CN103100442A - Preparation method of carrier material - Google Patents
Preparation method of carrier material Download PDFInfo
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- CN103100442A CN103100442A CN2011103558340A CN201110355834A CN103100442A CN 103100442 A CN103100442 A CN 103100442A CN 2011103558340 A CN2011103558340 A CN 2011103558340A CN 201110355834 A CN201110355834 A CN 201110355834A CN 103100442 A CN103100442 A CN 103100442A
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- molecular sieve
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- surfactant
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Abstract
The invention discloses a preparation method of a carrier material. The preparation method of the carrier material introduces molecular sieve slurry and a surfactant into amorphous silica-alumina in gelling so that molecular sieve and amorphous silica-alumina dispersion is uniform; molecular sieve agglomeration or channel blocking is avoided; a specific surface area, a pore volume and acidity of the carrier material are greatly improved; and catalyst performances are improved. The carrier material is suitable for being used as a catalytic material of a petroleum processing catalyst and especially used as a carrier component of hydrotreating and hydrocracking catalysts.
Description
Technical field
The present invention relates to a kind of preparation method of carrier material, a kind of preparation method who contains the catalyst carrier material of molecular sieve and amorphous aluminum silicide specifically is especially for the preparation method of the catalyst carrier that contains molecular sieve-amorphous aluminum silicide of hydrocracking catalyst.
Background technology
In general, hydrocracking catalyst is a kind of catalyst that has simultaneously cracking function and hydrogenation-dehydrogenation functionality.The cracking function is to be provided by acid carrier, and the hydrogenation dehydrogenation functionality is to be provided by reactive metal, the acid carrier major part is take aluminium oxide or amorphous aluminum silicide as carrier, be equipped with a certain amount of molecular sieve, its basic preparation process is first aluminium oxide or silicon-containing alumina and molecular sieve and other auxiliary agent directly to be mixed, then carry out moulding, drying and roasting, final impregnating metal and activation.Amorphous aluminum silicide requires itself must have enough large specific area and pore volume as one of important component of catalyst carrier, with the carrying active metal component; Molecular sieve is mainly the acidic cleavage component, and for catalyst, cooperation both is most important, only has both coordinative roles, the catalytic action of competence exertion the best.In prior art, because molecular sieve adds by physical mixed, can not be in other carrier material of catalyst Uniform Dispersion, affect the reactivity worth of catalyst.
CN1110304A 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 and phosphorus add with substep plastic method, can make like this silicon and phosphorus major part be dispersed in alumina surface, aluminium oxide aperture and pore volume are improved, but owing to having added more phosphorus, B acid amount greatly reduces to make the acid of alumina surface measure particularly, and acid strength obviously reduces, and its application is subject to certain restrictions.CN1184703A discloses a kind of preparation method of silicon-containing alumina.This silicon-containing alumina is a kind of alumina globule that silica is 5wt%～15wt% that contains, its preparation characteristic is that the silicon-containing alumina wet bulb after 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 some defectives due to balling-up aspect self, make this forming process complicated, product yield is low, the shortcomings such as preparation cost height.EP0339640 discloses a kind of method for preparing 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.Require two or more species co-precipitation under certain condition due to co-precipitation, 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 be also all best to two kinds of materials, and the method has characteristics and the shortcoming of itself thus.CN1060977A discloses a kind of preparation method who contains the ultrastable of amorphous aluminum silicide, Alusil is introduced in the NaY zeolite, then obtained containing the USY zeolite of amorphous aluminum silicide through conventional ammonium ion exchange, hydrothermal calcine process.The main deficiency of the method is: the part amorphous aluminum silicide is easy to enter in molecular sieve pore passage, not only stop up molecular sieve pore passage, pore volume and the specific area of molecular sieve have been reduced, but also covered the part acid site, affected the catalytic performance of molecular sieve, also affect simultaneously the modification process of molecular sieve, the catalytic performance of molecular sieve and amorphous aluminum silicide can not be played one's part to the full.
CN200610134151.1 discloses a kind of preparation method who contains the carrier material of molecular sieve and amorphous aluminum silicide.Molecular sieve in carrier is introduced in amorphous aluminum silicide plastic process.In the method, reuniting can appear in silica-alumina supports in molecular sieve, and perhaps molecular sieve and amorphous aluminum silicide enter mutually the other side's duct, have blocked the part duct and have covered a part of acid site, makes carrier specific area, pore volume and acidity increase limited.
