CN107999122A - Hydrated alumina composition and formed body and preparation method and application and catalyst and preparation method containing molecular sieve - Google Patents

Hydrated alumina composition and formed body and preparation method and application and catalyst and preparation method containing molecular sieve Download PDF

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Publication number
CN107999122A
CN107999122A CN201610928578.2A CN201610928578A CN107999122A CN 107999122 A CN107999122 A CN 107999122A CN 201610928578 A CN201610928578 A CN 201610928578A CN 107999122 A CN107999122 A CN 107999122A
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hydrated alumina
composition
formed body
weight
wet gel
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CN107999122B (en
Inventor
杨清河
辛靖
李明丰
聂红
胡志海
杨平
张毓莹
董松涛
王轶凡
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

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

Description

Hydrated alumina composition and formed body and preparation method and application containing molecular sieve And catalyst and preparation method
Technical field
The present invention relates to aluminium oxide field shaping technique, in particular it relates to a kind of hydrated alumina composition and Its preparation method, the invention further relates to by the hydrated alumina formed body that the hydrated alumina composition is formed and aluminium oxide into Type body, the invention further relates to a kind of to be added by the formed body that the hydrated alumina composition is formed as having for carrier Catalyst of hydrogen catalysis effect and preparation method thereof and the hydrotreating method using the catalyst.
Background technology
In conventional methods where, the aluminium oxide formed body containing molecular sieve, the gama-alumina shaping particularly containing molecular sieve Body, because it is with preferable pore structure, suitable ratio surface and higher heat-resistant stability, is urged frequently as adsorbent or support type The carrier of agent uses.This aluminium oxide is usually by dried hydrated alumina, and such as boehmite is through being molded, drying Afterwards, 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 molecular sieve, extrusion aid and optional chemistry Peptizing agent (inorganic acid and/or organic acid), through kneading aftershaping, molding is used as adsorbent after dry and optional roasting Or carrier uses.The main problem of this 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 before guaranteeing to be met the alumina support containing molecular sieve of industrial application requirement Put, simplify the preparation process flow of the alumina support containing molecular sieve and reduce operation energy consumption, while mitigate and contain molecule Dust pollution in the alumina support preparation process of sieve is still a technical problem urgently to be resolved hurrily.
The content of the invention
It is an object of the invention to simplify the preparation process flow of the alumina support containing molecular sieve, mitigation contains molecule Dust pollution in the alumina support preparation process of sieve, while the carrier prepared can also meet industrial application requirement.
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 hydrated alumina composition, said composition to contain Hydrated alumina, molecular sieve and the compound with least two proton acceptor sites,
The compositionIt is worth for less than 5, it is describedValue is measured using following methods：By composition described in 10g at 120 DEG C It is 240 minutes dry in air atmosphere, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
According to the second aspect of the invention, should the present invention provides a kind of preparation method of hydrated alumina composition Method includes mixing each component in a kind of feedstock composition, obtains the hydrated alumina composition, the material combination Thing contains hydrated alumina wet gel, molecular sieve and the compound with least two proton acceptor sites, the hydration oxygen Change the i values of aluminium wet gel as not less than 50%, the dosage of the compound with least two proton acceptor sites causes most The composition prepared eventuallyIt is worth for less than 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,
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 Standby hydrated alumina composition.
According to the fourth aspect of the present invention, the present invention provides a kind of hydrated alumina formed body, the hydrated alumina Formed body is as the hydrated alumina composition described in the first aspect of the present invention or the hydration described in third aspect of the present invention Alumina composition is formed.
According to the fifth aspect of the present invention, should the present invention provides a kind of preparation method of hydrated alumina formed body Method is included the hydrated alumina composition described in the first aspect of the present invention or the water described in third aspect of the present invention Close alumina composition to be molded, obtained molding is dried.
According to the sixth aspect of the invention, the present invention provides a kind of method system as described in the 5th aspect of the present invention Standby hydrated alumina formed body.
According to the seventh aspect of the present invention, the present invention provides a kind of aluminium oxide formed body, the aluminium oxide formed body by The hydrated alumina group described in hydrated alumina composition or third aspect of the present invention described in the first aspect of the present invention Compound is formed.
According to the eighth aspect of the present invention, the present invention provides a kind of preparation method of aluminium oxide formed body, this method Including by the hydrated alumina composition described in the first aspect of the present invention or the hydration oxygen described in third aspect of the present invention Change aluminium composition to be molded, obtained molding is dried and roasted.
According to the ninth aspect of the present invention, the present invention provides a kind of method system as described in the 8th aspect of the present invention Standby aluminium oxide formed body.
According to the tenth aspect of the present invention, the present invention provides a kind of production forming method of hydrated alumina, the party Method comprises the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed and solid-liquid Separation, obtains the first hydrated alumina wet gel, the condition of the separation of solid and liquid causes the first hydrated alumina wet gel I values be not less than 50%；
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,
(2) using the method described in second aspect of the present invention by the first hydrated alumina wet gel and with least The compound mixing in two proton acceptor sites, obtains hydrated alumina composition；
(3) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(4) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(5) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, this method is additionally included in the operation that mixed molecular sieve is carried out in step (1) and/or step (2), so that institute State hydrated alumina composition and contain molecular sieve.
According to the eleventh aspect of the present invention, should the present invention provides a kind of production forming method of hydrated alumina Method comprises the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the Monohydrate alumina wet gel；
(2) the first hydrated alumina wet gel is handled using (2-1) or (2-2), obtains the second aqua oxidation Aluminium wet gel,
(2-1) mixes the first hydrated alumina wet gel with water, forms slurries, and the slurries are carried out solid-liquid point From obtaining the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel,
In (2-1) and (2-2), the condition of the separation of solid and liquid make it that the i values of the second hydrated alumina wet gel are Not less than 50%,
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,
(3) using the method described in second aspect of the present invention by the second hydrated alumina wet gel and with least two The compound mixing in proton acceptor site, obtains hydrated alumina composition；
(4) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(5) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(6) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, this method be additionally included in one, two or three in step (1), step (2) and step (3) into The operation of row mixed molecular sieve, so that the hydrated alumina composition contains molecular sieve.
According to the twelfth aspect of the present invention, the present invention provides one kind by the tenth aspect of the present invention or the 11st Formed body prepared by the method described in a aspect.
13rd aspect according to the present invention, the present invention provides hydrated alumina formed body and oxidation according to the present invention Application of the aluminium formed body as carrier or adsorbent.
14th aspect according to the present invention, should the present invention provides a kind of catalyst with hydrogenation catalyst effect Catalyst contains the group VIII metallic element and vib metals element of carrier and load on the carrier, wherein, institute It is hydrated alumina formed body or the aluminium oxide formed body according to the present invention according to the present invention to state carrier.
15th aspect according to the present invention, the present invention provides a kind of system of the catalyst with hydrogenation catalyst effect Preparation Method, this method are included in supported on carriers group VIII metallic element and vib metals element, wherein, the carrier For the hydrated alumina formed body according to the present invention or aluminium oxide formed body according to the present invention.
16th aspect according to the present invention, the present invention provides a kind of hydrotreating method, this method, which is included in, to be added Under hydrogen treatment conditions, hydrocarbon ils is contacted with the catalyst with hydrogenation catalyst effect, wherein, this method is further included using the present invention Method described in 5th aspect, the 8th aspect, the tenth aspect or the tenth one side prepares the hydration as carrier Aluminium oxide formed body or aluminium oxide formed body.
With existing process (such as Fig. 1 that alumina support is prepared using boehmite dry glue powder as starting material Shown technique) compare, the present invention is directly used as molding starting using the hydrated alumina wet gel that synthetic reaction is prepared Raw material prepares the formed body containing molecular sieve, has the advantage that：
(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 with directly preparing formed body using hydrated alumina wet gel as starting material US4613585 is compared with CN103769118A, and technical process of the invention is more succinct, and operability is stronger, and can be effective Ground improves the intensity of the formed body finally prepared, while the pore-size distribution of the formed body finally prepared can be adjusted, can be full The requirement of a variety of use occasions of foot.The present invention can prepare containing with higher-strength by starting material of hydrated alumina wet gel There is the reason for formed body of molecular sieve may is that：Compound and hydrated alumina with least two proton acceptor sites are wet Free water in gel interacts to form hydrogen bond, adsorbs the Free water in hydrated alumina wet gel, while have at least two Also with the hydroxyl in hydrated alumina molecular structure interaction of hydrogen bond can occur for the compound in a proton acceptor site, play thing The effect of peptization is managed, so that hydrated alumina wet gel can not only be molded, and can be so that the formed body tool finally prepared There is higher intensity.
There is hydrogenation catalyst effect using formed body prepared by hydrated alumina composition according to the present invention as carrier Catalyst the catalytic activity of higher is shown in the hydrotreating of hydrocarbon ils.
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 preferred embodiment for the method for preparing hydrated alumina composition according to the present invention.
Fig. 3 is a kind of preferred embodiment of moulding process flow process 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 herein The accurate scope or value is not limited to any value, these scopes or value should be understood to comprising close to these scopes or value Value.For number range, between the endpoint value of each scope, between the endpoint value of each scope and single point value, with And can be individually combined with each other between point value and obtain one or more new number ranges, these number ranges should be considered as It is specific open herein.
According to the first aspect of the invention, the present invention provides a kind of hydrated alumina composition, said composition to contain Hydrated alumina, molecular sieve and the compound with least two proton acceptor sites.
The hydrated alumina can be more than one or both of gibbsite and a water aluminium oxide.It is described The instantiation of hydrated alumina can include but is not limited to boehmite, gibbsite, unformed hydrated alumina and plan Boehmite.The hydrated alumina preferably comprises a water aluminium oxide, more preferably a water aluminium oxide.In a kind of excellent of the present invention In the embodiment of choosing, the hydrated alumina contains boehmite, more preferably boehmite.According to the preferable reality The hydrated alumina composition for applying mode is used as the formed body of the catalyst carrier with hydrogenation catalyst effect particularly suitable for preparing.
Hydrated alumina composition according to the present invention, it is wet solidifying that the hydrated alumina is directed to hydrated alumina Glue, is not originating from hydrated alumina dry glue powder.In the present invention, term " hydrated alumina wet gel " refers to pass through synthetic reaction Obtain and do not live through the dehydration that its i value is reduced to less than 50% (preferably less than 55%, more preferably less than 60%) Aqueous alumina hydrate gel.In the present invention, i values are measured using following methods：By 10g hydrated alumina wet gels 120 It is 240 minutes dry DEG C in air atmosphere, 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, when placement 72 is small under environment temperature and sealing condition, The thing of hydrated alumina, which is met, in composition after placement changes.Depending on the environment temperature is with environment is placed, generally may be used Think 5-50 DEG C, such as 20-40 DEG C.The sealing condition refers to the composition being placed in closed vessel, the closed vessel Can be closure container (such as tank, bucket or case), or the flexible coating (such as sealed bag) of sealing, the flexible cladding Thing can be paper and/or polymeric material, be preferably polymeric material, such as plastics.
