CN1169614C - Silicon-containing aluminium hydroxide and prep. thereof - Google Patents

Abstract

The present invention relates to aluminium hydroxide containing silicon, and a preparation method thereof, and belongs to the field of catalyst basic materials. The present invention solves the following problems that the existing aluminium hydroxide containing silicon in the prior art can not well protect the pore structure of the original aluminum oxide after silicon is added, meanwhile, the surface physicochemical property is not suitable for the hydrotreatment or the conversion process of heavy oil, and the peptization is poor, which is adverse to the molding of carriers or catalysts in the preparation process. The present invention introduces inexpensive compositions containing silicon in the process of preparing the aluminium hydroxide with a CO2 method, adds a part of compositions containing silicon when gel is formed, and a residual amount of compositions are added and degraded after the gel is formed. The aluminium hydroxide containing silicon and prepared with the method has the advantages of favorable surface acidity, proper pore structure and good alternating solubility. The aluminium hydroxide containing silicon and prepared by the present invention can be used for various catalyst carriers, and can be especially suitable for catalyst carriers used in the hydrotreatment or the conversion process of heavy oil.

Description

A kind of siliceous aluminium hydroxide and preparation method thereof

Technical field

The present invention relates to a kind of siliceous aluminium hydroxide and preparation method thereof, siliceous aluminium oxide that the product surface Bronsted acid is stronger after the roasting and preparation method thereof particularly, and the siliceous aluminium hydroxide that directly obtains by this method.The inventive method belongs to catalytic base material technology field, specifically PETROLEUM PROCESSING particularly heavy-oil hydrogenation handle or the employed catalyst basic material of conversion process technical field.

Background technology

Usually, in the used Preparation of catalysts process of petroleum refining, adopt aluminium oxide usually or contain a small amount of one or more other elements such as γ～Al of Si, P, Ti, B, Mg, F etc. ₂O ₃Be carrier.In the preparation process of this type of aluminium oxide, can in system, introduce above-mentioned element in different phase, but the purpose of introducing above-mentioned element is a basically identical, i.e. regulating catalyst acid and/or improve interaction between active component and carrier.But in catalyst preparation process, add certain or more auxiliary agent can make the catalyst preparation process complexity, or cause problem such as shaping of catalyst difficulty; In the support material production process, just add the needed auxiliary agent of preparation catalyst, can make catalyst preparation process simple, more effectively physicochemical property such as the acidity of modulation carrier, porous and then more effectively regulating catalyst acid and/or improve interaction between active component and carrier also can reduce the problem of environmental pollution in catalyst preparation process simultaneously.To γ～Al ₂O ₃The method of middle introducing silicon is more, and selected silicon containing species is also varied.A large amount of documents and patent have been introduced the preparation method and the feature of amorphous silicon aluminium, as CN97116404.5, and US4758338, EP0788270 etc.But the amorphous silicon aluminium silicone content is often higher, peptization is relatively poor, moulding at carrier or catalyst is difficult, in carrier or catalyst preparation process, have in selected aluminium oxide, admix a part of amorphous silicon aluminium, can bring more trouble to catalyst preparation process like this, and the amorphous silicon aluminium applicable scope is limited, its pore structure and surface acid property often are not suitable for the hydrotreatment and the hydroconversion process of mink cell focus and residual oil.

CN1110304A has announced a kind of preparation method of aluminium oxide of siliceous and phosphorus of macropore, in the preparation process of this aluminium oxide, silicon becomes the glue method to add with phosphorus with substep, can make silicon and phosphorus major part be dispersed in alumina surface like this, but this alumina pore is big, and peptization is relatively poor, in catalyst or preparing carriers process, the aluminium oxide that has only the siliceous and phosphorus of a blending part, remaining adopt peptization preferably aluminium oxide so just can help moulding; Simultaneously its to contain silica volume low, only be 1w%～4w%, contain more phosphorus again, can make the acid matter of carrier surface like this a little less than, can be used to prepare Hydrobon catalyst, but be unwell to the catalyst that preparation heavy oil hydrogenation conversion catalyst or other requirement have conversion performance; This becomes the glue process to adopt AlCl ₃Be raw material, be carried out to glue, can make its cost higher like this, and have a large amount of pollutants to discharge with the ammoniacal liquor neutralization.