Summary of the invention
For the deficiencies in the prior art part, the invention provides a kind of preparation method with bigger serface, large pore volume, acid suitable carrier material.The method makes the more even of molecular sieve and amorphous aluminum silicide dispersion, having overcome molecular sieve easily occurs reuniting, perhaps molecular sieve and amorphous silicon aluminium enter mutually the other side's duct, the problem of blocking part duct and cover part acid centre, specific area and the pore volume of carrier material are greatly improved, and acidity improves.
The preparation method of carrier material of the present invention, described carrier material comprises molecular sieve and amorphous aluminum silicide, and wherein the content of molecular sieve is 5wt%～50wt%, and process is as follows:
(l) needed molecular sieve is added the water making beating;
(2) introduce the molecular sieve pulp that step (l) obtains in amorphous aluminum silicide plastic process;
(3) material after the amorphous aluminum silicide plastic comprises the treatment step of filtration, washing, drying, obtains containing the carrier material of molecular sieve and amorphous aluminum silicide;
Wherein, step (2) adds surfactant in amorphous aluminum silicide plastic process, and take final carrier material weight as benchmark, the addition of surfactant is 2wt%～20wt%.
The surfactant of step of the present invention (2) is preferably nonionic surface active agent, as: one or more in polyglycol ether, APES, AEO, polyoxyethylene carboxylate, polyoxyethylene amine, polyoxyethylate amide, fatty glyceride etc.Described surfactant preferably adds with the form of the aqueous solution, is about to surfactant and is added to the water the aqueous solution that formation contains surfactant.
Molecular sieve described in step (l) is known any molecular sieve, is preferably one or more of modified molecular screen.The selection of the concrete kind of molecular sieve and character can be determined according to the needs that use, at petrochemical industry, molecular sieve commonly used such as Y zeolite, beta-molecular sieve, ZSM Series Molecules sieve, SAPO Series Molecules 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, various solvent processing etc.For the required molecular sieve of petroleum refining catalyst, generally need carry out the modifying process such as ion-exchange, hydrothermal treatment consists.The weight concentration of molecular sieve pulp is generally 5%～40%.
Amorphous aluminum silicide plastic process described in step of the present invention (2) can be undertaken by process well known to those skilled in the art.Amorphous aluminum silicide plastic process is generally the neutralization reaction process of acid material and alkaline material, and the plastic process is general adopts two kinds of materials also to flow the plastic mode of operation, or a kind of material is placed on the mode of operation that another kind of material in plastic cans adds plastic continuously.In amorphous aluminum silicide plastic process, the introducing mode of molecular sieve pulp and surfactant can be selected arbitrarily, as adopting the one or more combination of following manner: (1) adds molecular sieve pulp and surfactant in plastic cans in plastic neutralization reaction process continuously; (2) molecular sieve pulp and surfactant are first joined in plastic cans, then will prepare in the acid material of amorphous aluminum silicide and alkaline material and plastic; (3) one or more with the plastic material of molecular sieve pulp and surfactant are mixed, then in the plastic material and plastic.The material that amorphous aluminum silicide plastic process is used and plastic condition are well known to those skilled in the art, and can specifically according to the requirement of using select to determine.Can carry out under optimum conditions burin-in process after plastic.
Process and condition that filtration, washing, drying and other steps described in step of the present invention (3) after plastic is well known to the skilled person.The processing procedure such as can also comprise pulverizing, sieve.Described drying generally adopts oven drying, and drying condition is as follows: drying is 6～10 hours under 80～120 ℃.
The carrier material that the inventive method obtains comprises molecular sieve and amorphous aluminum silicide, and molecular sieve content is 5 wt%～50wt%, and amorphous aluminum silicide content is 50 wt%～95wt%, and this carrier material has following character: specific area is 400m
2/ g～1000m
2/ g, pore volume are 0.6cm
3/ g～2.0cm
3/ g.
In the present invention, in amorphous aluminum silicide, dioxide-containing silica is 10wt%～50wt%.
