CN108014830A

CN108014830A - Catalyst with hydrogenation catalyst effect and its preparation method and application and heavy-oil hydrogenation depitching matter method

Info

Publication number: CN108014830A
Application number: CN201610971765.9A
Authority: CN
Inventors: 孙淑玲; 杨清河; 胡大为; 曾双亲; 戴立顺
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-10-28
Filing date: 2016-10-28
Publication date: 2018-05-11
Anticipated expiration: 2036-10-28
Also published as: CN108014830B

Abstract

The present invention relates to hydrocarbon oil hydrogenation technical field, specifically discloses catalyst with hydrogenation catalyst effect and its preparation method and application and heavy-oil hydrogenation depitching matter method.The hydrogenation activity component that the catalyst contains carrier and is supported on carrier, carrier be by containing hydrated alumina, have at least two proton acceptor sites compound and phosphorus-containing compound, andIt is worth for obtained from 1.8 5 hydrated alumina composition molding.The invention also discloses the heavy-oil hydrogenation de-asphalting method using the catalyst.The carrier with higher-strength is prepared by starting material of hydrated alumina wet gel in the catalyst of 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 preparing carrier using boehmite dry glue powder as raw material and triggering is avoided, greatly improves operating environment.Catalyst according to the invention has higher catalytic activity.

Description

Catalyst with hydrogenation catalyst effect and its preparation method and application and heavy oil add Hydrogen depitching matter method

Technical field

The present invention relates to hydrocarbon oil hydrogenation technical field, in particular it relates to a kind of urging with hydrogenation catalyst effect Agent and its preparation method and application, the invention further relates to a kind of heavy-oil hydrogenation depitching matter method using the catalyst.

Background technology

In traditional catalyst preparation method, aluminium oxide formed body, particularly gama-alumina formed body, because its have compared with Good pore structure, suitable ratio surface and higher heat-resistant stability, uses frequently as the carrier of loaded catalyst.This oxygen Change aluminium usually by dried hydrated alumina, such as boehmite through being molded, it is dry after, high-temperature roasting obtains again.

Based on above-mentioned cognition, as shown in Figure 1, the hydrated alumina wet gel being prepared needs to be dried, intended Boehmite dry glue powder, then using boehmite dry glue powder as starting point, adds extrusion aid and optional chemical peptizing agent (inorganic acid and/or organic acid), through kneading aftershaping, molding uses after dry and optional roasting as carrier.This The main problem of kind of preparation method is that dust pollution is larger and high energy consumption.

In order to reduce dust pollution, improve operating environment, researcher recognizes that shaping raw material used should be changed, opens Begin to attempt hydrated alumina wet gel or semiarid boehmite preparing aluminium oxide molding as raw material.

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

(a) aluminum sulfate solution and sodium aluminate solution are poured into the container equipped with deionized water at the same time, makes aluminum sulfate solution Reacted with sodium aluminate solution, reaction condition pH6.0-8.5, temperature is 50-65 DEG C, thus prepares first containing amorphous The aqueous slurry of aluminium hydroxide；

(b) sodium aluminate aqueous solution is added into the first aqueous slurry, the additive amount of the sodium aluminate aqueous solution is enough to neutralize institute The first aqueous slurry is stated, the total amount of the sodium aluminate solution used in step (a) and step (b) is equivalent to the sulphur used in step (a) Stoichiometric 0.95-1.05 of the amount of sour aluminium, thus prepares the second aqueous slurry, the Al of second aqueous slurry₂O₃Concentration is 7wt% or higher；

(c) amorphous hydroted alumina in the second aqueous slurry is filtered out, filter cake is obtained, is obtained first with dilute ammonia scrubbing Filter cake, then washed with dilute nitric acid solution, finally washed again with dilute ammonium hydroxide, with remove sulfate anion and Sodium cation impurity, while the pH of filter cake is adjusted in the range of 7.5-10.5；

(d) then, without the aging filter cake, on a filter press by the cake dewatering, and by its Al₂O₃Content improve to 28-35wt%, and in the range of pH is 7.5-10.5, mediate the filter cake in the mixer of a self-cleaning type, during stop Between be 10s or longer, boehmite particle is grown up in a short time, thus obtain the dough containing these particles；

(e) dough for obtaining step (d) is extruded into extrudate, and then dry and roasting obtains extrudate.

From the point of view of method disclosed in US4613585, although hydrated alumina wet gel can be molded by this method, from The preparation condition of amorphous hydroted alumina is all restricted to kneader device and kneading conditions, causes complex operation.Also, by Carrier prepared by this method should be unable to have very high intensity, it is difficult to meet the requirement of commercial Application, its reason is by this The content of Free water is high in extrudate prepared by method, and the extrudate obtained through dry and roasting is loose.Meanwhile using this method Carrier is prepared, it is difficult to regulate and control to the pore structure of carrier, so as to it is difficult to meet the needs of a variety of use occasions.

CN103769118A discloses a kind of heavy-oil hydrogenation catalyst, including carrier and active ingredient, and carrier is aluminium oxide, Active component is group VIII and/or the metal of group vib, and wherein group VIII metal is Co or Ni, and group vib metal is Mo or W, its In, it is prepared by the boehmite shaping that the alumina support contents on dry basis is less than 50%.The contents on dry basis is 50% The preparation process of following boehmite includes：(1) aluminum salt solution carries out neutralizing plastic reaction with precipitating reagent；(2) filter back The solid product of harvest glue reaction；(3) solid product obtains contents on dry basis as less than 50% after drying.

CN103769118A uses contents on dry basis to prepare alumina support, contents on dry basis for less than 50% boehmite Boehmite for less than 50% is then to be done the solid product separated from the mixture that plastic is reacted Obtained from dry, in actual mechanical process, it is difficult the method carried out that this, which is one, and main cause is as follows：

(1) the boehmite viscosity not being completely dried is stronger, and transfer is difficult, easily causes secondary dust to pollute；

(2) dry all since surface, to the wet solid separated from the mixture that plastic is reacted The drying that product carries out belongs to endless white drying, therefore there are sandwich biscuits phenomenon, the i.e. surface of part boehmite to be done Dry (that is, Free water being substantially free of by dry surface), and internal wet state is still maintained (that is, for not by dry Portion, the content of Free water keep dry substantially before level), since surface is dried, form hard particles, to it is this not Peptizing agent and/or binding agent are added in the boehmite parched completely when through mediating aftershaping, is formed in drying process Hard particles easily cause to block during extrusion, influence production efficiency；

(3) it is difficult to which the butt of stability contorting boehmite, butt is unstable to cause very big interference to shaping, make into Type process is also highly unstable, causes the increase of substandard product amount, and production efficiency is low；

(4) CN103769118A in shaping using conventional moulding process, the boehmite used yet with it Butt (for 35%-50%) far below conventional contents on dry basis (for 70% or so), i.e. water content height, in extrusion molding process Extrusion pressure will not be substantially produced, therefore the carrier that extrudate obtains after drying and roasting does not have mechanical strength substantially, as long as Apply some external force, will dusting, do not possess the possibility of commercial Application, this is the greatest problem that the technology faces.

In conclusion how on the premise of guaranteeing to be met the alumina support using industrial application requirement, letter Change the preparation process flow of alumina support and reduce operation energy consumption, while mitigate the powder in alumina support preparation process Dustiness dye is still a technical problem urgently to be resolved hurrily.

The content of the invention

For US4613585 and CN103769118A when preparing alumina support problem encountered, hair of the invention A person of good sense is off the beaten track, by the compound containing at least two proton acceptor sites in molecular structure and arises directly from synthetic reaction The mixing of hydrated alumina wet gel, the mixture of formation can not only be molded, and be obtained through dry and optional roasting To shaping physical efficiency have and meet the intensity of industrial requirements.The present invention is completed on this basis.

According to the first aspect of the invention, the present invention provides a kind of catalyst with hydrogenation catalyst effect, this is urged Agent contains the hydrogenation activity component of carrier and load on the carrier, wherein, the carrier is by a kind of aqua oxidation Obtained from aluminium composition molding, the hydrated alumina composition contains hydrated alumina, has at least two proton acceptors The compound and phosphorus-containing compound in site,

The compositionIt is worth for 1.8-5, it is describedValue is measured using following methods：By composition described in 10g 120 It is 240 minutes dry DEG C in air atmosphere, the quality through dry composition is denoted as w₁, calculated using Formulas IValue,

According to the second aspect of the invention, the present invention provides a kind of preparation of the catalyst with hydrogenation catalyst effect Method, this method include hydrogenation activity component being supported on carrier, wherein, the carrier uses method comprising the following steps It is made：

(1) each component in a kind of feedstock composition is mixed, obtains hydrated alumina composition, the feedstock composition Compound and phosphorus-containing compound containing hydrated alumina wet gel, with least two proton acceptor sites, the hydration The i values of aluminium oxide wet gel are not less than 60%, and the dosage of the compound with least two proton acceptor sites causes The hydrated alumina composition finally preparedIt is worth for 1.8-5,

The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of dryings in air atmosphere 240 minutes, the quality through dry sample is denoted as w₂, i values are calculated using Formula II,

It is describedValue is measured using following methods：10g compositions are dried 240 minutes at 120 DEG C in air atmosphere, will Quality through dry composition is denoted as w₁, calculated using Formulas IValue,

(2) by the hydrated alumina composition molding, molding is dried and is optionally roasted, obtained described Carrier.

According to the third aspect of the present invention, the present invention provides a kind of method system as described in second aspect of the present invention The standby catalyst with hydrogenation catalyst effect.

According to the fourth aspect of the present invention, the present invention provides described in the first aspect of the present invention or second aspect Have hydrogenation catalyst effect catalyst hydrocarbon oil hydrogenation processing in application.

According to the fifth aspect of the present invention, the present invention provides a kind of heavy-oil hydrogenation depitching matter method, this method bag Include at hydrotreating reaction conditions, by described in the heavy oil containing asphalitine and the first aspect of the present invention or the 3rd aspect Catalyst contact.

With existing process (such as Fig. 1 that alumina support is prepared using boehmite dry glue powder as starting material Shown technique) to compare, the hydrated alumina that the carrier in catalyst is directly prepared with synthetic reaction according to the present invention is wet Gel has the advantage that as molding starting material：

(1) the step of being used to dry hydrated alumina wet gel in existing process is eliminated, and is preparing shaping raw material When, boehmite dry glue powder is modulated into plastic material without additionally introducing water, simplifies overall craft flow, is reduced Overall operation energy consumption；

(2) dust pollution due to triggering using boehmite dry glue powder as raw material is avoided, is greatly improved Operating environment.

Existing process, such as US4613585 with directly preparing carrier using hydrated alumina wet gel as starting material Compared with CN103769118A, the preparation process for the carrier that catalyst according to the invention uses is more succinct, operable Property is stronger, and can effectively improve the intensity of the formed body finally prepared, while can be to the aperture of the formed body finally prepared Distribution is adjusted, and meets the requirement of a variety of use occasions.The present invention can be prepared by starting material of hydrated alumina wet gel The reason for formed body with higher-strength, may is that：Compound and aqua oxidation with least two proton acceptor sites Free water in aluminium wet gel interacts to form hydrogen bond, adsorb hydrated alumina wet gel in Free water, while have to Also with the hydroxyl in hydrated alumina molecular structure interaction of hydrogen bond can occur for the compound in few two proton acceptor sites, rise To the effect of physics peptization, so that hydrated alumina wet gel can not only be molded, and can be so that the shaping finally prepared Body has higher intensity.

Catalyst according to the invention has preferable catalytic performance, especially as heavy-oil hydrogenation depitching qualitative response During catalyst, the asphalt content and tenor that can be effectively reduced in heavy oil.

Brief description of the drawings

Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.

Fig. 1 is moulding process flow process usually used in current commercial Application.

Fig. 2 is a kind of preferably preparation process flow of support according to the present invention.

Embodiment

The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.

According to the first aspect of the invention, the present invention provides a kind of catalyst with hydrogenation catalyst effect, this is urged Agent contains the hydrogenation activity component of carrier and load on the carrier.

