CN101172259A - Method for preparing carrier material - Google Patents
Method for preparing carrier material Download PDFInfo
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- CN101172259A CN101172259A CNA2006101341511A CN200610134151A CN101172259A CN 101172259 A CN101172259 A CN 101172259A CN A2006101341511 A CNA2006101341511 A CN A2006101341511A CN 200610134151 A CN200610134151 A CN 200610134151A CN 101172259 A CN101172259 A CN 101172259A
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- glue
- molecular sieve
- amorphous aluminum
- aluminum silicide
- neutralized
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Abstract
The invention discloses a preparation method for a carrier material including molecular sieve and amorphous silica-alumina. The molecular sieve in the carrier of the invention is induced in the gelling process of the amorphous silica-alumina, so as to greatly improve the specific surface area and the acidity of the silica-alumina, and to facilitate the molecular sieve to be distributed uniformly in the silica-alumina carrier, and to be favorable for the dispersion of the reactive metal component in the catalyst and the coordination function of the two. The silica-alumina of the invention is suitable for being used as the catalyst material of petroleum processing catalyst, and is particularly suitable for being used as the carrier component of hydrotreating and hydrocracking catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of carrier material, especially for the preparation method of the molecular sieve-amorphous aluminum silicide composite carrier of hydrogenation catalyst.
Background technology
In general, the used bifunctional catalyst major part of PETROLEUM PROCESSING is to be carrier with aluminium oxide or amorphous aluminum silicide, be equipped with a certain amount of molecular sieve, and impregnating metal forms, its basic preparation process is earlier aluminium oxide or siliceous aluminium oxide and molecular sieve and other auxiliary agent directly to be mixed, carry out moulding then, drying and roasting, final impregnating metal and activation.Amorphous aluminum silicide requires itself must have enough big specific surface and pore volume as one of important carrier component of catalyst, with carrying reactive metal component; Molecular sieve is mainly the acidic cleavage component, and for catalyst, the cooperation of the two is most important, has only the two coordinative role, the catalyst action of competence exertion the best.In the prior art,, can not be uniformly dispersed, influence the reactivity worth of catalyst at other carrier material of catalyst because molecular sieve adds by physical mixed.
CN 1110304A discloses the preparation method of the siliceous and phosphorus oxidation aluminium of a kind 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, aluminium oxide aperture and pore volume are improved, but owing to added more phosphorus, B acid amount significantly reduces to make the acid of alumina surface measure particularly, acid strength obviously reduces, and makes its application be subjected to certain restriction.
CN 1184703A discloses a kind of preparation method of siliceous aluminium oxide.Its preparation be a kind of alumina globule that silica is 5wt%～15wt% that contains, its preparation characteristic is that the siliceous aluminium oxide wet bulb after the moulding carries out low temperature drying in containing the atmosphere of ammonia, the character of the alumina balls that obtain has obtained some improvement, but because some defectives of balling-up aspect self, make this forming process complexity, product yield is low, shortcomings such as preparation cost height.
EP0339640 discloses and has a kind ofly prepared the method for titanium-contained aluminum oxide with coprecipitation, because coprecipitation itself exists the problem that body is detained mutually, causes titanium dioxide can not give full play to the facilitation of aluminium oxide.Because co-precipitation requires two kinds or above species co-precipitation under certain condition, this condition to co-precipitation has proposed very harsh requirement, that is to say, even under certain conditions, two kinds of materials can precipitate simultaneously, but this condition may not all be best to two kinds of materials also, and this method has characteristics and the shortcoming of itself thus.
CN1060977A discloses a kind of preparation method who contains the ultrastable of amorphous aluminum silicide, and Alusil is introduced in the NaY zeolite, obtains containing the USY zeolite of amorphous aluminum silicide again through conventional ammonium ion exchange, hydrothermal calcine process.The main deficiency of this method is to introduce amorphous aluminum silicide before molecular sieve modified, and the modification processing procedure of molecular sieve is restricted, and the modification processing of molecular sieve also has considerable influence to the character of amorphous aluminum silicide simultaneously.And this preparation method is easy to amorphous aluminum silicide is incorporated in the molecular sieve pore passage, stops up molecular sieve pore passage, reduces the pore volume of molecular sieve, influences the catalytic performance of molecular sieve.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with the suitable silica-alumina supports carrier material of bigger serface, acid matter.Silica-alumina supports material preparation method of the present invention is introduced the preparation process of unbodied sial with the molecular sieve of crystal formation, and the two can be uniformly dispersed, and improves the serviceability of catalyst.