Silica-alumina supports material of the present invention is suitable for the catalyst component as the PETROLEUM PROCESSING catalyst, is particularly suitable for doing the carrier component of hydrotreatment and hydrocracking catalyst.
The present invention contains in the preparation process of molecular sieve and amorphous aluminum silicide carrier material, to introduce molecular sieve pulp in the plastic 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.introduced surfactant in addition in the plastic process, surfactant has the characteristics of dispersion, the surfactant molecule structure has amphipathic: an end is hydrophilic radical, the other end is the hydrophobic group, molecular sieve has hydrophobicity, amorphous silicon aluminium has hydrophily, amorphous silicon aluminium like this, surfactant and molecular sieve Uniform Dispersion, ordered arrangement, avoided molecular sieve can occur reuniting in silica-alumina supports, perhaps molecular sieve and amorphous silicon aluminium enter mutually the other side's duct, block part duct and cover part acid centre, specific area and the pore volume of carrier material are greatly improved, acid, the distribution of B acid and L acid improves, the acid amount increases, B/L acid ratio increases.
The specific embodiment
In the inventive method, amorphous aluminum silicide plastic process can adopt content well known to those skilled in the art.The plastic material generally comprises aluminium source (A1
2(SO
4)
3, A1Cl
3, Al (NO
3)
3, NaAlO
2Deng in one or more), silicon source (one or more in waterglass, Ludox and organosilicon etc.), precipitating reagent (NaOH, NH
3OH or CO
2Deng), to use according to the different choice of plastic process, conventional mode of operation mainly contains: (l) acid aluminium salt (A1
2(SO
4)
3, A1Cl
3, Al (NO3)
3) and basic aluminium salt (NaAlO
2) or alkaline precipitating agent (NaOH, NH
4OH) in and plastic, (2) basic aluminium salt (NaAlO
2) and acidic precipitation agent (CO
2) in and plastic.
Plastic cans is generally introduced in the silicon source in the plastic process, also can with aluminium source or precipitant mix after again in and plastic, as in carrying out in waterglass basic aluminium salt or alkaline precipitating agent and plastic, Ludox add carry out in acid aluminium salt in and plastic etc.The silicon source also can add in the rear material of aluminium source precipitation.Also can two or more be combined with aforesaid way.Said method is all well-known to those skilled in the art.
Below in conjunction with a kind of concrete plastic procedure declaration the inventive method.(a) required molecular sieve is added the water making beating;
(b) required surfactant is configured to working solution;
(c) in the reaction plastic cans that solution, a kind of aluminum salt solution and a kind of precipitating reagent that the slurries that step (a) obtained, step (b) obtain and stream join a small amount of deionized water, or a kind of aluminum salt solution and a kind of precipitating reagent and stream are joined in steps in the reaction vessel of the solution that slurries that (a) obtain and step (b) obtain, in pH value 7.0～11.0,30～90 ℃ of formation colloidal sols of temperature, the neutralization reaction time is 1～2 hour, and stablizes under the condition of pH 9～10 10～60 minutes.Also can adopt carbonizatin method, the slurries that add step (a) to obtain in the sodium aluminate solution, and then pass into CO
2Gas stops logical CO when reaching the appropriate pH value
2Gas; (d) in 5～10 minutes, a kind of silicon-containing compound is joined in step (c), also can be with silicon-containing compound in step (c) step first add aluminum salt solution and/or precipitating reagent, then carry out plastic; (e) mixed material of step (d) gained is under pH value 7.5～9.5,50～70 ℃ aging 10～60 minutes; (f) filter the also mixed material of washing step (e) gained; (g) with the mixed material drying and crushing of step (f) gained and obtain carrier material of the present invention.In carrier material preparation process of the present invention, any molecular sieve that in step (a), molecular sieve is known for oneself, surfactant in step (b) is preferably nonionic surface active agent, as: one or more in polyglycol ether, APES, AEO, polyoxyethylene carboxylate, polyoxyethylene amine, polyoxyethylate amide, fatty glyceride etc.
In step (c), 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, due to NaAlO
2, Al
2(SO
4)
3Inexpensive and be commonly used.In step (d), related silicon-containing compound can be waterglass, Ludox or organosilicon.
