CN107999119A - The hydrated alumina composition and catalyst and preparation method and hydroisomerization process of the molecular sieve of type containing ZSM-22 - Google Patents

Abstract

The invention discloses a kind of hydrated alumina composition of the 22 type molecular sieve containing ZSM and preparation method thereof and formed body and its preparation method and application, said composition contains hydrated alumina, 22 type molecular sieves of ZSM and the compound with least two proton acceptor sites, andIt is worth for less than 5.The invention also discloses using the hydroisomerisation catalysts and preparation method and hydroisomerization process by the formed body that the hydrated alumina composition is formed as carrier.The formed body with higher-strength is prepared by starting material of hydrated alumina wet gel in the present invention, eliminate for the step of drying hydrated alumina wet gel, simplify overall craft flow, reduce overall operation energy consumption, the dust pollution due to triggering using boehmite dry glue powder as raw material is avoided, greatly improves operating environment.Catalyst according to the invention shows more preferable catalytic activity in hygrogenating isomerization reaction.

Description

Hydrated alumina composition and catalyst containing ZSM-22 type molecular sieve and preparation method and hydroisomerization methods

technical field

The present invention relates to the technical field of alumina forming, specifically, the present invention relates to a hydrated alumina composition containing ZSM-22 molecular sieve and its preparation method, and the present invention also relates to the hydrated alumina formed from the hydrated alumina composition. Aluminum molded body and alumina molded body, the present invention further relates to a hydroisomerization catalyst using the molded body formed from the hydrated alumina composition as a carrier, a preparation method thereof, and a hydroisomerization process using the catalyst method.

Background technique

ZSM-22 molecular sieve is a new type of aluminosilicate molecular sieve material developed in the 1980s by Dwyer et al. of Mobil Corporation of the United States. It belongs to the orthorhombic crystal system, the space group is Mmc21, and the unit cell parameter is a=13. ZSM-22 molecular sieve has a TON structural topology framework, which includes five-membered rings, six-membered rings and ten-membered rings. The main channel is a one-dimensional channel with a ten-membered ring opening, the channel is parallel to the (001) direction, there is no intersecting channel, and the size of the orifice is oval channel. ZSM-22 molecular sieve is widely used in the isomerization reaction of linear alkanes because of its space-selective effect.

In the traditional method, the alumina formed body containing ZSM-22 molecular sieve, especially the γ-alumina formed body containing ZSM-22 type molecular sieve, because of its good pore structure, suitable specific surface and high Heat-resistant and stable, it is often used as a carrier for adsorbents or supported catalysts. 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 use pseudo-boehmite dry rubber powder as a starting point, add ZSM-22 Type molecular sieves, extrusion aids and optional chemical peptizers (inorganic and/or organic acids) are kneaded and shaped, and the formed product is used as an adsorbent or carrier after drying and optional roasting. 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 and has no possibility of industrial application. Sex, which is the biggest problem facing the technology.

In summary, how to simplify the preparation process of the alumina carrier containing the ZSM-22 molecular sieve and reduce the operating energy consumption under the premise of ensuring that the alumina carrier containing the ZSM-22 molecular sieve can meet the requirements of industrial use, At the same time, it is still a technical problem to be solved urgently to reduce the dust pollution during the preparation process of the alumina carrier containing ZSM-22 molecular sieve.

Contents of the invention

The purpose of the present invention is to simplify the preparation process of the alumina carrier containing the ZSM-22 molecular sieve, reduce the dust pollution in the preparation process of the alumina carrier containing the ZSM-22 molecular sieve, and the prepared carrier can also 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 the first aspect of the present invention, the present invention provides a hydrated alumina composition containing ZSM-22 type molecular sieve, which composition contains hydrated alumina, ZSM-22 type molecular sieve and at least two proton acceptor sites point compound,

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,

According to the second aspect of the present invention, the present invention provides a method for preparing a hydrated alumina composition containing ZSM-22 molecular sieve, the method comprising mixing the components in a raw material composition to obtain the Alumina hydrate composition, the raw material composition contains hydrated alumina wet gel, ZSM-22 type molecular sieve and a compound having at least two proton acceptor sites, the i value of the hydrated alumina wet gel is not Below 50%, the amount of the compound having at least two proton acceptor sites is such that the final prepared composition 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,

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

According to the third aspect of the present invention, the present invention provides a hydrated alumina composition containing ZSM-22 type molecular sieve prepared by the method described in the second aspect of the present invention.

According to the fourth aspect of the present invention, the present invention provides a hydrated alumina formed body, which is composed of the hydrated alumina composition containing ZSM-22 molecular sieve described in the first aspect of the present invention or the present invention. The hydrated alumina composition containing ZSM-22 molecular sieve described in the third aspect of the invention is formed.

According to a fifth aspect of the present invention, the present invention provides a method for preparing a hydrated alumina molded body, the method comprising adding the hydrated alumina composition containing ZSM-22 molecular sieve described in the first aspect of the present invention or The hydrated alumina composition containing ZSM-22 molecular sieve described in the third aspect of the present invention is molded, and the obtained molded product is dried.

According to the sixth aspect of the present invention, the present invention provides a hydrated alumina formed body prepared by the method described in the fifth aspect of the present invention.

According to the seventh aspect of the present invention, the present invention provides an alumina formed body, which is composed of the hydrated alumina composition containing ZSM-22 molecular sieve described in the first aspect of the present invention or the hydrated alumina composition of the present invention The hydrated alumina composition containing ZSM-22 molecular sieve described in the three aspects is formed.

According to the eighth aspect of the present invention, the present invention provides a method for preparing an alumina molded body, the method comprising the hydrated alumina composition containing ZSM-22 molecular sieve described in the first aspect of the present invention or the present invention The hydrated alumina composition containing ZSM-22 molecular sieve described in the third aspect of the invention is molded, and the obtained shaped product is dried and calcined.

According to a ninth aspect of the present invention, the present invention provides an alumina formed body prepared by the method described in the eighth aspect of the present invention.

According to a tenth 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 alumina monohydrate wet gel is not less than 50%;

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 second aspect of the present invention to mix the first alumina hydrate wet gel with a compound having at least two proton acceptor sites to obtain a alumina hydrate composition;

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

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

(5) Optionally, calcining at least part of the hydrated alumina shaped body to obtain an alumina shaped body;

Wherein, the method further includes the operation of mixing ZSM-22 molecular sieves in step (1) and/or step (2), so that the hydrated alumina composition contains ZSM-22 molecular sieves.

According to the eleventh aspect of the present invention, 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;

(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 50%,

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 second aspect of the present invention to mix the second alumina hydrate wet gel with a compound having at least two proton acceptor sites to obtain a alumina hydrate composition;

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

(5) drying the alumina hydrate formed body to obtain a hydrated alumina formed body;

(6) Optionally, calcining at least part of the alumina hydrate shaped body to obtain an alumina shaped body;

Wherein, the method also includes the operation of mixing ZSM-22 molecular sieves in one, two or three of step (1), step (2) and step (3), so that the hydrated alumina composition Contains ZSM-22 molecular sieve.

According to the twelfth aspect of the present invention, the present invention provides a molded body prepared by the method described in the tenth aspect or the eleventh aspect of the present invention.

According to a thirteenth aspect of the present invention, the present invention provides the alumina hydrate shaped body and the use of the alumina shaped body according to the invention as a carrier or adsorbent.

According to the fourteenth aspect of the present invention, the present invention provides a hydroisomerization catalyst, the catalyst contains a carrier and an active component loaded on the carrier, wherein the carrier is formed according to the hydrated alumina of the present invention body or the alumina shaped body according to the invention.

According to the fifteenth aspect of the present invention, the present invention provides a method for preparing a hydroisomerization catalyst, the method comprising loading an active ingredient on a carrier, wherein the method also includes adopting the fifth aspect of the present invention, The method of the eighth aspect, the tenth aspect or the eleventh aspect is a step of preparing a molded body as a carrier.

According to the sixteenth aspect of the present invention, the present invention provides a method for hydroisomerization, the method comprising contacting hydrocarbon oil with a hydroisomerization catalyst under hydroisomerization conditions, wherein the The hydroisomerization catalyst is the catalyst described in the fourteenth aspect of the present invention or the catalyst prepared by the method described in the fifteenth aspect of the present invention.

Compared with the existing process (the process shown in Figure 1) for preparing alumina molded body using pseudo-boehmite dry rubber powder as the starting material, the present invention directly prepares the hydrated alumina wet Gel is used as the starting material for molding to prepare moldings containing ZSM-22 molecular sieve, which 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 present invention can use alumina hydrate wet gel as a starting material to prepare a molded body containing ZSM-22 molecular sieve with higher strength. The free water in the gel interacts to form hydrogen bonds, and the free water in the hydrated alumina wet gel is adsorbed. At the same time, compounds with at least two proton acceptor sites can also hydrogen bond with the hydroxyl groups in the hydrated alumina molecular structure Interact with each other to play the role of physical peptization, so that the hydrated alumina wet gel can not only be formed, but also can make the final prepared molded body have higher strength.