In an example, the hydrated alumina for being directed to alumina hydrate gel contains boehmite and (is such as Boehmite) when, the composition is placed under environment temperature and sealing condition 72 it is small when, in the composition after placement Gibbsite content is higher than the gibbsite content in the composition before placing.In this example, with the combination before placement On the basis of the content of gibbsite in thing, the gibbsite content in the composition after placement generally at least improves 0.5%, 1% is preferably at least improved, more preferably improves 1.1-1.5%.
Hydrated alumina composition according to the present invention, also contains the compound with least two proton acceptor sites. Hydrated alumina composition according to the present invention, without being used as starting material using dry glue powder, you can (particularly extruded for being molded Shaping), and there is obtained formed body the reason for higher intensity may is that：It is described that there are at least two proton acceptor sites Compound and hydrated alumina wet gel in Free water interaction of hydrogen bond occurs, so as to adsorb Free water, while and water The hydroxyl closed in alumina molecule structure interacts, and plays the role of peptization.
In the compound with least two proton acceptor sites, the proton acceptor site refers to the compound Molecular structure in the position of hydrogen bond can be formed with water and hydroxyl.The instantiation in the proton acceptor site can include but It is not limited to more than one or both of fluorine (F), oxygen (O) and nitrogen (N).The chemical combination with least two proton acceptor sites The instantiation of thing can include but is not limited in molecular structure contain selected from hydroxyl, carboxyl, amino, ehter bond, aldehyde radical, carbonyl, The compound of group more than one or both of amide groups and fluorine atom, 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 one or more alkyl after the ether system derivative that is formed, wherein, multiple alkyl can be it is identical, It can also be difference.The alkyl is selected from the alkyl of substitution and unsubstituted alkyl.The unsubstituted alkyl is preferably alkyl (such as：C1-C5Alkyl).In the present invention, C1-C5The instantiation of alkyl include C1-C5Straight chained alkyl and C3-C5Branch Alkyl group, can be but be not limited to：It is methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, different Amyl group and tertiary pentyl.The substituted alkyl for example can be substituted by hydroxyl, carboxyl, cyano group or aryl alkyl (such as： C1-C5The alkyl being optionally substituted by a hydroxyl group, C1-C5The alkyl substituted by carboxyl, C1-C5The alkyl being substituted with aryl), the virtue Base can be phenyl or naphthyl.The instantiation of the substituted alkyl can include but is not limited to：Cyano group, benzyl, benzene Ethyl, methylol, ethoxy, hydroxypropyl, hydroxyl butyl, carboxymethyl, carboxyethyl and carboxylic propyl group.The instantiation of the cellulose ether It can include but is not limited to methylcellulose, hydroxyethylmethylcellulose, carboxymethyl cellulose, ethyl cellulose, benzyl fiber Element, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cyanethyl cellulose, benzyl cyanethyl cellulose, Carboxymethyl hydroxyethyl cellulose and benzyl cellulose.The polysaccharide can be the polysaccharide in various sources, such as：Can be with galactomannan Glycan may come from sesbania powder.
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 Block 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.The embodiment being more highly preferred to according to this, by composition shape according to the present invention Into formed body have higher intensity.It is further preferred that it is described there are at least two proton acceptor sites compound it is excellent Elect galactomannans and cellulose ether as.
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 10-80 weight %, be preferably 15-70 weight %, more preferably 30- 60 weight %；The content of the cellulose ether can be 20-90 weight %, be preferably 30-85 weight %, more preferably 40-70 Weight %.
Composition according to the present invention also contains molecular sieve.
The content of molecular sieve can make choice according to the concrete application occasion of said composition in the composition.In one kind In preferred embodiment, on the basis of the total amount of the composition after roasting, the content of molecular sieve can be 0.5-90 weight %, Preferably 1-80 weight %, more preferably 5-70 weight %, more preferably 10-60 weight %；The content of aluminium oxide can be with It is preferably 20-99 weight % for 10-99.5 weight %, more preferably 30-95 weight %, more preferably 40-90 weights % is measured, the roasting carries out at a temperature of 600 DEG C, when the duration of the roasting is 3 small.According to the preferable embodiment party Carrier of the composition of formula particularly suitable for preparing the catalyst with hydrogenation catalyst effect.
The molecular sieve can be common various types of molecular sieves.In a preferred embodiment, described point Son sieve is Y type molecular sieve and beta molecular sieve.In the preferred embodiment, the ratio between Y type molecular sieve and beta molecular sieve Example can make appropriate choice according to the use occasion of the formed body prepared by said composition.As an example, by the group Formed body prepared by compound is used as catalyst (particularly hydrocracking catalyst and hydro-upgrading catalysis with hydrogenation Agent) carrier when, on the basis of the total amount of molecular sieve, the content of the Y type molecular sieve is preferably 10-95 weight %, more preferably For 30-92 weight %, more preferably 50-90 weight %；The content of the beta molecular sieve is preferably 5-90 weight %, more Preferably 8-70 weight %, more preferably 10-50 weight %.
The Y type molecular sieve can be Hydrogen Y type molecular sieve, Hydrogen Y type molecular sieve, metal containing group ivb containing rare earth It is more than one or both of Y type molecular sieve of the Y type molecular sieve of (such as titanium), phosphorous Y type molecular sieve and dealuminzation.
The beta molecular sieve can be the beta molecular sieve containing rare earth, metal containing group ivb (such as titanium) beta molecular sieve, It is more than one or both of phosphorous beta molecular sieve and the beta molecular sieve of dealuminzation.
Composition according to the present inventionIt is worth for less than 5, preferably less than 4, more preferably less than 3.5.Value can be More than 1.2, it is preferably more than 1.3, more preferably more than 1.4.Specifically, hydrated alumina composition according to the present invention Value can be 1.2-5, be preferably 1.3-4, more preferably 1.3-3.5, more preferably 1.4-3.5.
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,
Composition according to the present invention, the content of the compound with least two proton acceptor sites is can make institute State compositionValue meets subject to above-mentioned requirements.Preferably, it is described to have extremely relative to hydrated alumina described in 100 parts by weight The content of the compound in few two proton acceptor sites can be 1-25 parts by weight, be preferably 2-20 parts by weight, more preferably 4- 18 parts by weight.
Composition according to the present invention, can contain peptizing agent, can not also contain peptizing agent.The peptizing agent can be The usually used reagent with gelatification of aluminium oxide formed body preparing technical field, its instantiation can include but unlimited In Aluminum sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid.
Composition according to the present invention, the compound with least two proton acceptor sites, particularly described It is described when compound with least two proton acceptor sites is containing polymer with least two proton acceptor sites The compound with least two proton acceptor sites can play physics peptization, so as to reduce the use of peptizing agent Amount, it might even be possible to without using peptizing agent.
In a kind of preferred embodiment of the present invention, relative to 100 parts by weight hydrated aluminas, the peptizing agent Content is more preferably below 2 parts by weight below 5 parts by weight, to be preferably below 3 parts by weight.
In a kind of particularly preferred embodiment of the present invention, composition according to the present invention does not contain peptizing agent.Root According to the composition of the particularly preferred embodiment, when being used to prepare formed body, even if the hydrated alumina formed body of preparation Without roasting, aluminium oxide formed body is transformed into, can also be used as adsorbent or carrier to use, because unfired water When conjunction aluminium oxide formed body contains peptizing agent, peptizing agent is being adsorbed and dissolved in dipping process, a large amount of to be lost in so that formed body goes out Now dissolving, dusting and duct are caved in phenomenon, finally lose shape, thus adsorbent and carrier can not be used as to use.
According to the second aspect of the invention, should the present invention provides a kind of preparation method of hydrated alumina composition Method includes mixing each component in a kind of feedstock composition, obtains the hydrated alumina composition, that is, is mixed to get Mixture is the hydrated alumina composition.
The preparation method of hydrated alumina composition according to the present invention, it is wet that the raw mixture contains hydrated alumina Gel, molecular sieve and the compound with least two proton acceptor sites.It is described that there are at least two proton acceptor sites Compound and its species and the molecular sieve and its species detailed description has been carried out above, it is no longer superfluous herein State.
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, aluminum nitrate.The instantiation of the aluminate can be included but not It is limited to more than one or both of sodium metaaluminate, potassium metaaluminate.
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 one or both of sodium metaaluminate, potassium metaaluminate with On.The degree of supersaturation of the aluminate solution can be conventional selection.
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 100-200 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.
The preparation method of hydrated alumina composition according to the present invention, the i values of the hydrated alumina wet gel is not Less than 50%, 55% is preferably not lower than, more preferably not less than 60%.The i values of the hydrated alumina wet gel are preferably Not higher than 95%, more preferably not above 90%, more preferably not higher than 85%, still more preferably for not higher than 82%.In one embodiment, the i values of the hydrated alumina wet gel are 50-95%, such as 50-90%.In one kind more In preferred embodiment, the i values of the hydrated alumina wet gel are 60-90%, more preferably 60-85%, more into One step is preferably 60-82%.Composition prepared by the embodiment being more highly preferred to according to this is when for being molded, the shaping of acquisition Body has the intensity of higher.
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 is pressure filtration and/or vacuum filter.At this In embodiment, by adjusting the pressure of application and/or the size of vacuum, carried out to obtaining hydrated alumina wet gel i values Control.The instantiation using device of the pressure filtration 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.
The preparation method of hydrated alumina composition according to the present invention, the hydrated alumina wet gel that separation of solid and liquid obtains It is general not live through the dehydration that its i value is reduced to less than 50% (being preferably less than 55%, more preferably less than 60%).
The preparation method of hydrated alumina composition according to the present invention, it is described that there are at least two proton acceptor sites The dosage of compound enables to the hydrated alumina composition finally preparedIt is worth for less than 5, is preferably less than 4, more preferably For less than 3.5.The dosage of the compound with least two proton acceptor sites is preferably so that the hydration oxygen finally prepared Change aluminium compositionIt is worth for more than 1.2.The dosage of the compound with least two proton acceptor sites more preferably causes The hydrated alumina composition finally preparedIt is worth for more than 1.3, more preferably so that the hydrated alumina composition finally prepared 'sIt is worth for more than 1.4.Specifically, the dosage of the compound with least two proton acceptor sites more preferably causes most The hydrated alumina composition prepared eventuallyIt is worth for 1.2-5, preferably 1.3-4, more preferably 1.3-3.5.
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 4-18 parts by weight, the aqua oxidation Aluminium wet gel is in terms of hydrated alumina.
The preparation method of hydrated alumina composition according to the present invention, the raw mixture can contain peptizing agent, Peptizing agent can not also be contained.Preferably, relative to 100 parts by weight hydrated aluminas, the content of the peptizing agent is 5 parts by weight Hereinafter, it is preferably below 3 parts by weight, more preferably below 2 parts by weight.It is highly preferred that the raw mixture does not contain peptization Agent.That is, the preparation method of hydrated alumina composition according to the present invention does not include more preferably adding into the raw mixture The step of adding peptizing agent.