In process of the present invention, pH value in step (c) is preferably 8.0～9.5, temperature is preferably 40～70 ℃, because application purpose is different, acidic cleavage function to sial has different requirements, can come by the addition of step (d) adjustment silicon-containing compound the silica-alumina supports material character of appropriate change process preparation of the present invention.This process of step (e) should be the ageing process of broad sense, and pH value, temperature, ageing time are all important control parameters, and general pH is best 8.0～9.0, best 55～65 ℃ of temperature, best 30～60 minutes of time.The dry general oven drying that adopts in step (g), drying is 6～10 hours under 80～120 ℃.
Composite of the present invention can be used as the component of hydrogenation catalyst, is particularly suitable as the component of hydrocracking catalyst.The specific area of product of the present invention and pore volume are to adopt ASAP2405, the low temperature liquid nitrogen determination of adsorption method.Acid amount and Acidity adopt infrared spectrometer to record, and the adsorbent that uses is pyridine.Wt% is mass fraction.
Further illustrate 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 150g modified Y molecular sieve (SiO
2/ A1
2O
3=42(molecular proportion), lattice constant is 2.430nm, and relative crystallinity is 101%, reference CN02144945.7 preparation, lower same), add in 2 liters of distilled water, stirring to pulp, form slurries (a), 120g polyoxyethylene amine solvent forms solution (b) in 1L water, 4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtaining aluminum sulfate solution (c), A1
2O
3Concentration is 4g/100ml approximately.It is the weak aqua ammonia (d) of 10wt% into about concentration that concentrated ammonia liquor is added appropriate distilled water diluting.10 liters of distilled water are joined in 4.8L concentrated sodium silicate (technical grade, modulus are 3.0), obtain rare water glass solution (e).Get the steel retort of one 15 liters, after adding 2 liters of distilled water in tank and being heated with stirring to 70 ℃, open simultaneously the valve of the container that has respectively aluminum sulfate and ammoniacal liquor, and slowly add (a) and (b) in the retort, by the flow of preparation 750g sial product setting value (c) so that the neutralization reaction time at one hour, adjust simultaneously (a) and (b) add speed, guarantee at (a) and (b) He (c) add simultaneously, and the flow of adjusting rapidly (d) makes the pH value of system remain on 7～8, and the temperature of the hierarchy of control is 65 ℃ of left and right.After reacting aluminum sulfate is completed, stop adding ammoniacal liquor, after the alumina sol of generation is stablized 20 minutes, by finally containing SiO
2Amount begins to add 3.3 liters of meterings (e), adds in 10 minutes, and the ageing process of beginning system keeps the pH value 8.0,60～65 ℃ of temperature.After aging 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 (f).After under 110 ℃ dry 8 hours, composite carrier F-1 pulverizes, sieves and to get with (f).Embodiment 2 is with 150g modified beta molecular sieve (SiO
2/ A1
2O
3=28(molecular proportion), structure cell is often 1.198nm, and relative crystallinity is 95%), add in 2 liters of distilled water, stirring to pulp, form slurries (a), the 110g polyglycol ether is dissolved in 1L water, forms solution (b), 4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtaining aluminum sulfate solution (c), A1
2O
3Concentration is 4g/100ml approximately.Add appropriate distilled water diluting into about 10% weak aqua ammonia (d) concentrated ammonia liquor.10 liters of distilled water are joined in 4.8L concentrated sodium silicate (technical grade, modulus are 3.0), obtain rare water glass solution (e).Get the steel retort of one 15 liters, after adding 2 liters of distilled water in tank and being heated with stirring to 70 ℃, open simultaneously the valve of the container that has respectively aluminum sulfate and ammoniacal liquor, and slowly add (a) and (b) in the retort, by preparation 750g sial product set (c) value flow so that the neutralization reaction time at one hour, adjust simultaneously (a) and (b) add speed, guarantee at (a) and (b) He (c) add simultaneously, and the flow of adjusting rapidly (d) makes the pH value of system remain on 7～8, and the temperature of the hierarchy of control is 65 ℃ of left and right.After reacting aluminum sulfate is completed, stop adding ammoniacal liquor, after the alumina sol of generation is stablized 20 minutes, by finally containing SiO
2Amount begins to add 3.3 liters of meterings (e), adds in 10 minutes, and the ageing process of beginning system keeps the pH value 8.0,60～65 ℃ of temperature.After aging 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 (f).After under 110 ℃ dry 8 hours, composite carrier F-2 pulverizes, sieves and to get with (f).