CN1015638B has announced that a kind of carbon dioxide process prepares the method for aluminium hydroxide (carbonizatin method), and this method employing prepares aluminium hydroxide with the method that carbon dioxide feeds sodium aluminate solution, and preparation process technology is simple, and contamination-free is discharged, and the carrier cost is lower.This process adds the silica of 1m%～2m%, and the physicochemical property of carrier is not improved, especially owing to become the glue process under alkaline environment, to carry out all the time, the surface acid property of aluminium oxide a little less than.Therefore, become how to prepare in the glue environment the suitable carrier of acid matter in alkalescence, it is essential to become, and in order to prepare the more good catalyst of performance, is necessary to prepare the good siliceous aluminium hydroxide carrier of physicochemical property.

CN96120987.9 has announced a kind of preparation method of siliceous aluminium oxide, be a kind of alumina globule that contains silica 5m%～15m%, its preparation main points are: the siliceous aluminium oxide wet rubber ball after the moulding carries out low temperature (＜100 ℃) drying in containing the atmosphere of ammonia.Its forming process complexity, yield is low, and a little less than its preparation process had determined this support acidity matter simultaneously, the purpose that adds silicon only was to adjust porous, the heat endurance of carrier and help the carrier balling-up.

Summary of the invention

The problem that siliceous aluminium oxide exists in the prior art is: add behind the silicon can not the original aluminium oxide of fine protection pore structure; surface physicochemical property is unsuitable for heavy-oil hydrogenation processing or conversion process simultaneously; and peptization is poor, is unfavorable for the moulding in carrier or the catalyst preparation process.Purpose of the present invention just is to provide a kind of surface acid property suitable, especially the higher siliceous aluminium hydroxide that does not destroy its pore structure of surperficial Bronsted acid amount (B acid) the invention provides a kind of preparation method with above-mentioned aluminium hydroxide of with low cost, non-environmental-pollution simultaneously.

Have following character behind the siliceous aluminium hydroxide shaping and roasting of the present invention, dioxide-containing silica is 2.0%～20.0% by weight, and pore volume is 0.6ml/g～1.2ml/g, is preferably 0.8ml/g～0.95ml/g, and specific area is 300m ²/ g～400m ²/ g, average pore size is 6.0nm～13.0nm, meleic acid behind this aluminium hydroxide shaping and roasting is distributed as: the total acid content in the time of 160 ℃ is 300 μ mol/g～600 μ mol/g, wherein Bronsted acid is 90 μ mol/g～300 μ mol/g, total acid content in the time of 250 ℃ is 200 μ mol/g～350, wherein Bronsted acid is 60 μ mol/g～200 μ mol/g, and the total acid content in the time of 350 ℃ is 60 μ mol/g～160, and wherein Bronsted acid is 40 μ mol/g～100.

The preparation method of the siliceous aluminium hydroxide of the present invention may further comprise the steps:

(1) preparation sodium aluminate solution, silicon-containing compound solution;

(2) under stirring condition, sodium aluminate solution, a part of silicon-containing compound solution (or not adding silicon-containing compound solution) are reacted into glue with carbon dioxide, material solution or slurries mix the back and feed carbon dioxide and become glue or wherein one or both to add into glue continuously when feeding carbon dioxide, stop to feed carbon dioxide after becoming glue to finish, aging then, filtration;

(3) (2) step gained filter cake is broken into add remainder behind the slurry again (or all) silicon-containing compound solution wears out, filters filter cake washing, drying again.