Silica-alumina supports material of the present invention comprises molecular sieve and amorphous aluminum silicide, and preparation process is as follows:
(1) needed molecular sieve is added the water making beating;
(2) become to introduce the molecular sieve pulp that step (1) obtains in the glue process at amorphous aluminum silicide, by final carrier material weight, the molecular sieve addition is 5%～80%;
(3) amorphous aluminum silicide becomes material behind the glue to comprise the processing of filtration, washing, drying and other steps, obtains containing the carrier material of molecular sieve and amorphous aluminum silicide.
Wherein molecular sieve is known any molecular sieve in the step (1), is preferably one or more of modified molecular screen.The selection of concrete kind of molecular sieve and character can be determined according to the needs that use, in the PETROLEUM PROCESSING field, molecular sieve commonly used such as Y zeolite, β zeolite, ZSM series molecular sieve, SAPO series molecular sieve etc. one or more, for the catalytic performance that obtains to wish, various molecular sieves can carry out suitable processing modifying process, the process that method of modifying is well known to those skilled in the art is as hydrothermal treatment consists modification, acid treatment modification, ion-exchange treatment, all kinds of solvents processing etc.For the required molecular sieve of petroleum refining catalyst, generally need carry out modifying process such as ion-exchange, hydrothermal treatment consists.The weight concentration of molecular sieve pulp is generally 5%～40%.
Amorphous aluminum silicide described in the step of the present invention (2) becomes the glue process to be undertaken by process well known to those skilled in the art.Amorphous aluminum silicide becomes the glue process to be generally the neutralization reaction process of acid material and alkaline material, becomes general two kinds of materials and the stream of adopting of glue process to become the glue mode of operation, or a kind of material is placed on into the mode of operation that another kind of material in the glue jar adds into glue continuously.Become in the glue process at amorphous aluminum silicide, the introducing mode of molecular sieve pulp can be selected arbitrarily, and as adopting the one or more combination of following manner: (1) adds into molecular sieve pulp in the glue jar in becoming glue neutralization reaction process continuously; (2) molecular sieve pulp is joined into earlier the glue jar, then acid material and alkaline material are neutralized into glue; (3) with molecular sieve pulp and one or more mixing that become the glue material, become the glue material to be neutralized into glue then.Amorphous aluminum silicide becomes the material that the glue process uses and becomes the adhesive tape part to be well known to those skilled in the art, can be definite according to the concrete selection of the requirement of using.Can carry out burin-in process under optimum conditions after becoming glue.
Filtration, washing, drying and other steps behind the glue of one-tenth described in the step of the present invention (3) are process well-known to those skilled in the art and condition.Processing procedure such as can also comprise pulverizing, sieve.
In the carrier material that comprises molecular sieve and amorphous aluminum silicide of the inventive method preparation, the molecular sieve weight content is 5%～80%, dioxide-containing silica is 10wt%～80wt% in the silica-alumina supports material, and this silica-alumina supports material has following character: specific area is 200m
2/ g～800m
2/ g, pore volume are 0.3cm
3/ g～1.8cm
3/ g, 〉=350 ℃ meleic acid amount is 0.04mmol/g～1.10mmol/g, wherein B acid accounts for 40%～60% of total acid.
The present invention contains in the preparation process of molecular sieve and amorphous aluminum silicide carrier material, molecular sieve pulp is introduced in the one-tenth glue process of amorphous aluminum silicide, molecular sieve and amorphous aluminum silicide are uniformly dispersed, both form good coordinative role in catalytic process, the serviceability that improves catalyst is had good facilitation.Molecular sieve can adopt various suitable methods to handle according to instructions for use before introducing, and the modification processing procedure of molecular sieve can not produce adverse influence to amorphous aluminum silicide.
