Disperse molybdenum oxide and basic nickel carbonate in water to form an impregnation solution, wherein the concentration of molybdenum oxide calculated as _MoO3 is 40g/L, and the concentration of basic nickel carbonate calculated as NiO is 170g/L. The alumina shaped body prepared in Preparation Example 7 was saturately impregnated with this impregnation solution at ambient temperature (25° C.) for 1 hour. After the impregnated alumina dry bar was dried in an air atmosphere at 150° C. under normal pressure for 1.5 hours, it was then calcined at 420° C. and under normal pressure in an air atmosphere for 2 hours, thereby obtaining the hydrogenation catalyst according to the present invention. Catalyst C-6, whose composition is listed in Table 2.

Experimental Example 7

Disperse molybdenum oxide and basic nickel carbonate in water to form an impregnation solution, wherein the concentration of molybdenum oxide calculated as _MoO3 is 40g/L, and the concentration of basic nickel carbonate calculated as NiO is 170g/L. The alumina shaped body prepared in Preparation Example 11 was saturately impregnated with this impregnation solution at ambient temperature (25° C.) for 1 hour. After the impregnated alumina dry bar was dried in an air atmosphere at 160° C. under normal pressure for 1 hour, it was then calcined at 460° C. and under normal pressure in an air atmosphere for 1.5 hours, thereby obtaining the hydrogenation catalyst according to the present invention. Catalyst C-7, whose composition is listed in Table 2.

Experimental Example 8

Disperse molybdenum oxide and basic nickel carbonate in water to form an impregnation solution, in which the concentration of _MoO3 is 238.4g/L, and the concentration of basic nickel carbonate in NiO is 57.5g/L. The alumina shaped body prepared in Preparation Example 14 was saturately impregnated with this impregnation solution at ambient temperature (25° C.) for 1 hour. After the impregnated alumina dry strips were dried in an air atmosphere at 120° C. under normal pressure for 2 hours, they were then calcined at 400° C. and under normal pressure in an air atmosphere for 3 hours, thereby obtaining the hydrogenation catalyst according to the present invention. Catalyst C-8, whose composition is listed in Table 2.

Experimental Example 9

Disperse molybdenum oxide and basic nickel carbonate in water to form an impregnation solution, wherein the concentration of molybdenum oxide calculated as _MoO3 is 150g/L, and the concentration of basic nickel carbonate calculated as NiO is 37g/L. The alumina shaped body prepared in Preparation Example 15 was saturately impregnated with this impregnation solution at ambient temperature (25° C.) for 1 hour. After the impregnated alumina dry strips were dried in an air atmosphere at 120° C. under normal pressure for 3 hours, they were then calcined at 480° C. and under normal pressure in an air atmosphere for 2 hours, thereby obtaining the hydrogenation catalyst according to the present invention. Catalyst C-9, whose composition is listed in Table 2.

Experimental Example 10

The catalyst was prepared by the same method as in Experimental Example 10, except that the alumina molded body prepared in Example 16 was used. Catalyst C-10 was prepared and its composition is listed in Table 2.

Table 2

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

Test Examples 1-10

The following methods were used to evaluate the catalytic performance of the catalysts prepared in Experimental Examples 1-10, and the experimental results are listed in Table 3.

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

Break the catalyst into particles with a diameter of 2-3mm and put them into the reactor, feed the raw oil to react, wherein the reaction temperature is 380°C, the hydrogen partial pressure is 14MPa, and the volume space velocity of the raw oil is 0.6h ^-1 .

Refer to the method specified in the petrochemical analysis method RIPP62-90, use the coulometric method to measure the sulfur content in the oil; refer to the method specified in GB/T17144, measure the carbon residue in the oil, the instrument used is MCRT-160 of the American ALCOR company Type trace carbon residual analyzer; the content of metal nickel and vanadium in the oil sample is determined by inductively coupled plasma emission spectrometer (ICP-AES) (the instrument used is the PE-5300 plasma light meter of the American PE company, and the specific method is shown in Petrochemical Analytical method RIPP124-90); referring to the method specified in petrochemical analysis method RIPP63-90, the nitrogen content in the oil is determined by the coulometric method. According to the measurement results, the removal rate of impurities is calculated according to the following formula, wherein the removal rate of metal refers to the removal rate of nickel and vanadium:

Test comparative examples 1-4

The catalytic performance of the catalysts prepared in Experimental Comparative Examples 1-4 was evaluated by the same method as in Test Examples 1-11, and the results are listed in Table 3.

