CN1352228A - Heavy oil hydrogenation conversion catalyst and its preparing method - Google Patents

Abstract

The present invention discloses a kind of catalyst for hydrogenizing treatment, especially hydrogenizing treatment, especially hydrogenizing treatment of heavy oil and residual oil, and its preparation. The catalyst has high metal dispersity, large specific surface area and high hydrodenitrification and hydrodecarbonization activity. The catalyst is prepared with one kind of titanium containing aluminium hydroxide as material and through complete mixing and kneading process. The catalyst is easy to form and low in cost.

Description

Heavy oil hydrogenation conversion catalyst and preparation method thereof

The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, particularly heavy, residuum hydroconversion and heavy, residual hydrogenation denitrogenation (HDN) and take off the carbon residue Catalysts and its preparation method.

In the residual hydrocracking process, owing to contain a large amount of heavy metals such as nickel, vanadium in the residual oil, they are accumulated on the catalyzer, make the catalyzer behind the inactivation be difficult to regeneration.And owing to residual oil viscosity height, wherein contain impurity such as a large amount of S, N, thereby the air speed of residual hydrocracking process is very little, so catalyst consumption increases greatly than other oil refining process.So the very big factor of this process technology economic feasibility of decision is how to reduce the cost of catalyzer, makes the cost of whole hydrotreatment process more favourable on Technological Economy.Therefore, guaranteeing to reduce the catalyzer cost under the prerequisite that the every use properties of catalyzer does not descend, be long term studies problem in this area.

The catalyzer cost comprises two aspects, i.e. material cost and production cost.If raw materials variations is little, only on preparation technology, full kneading method has been save carrier roasting, dipping, dipping humectant drying and other steps than pickling process, thereby the former is more more economical, but, often cause the use properties of catalyzer not good because active metal component can not play one's part to the full.Its chief reason is, the catalyst metal degree of scatter of full kneading method preparation is low than catalyst prepared, and metal easily generates the extremely strong inactive substance of interaction with carrier in the full kneading process; For making catalyzer reach certain activity, its terms of settlement is to strengthen the add-on of reactive metal, and this just makes the cost of catalyzer improve greatly.

Usually, the hydrotreating catalyst of hydrocarbon feed is all with γ～Al ₂O ₃Or contain γ～Al of a small amount of one or more other elements such as Si, P, Ti, B, Mg, F etc. ₂O ₃Be carrier.In catalyst preparation process, can in system, introduce above-mentioned element in different steps, but the purpose of introducing above-mentioned element is a basically identical, i.e. regulating catalyst acid and/or improve interaction between active ingredient 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 catalyzer, can make catalyst preparation process simple, more effectively physico-chemical property such as the acidity of modulation carrier, micropore character and then more effectively regulating catalyst acid and/or improve interaction between active ingredient and carrier simultaneously, impel the homodisperse of active metal component on carrier surface, also can suppress active metal component and Al simultaneously ₂O ₃Generate nonactive thing phase, also can reduce the problem of environmental pollution in catalyst preparation process.To γ～Al ₂O ₃In to introduce the method for titanium more, selected to contain titanium species also varied, even can directly add TiO in aluminum oxide ₂, rely on the high temperature migration then in the hope of its homodisperse at alumina surface.These class methods are feasible to the preparing carriers process of most catalyzer, because carrier does not contain active ingredient in the process, promptly do not have competition when titanium and aluminum oxide interaction.US5089453 adopts full kneading method to prepare residual oil hydrocatalyst, uses a large amount of TiCl in its preparation process ₄Make improvements agent, contain TiO in the catalyzer ₂Amount reaches 4～6w%, because TiCl ₄Hydrolytic process easily produces harmful fog, makes will use specific equipment in the production process, and the production technique more complicated, the production difficulty is big, and security is low, and cost is higher.CN1070418A adopts the catalyzer of full kneading method preparation, is improving agent with titanium, boron, and its initial activity is better, but because its acidity is stronger, NH ₄One TPD acidity reaches 1.449mmol/g, and carbon deposit speed is fast, and catalyst deactivation is fast, the life-span is short; Because it is to adopt aluminium hydrate powder directly to mix with each active ingredient, carry out kneading and compacting, be prepared into catalyzer through the comparatively high temps activation, make active metal component fully not disperse, a part of active metal component and aluminum oxide interact simultaneously, generate nonactive phases such as molybdic acid aluminium and nickel aluminate, disperse insufficient influence in order to offset nonactive phase and metal to catalyst activity, have to increase the content of reactive metal in catalyzer, make the catalyzer cost increase like this, the shaping of catalyst difficulty increases, and can not prepare small grain size abnormity (trifolium or Herba Galii Bungei etc.) strip catalyst with this patented method, can only prepare the cylinder bar shaped catalyst.CN1098433A adopts amalgamation to soak the bonded production technique, can partly solve the dispersity problem of reactive metal like this, but still will advance dipping, step such as drying and activation again after pinching the part reactive metal mixing, Production Flow Chart is long, complicated process of preparation causes Preparation of Catalyst cost height.