The specific embodiment
In the inventive method, amorphous aluminum silicide becomes the glue process can adopt content well known to those skilled in the art.
Become the glue material to generally comprise aluminium source (Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3And NaAlO
2Deng in one or more), silicon source (one or more in waterglass, Ludox and the organosilicon etc.), precipitating reagent (NaOH, NH
4OH or CO
2Deng), to use according to the different choice that becomes the glue process, conventional mode of operation mainly contains: (1) acid aluminium salt (Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3) and basic aluminium salt (NaAlO
2) or alkaline precipitating agent (NaOH, NH
4OH) be neutralized into glue, (2) basic aluminium salt (NaAlO
2) and acidic precipitation agent (CO
2) be neutralized into glue.
The glue jar is generally introduced in the silicon source in becoming the glue process, also can with aluminium source or precipitant mix after be neutralized into glue again, in adding basic aluminium salt or alkaline precipitating agent, be neutralized into glue as the water glass, Ludox adds in the acid aluminium salt and is neutralized into glue etc.The silicon source also can add in the post precipitation material of aluminium source.Also can two or more be used in combination with aforesaid way.Said method all is well-known to those skilled in the art.
Below in conjunction with a kind of concrete one-tenth glue procedure declaration the inventive method.
(a) required molecular sieve is added the water making beating.
(b) slurries of (a), a kind of aluminum salt solution and a kind of precipitating reagent and stream are joined being reacted in the glue jar of small amount of deionized water, or a kind of aluminum salt solution and a kind of precipitating reagent and stream are joined in the reaction vessel of slurries of (a), at pH value 7.0-11.0, temperature 30-90 ℃ forms colloidal sol, the neutralization reaction time is 1-2 hour, and stablizes under the condition of pH8-10 0-60 minute.Also can adopt carbonizatin method, in sodium aluminate solution, add the slurries of (a), and then feed the CO of finite concentration, flow
2Gas stops logical CO when reaching the appropriate pH value
2Gas.
(c) in 5-10 minute, a kind of silicon compound is joined in (b), also silicon compound can be added in aluminum salt solution and/or the precipitating reagent earlier in (b) step, be carried out to glue again.
(d) at pH value 7.5-9.5,50-70 ℃ following ℃ aging (c) 10-60 minute.
(e) filter and wash (d).
(f) (e) drying and crushing is obtained product.
In the sial preparation process of the present invention, (a) middle molecular sieve is known any molecular sieve, and (b) middle aluminium salt can be Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3, NaAlO
2Deng in a kind of, precipitating reagent can be NaOH, NH
4OH, NaAlO
2, CO
2Deng in a kind of.But in commercial Application, because NaAlO
2, Al
2(SO
4)
3Inexpensive and be commonly used.(c) related silicon compound can be waterglass, Ludox or organosilicon in.
In the process of the present invention, (b) the pH value in is generally at 7.0-11, best 7.5-8.5, the best 50-70 of temperature ℃, (b) the general 0-60 of the stabilizing take in minute, preferably 15-45 minute.
Because the difference of application purpose, the acidic cleavage function of sial there is different requirements, can adjust the sial character that the addition of silicon compound come appropriate change process of the present invention to prepare by step (c).
(d) this journey should be the ageing process of broad sense, and pH value, temperature, ageing time all are important control parameters, general pH value 7.5-9.5, best 8.0-9.0, temperature 50-70 ℃, preferably 55-65 ℃, general 0-60 of time minute, preferably 15-45 minute.
Behind aging the end, process (e) and (d) can be according to the method for routine, with the sial product washing that obtains removing impurity such as iron ion, sodium ion, sulfate radical, chlorion, and dry, pulverizing and obtain aluminium of the present invention.The purpose that removes impurity is at sial of the present invention during as the component of catalyst, unlikely activity of such catalysts or the stability of having influence on of its impurity level.The drying of sial of the present invention can be used oven drying or spray-drying, generally adopts oven drying, descends dry 6-10 hour at 110 ℃, makes the butt of final sial product reach 60-100w%.Dried sial product sieves, below particle diameter 150 orders, below best 200 orders.