The hydroisomerization catalyst prepared with the shaped body prepared from the hydrated alumina composition according to the present invention as a carrier exhibits higher catalytic activity in the hydroisomerization reaction of hydrocarbon oil.

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.

Figure 2 is a preferred embodiment of a method of preparing a hydrated alumina composition according to the present invention.

Fig. 3 is a preferred embodiment of the molding process flow 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 a first aspect of the present invention, the present invention provides a hydrated alumina composition comprising hydrated alumina, ZSM-22 type molecular sieve and a compound having at least two proton accepting sites.

The alumina hydrate may be one or more selected from alumina trihydrate and alumina monohydrate. Specific examples of the hydrated alumina may include, but are not limited to, boehmite, alumina trihydrate, amorphous hydrated alumina, and pseudoboehmite. The hydrated alumina preferably contains alumina monohydrate, more preferably alumina monohydrate. 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 supports for hydroisomerization catalysts.

According to the hydrated alumina composition of the present invention, 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 water-containing gel obtained through a synthetic reaction and has not undergone a dehydration process to reduce its i value to below 50% (preferably below 55%, more preferably below 60%) hydrated alumina gel. 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.

Unlike the hydrated alumina derived from dry rubber powder, the phase of the hydrated alumina directly derived from the hydrated alumina wet 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). The flexible wrap may be paper and/or a polymeric material, preferably a polymeric material such as plastic.

In one example, where the hydrated alumina directly derived from the hydrated alumina wet gel contains pseudo-boehmite, such as pseudo-boehmite, the composition is placed under closed conditions at ambient temperature for 72 hours , the alumina trihydrate content in the composition after placement is higher than the alumina trihydrate content in the composition before placement. In this example, based on the content of alumina trihydrate in the composition before placement, the content of alumina trihydrate in the composition after placement generally increases by at least 0.5%, preferably at least 1%, more preferably by 1.1%. -1.5%.

The hydrated alumina composition according to the present invention 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, molecular structures containing one selected from hydroxyl, carboxyl, amino, ether bond, aldehyde, carbonyl, amide, and fluorine atoms. Compounds with two or more groups are preferably hydroxyl groups and/or ether bonds.

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 by substituting hydrogen atoms on some of the hydroxyl groups in the cellulose molecule with one or more hydrocarbon groups, wherein the multiple 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 their ether compounds can be provided in various forms, for example, galactomannan can be derived from safflower 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 block 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 acid type polymer specifically can enumerate 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 further preferred embodiment, the shaped bodies formed from the composition according to the invention have a 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. -65% by weight, more preferably 25-60% by weight; the content of the cellulose ether may be 30-90% by weight, preferably 35-85% by weight, more preferably 40-75% by weight.

The compositions according to the invention also contain molecular sieves of type ZSM-22. The ZSM-22 type molecular sieve can be hydrogen type ZSM-22 molecular sieve (that is, H-ZSM-22 molecular sieve), hydrogen type ZSM-22 molecular sieve containing rare earth (such as La-H-ZSM-22, Ce-H-ZSM -22, Pr-H-ZSM-22, Pm-H-ZSM-22, Sm-H-ZSM-22, Eu-H-ZSM-22), hydrogen ZSM-22 molecular sieve containing alkaline earth metal elements (such as Mg -H-ZSM-22, Ni-H-ZSM-22, Ca-H-ZSM-22, Sr-H-ZSM-22, Ba-H-ZSM-22, Al-H-ZSM-22In-H-ZSM -22, one or more of Be-H-ZSM-22).

The silicon-alumina ratio of the ZSM-22 molecular sieve (that is, the molar ratio of silicon oxide/alumina) can be selected according to the specific application of the hydrated alumina composition. In one embodiment, the silicon-aluminum ratio of the ZSM-22 molecular sieve may be 10-200, preferably 30-150, more preferably 40-100, such as 50-90. The shaped bodies produced from the hydrated alumina composition according to this preferred embodiment are particularly suitable as supports for hydroisomerization catalysts.

The content of the ZSM-22 molecular sieve in the composition can be selected according to the specific application of the composition. In a preferred embodiment, based on the total amount of the calcined composition, the content of the ZSM-22 molecular sieve can be 0.5-90% by weight, preferably 5-88% by weight, more preferably 15-86% by weight. % by weight, more preferably 30-85% by weight, more preferably 40-85% by weight; the content of alumina can be 10-99.5% by weight, preferably 12-95% by weight, more preferably 14-85% by weight , more preferably 15-70% by weight, more preferably 15-60% by weight, the calcination is carried out at a temperature of 600° C., and the duration of the calcination is 3 hours. The composition according to this preferred embodiment is particularly suitable for making a support for a hydroisomerization catalyst.

of the composition according to the invention The value is 5 or less, preferably 4.5 or less, more preferably 4 or less, still more preferably 3.5 or less. The value may be 1.2 or more, preferably 1.3 or more, more preferably 1.4 or more, still more preferably 1.5 or more. In one example, the composition according to the invention is The value may be 1.2-5, preferably 1.2-4.5, more preferably 1.3-4, further preferably 1.4-3.5, such as 1.5-3.5.

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 parts by weight, preferably 2-22 parts by weight, more preferably 3- 20 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. According to the composition of this particularly preferred embodiment, when used to prepare a shaped body, the prepared alumina hydrate shaped body can be used as an adsorbent or a carrier even if it is converted into an alumina shaped body without roasting, because When the uncalcined hydrated alumina molding contains peptizer, the peptizer dissolves in the process of adsorption and impregnation, and is lost in large quantities, causing the molding to dissolve, pulverize, and collapse, and eventually lose its shape, so it cannot be used as an adsorbent and carrier used.

According to a second aspect of the present invention, the present invention provides a method for preparing a hydrated alumina composition, the method comprising mixing components in a raw material composition to obtain the hydrated alumina composition, namely The resulting mixture is the hydrated alumina composition.

According to the preparation method of the hydrated alumina composition of the present invention, the raw material mixture contains hydrated alumina wet gel, ZSM-22 molecular sieve and a compound having at least two proton acceptor sites. The compound having at least two proton acceptor sites and its type, as well as the ZSM-22 molecular sieve and its type have been described in detail above, and will not be repeated here.

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

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.

According to the preparation method of the hydrated alumina composition of the present invention, the i value of the hydrated alumina wet gel is not less than 50%, preferably not less than 55%, more preferably not less than 60%, even more preferably for not less than 62%. The i value of the alumina hydrate wet gel is preferably not higher than 95%, more preferably not higher than 90%, further preferably not higher than 85%, even more preferably not higher than 82%. In one embodiment, the i value of the alumina hydrate wet gel is 50-95%, preferably 55-90%, more preferably 60-85%, further preferably 62-82%. When the composition prepared according to this more preferred embodiment is used for molding, the resulting shaped body has higher strength.

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.

According to the preparation method of the hydrated alumina composition of the present invention, the hydrated alumina wet gel obtained by solid-liquid separation generally has not undergone the reduction of its i value to below 50% (preferably below 55%, more preferably below 60%) dehydration treatment.

According to the preparation method of the hydrated alumina composition of the present invention, the amount of the compound having at least two proton acceptor sites can make the final prepared hydrated alumina composition The value is 5 or less, preferably 4.5 or less, more preferably 4 or less, still more preferably 3.5 or less. The amount of the compound having at least two proton acceptor sites is preferably such that the final prepared hydrated alumina composition The value is 1.2 or more. The amount of the compound having at least two proton acceptor sites is more preferably such that the final prepared hydrated alumina composition The value is 1.3 or more, more preferably 1.4 or more, still more preferably 1.5 or more. Generally, relative to 100 parts by weight of alumina hydrate wet gel, the amount of the compound having at least two proton acceptor sites can be 1-25 parts by weight, preferably 2-22 parts by weight, more preferably 3 parts by weight. -20 parts by weight, the alumina hydrate wet gel is calculated as alumina hydrate.

According to the preparation method of the hydrated alumina composition of the present invention, 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. More preferably, the raw material mixture does not contain peptizing agent. That is, the method for preparing the hydrated alumina composition according to the present invention more preferably does not include the step of adding a peptizing agent to the raw material mixture.

According to the preparation method of the hydrated alumina composition of the present invention, conventional methods can be used to mix the hydrated alumina wet gel with ZSM-22 molecular sieve and a compound having at least two proton acceptor sites. Alumina hydrate wet gels can be mixed with a ZSM-22 type molecular sieve and a compound having at least two proton accepting sites under shear. In one embodiment, the mixing method is stirring. Alumina hydrate wet gel, ZSM-22 type molecular sieve and a compound having at least two proton acceptor sites can be mixed uniformly by stirring in a container with a stirring device, so as to obtain the hydrated oxide according to the present invention Aluminum composition. 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. Alumina hydrate wet gel can be kneaded with ZSM-22 type molecular sieve and a compound having at least two proton accepting sites in a kneader, so as to obtain the hydrated alumina composition according to the present invention. The type of the kneader is not particularly limited. According to the preparation method of the hydrated alumina composition of the present invention, stirring and mixing may be used in combination to mix the hydrated alumina 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.