One of purpose of the present invention provides that a kind of reactive metal is uniformly dispersed on alumina surface, specific surface area and suitable weight, the hydrotransforming catalyst for residual oil of big, the acid matter of pore volume.Two of purpose of the present invention be by adopt a kind of novel Ti-contained aluminium hydroxide for carrier provides that a kind of technology is simple, with low cost, shaping of catalyst smoothly, can prepare the preparation method of high performance heavy, the hydrotransforming catalyst for residual oil of special-shaped catalyst.

Hydrotransforming catalyst for residual oil of the present invention contains VIII family metal oxide 4～10% by weight, and group vib metal oxide 15～30% contains SiO ₂2～10%, contain titanium dioxide 4～15%, surplus is an aluminum oxide.The pore volume of catalyzer is 0.40～0.55cm ³/ g, specific surface area is 220～300m ²/ g.The reactive metal dispersity is: I _VIB/ I _Al(* 100) are 12.0～24.0, I _VIII/ I _Al(* 100) are 4.0～15.0.

Hydrotransforming catalyst for residual oil of the present invention is a carrier with the titanium-contained aluminum oxide, is active constituent with group vib and VIII family metal, NH ₄-TPD acidity is between 0.80～1.20mmol/g, and meleic acid acidity (〉=350 ℃) is between 0.150～0.250mmol/g.Above-mentioned group vib metal is molybdenum or tungsten, is preferably molybdenum, and described VIII metal is nickel or cobalt, is preferably nickel.Contain the VIII family metal oxide in the catalyzer by weight and be preferably 7～10%, the group vib metal oxide is preferably 17～24%, contains SiO ₂Be preferably 4～8%, contain titanium dioxide and be preferably 5～10%.The reactive metal dispersity is preferably: I _Mo/ I _Al(* 100) are 15.0～22.0, I _Ni/ I _Al(* 100) are 6.0～10.0, and the dispersity of auxiliary agent is: I _Ti/ I _Al(* 100) are 14.0～30.0, I _Si/ I _Al(* 100) are 10～35, are preferably I _Ti/ I _Al(* 100) are 16.0～25.0, I _Si/ I _Al(* 100) are 14～25.

Preparation of catalysts method of the present invention may further comprise the steps:

(1) Ti-contained aluminium hydroxide and Powdered group vib compound and Powdered VIII compounds of group mix;

(2) the mixture elder generation adding aqueous solution that (1) is obtained carries out pre-mixing, makes itself and aluminum oxide be able to preferential interaction, and its purpose is to reduce next step and adds peptization acid to the alumina pore structural damage; And then adding the mixed plastic of pinching into of peptization acid solution, plastic extruded moulding and dry, roasting with obtaining promptly make preformed catalyst.