Catalyst according to the invention, the carrier be by obtained from a kind of hydrated alumina composition molding, it is described Hydrated alumina composition contains hydrated alumina, the compound with least two proton acceptor sites and phosphorous chemical combination Thing.

The hydrated alumina can be more than one or both of gibbsite and a water aluminium oxide.It is described Hydrated alumina preferably comprises a water aluminium oxide, more preferably a water aluminium oxide.The instantiation of the hydrated alumina can be with Including but not limited to boehmite, gibbsite, unformed hydrated alumina and boehmite.In a kind of excellent of the present invention In the embodiment of choosing, the hydrated alumina contains boehmite, more preferably boehmite.

In the hydrated alumina composition, the hydrated alumina is directed to hydrated alumina wet gel, and Non-sourcing is in hydrated alumina dry glue powder.In the present invention, term " hydrated alumina wet gel " refers to obtain by synthetic reaction And the aqueous hydrated alumina for not living through the dehydration that its i value is reduced to less than 60% (preferably less than 62%) coagulates Glue.In the present invention, i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of dryings in air atmosphere 240 minutes, the quality through dry sample is denoted as w₂, i values are calculated using Formula II,

The synthetic reaction refers to the reaction for preparing gel aluminum hydroxide, can be aqua oxidation commonly used in the art Alumina gel synthetic reaction, specific examples thereof include the precipitation method (including acid system and alkaline process), Hydrolyze method, kind point-score and fast dewatering Method.The alumina hydrate gel of synthesis can be the alumina hydrate gel without going through aging, or live through aging Alumina hydrate gel.The precipitation method, Hydrolyze method, kind point-score and rapid dehydration method concrete operation method and condition can be with For conventional selection, will hereinafter illustrate.The hydrated alumina wet gel can be by the hydration that obtains synthetic reaction After alumina gel alternatively carries out aging, carry out washing and separation of solid and liquid and collect solid phase and obtain.

It is different from the hydrated alumina from dry glue powder, it is directed to the aqua oxidation of alumina hydrate gel Aluminium thing of hydrated alumina in storage process, which is met, to change.For example, it is small that 72 are placed under environment temperature and sealing condition When, the thing of hydrated alumina, which is met, in the composition after placement changes.Depending on the environment temperature is with environment is placed, generally It can be 5-50 DEG C, such as 20-40 DEG C.The sealing condition refers to the composition being placed in closure container, the closed appearance Device can be closure container (such as tank, bucket or case), or the flexible coating (such as sealed bag) of sealing, the flexible bag It can be paper and/or polymeric material to cover thing, be preferably polymeric material, such as plastics.

In an example, the hydrated alumina for being directed to alumina hydrate gel contains boehmite (as directly It is boehmite to fetch and come from the hydrated alumina of alumina hydrate gel) when, by the composition in environment temperature and envelope When placement 72 is small under the conditions of closing, the gibbsite content in the composition after placement is higher than three water in the composition before placing Alumina content.In this example, on the basis of the total amount of the content of the gibbsite in the composition before placement, after placement Composition in gibbsite content generally at least improve 0.5%, preferably at least improve 1%, preferably improve 1.1% to 2%.

The hydrated alumina composition also contains the compound with least two proton acceptor sites.It is described to have extremely In the compound in few two proton acceptor sites, proton acceptor site refers to can be with water and hydroxyl in the molecular structure of the compound Base forms the position of hydrogen bond.The instantiation in the proton acceptor site can include but be not limited to fluorine (F), oxygen (O) and nitrogen One or both of (N) more than.The instantiation of the compound with least two proton acceptor sites can include But it is not limited in molecular structure containing one in hydroxyl, carboxyl, amino, ehter bond, aldehyde radical, carbonyl, amide groups and fluorine atom The compound of kind or two or more groups, is preferably hydroxyl and/or ehter bond.

The compound with least two proton acceptor sites can be organic compound, or inorganic chemical Thing, can also be the combination of organic compound and inorganic compound.Using organising with least two proton acceptor sites Compound, the organic compound can be removed by roasting process.Using the inorganic chemical with least two proton acceptor sites Thing, the Partial Elements in the inorganic compound can be retained in the formed body finally prepared, it is possible thereby to inorganization by this Compound introduces auxiliary element in formed body.

In a kind of preferred embodiment of the present invention, it is described there are at least two proton acceptor sites compound be There is the polymer in multiple (such as more than three) proton acceptor sites in molecular structure.According to the preferred embodiment, can obtain Physically better peptization is obtained, so that the intensity of the formed body finally prepared is further improved, particularly using extrusion work When skill is molded, the intensity of the formed body finally prepared can be further improved.Preferably, the polymer is organic polymer Thing.According to the preferred embodiment, the instantiation of the compound with least two proton acceptor sites can wrap Include but be not limited to polyol, is more than one or both of polyethers and acrylic acid polymer.

The polyol can include but be not limited to polysaccharide, the etherate and polyalcohol of polysaccharide.

The polysaccharide can be homopolysaccharide, or heteroglycan, can also be the combination of homopolysaccharide and heteroglycan.It is described Polysaccharide and its etherate specific examples thereof include but be not limited to glucan, galactan, mannosan, galactomannans, fibre Dimension plain ether, starch, chitin, glycosaminoglycan and glycosaminoglycan.The cellulose ether refers to the part of hydroxyl in cellulosic molecule On hydrogen atom substituted by alkyl after the ether system derivative that is formed, wherein, multiple alkyl can be identical, or no Together.The alkyl is selected from the alkyl of substitution and unsubstituted alkyl.The unsubstituted alkyl be preferably alkyl (such as：C₁-C₅ Alkyl).In the present invention, C₁-C₅The instantiation of alkyl include C₁-C₅Straight chained alkyl and C₃-C₅Branched alkyl, can be with For but be not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl and uncle penta Base.The substituted alkyl for example can be substituted by hydroxyl, carboxyl, cyano group or aryl alkyl (such as：C₁-C₅By hydroxyl Alkyl, the C of base substitution₁-C₅The alkyl substituted by carboxyl, the C that is substituted with aryl₁-C₅Alkyl), the aryl can be benzene Base or naphthyl.The instantiation of the substituted alkyl can include but is not limited to：Cyano group, benzyl, phenethyl, hydroxyl first Base, ethoxy, hydroxypropyl, hydroxyl butyl, carboxymethyl, carboxyethyl and carboxylic propyl group.The instantiation of the cellulose ether can include But it is not limited to methylcellulose, hydroxyethylmethylcellulose, carboxymethyl cellulose, ethyl cellulose, benzylcellulose, ethoxy Cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cyanethyl cellulose, benzyl cyanethyl cellulose, carboxymethyl hydroxyl second Base cellulose and benzyl cellulose.

The polyalcohol specific examples thereof include but be not limited to polyvinyl alcohol, part acetalation polyvinyl alcohol (acetalizing degree Can be less than 95%, be preferably less than 80%, more preferably less than 70%, more preferably less than 50%), polyether polyols It is more than one or both of alcohol and polyester polyol.

The polyethers specific examples thereof include but be not limited to polyethylene oxide, polypropylene oxide, epoxy ethane-epoxy propane Copolymer and PolyTHF.

The acrylic acid polymer refers to the polymer containing acrylic monomer unit, the acrylic monomer list Member be specifically as follows but be not limited to acrylic monomer units and acrylate monomer units (be preferably C₁-C₅Alkyl acrylic Monomeric unit, more preferably methacrylic acid monomer units).Specific examples thereof include polypropylene for the acrylic acid polymer Acid, polymethylacrylic acid, copolymer of acrylic acid and methyl acrylate, acryl acid-methyl methacrylate copolymer, metering system Acid-methyl acrylate copolymer and EUDRAGIT L100.

In the preferred embodiment, it is described there are at least two proton acceptor sites compound it is further preferably more The etherate of sugar and/or polysaccharide, the more preferably etherate of polysaccharide and/or polysaccharide.

In a kind of embodiment being more highly preferred to of the present invention, the chemical combination with least two proton acceptor sites Thing contains galactomannans and cellulose ether.There is the intensity of higher according to the carrier of the embodiment being more highly preferred to.Into Preferably, the compound with least two proton acceptor sites is preferably galactomannans and cellulose ether to one step.

In the embodiment that this is more highly preferred to, with the total amount of the compound with least two proton acceptor sites On the basis of, the content of the galactomannans can be 10-70 weight %, be preferably 15-68 weight %, more preferably 20- 65 weight %；The content of the cellulose ether can be 30-90 weight %, be preferably 32-85 weight %, more preferably 35-80 Weight %.

The phosphorus-containing compound can be the phosphorus-containing compound of this area routine, for example, the phosphorus-containing compound can select From at least one of phosphoric acid, sodium phosphate, aluminum phosphate, phosphorus chloride, phosphorus pentoxide, ammonium hydrogen phosphate and ammonium phosphate.Preferably, institute State phosphorus-containing compound and be selected from least one of phosphoric acid, sodium phosphate, aluminum phosphate and phosphorus pentoxide.

The content of phosphorus-containing compound can be conventional selection in the hydrated alumina composition.Usually, urged with described On the basis of the total amount of agent, with P₂O₅The phosphorus content of meter can be 1-6 weight %, be preferably 1.5-4 weight %.

The hydrated alumina compositionIt is worth for 1.8-5, is preferably not lower than 1.85, such as can is 1.85-3.5, More preferably it is not less than 1.9, such as can is 1.9-3.2.The load prepared according to the hydrated alumina composition of the embodiment The aperture of body is in bimodal distribution.

In the present invention,Value is measured using following methods：By composition described in 10g in 120 DEG C of dryings in air atmosphere 240 minutes, the quality through dry composition is denoted as w₁, calculated using Formulas IValue,

In the hydrated alumina composition, the content of the compound with least two proton acceptor sites is with energy Make the compositionValue meets subject to above-mentioned requirements.Preferably, relative to hydrated alumina described in 100 parts by weight, the tool The content for having the compound at least two proton acceptor sites can be 1-25 weight %, be preferably 2-20 parts by weight, more preferably For 3-18 parts by weight, more preferably 3.5-17 parts by weight.

The hydrated alumina composition can contain peptizing agent, can not also contain peptizing agent.The peptizing agent can be with For the usually used reagent with gelatification of aluminium oxide formed body preparing technical field, its instantiation can be included but not It is limited to Aluminum sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid.

The compound with least two proton acceptor sites, particularly has at least two proton acceptors described It is described that there are at least two proton acceptors when the compound in site is containing polymer with least two proton acceptor sites The compound in site can play the role of physics peptization, so as to reduce the dosage of peptizing agent, it might even be possible to without using peptization Agent.

In a kind of preferred embodiment of the present invention, relative to 100 parts by weight hydrated aluminas, the peptizing agent Content is below 5 parts by weight, is preferably below 3 parts by weight.

In a kind of particularly preferred embodiment of the present invention, the hydrated alumina composition does not contain peptizing agent. According to the composition of the particularly preferred embodiment, though the hydrated alumina formed body of preparation without roasting, by its turn It is changed into aluminium oxide formed body, can be also used as carrier, because when unfired hydrated alumina formed body contains peptizing agent, Peptizing agent adsorb and dipping process in dissolve, it is a large amount of to be lost in so that there is dissolving, dusting and duct and caves in phenomenon in formed body, It is final to lose shape, thus adsorbent and carrier can not be used as to use.Thus, catalyst according to the invention, the carrier are Formed body obtained from the molding of the hydrated alumina composition is dried and is optionally roasted, can be through roasting The aluminium oxide formed body of burning, when the hydrated alumina composition is free of peptizing agent, or unfired hydration oxygen Change aluminium formed body.The roasting refers at a temperature of not less than 355 DEG C, be heat-treated in air atmosphere, usually, institute State roasting to carry out at a temperature of 355 DEG C to 1800 DEG C, carried out preferably at a temperature of 800-1000 DEG C, the roasting continues When time can be 0.1-20 small, when being preferably 2-6 small.