The preparation method of hydrated alumina composition according to the present invention, can use conventional method that hydrated alumina is wet Gel is mixed with molecular sieve with the compound with least two proton acceptor sites.Can be under shear action by aqua oxidation Aluminium wet gel is mixed with molecular sieve with the compound with least two proton acceptor sites.In one embodiment, it is described The mode of mixing is stirring.Can be by hydrated alumina wet gel and molecular sieve and change with least two proton acceptor sites The two is uniformly mixed, so as to obtain being hydrated oxygen according to the present invention by compound in the container with agitating device by stirring Change aluminium composition.The stirring can carry out in the container with agitating device, can also be carried out in beater.Another In kind embodiment, the mode of the mixing is kneading.Can be by hydrated alumina wet gel and molecular sieve and with least two The compound in a proton acceptor site is mediated in kneader, so as to obtain hydrated alumina combination according to the present invention Thing.The type of the kneader is not particularly limited.The preparation method of hydrated alumina composition according to the present invention, can incite somebody to action Stirring and hybrid combining use, and hydrated alumina wet gel and the compound with least two proton acceptor sites are mixed Close.At this time, preferably first it is stirred, then is mediated.
The preparation method of hydrated alumina composition according to the present invention, can use various order by merging by the molecule Sieve, the compound with least two proton acceptor sites and the mixing of hydrated alumina wet gel.
In one embodiment, Y type molecular sieve and β types can be mixed during hydrated alumina wet gel is prepared Y type molecular sieve and beta molecular sieve, can also be added in the hydrated alumina wet gel being prepared by molecular sieve, can be with Mixing portion Y type molecular sieve and beta molecular sieve during hydrated alumina wet gel is prepared, remainder Y type molecular sieve It is added to beta molecular sieve in the hydrated alumina wet gel being prepared, mixes the operation of Y type molecular sieve and beta molecular sieve It can be carried out in one of above-mentioned addition opportunity, both or three.During hydrated alumina wet gel is prepared Mix Y type molecular sieve and during beta molecular sieve, can be in precipitation reaction process, ageing process, separation of solid and liquid process and washed One of journey, both, the operation of mixing Y type molecular sieve and beta molecular sieve is carried out in three or four.Can be according to precipitation The type of reaction choose whether to mix during hydrated alumina wet gel is prepared Y type molecular sieve and beta molecular sieve and The opportunity of mixing, so that subject to the structure of Y type molecular sieve and beta molecular sieve will not or will not be destroyed substantially.Preferably, The operation of mixing Y type molecular sieve and beta molecular sieve is carried out in separation of solid and liquid process.
In another embodiment, Y type molecular sieve and β type molecules are mixed after the completion of the preparation of hydrated alumina wet gel Sieve.In this embodiment, first Y type molecular sieve and beta molecular sieve can be mixed with hydrated alumina wet gel, then mixed Compound with least two proton acceptor sites；Can also first by the compound with least two proton acceptor sites with Hydrated alumina wet gel mixes, and then mixes Y type molecular sieve and beta molecular sieve；Can also be at the same time by Y type molecular sieve, β types point Son sieve and the compound with least two proton acceptor sites are mixed with hydrated alumina wet gel.
The preparation method of hydrated alumina composition according to the present invention, preferably prepares in hydrated alumina wet gel and completes Y type molecular sieve and beta molecular sieve are mixed afterwards.
The preparation method of hydrated alumina composition according to the present invention, in mixed process, can supplement addition water, Addition water can not be supplemented, as long as can cause the hydrated alumina composition of preparationValue meets above-mentioned requirements.Generally Ground, in the angle from the uniformity for improving mixing, can supplement addition water in mixed process.Usually, supplement addition Water and the weight ratio of compound with least two proton acceptor sites can be 5-15：1, it is preferably 8-12：1.
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 Standby hydrated alumina composition.
Hydrated alumina composition according to the present invention can use conventional method to be molded, so as to obtain hydration oxygen Change aluminium formed body or aluminium oxide formed body.
According to the fourth aspect of the present invention, the present invention provides a kind of hydrated alumina formed body, the hydrated alumina Formed body is as the hydrated alumina composition described in the first aspect of the present invention or the hydration described in third aspect of the present invention Alumina composition is formed.
Hydrated alumina composition according to the present invention can be molded, obtained molding is dried, from And obtain hydrated alumina formed body according to the present invention.
The molding mode is not particularly limited, and can use various molding modes commonly used in the art, such as：Squeeze Bar, spraying, round as a ball, tabletting or combinations thereof.The present invention a kind of preferred embodiment in, by way of extrusion come Shaping.
The temperature that the molding is dried can be the conventional selection of this area.Usually, the temperature of the drying Degree can be preferably 70-300 DEG C for 60 DEG C less than 350 DEG C, more preferably 100-250 DEG C.The time of the drying can To be made appropriate choice according to dry temperature, so as to so that volatile matter contains in the hydrated alumina formed body finally obtained Amount meets subject to requirement.Usually, when the duration of the drying can be 1-48 small, when being preferably 2-24 small, more When preferably 2-12 is small, when more preferably 2-6 is small.The drying can carry out in oxygen-containing atmosphere (such as air atmosphere), It can also carry out in inert atmosphere (atmosphere that such as nitrogen and/or zero group gas are formed), be carried out preferably in oxygen-containing atmosphere.
Hydrated alumina formed body according to the present invention, can be had according to specifically used requirement it is variously-shaped, such as：Ball Shape, bar shaped, annular, cloverleaf pattern, honeycombed, bird-nest-shaped, cylinder, Rasching ring or butterfly.
Hydrated alumina formed body according to the present invention has abundant pore structure, and pore-size distribution is adjustable.
In one embodiment, measured by mercury injection method, the pore-size distribution of hydrated alumina formed body is in bimodal distribution.Its In, most probable pore size be respectively 4-20nm (be preferably 5-15nm, more preferably 6-10nm) and more than 20nm (such as 20.5-35nm, Preferably 21-32nm).
In another embodiment, measured by mercury injection method, the aperture of hydrated alumina formed body is in Unimodal Distribution.Its In, most probable pore size 4-30nm, is preferably 10-25nm, more preferably 12-23nm.
Hydrated alumina formed body according to the present invention, the hydrated alumina formed body have higher intensity.Usually, The radial direction crushing strength of hydrated alumina formed body according to the present invention is more than 10N/mm, is preferably more than 12N/mm, more excellent Elect more than 15N/mm as.Specifically, the radial direction crushing strength of the hydrated alumina formed body can be 10-50N/mm, be preferably 15-35N/mm.In the present invention, using the radial direction crushing strength of method measure formed body specified in RIPP 25-90.
According to the fifth aspect of the present invention, should the present invention provides a kind of preparation method of hydrated alumina formed body Method is included the hydrated alumina composition described in the first aspect of the present invention or the water described in third aspect of the present invention Close alumina composition to be molded, obtained molding is dried, so as to obtain the hydrated alumina formed body.
The shaping and the 4th aspect of dry method and condition and the present invention are described identical, are no longer described in detail herein.
The preparation method of hydrated alumina formed body according to the present invention, can be by varying hydrated alumina compositionValue come obtain with different pore size distribution hydrated alumina formed body.
In one embodiment of the invention, the hydrated alumina compositionIt is worth for not less than 1.8, such as can Think 1.8-5.Preferably, the hydrated alumina compositionIt is worth for not less than 1.85, such as can is 1.85-4.It is more excellent Selection of land, the hydrated alumina compositionIt is worth for not less than 1.9, such as can is 1.9-3.5.Measured by mercury injection method, according to The pore-size distribution of hydrated alumina formed body prepared by the embodiment is in bimodal distribution.Most probable pore size is respectively 4-20nm (being preferably 5-15nm, more preferably 6-10nm) and more than 20nm (such as 20.5-35nm, is preferably 21-32nm).
In another embodiment of the invention, the hydrated alumina compositionIt is worth for less than 1.8, such as can 1.2 are thought to less than 1.8.Preferably, the hydrated alumina compositionIt is worth for not higher than 1.7, such as can is 1.3- 1.7, it is preferably 1.4-1.7.Measured by mercury injection method, the pore-size distribution of the hydrated alumina formed body prepared according to the embodiment In Unimodal Distribution.Most probable pore size is 4-30nm, is preferably 10-25nm, more preferably 12-23nm.
According to the sixth aspect of the invention, the present invention provides a kind of method system as described in the 5th aspect of the present invention Standby hydrated alumina formed body.
The hydrated alumina formed body prepared by the method for the present invention has higher intensity.Usually, by the present invention's The radial direction crushing strength of hydrated alumina formed body prepared by method is more than 10N/mm, is preferably more than 12N/mm, more preferably For more than 15N/mm.Specifically, can be by the radial direction crushing strength of the hydrated alumina formed body of the method preparation of the present invention 10-50N/mm, is preferably 15-35N/mm.
According to the seventh aspect of the present invention, the present invention provides a kind of aluminium oxide formed body, the aluminium oxide formed body by The hydrated alumina group described in hydrated alumina composition or third aspect of the present invention described in the first aspect of the present invention Compound is formed.
Hydrated alumina composition according to the present invention can be molded, obtained molding is successively dried And roasting, so as to obtain the aluminium oxide formed body.
The shaping and the 4th aspect of dry method and condition and the present invention are described identical, are no longer described in detail herein.
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 400-950 DEG C, be preferably 450-900 DEG C, more preferably 480-650 DEG C；The duration of the roasting When can be 2-10 small, when being preferably 3-8 small.The roasting can carry out in oxygen-containing atmosphere (such as air atmosphere), can also Carry out in inert atmosphere (atmosphere that such as nitrogen and/or zero group gas are formed), carried out preferably in oxygen-containing atmosphere.
Aluminium oxide formed body according to the present invention, can be had according to specifically used requirement it is variously-shaped, such as：Spherical, Bar shaped, annular, cloverleaf pattern, honeycombed, bird-nest-shaped, cylinder, Rasching ring or butterfly.
Aluminium oxide formed body according to the present invention has abundant pore structure, and pore-size distribution is adjustable.
In one embodiment, measured by mercury injection method, the pore-size distribution of aluminium oxide formed body is in bimodal distribution.Most probable Aperture is respectively 4-20nm (being preferably 5-15nm, more preferably 6-10nm) and (such as 20.5-35nm, is preferably 21- more than 20nm 32nm)。
In another embodiment, measured by mercury injection method, the pore-size distribution of aluminium oxide formed body is in Unimodal Distribution.Most may be used Several apertures are 4-30nm, are preferably 10-25nm, more preferably 12-23nm.
Aluminium oxide formed body according to the present invention, the aluminium oxide formed body have higher intensity.Usually, according to this hair The radial direction crushing strength of bright aluminium oxide formed body is more than 10N/mm, is preferably more than 12N/mm, is preferably more than 15N/mm. Specifically, the radial direction crushing strength of the aluminium oxide formed body can be 10-50N/mm, be preferably 15-35N/mm.
According to the eighth aspect of the present invention, the present invention provides a kind of preparation method of aluminium oxide formed body, this method Including by the hydrated alumina composition described in the first aspect of the present invention or the hydration oxygen described in third aspect of the present invention Change aluminium composition to be molded, obtained molding is dried and roasted.
The shaping, dry and roasting method and the 7th aspect of condition and the present invention are described identical, no longer superfluous herein State.
The preparation method of aluminium oxide formed body according to the present invention, can be by varying alumina compositionValue obtains There must be the aluminium oxide formed body of different pore size distribution.