A kind of concrete preparation method of catalyzer of the present invention is: take by weighing Ti-contained aluminium hydroxide powder, Powdered VIII metallic compound preferably basic nickel carbonate and Powdered VIIIVIB metallic compound preferably molybdic oxide or ammonium molybdate and extrusion aid preferably the sesbania powder mix, add 10～40% of institute's water requirement and mix mixing time 10～60 minutes; Add acetate or dilute hydrochloric acid solution again, the add-on of acid is than reducing 30～60m%, every 100g Al with general aluminium hydroxide ₂O ₃Add acetate 4～15g, preferably add acetate 6～12g, mix and pinched moulding on banded extruder 0.5～3 hour.The strip of gained 100～150 ℃ dry 2～6 hours down, the catalyzer finished product is promptly made in 450～700 ℃ of following roastings 2～6 hours.

The preparation method of the used Ti-contained aluminium hydroxide of the present invention may further comprise the steps:

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

(2) under agitation condition, sodium aluminate solution, titanium-containing compound slurries and carbon dioxide are reacted into glue, 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 carbonic acid gas, stop to feed carbon dioxide after becoming glue to finish;

(3) the liquid-solid mixture of (2) step gained is filtered filter cake washing, drying.

The concentration of above-mentioned sodium aluminate solution is 5～60gAl ₂O ₃/ l.Above-mentioned titanium-containing compound slurries become granularity less than 65 μ m slurry like material by titanium-containing compounds such as metatitanic acid, titanium dioxide through adding water mill, are preferably the slurry like material of granularity less than 25 μ m, then thin up to 5～40gTiO ₂/ l, its pH value is adjusted to 7～11, is preferably 7～8, and carries out under agitation condition, and its pH is suitable to be regulated with ammoniacal liquor, and ammonia concn is preferably 0.2～10%.The add-on of titanium-containing compound slurries is benchmark with the finished product, and wherein containing titanium dioxide is 6～25w%, is preferably 6～20w%.Become the glue temperature to be controlled at 10～45 ℃ according to the porous of needed Ti-contained aluminium hydroxide, concentration of carbon dioxide is controlled at 10～50v% (preferably 20～40v%).Be controlled to the glue slurry pH value and be at 9～12 o'clock and stop logical carbonic acid gas.Can wear out and also can not wear out, digestion time is no more than 2.0 hours at most.The filter cake that obtains behind dope filtration deionized water wash 1～5 time contains Na in the aluminium hydroxide of preparation ⁺By weight＜0.05%, following dry 2～12 hours at 80～180 ℃ then.

In becoming the glue process, can add the solution of silicon-containing compound as required, can add a certain amount of silicon-containing material, make SiO in order to make aluminium hydroxide have physico-chemical properties such as better acidity and thermostability ₂In Ti-contained aluminium hydroxide, account for 4～20% by weight.Silicon-containing compound solution is selected from water glass and silicon sol usually, and its concentration is generally 5～40gSiO ₂/ l.

Advantage heavy, hydrotransforming catalyst for residual oil of the present invention is: catalyzer has good metal dispersity and suitable surface acid property, have physico-chemical properties such as big pore volume and specific surface area simultaneously, thereby has good result of use, when being used for residual hydrocracking, have higher hydrogenation and take off impurity activity and hydrocracking performance, higher hydrodenitrification and removal of ccr by hydrotreating activity are particularly arranged.

The advantage of method for preparing catalyst of the present invention is: (1) Catalyst Production technology is simple, adopts " complete mixing pinched " method, and flow process is short, and productive expense is low significantly.(2) to adopt novel cheap Ti-contained aluminium hydroxide be carrier to catalyzer, has good peptization, only adds a spot of peptization acid and just can mix kneading and be equipped with moulding, makes catalyzer have large pore volume and specific surface area.(3) in kneading process, at first add small amount of deionized water; make the aluminum oxide pre-wetted, make it when next step contacts with acid solution, some part is protected; thereby reduce the destruction of acid, guarantee that finally catalyzer has bigger pore volume the aluminum oxide microvoid structure.