Catalyst according to the invention, the carrier can have it is variously-shaped, such as：Spherical, piece shape, bar shaped, honeycomb Shape or bird-nest-shaped.Described shape and the instantiation of bar shaped can include but is not limited to cloverleaf pattern, butterfly, cylinder and draw west Ring.

Catalyst according to the invention, can use this area conventional method by the hydrated alumina composition into Type, and molding is dried and is optionally roasted, so as to obtain the carrier.The shaping, drying and roasting Specific method and condition will be described in detail in second aspect of the present invention, as space is limited the reason for, do not repeat herein.

Catalyst according to the invention, the carrier have higher intensity, meet that the use as catalyst carrier will Ask.Usually, the radial direction crushing strength of the carrier is more than 10N/mm, preferably more than 12N/mm (such as can be 12- 55N/mm), it is more preferably more than 15N/mm.In an example, the radial direction crushing strength of the carrier for 10-35N/mm (such as 12-35N/mm).In the example that one is more highly preferred to, the radial direction crushing strength of the carrier is 15-32N/mm.In the present invention, Using the radial direction crushing strength of method measure carrier specified in RIPP 25-90.

Catalyst according to the invention, the carrier are porous material, its aperture is in bimodal distribution.Wherein, most probable Aperture is respectively 4-20nm (be preferably 5-15nm) and more than 20nm (such as 20.5-35nm, is preferably 21-30nm).

Catalyst according to the present invention with hydrogenation catalyst effect, the hydrogenation activity component can be common to hydrocarbon Component of the oil hydrogenation with catalytic action.Preferably, the hydrogenation activity component is at least one vib metals element and extremely A kind of few group VIII metallic element.The vib metals element is preferably molybdenum and/or tungsten.The group VIII metal member Element is preferably cobalt and/or nickel.

Depending on the load capacity of the hydrogenation activity component on the carrier is with the specific species of hydrogenation activity component.As One example, when the hydrogenation activity component is vib metals element and group VIII metallic element, with the catalyst Total amount on the basis of, the content of the group VIII metallic element in terms of oxide can be 0.8-3 weight %, be preferably 1-2 weight % is measured, the content of the vib metals element in terms of oxide can be 3-10 weight %, be preferably 4-8 weight %.

The hydrogenation activity component can load on the carrier in the form of the oxide, can also be with non-oxidized substance The form of (such as salt and/or simple substance) is supported on carrier, can also be the combination of oxide and non-oxidized substance.

Catalyst according to the invention, when hydrogenation activity component is supported on carrier in the form of its non-activated state, Before use, the conventional method of this area can be used to be activated, the hydrogenation activity conversion of its non-activated state is become The state of activation.

According to the second aspect of the invention, the present invention provides a kind of preparation of the catalyst with hydrogenation catalyst effect Method, this method include hydrogenation activity component being supported on carrier.

Preparation in accordance with the present invention, the carrier are made using method comprising the following steps：

It is described that there is the species of compound at least two proton acceptor sites and the species of the phosphorus-containing compound to exist Detailed description has been carried out above, details are not described herein again.

The hydrated alumina wet gel can use conventional method to synthesize, for example with the precipitation method (including acid system and alkali Method), Hydrolyze method, kind one or both of point-score and rapid dehydration method more than method be made.Usually by hydrated alumina After gel solution alternatively carries out aging, carry out washing and separation of solid and liquid obtained from.

The precipitation method include acid system and alkaline process.The acid system is that aluminium salt is carried out precipitation reaction with alkali compounds.Institute It is that aluminate is carried out precipitation reaction with acid compound to state alkaline process.In the precipitation method, the mixture that precipitation reaction obtains is optional After ground carries out aging (preferably carrying out aging), separation of solid and liquid is carried out, the solid phase isolated is washed, obtains the hydration Aluminium oxide wet gel.

The aluminium salt and the species of the aluminate can be conventional selection.The instantiation of the aluminium salt can include but It is not limited to more than one or both of aluminum sulfate, aluminium chloride and aluminum nitrate.The instantiation of the aluminate can include but It is not limited to more than one or both of sodium metaaluminate, potassium metaaluminate and meta-aluminic acid phosphorus.

The alkali compounds and the acid compound can be conventional selection.The alkali compounds can be common It is various can make water in alkalescence compounds, ammonium hydroxide, hydroxide and basic salt can be selected from.The hydroxide can be normal The water soluble hydroxide seen, such as alkali metal hydroxide.The basic salt can be that common decomposition in water make it that water is in The salt of alkalescence, such as meta-aluminate, carbonate and bicarbonate.The instantiation of the alkali compounds can include but is not limited to Ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium metaaluminate, potassium metaaluminate, ammonium hydrogen carbonate, ammonium carbonate, sodium acid carbonate, sodium carbonate, carbonic acid It is more than one or both of hydrogen potassium and potassium carbonate.The acid compound can be the common various changes that can make water in acidity Compound, can be inorganic acid and/or organic acid.The instantiation of the acid compound can include but is not limited to sulfuric acid, salt It is more than one or both of acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid.The carbonic acid can be by leading Enter carbon dioxide and generation in situ.

The precipitation reaction can carry out under normal conditions, this is not particularly limited in the present invention.Usually, the alkali The dosage of the property compound either acid compound causes the pH of the aluminum salt solution or the aluminate solution to be 6-10, Preferably 7-9.The precipitation reaction can carry out at a temperature of 30-90 DEG C, preferably 40-80 DEG C.

The method of hydrated alumina wet gel is prepared using Hydrolyze method to be included：Aluminum contained compound is hydrolyzed instead Should, after the mixture that hydrolysis is obtained alternatively carries out aging (preferably carrying out aging), separation of solid and liquid is carried out, will be isolated Solid phase washed, so as to obtain the hydrated alumina wet gel.

The aluminum contained compound can prepare the calorize that contains usually used in alumina hydrate gel technique for Hydrolyze method and close Thing.The aluminum contained compound is preferably the organo-aluminum compound that hydrolysis can occur, more preferably aluminium alcoholates.It is described to contain calorize The instantiation of compound can include but is not limited to aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and different It is more than one or both of octanol aluminium.

The present invention is not particularly limited for the actual conditions of hydrolysis, can carry out under normal conditions.Usually, The hydrolysis can be 3-11 in pH, be carried out under conditions of preferably 6-10.The hydrolysis can 30-90 DEG C, It is preferred that carried out at a temperature of 40-80 DEG C.

In the precipitation method and Hydrolyze method, the condition of the aging is not particularly limited, and can carry out under normal conditions.One As, the aging can carry out at a temperature of 35-98 DEG C, preferably 40-80 DEG C.The duration of the aging can be When 0.2-6 is small.

The method of hydrated alumina wet gel is prepared using kind of point-score to be included：Added into supersaturated aluminate solution Crystal seed, decomposes and produces aluminium hydroxide, and the mixture that decomposition is obtained carries out separation of solid and liquid, and the solid phase isolated is washed, So as to obtain the hydrated alumina wet gel.The instantiation of the aluminate can include but is not limited to sodium metaaluminate, partially It is more than one or both of potassium aluminate and meta-aluminic acid phosphorus.

The method of hydrated alumina wet gel is prepared using rapid dehydration method to be included：By hydrated alumina in 600- Roasted at a temperature of 950 DEG C, preferably 650-800 DEG C, product of roasting carries out hydro-thermal process, the mixing that hydro-thermal process is obtained Thing carries out separation of solid and liquid, so as to obtain hydrated alumina wet gel.When the duration of the roasting can be 1-6 small, preferably For 2-4 it is small when.The hydro-thermal process can carry out at a temperature of 120-200 DEG C, preferably 140-160 DEG C.The hydro-thermal process Usually in closed container, carried out under self-generated pressure.

The precipitation method, Hydrolyze method, kind point-score and rapid dehydration method in, the separation of solid and liquid can use conventional method into OK, it is specifically as follows the combination of filtering, centrifugation or both.

In step (1), the i values of the hydrated alumina wet gel are not less than 60%, are preferably not lower than 62%.It is described The i values of hydrated alumina wet gel are preferably not higher than 82%, more preferably not above 80%, are more preferably not higher than 78.5%.

Can be by the way that separation of solid and liquid bar during separation of solid and liquid be carried out containing alumina hydrate gel solution to being prepared Part is controlled, so as to obtain the hydrated alumina wet gel that i values meet above-mentioned requirements.In one embodiment of the present invention In, separation of solid and liquid is more than once or twice, at least last time separation of solid and liquid fills for pressure filter and/or vacuum filter Put.In this embodiment, by adjusting the pressure of application and/or the size of vacuum, to obtaining hydrated alumina wet gel i Value is controlled.The instantiation of the pressure filter can include but be not limited to plate and frame type filter-press, belt type filter The combination of machine or both.In order to control the i values of the hydrated alumina wet gel of acquisition, natural wind or with pressure can also be used Wind purges isolated solid phase, so as to improve the efficiency of moisture abjection.The pressure of the wind with pressure can be conventional Selection, generally can be 0.1-12MPa, be preferably 0.5-10MPa.

In step (1), hydrated alumina wet gel that separation of solid and liquid obtains does not live through generally is reduced to 60% by its i value The dehydration of (preferably less than 62%) below.

In step (1), the dosage of the compound with least two proton acceptor sites enables to finally prepare Hydrated alumina compositionIt is worth for 1.8-5, is preferably not lower than 1.85, such as can be 1.85-3.5, more preferably not Less than 1.9, such as can be 1.9-3.2.The aperture of the carrier prepared according to the hydrated alumina composition of the embodiment is in Bimodal distribution.

Usually, it is described that there are at least two proton acceptor sites relative to 100 parts by weight hydrated alumina wet gels The dosage of compound can be 1-25 parts by weight, be preferably 2-20 parts by weight, more preferably 3-18 parts by weight, more preferably 3.5-17 parts by weight.

In step (1), in a kind of embodiment being more highly preferred to, the change with least two proton acceptor sites Compound contains galactomannans and cellulose ether.The carrier formed by the composition for the embodiment being more highly preferred to according to this has There is the intensity of higher.It is further preferred that the compound with least two proton acceptor sites is preferably galactomannan Glycan and cellulose ether.

The content of phosphorus-containing compound can be according to it is contemplated that introduce in the catalyst finally prepared in the raw mixture The content of phosphorus make choice.Usually, the content of phosphorus-containing compound to urge with what is finally prepared in the raw mixture On the basis of the total amount of agent, with P₂O₅The phosphorus content of meter can be 1-6 weight %, be preferably 1.5-4 weight %.

The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, can use various order by merging will The phosphorus-containing compound, the compound with least two proton acceptor sites and the mixing of hydrated alumina wet gel.

In one embodiment, phosphorus-containing compound can be mixed during hydrated alumina wet gel is prepared, Phosphorus-containing compound can be added in the hydrated alumina wet gel being prepared, can also be to prepare hydrated alumina wet solidifying Mixing portion phosphorus-containing compound during glue, it is wet solidifying that remainder phosphorus-containing compound is added to the hydrated alumina being prepared In glue, mixing the operation of phosphorus-containing compound can carry out in one of above-mentioned addition opportunity, both or three.Preparing , can be in precipitation reaction process, ageing process, separation of solid and liquid when phosphorus-containing compound is mixed during hydrated alumina wet gel One of process and washing process, both, the operation of mixing phosphorus-containing compound is carried out in three or four.Preferably, The operation of mixing phosphorus-containing compound is carried out in separation of solid and liquid process.

In another embodiment, phosphorus-containing compound is mixed after the completion of the preparation of hydrated alumina wet gel.In the reality Apply in mode, first can mix phosphorus-containing compound with hydrated alumina wet gel, then mixing have at least two protons by The compound of position point；First the compound with least two proton acceptor sites can also be mixed with hydrated alumina wet gel Close, then mix phosphorus-containing compound；First part phosphorus-containing compound can also be mixed with hydrated alumina wet gel, then will be surplus Remaining part divides phosphorus-containing compound and the compound with least two proton acceptor sites to mix.