In one embodiment of the invention, the alumina compositionIt is worth for not less than 1.8, such as can is 1.8-5.Preferably, the hydrated alumina compositionIt is worth for not less than 1.85, such as can is 1.85-4.It is highly preferred that The hydrated alumina compositionIt is worth for not less than 1.9, such as can is 1.9-3.5.Measured by mercury injection method, according to the reality The pore-size distribution of aluminium oxide formed body prepared by the mode of applying is in bimodal distribution.Most probable pore size is respectively that 4-20nm (is preferably 5- 15nm, more preferably 6-10nm) and more than 20nm (such as 20.5-35nm, is preferably 21-32nm).
In another embodiment of the invention, the alumina compositionIt is worth for less than 1.8, such as can is 1.2 to less than 1.8.Preferably, the hydrated alumina compositionIt is worth for not higher than 1.7, such as can is 1.3-1.7, it is excellent Elect 1.4-1.7 as.Measured by mercury injection method, the pore-size distribution of the aluminium oxide formed body prepared according to the embodiment is in unimodal point Cloth.Most probable pore size is 4-30nm, is preferably 10-25nm, more preferably 12-23nm.
According to the ninth aspect of the present invention, the present invention provides a kind of method system as described in the 8th aspect of the present invention Standby aluminium oxide formed body.
The aluminium oxide formed body prepared by the method for the present invention has higher intensity.Usually, by the method for the present invention The radial direction crushing strength of the aluminium oxide formed body of preparation is more than 10N/mm, is preferably more than 12N/mm, more preferably 15N/mm More than.Specifically, the radial direction crushing strength of the aluminium oxide formed body prepared by the method for the present invention can be 10-50N/mm, excellent Elect 15-35N/mm as.
According to the tenth aspect of the present invention, the present invention provides a kind of production forming method of hydrated alumina, such as Fig. 2 Shown in Fig. 3, this method comprises the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the Monohydrate alumina wet gel；
Optionally (2), are handled the first hydrated alumina wet gel using (2-1) or (2-2),
The first hydrated alumina wet gel and aqueous mixtures are formed slurries by (2-1), and the slurries are carried out solid-liquid Separation, obtains the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel；
(3) by hydrated alumina wet gel and there are at least two protons using the method described in second aspect of the present invention The compound mixing of acceptor site, obtains hydrated alumina composition, and the hydrated alumina wet gel is the described first hydration Aluminium oxide wet gel or the second hydrated alumina wet gel；
(4) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(5) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(6) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, this method be additionally included in one of step (1), step (2) and step (3), both or three into The operation of row mixed molecular sieve, so that the hydrated alumina composition contains molecular sieve.
Production forming method according to the present invention, the side described in second aspect of method and the present invention of mixed molecular sieve Method is identical with order, is no longer described in detail herein.
In step (1), 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 (1) 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 (1) 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 (1), 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 meet the present invention second aspect described in with The i values of the hydrated alumina wet gel of the compound mixing at least two proton acceptor sites, or higher than of the invention the The i values of the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites described in two aspects.
In one embodiment, the i values of the first hydrated alumina wet gel meet second aspect institute of the present invention The i values for the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites stated, i.e., described first The i values of hydrated alumina wet gel are not less than 50%, 55% are preferably not lower than, more preferably not less than 60%.In the reality To apply in mode, the i values of the first hydrated alumina wet gel are preferably not higher than 95%, more preferably not above 90%, into One step is preferably not higher than 85%, more preferably not higher than 82%.In an example, first hydrated alumina is wet The i values of gel are 50-95%, are preferably 50-90%, more preferably 60-90%, more preferably 60-85%, further Preferably 60-82%.
According to the embodiment, the first hydrated alumina wet gel can be sent directly into step (3), and with extremely The compound mixing in few two proton acceptor sites.This is especially suitable for meeting occasion claimed below：(A) in wash mill Solid-liquid separating equipment has preferable separating capacity, it is sufficient to which the i values control of the first hydrated alumina wet gel is above-mentioned to meet Scope；(B) wash mill compact can be set with mixing arrangement so that the discharging of wash mill can be directly entered mixing dress Put.
According to the embodiment, the first hydrated alumina wet gel can also be sent into step (2), using (2-1) Handled.This is especially suitable for meeting occasion claimed below：(A) 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；(B) 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 more than 95%, can not meet the present invention The requirement mixed with the compound with least two proton acceptor sites described in second aspect.According to the embodiment, The first hydrated alumina wet gel is sent into step (2), is handled using (2-1) or (2-2).
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 for meet the occasion of second aspect requirement of the present invention and Wash mill and mixing arrangement can not compact setting occasion.
In step (2), the first hydrated alumina wet gel is handled using (2-1) or (2-2), obtains second Hydrated alumina wet gel.
In (2-1), the first hydrated alumina wet gel is mixed with water, slurries is formed, can so improve aqua oxidation Aluminium wet gel transports performance.In (2-1), the first hydrated alumina wet gel is mixed with water, is diluted, form slurry Liquid, can so improve hydrated alumina wet gel transports performance.In (2-1), the additive amount of water can be met with the slurries formed Transport subject to requirement, can be made choice according to specific conveying equipment.
The i values for the second hydrated alumina wet gel that step (2) obtains meet described in second aspect of the present invention The i values of the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites, i.e., described aqua oxidation The i values of aluminium wet gel are not less than 50%, 55% are preferably not lower than, more preferably not less than 60%.The second hydration oxygen The i values for changing aluminium wet gel are preferably not higher than 95%, more preferably not above 90%, more preferably not higher than 85%, into One step is preferably not higher than 82%.In one embodiment, the i values of the second hydrated alumina wet gel are 50-95%, Preferably 50-90%, more preferably 60-90%, more preferably 60-85%, are still more preferably 60-82%.
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 (2) 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.
As shown in Figures 2 and 3, at least part Y type molecular sieve and beta molecular sieve can be mixed in step (2).For using When mode described in (2-1) carries out, as shown in Figures 2 and 3, Y types can be mixed in dilution operation and/or separation of solid and liquid operation Molecular sieve and beta molecular sieve.
In step (3), using the method described in second aspect of the present invention by the first hydrated alumina wet gel or the Two hydrated alumina wet gels are mixed with the compound with least two proton acceptor sites, so as to obtain hydrated alumina group Compound.The i values of the first hydrated alumina wet gel and the second hydrated alumina wet gel of being sent into step (3) meet of the invention the The i values of the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites described in two aspects.
, can be according to expected hydrated alumina formed body or the pore-size distribution of aluminium oxide formed body, really in step (3) Determine hydrated alumina compositionValue, this is the 8th in the method described in the 5th according to the present invention aspect and according to the present invention It is illustrated in method described in a aspect, is no longer described in detail herein.
In step (4), the hydrated alumina composition that step (3) obtains is molded, obtains hydrated alumina shaping Thing.The shape of the molding method and molding is referred to retouch on molding correlation in the first aspect of the present invention State, details are not described herein again.
In step (5), the hydrated alumina forming matter that step (3) obtains is dried, obtains hydrated alumina shaping Body.Hydrated alumina forming matter is dried to obtain the drying condition of hydrated alumina formed body, in the 5th side of the invention Have been carried out being described in detail in method described in face, details are not described herein again.
According to the type of expected formed body, step (6) can be carried out, step (6) can not also be carried out.Carrying out step (6) when, the whole hydrated alumina formed bodys that can obtain step (5) are sent into step (6), are roasted；It can also incite somebody to action The partially hydrated aluminium oxide formed body that step (5) obtains is sent into step (6), can so prepare hydrated alumina shaping at the same time Body and aluminium oxide formed body.The condition of the roasting has been carried out detailed in the method described in the 8th aspect of the present invention Illustrate, details are not described herein again.
According to the eleventh aspect of the present invention, the present invention provides a kind of method as described in the tenth aspect of the present invention The hydrated alumina formed body or aluminium oxide formed body of preparation.
Had as hydrated alumina formed body and aluminium oxide formed body prepared by the method described in the tenth aspect of the present invention Higher intensity.Usually, the radial direction crushing strength of hydrated alumina formed body and aluminium oxide formed body can be each 10N/ More than mm, respectively preferably more than 12N/mm, respectively more preferably more than 15N/mm.In an example, hydrated alumina into The radial direction crushing strength of type body and aluminium oxide formed body is respectively 10-50N/mm.In the example that one is more highly preferred to, oxygen is hydrated The radial direction crushing strength for changing aluminium formed body and aluminium oxide formed body is respectively 15-35N/mm.
Formation system can be produced in a kind of hydrated alumina according to the tenth aspect of the present invention to carry out, production shaping System includes alumina hydrate gel production unit, separation of solid and liquid and washing unit, mixed cell, forming unit, drying unit 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, obtains hydrated alumina wet gel, the hydrated alumina wet gelValue Meet the requirement that can be mixed with the compound with least two proton acceptor sites described in second aspect of the present invention.
The separation of solid and liquid and washing unit can use common various methods to carry out separation of solid and liquid and washing, so that ArriveValue meets to mix desired alumina hydrate gel with the compound with least two proton acceptor sites.The solid-liquid Separation and washing unit can use conventional equipment for separating liquid from solid, such as：The group of filtration apparatus, centrifugal device or both Close.When separation of solid and liquid and washing unit include filtration apparatus, the filtration apparatus can be gravity filter device, pressure filtration One or more kinds of combinations in device and vacuum apparatus.Preferably, the filtration apparatus includes at least pressurization Filtration apparatus.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 are also It can include blow device, isolated solid phase is purged using natural wind or wind with pressure, is taken off so as to improve moisture The efficiency gone out.The pressure of the 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 separation of solid and liquid and washing unit obtainValue can meet the present invention second The requirement mixed with the compound with least two proton acceptor sites described in a aspect.By adjusting application pressure or The size of person's vacuum, can be to the hydrated alumina wet gel finally obtainedValue is adjusted.The separation of solid and liquid and wash When washing unit includes two or more separation of solid and liquid subelement, except last separation of solid and liquid subelement preferably use using pressure as Outside the solid-liquid separation method of motive force, remaining separation of solid and liquid separation subelement can use pressure filter and/or vacuum Filtration apparatus, can not also use pressure filter and vacuum apparatus, it is preferred to use pressure filter and/or vacuum 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.
For the trend of alumina hydrate gel material flow, separation of solid and liquid and washing unit are arranged on hydrated alumina and coagulate Between glue production unit and mixed cell, the gel solution for alumina hydrate gel production unit to be exported is separated, ObtainValue 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, the separation of solid and liquid and washing unit can include washing subelement, dilution Subelement, 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.
Production formation system according to the present invention, on the basis of the flow direction of alumina hydrate gel, the production formation system The solid-phase material of separation of solid and liquid and washing unit discharge port to mixed cell hydrated alumina wet gel input port it Between be not provided with being enough the i values of hydrated alumina wet gel are reduced to less than 50% (preferably less than 55%, more preferably 60% with Under) dewatering unit.
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 integration so as to fulfill alumina hydrate gel.
According to the twelfth aspect of the present invention, the present invention provides hydrated alumina formed body according to the present invention or Application of the aluminium oxide formed body as carrier or adsorbent.
Hydrated alumina formed body and aluminium oxide formed body according to the present invention are particularly suitable as loaded catalyst Carrier.The loaded catalyst can be it is commonly used in the art it is various can be with hydrated alumina formed body and/or aluminium oxide Catalyst of the formed body as carrier.Preferably, the catalyst is the catalyst with hydrogenation catalyst effect.That is, according to this The hydrated alumina formed body and aluminium oxide formed body of invention are particularly suitable as the load for the catalyst that there is hydrogenation catalyst to act on Body.