Catalyzer of the present invention can be used for the hydrocracking and the hydrotreatment of distillate and residual oil, especially cooperates with residuum hydrogenating and metal-eliminating catalyst, is used for weight, residuum hydrodesulfurization, takes off carbon residue (HDCR) and/or hydrodenitrification (HDN) process.

Following examples further specify the present invention.

Embodiment 1

(1) preparation of catalyzer used carrier (Ti-contained aluminium hydroxide powder)

With concentration is 30gAl ₂O ₃The sodium aluminate solution of/l places in the glue jar, 25 ℃ of controlled temperature, and adding concentration is 20gSiO ₂The sodium silicate solution of/l stirs, and making carrier contain silicon-dioxide is 6.0% by weight, and feeding concentration is the carbon dioxide of 40v%, and the concentration that adds pulp under continuous whipped state is 20gTiO ₂/ l metatitanic acid slurries (the pH value is 8.0, and granularity is less than 40 μ) make carrier contain TiO ₂Being 10% by weight, continue feeding carbon dioxide, is to stop logical carbon dioxide at 10 o'clock until slurry pH value, and slurries are aging 1.0hr under whipped state, filters then, uses deionized water wash, contains Na in carrier ⁺By weight＜0.05% o'clock, dry (110 ℃) 4 hours are crushed to 180 orders again, promptly make to contain TiO ₂-Al ₂O ₃70w% Ti-contained aluminium hydroxide powder;

(2) Preparation of catalysts

Take by weighing (1) Ti-contained aluminium hydroxide powder among the 1000g, the Powdered molybdic oxide of 260g (contains MoO ₃95.2w%) Powdered basic nickel carbonate of 200.0g (containing NiO 56.3w%) and sesbania powder 20.0g mix, in mixing process with the vaporific 150g deionized water that sprays into, premix 30 minutes, the mixture that adds 60gHAc and 350g deionized water again mixes and pinched 1.5 hours, and the strip or the major axis that are extruded into Φ 0.85mm on banded extruder are 1.5mm, minor axis is the Herba Galii Bungei strip of 1.2mm, this strip was descended dry 4 hours at 110 ℃, 610 ℃ of following roastings 4 hours, promptly made product of the present invention.

Embodiment 2

(1) preparation of catalyzer used carrier (Ti-contained aluminium hydroxide powder)

Compare with embodiment 1 (1), sodium aluminate solution, sodium silicate solution and metatitanic acid slurries are mixed, sodium aluminate solution concentration is brought up to 50gAl ₂O ₃/ l, making carrier contain silicon-dioxide is 10.0% by weight, temperature to 20 when being lowered into glue ℃, feeding concentration is the carbon dioxide of 25v%, until slurry pH value is to stop logical carbon dioxide at 12 o'clock, need not wear out after becoming glue, the unclassified stores consumption is identical with embodiment 1 with operational condition, promptly makes the Ti-contained aluminium hydroxide powder;

(2) Preparation of catalysts

Compare with embodiment 1 (2) method, add entry 200g in the premix stage, premix 50min, the roasting temperature is 640 ℃, and roasting time is 3 hours, and other is identical with embodiment 1 (2), i.e. the cost example.

Embodiment 3

(1) preparation of catalyzer used carrier (Ti-contained aluminium hydroxide powder)

Compare with embodiment 1, sodium aluminate solution and metatitanic acid slurries are mixed, sodium aluminate solution concentration is brought up to 35gAl ₂O ₃/ l, the temperature to 30 when raising into glue ℃, feeding concentration is the carbon dioxide of 50v%, feeding concentration simultaneously is 40gSiO ₂The sodium silicate solution of/l, making carrier contain silicon-dioxide is 8.0% by weight, the unclassified stores consumption is identical with embodiment 1 with operational condition, promptly makes the Ti-contained aluminium hydroxide powder;

(2) Preparation of catalysts

Compare with embodiment 1 (2) method, add entry 100g in the premix stage, premix 20min, the roasting temperature is 540 ℃, and roasting time is 4 hours, and other is identical with embodiment 1 (2), i.e. the cost example.