In step (1), the raw mixture can contain peptizing agent, can not also contain peptizing agent.Preferably, relatively In 100 parts by weight hydrated aluminas, the content of the peptizing agent is below 5 parts by weight, is preferably below 3 parts by weight.More preferably Ground, the raw mixture do not contain peptizing agent.That is, in step (1), do not include more preferably adding into the raw mixture Peptizing agent.

In step (1), conventional method can be used by hydrated alumina wet gel and there are at least two proton acceptor positions Compound and the phosphorus-containing compound mixing of point.Can be under shear action by hydrated alumina wet gel and with least two Compound and the phosphorus-containing compound mixing in proton acceptor site.In one embodiment, the mode of the mixing is stirring. Can by hydrated alumina wet gel with least two proton acceptor sites compound and phosphorus-containing compound with In the container of agitating device, three is uniformly mixed by stirring, so as to obtain the hydrated alumina composition.The stirring It can carry out, can also be carried out in beater in the container with agitating device.In another embodiment, it is described mixed The mode of conjunction is kneading.Can be by hydrated alumina wet gel with there is the compound at least two proton acceptor sites and contain Phosphorus compound is mediated in kneader, so as to obtain the hydrated alumina composition.The type of the kneader does not have It is particularly limited to.In step (1), stirring and hybrid combining can be used, by hydrated alumina wet gel with having at least two Compound and the phosphorus-containing compound mixing in a proton acceptor site.At this time, preferably first it is stirred, then is mediated.

In step (1), in mixed process, addition water can be supplemented, addition water can not also be supplemented, as long as can be so that system In standby hydrated alumina compositionValue meets above-mentioned requirements.Usually, go out from the angle for the uniformity for improving mixing Hair, can supplement addition water in mixed process.Usually, the water of addition is supplemented with having at least two proton acceptor sites The weight ratio of compound can be 5-15：1, it is preferably 8-12：1, more preferably 9-10：1.

In step (2), the molding mode is not particularly limited, and can use various shaping sides commonly used in the art Formula, such as：Extrusion, spraying, round as a ball, tabletting or combinations thereof.In a kind of preferred embodiment of the present invention, by squeezing The mode of bar is molded.

In step (2), the temperature that molding is dried can be the conventional selection of this area.Usually, it is described dry Dry temperature can be more than 60 DEG C and be not higher than 350 DEG C, preferably 80-300 DEG C, be more preferably 110-260 DEG C.The drying Time can be made appropriate choice according to dry temperature.Usually, the duration of the drying can be that 1-48 is small When, when being preferably 2-24 small, when more preferably 2-12 is small, when more preferably 2-4 is small.The drying can be in oxygen-containing atmosphere Carry out, can also be carried out in inert atmosphere (atmosphere that such as nitrogen and/or zero group gas are formed) in (such as air atmosphere), it is excellent It is selected in oxygen-containing atmosphere and carries out.

The present invention is not particularly limited for the condition of roasting, can be the conventional selection of this area.Specifically, the roasting The temperature of burning can be 450-1500 DEG C.Furthermore it is also possible to the temperature of roasting is optimized according to the species of hydrated alumina. In one embodiment, the hydrated alumina is boehmite, and the temperature of the roasting is preferably 450-1100 DEG C, more Preferably 460-1000 DEG C, more preferably 500-950 DEG C.In another embodiment, the hydrated alumina is three Diaspore, the temperature of the roasting is preferably 800-1500 DEG C, more preferably 900-1400 DEG C.The duration of the roasting can When thinking that 1-8 is small.The roasting can carry out in oxygen-containing atmosphere (such as air atmosphere), can also be in inert atmosphere (such as nitrogen The atmosphere that gas and/or zero group gas are formed) in carry out, carried out preferably in oxygen-containing atmosphere.

In step (2), described be roasted to can selection operation.Usually, peptizing agent is free of in the hydrated alumina composition When, it can be used through dry molding directly as carrier, but can also be roasted；Combined in the hydrated alumina When thing contains peptizing agent, then roasted through dry molding, so as to obtain carrier.

Preparation in accordance with the present invention, the carrier have higher intensity, meet the use as catalyst carrier It is required that.Usually, the radial direction crushing strength of carrier prepared by step (2) is more than 10N/mm, preferably more than 12N/mm (such as Can be 12-55N/mm), more preferably more than 15N/mm.In an example, the radial direction crushing of carrier prepared by step (2) Intensity is 10-35N/mm (such as 12-35N/mm).In the example that one is more highly preferred to, the radial direction pressure of carrier prepared by step (2) Broken intensity is 15-32N/mm.

Preparation in accordance with the present invention, the carrier are porous material, its aperture is in bimodal distribution.Wherein, most may be used Several apertures are respectively 4-20nm (be preferably 5-15nm) and more than 20nm (such as 20.5-35nm, is preferably 21-30nm).

Preparation in accordance with the present invention, the carrier can have it is variously-shaped, such as：Spherical, piece shape, bar shaped, bee Nest shape or bird-nest-shaped.Described shape and the instantiation of bar shaped can include but is not limited to cloverleaf pattern, butterfly, cylinder and drawing Western ring.

Figure (2) shows a kind of preferred embodiment for preparing the carrier, as shown in Fig. 2, the preferred embodiment bag Include following steps：

(A) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the Monohydrate alumina wet gel；

Optionally (B), is handled the first hydrated alumina wet gel using (B-1) or (B-2),

(B-1) by the first hydrated alumina wet gel and aqueous mixtures, slurries are formed, the slurries are subjected to solid-liquid Separation, obtains the second hydrated alumina wet gel；

(B-2) the first hydrated alumina wet gel is subjected to separation of solid and liquid, obtains the second hydrated alumina wet gel；

(C) by hydrated alumina wet gel and compound and phosphorus-containing compound with least two proton acceptor sites Mixing, obtains hydrated alumina composition, the hydrated alumina wet gel for the first hydrated alumina wet gel or The second hydrated alumina wet gel；

(D) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；

(E) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；

(F) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；

Wherein, mixing is carried out in one of step (A), step (B) and step (C), both or three and contains phosphatization The operation of compound, so that the hydrated alumina composition contains phosphorus.Mix the method and the present invention second of phosphorus-containing compound Method described in a aspect is identical with order, is no longer described in detail herein.

In step (A), the alumina hydrate gel solution refers to alumina hydrate gel synthetic reaction obtains, process Or the solution containing alumina hydrate gel without aging.The alumina hydrate gel solution can be prepared in situ Alumina hydrate gel solution that is obtaining or coming from the transport of other production scenes.Preferably, the aqua oxidation Alumina gel solution is the hydrated alumina wet gel solution being prepared in situ.The synthetic method and condition of alumina hydrate gel Have been carried out being described in detail above, details are not described herein again.

Since the alumina hydrate gel solution that synthetic reaction obtains has an acid-base property, to hydrated alumina in step (A) Wet gel is washed, and to remove acidic materials and alkaline matter therein, avoids the presence pair of acidic materials and alkaline matter The adverse effect that alumina hydrate gel produces, while improve the solid content of alumina hydrate gel solution.Described in step (A) Washing can carry out under normal conditions, as long as can be by the acidic materials and the amount of alkaline matter in alumina hydrate gel solution Satisfaction is reduced to usually require that.

In step (A), separation of solid and liquid is directed in washing process, washings are extruded, obtain the first aqua oxidation Aluminium wet gel.The i values of the first hydrated alumina wet gel can be to meet previously described and have at least two protons The i values of the hydrated alumina wet gel of compound and the phosphorus-containing compound mixing of acceptor site, or higher than institute above The i values for the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites stated.

In one embodiment, the i value contents of the first hydrated alumina wet gel meet previously described with having There are the compound at least two proton acceptor sites and the i values of the hydrated alumina wet gel of phosphorus-containing compound mixing, i.e. institute The i values for stating the first hydrated alumina wet gel are not less than 60%, are preferably not lower than 62%.In this embodiment, it is described The i values of first hydrated alumina wet gel are preferably not higher than 82%, more preferably not above 80%, more preferably not high In 78.5%.

According to the embodiment, the first hydrated alumina wet gel can be sent directly into step (C), and with extremely The compound in few two proton acceptor sites and phosphorus-containing compound mixing.This is especially suitable for meeting occasion claimed below： (I) solid-liquid separating equipment in wash mill has preferable separating capacity, it is sufficient to by the i values of the first hydrated alumina wet gel Control to meet above range；(II) wash mill compact can be set with mixing arrangement so that the discharging of wash mill can be with It is directly entered mixing arrangement.

According to the embodiment, the first hydrated alumina wet gel can also be sent into step (B), using (B-1) Handled.This is especially suitable for meeting occasion claimed below：(I) solid-liquid separating equipment in wash mill has preferable Separating capacity, it is sufficient to control the i values of the first hydrated alumina wet gel to meet above range；(II) wash mill is with mixing Device compact can not be set, so that the discharging of wash mill can not be directly entered mixing arrangement.

In another embodiment, the i values of the first hydrated alumina wet gel are higher than 82%, can not meet the present invention The requirement mixed with the compound with least two proton acceptor sites and phosphorus-containing compound described in second aspect.Root According to the embodiment, the first hydrated alumina wet gel is sent into step (B), is located using (B-1) or (B-2) Reason.

The embodiment especially suitable for the solid-liquid separating equipment in wash mill separating capacity or operating condition not Be enough by the control of the i values of the first hydrated alumina wet gel be meet previously described requirement occasion and wash mill with Mixing arrangement can not compact setting occasion.

In step (B), the first hydrated alumina wet gel is handled using (B-1) or (B-2), obtains second Hydrated alumina wet gel.

In (B-1), the first hydrated alumina wet gel is mixed with water, slurries is formed, can so improve aqua oxidation Aluminium wet gel transports performance.(B-1) in, the additive amount of water, which is subject to the slurries to be formed, can meet to transport requirement, can basis Specific conveying equipment makes choice.

The i values for the second hydrated alumina wet gel that step (B) obtains meet previously described with having at least two The i values of the hydrated alumina wet gel of the compound mixing in a proton acceptor site, i.e., the i values of described hydrated alumina wet gel Not less than 60%, to be preferably not lower than 62%.The i values of the second hydrated alumina wet gel are preferably not higher than 82%, More preferably not above 80%, more preferably not higher than 78.5%.

The second water that i values meet above-mentioned requirements can be obtained by the condition of separation of solid and liquid described in rate-determining steps (B) Close aluminium oxide wet gel.The method of the i values of hydrated alumina wet gel is adjusted by selecting solid-liquid separating method and its condition Have been carried out being described in detail above, be no longer described in detail herein.

In step (C), by the first hydrated alumina wet gel or the second hydrated alumina wet gel with having at least two Compound and the phosphorus-containing compound mixing in a proton acceptor site, so as to obtain hydrated alumina composition.It is sent into step (C) The first hydrated alumina wet gel and the second hydrated alumina wet gel i values meet it is previously described with least two The i values of the hydrated alumina wet gel of compound and the phosphorus-containing compound mixing in proton acceptor site.

In step (D), the hydrated alumina composition that step (C) obtains is molded, obtains hydrated alumina shaping Thing.

In step (E), the hydrated alumina forming matter that step (C) obtains is dried, in the hydrated alumina group When compound is free of peptizing agent, obtained hydrated alumina formed body can be used as carrier.

According to the type of expected formed body, step (F) can be carried out, step (F) can not also be carried out.Carrying out step (F) when, the whole hydrated alumina formed bodys that can obtain step (E) are sent into step (F), are roasted；It can also incite somebody to action The partially hydrated aluminium oxide formed body that step (E) obtains is sent into step (F), can so prepare hydrated alumina shaping at the same time Body and aluminium oxide formed body.When the hydrated alumina composition contains peptizing agent, the whole that step (E) is obtained is hydrated oxygen Change aluminium formed body to be sent into step (F).When the hydrated alumina composition does not contain peptizing agent, step (F) can be carried out, It can not also carry out step (F).