According to the preparation method of the hydrated alumina composition of the present invention, the ZSM-22 molecular sieve, the compound having at least two proton acceptor sites and the hydrated alumina wet gel can be mixed in various mixing sequences.

In one embodiment, the ZSM-22 type molecular sieve can be mixed in the process of preparing the alumina hydrate wet gel, or the ZSM-22 type molecular sieve can be added to the prepared alumina hydrate wet gel, or in In the process of preparing alumina hydrate wet gel, part of ZSM-22 molecular sieve is mixed, and the remaining part of ZSM-22 molecular sieve is added to the prepared alumina hydrate wet gel. The operation of mixing ZSM-22 molecular sieve can be added in the above One, two, or three of the opportunities. When mixing ZSM-22 molecular sieves in the process of preparing hydrated alumina wet gel, it can be carried out in one, two, three or four of the precipitation reaction process, aging process, solid-liquid separation process and washing process Operation of mixing ZSM-22 molecular sieves. Whether to mix ZSM-22 molecular sieves in the process of preparing alumina hydrate wet gel, and the timing of mixing can be selected according to the type of precipitation reaction, so that the structure of ZSM-22 molecular sieves will not or will not be destroyed. , For example: when adding ZSM-22 molecular sieves in the process of preparing hydrated alumina wet gel, it is preferable that the preparation conditions are not strongly alkaline, such as the pH value is less than 10. Preferably, the operation of mixing ZSM-22 type molecular sieves is carried out during the solid-liquid separation process.

In another embodiment, the ZSM-22 type molecular sieve is mixed after the alumina hydrate wet gel is prepared. In this embodiment, the ZSM-22 molecular sieve can be mixed with the hydrated alumina wet gel first, and then the compound with at least two proton acceptor sites can be mixed; it is also possible to first mix the compound with at least two proton acceptor sites The compound is mixed with the hydrated alumina wet gel, and then mixed with the ZSM-22 molecular sieve; it is also possible to simultaneously mix the ZSM-22 type molecular sieve and the compound having at least two proton acceptor sites with the hydrated alumina wet gel.

According to the preparation method of the hydrated alumina composition of the present invention, during the mixing process, water may or may not be 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 supplemental added water to compound having at least two proton acceptor sites may be 5-15:1.

According to a third aspect of the present invention, the present invention provides a hydrated alumina composition prepared by the method described in the second aspect of the present invention.

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

According to the fourth aspect of the present invention, the present invention provides a hydrated alumina formed body, the hydrated alumina formed body is composed of the hydrated alumina composition described in the first aspect of the present invention or the hydrated alumina composition described in the third aspect of the present invention The hydrated alumina composition is formed.

The hydrated alumina composition according to the present invention can be molded, and the obtained molded product can be dried to obtain the hydrated alumina molded product according to the present invention.

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.

The temperature for drying the molded article can be selected conventionally in this field. Generally, the drying temperature may be above 60°C and below 350°C, preferably 65-300°C, more preferably 70-250°C. The duration of the drying can be properly selected according to the drying temperature, so as to make the volatile content in the finally obtained hydrated alumina molding meet the requirements for use. Generally, the duration of the drying may be 1-48 hours, preferably 2-24 hours, more preferably 2-12 hours, further preferably 2-6 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.

According to the present invention, the hydrated alumina molded body can have various shapes according to specific application requirements, for example: spherical, strip, ring, clover, honeycomb, bird's nest, cylinder, Raschig ring or butterfly.

The alumina hydrate shaped body according to the invention has a rich pore structure and an adjustable pore size distribution.

In one embodiment, the pore size distribution of the alumina hydrate shaped body is bimodal as measured by mercury porosimetry. Wherein, the most probable pore diameters are respectively 4-20nm (preferably 5-15nm, more preferably 6-10nm) and greater than 20nm (such as 20.5-35nm, preferably 21-30nm, more preferably 21-25nm).

In another embodiment, the alumina hydrate shaped body has a unimodal distribution of pore sizes as determined by mercury porosimetry. Wherein, the most probable pore diameter is 4-25 nm, preferably 5-20 nm, more preferably 6-10 nm.

According to the alumina hydrate shaped body of the present invention, the alumina hydrate shaped body has relatively high strength. Generally, the radial crushing strength of the alumina hydrate shaped body according to the present invention is above 15 N/mm, such as 15-40 N/mm, preferably above 18 N/mm, such as 18-35 N/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 the fifth aspect of the present invention, the present invention provides a method for preparing a hydrated alumina molded body, the method comprising mixing the hydrated alumina composition described in the first aspect of the present invention or the hydrated alumina composition described in the third aspect of the present invention The above alumina hydrate composition is molded, and the obtained molded product is dried to obtain the alumina hydrate molded body.

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

In one embodiment of the present invention, the hydrated alumina composition The value is not lower than 1.8, for example, it can be 1.8-5. Preferably, the hydrated alumina composition The value is not lower than 1.85, for example, it can be 1.85-4. More preferably, the hydrated alumina composition The value is not lower than 1.9, for example, it can be 1.9-3.5. The pore size distribution of the alumina hydrate shaped bodies produced according to this embodiment is bimodal, as determined by mercury intrusion porosimetry. The most probable pore diameters are respectively 4-20nm (preferably 5-15nm, more preferably 6-10nm) and greater than 20nm (such as 20.5-35nm, preferably 21-30nm, more preferably 21-25nm).

In another embodiment of the present invention, the hydrated alumina composition The value is less than 1.8, such as 1.2 to less than 1.8. Preferably, the hydrated alumina composition The value is not higher than 1.75 (such as not higher than 1.7), for example, it can be 1.3-1.75, preferably 1.5-1.7. The pore size distribution of the aluminum oxide hydrate shaped bodies produced according to this embodiment exhibits a monomodal distribution as determined by mercury porosimetry. The most probable pore diameter is 4-25 nm, preferably 5-20 nm, more preferably 6-10 nm.

According to the sixth aspect of the present invention, the present invention provides a hydrated alumina formed body prepared by the method described in the fifth aspect of the present invention.

The alumina hydrate shaped body produced by the method of the present invention has relatively high strength. Generally, the radial crushing strength of the alumina hydrate formed body prepared by the method of the present invention is above 15 N/mm, such as 15-40 N/mm, preferably above 18 N/mm, such as 18-35 N/mm.

According to the seventh aspect of the present invention, the present invention provides an alumina formed body, which is composed of the hydrated alumina composition described in the first aspect of the present invention or the hydrated alumina composition described in the third aspect of the present invention An alumina composition is formed.

The hydrated alumina composition according to the present invention can be molded, and the obtained molded product is dried and fired successively, so as to obtain the alumina molded body.

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

In the present invention, the conditions for firing are not particularly limited, and may be conventional choices in the art. Specifically, the temperature of the calcination may be 400-950°C, preferably 450-800°C, more preferably 480-700°C; the duration of the calcination may be 2-10 hours, preferably 3-8 hours. The calcination can be carried out in an oxygen-containing 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 alumina molded body according to the present invention can have various shapes according to specific usage requirements, for example: spherical shape, strip shape, ring shape, clover shape, honeycomb shape, bird's nest shape, cylinder shape, Raschig ring shape or butterfly shape.

The alumina shaped body according to the invention has a rich pore structure and an adjustable pore size distribution.

In one embodiment, the pore size distribution of the alumina shaped body is bimodal as measured by mercury intrusion porosimetry. The most probable pore diameters are respectively 4-20nm (preferably 5-15nm, more preferably 6-10nm) and greater than 20nm (such as 20.5-35nm, preferably 21-30nm, more preferably 21-25nm).

In another embodiment, the alumina shaped body has a unimodal distribution of pore sizes as determined by mercury intrusion porosimetry. The most probable pore diameter is 4-20 nm, preferably 5-20 nm, more preferably 6-10 nm.

According to the alumina shaped body of the present invention, the alumina shaped body has relatively high strength. Generally, the radial crushing strength of the alumina shaped body according to the present invention is above 15 N/mm, such as 15-40 N/mm, preferably above 18 N/mm, such as 18-35 N/mm.

According to the eighth aspect of the present invention, the present invention provides a method for preparing an alumina molded body, the method comprising: mixing the hydrated alumina composition described in the first aspect of the present invention or the hydrated alumina composition described in the third aspect of the present invention The hydrated alumina composition is molded, and the obtained molded product is dried and calcined.

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

According to the preparation method of alumina molded body of the present invention, can change the composition of alumina value to obtain alumina shaped bodies with different pore size distributions.