Embodiment 4

(1) preparation of catalyzer used carrier (Ti-contained aluminium hydroxide powder)

Compare with embodiment 1, making carrier contain silicon-dioxide is 4.0% by weight, makes carrier contain TiO ₂Be 15.0% by weight, the unclassified stores consumption is identical with embodiment 1 with operational condition, promptly makes the Ti-contained aluminium hydroxide powder;

(2) Preparation of catalysts

Compare with embodiment 1 (2) method, add entry 50g in the premix stage, premix 40min, the roasting temperature is 580 ℃, and roasting time is 3 hours, and other is identical with embodiment 1 (2), i.e. the cost example.

Comparative example 1 (pressing the preparation of CN1070418A method)

Take by weighing aluminum hydroxide solid elastomer (containing butt 65%), (contain TiCl with Titanium Trichloride Solution ₃17%) 45g mixes.Measure 200ml distilled water, add 6gNH ₄HCO ₃And 7gH ₃BO ₃, stirring and dissolving is added to this solution and contains in the Ti-Al mixture, mixes.Add 40g1 again: 1 salpeter solution mixes.Add 100gMoO again ₃Mix with 36g basic nickel carbonate (containing NiO56.3%) and to pinch into uniform plastic.On banded extruder, be extruded into the cylindrical bar of Φ=0.85mm.Descended dry 4 hours at 100 ℃ then, 550 ℃ of following roastings 3 hours.

Embodiment 5

This example is the physico-chemical property and the activity rating result of above each routine catalyzer.

The physico-chemical property of each routine catalyzer sees Table 1.Estimate and see Table 2 with stock oil character.Evaluation result sees Table 3.

During evaluate catalysts, from top to bottom by beds, elder generation was through first reactor hydrogenating desulfurization (HDS) catalyzer, again through above each routine catalyzer in second reactor after hydrogen and stock oil mixed, take One-through design, the HDS catalyzer is with batch Industrial products.The processing condition of estimating each routine catalyzer employing are all identical, are respectively: reaction pressure (hydrogen dividing potential drop), 14.6MPa; Temperature of reaction, 390 ℃; Total liquid hourly space velocity, 0.40h ^-1Hydrogen-oil ratio (v), 1000.Reactor volume is: φ 25mm * 2000mm.Loaded catalyst is respectively: HDS catalyzer, 180cm ³More than each routine catalyzer, 270cm ³Evaluation result sees Table 3.Above-mentioned Hydrobon catalyst is that the trade mark that first fertilizer plant of Qilu Petrochemical company produces is the Hydrobon catalyst of ZTS-01.As can be seen from Table 1, the pore volume specific surface area of each embodiment is all bigger, and metal is scattered, and acid matter is suitable, has guaranteed that catalyzer has good use properties.Further illustrate each embodiment by table 3 evaluation result and have good activity.

The measuring method of metal dispersity is an X-ray photoelectron spectroscopy among the present invention.The Mo electron binding energy is 233.6ev, and the Ni electron binding energy is 856.6ev, and the Ti electron binding energy is 158.7ev, and the Si electron binding energy is 102.8ev.Dispersity numerical value is big more, illustrates that the dispersion in aluminum oxide of metal or auxiliary agent is even more.Count number as can be seen from table 1, the metal of catalyzer of the present invention and auxiliary agent disperse more even than existing catalyzer.Above-mentioned meleic acid is that infrared measurement catalyst surface acid process obtains 〉=350 ℃ of meleic acid data.