Preferred embodiment shown in Fig. 2 can be implemented in a kind of hydrated alumina produces formation system, this is produced into Type system includes alumina hydrate gel production unit, separation of solid and liquid and washing unit, mixed cell, forming unit, dry list First and optional roasting unit,

The alumina hydrate gel solution output port of the alumina hydrate gel production unit and the separation of solid and liquid And the washing material input port to be separated of washing unit is connected, the solid-phase material output of the separation of solid and liquid and washing unit Port is connected with the solid-phase material input port of the mixed cell, the mixed material output port of mixed cell with it is described into The raw material input port of type unit is connected, the material to be dried input port of the drying unit and the forming unit into Type thing output port is connected, and the dried material of the material input port to be roasted and the drying unit of the roasting unit is defeated Exit port is connected.

The alumina hydrate gel production unit is used to generate alumina hydrate gel solution by synthetic reaction.Synthesis The method of alumina hydrate gel can be conventional method, the precipitation method as previously described, Hydrolyze method, kind point-score and quick de- Water law, is not described in detail herein.

The alumina hydrate gel production unit can use conventional reactor to carry out synthetic reaction, so as to obtain water Alumina gel solution is closed, this is not particularly limited in the present invention.

The separation of solid and liquid and washing unit are used for the aqua oxidation for exporting the alumina hydrate gel production unit Alumina gel aqueous solution carries out separation of solid and liquid and washing, obtainsValue meets the hydrated alumina wet gel of requirement described previously.

The separation of solid and liquid and washing unit can carry out separation of solid and liquid and washing in common various methods, so as to obtain Value meets to mix desired alumina hydrate gel with the compound with least two proton acceptor sites.The separation of solid and liquid And washing unit can use conventional equipment for separating liquid from solid, such as：The combination of filtration apparatus, centrifugal device or both. When solid-liquid separation unit includes filtration apparatus, the filtration apparatus can be gravity filter device, pressure filter and true One or more kinds of combinations in empty filtration apparatus.Preferably, the filtration apparatus includes at least pressure filter. The instantiation of the pressure filter can include but be not limited to plate and frame type filter-press, band filter or both Combination.In order to control the hydrated alumina wet gel of acquisitionValue, the separation of solid and liquid and washing unit can also include blowing Sweeping device, purges isolated solid phase using natural wind or wind with pressure, so as to improve the efficiency of moisture abjection.Institute The pressure for stating wind with pressure can be conventional selection, generally can be 0.1-12MPa, be preferably 0.5-10MPa.

The separation of solid and liquid and washing unit can include one or more separation of solid and liquid subelement, preferably at least one A separation of solid and liquid subelement and last separation of solid and liquid subelement are pressure filter and/or vacuum apparatus, so that Obtain the solid-phase material (that is, hydrated alumina wet gel) that solid-liquid separation unit obtainsValue can meet second aspect of the present invention The requirement mixed with the compound with least two proton acceptor sites and phosphorus-containing compound.By adjusting application Pressure or vacuum size, can be to the hydrated alumina wet gel finally obtainedValue is adjusted.The solid-liquid When separative element includes two or more separation of solid and liquid subelement, made except last separation of solid and liquid subelement is preferably used with pressure Outside the solid-liquid separation method of motive force, remaining separation of solid and liquid separation subelement can use pressure filter and/or true Empty filtration apparatus, can not also use pressure filter and vacuum apparatus, it is preferred to use pressure filter and/or true Empty filtration apparatus.

The separation of solid and liquid and washing unit can use conventional wash mill to wash the solid phase isolated. It is for instance possible to use washings are sprayed to the solid phase surface isolated by spray equipment.In order to improve washing effect and washing Efficiency, shearing and/or vibration can be applied to solid phase during the spray or after the completion of spray, by shower water with it is solid Mix uniformly, the shearing is for example stirred.

On the basis of the trend of alumina hydrate gel material flow, solid-liquid separation unit is arranged on alumina hydrate gel life Produce between unit and mixed cell, the gel solution for alumina hydrate gel production unit to be exported is separated, and is obtained Value meets the hydrated alumina wet gel that mixing requires, and raw material is provided for mixed cell.

On the premise of the alumina hydrate gel met the requirements being provided for mixed cell, from the conveying easy to material Angle is set out, and in a preferred embodiment, it is single that the solid-liquid separation unit can include washing subelement, dilution Member, conveying subelement and the second separation of solid and liquid subelement,

The washing subelement is used for the alumina hydrate gel for collecting the alumina hydrate gel production unit output Solid phase in solution is simultaneously washed；

The dilution subelement is used to the solid phase of the washing subelement output being diluted with water, obtains slurries；

The conveying subelement is used to the slurries of the dilution subelement output being sent into the second separation of solid and liquid subelement；

The second separation of solid and liquid subelement is used to the slurries carrying out separation of solid and liquid, and it is wet solidifying to obtain hydrated alumina Glue.

The conveying subelement can use conventional various conveying devices, such as conveyer belt.The conveying subelement and institute Stating washing subelement can integrate, such as integrate in one apparatus, so as to be washed during conveying, carry High efficiency.Such as：Using the conveyer belt with solid-liquid separation function, while spray is set above the solid-phase material of conveyer belt Shower device, so as to be washed during transporting and separation of solid and liquid.

The mixed cell includes the assistant feeding device that auxiliary agent is added into hydrated alumina wet gel, in the production system During system operation, the assistant feeding device adds at least into hydrated alumina wet gel has at least two proton acceptor sites Compound.

The mixed cell can use conventional mixing arrangement, such as common various mixers, kneader or two The combination of person.The forming unit can use conventional molding machine, such as：Extrusion device, spraying device, circle rolling device, Preforming device or two or more combinations.The drying unit can use conventional drying device, and the present invention does not have this It is particularly limited to.This is also not particularly limited in the conventional calciner that the roasting unit can use, the present invention.

On the basis of the flow direction of alumina hydrate gel, the production formation system is in separation of solid and liquid and the solid phase of washing unit Material discharging port is wet by hydrated alumina to being not provided with being enough between the hydrated alumina wet gel input port of mixed cell The i values of gel are reduced to the dewatering unit of less than 60% (preferably less than 62%).

In the actual production process, mixing can be added on the basis of existing alumina hydrate gel process units Unit, forming unit, drying unit and roasting unit, production and molding one so as to fulfill alumina hydrate gel Change.

Preparation in accordance with the present invention, the hydrogenation activity component can have catalytic action to be common to hydrocarbon oil hydrogenation Component.Preferably, the hydrogenation activity component is at least one vib metals element and at least one group VIII metal Element.The vib metals element is preferably molybdenum and/or tungsten.The group VIII metallic element is preferably cobalt and/or nickel.

Depending on the load capacity of the hydrogenation activity component on the carrier is with the specific species of hydrogenation activity component.As One example, when the hydrogenation activity component is vib metals element and group VIII metallic element, the hydrogenation activity The load capacity of component on the carrier causes on the basis of the total amount of the catalyst finally prepared, the Section VIII in terms of oxide The content of race's metallic element is 0.8-3 weight %, is preferably 1-2 weight %, and the vib metals element in terms of oxide contains Measure as 3-10 weight %, preferably 4-8 weight %.

Preparation in accordance with the present invention, when hydrogenation activity component is supported on carrier in the form of its non-activated state, Before use, can use this area conventional method be activated, by the hydrogenation activity conversion of its non-activated state into For the state of activation.Conventional method can be used to load the hydrogenation activity component on the carrier.It is preferable as one Example, is loaded the hydrogenation activity component on the carrier by the method for dipping.Specifically, it can use and add containing described The maceration extract of hydrogen activity component impregnates the carrier, and the carrier through dipping is dried, is alternatively carried out through dry carrier Roasting, so as to obtain catalyst according to the invention.

Conventional method can be used to prepare the maceration extract, such as：Can be by the compound containing hydrogenation activity component point Dissipate in a solvent, so as to form maceration extract.It is vib metals element and group VIII metal member in the hydrogenation activity component When plain, the instantiation of the compound containing vib metals element can include but is not limited to ammonium molybdate, ammonium paramolybdate, partially Ammonium tungstate, molybdenum oxide and tungsten oxide.The compound of the metallic element containing group VIII can be selected from the nitre of group VIII metallic element Hydrochlorate, the chloride of group VIII metallic element, the sulfate of group VIII metallic element, the formic acid of group VIII metallic element Salt, the acetate of group VIII metallic element, the phosphate of group VIII metallic element, the citric acid of group VIII metallic element Salt, the oxalates of group VIII metallic element, the carbonate of group VIII metallic element, the alkali formula carbon of group VIII metallic element Hydrochlorate, the hydroxide of group VIII metallic element, the phosphate of group VIII metallic element, the phosphorus of group VIII metallic element Compound, the sulfide of group VIII metallic element, the aluminate of group VIII metallic element, the molybdic acid of group VIII metallic element The water-soluble oxide of salt, the tungstates of group VIII metallic element and group VIII metallic element.Specifically, it is described to contain The instantiation of the compound of group VIII metal element can include but is not limited to nickel nitrate, nickel sulfate, nickel acetate, basic carbonate Nickel, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chloride.

The solvent of the maceration extract can be water and/or alcohol.Preferably, the solvent of the maceration extract is water.

The dipping can be that saturation impregnates, or excessive dipping.

When the hydrogenation activity component is two or more, the hydrogenation activity component can be supported at the same time On carrier, the hydrogenation activity component can also be supported on carrier by several times.

Carrier through dipping can be dried under normal conditions, to remove volatile matter therein.Usually, it is described dry It is dry to be carried out at a temperature of 80-250 DEG C, preferably 100-140 DEG C.The drying can be at normal pressure (that is, 1 standard atmospheric pressure) Lower progress, can also carry out at reduced pressure.The duration of the drying can be according to dry temperature and progress Dry pressure makes choice.Usually, when the duration of the drying can be 1-10 small, when being preferably 1-6 small.

The carrier being dried can be used directly as catalyst.After can also further being roasted, as catalysis Agent uses.The present invention is not particularly limited for the condition of roasting, can carry out under normal conditions.Usually, the roasting It can carry out at a temperature of 360-500 DEG C, be carried out preferably at a temperature of 360-450 DEG C.The duration of the roasting can Made choice with the temperature according to roasting.Usually, it is preferably 2-6 small when the duration of the roasting can be 1-10 small When.

According to the fourth aspect of the present invention, the present invention provides described in the first aspect of the present invention and the 3rd aspect Application in hydrocarbon oil hydrogenation processing with hydrogenation catalyst effect.

The catalyst with hydrogenation catalyst effect of the present invention can be used as the catalyst of various hydrocarbon oils hydrotreating, The hydrocarbon ils can be various heavy mineral oil or heavy mineral oil, such as in heavy deasphalted oil, reduced crude and decompression residuum One or more.The heavy oil that the catalyst that there is hydrogenation catalyst to act on of the present invention is particularly suitable as asphaltenes adds The catalyst of hydrogen depitching matter, the asphalt content that can be effectively reduced in heavy oil.

The heavy oil can be the common various heavy oil containing asphalitine, can be various heavy mineral oils, such as：It is described Hydrocarbon ils can be the one or more in reduced crude, decompression residuum, decompressed wax oil and wax tailings.

The condition of the hydrotreating can include：Temperature is 330-410 DEG C；In terms of gauge pressure, pressure 10-18MPa；Weight Volume space velocity is 0.2-1h during the liquid of oil^-1；Hydrogen to oil volume ratio is 400-1000.

The present invention will be described in detail with reference to embodiments, but the scope being not intended to limit the present invention.

In following embodiments and comparative example, the radial direction of the molding prepared using method measure specified in RIPP 25-90 Crushing strength.