Carrier material of the present invention also can add other auxiliary agent as required, as phosphorus, boron, titanium, zirconium etc.
Carrier material of the present invention can be used as the component of catalytic hydroprocessing agent, is particularly suitable as the component of hydrocracking catalyst.
The specific area of product of the present invention and pore volume are to adopt ASAP2400, and cryogenic nitrogen absorption (77K) calculates according to BET formula.Acid amount and acid matter adopt infrared spectrometer to record, and the adsorbent that uses is pyridine.SiO
2And TiO
2Content adopt gravimetric method and AAS to record respectively.
Further specify technical scheme of the present invention below in conjunction with specific embodiment.
Embodiment 1
Carrier material according to method preparation provided by the invention.
With the Hydrogen Y molecular sieve (SiO of 150g through modification
2/ Al
2O
3=5.1 (molecular proportions, down together), lattice constant is
Relative crystallinity is 90%) add in 2 liters of distilled water, stirring to pulp forms slurries (a), and 4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heats simultaneously and is stirred to dissolving, obtains aluminum sulfate solution (b), Al
2O
3The about 4g/100ml of concentration.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (c).10 liters of distilled water are joined in the concentrated sodium silicate of modulus 3.0 of 4.8 liters of a kind of technical grades, obtain rare water glass solution (d).Get one 15 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate and ammoniacal liquor respectively simultaneously, and slowly adding (a) in retort, by preparation 750g sial product set (b) flow so that the neutralization reaction time at one hour, adjust the adding speed of (a) simultaneously, guarantee (b) when adding (a) also add, and the flow of adjusting rapidly (c) makes the pH value of system remain on 7-8, and the temperature of the hierarchy of control is about 65 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 15 minutes, by finally containing SiO
2Amount begins to add metering (d) 3.3 liters, adds in 10 minutes, and the ageing process of beginning system keeps the pH value 8.0, temperature 60-65 ℃.Aging after 50 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (e).With (e) at 110 ℃ down after dry 8 hours, pulverize, sieve carrier material S-1.
Embodiment 2
With 150g through the Hydrogen β of modification (SiO
2/ Al
2O
3=28, lattice constant is
Relative crystallinity is 87%) molecular sieve adds in 2 liters of distilled water, and stirring to pulp forms slurries (a), and 4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heats simultaneously and is stirred to dissolving, obtains aluminum sulfate solution (b), Al
2O
3The about 4g/100ml of concentration.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (c).10 liters of distilled water are joined in the concentrated sodium silicate of modulus 3.0 of 4.8 liters of a kind of technical grades, obtain rare water glass solution (d).Get one 15 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate and ammoniacal liquor respectively simultaneously, and slowly adding (a) in retort, by preparation 750g sial product set (b) flow so that the neutralization reaction time at one hour, adjust the adding speed of (a) simultaneously, guarantee (b) when adding (a) also add, and the flow of adjusting rapidly (c) makes the pH value of system remain on 7-8, and the temperature of the hierarchy of control is about 65 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 15 minutes, by finally containing SiO
2Amount begins to add metering (d) 3.3 liters, adds in 10 minutes, and the ageing process of beginning system keeps the pH value 8.0, temperature 60-65 ℃.Aging after 50 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (e).With (e) at 110 ℃ down after dry 8 hours, pulverize, sieve sial product S-2.
Embodiment 3
With the Hydrogen Y molecular sieve (SiO of 150g through modification
2/ Al
2O
3=5.1, lattice constant is
Relative crystallinity is 90%) add in 2 liters of distilled water, stirring to pulp forms slurries (a), and 4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heats simultaneously and is stirred to dissolving, obtains aluminum sulfate solution (b), Al
2O
3The about 4g/100ml of concentration.Be mixed into (a) with (b) (b ').Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (c).10 liters of distilled water are joined in the concentrated sodium silicate of modulus 3.0 of 4.8 liters of a kind of technical grades, obtain rare water glass solution (d).Get one 15 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate (containing molecular sieve pulp) and ammoniacal liquor respectively simultaneously, by preparation 750g sial product set (b ') flow so that the neutralization reaction time at one hour, the flow of adjusting (c) makes the pH value of system remain on 7-8, and the temperature of the hierarchy of control is about 65 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 15 minutes, by finally containing SiO
2Amount begins to add metering (d) 3.3 liters, adds in 10 minutes, and the ageing process of beginning system keeps the pH value 8.0, temperature 60-65 ℃.Aging after 50 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (e).After (e) pulled an oar once more, add 17.6ml phosphoric acid, continue to stir filter after 30 minutes filter cake (f), will (f) 110 ℃ of dryings after 8 hours down, pulverize, sieve sial product S-3.