Can use various methods commonly used in the art (such as：Dipping) it will be born with the active component that hydrogenation catalyst acts on It is loaded on hydrated alumina formed body or aluminium oxide formed body according to the present invention, such as：Can be by using containing the activity The formed body of the aqueous solution dipping present invention of component, the formed body for being loaded with the active component then be dried and appointed The roasting of choosing, so as to obtain the catalyst that there is hydrogenation catalyst to act on.
13rd aspect according to the present invention, should the present invention provides a kind of catalyst with hydrogenation catalyst effect Catalyst contains the group VIII metallic element and vib metals element of carrier and load on the carrier, wherein, institute It is hydrated alumina formed body and/or the aluminium oxide formed body according to the present invention according to the present invention to state carrier.
The group VIII metallic element and the vib metals element can be it is commonly used in the art it is various have plus The element of hydrogen catalysis effect.Preferably, the group VIII metallic element is cobalt and/or nickel, and the vib metals element is Molybdenum and/or tungsten.The content of the group VIII metallic element and vib metals element can be according to the concrete application of catalyst Occasion makes appropriate choice.For example, when catalyst according to the invention is used for the hydrotreating of hydrocarbon ils, with the catalyst Total amount on the basis of, in terms of oxide, the content of the group VIII metallic element can be 1-10 weight %, be preferably 1.5- 8 weight %, more preferably 2-6 weight %；In terms of oxide, the content of the vib metals element can be 5-50 weights % is measured, is preferably 10-35 weight %, more preferably 20-30 weight %.
Catalyst according to the present invention with hydrogenation catalyst effect, preferably comprises organic additive, organic addition Agent is oxygen-containing organic compound and/or organic compounds containing nitrogen.The oxygen-containing organic compound is preferably selected from alcohol and carboxylic acid.It is described Organic compounds containing nitrogen is preferably selected from amine.The instantiation of the organic additive can include but is not limited to ethylene glycol, the third three Alcohol, polyethylene glycol (preferably average molecular weight is 200-1500, the average molecular weight measured using hydrogen nuclear magnetic resonance spectroscopy or Known by product description), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexane diamines Tetraacethyl, citric acid, tartaric acid, malic acid, ethylenediamine, ethylenediamine tetra-acetic acid and ethylenediamine tetra-acetic acid ammonium salt in one kind or It is two or more.
The organic additive and the group VIII metallic element in terms of oxide and the sum of vib metals element rub Your ratio can be 0.03-2：1, it is preferably 0.08-1.5：1, more preferably 0.1-1：1, more preferably 0.2-0.8：1, Still more preferably it is 0.3-0.5：1.
14th aspect according to the present invention, the present invention provides a kind of system of the catalyst with hydrogenation catalyst effect Preparation Method, this method are included in supported on carriers group VIII metallic element and vib metals element, wherein, this method is also Including preparing hydrated alumina formed body and/or aluminium oxide formed body as carrier using the previously described method of the present invention.
The group VIII metallic element is preferably cobalt and/or nickel, the vib metals element be preferably molybdenum and/or Tungsten.Load capacity of the hydrogenation active component on carrier can carry out appropriate choosing according to the concrete application occasion of catalyst Select.For example, when the catalyst of preparation is used for the hydrotreating of hydrocarbon ils, on the basis of the total amount of the catalyst of preparation, described the The load capacity of group VIII metal element and vib metals element on the carrier causes in the catalyst that finally prepares The content of group VIII metal element and vib metals element disclosure satisfy that the requirement described in the 13rd aspect of the present invention.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, can use commonly used in the art each Kind method loads group VIII metallic element and vib metals element on the carrier, such as：Dipping.The dipping It can be that saturation impregnates, or excessive dipping.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, can be at the same time by group VIII metal Element and the load of vib metals element on the carrier, can also be by several times by group VIII metallic elements and group VIB gold Belong to element load on the carrier.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, by group VIII metallic element and Vib metals element load on the carrier before, among or afterwards, be preferably also included in the supported on carriers extremely A kind of the step of few organic additive, the organic additive and its species and load capacity in the 13rd aspect of the present invention Through being described in detail, no longer it is described in detail herein.The organic additive can be supported on by the load using conventional method On body, it is preferable that loaded the organic additive on the carrier using the method for dipping.It is highly preferred that by carrier with Maceration extract contact containing group VIII metallic element, vib metals element and the organic additive, so that by the Group VIII metal element, vib metals element and organic additive load on the carrier at the same time.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, can be in condition commonly used in the art The lower carrier for obtaining dipping is dried and optionally roasts.Usually, the condition of the drying includes：Temperature can be 100-300 DEG C, be preferably 100-280 DEG C, more preferably 120-250 DEG C；It is preferably 2-8 when duration can be 1-12 small Hour, when more preferably 3-6 is small.The condition of the roasting includes：Temperature can be 350-550 DEG C, be preferably 400-500 DEG C； When duration can be 1-10 small, when being preferably 2-8 small.
15th aspect according to the present invention, the present invention provides a kind of hydrotreating method, this method, which is included in, to be added Under hydrogen treatment conditions, hydrocarbon ils is contacted with the catalyst with hydrogenation catalyst effect, wherein, it is described to have what hydrogenation catalyst acted on Catalyst is prepared for the catalyst described in the 13rd aspect of the present invention or as the method described in the 14th aspect of the present invention Catalyst.
The hydrotreating method of the present invention is not particularly limited for the species and hydroprocessing condition of hydrocarbon ils, can be this The conventional selection in field.Specifically, the hydrocarbon ils can be selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, take Hold in the palm the one or more in artificial oil, liquefied coal coil, frivolous coal tar and heavy deasphalted oil.The hydrotreating method of the present invention is special Hydrocarbon ils Shi Yongyu be hydrocracked or hydro-upgrading is carried out to poor ignition quality fuel.
Hydrotreating method according to the present invention, the catalyst before the use, can be in the normal conditions of this area Lower carry out presulfurization.The condition of presulfurization for example can be in presence of hydrogen, with sulphur, vulcanization at a temperature of 140-370 DEG C Hydrogen carries out presulfurization containing sulfur feedstock, and the presulfurization can carry out also In-situ sulphiding in reactor outside reactor.
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 10g hydration compositions 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), water absorption rate is calculated using formula III：
In following embodiments and comparative example, butt measures sample to be tested when 600 DEG C of roastings 4 are small, for roasting Afterwards before the quality of sample and roasting the quality of sample ratio.
In following embodiments and comparative example, using the 3271 type x-ray fluorescence light of Japanese mechanics electric machine industry Co., Ltd. Spectrometer, the composition of method measure catalyst with reference to specified in Petrochemical Engineering Analysis method RIPP133-90.
In following embodiments and comparative example, using U.S.'s Kang Ta companies Poremaster33 type mercury injection apparatuses, with reference to GB/T Mercury injection method specified in 21650.1-2008 measures most probable pore size.
Embodiment 1-11 is used to illustrate hydrated alumina composition, formed body of the present invention and preparation method thereof.
Embodiment 1
The hydrated alumina wet gel used in the present embodiment is that (sodium metaaluminate-aluminum sulfate method, is derived from Chinese stone by acid system Change Chang Ling branch company) prepare alumina hydrate gel solution washed and be obtained by filtration boehmite wet cake (will Wet cake numbering is SLB-1), after measured, the i values of the wet cake are 78.2%.
(1) (the sinopec catalyst Chang Ling branch company production of 4.94kg Y type molecular sieves is added into 50kg wet cakes SLB-1 Product, lattice constant areButt is 0.75, and sodium oxide content is less than 0.8 weight %) and 0.51kg beta molecular sieves (middle stone Change catalyst Chang Ling branch company product, silica alumina ratio 50, butt 0.81, sodium oxide content are less than 0.05 weight %), then add 10kg water is mixed with beating 5 minutes, is then filtered slurries with band filter, obtains wet cake SLBY-1.After measured should The i values of wet cake SLBY-1 are 80.8%；By wet cake SLBY-1 600 DEG C roasting 3 it is small when after, measure, aluminium oxide with point The weight ratio of son sieve is 65：35, the weight ratio of beta molecular sieve and Y type molecular sieve is 10：90.
(2) wet cake that 200g numberings are SLBY-1 is placed in beaker, then adds 4.2g methylcellulose and (be purchased from Zhejiang Jiang Haishen Chemical Co., Ltd.s, similarly hereinafter) and 3.6g sesbania powders (content of galactomannans is 80 weight %, purchased from Beijing Reagent Company is learned, similarly hereinafter), using mechanical agitator stirring after ten minutes, obtained mixture is hydrated alumina of the invention Composition, its nature parameters are listed in table 1.
(3) the hydrated alumina composition for preparing step (2) is in F-26 types double screw extruder (section of South China Science ＆ Engineering University On skill industry head factory system, similarly hereinafter) extrusion is carried out using the dish-shaped orifice plate of Ф 1.6mm.Wherein, extrusion process is smooth, extrudate table Face Glabrous thorn.
(4) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 3 is small in 120 DEG C, air atmosphere, Hydrated alumina formed body HT-1 is obtained, its nature parameters is listed in table 1.
(5) by step (4) prepare hydrated alumina formed body roasted in 580 DEG C, air atmosphere 4 it is small when, obtain oxygen Change aluminium formed body OT-1, its nature parameters is listed in table 1.
Comparative example 1
(1) wet cake that 100kg numberings are SLB-1 is spray-dried, obtains boehmite dry glue powder, the plan is thin The butt of diaspore dry glue powder is 0.7.The boehmite powder (is placed in sealing in environment temperature (25-30 DEG C) and sealing condition In polybag) under place 72 it is small when, do not detected after placement and form gibbsite.
The boehmite dry glue powder and the 135.6g Y type molecular sieves (with embodiment 1) that (2) prepare 300g steps (1), (weight ratio of aluminium oxide and molecular sieve is 65 to 13.9g beta molecular sieves (with embodiment 1)：35, beta molecular sieve and Y type molecular sieve Weight ratio be 10：90), 4.7g methylcellulose (with embodiment 1), 4.1g sesbania powders (with embodiment 1) and 400mL contain 11mL concentration is that the aqueous solution of the concentrated nitric acid of 65 weight % is stirred after ten minutes using mechanical agitator, obtains mixture.
(3) mixture prepared by step (2) is used into method extrusion same as Example 1, prepares aqua oxidation respectively Aluminium formed body DHT-1 and aluminium oxide formed body DOT-1, its nature parameters are listed in table 1.
Embodiment 2
(1) wet cake and 500g deionized waters that 5kg numberings are SLBY-1 are mixed with beating 1 minute, then will obtained Slurries are sent into plate and frame type filter-press, and the pressure of sheet frame is adjusted to 0.7MPa and is kept for 15 minutes, and obtaining wet cake, (numbering is LBY-1).After measured, the i values for the wet cake that numbering is LBY-1 are 67%.