In following embodiments and comparative example, measured using following methodsValue：By composition described in 10g at 120 DEG C in air It is 240 minutes dry in atmosphere, the quality through dry composition is denoted as w₁, calculated using Formulas IValue,

In following embodiments and comparative example, i values are measured using following methods：By 10g hydrated aluminas wet gel at 120 DEG C It is 240 minutes dry in air atmosphere, the quality through dry sample is denoted as w₂, i values are calculated using Formula II,

In following embodiments and comparative example, the water absorption rate of the formed body prepared using following methods measure：By shaping to be measured Then body is sieved with 40 the polished standard screens when 120 DEG C of dryings 4 are small, weighs 20g oversizes and (be denoted as sample to be tested w₃), sample to be tested 50g deionized waters are soaked 30 minutes, after filtering, solid phase are drained 5 minutes, what then weighing drained consolidates The weight of phase (is denoted as w₄), calculate water absorption rate with the following formula：

In following embodiments and comparative example, the pore-size distribution of the formed body prepared using mercury injection method measure.

In following embodiments and comparative example, contents on dry basis measures sample to be tested when 600 DEG C of roastings 4 are small.

In following embodiments and comparative example, the method with reference to specified in Petrochemical Engineering Analysis method RIPP133-90, in day The composition of catalyst is measured on 3271 type Xray fluorescence spectrometer of this Liue electrical machinery Industrial Co., Ltd.

Prepare embodiment 1-10 and be used to prepare carrier.

Prepare embodiment 1

The hydrated alumina wet gel used in this preparation embodiment is by acid system (sodium metaaluminate-aluminum sulfate method, in being derived from State's petrochemical industry Chang Ling branch company) the alumina hydrate gel solution for preparing adds phosphoric acid in ageing process, and is washed and mistake Obtained phosphorous boehmite wet cake (being SLB-1 by wet cake numbering) is filtered, after measured, the i values of the wet cake are 77.7%.

(1) wet cake that 200g numberings are SLB-1 is placed in beaker, then adds 5g methylcellulose and (be purchased from Zhejiang Hai Shen Chemical Co., Ltd.s, similarly hereinafter) and 3g sesbania powders (content of galactomannans is 80 weight %, is tried purchased from Beijing chemistry Agent company, similarly hereinafter), using mechanical agitator stirring after ten minutes, obtained mixture is phosphorous hydrated alumina of the invention Composition, its nature parameters are listed in table 1.

(2) (south China science and engineering is big in F-26 types double screw extruder for the phosphorous hydrated alumina composition for preparing step (1) On subject skill industry head factory system, similarly hereinafter) extrusion is carried out using the dish-shaped orifice plate of Ф 1.5mm.Wherein, extrusion process is smooth, extrusion Thing surface Glabrous thorn.

(3) extrudate is cut into the wet bar that length is about 6cm, when by wet bar, drying 4 is small in 120 DEG C, air atmosphere, The dry bar HT-1 of hydrated alumina is obtained, its nature parameters is listed in table 1.

(4) by step (3) prepare the dry bar of hydrated alumina roasted in 900 DEG C, air atmosphere 4 it is small when, aoxidized The dry bar OT-1 of aluminium, its nature parameters are listed in tables 1 and 2.

Prepare embodiment 2

Carrier is prepared using the method identical with preparing embodiment 1, unlike, in step (4), prepared through step (3) The dry bar of hydrated alumina roasted in 980 DEG C, air atmosphere 3 it is small when, obtain alumina dry bar OT-2, its nature parameters is in table Listed in 1.

Prepare embodiment 3

Carrier is prepared using the method identical with preparing embodiment 1, unlike, without using sesbania powder, first in step (2) The dosage of base cellulose is 7.4g, the dry bar HT-3 of phosphorous hydrated alumina composition, hydrated alumina and aluminium oxide of preparation The property of dry bar OT-3 is listed in table 1.

Prepare embodiment 4

Carrier is prepared using the method identical with preparing embodiment 1, unlike, without using Methyl cellulose in step (2) Element, the dosage of sesbania powder is 9.3g, the dry bar HT-4 of phosphorous hydrated alumina composition, hydrated alumina and aluminium oxide of preparation The property of dry bar OT-4 is listed in table 1.

Prepare embodiment 5

Carrier is prepared using method same as Example 1, unlike, in step (2), addition methylcellulose and During sesbania powder, 3g nitric acid (HNO is also added₃Content be 65 weight %), the phosphorous hydrated alumina composition of preparation, hydration oxygen The property for changing the dry bar HT-5 and alumina dry bar OT-5 of aluminium is listed in table 1.

Prepare comparative example 1

(1) by 500g numberings be SLB-1 wet cake in 90 DEG C, air atmosphere it is dry 4 it is small when, obtain boehmite Powder, the i values of the boehmite powder are 38%.The boehmite powder (is placed in environment temperature (25-30 DEG C) and sealing condition In sealed plastic bag) under place 72 it is small when, do not detected after placement and form gibbsite.

(2) the boehmite powder for preparing step (1) utilizes the dish of Ф 1.5mm on F-26 type double screw extruders Orifice plate carries out extrusion.Wherein, extruder caloric value is larger during extrusion (it is hot to show as banded extruder fuselage, has a large amount of hot gas to emit Go out), and extrusion process extruder Frequent trip, extrudate surface are jagged.

(3) extrudate is cut into the wet bar that length is about 6cm, when by wet bar, drying 4 is small in 120 DEG C, air atmosphere, The dry bar DHT-1 of hydrated alumina is obtained, its nature parameters is listed in table 1.

(4) by step (3) prepare the dry bar of hydrated alumina roasted in 900 DEG C, air atmosphere 4 it is small when, aoxidized The dry bar DOT-1 of aluminium, its nature parameters are listed in table 1.

Prepare comparative example 2

Carrier is prepared using the method identical with preparing embodiment 1, unlike, without using wet cake in step (1) SLB-1, but the boehmite powder for the preparation comparative example 1 of weight (in terms of butt) such as using to prepare, wherein, extrusion squeezes Go out machine Frequent trip, extrudate surface is jagged.Alumina dry bar DHT-2 and alumina dry bar DOT-2 is prepared respectively, Its nature parameters is listed in table 1.

Prepare comparative example 3

Carrier is prepared using the method identical with preparing embodiment 1, unlike, without using wet cake in step (1) SLB-1, but by wet cake SLB-1 in 100 DEG C, air atmosphere it is dry 3 it is small when, obtain boehmite powder, the thin water of the plan The i values of aluminium mountain flour are 30%, which (is placed in sealed plastic bag in environment temperature (25-30 DEG C) and sealing condition In) under place 72 it is small when, do not detected after placement and form gibbsite.Wherein, extrusion process extruder Frequent trip, Extrudate surface is smooth.Alumina dry bar DHT-3 and alumina dry bar DOT-3 is prepared respectively, its nature parameters is in table 1 In list.

Prepare comparative example 4

Carrier is prepared using the method identical with preparing embodiment 1, unlike, without using wet cake in step (1) SLB-1, but the boehmite dry glue powder of weight (in terms of butt) such as use (to be purchased from Sinopec Chang Ling branch company, i values are 30%, which places under environment temperature (25-30 DEG C) and sealing condition (being placed in sealed plastic bag) 72 it is small when, do not detected after placement and form gibbsite), wherein, extrusion process extruder Frequent trip, extrudate table Face is smooth.The dry bar DHT-4 of hydrated alumina is prepared respectively and alumina dry bar DOT-4, its nature parameters arrange in table 1 Go out.

Prepare comparative example 5

Carrier is prepared using the method identical with preparing comparative example 4, unlike, in step (1), when being mixed, Also add 6g nitric acid (HNO₃Concentration be 65 weight %), wherein, extrusion process is smooth, and extrudate surface is smooth.Prepare respectively Obtain the dry bar DHT-5 of hydrated alumina and alumina dry bar DOT-5, its nature parameters are listed in table 1.

Prepare comparative example 6

Carrier is prepared using the method identical with preparing embodiment 1, unlike, without using methylcellulose and sesbania Powder, but with 6.0g paraffin.As a result the phosphorous hydrated alumina composition preparedIt is worth for 0.62, the phosphorous hydrated alumina Composition can not carry out extrusion molding.

Prepare comparative example 7

Prepare carrier using with preparing the identical method of embodiment 1, unlike, without using hydroxyethylmethylcellulose and Sesbania powder, but with 6.0g wood powders.As a result the phosphorous hydrated alumina composition preparedIt is worth for 0.50, the phosphorous hydration oxygen Extrusion molding can not be carried out by changing aluminium composition.

Prepare comparative example 8

Will number be SLB-1 wet cake be sent directly into F-26 type double screw extruders utilize Ф 2.0mm round hole Plate carries out extrusion, as a result can not carry out extrusion molding.

Prepare embodiment 6

(1) by the wet cake that 5kg numberings are SLB-1 and 500g deionized waters, 33g methylcellulose and 20g sesbania powders (half The content of newborn mannosan is 80 weight %) it is mixed with beating 1 minute, then obtained slurries are sent into plate and frame type filter-press, The pressure of sheet frame is adjusted to 0.7MPa and is kept for 15 minutes, the wet cake that sheet frame pressure release obtains is phosphorous hydration oxygen of the invention Change aluminium composition, its nature parameters is listed in table 1.

(2) phosphorous hydrated alumina composition prepared by step (1) is utilized into Ф on F-26 type double screw extruders The dish-shaped orifice plate of 1.5mm carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.

(3) extrudate is cut into the wet bar that length is about 6cm, when by wet bar, drying 4 is small in 120 DEG C, air atmosphere, The dry bar HT-6 of hydrated alumina is obtained, its nature parameters is listed in table 1.

(4) by step (3) prepare the dry bar of hydrated alumina roasted in 900 DEG C, air atmosphere 3 it is small when, aoxidized The dry bar OT-6 of aluminium, its nature parameters are listed in table 1.

Prepare embodiment 7

(1) the hydrated alumina wet gel used in this preparation embodiment is that (sodium metaaluminate-aluminum sulfate method, takes by acid system From Sinopec Chang Ling branch company) the alumina hydrate gel solution for preparing adds phosphoric acid in ageing process, and washed With the boehmite wet cake (being SLB-1 by wet cake numbering) being obtained by filtration, after measured, the i values of the wet cake are 77.5%.

The wet cake that 5kg numberings are SLB-1 is mixed with beating 1 minute with 700g deionized waters, the slurries that then will be obtained It is sent into plate and frame type filter-press, the pressure of sheet frame is adjusted to 0.5MPa and is kept for 3 minutes, then with the wind with pressure of 0.5MPa The filter cake in sheet frame is swept after 3 minutes, sheet frame pressure release obtains wet cake (numbering LB-1).After measured, numbering is LB-1's The i values of wet cake are 75 weight %.

(2) wet cake that 1000g numberings are LB-1 is placed in beaker, adds 16g hydroxypropyl methyl celluloses and 20g fields Cyanines powder (content of galactomannans is 85 weight %), using mechanical agitator stirring after ten minutes, obtains containing for the present invention Phosphorus hydrated alumina composition, its nature parameters are listed in table 1.

(3) phosphorous hydrated alumina composition prepared by step (2) is utilized into Ф on F-26 type double screw extruders The circular orifice of 1.5mm carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.

(4) extrudate is cut into the wet bar that length is about 6cm, when by wet bar, drying 4 is small in 120 DEG C, air atmosphere, The dry bar HT-7 of hydrated alumina is obtained, its nature parameters is listed in table 1.

(5) by step (4) prepare the dry bar of hydrated alumina roasted in 900 DEG C, air atmosphere 4 it is small when, aoxidized The dry bar OT-7 of aluminium, its nature parameters are listed in tables 1 and 2.

Prepare embodiment 8

Carrier is prepared using the method identical with preparing embodiment 7, unlike, in step (2), without using hydroxypropyl first Base cellulose, but use 39g sesbania powders.Hydrated alumina dry bar HT-8 and alumina dry bar OT-8, its property are prepared respectively Parameter is listed in table 1.

Prepare embodiment 9

Carrier is prepared using with preparing the identical method of embodiment 7, unlike, in step (2), without using sesbania powder, But use 33g hydroxypropyl methyl celluloses.Hydrated alumina dry bar HT-9 and alumina dry bar OT-9, its property are prepared respectively Parameter is listed in table 1.