Embodiment 4
With the Hydrogen Y molecular sieve (SiO of 150g through modification
2/ Al
2O
3=5.1, lattice constant is
Relative crystallinity is 90%) add in 2 liters of distilled water, stirring to pulp forms slurries (a), and it is 200g Al that solid sodium aluminate is mixed with concentration
2O
3The dense sodium aluminate solution of/l, being diluted to concentration again is 20g Al
2O
3/ l sodium aluminate working solution is got and is contained SiO
2The sodium silicate solution of 28wt%, being diluted to concentration again is 100g SiO
2/ l sodium metasilicate working solution.Get 10L sodium aluminate working solution and place in the glue jar, add 0.3L sodium metasilicate working solution then, add slurries (a) 0.2L again, 24 ℃ of control reaction temperatures, the feeding flow is 6Nm
3/ h, concentration are the CO of 50v%
2Gas stops logical CO when the pH value reaches 10.0
2, add 0.6L sodium metasilicate working solution, to stablize then 10 minutes, dope filtration also is washed till neutrality with 75 ℃ of deionized waters.120 ℃ of dryings 8 hours, crushing screening got amorphous aluminum silicide product S-4.
Embodiment 5
With 150g through the Hydrogen β of modification (SiO
2/ Al
2O
3=28, lattice constant is
Relative crystallinity is 87%) molecular sieve adds in 2 liters of distilled water, and stirring to pulp forms slurries (a), and 4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heats simultaneously and is stirred to dissolving, obtains aluminum sulfate solution (b), Al
2O
3The about 4g/100ml of concentration.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (c).10 liters of distilled water are joined in the concentrated sodium silicate of modulus 3.0 of 4.8 liters of a kind of technical grades, obtain rare water glass solution (d).Get one 15 liters steel retort, add in jar 2 liters of distilled water and (a) the slurries consumption 50%, and after being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate, ammoniacal liquor and waterglass respectively simultaneously, by preparation 750g sial product set (b) flow so that the neutralization reaction time at one hour, adjust the adding speed of (a) simultaneously, guarantee that remaining slurries (a) when adding at (b), (d) also adds, and the flow of adjusting rapidly (c) makes the pH value of system remain on 7-8, and the temperature of the hierarchy of control is about 65 ℃.Carry out burin-in process then, keep the pH value, temperature 60-65 ℃ 8.0.Aging after 50 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (e).With (e) at 110 ℃ down after dry 8 hours, pulverize, sieve sial product S-5.
Table 1. carrier material main character
Embodiment 6
With product S-1 carrier material 80 grams, adhesive 20 grams mix extruded moulding after rolling, dry and roasting is placed in the reaction vessel, take by weighing ammonium metatungstate 50 grams and be dissolved in water into 200 ml solns, solution was joined the reaction vessel dipping 3 hours with nickel nitrate 23 grams, dry down at 120 ℃ then, after dry 180 minutes, dried catalyst is carried out high-temperature roasting again, 500 ℃, roasting 4 hours, obtain catalyst A, its composition sees Table 2.
Embodiment 7
With industrial sial 50 grams, modification Hydrogen Y molecular sieve (SiO
2/ Al
2O
3=5.1, lattice constant is
Relative crystallinity is 90%) 20 grams and adhesive 20 gram mixing, extruded moulding after rolling, dry and roasting is placed in the reaction vessel, takes by weighing ammonium metatungstate 50 grams and is dissolved in water into 200 ml solns with nickel nitrate 23 grams, solution was joined the reaction vessel dipping 3 hours, dry under 120 ℃ then, after dry 180 minutes, dried catalyst is carried out high-temperature roasting again, 500 ℃, roasting 4 hours obtains catalyst B, and its composition sees Table 2.