In one embodiment of the present invention, the alumina composition The value is not lower than 1.8, for example, it can be 1.8-5. Preferably, the hydrated alumina composition The value is not lower than 1.85, for example, it can be 1.85-4. More preferably, the hydrated alumina composition The value is not lower than 1.9, for example, it can be 1.9-3.5. The aluminum oxide shaped bodies produced according to this embodiment have a bimodal distribution of pore sizes as determined by mercury intrusion porosimetry. The most probable pore diameters are respectively 4-20nm (preferably 5-15nm, more preferably 6-10nm) and greater than 20nm (such as 20.5-35nm, preferably 21-30nm, more preferably 21-25nm).

In another embodiment of the present invention, the alumina composition The value is less than 1.8, such as 1.2 to less than 1.8. Preferably, the hydrated alumina composition The value is not higher than 1.75 (such as not higher than 1.7), for example, it can be 1.3-1.75, preferably 1.5-1.7. The pore size distribution of the aluminum oxide shaped bodies produced according to this embodiment exhibits a monomodal distribution as determined by mercury intrusion porosimetry. The most probable pore diameter is 4-25 nm, preferably 5-20 nm, more preferably 6-10 nm.

According to a ninth aspect of the present invention, the present invention provides an alumina formed body prepared by the method described in the eighth aspect of the present invention.

The alumina shaped bodies produced by the method of the invention have relatively high strength. Generally, the radial crushing strength of the alumina formed body prepared by the method of the present invention is above 15 N/mm, such as 15-40 N/mm, preferably above 18 N/mm, such as 18-35 N/mm.

According to the tenth aspect of the present invention, the present invention provides a production and molding method of hydrated alumina, as shown in Figure 2 and Figure 3, the method comprises 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;

Optional (2), using (2-1) or (2-2) to treat the first hydrated alumina 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;

(3) Using the method described in the second aspect of the present invention to mix the alumina hydrate wet gel with a compound having at least two proton acceptor sites to obtain a hydrated alumina composition, the alumina hydrate wet gel is the first hydrated alumina wet gel or the second hydrated alumina wet gel;

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

(5) drying the alumina hydrate formed body to obtain a hydrated alumina formed body;

(6) Optionally, calcining at least part of the alumina hydrate shaped body to obtain an alumina shaped body;

Wherein, the method also includes the operation of mixing ZSM-22 type molecular sieves in one, two or three of step (1), step (2) and step (3), so that the hydrated alumina is combined The product contains ZSM-22 molecular sieve. In the present invention, "optional" means "includes or does not include", "includes or does not include".

According to the production molding method of the present invention, the method of mixing ZSM-22 molecular sieves is the same as the method and sequence described in the second aspect of the present invention, 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 hydrated alumina gel solution is a hydrated alumina 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 or 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 second aspect of the present invention, or It may be higher than the i value of the alumina hydrate wet gel mixed with the compound having at least two proton accepting sites according to the second aspect of the present invention.

In one embodiment, the i value of the first alumina hydrate wet gel satisfies the alumina hydrate wet gel mixed with a compound having at least two proton acceptor sites according to the second aspect of the present invention i value, that is, the i value of the first alumina hydrate wet gel is not lower than 50%, preferably not lower than 55%, more preferably not lower than 60%. In this embodiment, the i value of the first alumina hydrate wet gel is preferably not higher than 95%, more preferably not higher than 90%, even more preferably not higher than 85%, even more preferably not higher than higher than 82%. In one example, the i value of the first hydrated alumina wet gel is 50-95%, preferably 55-90%, more preferably 60-85%, further preferably 62-82%.

According to this embodiment, the first hydrated alumina wet gel can be directly sent to step (3) to be mixed with the compound having at least two proton acceptor sites. 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 hydrated alumina wet gel is 95% or more, which cannot meet the requirement of mixing with a compound having at least two proton acceptor sites as described in the second aspect of the present invention . 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 capability 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 second 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 second aspect of the present invention. The i value, that is, the i value of the alumina hydrate wet gel is not lower than 50%, preferably not lower than 55%, more preferably not lower than 60%, further preferably not lower than 62%. The i value of the second alumina hydrate wet gel is preferably not higher than 95%, more preferably not higher than 90%, further preferably not higher than 85%, even more preferably not higher than 82%. In one embodiment, the i value of the second alumina hydrate wet gel is 50-95%, preferably 55-90%, more preferably 60-85%, even more preferably 62-82%. 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.

As shown in Figure 2 and Figure 3, at least part of the ZSM-22 type molecular sieve can be mixed in step (2). When carrying out in the manner described in (2-1), as shown in Figure 2 and Figure 3, ZSM-22 molecular sieves can be mixed in the dilution operation and/or solid-liquid separation operation.

In step (3), the method described in the second aspect of the present invention is used to mix the first hydrated alumina wet gel or the second hydrated alumina wet gel with a compound having at least two proton acceptor sites, so that A hydrated alumina composition is obtained. The i value of the first alumina hydrate wet gel and the second alumina hydrate wet gel sent to step (3) meets the second aspect of the present invention when mixed with a compound having at least two proton acceptor sites The i-value of the hydrated alumina wet gel.

In step (3), the hydrated alumina composition can be determined according to the expected hydrated alumina formed body or the pore size distribution of the alumina formed body. value, which is described in the method according to the fifth aspect of the present invention and the method according to the eighth aspect of the present invention, and will not be described in detail here.

In step (4), the alumina hydrate composition obtained in step (3) is molded to obtain a hydrated alumina molding. For the molding method and the shape of the molded object, reference may be made to the related description about molding in the first aspect of the present invention, which will not be repeated here.

In step (5), the alumina hydrate formed body obtained in step (3) is dried to obtain a hydrated alumina formed body. The drying conditions for drying the alumina hydrate shaped body to obtain the alumina hydrate shaped body have been described in detail in the method described in the fifth aspect of the present invention, and will not be repeated here.

Depending on the type of shaped body desired, step (6) may or may not be carried out. When carrying out step (6), all the hydrated alumina formed bodies obtained in step (5) can be sent into step (6) for roasting; the partly hydrated alumina formed bodies obtained in step (5) can also be sent into In step (6), the alumina hydrate shaped body and the alumina shaped body can thus be produced simultaneously. The calcination conditions have been described in detail in the method described in the eighth aspect of the present invention, and will not be repeated here.

According to an eleventh aspect of the present invention, the present invention provides a hydrated alumina formed body or an alumina formed body prepared by the method described in the tenth aspect of the present invention.

The hydrated alumina molded body and the alumina molded body prepared by the method described in the tenth aspect of the present invention have relatively high strength. Generally, the radial crushing strength of the hydrated alumina formed body and the alumina formed body may be above 15 N/mm, such as 15-40 N/mm, preferably above 18 N/mm, such as 18-35 N/mm.

According to the tenth aspect of the present invention, it can be carried out in a hydrated 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, a drying unit, and a The selected 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 dry material of the drying unit.

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 a compound having at least two proton accepting sites according to the second 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 adopt 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 may 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 filter device includes at least a pressure filter device and/or a vacuum filter 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 blowing device, which uses natural wind or pressurized wind to blow 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-liquid separation and the solid phase material (ie, hydrated alumina wet gel) obtained by the washing unit The value satisfies the requirements of the second aspect of the invention for mixing with compounds having at least two proton accepting sites. 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 use Pressure filtering device and/or vacuum filtering device, also can not adopt pressure filtering device and vacuum filtering device, preferably adopt pressure filtering device and/or vacuum filtering 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.

As far as the direction of the hydrated alumina gel material flow is concerned, the solid-liquid separation and washing unit is arranged between the hydrated alumina gel production unit and the mixing unit, and is used to carry out 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, a dilution subunit, a delivery subunit and a second 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 to the second solid-liquid separation subunit;

The second 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. Compounds at the receptor site. 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 conventional roasting device that can be used by the roasting unit is not particularly limited in the present invention.

According to the production molding system of the present invention, based on the flow direction of the hydrated alumina gel, the production molding system is between the solid-phase material discharge port of the solid-liquid separation and washing unit and the input port of the hydrated alumina wet gel of the mixing unit. There is no dehydration unit that is sufficient to reduce the i value of the alumina hydrate wet gel to below 50% (preferably below 55%, more preferably below 60%).

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 a twelfth aspect of the present invention, the present invention provides the alumina hydrate shaped body or the use of the alumina shaped body according to the invention as a carrier or adsorbent.

The alumina hydrate shaped bodies and shaped alumina bodies 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 use a hydrated alumina molded body and/or an alumina molded body as a carrier. Preferably, the catalyst is a hydroisomerization catalyst. That is, the alumina hydrate shaped bodies and shaped alumina bodies according to the invention are particularly suitable as supports for hydroisomerization catalysts.