Prepare embodiment 10

The hydrated alumina wet gel used in this preparation embodiment is by CO₂Method (sodium aluminate-CO₂Method, is derived from Shanxi Province The emerging great catalyst new material Co., Ltd in Shan County) the alumina hydrate gel solution plan being washed and be obtained by filtration for preparing is thin Diaspore wet cake (being SLB-2 by wet cake numbering), after measured, the i values of the wet cake are 65.3%.

(1) wet cake that 1000g numberings are SLB-2 is placed in beaker, then adds 15g methylcellulose and (be purchased from Zhejiang Jiang Haishen Chemical Co., Ltd.s), (content of galactomannans is 80 weight % to 20g sesbania powders, public purchased from Beijing chemical reagent Department) and 23.61g sodium phosphates, using mechanical agitator stirring after ten minutes, obtained mixture is phosphorous hydration oxygen of the invention Change aluminium composition, its nature parameters is listed in table 1.

(2) phosphorous hydrated alumina composition prepared by step (1) is utilized into Ф on F-26 type double screw extruders The dish-shaped orifice plate of 2.4mm carries out extrusion, and extrusion process is smooth, extrudate surface Glabrous thorn.

(3) extrudate is cut into the wet bar that length is about 5cm, when by wet bar, drying 3 is small in 140 DEG C, air atmosphere, The dry bar HT-10 of hydrated alumina containing halogen is obtained, its nature parameters is listed in table 1.

(4) by step (3) prepare the dry bar of hydrated alumina containing halogen roasted in 560 DEG C, air atmosphere 4 it is small when, obtain To the bar OT-10 of alumina dry containing halogen, its nature parameters is listed in table 1.

Prepare comparative example 9

Dry glue powder P1 (the pore volume 0.9mL/g, specific surface area 280m that 500g sinopecs Chang Ling branch company is produced²/ g, Most probable pore size is 8.5nm) and 500g Sinopecs Chang Ling branch company production dry glue powder P2 (pore volume 1.2mL/g, compares surface Product is 280m²/ g, most probable pore size 15.8nm) after mixing, adding 1300mL nitric acid containing 10mL, (concentration is 65 weights Amount %) and the aqueous solution of 25,44g sodium phosphate be uniformly mixed, then by mixture use and preparation 1 step of embodiment (2) to (4) Identical method is molded, and the hydrated alumina formed body being prepared is denoted as DHT-6, the aluminium oxide formed body being prepared DOT-6 is denoted as, its nature parameters is listed in table 2.

Prepare comparative example 10

(pore volume 0.9mL/g, specific surface area are the dry glue powder P2 that 400g Qimao Catalysts Co., Ltd. is produced 290m²/ g, most probable pore size 8.3nm) and the dry glue powder P2 of 600g Yantai Heng Hui Chemical Co., Ltd.s production (pore volume is 1.1mL/g, specific surface area 260m²/ g, most probable pore size 12nm) after mixing, it is (dense to add 1300mL nitric acid containing 10mL Spend for 65 weight %) and the aqueous solution of 67.85g sodium phosphates be uniformly mixed, then by mixture use and prepare 1 step of embodiment (2) it is molded to (4) identical method, the hydrated alumina formed body being prepared is denoted as DHT-7, the oxidation being prepared Aluminium formed body is denoted as DOT-7, its nature parameters is listed in table 2.

Table 1

¹：When placement 72 is small under environment temperature (25-30 DEG C) and sealing condition (being placed in sealed plastic bag), after placement The content of gibbsite in composition is compared with the increase rate before placement.

Prepare embodiment 1-10's as a result, it was confirmed that the present invention by hydrated alumina wet gel without being dried to dry glue powder or half Dry rubber powder, but directly mixed with the compound with least two proton acceptor sites, obtained mixture can be straight Connect for being molded, and obtained formed body has the intensity of higher, so as to avoid existing with dry glue powder or semiarid glue Existing operating environment is severe when preparing formed body as starting material for powder, the high energy consumption and formed body intensity for preparing is not high asks Topic.

Table 2

Embodiment 1-10 is used to illustrate catalyst according to the present invention with hydrogenation catalyst effect and preparation method thereof.

Embodiment 1

(1) molybdenum oxide and basic cobaltous carbonate are dispersed in water, form maceration extract, wherein, MoO₃Concentration be 75.0g/ L, the concentration of basic cobaltous carbonate is counted as 12.5g/L using CoO.With the maceration extract, under environment temperature (for 25 DEG C) prepared by saturation dipping When the dry bar HT-1 1 of hydrated alumina prepared by embodiment 1 is small.The dry bar of hydrated alumina through dipping under 120 DEG C, normal pressure in After when drying 2 is small in air atmosphere, when then roasting 3 is small in air atmosphere under 420 DEG C, normal pressure, so as to obtain according to this The catalyst CH-1 with hydrogenation catalyst effect of invention, it is formed shown in table 3.

(2) catalyst is prepared using the method identical with (1), unlike, carrier is to prepare oxidation prepared by embodiment 1 The dry bar OT-1 of aluminium, obtains the catalyst CO-1 of the present invention, it is formed shown in table 3.

Embodiment 2

Catalyst is prepared using the method identical with (1) in embodiment 1, unlike, carrier is made to prepare embodiment 2 Standby alumina dry bar OT-2, also, the carrier through dipping after drying without roasting so that obtain the present invention catalysis Agent CO-2, its composition are listed in table 3.

Embodiment 3

(1) catalyst is prepared using the method identical with (1) in embodiment 1, unlike, carrier is preparation embodiment The 3 dry bar HT-3 of hydrated alumina prepared, obtain catalyst CH-3, its composition is listed in table 3.

(2) catalyst is prepared using the method identical with (2) in embodiment 1, unlike, carrier is preparation embodiment The 3 alumina dry bar OT-3 prepared, obtain catalyst CO-3, its composition is listed in table 3.

Embodiment 4

(1) catalyst is prepared using the method identical with (1) in embodiment 1, unlike, carrier is preparation embodiment The 4 dry bar HT-4 of hydrated alumina prepared, obtain catalyst CH-4, its composition is listed in table 3.

(2) catalyst is prepared using the method identical with (2) in embodiment 1, unlike, carrier is preparation embodiment The 4 alumina dry bar OT-4 prepared, obtain catalyst CO-4, its composition is listed in table 3.

Embodiment 5

(1) catalyst is prepared using the method identical with (1) in embodiment 1, unlike, carrier is preparation embodiment 5 prepare the dry bar HT-5 of hydrated alumina, as a result the dry bar of hydrated alumina dusting occurs in dipping process, shaping can not be prepared Catalyst.

(2) catalyst is prepared using the method identical with (2) in embodiment 1, unlike, carrier is preparation embodiment The 5 alumina dry bar OT-5 prepared, obtain catalyst CO-5, its composition is listed in table 3.

Comparative example 1

(1) catalyst is prepared using the method identical with (1) in embodiment 1, unlike, carrier is preparation comparative example The 3 dry bar DHT-3 of hydrated alumina prepared, obtain catalyst DCH-1, its composition is listed in table 3.

(2) catalyst is prepared using the method identical with (2) in embodiment 1, unlike, carrier is preparation comparative example The 3 alumina dry bar DOT-3 prepared, obtain catalyst DCO-1, its composition is listed in table 3.

Comparative example 2

(1) catalyst is prepared using the method identical with (1) in embodiment 1, unlike, carrier is preparation comparative example The 4 dry bar DHT-4 of hydrated alumina prepared, obtain catalyst DCH-2, its composition is listed in table 3.

(2) catalyst is prepared using the method identical with (2) in embodiment 1, unlike, carrier is preparation comparative example The 4 alumina dry bar DOT-4 prepared, obtain catalyst DCO-2, its composition is listed in table 3.

Comparative example 3

(1) catalyst is prepared using the method identical with (1) in embodiment 1, unlike, carrier is preparation comparative example 5 prepare the dry bar DHT-5 of hydrated alumina, as a result the dry bar of hydrated alumina dusting occurs in dipping process, can not be prepared into Type catalyst.

(2) catalyst is prepared using the method identical with (2) in embodiment 1, unlike, carrier is preparation comparative example The 5 alumina dry bar DOT-5 prepared, obtain catalyst DCO-3, its composition is listed in table 3.

Comparative example 4

(1) catalyst is prepared using the method identical with (1) in embodiment 1, unlike, carrier is preparation comparative example 9 prepare the dry bar DHT-6 of hydrated alumina, as a result the dry bar of hydrated alumina dusting occurs in dipping process, can not be prepared into Type catalyst.

(2) catalyst is prepared using the method identical with (2) in embodiment 1, unlike, carrier is preparation comparative example The 9 alumina dry bar DOT-6 prepared, obtain catalyst DCO-4, its composition is listed in table 3.

Embodiment 6

(1) molybdenum oxide and basic nickel carbonate are dispersed in water, form maceration extract, wherein, MoO₃Concentration be 57.1g/ L, using the concentration of the NiO basic nickel carbonates counted as 11.4g/L.With the maceration extract, saturation dipping is made under environment temperature (for 35 DEG C) When the dry bar HT-6 1 of hydrated alumina prepared by standby embodiment 6 is small.The dry bar of hydrated alumina through dipping is under 150 DEG C, normal pressure After when drying 1 is small in air atmosphere, when then roasting 2 is small in air atmosphere under 450 DEG C, normal pressure, so as to obtain basis The catalyst CH-6 with hydrogenation catalyst effect of the present invention, it is formed shown in table 3.

(2) catalyst is prepared using the method identical with (1), unlike, carrier is to prepare oxidation prepared by embodiment 6 The dry bar OT-6 of aluminium, obtains the catalyst CO-6 of the present invention, it is formed shown in table 3.

Embodiment 7

(1) molybdenum oxide and basic cobaltous carbonate are dispersed in water, form maceration extract, wherein, MoO₃Concentration be 81.2g/ The concentration of L, CoO are 18.7g/L.With the maceration extract, saturation dipping prepares prepared by embodiment 7 under environment temperature (for 30 DEG C) When the dry bar HT-7 2 of hydrated alumina is small.The dry bar of hydrated alumina through dipping is dry in air atmosphere under 160 DEG C, normal pressure 1 it is small when after, then under 400 DEG C, normal pressure in air atmosphere roasting 4 it is small when so that obtain according to the present invention have hydrogenation The catalyst CH-7 of catalytic action, it is formed shown in table 3.

(2) catalyst is prepared using the method identical with (1), unlike, carrier is to prepare oxidation prepared by embodiment 7 The dry bar OT-7 of aluminium, obtains the catalyst CO-7 of the present invention, it is formed shown in table 3.

Comparative example 5

(1) catalyst is prepared using the method identical with (1) in embodiment 7, unlike, carrier is preparation comparative example 10 prepare the dry bar DHT-7 of hydrated alumina, as a result the dry bar of hydrated alumina dusting occurs in dipping process, can not be prepared into Type catalyst.

(2) catalyst is prepared using the method identical with (2) in embodiment 7, unlike, carrier is preparation comparative example The 10 alumina dry bar DOT-7 prepared, obtain catalyst DCO-5, its composition is listed in table 3.

Embodiment 8

(1) catalyst is prepared using the method identical with (1) in embodiment 7, unlike, carrier is preparation embodiment The 8 dry bar HT-8 of hydrated alumina prepared, obtain the catalyst CH-8 of the present invention, its composition is listed in table 3.

(2) catalyst is prepared using the method identical with (2) in embodiment 7, unlike, carrier is preparation embodiment The 8 alumina dry bar OT-8 prepared, obtain the catalyst CO-8 of the present invention, its composition is listed in table 3.

Embodiment 9

(1) catalyst is prepared using the method identical with (1) in embodiment 7, unlike, carrier is preparation embodiment The 9 dry bar HT-9 of hydrated alumina prepared, obtain the catalyst CH-9 of the present invention, its composition is listed in table 3.

(2) catalyst is prepared using the method identical with (2) in embodiment 7, unlike, carrier is preparation embodiment The 9 alumina dry bar OT-9 prepared, obtain the catalyst CO-9 of the present invention, its composition is listed in table 3.