table 3

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

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

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (43)

1. A method for preparing an aluminum oxide molded body containing the IVB group metal element, the method may further comprise the steps: (1) A hydrated alumina composition is molded to obtain a molded product. The hydrated alumina composition contains hydrated alumina, a compound having at least two proton acceptor sites, and at least one compound containing a Group IVB metal compounds of elements, of the composition value below 5, the The value is determined by the following method: 10 g of the composition is dried in an air atmosphere at 120° C. for 240 minutes, and the mass of the dried composition is recorded as w ₁ , and calculated by formula I value, Optionally, (2) drying the molded product obtained in step (1) to obtain a dried molded product; (3) In the presence of water vapor, calcining the molded product obtained in step (1) or the dried molded product obtained in step (2) in an oxygen-containing atmosphere. 2. The method according to claim 1, wherein, relative to 100 parts by weight of the hydrated alumina, the content of the compound having at least two proton acceptor sites is 1-25 parts by weight, preferably 2- 20 parts by weight, more preferably 3-18 parts by weight, even more preferably 3.5-17 parts by weight. 3. The method according to claim 1 or 2, wherein, in the compound having at least two proton acceptor sites, the proton acceptor sites are among F, O and N capable of forming hydrogen bonds with water one or more; Preferably, the compound having at least two proton acceptor sites is a compound containing a hydroxyl group in its molecular structure; More preferably, said compound having at least two proton acceptor sites is a polyhydroxy organic compound; Further preferably, the compound having at least two proton acceptor sites is a polysaccharide and/or an etherified polysaccharide; Even more preferably, the compound having at least two proton acceptor sites is one or more of galactan, mannan, galactomannan and cellulose ether, and the cellulose The ether is preferably one or more of methylcellulose, hydroxyethylcellulose and hydroxypropylcellulose; Particularly preferably, the compound with at least two proton acceptor sites is galactomannan and cellulose ether, preferably, based on the total amount of the compound with at least two proton acceptor sites , the content of the galactomannan is 10-70% by weight, preferably 15-68% by weight, more preferably 20-65% by weight; the content of the cellulose ether is 30-90% by weight, preferably 32-85% by weight, more preferably 35-80% by weight. 4. The method according to any one of claims 1-3, wherein the hydrated alumina contains pseudoboehmite; Preferably, the hydrated alumina is pseudo-boehmite. 5. The method according to claim 4, wherein, the composition is placed at ambient temperature and under closed conditions for 72 hours, and the content of alumina trihydrate in the composition after placement is higher than that in the composition before placement content of alumina trihydrate; Preferably, based on the content of alumina trihydrate in the composition before placement, the content of alumina trihydrate in the composition after placement is at least increased by 0.5%; More preferably, based on the content of alumina trihydrate in the composition before standing, the content of alumina trihydrate in the composition after standing is increased by at least 1%, preferably by 1.1% to 2%. 6. The method of any one of claims 1-5, wherein the hydrated alumina is derived directly from a hydrated alumina wet gel. 7. The method according to any one of claims 1-6, wherein, relative to 100 parts by weight of hydrated alumina, the content of the compound containing the metal element of Group IVB in terms of oxide is 1.5-85 parts by weight, It is preferably 2-80 parts by weight, more preferably 3-75 parts by weight. 8. The method according to any one of claims 1-7, wherein the Group IVB metal element is selected from titanium and zirconium. 9. The method according to any one of claims 1-8, wherein the compound containing the Group IVB metal element is selected from the group consisting of zirconium oxychloride, zirconium acetate, zirconium sulfate, zirconium nitrate, zirconium carbonate, zirconium hydroxide , ammonium zirconium basic, zirconium dioxide, titanic acid, metatitanic acid, titanium dioxide, titanium sulfate and the compound shown in formula III, TiX _n (OR) _4-n (Formula III), In formula III, X is halogen, R is C ₁ -C ₅ alkyl, and n is an integer of 0-4. 10. The method according to any one of claims 1-9, wherein the composition is free of peptizers. 