Various methods (for example: impregnation) commonly used in the art can be used to support the active component with hydrogenation catalysis on the hydrated alumina molding or the alumina molding according to the present invention, for example: by using the The catalyst is obtained by impregnating the shaped body of the invention with an aqueous solution of the active component, then drying and optionally calcining the shaped body loaded with the active component.

According to the thirteenth aspect of the present invention, the present invention provides a hydroisomerization catalyst, the catalyst contains a carrier and an active ingredient loaded on the carrier, wherein the carrier is formed according to the hydrated alumina of the present invention body and/or the alumina shaped body according to the invention.

The active ingredient may be a common ingredient that has a catalytic effect on hydroisomerization. Generally, the active ingredient is selected from Group VIII noble metal elements. The Group VIII noble metal element may be a Group VIII noble metal element commonly used in a catalyst having a hydroisomerization effect using a noble metal as an active component, such as one or more of ruthenium, osmium, palladium, platinum, rhodium and iridium. Two or more. Preferably, the active ingredient is palladium and/or platinum. The active ingredient can be loaded on the carrier in the form of a simple substance, or in the form of a compound.

The content of the active ingredient can be conventionally selected. For example, based on the total amount of the catalyst, the content of the active ingredient in terms of elements may be 0.1-5% by weight, preferably 0.2-2% by weight, more preferably 0.3-1% by weight.

According to the fourteenth aspect of the present invention, the present invention provides a method for preparing a hydroisomerization catalyst, the method comprising loading an active ingredient on a carrier, wherein the method also includes adopting the method described above in the present invention A step for producing a hydrated alumina shaped body or a shaped alumina body as a support.

The types of the active ingredients are the same as those described in the thirteenth aspect of the present invention, and will not be repeated here.

The loading amount of the active ingredient on the carrier can be properly selected according to the specific application of the catalyst. For example, when the prepared catalyst is used for hydroisomerization of hydrocarbon oil, based on the total amount of the prepared catalyst, the loading amount of the active ingredient on the carrier is such that the content of the active ingredient in the final prepared catalyst is The requirements described in the thirteenth aspect of the present invention can be met.

According to the preparation method of the hydroisomerization catalyst of the present invention, various methods commonly used in the art can be used to load the active ingredient on the carrier, for example: impregnation. The impregnation may be saturated or excessive impregnation.

According to the preparation method of the hydroisomerization catalyst 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 100-300° C., preferably 100-280° C.; the duration may be 1-12 hours, preferably 2-8 hours. The conditions of the calcination include: the temperature may be 350-550° C., preferably 400-500° C.; the duration may be 1-10 hours, preferably 2-8 hours.

According to the fifteenth aspect of the present invention, the present invention provides a method for hydroisomerization, the method comprising contacting hydrocarbon oil with a hydroisomerization catalyst under hydrotreating conditions, wherein the hydroisomerization The hydroisomerization catalyst is the catalyst described in the thirteenth aspect of the present invention or the catalyst prepared by the method described in the fourteenth aspect of the present invention.

The hydrocarbon oil can be various common hydrocarbon oils that require hydroisomerization treatment, such as: hydrocracking tail oil, distillate oil, solvent refined oil, white oil, coal liquefied oil, light deasphalted oil and heavy One or more than two kinds of deasphalted oil.

According to the hydroisomerization method of the present invention, before the catalyst is used, the hydroisomerization catalyst can be activated under the conventional conditions in the art, such as reduction, and the reduction can be carried out outside the reactor, It can also be carried out in a reactor.

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 ), The water absorption rate is calculated using formula III:

In the following examples and comparative examples, the most probable pore diameter was determined by using the Poremaster 33 type mercury porosimeter from Kanta Corporation of the United States, referring to the mercury porosimetry specified in GB/T21650.1-2008.

In the following examples and comparative examples, the dry basis is determined by roasting the sample to be tested at 600° C. for 4 hours, and is the ratio of the mass of the sample after roasting to the mass of the sample before roasting.

In the following examples and comparative examples, the 3271 type X-ray fluorescence spectrometer of Nippon Kyiki Denki Industry Co., Ltd. was used to measure the composition of the catalyst with reference to the method specified in the petrochemical analysis method RIPP133-90.

In the following examples and comparative examples, the specific surface area and the pore volume adopt the multi-point BET method in the commercially available model from Quantachrome Company. Tested on the six-station fully automatic specific surface and pore size distribution tester.

Examples 1-11 are used to illustrate the alumina hydrate composition, shaped body and preparation method thereof of the present invention.

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 80.2%.

(1) Add 5.48kg H-ZSM-22 molecular sieve (product of Sinopec Catalyst Branch Company, silicon-aluminum ratio is 50, dry basis is 0.98) in 50kg wet filter cake SLB-1, then add 10kg water and mix beating for 5 minutes, Then the slurry was filtered with a belt filter to obtain 15.2 kg of wet filter cake SLBZ-1. It was determined that the i value of the wet filter cake SLBZ-1 was 80.2%; after the wet filter cake SLBZ-1 was roasted at 600°C for 3 hours, it was determined that the weight ratio of alumina to ZSM-22 molecular sieve was 58:42 .

(2) Put 200g of wet filter cake numbered SLBZ-1 in a beaker, then add 5g of methylcellulose (purchased from Zhejiang Haishen Chemical Co., Ltd., the same below) and 3g of scallop powder (galactomannan The content is 80% by weight, purchased from Beijing Chemical Reagent Company), 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) Extrude the hydrated alumina composition prepared in step (2) 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 Ф1.6mm. strip. 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, dry the wet strip at 120°C in an air atmosphere for 3 hours, and obtain a hydrated alumina molded body HT-1, and its property parameters are listed in Table 1 .

(5) Calcining the hydrated alumina compact prepared in step (4) at 580° C. for 4 hours in an air atmosphere to obtain the alumina compact OT-1, whose property parameters are listed in Table 1.

Comparative example 1

(1) Spray-dry 100 kg of the wet filter cake numbered SLB-1 to obtain pseudo-boehmite dry rubber powder, the dry basis of the pseudo-boehmite dry rubber powder is 0.7. 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) Pseudoboehmite dry rubber powder prepared by 300g step (1) and 162g ZSM-22 type molecular sieve (same as Example 1), 6.3g methyl cellulose (same as Example 1), 3.7g Sinensis powder (same as Example 1), and 400 mL of nitric acid solution containing 12 mL of concentrated nitric acid (concentration: 65% by weight) was stirred with a mechanical stirrer for 10 minutes to obtain a mixture.

(3) Extrude the mixture prepared in step (2) on a F-26 type twin-screw extruder using a disc-shaped orifice plate of Ф1.6 mm.

(4) Cut the extrudate into a wet strip with a length of about 6mm, dry the wet strip at 120°C in an air atmosphere for 3 hours, and obtain the hydrated alumina molded body DHT-1, and its property parameters are listed in Table 1 .

(5) Calcining the hydrated alumina compact prepared in step (4) at 580° C. for 4 hours in an air atmosphere to obtain the alumina compact DOT-1, whose property parameters are listed in Table 1.

Example 2

(1) Mix 5 kg of wet filter cake numbered SLBZ-1 with 500 g of deionized water for beating for 1 minute, then send the resulting 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 LBZ-1) was obtained. It has been determined that the i value of the wet filter cake numbered LBZ-1 is 63%.

(2) 300g of wet filter cake numbered LBZ-1 was placed in a beaker, and 4.3g of hydroxyethyl methylcellulose (purchased from Shanghai Huiguang Fine Chemical Co., Ltd., the same below) and 1.7g of scallop powder ( The content of galactomannan is 85% by weight (purchased from Beijing Chemical Reagent Company). After stirring for 10 minutes with a mechanical stirrer, the hydrated alumina composition of the present invention is obtained, and its properties 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 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, and dry the wet strip at 150°C in an air atmosphere for 2 hours to obtain a hydrated alumina molded body HT-2, and its property parameters are listed in Table 1 .

(5) Calcining the hydrated alumina formed body prepared in step (4) at 480° C. in an air atmosphere for 8 hours to obtain the alumina formed body OT-2, whose property parameters are listed in Table 1.

Example 3

The molded body was prepared by the same method as in Example 2, the difference was that no scallop powder was used in step (2), the amount of hydroxyethyl methylcellulose was 5.7g, and the prepared hydrated alumina composition, hydrated oxide The properties of the aluminum shaped body HT-3 and the aluminum oxide shaped body OT-3 are listed in Table 1.

Example 4

The 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 6.8g. The prepared hydrated alumina composition, hydrated oxide The properties of the aluminum shaped body HT-4 and the aluminum oxide shaped body OT-4 are listed in Table 1.

Example 5

Adopt the method identical with embodiment 2 to prepare molded body, difference is, in step (2), when adding hydroxyethyl methylcellulose and safflower powder, also add 2.8g concentrated nitric acid ( _HNO The content is 65% by weight %), properties of the prepared hydrated alumina composition, hydrated alumina shaped body HT-5 and alumina shaped body OT-5 are listed in Table 1.