Introduce cheap siliceous compound (sodium metasilicate) in the process of the siliceous aluminium hydroxide employing of the present invention Carbonization Preparation aluminium hydroxide.Preparation process technology is simple, does not have the discharge of pollutant, non-environmental-pollution, and cost is low; Silica is uniformly dispersed at alumina surface simultaneously, has prevented the influence of process to the aluminium oxide microstructure; The siliceous aluminium hydroxide of the present invention has good peptization, particularly improved the silicon content shortcoming of its peptization variation more for a long time, make that moulding is easy when using siliceous preparation of aluminium hydroxide catalyst carrier of the present invention or catalyst, and then the Preparation of Catalyst cost is reduced.

In the preparation process of aluminium hydroxide of the present invention, silicon-containing compound is to adopt the substep addition method to add, the small part silicon-containing compound be carried out to glue after sodium aluminate solution mixes, most silicon-containing compound is after becoming glue or add in the ageing process, can reach with few silicone content of trying one's best like this and regulate the acid matter of surface of aluminum hydroxide, most silicon is distributed in the surface of aluminium hydroxide, effectively performance silicon is regulated the effect of surface of aluminum hydroxide physicochemical property, the effect that has the adjustment hole structure simultaneously.The siliceous aluminium hydroxide of the present invention has good acid matter heat endurance, the acid matter that is carrier surface changes less with the variation of sintering temperature, can in carrier or Preparation of catalysts process, improve sintering temperature like this, in order to improve the average pore size of carrier or catalyst, and not or the surface acid property of less change carrier or catalyst, promptly can not prepare big and still stronger carrier or the catalyst of surface acid property of average pore size.Use catalyst carrier physico-chemical property that siliceous aluminium hydroxide of the present invention makes as raw material and do not add silicon or silicone content raw aluminum hydroxide seldom is close, even further having improved the physical and chemical performance of carrier, pore size distribution is concentrated more, pore volume, specific area further strengthen.The heavy oil of the preparation of aluminium hydroxide that use the present invention is siliceous or residual hydrocracking and reforming catalyst have the active and hydro-conversion activity of good hydrotreatment, realize residual oil conversion ratio largely, in order to improve the productive rate of naphtha, aviation kerosine and diesel oil.The present invention has maximally utilised cheap silicon resource, and as auxiliary agent, has weakened the competition of silicon and reactive metal effectively, has improved the utilization rate of reactive metal; The inventive method equally also is applicable to the preparation method with aluminum nitrate method, alchlor process, aluminum sulfate method etc. in addition.

The specific embodiment

Preferably have following character behind the siliceous aluminium hydroxide shaping and roasting of the present invention, dioxide-containing silica is preferably 4.0%～15.0% by weight, is preferably 4.0%～12.0%.Be distributed as by the measured acid of meleic acid distribution: the total acid content in the time of 160 ℃ is preferably 400 μ mol/g～500 μ mol/g, and wherein Bronsted acid (B acid) acid amount is preferably 110 μ mol/g～260 μ mol/g, is preferably 120 μ mol/g～250 μ mol/g; Total acid content in the time of 250 ℃ is preferably 200 μ mol/g～300 μ mol/g, and wherein Bronsted acid (B acid) acid amount is preferably 90 μ mol/g～180 μ mol/g; Total acid content in the time of 350 ℃ is preferably 70 μ mol/g～120 μ mol/g, and wherein Bronsted acid (B acid) acid amount is preferably 50 μ mol/g～90 μ mol/g.Pore volume is preferably 0.7ml/g～1.0ml/g, is preferably 0.8ml/g～0.95ml/g, and specific area is 300m ²/ g～400m ²/ g, average pore size is 6.0nm～13.0nm.