(2) wet cake that 300g numberings are LBY-1 is placed in beaker, adds 4.0g hydroxyethylmethylcelluloses and (be purchased from Shanghai Hui Guang Fine Chemical Co., Ltd, similarly hereinafter) and 2.0g sesbania powders (content of galactomannans is 85 weight %, is purchased from Beijing chemical reagents corporation), using mechanical agitator stirring after ten minutes, the hydrated alumina composition of the present invention is obtained, its Property is listed in table 1.
(3) the hydrated alumina composition for preparing step (2) utilizes Ф 2.0mm's on F-26 type double screw extruders Circular orifice carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(4) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 2 is small in 150 DEG C, air atmosphere, Hydrated alumina formed body HT-2 is obtained, its nature parameters is listed in table 1.
(5) by step (4) prepare hydrated alumina formed body roasted in 480 DEG C, air atmosphere 8 it is small when, obtain oxygen Change aluminium formed body OT-2, its nature parameters is listed in table 1.
Embodiment 3
Formed body is prepared using method same as Example 2, unlike, without using sesbania powder, hydroxyl second in step (2) The dosage of ylmethyl cellulose is 5.7g, hydrated alumina composition, hydrated alumina formed body HT-3 and the oxidation of preparation The property of aluminium formed body OT-3 is listed in table 1.
Embodiment 4
Formed body is prepared using method same as Example 2, unlike, without using hydroxyethyl methyl in step (2) Cellulose, the dosage of sesbania powder are 6.7g, hydrated alumina composition, hydrated alumina formed body HT-4 and the oxidation of preparation The property of aluminium formed body OT-4 is listed in table 1.
Embodiment 5
Formed body is prepared using method same as Example 2, unlike, in step (2), in addition hydroxyethyl methyl When cellulose and sesbania powder, 2.9g nitric acid (HNO is also added3Content be 65 weight %), the hydrated alumina composition of preparation, The property of hydrated alumina formed body HT-5 and aluminium oxide formed body OT-5 are listed in table 1.
Comparative example 2
(1) by 300g numberings be LBY-1 wet cake in 95 DEG C, air atmosphere it is dry 2 it is small when, obtain boehmite Powder, the i values of the boehmite powder are 40%.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) boehmite powder prepared by 165g steps (1) is placed in beaker, adds 4.0g hydroxyethylmethylcelluloses (with embodiment 2) and 2.0g sesbania powders (with embodiment 2), using mechanical agitator stirring after ten minutes, obtain boehmite Composition.
(3) boehmite combination of compositions thing prepared by step (2) is utilized into Ф on F-26 type double screw extruders The circular orifice of 2.0mm carries out extrusion.Wherein, extruder Frequent trip during extrusion, extrudate surface are smooth.
(4) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 2 is small in 150 DEG C, air atmosphere, Hydrated alumina formed body DHT-2 is obtained, its nature parameters is listed in table 1.
(5) by step (4) prepare hydrated alumina formed body roasted in 480 DEG C, air atmosphere 8 it is small when, obtain oxygen Change aluminium formed body DOT-2, its nature parameters is listed in table 1.
Comparative example 3
Hydrated alumina composition is prepared using method same as Example 2, unlike, without using hydroxyethyl methyl Cellulose and sesbania powder, but with 6.0g paraffin.As a result the hydrated alumina composition can not carry out extrusion molding.
Comparative example 4
Hydrated alumina composition is prepared using method same as Example 2, unlike, without using hydroxyethyl methyl Cellulose and sesbania powder, but with 6.0g wood powders.As a result the hydrated alumina composition can not carry out extrusion molding.
Comparative example 5
It is molded using the method identical with comparative example 2, unlike, without step (2), but by step (1) The boehmite powder of preparation, which is sent directly into step (3), carries out extrusion.Wherein, extruder caloric value larger (performance during extrusion It is hot for banded extruder fuselage, there are a large amount of hot gas to emerge), and extruder Frequent trip during extrusion, extrudate surface hairiness Thorn.The hydrated alumina formed body being prepared is labeled as DHT-3, and the aluminium oxide formed body being prepared is labeled as DOT-3, its Nature parameters are listed in table 1 respectively.
Embodiment 6
(1) wet cake that 300g numberings are LBY-1 is placed in beaker, adds 3.0g hydroxypropyl methyl celluloses and (be purchased from Zhejiang Hai Shen Chemical Co., Ltd.s, similarly hereinafter) and 2.9g sesbania powders (content of galactomannans is 85 weight %), using machinery Blender stirs the hydrated alumina composition for after ten minutes, obtaining the present invention, its property is listed in table 1.
(2) the hydrated alumina composition for preparing step (1) is in SK132S/4 types single screw extrusion machine (U.S. BONNT Company system) on using the orifice plate that the circular and middle cylinder with a 1.5mm for being Ф 4.5mm by overall diameter collectively constitutes into Row extrusion.Wherein, extrusion process is smooth, extrudate (for Raschig ring) surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 5mm, when drying 3 is small in 70 DEG C, air atmosphere by wet bar Afterwards, when then drying 2 is small in 100 DEG C, air atmosphere, hydrated alumina formed body HT-6 is obtained, its nature parameters is in table 1 List.
(4) by step (4) prepare hydrated alumina formed body roasted in 650 DEG C, air atmosphere 3 it is small when, obtain oxygen Change aluminium formed body OT-6, its nature parameters is listed in table 1.
Embodiment 7
(1) wet cake that 300g numberings are LBY-1 is placed in beaker, adds 2.7g methylcellulose, 1.5g hydroxypropyls Methylcellulose and 4g sesbania powders (content of galactomannans is 85 weight %), are stirred 10 minutes using mechanical agitator Afterwards, the hydrated alumina composition of the present invention is obtained, its nature parameters is listed in table 1.
(2) the hydrated alumina composition for preparing step (1) utilizes Ф 3.0mm's on F-26 type double screw extruders Cloverleaf pattern orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 3 is small in 120 DEG C, air atmosphere, Hydrated alumina formed body HT-7 is obtained, its nature parameters is listed in table 1.
(4) by step (4) prepare hydrated alumina formed body roasted in 600 DEG C, air atmosphere 4 it is small when, obtain oxygen Change aluminium formed body OT-7, its nature parameters is listed in table 1.
Embodiment 8
(1) wet cake that 300g numberings are LBY-1 is placed in beaker, adds 2.6g hydroxyethylmethylcelluloses and 1.4g Hydroxypropyl methyl cellulose, using mechanical agitator stirring after ten minutes, obtains the hydrated alumina composition of the present invention, its property Matter parameter is listed in table 1.
(2) the hydrated alumina composition for preparing step (1) utilizes Ф 1.8mm's on F-26 type double screw extruders Dish-shaped orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 5mm, when by wet bar, drying 2 is small in 250 DEG C, air atmosphere, Hydrated alumina formed body HT-8 is obtained, its nature parameters is listed in table 1.
(4) by step (4) prepare hydrated alumina formed body roasted in 600 DEG C, air atmosphere 3 it is small when, obtain oxygen Change aluminium formed body OT-8, its nature parameters is listed in table 1.
Embodiment 9
Hydrated alumina composition, hydrated alumina formed body and aluminium oxide are prepared using method same as Example 2 Formed body, unlike, without step (2), but in step (1), added while adding 650g water and being mixed with beating Methylcellulose and sesbania powder, wherein, the dosage of methylcellulose is 24g, and (content of galactomannans is 80 weights to sesbania powder Measure %) dosage be 32g；
In step (3), hydrated alumina composition prepared by step (2) is utilized into Ф on F-26 type double screw extruders The dish-shaped orifice plate of 1.5mm carries out extrusion；
In step (5), by step (4) prepare hydrated alumina formed body roasted in 600 DEG C, air atmosphere 3 it is small when.
The property ginseng of the hydrated alumina composition of preparation, hydrated alumina formed body HT-9 and aluminium oxide formed body OT-9 Number is listed in table 1.
Embodiment 10
The hydrated alumina wet gel used in the present embodiment is by CO2Method (sodium aluminate-CO2Method, is derived from Shanxi Province Shan County Emerging great catalyst new material Co., Ltd) the alumina hydrate gel solution thin water aluminium of plan that is washed and be obtained by filtration for preparing Stone wet cake (being SLB-2 by wet cake numbering), after measured, the i values of the wet cake are 65.3%.
(1) (the sinopec catalyst Chang Ling branch company production of 0.027kg Y type molecular sieves is added into 1kg wet cakes SLB-2 Product, lattice constant areButt is 0.5, and sodium oxide content is less than 0.8 weight %) and 0.026kg beta-molecular sieve (sinopecs Catalyst Chang Ling branch company product, silica alumina ratio 40, butt 0.52, sodium oxide content are less than 0.05 weight %), then add 0.5kg water is mixed with beating 10 minutes, is then filtered slurries with band filter, obtains wet cake SLBY-2.After measured The i values of wet cake SLBY-2 are 61.2%；By wet cake SLBY-2 600 DEG C roasting 3 it is small when after, measure aluminium oxide with point The weight ratio of son sieve is 90：10, the weight ratio of Y type molecular sieve and beta molecular sieve is 50：50.
(2) wet cake that 1.12kg numberings are SLBY-2 is placed in beaker, then adds 14g methylcellulose and 22g Sesbania powder (content of galactomannans is 80 weight %), using mechanical agitator stirring after ten minutes, obtained mixture For the hydrated alumina composition of the present invention, its nature parameters is listed in table 1.
(2) the hydrated alumina composition for preparing step (1) utilizes Ф 2.4mm's on F-26 type double screw extruders Dish-shaped orifice plate carries out extrusion, and extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 2 is small in 130 DEG C, air atmosphere, Hydrated alumina formed body HT-10 is obtained, its nature parameters is listed in table 1.
(4) by step (3) prepare hydrated alumina formed body roasted in 550 DEG C, air atmosphere 3 it is small when, obtain oxygen Change aluminium formed body OT-10, its nature parameters is listed in table 1.
Embodiment 11
The hydrated alumina wet gel used in the present embodiment is derived from the neat cyclopentadienyl catalyst Co., Ltd of Shandong Zibo, be by Boehmite dry powder (butt 0.7) prepared by 1000g acid systems (sodium aluminate-aluminum sulfate method) roasts in 700 DEG C, air atmosphere Burn 3 it is small when, obtain 700g aluminium oxide, 700g aluminium oxide be placed in 10L autoclaves, stirred evenly with 5L deionized waters Afterwards, autoclave is sealed, 6h is reacted under 150 DEG C, self-generated pressure, after reaction, the temperature of autoclave is down to After room temperature (for 25 DEG C), the slurries that reaction is obtained are sent into plate and frame type filter-press, by the sheet frame pressure tune of plate and frame filter Save as 0.5MPa and kept for 10 minutes, the filter cake 3 minutes in sheet frame is then swept with the wind with pressure of 10MPa, sheet frame pressure release obtains Hydrated alumina wet cake LB-3.After measured, the thing of the wet cake is mutually boehmite, and the i values of the wet cake are 63.0%.