The physico-chemical property of each catalyzer of table 1

Physico-chemical property	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Comparative example 1
						Particle shape	Four leaves/cylinder	Four leaves/cylinder	Four leaves/cylinder	Four leaves/cylinder	Cylinder
Pore volume/cm 3·g -1	????0.445	????0.505	????0.404	????0.426	????0.391
						Specific surface area/m 2·g -1	????225	????230	????252	????245	????195
Meleic acid/mmolg -1(≥350 ℃)	????0.203	????0.242	????0.228	????0.187	????0.267
						?NH 4-TPD/mmo1·g -1	????0.97	????1.15	????1.02	????0.89	????1.50
Metal disperses * 100 I Mo/I Al????I Ni/I Al????I Ti/I Al????I Si/I Al	????20.5 ????8.8 ????18.6 ????23.5	????16.4 ????8.2 ????20.7 ????14.6	????19.3 ????7.5 ????19.2 ????16.4	????17.3 ????7.7 ????27.6 ????18.3	????11.2 ????5.5 ????10.2 ????8.1
						????MoO 3/w％	????22.5	????23.6	????22.0	????23.9	????24.7
????NiO/w％	????9.21	????8.73	????8.60	????8.50	????9.45
						????TiO 2/w％	????6.7	????6.9	????6.6	????9.6	????1.7
????SiO 2/w％	????4.05	????7.02	????5.51	????2.50	????4.54

Table 2 stock oil character

Character	Normal slag in the sand
		Density (20 ℃), g/cm 3	????0.98
????S，w％	????4.12
		????N，w％	????0.26
????CCR，w％	????14.5

Table 3 evaluation result

Catalyzer	???HDS％	???HDCR％	???HDN％
				Embodiment 1	????86.0	????67.2	????72.2
Embodiment 2	????85.2	????66.7	????72.0
				Embodiment 3	????84.2	????66.3	????70.6
Embodiment 4	????86.6	????64.8	????69.3
				Comparative example 1	????80.2	????66.5	????70.7

Claims (25)

1, a kind of hydrogenation conversion catalyst contains VIII family metal oxide 4～10% by weight, and group vib metal oxide 15～30% contains SiO ₂2～10%, contain titanium dioxide 4～15%, surplus is an aluminum oxide, the pore volume of catalyzer is 0.40～0.55cm ³/ g, specific surface area is 220～300m ²/ g, the reactive metal dispersity is: I _VIB/ I _Al(* 100) are 12.0～24.0, I _VIII/ I _Al(* 100) are 4.0～15.0.

2,, it is characterized in that the NH of catalyzer according to the described catalyzer of claim 1 ₄-TPD acidity is 0.80～1.20mmol/g, and 〉=350 ℃ of meleic acid acidity are 0.150～0.250mmol/g.

3, according to the described catalyzer of claim 1, it is characterized in that described group vib metal is molybdenum or tungsten, the VIII metal is nickel or cobalt.

4, according to the described catalyzer of claim 1, it is characterized in that described group vib metal is a molybdenum, the VIII metal is a nickel.

5, according to the described catalyzer of claim 1, it is characterized in that containing VIII family metal oxide 7～10% in the catalyzer by weight, group vib metal oxide 17～24% contains SiO ₂Be 4～8%, containing titanium dioxide is 5～10%.

6,, it is characterized in that the reactive metal dispersity is: I according to the described catalyzer of claim 4 _Mo/ I _Al(* 100) are 15.0～22.0, I _Ni/ I _Al(* 100) are 6.0～10.0.

7,, it is characterized in that the dispersity of Si and Ti is: I according to the described catalyzer of claim 1 _Ti/ I _Al(* 100) are 14.0～30.0, I _Si/ I _Al(* 100) are 10.0～35.0.