Comparative example 2

(1) Dry 300 g of the wet filter cake numbered LBZ-1 at 95° C. in an air atmosphere for 2 hours to obtain pseudo-boehmite powder, the i value of which 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 185g step (1) is placed in a beaker, add 4.3g hydroxyethyl methylcellulose (same as Example 2) and 1.7g 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) Cut the extrudate into a wet strip with a length of about 6mm, dry the wet strip at 150°C in an air atmosphere for 2 hours, and obtain the hydrated alumina molding DHT-2, and its property parameters are listed in Table 1 .

(5) Calcining the hydrated alumina compact prepared in step (4) at 480° C. in an air atmosphere for 8 hours to obtain the alumina compact DOT-2, whose property parameters are listed in Table 1.

Comparative example 3

Molding was carried out in the same method as Comparative Example 2, except that step (2) was not carried out, but the pseudo-boehmite powder prepared in step (1) was directly sent into step (3) for extrusion. 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. The prepared hydrated alumina shaped body is marked as DHT-3, and the prepared alumina shaped body is marked as DOT-3, and their property parameters are listed in Table 1 respectively.

Comparative example 4

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 hydrated alumina composition could not be extruded.

Comparative example 5

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 hydrated alumina composition could not be extruded.

Example 6

(1) Put 300g of wet filter cake numbered LBZ-1 in a beaker, add 2.8g of hydroxypropyl methylcellulose (purchased from Zhejiang Haishen Chemical Co. The content of lactomannan 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 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, dry the wet strip at 70°C in an air atmosphere for 3 hours, and then dry at 100°C in an air atmosphere for 2 hours to obtain a hydrated alumina molded body HT-6, whose property parameters are listed in Table 1.

(4) Calcining the hydrated alumina compact prepared in step (4) at 650° C. for 3 hours in an air atmosphere to obtain the alumina compact OT-6, whose property parameters are listed in Table 1.

Example 7

(1) 300g of wet filter cakes numbered LBZ-1 are placed in a beaker, and 2.5g of methylcellulose, 1.2g of hydroxypropylmethylcellulose and 4g of turnip powder are added (the content of galactomannan is 85% by weight), and 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) 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, and dry the wet strip at 120°C in an air atmosphere for 3 hours to obtain a hydrated alumina molded body HT-7, and its property parameters are listed in Table 1 .

(4) Calcining the hydrated alumina compact prepared in step (4) at 600° C. in an air atmosphere for 4 hours to obtain the alumina compact OT-7, whose property parameters are listed in Table 1.

Example 8

(1) 300g of wet filter cake numbered LBZ-1 is placed in a beaker, 2.4g of hydroxyethylmethylcellulose and 1.8g of hydroxypropylmethylcellulose are added, and after stirring with a mechanical stirrer for 10 minutes, the obtained The property parameters of the hydrated alumina composition of the present invention 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, dry the wet strip at 250°C in an air atmosphere for 2 hours, and obtain the hydrated alumina molded body HT-8, and its property parameters are listed in Table 1 .

(4) Calcining the hydrated alumina compact prepared in step (4) at 650° C. for 3 hours in an air atmosphere to obtain the alumina compact OT-8, whose property parameters are listed in Table 1.

Example 9

The same method as in Example 2 was used to prepare the hydrated alumina composition, the hydrated alumina molded body and the alumina molded body. The difference was that in step (1), 5kg of the wet filter cake numbered SLBZ-1 was mixed with 650g of Ionized water, 30 g of methylcellulose and 23 g of turnip powder (the content of galactomannan is 85% by weight) were mixed and beaten for 1 minute.

The property parameters of the prepared hydrated alumina composition, hydrated alumina shaped body HT-9 and alumina shaped body OT-9 are listed in Table 1.

Example 10

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) Add 0.22kg H-ZSM-22 molecular sieve (product of Sinopec Catalyst Branch Company, silicon-alumina ratio is 90, dry basis is 0.98) to 1kg wet filter cake SLB-2, then add 0.5kg water and mix for 10 minutes , The slurry is filtered with a belt filter to obtain 1.12kg of wet filter cake SLBZ-2. It was determined that the i value of the wet filter cake SLBZ-2 was 68.6%; after the wet filter cake SLBZ-2 was roasted at 600°C for 3 hours, the weight ratio of alumina to ZSM-22 molecular sieve was determined to be 55:45.

(2) 1.12kg of wet filter cake numbered as SLBZ-2 is placed in a beaker, then 16g of methyl cellulose and 20g of turnip powder (the content of galactomannan is 80% by weight) are added, and a mechanical stirrer is used After stirring 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) 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 6mm, dry the wet strip at 130°C in an air atmosphere for 2 hours, and obtain a hydrated alumina molded body HT-10, and its property parameters are listed in Table 1 .

(4) Calcining the hydrated alumina compact prepared in step (3) at 550° C. for 3 hours in an air atmosphere to obtain the alumina compact OT-10, whose property parameters are listed in Table 1.

Comparative example 6

(1) Spray-dry 100 kg of the wet filter cake numbered SLB-2 to obtain pseudo-boehmite dry rubber powder, the dry basis of the pseudo-boehmite dry rubber powder is 0.7. 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) Pseudoboehmite dry rubber powder prepared by 300g step (1) and 175g H-ZSM-22 molecular sieve (same as Example 10), 4.4g methylcellulose (same as Example 10), 5.6g field Cyanine powder (same as Example 10) and 400 mL of nitric acid solution containing 12 mL of concentrated nitric acid (concentration: 65% by weight) were stirred with a mechanical stirrer for 10 minutes to obtain a mixture.

(3) Extrude the mixture prepared in step (2) on a F-26 type twin-screw extruder using a disc-shaped orifice plate of Ф1.6 mm.

(4) Cut the extrudate into a wet strip with a length of about 6mm, dry the wet strip at 130°C in an air atmosphere for 2 hours, and obtain the hydrated alumina molded body DHT-4, and its property parameters are listed in Table 1 .

(5) Calcining the hydrated alumina compact prepared in step (4) at 580° C. for 4 hours in an air atmosphere to obtain the alumina compact DOT-4, whose property parameters are listed in Table 1.

Example 11

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 the plate frame is depressurized to obtain hydrated alumina wet filter cake LB-3. It was determined that the phase of the wet filter cake was boehmite, and the i value of the wet filter cake was 63.0%.

(1) Add 1.68kg H-ZSM-22 molecular sieve (product of Sinopec Catalyst Branch Company, silicon-aluminum ratio is 80, dry basis is 0.75) to 825g wet filter cake LB-3, then add 0.5kg water and mix for 10 minutes , Then the slurry is filtered with a belt filter to obtain 1.12kg wet cake SLBZ-3. It was determined that the i value of the wet filter cake SLBZ-3 was 65.3%; after the wet filter cake SLBZ-3 was roasted at 600°C for 3 hours, the weight ratio of alumina to ZSM-22 molecular sieve was determined to be 15:85.

(2) 300g of wet filter cake numbered SLBZ-3 is placed in a beaker, then 3.2g of methyl cellulose and 5g of turnip powder (the content of galactomannan is 85% by weight) are added, and a mechanical stirrer is used After stirring for 10 minutes, 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, dry the wet strip at 150°C in an air atmosphere for 2 hours, and obtain the hydrated alumina molded body HT-11, and its property parameters are listed in Table 1 .

(5) Calcining the hydrated alumina compact prepared in step (3) at 590° C. for 4 hours in an air atmosphere to obtain the alumina compact OT-11, whose property parameters are listed in Table 1.

Comparative example 7

The hydrated alumina wet filter cake LB-3 prepared in Example 11 was spray-dried to obtain pseudo-boehmite dry rubber powder (dry basis: 0.7). The pseudo-boehmite dry rubber 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.

With 300g step pseudo-boehmite dry rubber powder and 1587g H-ZSM-22 molecular sieve (same as embodiment 11), 3.9g methylcellulose (same as embodiment 11), 6.1g squash powder (same as embodiment 11) , and 400 mL of nitric acid solution containing 12 mL of concentrated nitric acid (concentration: 65% by weight) was stirred with a mechanical stirrer for 10 minutes to obtain a mixture. After the prepared mixture was extruded by the same method as in Example 11, the hydrated alumina molded body DHT-5 and the alumina molded body DOT-5 were respectively prepared, and their property parameters are listed in Table 1.

Comparative example 8

The wet filter cake SLBZ-3 prepared by the same method as in Example 11 step (1) was extruded by the same method as in Example 11 steps (3) and (4), but extrusion molding could not be performed.