Embodiment 3
With 150g modified Y molecular sieve (with embodiment 1), add in 2 liters of distilled water, stirring to pulp, form slurries (a), the 100g fatty glyceride is dissolved in 1L water, forms solution (b), 4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtaining aluminum sulfate solution (c), A1
2O
3Concentration is 4g/100ml approximately.With (a) and (b) and (c) be mixed into (c) '.Add appropriate distilled water diluting into about 10wt% weak aqua ammonia (d) concentrated ammonia liquor.10 liters of distilled water are joined in 4.8L concentrated sodium silicate (technical grade, modulus are 3.0), obtain rare water glass solution (e).Get the steel retort of one 15 liters, after adding 2 liters of distilled water in tank and being heated with stirring to 70 ℃, open simultaneously and have respectively solution (c) ' valve of the container of (containing aluminum sulfate, molecular sieve pulp and surfactant) and ammoniacal liquor, by preparation 750g sial product setting value (c) ' flow so that the neutralization reaction time at one hour, the flow of adjusting (d) makes the pH value of system remain on 7～8, and the temperature of the hierarchy of control is 65 ℃ of left and right.After reacting aluminum sulfate is completed, stop adding ammoniacal liquor, after the alumina sol of generation is stablized 20 minutes, by finally containing SiO
2Amount begins to add 3.3 liters of meterings (e), adds in 10 minutes, and the ageing process of beginning system keeps the pH value 8.0,60～65 ℃ of temperature.After aging 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 (f).After under 110 ℃ dry 8 hours, composite carrier F-3 pulverizes, sieves and to get with (f).
Embodiment 4
With 150g modified Y molecular sieve (with embodiment 1), add in 2 liters of distilled water, stirring to pulp forms slurries (a), and the 150g polyglycol ether is dissolved in 1L water, forms solution (b), and it is 200gAl that solid sodium aluminate is mixed with concentration
2O
3The dense sodium aluminate solution of/L, then to be diluted to concentration be 20gAl
2O
3/ L sodium aluminate working solution is got and is contained SiO
2The sodium silicate solution of 28wt%, then to be diluted to concentration be 100g SiO
2/ L sodium metasilicate working solution.Get 10L sodium aluminate working solution and be placed in plastic cans, then add 0.3L sodium metasilicate working solution, then add slurries (a) 0.2L and solution (b), control 24 ℃ of reaction temperatures, passing into flow is 6Nm
3/ h, concentration are the CO of 50v%
2Gas stops logical CO when the pH value reaches 10.0
2, then add 0.6L sodium metasilicate working solution, then ventilate and stablized 20 minutes, dope filtration also spends 75 ℃ of ionized waters washings to neutral, and 120 ℃ of dryings 8 hours pulverize and sieve to get complex carrier F-4.
Comparative example 1
150g modified Y molecular sieve (with embodiment 1) is added 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), A1
2O
3Concentration is 4g/100ml approximately.Add appropriate distilled water diluting into about 10% weak aqua ammonia (c) concentrated ammonia liquor.10 liters of distilled water are joined in 4.8L concentrated sodium silicate (technical grade, modulus are 3.0), obtain rare water glass solution (d).Get the steel retort of one 15 liters, after adding 2 liters of distilled water in tank and being heated with stirring to 70 ℃, open simultaneously the valve of the container that has respectively aluminum sulfate and ammoniacal liquor, and slowly add (a) in retort, by the flow of preparation 750g sial product setting value (b) so that the neutralization reaction time at one hour, adjust simultaneously the speed that adds of (a), guarantee to add simultaneously at (a) with (b), 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 65 ℃ of left and right.After reacting aluminum sulfate is completed, stop adding ammoniacal liquor, after the alumina sol of generation is stablized 20 minutes, by finally containing SiO
2Amount begins to add 3.3 liters of meterings (d), adds in 10 minutes, and the ageing process of beginning system keeps the pH value 8.0,60～65 ℃ of temperature.After aging 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 under 110 ℃ dry 8 hours, pulverize, sieve to such an extent that composite carrier CF-1(comparative example 1 is reference CN200610134151.1 preparation with (e)).Comparative example 2
With the amorphous aluminum silicide (not adding Y and surfactant) of 15g modified Y molecular sieve (with embodiment 1), 75g embodiment 1 method preparation, 10gSB aluminium oxide and rare nitric acid kneading roll, but make the paste of extrusion, extruded moulding, 110 ℃ of dryings 6 hours make reference support C F-2.