Table 2. catalyst physico-chemical property
The invention described above catalyst and reference catalyst thereof are estimated.Estimating with feedstock oil is triumph VGO, reaction pressure 14MPa, hydrogen to oil volume ratio 1500, air speed 1.5h
-1Main character sees Table the activity that 3 height of estimating (65w%) reaction temperature when reaching identical conversion per pass by contrast are evaluated hydrocracking catalyst, and evaluate selection of catalysts according to the difference that product under the given conversion ratio distributes, the calculating of middle distillates oil selectivity obtains by " intermediate oil yield/＜370 ℃ product yield ".
Find out that from table 2 body and catalyst physico-chemical property the catalyst pore volume and the specific surface of comparative example are suitable with catalyst of the present invention.But shown then that from table 4 evaluation result catalyst of the present invention is at a kind of high aromatic hydrocarbons of processing, when height is done heavy raw oil, keep certain conversion ratio, middle distillates oil selectivity is higher, and reaction temperature is not higher than comparative example, illustrate that thus catalyst of the present invention on the basis that keeps greater activity, has good middle distillates oil selectivity.
Table 3 raw material oil properties
Table 4 evaluating catalyst result
Claims (9)
1. the preparation method of a carrier material, carrier material comprises molecular sieve and amorphous aluminum silicide, and preparation process is as follows:
(1) needed molecular sieve is added the water making beating;
(2) become to introduce the molecular sieve pulp that step (1) obtains in the glue process at amorphous aluminum silicide, by final carrier material weight, the molecular sieve addition is 5%～80%;
(3) amorphous aluminum silicide becomes material behind the glue to comprise filtration, washing, dry treatment step, obtains containing the carrier material of molecular sieve and amorphous aluminum silicide.
2. in accordance with the method for claim 1, it is characterized in that molecular sieve described in the described step (1) is one or more in Modified Zeolite Y, β zeolite, ZSM series molecular sieve and the SAPO series molecular sieve.
3. in accordance with the method for claim 1, the weight concentration that it is characterized in that the described molecular sieve pulp of step (1) is 5%～40%.
4. in accordance with the method for claim 1, it is characterized in that it is the neutralization reaction process of acid material and alkaline material that the amorphous aluminum silicide described in the step (2) becomes the glue process, become the glue process to adopt two kinds of materials and stream to become the glue mode of operation, or a kind of material is placed on into the mode of operation that another kind of material in the glue jar adds into glue continuously.
5. according to claim 1 or 4 described methods, it is characterized in that the described amorphous aluminum silicide of step (2) becomes in the glue process, the introducing mode of molecular sieve pulp adopts the one or more combination of following manner: (1) adds into molecular sieve pulp in the glue jar in becoming glue neutralization reaction process continuously; (2) molecular sieve pulp is joined into earlier the glue jar, then acid material and alkaline material are neutralized into glue; (3) with molecular sieve pulp and one or more mixing that become the glue material, be neutralized into the glue process then.
6. according to the described method of claim 1, it is characterized in that described amorphous aluminum silicide becomes the required material of glue to comprise aluminium source, silicon source and precipitating reagent.
7. in accordance with the method for claim 6, it is characterized in that described aluminium source is Al
2(SO
4)
3, AlCl
3, Al (N7O
3)
3And NaAlO
2In one or more, the silicon source is one or more in waterglass, Ludox and the organosilicon, precipitating reagent is NaOH, NH
4OH or CO
2
8. in accordance with the method for claim 7, it is characterized in that it is that acid aluminium salt and basic aluminium salt or alkaline precipitating agent are neutralized into glue that described amorphous aluminum silicide becomes the mode of operation of glue process, or basic aluminium salt and acidic precipitation agent are neutralized into glue.
9. in accordance with the method for claim 6, it is characterized in that the silicon source introduces into the glue jar in becoming the glue process, or with the aluminium source or with precipitant mix after be neutralized into glue again, or add in the post precipitation material of aluminium source, or aforesaid way two or more be used in combination.
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