The results of Examples 1-11 confirm that the present invention does not dry the hydrated alumina wet gel into a dry rubber powder, but directly mixes it with a compound having at least two proton acceptor sites, and the resulting mixture can be directly used for molding, and the obtained molded body has high strength, thereby avoiding the existing problems of harsh working environment and high energy consumption when dry rubber powder is used as the starting material to prepare the molded body. And, according to the hydrated alumina composition of the present invention by adjusting The value can adjust the pore size distribution of the prepared molded body to obtain a molded body with a unimodal distribution or a bimodal distribution of the pore size.

Experimental Examples 1-11 are used to illustrate the hydroisomerization catalyst and the preparation method thereof according to the present invention.

Experimental Example 1

(1) At a temperature of 25° C., 100 g of the alumina molded body OT-1 prepared in Example 1 was impregnated with 127 mL of tetraammine dichloroplatinum solution (the mass content of Pt was 0.5%) for 1 hour. The impregnated mixture was dried at 120° C. for 2 hours, followed by 150° C. for 3 hours to obtain catalyst OC-1, whose composition is listed in Table 2.

(2) The catalyst was prepared by the same method as in step (1), except that the hydrated alumina formed body HT-1 prepared in Example 1 was used instead. The prepared catalyst is denoted as HC-1, and its composition is listed in Table 2.

Experimental Comparative Example 1

(1) The catalyst was prepared by the same method as in Experimental Example 1, except that the alumina molded body was the alumina molded body DOT-1 prepared in Comparative Example 1. The prepared catalyst is denoted as DOC-1, and its composition is listed in Table 2.

(2) The catalyst was prepared by the same method as in step (2) of Experimental Example 1. The difference was that the alumina hydrate molded body prepared in Comparative Example 1 was used. As a result, the structure of the molded body collapsed during the impregnation process, and the molded catalyst could not be obtained. .

Experimental example 2

(1) At a temperature of 25° C., 100 g of the alumina molded body OT-2 prepared in Example 2 was impregnated with 86 mL of tetraammine platinum solution (the mass content of Pt was 0.5%) for 1 hour. The impregnated mixture was dried at 120° C. for 2 hours, followed by 150° C. for 3 hours to obtain catalyst OC-2, whose composition is listed in Table 2.

(2) The catalyst was prepared by the same method as in step (1), except that the hydrated alumina molded body HT-2 prepared in Example 2 was used instead. The prepared catalyst is denoted as HC-2, and its composition is listed in Table 2.

Experimental Example 3

(1) The catalyst was prepared by the same method as in step (1) of Experimental Example 2, except that the alumina molded body was the alumina molded body OT-3 prepared in Example 3. The prepared catalyst is denoted as OC-3 and its composition is listed in Table 2.

(2) The catalyst was prepared by the same method as in step (2) of Experimental Example 2, except that the hydrated alumina shaped body HT-3 prepared in Example 3 was used. The prepared catalyst is denoted as HC-3 and its composition is listed in Table 2.

Experimental Example 4

(1) The catalyst was prepared by the same method as in step (1) of Experimental Example 2, except that the alumina molded body was the alumina molded body OT-4 prepared in Example 4. The prepared catalyst is denoted as OC-4 and its composition is listed in Table 2.

(2) The catalyst was prepared by the same method as in step (2) of Experimental Example 2, except that the alumina hydrate shaped body was the alumina hydrate shaped body HT-4 prepared in Example 4. The prepared catalyst is denoted as HC-4 and its composition is listed in Table 2.

Experimental Example 5

(1) The catalyst was prepared by the same method as in step (1) of Experimental Example 2, except that the alumina molded body was the alumina molded body OT-5 prepared in Example 5. The prepared catalyst is denoted as OC-5 and its composition is listed in Table 2.

(2) The catalyst was prepared by the same method as in step (2) of Experimental Example 2, except that the alumina hydrate shaped body prepared in Example 5 was used. As a result, the structure of the shaped body collapsed during the impregnation process, and the shaped catalyst could not be obtained. .

Experimental Example 6

At a temperature of 25° C., 100 g of the alumina molded body OT-6 prepared in Example 6 was impregnated with 83 mL of tetraammine dichloroplatinum solution (the mass content of Pt was 0.5%) for 1 hour. The impregnated mixture was dried at 120° C. for 2 hours, followed by 150° C. for 3 hours to obtain catalyst OC-6, the composition of which is listed in Table 2.

Experimental Example 7

At a temperature of 25° C., 100 g of the alumina molded body OT-7 prepared in Example 7 was impregnated with 93 mL of tetraammine dichloroplatinum solution (the mass content of Pt was 0.5%) for 1 hour. The impregnated mixture was dried at 120°C for 2 hours, followed by 150°C for 3 hours to obtain catalyst OC-7, the composition of which is listed in Table 2.

Experimental Example 8

At a temperature of 25° C., 100 g of the alumina molded body OT-8 prepared in Example 8 was impregnated with 86 mL of tetraammine dichloroplatinum solution (the mass content of Pt was 0.5%) for 1 hour. The impregnated mixture was dried at 120° C. for 2 hours, followed by 150° C. for 3 hours to obtain catalyst OC-8, the composition of which is listed in Table 2.

Experimental Example 9

At a temperature of 25° C., 100 g of the alumina molded body OT-9 prepared in Example 9 was impregnated with 93 mL of tetraammine dichloroplatinum solution (the mass content of Pt was 0.5%) for 1 hour. The impregnated mixture was dried at 120° C. for 2 hours, followed by 150° C. for 3 hours to obtain catalyst OC-9, the composition of which is listed in Table 2.

Experimental Example 10

At a temperature of 25° C., 100 g of the alumina molded body OT-10 prepared in Example 10 was impregnated with 38 mL of platinum dichlorotetraammine solution (the mass content of Pt was 0.5%) for 1 hour. The impregnated mixture was dried at 120°C for 2 hours, followed by drying at 180°C for 2 hours to obtain catalyst OC-10, the composition of which is listed in Table 2.

Experimental comparative example 2

The catalyst was prepared by the same method as in Experimental Example 10, except that the alumina molded body was the alumina molded body prepared in Comparative Example 6. The prepared catalyst is denoted as DOC-2, and its composition is listed in Table 2.

Experimental Example 11

At a temperature of 25° C., 100 g of the alumina molded body OT-11 prepared in Example 11 was impregnated with 38 mL of platinum dichlorotetraammine solution (the mass content of Pt was 1%) for 1 hour. The impregnated mixture was dried at 120°C for 2 hours, then at 150°C for 3 hours, and finally calcined at 350°C for 2 hours in an air atmosphere to obtain catalyst OC-11, whose composition is listed in Table 2.

Experimental comparative example 3

The catalyst was prepared by the same method as in Experimental Example 11, except that the alumina molded body was the alumina molded body prepared in Comparative Example 7. The prepared catalyst is denoted as DOC-3, and its composition is listed in Table 2.

Table 2

Test Examples 1-11 serve to illustrate the hydroisomerization process according to the present invention.

Test Examples 1-11

Taking n-decane with a purity of 99% by weight as raw material (analytical pure), evaluate the catalytic performance of the catalyst prepared in Experimental Examples 1-11 on a micro-fixed bed, wherein the loading amount of the catalyst is 1.2 grams, and the reaction conditions are: temperature 330 °C, pressure 4.0MPa, raw material space velocity 5h ^-1 . The product was analyzed online by gas chromatography, and the raw material conversion rate and product selectivity were calculated according to the following formulas:

Raw material conversion = (1- peak area ratio of unconverted n-decane) × 100%

Product selectivity = [isoparaffin peak area ratio/(1-unconverted n-decane peak area ratio)]×100%

The experimental results are listed in Table 3.

Test Comparative Example 1-3

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

table 3

The results of test examples 1-11 confirmed that the hydroisomerization catalyst prepared with the hydrated alumina shaped body and the alumina shaped body according to the present invention as a support showed higher catalytic performance in the hydroisomerization reaction. active.