The concrete optimum condition of the siliceous preparation method of aluminium hydroxide of the present invention is as follows:

The concentration of employed sodium aluminate solution is 5gAl ₂O ₃/ l～60gAl ₂O ₃/ l.Silicon-containing compound is sodium metasilicate (being commonly called as waterglass) preferably, and containing silica in the adjusting sodium silicate solution is 5g/l～40g/l, and the silicon-containing compound addition accounts for 0%～50% of total addition.Become the glue temperature to be controlled at 15 ℃～35 ℃, be preferably between 18 ℃～30 ℃, be preferably between 18 ℃～25 ℃ according to the porous of needed siliceous aluminium hydroxide.Concentration of carbon dioxide is controlled at 10v%～50v% (20v%～40v%) preferably.Be controlled to the glue slurry pH value and be at 9～12 o'clock and stop logical carbon dioxide.Can wear out and also can not wear out, ageing time is 0 minute～60 minutes, preferably aging 10 minutes～60 minutes.Filter cake behind the dope filtration is pulled an oar after adding entry, adds the remainder silicon-containing compound of amount of calculation under stirring, aging 10 minutes～120 minutes again, be preferably 40 minutes～80 minutes, be preferably 40 minutes～60 minutes, control temperature at 20 ℃～35 ℃, filter then filter cake.With conventional method washing 1～6 time, in the aluminium hydroxide of preparation, contain Na ⁺By weight＜0.05%.The control wash temperature is preferably 20 ℃～30 ℃ at 20 ℃～40 ℃, and washing times is preferably 3 times～6 times, most preferably is 3 times～4 times.Under 80 ℃～180 ℃, preferred 100 ℃～150 ℃ following dryings 2 hours～12 hours promptly get the alleged product of the present invention then.

Become the adding mode of the various material solutions in the glue process specifically to select as required, as adopting following manner: (1) feeds sodium aluminate solution with carbon dioxide, adds silicon-containing compound solution with certain flow simultaneously; (2) with adding silicon-containing compound in the sodium aluminate solution, feed carbon dioxide then; Its charging sequence also can specifically be selected as required.

Siliceous aluminium hydroxide with the inventive method preparation is raw material, can make siliceous alumina support through moulding, roasting, or with kneading method and mix the method pinch-flood combination and make hydrogenation catalyst, be specially adapted to make hydrotreatment or hydrogenation conversion catalyst with kneading method or mixed method of pinching-flooding combination.The catalyst of preparation composition is by weight thus: tungsten oxide and/or molybdenum oxide, 15%～25%; Cobalt oxide and/or nickel oxide, 2%～10%; Silica, 2%～10%; Surplus is aluminium oxide.Can suitably adjust each components contents at different raw material (as: various distillates, wax tailings, deasphalted oil and residual oil etc.), or introduce proper assistant.

Further specify technical solution of the present invention by the following examples.

Embodiment 1

With concentration is 30gAl ₂O ₃The sodium aluminate solution of/l places in the glue jar, 20 ℃ of control temperature, and adding concentration is 20gSiO ₂The sodium silicate solution of/l stirs, and the sodium metasilicate of adding is with SiO ₂The content of meter in siliceous aluminium hydroxide is 2.0% by weight, feeding concentration is the carbon dioxide of 30v%, until slurry pH value is to stop logical carbon dioxide at 11 o'clock, slurries are aging 0.5hr under stirring, filter then, filter cake adds the deionized water reslurry and stirs, and adds the remainder sodium silicate solution of amount of calculation then, makes silicon-containing compound with SiO ₂The final content of meter in siliceous aluminium oxide is 8.0m%, and then aging 0.5 hour, filter, wash 4 times, make to contain Na in the carrier ⁺By weight＜0.05%, dry (110 ℃) 4 hours are crushed to 180 orders again, promptly make the alleged product of the present invention.

Embodiment 2

Compare with embodiment 1, after becoming glue, filter, the remainder sodium silicate solution addition behind the filter cake reslurry is improved, make silicon-containing compound with SiO ₂The content of meter in siliceous aluminium oxide is 12.0m%, and the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. the cost example.