11. The method according to any one of claims 1-10, wherein the alumina hydrate composition is prepared by a method comprising the steps of: mixing the components of a raw material composition to obtain the The hydrated alumina composition, the raw material composition contains hydrated alumina wet gel, a compound having at least two proton acceptor sites, and at least one compound containing a Group IVB metal element, the hydrated alumina wet gel The i value of the gel is not less than 60%, and the amount of the compound having at least two proton acceptor sites is such that the final prepared composition has value below 5, The i value is determined by the following method: 10 g of alumina hydrate wet gel is dried in an air atmosphere at 120° C. for 240 minutes, the mass of the dried sample is recorded as w ₂ , and the i value is calculated using formula II, 12. The method according to claim 11, wherein the i value of the alumina hydrate wet gel is not less than 62%; Preferably, the i value of the alumina hydrate wet gel is not higher than 82%, preferably not higher than 80%, more preferably not higher than 78.5%. 13. The method according to claim 11 or 12, wherein the alumina hydrate wet gel is an alumina hydrate wet gel that has not been subjected to a dehydration treatment such that its i value is 60% or less. 14. The method according to any one of claims 11-13, wherein the alumina hydrate wet gel is washed and solidified after optionally aging at least one alumina hydrate gel solution obtained by separation; Preferably, the hydrated alumina gel solution is prepared by one or more methods of precipitation, hydrolysis, seed separation and rapid dehydration. 15. The method according to claim 14, wherein the solid-liquid separation is performed one or more times, at least the last solid-liquid separation is pressure filtration and/or vacuum filtration. 16. The method according to any one of claims 11-15, wherein the raw material composition does not contain a peptizer. 17. The method according to any one of claims 1-16, wherein the drying temperature in step (2) is above 60°C and not higher than 350°C, preferably 80-300°C, more preferably 110°C -260°C. 18. The method according to any one of claims 1-17, wherein, in step (3), the consumption of water vapor is 0.01-0.8L/(min·g molding), and the molding is hydrated and oxidized Aluminum gauge. 19. The method according to any one of claims 1-18, wherein the method comprises step (2), at least part of the water vapor is the water vapor generated during the drying described in step (2). 20. according to the method described in any one in claim 1-19, wherein, the molded thing that step (1) obtains directly sends in the step (3), at least part steam is the process of the described roasting of step (3) water vapor produced. 21. The method according to claim 20, wherein, in step (3), during the roasting process, the gas in the container containing the molding is drawn out, and at least part of the drawn gas is circulated into the in said container; Preferably, 10-90% by volume, preferably 20-88% by volume, more preferably 30-85% by volume, further preferably 60-85% by volume of the extracted gas is recycled into the container. 22. The method according to any one of claims 1-21, wherein the calcination temperature in step (3) is 400-1200°C, preferably 450-1100°C, more preferably 500-1000°C. 23. The method according to any one of claims 1-22, wherein the duration of roasting described in step (3) is 1-20 hours, preferably 1.5-15 hours, more preferably 2-12 hours . 24. The method according to any one of claims 1-23, wherein, in step (3), the temperature in the container containing the molding is raised to the firing temperature at a rate of 10-400° C./hour, Preferably it is 30-350°C/hour, more preferably 60-300°C/hour, still more preferably 100-200°C/hour. 25. The method of any one of claims 1-24, wherein the The value is 4 or less, preferably 3.5 or less, more preferably 3.2 or less; More preferably, the The value is 1.2 or more, preferably 1.3 or more, more preferably 1.4 or more. 26. The method of any one of claims 1-25, wherein the hydrated alumina composition is The value is not lower than 1.8, preferably 1.9-4, more preferably 2-3.5. 27. The method of any one of claims 1-25, wherein the hydrated alumina composition has The value is less than 1.8, preferably not higher than 1.7, more preferably 1.3-1.7. 28. An alumina molded body containing Group IVB metal elements prepared by the method according to any one of claims 1-27. 29. An alumina molded body containing a Group IVB metal element prepared by the method of claim 26. 30. The molded body according to claim 29, wherein, as determined by mercury intrusion porosimetry, the pore size of the aluminum oxide molded body containing Group IVB metal elements is a bimodal distribution, and the most probable pore diameters are 4-60 nm and greater than 60 nm, respectively. ; Preferably, the most probable pore diameters are 5-40nm and 80-500nm respectively. 31. An alumina molded body containing a Group IVB metal element prepared by the method of claim 27. 