Embodiment 10

(1) ammonium metatungstate and basic nickel carbonate are dispersed in water, form maceration extract, wherein, WO₃Concentration be 81.2g/ The concentration of L, NiO are 18.7g/L.With the maceration extract, saturation dipping prepares prepared by embodiment 10 under environment temperature (for 30 DEG C) When the dry bar HT-10 2 of hydrated alumina is small.The dry bar of hydrated alumina through dipping is done under 140 DEG C, normal pressure in air atmosphere It is dry 2 it is small when after, then under 180 DEG C, normal pressure in air atmosphere it is dry 3 it is small when so that obtain having according to the present invention plus The catalyst CH-10 of hydrogen catalysis effect, it is formed shown in table 3.

(2) catalyst is prepared using the method identical with (1), unlike, carrier is to prepare oxygen prepared by embodiment 10 Change the dry bar OT-10 of aluminium, obtain the catalyst CO-10 of the present invention, it is formed shown in table 3.

Table 3

EXPERIMENTAL EXAMPLE 1-10

EXPERIMENTAL EXAMPLE 1-10 is used to illustrate heavy-oil hydrogenation depitching matter method according to the present invention.

The catalytic performance of the embodiment 1-10 catalyst prepared is evaluated using following methods.

The particle of catalyst breakage prepared by above-described embodiment into diameter 2-3mm are loaded into the miniature fixed beds of 100mL respectively Reactor.Feedstock oil be the mass content of Ni elements be 29.3ppm, the mass content of V element be that 83ppm, S content are 4.7 weights Measure %, Kuwait's normal pressure slag that N content is 0.3 weight %, carbon residue is 15.1 weight % and asphalt content is 6.8 weight % Oil.Reaction condition is：Reaction temperature is 380 DEG C, hydrogen dividing potential drop 14MPa, and volume space velocity is 0.6h during the liquid of feedstock oil^-1.Using Inductive coupling plasma emission spectrograph (the PE-5300 types plasma spectrometer of PE companies of the U.S.) is with reference to petrochemical industry point The total content of Ni and V in oil before and after method measure hydrotreating specified in analysis method RIPP124-90, according to the following formula Metal removal rate is calculated, is as a result listed in table 4；According to oil before and after method measure hydrotreating specified in SH/T0509-92 The mass content of studies on asphaltene, calculates asphaltene removal, as a result lists in table 4 according to the following formula：

Experimental comparison's example 1-5

Using the method identical with EXPERIMENTAL EXAMPLE 1-10 respectively to comparative example 1-5 prepare catalyst catalytic performance into Row evaluation, experimental result are listed in table 4.

Table 4

EXPERIMENTAL EXAMPLE 1-10's as a result, it was confirmed that the catalyst according to the present invention with high active of hydrogenation catalysis with higher Catalytic activity.

The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims

1. a kind of catalyst with hydrogenation catalyst effect, which contains the hydrogenation of carrier and load on the carrier Active ingredient, it is characterised in that the carrier is the aqua oxidation by obtained from a kind of hydrated alumina composition molding Aluminium composition contains hydrated alumina, has the compound and phosphorus-containing compound at least two proton acceptor sites,

The compositionIt is worth for 1.8-5, it is describedValue is measured using following methods：By composition described in 10g at 120 DEG C in sky It is 240 minutes dry in gas atmosphere, the quality through dry composition is denoted as w₁, calculated using Formulas IValue,

2. composition according to claim 1, wherein, it is describedIt is worth not less than 1.85, to be preferably 1.9-3.2.

3. catalyst according to claim 1 or 2, wherein, relative to hydrated alumina described in 100 parts by weight, the tool The content for having the compound at least two proton acceptor sites is 1-25 parts by weight, is preferably 2-20 parts by weight, more preferably 3- 18 parts by weight, more preferably 3.5-17 parts by weight.

4. according to the catalyst described in any one in claim 1-3, wherein, it is described that there are at least two proton acceptor sites Compound in, proton acceptor site is can form more than one or both of F, O and N of hydrogen bond with water；

Preferably, the compound with least two proton acceptor sites is the compound containing hydroxyl in molecular structure；

It is highly preferred that the compound with least two proton acceptor sites is polyhydroxy organic compound；

It is further preferred that the compound with least two proton acceptor sites is polysaccharide and/or the etherate of polysaccharide；

It is further preferred that the compound with least two proton acceptor sites is galactan, mannosan, half More than one or both of newborn mannosan and cellulose ether, the cellulose ether is preferably methylcellulose, ethoxy fibre It is more than one or both of dimension element and hydroxypropyl cellulose；

It is particularly preferred that the compound with least two proton acceptor sites is galactomannans and cellulose ether, Preferably, on the basis of the total amount of the compound with least two proton acceptor sites, the galactomannans Content is 10-70 weight %, is preferably 15-68 weight %, more preferably 20-65 weight %；The content of the cellulose ether is 30-90 weight %, are preferably 32-85 weight %, more preferably 35-80 weight %.

5. according to the catalyst described in any one in claim 1-4, wherein, the hydrated alumina, which contains, intends thin water aluminium Stone；

Preferably, the hydrated alumina is boehmite.

6. catalyst according to claim 5, wherein, the composition is placed 72 under environment temperature and sealing condition Hour, the content of the gibbsite in composition after placement is higher than containing for the gibbsite in the composition before placing Amount；

Preferably, on the basis of the total amount of the content of the gibbsite in the composition before placement, in the composition after placement Gibbsite content at least improve 0.5%；

It is highly preferred that on the basis of the total amount of the content of the gibbsite in the composition before placement, the composition after placement In the content of gibbsite at least improve 1%, preferably improve 1.1% to 2%.

7. according to the catalyst described in any one in claim 1-6, wherein, the hydrated alumina is directed to hydration Aluminium oxide wet gel.

8. according to the catalyst described in any one in claim 1-7, wherein, on the basis of the total amount of the catalyst, with P₂O₅The phosphorus content of meter is 1-6 weight %, is preferably 1.5-4 weight %.

9. according to the catalyst described in any one in claim 1-8, wherein, the phosphorus-containing compound is selected from phosphoric acid, phosphoric acid At least one of sodium, aluminum phosphate, phosphorus chloride, phosphorus pentoxide, ammonium hydrogen phosphate and ammonium phosphate.

10. according to the catalyst described in any one in claim 1-9, wherein, the composition is free of peptizing agent.

11. according to the catalyst described in any one in claim 1-10, wherein, the carrier is by the hydrated alumina Obtained from the molding of composition is dried and optionally roasts.

12. according to the catalyst described in any one in claim 1-11, wherein, the hydrogenation activity component is at least one Vib metals element and at least one group VIII metallic element；

Preferably, the vib metals element is molybdenum and/or tungsten；

Preferably, the group VIII metallic element is cobalt and/or nickel.

13. catalyst according to claim 12, wherein, on the basis of the total amount of the catalyst, in terms of oxide The content of group VIII metallic element is 0.8-3 weight %, is preferably 1-2 weight %, the vib metals member in terms of oxide The content of element is 3-10 weight %, is preferably 4-8 weight %.

14. a kind of preparation method of the catalyst with hydrogenation catalyst effect, this method include hydrogenation activity component being supported on On carrier, it is characterised in that the carrier is made using method comprising the following steps：

(1) each component in a kind of feedstock composition is mixed, obtains hydrated alumina composition, the feedstock composition contains Hydrated alumina wet gel, the compound and phosphorus-containing compound with least two proton acceptor sites, the aqua oxidation The i values of aluminium wet gel are not less than 60%, and the dosage of the compound with least two proton acceptor sites causes finally The hydrated alumina composition of preparationIt is worth for 1.8-5,

The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of 240 points of dryings in air atmosphere Clock, w is denoted as by the quality through dry sample₂, i values are calculated using Formula II,

It is describedValue is measured using following methods：10g compositions are dried 240 minutes at 120 DEG C in air atmosphere, will be through dry The quality of dry composition is denoted as w₁, calculated using Formulas IValue,

(2) by the hydrated alumina composition molding, molding is dried and is optionally roasted, obtains the load Body.

15. according to the method for claim 14, wherein, it is described that there are at least two proton acceptor sites in step (1) The dosage of compound causes the hydrated alumina composition preparedIt is worth not less than 1.85, to be preferably 1.9-3.2.

16. the method according to claims 14 or 15, wherein, in step (1), the i values of the hydrated alumina wet gel For not less than 62%；

Preferably, the i values of the hydrated alumina wet gel are not higher than 82%, are preferably not higher than 80%, more preferably not Higher than 78.5%.

17. according to the method described in any one in claim 14-16, wherein, in step (1), the hydrated alumina is wet Gel is the hydrated alumina wet gel for not undergoing the dehydration for making that its i value is less than 60%.

18. according to the method described in any one in claim 14-17, wherein, in step (1), the hydrated alumina is wet Gel is after at least one alumina hydrate gel solution alternatively is carried out aging, carries out washing and separation of solid and liquid and obtains 's；

Preferably, the alumina hydrate gel solution is prepared into using the precipitation method, Hydrolyze method, kind point-score and rapid dehydration method Arrive.

19. according to the method described in any one in claim 14-18, wherein, phosphorus-containing compound in the raw mixture Content cause on the basis of the total amount of the catalyst finally prepared, with P₂O₅The phosphorus content of meter is 1-6 weight %, is preferably 1.5-4 weight %.

20. according to the method described in any one in claim 14-19, wherein, the phosphorus-containing compound is selected from phosphoric acid, phosphoric acid At least one of sodium, aluminum phosphate, phosphorus chloride, phosphorus pentoxide, ammonium hydrogen phosphate and ammonium phosphate.

21. according to the method described in any one in claim 14-20, wherein, in step (1), the feedstock composition is not Containing peptizing agent.

22. according to the method described in any one in claim 14-21, wherein, it is described to have at least two in step (1) In the compound in proton acceptor site, proton acceptor site for can be formed with water one or both of F, O and N of hydrogen bond with On；

23. according to the method described in any one in claim 14-22, wherein, in step (2), the drying at 60 DEG C extremely Carried out at a temperature of less than 350 DEG C, when the duration of the drying is 1-48 small；The roasting is at 355 DEG C to 1800 DEG C At a temperature of carry out, carried out preferably at a temperature of 800-1000 DEG C, duration of the roasting for 0.1-20 it is small when, be preferably When 2-6 is small.

24. according to the method described in any one in claim 14-23, wherein, the hydrogenation activity component is at least one Vib metals element and at least one group VIII metallic element；

Preferably, the vib metals element is molybdenum and/or tungsten；

Preferably, the group VIII metallic element is cobalt and/or nickel.

25. according to the method for claim 24, wherein, the load capacity of the hydrogenation activity component on the carrier causes On the basis of the total amount of the catalyst finally prepared, the content for the group VIII metallic element counted using oxide is 0.8-3 weight % is measured, is preferably 1-2 weight %, the content for the vib metals element counted using oxide is preferably 4-8 as 3-10 weight % Weight %.

26. according to the method described in any one in claim 14-25, wherein, hydrogenation activity component is supported on the load Method on body includes：The carrier is impregnated with the maceration extract containing the hydrogenation activity component, the carrier through dipping is carried out It is dry, alternatively roasted through dry carrier.

27. the method according to claim 11, wherein, temperature of the carrier through dipping at 80-250 DEG C, preferably 100-140 DEG C It is dried under degree；Roasted through dry carrier at a temperature of 360-500 DEG C, preferably 360-450 DEG C.

28. the catalyst with hydrogenation catalyst effect prepared by a kind of method in 14-27 as claim described in any one.

29. application of the catalyst in hydrocarbon oil hydrogenation processing in claim 1-13 and 28 described in any one.

30. a kind of heavy-oil hydrogenation depitching matter method, this method includes that at hydrotreating reaction conditions, asphalitine will be contained Heavy oil is contacted with the catalyst described in any one in claim 1-13 and 28.