Embodiment 3

Compare with embodiment 1, after becoming glue, filter, the remainder sodium silicate solution addition behind the filter cake reslurry is reduced, make silicon-containing compound with SiO ₂The final content of meter in siliceous aluminium oxide is 5.0m%, and the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. the cost example.

Embodiment 4

Compare with embodiment 1, after becoming glue, filter, the remainder sodium silicate solution addition behind the filter cake reslurry is improved, make silicon-containing compound with SiO ₂The content of meter in siliceous aluminium oxide is 16.0m%, and the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. the cost example.

Embodiment 5

Compare with embodiment 1, will become the addition of glue process mesosilicic acid sodium solution to improve, the sodium metasilicate that makes adding be with SiO ₂The content of meter in siliceous aluminium oxide is 4.0% by weight, and the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. the cost example.

Embodiment 6

Compare with embodiment 1, will become the addition of glue process mesosilicic acid sodium solution to reduce, the sodium metasilicate that makes adding be with SiO ₂The content of meter in siliceous aluminium oxide is 1.0% by weight, and the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. the cost example.

Embodiment 7

Compare with embodiment 1, will become not add sodium silicate solution in the glue process, the silicon-containing compound of amount of calculation all adds in the ageing process after becoming glue, and the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. the cost example.

Embodiment 8

Compare with embodiment 1, after becoming the glue reaction to finish, under stirring fast, promptly add the remainder sodium silicate solution of amount of calculation simultaneously, continue then to stir, aging 1.5hr, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. the cost example.

Embodiment 9

Compare with embodiment 1, sodium aluminate solution concentration is brought up to 50gAl ₂O ₃/ l, the temperature to 25 when improving into glue ℃, feeding concentration is the carbon dioxide of 40v%, is to stop logical carbon dioxide at 12 o'clock until slurry pH value, aging 1.5hr, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. the cost example.

Embodiment 10

Compare with embodiment 1, the temperature to 30 when raising into glue ℃, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. the cost example.

Embodiment 11

Compare with embodiment 1, the temperature to 35 when raising into glue ℃, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. the cost example.

Comparative example 1

With concentration is 40gAl ₂O ₂The sodium aluminate solution of/l places in the glue jar, 20 ℃ of control temperature, and feeding concentration is the carbon dioxide of 40v%, adds a certain amount of sodium silicate solution, makes to contain SiO in the carrier ₂Be 2.0%, control pH value is to stop into glue at 10 o'clock, and the slurries 1.0h that wears out filters then, spends deionised water, 120 ℃ of dryings, is crushed to 180 orders again.(CN 1015638B method therefor)

Embodiment 12

Add certain peptization acid, pinch through mixing then, after the extrusion, drying and moulding, under 550 ℃, above-mentioned each sample roasting to be obtained catalyst carrier in 3 hours.Its physico-chemical parameter is listed in table 1.

As can be seen from Table 1, SiO in the carrier ₂Content is when the 8.0m% left and right sides, and the physicochemical property of carrier is more suitable, and acid matter is also more suitable, within the specific limits, and along with SiO ₂The raising of content, the acid amount and the acid strength of carrier all increase, but content is when surpassing certain limit, and the inventive method is at SiO ₂When content surpassed 12.0m%, its acid amount and acid strength improved and are little, SiO ₂When content surpassed 16.0m%, its acid amount and acid strength descended on the contrary, with SiO ₂It is roughly the same when content is 5.0m%.Simultaneously, SiO ₂When content was very low, for example comparative example 1, and then its acid strength reduces, and was in particular in that its B acid amount descends significantly; In the preparing carriers process, the addition sequence that silicon-containing compound is different then has considerable influence to pore size distribution and the pore volume of regulating carrier, promptly adds more silicon-containing compound in becoming the glue process, and it is big that the pore volume of carrier becomes, the pore size distribution disperse; And after becoming glue, adding silicon-containing compound in the ageing process, carrier then still keeps CO ₂The characteristics of aluminium oxide, pore size distribution is more concentrated, and peptization is good.Therefore, in order to regulate the physicochemical property of carrier, make SiO simultaneously ₂Be evenly distributed at carrier surface, should after becoming glue to finish, add silicon-containing compound.In addition, the pore volume of carrier is become the glue Temperature Influence bigger, so should note being controlled to the glue temperature in becoming the glue process.