32. The molded body according to claim 31, wherein, as measured by mercury intrusion porosimetry, the pore size of the aluminum oxide molded body containing Group IVB metal elements is a unimodal distribution, and the most probable pore size is 4-60 nm, preferably 4.5 nm. -40nm. 33. The molded body according to any one of claims 28-32, wherein the radial crushing strength of the aluminum oxide molded body containing Group IVB metal elements is 10-50 N/mm, preferably 14-50 N/mm mm. 34. A production and molding method of hydrated alumina, the method comprising the following steps: (1) A hydrated alumina gel solution is provided, and the hydrated alumina gel solution is washed and solid-liquid separated to obtain the first hydrated alumina wet gel, and the conditions of the solid-liquid separation make the first The i value of the alumina monohydrate wet gel is not lower than 60%, preferably not lower than 62%, more preferably not higher than 82%, further preferably not higher than 80%, still more preferably not higher than 78.5%, The i value is determined by the following method: 10 g of alumina hydrate wet gel is dried in an air atmosphere at 120° C. for 240 minutes, the mass of the dried sample is recorded as w ₂ , and the i value is calculated using formula II, (2) using the method described in any one of claims 1-27 to mix the first alumina hydrate wet gel with a compound having at least two proton acceptor sites, then carry out shaping, optional drying, And roasting, so as to prepare the aluminum oxide molded body containing the Group IVB metal element; Wherein, in the step (1) and/or step (2), the operation of mixing the compound containing the Group IVB metal element is performed, so that the hydrated alumina composition contains the compound containing the Group IVB metal element. 35. A production and molding method of hydrated alumina, the method comprising the following steps: (1) A hydrated alumina gel solution is provided, and the hydrated alumina gel solution is washed to obtain a first hydrated alumina wet gel; (2) using (2-1) or (2-2) to process the first alumina hydrate wet gel to obtain a second alumina hydrate wet gel, (2-1) mixing the first hydrated alumina wet gel with water to form a slurry, and subjecting the slurry to solid-liquid separation to obtain a second hydrated alumina wet gel; (2-2) performing solid-liquid separation on the first alumina hydrate wet gel to obtain a second alumina hydrate wet gel, In (2-1) and (2-2), the condition of the solid-liquid separation is such that the i value of the second alumina hydrate wet gel is not less than 60%, preferably not less than 62%, more preferably Preferably not higher than 82%, more preferably not higher than 80%, even more preferably not higher than 78.5%, The i value is determined by the following method: 10 g of alumina hydrate wet gel is dried in an air atmosphere at 120° C. for 240 minutes, the mass of the dried sample is recorded as w ₂ , and the i value is calculated using formula II, (3) using the method described in any one of claims 1-27 to mix the second alumina hydrate wet gel with a compound having at least two proton acceptor sites, followed by molding, optional drying, And roasting, so as to prepare the aluminum oxide molded body containing the Group IVB metal element; Wherein, in step (1), step (2) and step (3), the operation of mixing the compound containing Group IVB metal element is carried out in one, both or three, so that the hydrated alumina composition Compounds containing Group IVB metal elements. 36. The method according to claim 34 or 35, wherein the solid-liquid separation is performed one or more times, at least the last solid-liquid separation is pressure filtration and/or vacuum filtration. 37. The method according to any one of claims 34-36, wherein the hydrated alumina gel solution is aged or not aged by precipitation method, hydrolysis method, seed separation method and rapid dehydration method The resulting reaction mixture was prepared by one or two of the above methods. 38. An alumina molded body containing a Group IVB metal element prepared by the method according to any one of claims 34-37. 39. The use of the alumina shaped body containing Group IVB metal elements as described in any one of claims 28-33 and 38 as a carrier or an adsorbent. 40. The use according to claim 39, wherein the carrier is a carrier of a supported catalyst, preferably a carrier of a supported hydrogenation catalyst. 41. A catalyst with hydrogenation catalysis, the catalyst contains a carrier and a Group VIII metal element and a Group VIB metal element supported on the carrier, wherein the carrier is the one of claims 28-33 and 38 Any one of the alumina moldings containing Group IVB metal elements. 42. A method for preparing a catalyst with hydrogenation catalysis, the method comprising loading Group VIII metal elements and Group VIB metal elements on a carrier, wherein the method also includes using claims 1-27 and 34-37 The method described in any one of the above prepares the alumina carrier containing the Group IVB metal element. 43. A method for hydroprocessing, the method comprising contacting hydrocarbon oil with a catalyst having a hydrocatalytic effect under hydrotreating conditions, wherein the catalyst having a hydrocatalytic effect is the one described in claim 41 A catalyst or a catalyst prepared by the method of claim 42.