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 (39)

1. A hydrated alumina composition containing ZSM-22 type molecular sieve, the composition contains hydrated alumina, ZSM-22 type molecular sieve and a compound with at least two proton acceptor sites, 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, 2. The composition according to claim 1, wherein the The value is less than 4.5, preferably less than 4, more preferably less than 3.5; More preferably, the The value is 1.2 or more, preferably 1.3 or more, more preferably 1.4 or more, further preferably 1.5 or more; Further preferably, the The value is 1.2-5, preferably 1.3-4.5, more preferably 1.4-4, further preferably 1.5-3.5. 3. The composition according to claim 1 or 2, 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 2-22 parts by weight, more preferably 3-20 parts by weight. 4. The composition according to any one of claims 1-3, wherein the hydrated alumina contains pseudoboehmite; Preferably, the hydrated alumina is pseudo-boehmite. 5. The composition according to claim 4, wherein, the composition is placed at ambient temperature and under closed conditions for 72 hours, and the content of aluminum trihydrate in the composition after placement is higher than that of the composition before placement The content of alumina trihydrate in 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 being placed, the content of alumina trihydrate in the composition after being placed is increased by at least 1%, preferably by 1.1-1.5%. 6. The composition of any one of claims 1-5, wherein the hydrated alumina is derived directly from a hydrated alumina wet gel. 7. The composition according to any one of claims 1-6, wherein, based on the total amount of the calcined composition, the content of the ZSM-22 type molecular sieve is 0.5-90% by weight, preferably 5-90%. 88% by weight, more preferably 15-86% by weight, further preferably 30-85% by weight, the content of alumina is 10-99.5% by weight, preferably 12-95% by weight, more preferably 14-85% by weight, It is further preferably 15-70% by weight. The calcination is carried out at a temperature of 600° C., and the duration of the calcination is 3 hours. 8. The composition according to any one of claims 1-7, wherein the composition is free of peptizers. 9. A method for preparing a hydrated alumina composition containing a ZSM-22 molecular sieve, the method comprising mixing components in a raw material composition to obtain the hydrated alumina composition, and the raw material composition A compound containing hydrated alumina wet gel, ZSM-22 molecular sieve and at least two proton acceptor sites, the i value of the hydrated alumina wet gel is not less than 50%, and the compound with at least two The amount of the compound at the proton acceptor site is such that the composition of the final preparation 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, said The value is determined by the following method: 10g of the composition is dried in an air atmosphere at 120°C for 240 minutes, the mass of the dried composition is recorded as w ₁ , and calculated using formula I value, 10. The method according to claim 9, wherein the amount of the compound having at least two proton acceptor sites is such that the prepared alumina hydrate composition has The value is less than 4.5, preferably less than 4, more preferably less than 3.5; Preferably, the amount of the compound having at least two proton acceptor sites is such that the prepared hydrated alumina composition The value is 1.2 or more, preferably 1.3 or more, more preferably 1.4 or more, further preferably 1.5 or more; More preferably, the amount of the compound having at least two proton acceptor sites is such that the prepared hydrated alumina composition has The value is 1.2-5, preferably 1.3-4.5, more preferably 1.4-4, further preferably 1.5-3.5. 11. The method according to claim 9 or 10, wherein the i value of the alumina hydrate wet gel is not higher than 95%, more preferably 50-95%, further preferably 55-90%, more preferably More preferably 60-85%, particularly preferably 62-82%. 12. The method according to any one of claims 9-11, wherein the hydrated alumina wet gel is a hydrated alumina wet gel that has not been subjected to a dehydration treatment such that its i value is 50% or less. 13. The method according to any one of claims 9-12, 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. 14. The method according to any one of claims 9-13, wherein the raw material composition does not contain a peptizer. 15. The method according to any one of claims 9-14, wherein the content of the ZSM-22 molecular sieve in the raw material mixture is based on the total amount of the calcined alumina hydrate composition, ZSM-22 The content of type molecular sieve is 0.5-90% by weight, preferably 5-88% by weight, more preferably 15-86% by weight, further preferably 30-85% by weight, the content of alumina is 10-99.5% by weight, preferably 12-95% by weight, more preferably 14-85% by weight, further preferably 15-70% by weight, the calcination is carried out at a temperature of 600° C., and the duration of the calcination is 3 hours. 16. The method according to any one of claims 9-15, wherein the mixing method is stirring and/or kneading. 17. The method according to any one of claims 9-16, wherein, relative to 100 parts by weight of hydrated alumina wet gel, the amount of the compound having at least two proton acceptor sites is 1-25 Parts by weight, preferably 2-22 parts by weight, more preferably 3-20 parts by weight, the alumina hydrate wet gel is calculated as alumina hydrate. 18. The composition according to any one of claims 1-8 or the method according to any one of claims 9-17, wherein, in the compound with at least two proton acceptor sites, proton The acceptor site is one or more of F, O and N that can form hydrogen bonds with water; 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 15-65% by weight, more preferably 25-60% by weight; the content of the cellulose ether is 30-90% by weight, preferably 35-85% by weight, more preferably 40-75% by weight. 19. A hydrated alumina composition containing ZSM-22 type molecular sieve prepared by the method according to any one of claims 9-18. 20. A hydrated alumina formed body formed from the hydrated alumina composition of any one of claims 1-8 and 18 or the hydrated alumina composition of claim 19. 21. A method for preparing a hydrated alumina formed body, the method comprising molding the hydrated alumina composition according to any one of claims 1-8 and 18 or the hydrated alumina composition according to claim 19 , drying the obtained molding. 22. An alumina hydrate shaped body produced by the method of claim 21. 23. An alumina shaped body formed from the hydrated alumina composition of any one of claims 1-8 and 18 or the hydrated alumina composition of claim 19. 24. A method for preparing an alumina formed body, the method comprising molding the hydrated alumina composition according to any one of claims 1-8 and 18 or the hydrated alumina composition according to claim 19, The obtained molding is dried and fired. 25. An alumina shaped body produced by the method of claim 24. 26. Alumina hydrate shaped body according to any one of claims 20 and 22, alumina shaped body according to any one of claims 23 and 25, wherein said hydrated alumina shaped body and said The radial crush strength of the alumina shaped bodies is in each case 15-40 N/mm, preferably 18-35 N/mm. 27. 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 50%, preferably not lower than 55%, more preferably not lower than 60%, more preferably not higher than 95%, further preferably not higher than 90% %, more preferably not higher than 85%, even more preferably not higher than 82%; 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) Mixing the first alumina hydrate wet gel with a compound having at least two proton acceptor sites by the method according to any one of claims 9-18 to obtain a alumina hydrate composition; (3) molding the hydrated alumina composition to obtain a hydrated alumina molding; (4) drying the hydrated alumina shaped body to obtain a hydrated alumina shaped body; (5) Optionally, calcining at least part of the hydrated alumina shaped body to obtain an alumina shaped body; Wherein, the method further includes the operation of mixing ZSM-22 molecular sieves in step (1) and/or step (2), so that the hydrated alumina composition contains ZSM-22 molecular sieves. 28. 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 50%, preferably not less than 55%, more preferably Preferably not lower than 60%, more preferably not higher than 95%, further preferably not higher than 90%, further preferably not higher than 85%, even more preferably not higher than 82%, 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 9-18 to mix the second alumina hydrate wet gel with a compound having at least two proton acceptor sites to obtain a alumina hydrate composition; (4) molding the hydrated alumina composition to obtain a hydrated alumina molding; (5) drying the alumina hydrate formed body to obtain a hydrated alumina formed body; (6) Optionally, calcining at least part of the alumina hydrate shaped body to obtain an alumina shaped body; Wherein, the method also includes the operation of mixing ZSM-22 molecular sieves in one, two or three of step (1), step (2) and step (3), so that the hydrated alumina composition Contains ZSM-22 molecular sieve. 29. The method according to claim 27 or 28, 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. 30. The method according to any one of claims 27-29, wherein the hydrated alumina gel solution is aged or not aged by precipitation method, hydrolysis method, seeding method and rapid dehydration method prepared by one or more than two methods. 31. A shaped body produced by the method of any one of claims 27-30. 32. The shaped body according to claim 31, wherein the radial crush strength of the shaped body is 15-40 N/mm, preferably 18-35 N/mm. 33. A hydrated alumina shaped body according to any one of claims 20, 22 and 26, an alumina shaped body according to any one of claims 23, 25 and 26 or any one of claims 31 and 32 The application of the molded body as a carrier or an adsorbent. 34. The use according to claim 33, wherein the carrier is a carrier of a supported catalyst, preferably a carrier of a supported hydrogenation catalyst. 35. A hydroisomerization catalyst, the catalyst contains a carrier and an active component loaded on the carrier, wherein the carrier is the hydrated alumina shaped according to any one of claims 20, 22 and 26 body, the alumina shaped body according to any one of claims 23, 25 and 26 or the shaped body according to any one of claims 31 and 32. 36. The catalyst according to claim 35, wherein the active ingredient is selected from Group VIII noble metal elements, preferably platinum and/or palladium; Preferably, based on the total amount of the catalyst, the content of the active ingredient in terms of elements is 0.1-5% by weight, preferably 0.2-2% by weight, more preferably 0.3-1% by weight. 37. A method for preparing a hydroisomerization catalyst, the method comprising loading an active component on a carrier, wherein the method also comprises preparing the catalyst as The step of the shaped body of the carrier. 38. The preparation method according to claim 37, wherein the active ingredient is selected from Group VIII noble metal elements, preferably platinum and/or palladium; Preferably, the loading amount of the active ingredient on the carrier is such that, based on the total amount of the final prepared catalyst, the content of the active ingredient in terms of elements is 0.1-5% by weight, preferably 0.2-2% by weight , more preferably 0.3-1% by weight. 39. A hydroisomerization process comprising contacting a hydrocarbon oil with a hydroisomerization catalyst under hydroisomerization conditions, wherein said hydroisomerization catalyst is the The catalyst described in any one in 36 or the catalyst prepared by the method described in any one in claim 37-38.