The assay method of meleic acid is to adopt the acid matter of infrared spectroscopic determination.The method that the present invention adopts is to utilize pyridine (C ₅H ₅N) lip-deep L acid of determining adsorption oxide (the present invention refers to siliceous aluminium oxide) and B acid promptly utilize at 1640cm ^-1～1500cm ^-1And 1500cm ^-1～1440cm ^-1Difference on the range of spectra can be distinguished the physical absorption pyridine and be coordinated to the pyridine at L acid position and the pyridine that is adsorbed on B acid position, according to the amount of how much coming to determine oxide surface L acid and B acid of absorption pyridine amount.

With siliceous aluminium hydroxide 1000g (butt 71.5%) gram of embodiment 1, with 300gMoO ₃, 217g basic nickel carbonate, 75gHAc and 20g extrusion aid mix and pinch, extruded moulding after 120 ℃ of following dryings, 580 ℃ of roastings 3 hours, obtains a kind of hydrotransforming catalyst for residual oil.At hydrogen dividing potential drop 14.7MPa, LHSV0.40h ^-1, H ₂/ oil 1000, handle Saudi Arabia's intermediate base decompression residuum (sulphur 4.5%, nitrogen 0.26%, carbon residue 14.6%) under the process conditions that reaction temperature is 390 ℃, and its desulfurization degree is 92.0%, and denitrification percent is 65%, and taking off carbon yield is 75%.Can generate a part of fine-quality diesel oil and naphtha, heavy distillate behind the hydrogenation (as VGO etc.) and normal slag can be used as FCC apparatus charging or ethylene unit cracking material.Illustrate that the catalyst that uses siliceous aluminium hydroxide of the present invention to make as raw material has good serviceability.

The physicochemical property of each embodiment carrier of table 1

Physicochemical property	Pore volume/cm 3g -1	Specific area/m 2g -1	4～15nm pore volume integration rate/%	Meleic acid distribution/μ mol g -1			SiO 2 /m％
								160 ℃ of total acid/B acid	250 ℃ of total acid/B acid	350 ℃ of total acid/B acid
				Embodiment 1	0.85	320					80	435/236	265/175	87/71	8.0
Embodiment 2	0.86	331	81				455/241	265/114	106/86	12.0
				Embodiment 3	0.88	351					85 (concentrating)	423/210	249/110	83/70	5.1
Embodiment 4	0.87	345	79				410/213	225/120	85/75	16.0
				Embodiment 5	0.90	340					75 (than disperses)	445/245	275/165	105/60	8.0
Embodiment 6	0.87	345	83				425/200	255/145	85/75	8.0
				Embodiment 7	0.87	310					85 (concentrating)	435/214	251/115	80/70	8.0
Embodiment 8	0.91	332	70 (disperses)				445/265	235/125	90/85	8.20
				Embodiment 9	0.75	310					81(3～15nm)	445/189	245/135	100/68	7.8
Embodiment 10	0.65	360	82(3～15nm)				403/176	224/103	94/46	8.0
				Embodiment 11	0.54	350					85(2～12nm)	421/146	246/98	86/56	7.5
Comparative example 1	0.82	325	78				423/86	275/42	90/0	2.0

Claims (9)

1, a kind of preparation method of siliceous aluminium hydroxide may further comprise the steps:

(1) preparation sodium aluminate solution, silicon-containing compound solution;