8,, it is characterized in that the dispersity of described Si and Ti is: I according to the described catalyzer of claim 1 _Ti/ I _AlBe (* 100) 16.0～25.0, I _Si/ I _Al(* 100) are 14.0～25.0.

9, the described Preparation of catalysts method of a kind of claim 1 may further comprise the steps:

(1) Ti-contained aluminium hydroxide and Powdered group vib compound and Powdered VIII compounds of group mix;

(2) the mixture elder generation adding aqueous solution that (1) is obtained carries out pre-mixing, and then adds the mixed plastic of pinching into of peptization acid solution, and also drying, the roasting of plastic extruded moulding with obtaining promptly makes preformed catalyst.

10, in accordance with the method for claim 9, it is characterized in that described Powdered VIII metallic compound is a basic nickel carbonate, Powdered VIIIVIB metallic compound is molybdic oxide or ammonium molybdate.

11, in accordance with the method for claim 9, it is characterized in that the add-on that adds the aqueous solution in (2) step is 10～40% of institute's water requirement, mixing time is 10～60 minutes.

12, in accordance with the method for claim 9, it is characterized in that the add-on of acetate is every 100g Al in (2) step ₂O ₃Add acetate 4～15g, mix and pinched 0.5～3 hour.

13, in accordance with the method for claim 9, it is characterized in that described drying and roasting condition is: drying was 2～6 hours under 100～150 ℃, 450～700 ℃ of following roastings 2～6 hours.

14, in accordance with the method for claim 9, it is characterized in that the preparation method of described Ti-contained aluminium hydroxide, may further comprise the steps:

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

(2) under agitation condition, sodium aluminate solution, titanium-containing compound slurries and carbon dioxide are reacted into glue, 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 carbonic acid gas, stop to feed carbon dioxide after becoming glue to finish;

(3) the liquid-solid mixture of (2) step gained is filtered filter cake washing, drying.

15, in accordance with the method for claim 14, it is characterized in that the concentration of sodium aluminate solution is 5～60gAl described in (1) step ₂O ₃/ l.

16, in accordance with the method for claim 14, it is characterized in that the titanium-containing compound slurries described in (1) step become granularity less than 65 μ m slurry like material, thin up to 5～40gTiO then by metatitanic acid or titanium dioxide through adding water mill ₂/ l, its pH value is adjusted to 7～11.

17, in accordance with the method for claim 16, the granularity that it is characterized in that described titanium-containing compound slurries is less than 25 μ m, and the pH value is adjusted to 7～8.

18,, it is characterized in that with concentration being that 0.2～10% ammoniacal liquor is regulated the pH value according to claim 16 or 17 described methods.

19, in accordance with the method for claim 14, it is characterized in that the add-on of titanium-containing compound slurries is a benchmark with final Ti-contained aluminium hydroxide, make that wherein to contain titanium dioxide be 6～25w%.

20, in accordance with the method for claim 19, it is characterized in that described content of titanium dioxide is 6～20w%.

21, in accordance with the method for claim 14, it is characterized in that the one-tenth glue temperature described in (2) step is 10～45 ℃, the concentration of carbon dioxide of using is 10～50v%, and one-tenth rubber cement liquid pH value to 9～12 o'clock stops to lead to carbonic acid gas.

22, in accordance with the method for claim 14, it is characterized in that the filter cake washing described in (3) step is 1～5 time, to the aluminium hydroxide of preparation, contain Na ⁺By weight＜0.05%.

23, in accordance with the method for claim 14, it is characterized in that the drying conditions described in (3) step is: drying is 2～12 hours under 80～180 ℃.

24, in accordance with the method for claim 14, it is characterized in that in described one-tenth glue process, adding the solution of silicon-containing compound, make SiO ₂In the Ti-contained aluminium hydroxide product, account for 4～20% by weight.

25, in accordance with the method for claim 24, it is characterized in that described silicon-containing compound solution is selected from water glass and silicon sol, its concentration is 5～40gSiO ₂/ l.