(1) 0.32kg Y type molecular sieves (with embodiment 10) and 0.31kg β type molecules are added into 825g wet cakes LB-3 Sieve then adds 0.5kg water and is mixed with beating 10 minutes, then filtered slurries with band filter (with embodiment 10), Obtain wet cake SLBY-3.The i values of wet cake SLBY-3 are 63.9% after measured；By wet cake SLBY-3 in 600 DEG C of roastings Burn 3 it is small when after, the weight ratio for measuring aluminium oxide and molecular sieve is 40：60, the weight ratio of Y type molecular sieve and beta molecular sieve is 50： 50。
(2) wet cake that 300g numberings are SLBY-3 is placed in beaker, then adds 3.2g methylcellulose and 5g fields Cyanines powder (content of galactomannans is 85 weight %), using mechanical agitator stirring after ten minutes, obtained mixture is The hydrated alumina composition of the present invention, its nature parameters are listed in table 1.
(3) the hydrated alumina composition for preparing step (1) utilizes Ф 2.4mm's on F-26 type double screw extruders Dish-shaped orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(4) extrudate is cut into the wet bar that length is about 5mm, when by wet bar, drying 2 is small in 150 DEG C, air atmosphere, Hydrated alumina formed body HT-11 is obtained, its nature parameters is listed in table 1.
(5) by step (3) prepare hydrated alumina formed body roasted in 600 DEG C, air atmosphere 4 it is small when, obtain oxygen Change aluminium formed body OT-11, its nature parameters is listed in table 1.
Comparative example 6
Hydrated alumina wet cake LB-3 prepared by embodiment 11 is spray-dried, obtains boehmite dry glue powder (butt 0.7).The boehmite dry glue powder is under environment temperature (25-30 DEG C) and sealing condition (being placed in sealed plastic bag) Place 72 it is small when, do not detected after placement and form gibbsite.
By 300g boehmites dry glue powder and 315g Y type molecular sieves (with embodiment 11), 303g beta-molecular sieves (same to embodiment 11), 3.6g methylcellulose (with embodiment 11), 5.7g sesbania powders (with embodiment 11) and 400mL concentration containing 11mL are 65 The aqueous solution of the concentrated nitric acid of weight % is stirred after ten minutes using mechanical agitator, obtains mixture.
The mixture of preparation is used into the method extrusion identical with embodiment 11, prepares hydrated alumina formed body respectively DHT-4 and aluminium oxide formed body DOT-4, its nature parameters are listed in table 1.
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 Increase rate before the content of gibbsite in composition and relatively placement.
Embodiment 1-11's as a result, it was confirmed that the present invention by hydrated alumina wet gel without being dried to dry glue powder, but directly Connect and mixed with the compound with least two proton acceptor sites, obtained mixture is used directly for being molded, and obtains Formed body there is higher intensity, so as to avoid it is existing prepare formed body using dry glue powder as starting material when existing work The problem of industry bad environments and high energy consumption.Also, hydrated alumina composition according to the present invention, by adjusting itValue, can be with Aperture is prepared in bimodal distribution or the formed body of Unimodal Distribution, so as to meet the requirement of different use occasions.
EXPERIMENTAL EXAMPLE 1-8 is used to illustrate catalyst according to the present invention with hydrogenation catalyst effect and preparation method thereof And hydrotreating method.
EXPERIMENTAL EXAMPLE 1
At a temperature of 25 DEG C, by the dissolving of ammonium metatungstate, nickel nitrate and citric acid in deionized water, maceration extract is formed, When the aluminium oxide formed body 1 prepared using saturation impregnation 100g embodiments 1 is small, obtained mixture will be impregnated in 120 It is DEG C dry 2 it is small when, then 150 DEG C it is dry 3 it is small when, obtain catalyst OC-1.Wherein, in the maceration extract, citric acid with The tungsten of oxide meter and the molar ratio of nickel are 0.3.By the catalyst OC-1 of preparation in 600 DEG C roasting 4 it is small when after measure its composition, As a result listed in table 2.
Experimental comparison's example 1
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike, aluminium oxide formed body is comparative example 1 The aluminium oxide formed body of preparation.The catalyst being prepared is denoted as DOC-1, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 2
At a temperature of 30 DEG C, by the dissolving of ammonium metatungstate, nickel nitrate and ethylenediamine in deionized water, maceration extract is formed, When the aluminium oxide formed body 1 prepared using saturation impregnation 100g embodiments 2 is small, obtained mixture will be impregnated in 120 It is DEG C dry 2 it is small when, then 180 DEG C it is dry 3 it is small when, obtain catalyst HC-2.Wherein, in the maceration extract, ethylenediamine with The tungsten of oxide meter and the molar ratio of nickel are 0.36.By the catalyst OC-2 of preparation in 600 DEG C roasting 4 it is small when after measure its group Into as a result being listed in table 2.
EXPERIMENTAL EXAMPLE 3
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 2, unlike, aluminium oxide formed body is embodiment 3 The aluminium oxide formed body of preparation.The catalyst of preparation is denoted as OC-3, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 4
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 2, unlike, aluminium oxide formed body is embodiment 4 The aluminium oxide formed body of preparation.The catalyst of preparation is denoted as OC-4, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 5
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 2, unlike, aluminium oxide formed body is embodiment 5 The aluminium oxide formed body of preparation.The catalyst of preparation is denoted as OC-5, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 6
At a temperature of 35 DEG C, ammonium metatungstate, ammonium molybdate, nickel nitrate and citric acid are dissolved in deionized water, formed Maceration extract, when the aluminium oxide formed body 1 prepared using saturation impregnation 100g embodiments 11 is small, will impregnate obtained mixing Thing then when 180 DEG C of dryings 4 are small, obtains catalyst HC-6 when 120 DEG C of dryings 2 are small.Wherein, in the maceration extract, lemon The molar ratio of acid and molybdenum, nickel and the tungsten counted using oxide is 0.36.By the catalyst OC-6 of preparation in 600 DEG C roasting 4 it is small when after Its composition is measured, is as a result listed in table 2.
Experimental comparison's example 2
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 6, unlike, aluminium oxide formed body is comparative example 6 The aluminium oxide formed body of preparation.The catalyst being prepared is denoted as DOC-2, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 7
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike, aluminium oxide formed body embodiment 1 The hydrated alumina formed body of preparation replaces.The catalyst being prepared is denoted as HC-1, its composition is listed in table 2.
Experimental comparison's example 3
Catalyst is prepared using the method identical with Experimental comparison's example 1, unlike, aluminium oxide formed body comparative example 1 The hydrated alumina formed body of preparation replaces.As a result, during dipping, the structural breakdown of hydrated alumina formed body, nothing Method prepares preformed catalyst.
EXPERIMENTAL EXAMPLE 8
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 6, unlike, aluminium oxide formed body embodiment 11 The hydrated alumina formed body of preparation replaces.The catalyst being prepared is denoted as HC-2, its composition is listed in table 2.
Experimental comparison's example 4
Catalyst is prepared using the method identical with Experimental comparison's example 2, unlike, aluminium oxide formed body comparative example 6 The hydrated alumina formed body of preparation replaces.As a result, during dipping, the structural breakdown of hydrated alumina formed body, nothing Method prepares preformed catalyst.
Table 2
Testing example 1-8 is used to illustrate method for hydrogen cracking according to the present invention.
Testing example 1-8
The catalytic performance of the EXPERIMENTAL EXAMPLE 1-8 catalyst prepared is evaluated using following methods, experimental result exists Listed in table 3.
It is real to experiment respectively on micro fixed-bed reactor using the naphthane of 99 weight % of purity as raw material (analysis is pure) A catalytic performance of the catalyst of 1-8 preparations in naphthane reaction is applied, wherein, the loadings of catalyst are 1.0g, reaction temperature Spend for 370 DEG C, pressure is 5.0MPa (gauge pressure), air speed 6h-1。
Using DOC-1 prepared by Experimental comparison's example 1 as reference catalyst, its catalytic performance is defined as 100%, is calculated At a temperature of 370 DEG C remaining catalyst relative to DOC-1 relative conversion, naphthane conversion ratio be 35% under conditions of its Remaining catalyst relative to DOC-2 relative selectivity.
Wherein, conversion ratio refers to the conversion ratio of naphthane, is calculated using formula IV：
In formula IV, C is the conversion ratio of naphthane,
m1For the mass fraction of naphthane in raw material,
m2For the mass fraction of naphthane in product；
Selectivity refers to the overall selectivity of benzene, toluene and dimethylbenzene, is calculated using Formula V：
In Formula V, m3For the mass fraction of benzene, toluene and dimethylbenzene in product,
C is the conversion ratio of naphthane.
Test comparison example 1-2
Using the method identical with testing example 1-8 respectively to the catalytic of Experimental comparison's example 1-2 catalyst prepared It can be evaluated, experimental result is listed in table 3.
Table 3
Numbering Catalyst is numbered Relative conversion (%) Relative selectivity (%)
Testing example 1 OC-1 110 116
Test comparison example 1 DOC-1 100 100
Testing example 2 OC-2 107 120
Testing example 3 OC-3 104 114
Testing example 4 OC-4 103 112
Testing example 5 OC-5 103 113
Testing example 6 OC-6 153 149
Test comparison example 2 DOC-2 125 123
Testing example 7 HC-1 114 121
Testing example 8 HC-2 162 157
Testing example 1-8's as a result, it was confirmed that with hydrated alumina formed body according to the present invention and aluminium oxide formed body As catalyst prepared by carrier in hydrocarbon oil hydrogenation processing reaction, the catalytic activity of higher is shown.
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 described in above-mentioned embodiment Each particular technique feature, in the case of reconcilable, can be combined by any suitable means, in order to avoid not Necessary repetition, the present invention no longer separately illustrate various combinations of possible ways.In addition, a variety of implementations of the present invention It can also be combined between mode, as long as it without prejudice to the thought of the present invention, it is public that it should equally be considered as institute of the invention The content opened.

Claims (44)

1. a kind of hydrated alumina composition, said composition contains hydrated alumina, molecular sieve and has at least two protons The compound of acceptor site,
The compositionIt is worth for less than 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 for less than 4, preferably less than 3.5；
It is it is highly preferred that describedIt is worth for more than 1.2, preferably more than 1.3, more preferably more than 1.4；
It is further preferred thatIt is worth for 1.2-5, preferably 1.3-4, more preferably 1.3-3.5.
3. composition 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 4- 18 parts by weight.
4. according to the composition described in any one in claim 1-3, wherein, the hydrated alumina, which contains, intends thin water aluminium Stone；
Preferably, the hydrated alumina is boehmite.
5. composition according to claim 4, 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 1.1-1.5%.
6. according to the composition described in any one in claim 1-5, wherein, the hydrated alumina is directed to hydration Aluminium oxide wet gel.
7. according to the composition described in any one in claim 1-6, wherein, using the total amount of the composition after roasting as base Standard, the content of molecular sieve is 0.5-90 weight %, is preferably 1-80 weight %, more preferably 5-70 weight %, further preferably For 10-60 weight %；The content of aluminium oxide is 10-99.5 weight %, is preferably 20-99 weight %, more preferably 30-95 weights %, more preferably 40-90 weight % are measured, the roasting carries out at a temperature of 600 DEG C, and the duration of the roasting is 3 it is small when.
8. according to the composition described in any one in claim 1-7, wherein, the composition is free of peptizing agent.