(2) under stirring condition, sodium aluminate solution, silicon-containing compound solution and carbon dioxide are reacted into glue, stop to feed carbon dioxide after becoming glue to finish, aging then, filtration, wherein silicon-containing compound solution addition is 0%～50% of a final siliceous alumina product silicon content;

(3) (2) step gained filter cake is broken into the silicon-containing compound solution that adds remainder behind the slurry again, wear out again, filtration, filter cake washing and dry, obtain final products;

Wherein the concentration of the sodium aluminate solution described in the step (1) is 5gAl ₂O ₃/ 1～60gAl ₂O ₃/ l, silicon-containing compound is selected from sodium metasilicate, and dioxide-containing silica is 5g/l～40g/l in the sodium silicate solution; The described concentration of carbon dioxide of step (2) is controlled at 10v%～50v%, becomes the glue temperature to be controlled at 15 ℃～35 ℃, and becoming the glue slurry pH value is to stop logical carbon dioxide at 9～12 o'clock; The described drying condition of step (3) is following dry 2～12 hours at 80 ℃～180 ℃; The silicon-containing compound addition is for to contain silica 2.0%～20.0% by the siliceous alumina weight after the roasting.

2, according to the preparation method of the described siliceous aluminium hydroxide of claim 1, it is characterized in that described one-tenth glue temperature is made as between 15 ℃～30 ℃, concentration of carbon dioxide is controlled at 20v%～40v%, the ageing time described in (2) step 0～60 minute.

3, according to the preparation method of the described siliceous aluminium hydroxide of claim 2, it is characterized in that described one-tenth glue temperature is 18 ℃～25 ℃, described ageing time is 10 minutes～60 minutes.

4, according to the preparation method of the described siliceous aluminium hydroxide of claim 1, it is characterized in that the ageing time described in described (3) step is 10 minutes～120 minutes, aging temperature is 20 ℃～35 ℃, washs 1 time～6 times down at 20 ℃～40 ℃ then.

5, according to the preparation method of the described siliceous aluminium hydroxide of claim 4, it is characterized in that described ageing time is 40 minutes～80 minutes, wash 3 times～6 times down at 20 ℃～30 ℃ then, under 100 ℃～150 ℃, carry out drying then.

6, according to the preparation method of the described siliceous aluminium hydroxide of claim 4, it is characterized in that described ageing time is 40 minutes～60 minutes, washing times is 3 times～5 times.

7, the aluminium hydroxide that makes of a kind of described preparation method of claim 1 is through the siliceous aluminium oxide through preference temperature roasting gained, it is characterized in that siliceous aluminium oxide by weight dioxide-containing silica be 2.0%～20.0%, pore volume is 0.6ml/g～1.2ml/g, and specific area is 300m ²/ g～400m ²/ g, average pore size is 6.0nm～13.0nm; Meleic acid is distributed as: the total acid content in the time of 160 ℃ is 300 μ mol/g～600 μ mol/g, wherein Bronsted acid is 90 μ mol/g～300 μ mol/g, total acid content in the time of 250 ℃ is 200 μ mol/g～350, wherein Bronsted acid is 60 μ mol/g～200 μ mol/g, total acid content in the time of 350 ℃ is 60 μ mol/g～160, and wherein Bronsted acid is 40 μ mol/g～100.

8, according to the described siliceous aluminium oxide of claim 7, it is characterized in that described dioxide-containing silica is 4.0%～15.0%, pore volume is 0.8ml/g～0.95ml/g.

9, according to the described siliceous aluminium oxide of claim 7, total acid content when it is characterized in that described 160 ℃ is 400 μ mol/g～500 μ mol/g, wherein Bronsted acid is 110 μ mol/～260 μ mol/g, total acid content in the time of 250 ℃ is 200 μ mol/g～300 μ mol/g, wherein Bronsted acid is 90 μ mol/g～180 μ mol/g, total acid content in the time of 350 ℃ is 70 μ mol/g～120 μ mol/g, and wherein Bronsted acid is 50 μ mol/g～90 μ mol/g.