The physico-chemical property of table 1 carrier material
| Numbering | F-1 | F-2 | F-3 | F-4 | CF-1 | CF-2 |
| Specific area, m 2/g | 460 | 537 | 482 | 475 | 380 | 310 |
| Pore volume, ml/g | 0.69 | 1.11 | 0.72 | 0.67 | 0.59 | ?0.48 |
| Infrared total acid content, mmol/g | 0.447 | 0.912 | 0.475 | 0.462 | 0.405 | 0.392 |
| B acid/L acid | 1.74 | 2.50 | 1.79 | 1.76 | 1.44 | 1.12 |
Claims (10)
1. the preparation method of a carrier material, carrier material comprises molecular sieve and amorphous aluminum silicide, and molecular sieve content is 5 wt%～50wt%, and process comprises:
(l) needed molecular sieve is added the water making beating;
(2) introduce the molecular sieve pulp that step (l) obtains in amorphous aluminum silicide plastic process;
(3) material after the amorphous aluminum silicide plastic comprises the treatment step of filtration, washing, drying, obtains containing the carrier material of molecular sieve and amorphous aluminum silicide;
Wherein, step (2) adds surfactant in amorphous aluminum silicide plastic process, and take the weight of final carrier material as benchmark, the addition of surfactant is 2wt%～20wt%.
2. in accordance with the method for claim 1, it is characterized in that described surfactant is nonionic surface active agent.
3. in accordance with the method for claim 2, it is characterized in that described nonionic surface active agent is one or more in polyglycol ether, APES, AEO, polyoxyethylene carboxylate, polyoxyethylene amine, polyoxyethylate amide and fatty glyceride.
4. according to claim 1,2 or 3 described methods, it is characterized in that described surfactant adds with the form of the aqueous solution.
5. in accordance with the method for claim 1, it is characterized in that in described amorphous aluminum silicide, dioxide-containing silica is 10wt%～50wt%.
6. according to carrier material claimed in claim 1, it is characterized in that described molecular sieve is modified molecular screen.
7. according to the described carrier material of claim 1 or 6, it is characterized in that described molecular sieve is that Y zeolite, beta-molecular sieve, ZSM Series Molecules sieve, SAPO Series Molecules sieve one or more.
8. the weight concentration that in accordance with the method for claim 1, it is characterized in that the described molecular sieve pulp of step (1) is 5%～40%.
9. in accordance with the method for claim 1, it is characterized in that the amorphous aluminum silicide plastic process described in step (2) is the neutralization reaction process of acid material and alkaline material, the plastic process adopts two kinds of materials also to flow the plastic mode of operation, or a kind of material is placed on the mode of operation that another kind of material in plastic cans adds plastic continuously.
10. in accordance with the method for claim 1, it is characterized in that in the described amorphous aluminum silicide plastic of step (2) process, the introducing mode of molecular sieve pulp and surfactant adopts the one or more combination of following manner: (1) adds molecular sieve pulp and surfactant in plastic cans in plastic neutralization reaction process continuously; (2) molecular sieve pulp and surfactant are first joined in plastic cans, then will prepare in the acid material of amorphous aluminum silicide and alkaline material and plastic; (3) one or more with the plastic material of molecular sieve pulp and surfactant are mixed, then in the plastic material and plastic.
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|---|---|---|---|
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172259A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Method for preparing carrier material |
| CN101239328A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Amorphous silica-alumina and its preparing method |
-
2011
- 2011-11-11 CN CN201110355834.0A patent/CN103100442B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172259A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Method for preparing carrier material |
| CN101239328A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Amorphous silica-alumina and its preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 何琳琳等: "纳米Y型分子筛/无定形硅铝复合材料的制备", 《第15届全国分子筛学术大会论文集》, 11 October 2009 (2009-10-11) * |
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