9. a kind of preparation method of hydrated alumina composition, this method includes mixing each component in a kind of feedstock composition Close, obtain the hydrated alumina composition, the feedstock composition contains hydrated alumina wet gel, molecular sieve and has The compound at least two proton acceptor sites, the i values of the hydrated alumina wet gel be not less than 50%, it is described to have extremely The dosage of the compound in few two proton acceptor sites causes the composition finally preparedIt is worth for less than 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,
10. according to the method described in claim 9, wherein, the use of the compound with least two proton acceptor sites Amount causes the hydrated alumina composition preparedIt is worth for less than 4, preferably less than 3.5；
It is highly preferred that the dosage of the compound with least two proton acceptor sites causes the hydrated alumina group prepared CompoundValue more than 1.2, is preferably more than 1.3, and more preferably more than 1.4；
It is further preferred thatIt is worth for 1.2-5, preferably 1.3-4, more preferably 1.3-3.5.
11. the method according to claim 9 or 10, wherein, the i values of the hydrated alumina wet gel be not higher than 95%, 90%, more preferably not above 85% are preferably not higher than, more preferably not higher than 82%；
Preferably, the i values of the hydrated alumina wet gel are not less than 55%, are preferably not lower than 60%；
It is highly preferred that the i values of the hydrated alumina wet gel are 50-95%, and it is preferably 50-90%, more preferably 60- 90%, more preferably 60-85%, are still more preferably 60-82%.
12. according to the method described in any one in claim 9-11, wherein, the hydrated alumina wet gel is not undergo Make the hydrated alumina wet gel for the dehydration that its i value is less than 50%, preferably less than 55%, more preferably less than 60%.
13. according to the method described in any one in claim 9-12, wherein, the hydrated alumina wet gel is by least After a kind of alumina hydrate gel solution alternatively carries out aging, carry out washing and separation of solid and liquid obtained from；
Preferably, the alumina hydrate gel solution is using one kind in the precipitation method, Hydrolyze method, kind point-score and rapid dehydration method Or two or more methods are prepared.
14. according to the method described in any one in claim 9-13, wherein, the feedstock composition is free of peptizing agent.
15. according to the method described in any one in claim 9-14, wherein, the content of molecular sieve in the raw mixture So that on the basis of the total amount of the hydrated alumina composition after roasting, the content of molecular sieve is 0.5-90 weight %, is preferably 1-80 weight %, more preferably 5-70 weight %, more preferably 10-60 weight %；The content of aluminium oxide is 10-99.5 weights % is measured, is preferably 20-99 weight %, more preferably 30-95 weight %, more preferably 40-90 weight %, the roasting exist Carried out at a temperature of 600 DEG C, when the duration of the roasting is 3 small.
16. according to the method described in any one in claim 9-15, wherein, in the raw mixture, relative to 100 weights Part hydrated alumina wet gel is measured, the content of the compound with least two proton acceptor sites is 1-25 parts by weight, Preferably 2-20 parts by weight, more preferably 4-18 parts by weight, the hydrated alumina wet gel is in terms of hydrated alumina.
17. according to the method described in any one in claim 9-16, wherein, the method for the mixing for stirring and/or is pinched Close.
18. in the composition or claim 9-17 according to any one in claim 1-8 described in any one Method, wherein, in the compound with least two proton acceptor sites, proton acceptor site is can form hydrogen bond with water One or both of F, O and N more than；
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 10-80 weight %, is preferably 15-70 weight %, more preferably 30-60 weight %；The content of the cellulose ether is 20-90 weight %, are preferably 30-85 weight %, more preferably 40-70 weight %.
19. any one institute in the composition or claim 9-18 according to any one in claim 1-8 and 18 The method stated, wherein, the molecular sieve contains Y type molecular sieve and beta molecular sieve；
Preferably, on the basis of the total amount of molecular sieve, the content of the Y type molecular sieve is 10-95 weight %, is preferably 30-92 Weight %, more preferably 50-90 weight %；The content of the beta molecular sieve is 5-90 weight %, is preferably 8-70 weight %, More preferably 10-50 weight %.
20. hydrated alumina composition prepared by a kind of method in 9-19 as claim described in any one.
21. a kind of hydrated alumina formed body, the hydrated alumina formed body is by any one in claim 1-8 and 18-19 Hydrated alumina composition described in the hydrated alumina composition or claim 20 is formed.
22. hydrated alumina formed body according to claim 21, wherein, measured by mercury injection method, the hydrated alumina into The pore-size distribution of type body is in bimodal distribution, and most probable pore size is respectively 4-20nm and more than 20nm；Or
Measured by mercury injection method, the pore-size distribution of the hydrated alumina formed body is in Unimodal Distribution, most probable pore size 4-30nm.
23. a kind of preparation method of hydrated alumina formed body, this method includes will be any one in claim 1-8 and 18-19 Hydrated alumina composition described in or the hydrated alumina composition described in claim 20 are molded, by what is obtained Molding is dried.
24. the method according to claim 11, wherein, the hydrated alumina compositionIt is worth for 1.8-5, is preferably 1.85-4, more preferably 1.9-3.5；Or
The hydrated alumina compositionIt is worth for 1.2 to less than 1.8, being preferably 1.3-1.7, is more preferably 1.4-1.7.
A kind of 25. hydrated alumina formed body prepared by method as described in claim 23 or 24.
26. a kind of aluminium oxide formed body, the aluminium oxide formed body is as the water described in any one in claim 1-8 and 18-19 Hydrated alumina composition described in conjunction alumina composition or claim 19 is formed.
27. aluminium oxide formed body according to claim 26, wherein, measured by mercury injection method, the hole of the aluminium oxide formed body Footpath distribution is in bimodal distribution, and most probable pore size is respectively 4-20nm and more than 20nm；Or
Measured by mercury injection method, the pore-size distribution of the aluminium oxide formed body is in Unimodal Distribution, most probable pore size 4-30nm.
28. a kind of preparation method of aluminium oxide formed body, this method is included any one institute in claim 1-8 and 18-19 The hydrated alumina composition described in hydrated alumina composition or claim 20 stated is molded, the shaping that will be obtained Thing is dried and roasts.
29. the method according to claim 11, wherein, the alumina compositionIt is worth for 1.8-5, preferably 1.85- 4, more preferably 1.9-3.5；Or
The alumina compositionIt is worth for 1.2 to less than 1.8, being preferably 1.3-1.7, is more preferably 1.4-1.7.
A kind of 30. aluminium oxide formed body prepared by method as described in claim 28 or 29.
31. hydrated alumina formed body, claim 26,27 and according to any one in claim 21,22 and 25 Aluminium oxide formed body in 30 described in any one, wherein, the hydrated alumina formed body and the aluminium oxide formed body Radial direction crushing strength is respectively 10-50N/mm, is preferably 15-35N/mm.
32. a kind of production forming method of hydrated alumina, this method comprise the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed and separation of solid and liquid, The first hydrated alumina wet gel is obtained, the condition of the separation of solid and liquid causes the i values of the first hydrated alumina wet gel Not less than 50%, to be preferably not lower than 55%, more preferably not less than 55%, more preferably not above 95%, it is further excellent Elect as not higher than 90%, more preferably not higher than 85%, more preferably not higher than 82%；
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,
(2) use the method in claim 9-19 described in any one by the first hydrated alumina wet gel with having extremely The compound mixing in few two proton acceptor sites, obtains hydrated alumina composition；
(3) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(4) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(5) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, this method is additionally included in the operation that mixed molecular sieve is carried out in step (1) and/or step (2), so that the water Close alumina composition and contain molecular sieve.
33. a kind of production forming method of hydrated alumina, this method comprise the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the first water Close aluminium oxide wet gel；
(2) the first hydrated alumina wet gel is handled using (2-1) or (2-2), it is wet obtains the second hydrated alumina Gel,
(2-1) mixes the first hydrated alumina wet gel with water, forms slurries, and the slurries are carried out separation of solid and liquid, Obtain the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel,
In (2-1) and (2-2), the condition of the separation of solid and liquid make it that the i values of the second hydrated alumina wet gel are not low In 50%, 55% is preferably not lower than, more preferably not less than 60%, is more preferably not above 95%, more preferably not Higher than 90%, more preferably not higher than 85%, more preferably not higher than 82%,
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,
(3) use the method in claim 9-19 described in any one by the second hydrated alumina wet gel with having at least two The compound mixing in a proton acceptor site, obtains hydrated alumina composition；
(4) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(5) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(6) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, mixed in this method is additionally included in step (1), step (2) and step (3) one, two or three The operation of molecular sieve is closed, so that the hydrated alumina composition contains molecular sieve.
34. the method according to claim 32 or 33, wherein, the separation of solid and liquid carries out one or more times, at least most A separation of solid and liquid is pressure filtration and/or vacuum filter afterwards.
35. according to the method described in any one in claim 32-34, wherein, the alumina hydrate gel solution is warp Cross aging or without aging by more than the precipitation method, Hydrolyze method, kind one or both of point-score and rapid dehydration method The reaction mixture that method is prepared.
36. formed body prepared by a kind of method in claim 32-35 described in any one.
37. formed body according to claim 36, wherein, the radial direction crushing strength of the formed body is 10-50N/mm, preferably For 15-35N/mm.
38. in the hydrated alumina formed body, claim 26,27 and 30 in claim 21,22 and 25 described in any one Formed body in aluminium oxide formed body or claim 31,36 and 37 described in any one described in any one is as carrier Or the application of adsorbent.
39. the application according to claim 38, wherein, the carrier is the carrier of loaded catalyst, is preferably loaded The carrier of type hydrogenation catalyst.
40. a kind of catalyst with hydrogenation catalyst effect, which contains the of carrier and load on the carrier Group VIII metal element and vib metals element, wherein, the carrier is any one institute in claim 21,22 and 25 Aluminium oxide formed body or right in the hydrated alumina formed body stated, claim 26,27 and 30 described in any one will Seek the formed body described in any one in 31,36 and 37.
41. catalyst according to claim 40, wherein, on the basis of the total amount of the catalyst, in terms of oxide, institute The content for stating group VIII metallic element is 1-10 weight %, is preferably 1.5-8 weight %, more preferably 2-6 weight %；It is described The content of vib metals element is 5-50 weight %, is preferably 10-35 weight %, more preferably 20-30 weight %.
42. a kind of preparation method of the catalyst with hydrogenation catalyst effect, this method are included in supported on carriers group VIII Metallic element and vib metals element, wherein, this method is further included using described in any one in claim 23-24 Method in method or claim 32-35 in method, claim 28-29 described in any one described in any one Prepare the hydrated alumina formed body or aluminium oxide formed body as carrier.
43. preparation method according to claim 42, wherein, the compound of the metallic element containing group VIII and contain Load capacity of the compound of vib metals element on carrier causes, on the basis of the total amount of the catalyst finally prepared, with Oxide meter, the content of the group VIII metallic element is 1-10 weight %, is preferably 1.5-8 weight %, more preferably 2-6 Weight %；The content of the vib metals element is 5-50 weight %, is preferably 10-35 weight %, more preferably 20-30 Weight %.
44. a kind of hydrotreating method, this method is included under hydroprocessing conditions, by hydrocarbon ils with having hydrogenation catalyst effect Catalyst contacts, wherein, the catalyst with hydrogenation catalyst effect is urging described in any one in claim 40-41 Agent or the catalyst prepared as the method described in any one in claim 42-43.
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