CN103100443A - Preparation method of catalyst carrier material containing molecular sieve and amorphous silica-alumina - Google Patents
Preparation method of catalyst carrier material containing molecular sieve and amorphous silica-alumina Download PDFInfo
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- CN103100443A CN103100443A CN2011103558355A CN201110355835A CN103100443A CN 103100443 A CN103100443 A CN 103100443A CN 2011103558355 A CN2011103558355 A CN 2011103558355A CN 201110355835 A CN201110355835 A CN 201110355835A CN 103100443 A CN103100443 A CN 103100443A
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Abstract
The invention discloses a preparation method of a catalyst carrier material containing a molecular sieve and amorphous silica-alumina. The preparation method comprises the following steps of adding a mixture of a molecular sieve and an organic amine, and an organic alcohol and/or an organic acid into amorphous silica-alumina in gelling, after gelling of the amorphous silica-alumina, carrying out aging, then carrying out hydrothermal treatment and then carrying out filtration, washing and drying to obtain the catalyst carrier material. The preparation method realizes ordered arrangement and uniform deposition of the silica-alumina on the surface of the molecular sieve, improves the binding strength of the molecular sieve and the silica-alumina, avoids agglomeration of the amorphous silica-alumina and the molecular sieve and channel blocking caused by the agglomeration, realizes mutual communication of channels of the silica-alumina and the molecular sieve, and fully develops synergism of the silica-alumina and the molecular sieve. The hydrothermal treatment is conducive to formation of regular mesoporouses in the amorphous silica-alumina so that catalyst use performances are improved. The catalyst carrier material can be used as an acidic component in a catalyst and is especially suitable for being used as a hydrocracking catalyst carrier.
Description
Technical field
The present invention relates to a kind of preparation method who contains the catalyst carrier material of molecular sieve and amorphous aluminum silicide, especially for the preparation method of amorphous aluminum silicide composite carrier of the molecular sieve of hydrogenation catalyst-in order.
Background technology
Developing rapidly and crude oil variation progressively of World Economics makes market increase year by year the demand of light-end products and industrial chemicals.Hydrocracking technology is that one of important means of crude oil secondary operations, heavy oil lighting has obtained increasingly extensive application.
The crucial hydrocracking catalyst of hydrocracking technology.Hydrocracking catalyst is a kind of bifunctional catalyst, and its lytic activity and hydrogenation activity are to be provided respectively by the acidic components in catalyst and hydrogenation activity component.Acidic components in catalyst are generally to be provided by molecular sieve contained in catalyst and/or amorphous aluminum silicide.The characteristics such as molecular sieve has stronger acidity, is the main cracking component in catalyst, has reaction temperature low, and activity is strong.The amorphous aluminum silicide catalyst reaction temperatures is higher, but reaction comparatively relaxes, and middle distillates oil selectivity is good.It is the main direction of hydrocracking catalyst development that molecular sieve is used in combination with amorphous aluminum silicide and molecular sieve.And have good activity, selective and stability by molecular sieve and the prepared catalyst of amorphous aluminum silicide, be suitable for long-term operation.
Between conjugation between molecular sieve in carrier and amorphous aluminum silicide and decentralization and its reactivity worth, inseparable relation is arranged, the good dispersion acid site of carrier is evenly distributed, and it is comparatively even that reaction mass reacts in catalyst; Affect to a great extent the active of catalyst and selective to various purpose products.The dispersiveness that how to solve between molecular sieve and amorphous silicon alumina supporter is that preparation has the key of sound response performance catalyst.
In the patents such as CN201010197869.1, CN200810117102.6, CN00105235.7, disclosed hydrocracking catalyst is all that the raw material that molecular sieve, aluminium oxide etc. are single prepares through after mechanical mixture.The prepared catalyst of the method can be inhomogeneous because of various raw materials mixing, affects the performance of each component property.
CN1060976A discloses a kind of preparation method who contains the ultrastable of amorphous alumina.The method is that to add ammoniacal liquor to regulate the pH value in aluminum sulfate solution be 3.5～7.5, then add NaY zeolite or HNaY zeolite, mix, then prepare USY zeolite process by hydro-thermal method and carry out the subsequent treatment such as ammonium ion exchange and hydrothermal treatment consists, obtain containing the ultrastable of amorphous alumina.The method is after the aluminium oxide plastic, adds the zeolite raw material, then the composite of modification gained according to a conventional method.The method exists amorphous alumina agglomeration easily to occur, make the skewness of amorphous alumina on molecular sieve, even stop up the duct of molecular sieve, specific area and the pore volume of catalyst are significantly reduced, and the patency in molecular sieve and aluminium oxide duct is relatively poor, affects the performance of catalyst.Carry out hydrothermal treatment consists and ammonium exchange process after the method is compound with amorphous alumina by the NaY zeolite again, strengthened treating capacity, reduced the efficient of processing, in processing procedure, amorphous alumina can be processed together, easily aluminium oxide produced ill effect.
CN200610134151.1 discloses a kind of preparation method of carrier material, and the method is directly to add the method for molecular sieve to prepare in amorphous aluminum silicide plastic process.In the method, agglomeration easily appears in amorphous aluminum silicide, also easily enter the other side's duct or the aperture of obstruction molecular sieve, affect the distribution of amorphous aluminum silicide on molecular sieve, the connectivity in molecular sieve and amorphous aluminum silicide duct is relatively poor, specific area and the pore volume of catalyst are reduced, affect the performance of catalyst.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of preparation method who contains the catalyst carrier material of molecular sieve and amorphous aluminum silicide.Catalyst carrier by the method preparation can combine molecular sieve and amorphous aluminum silicide, has good conjugation and decentralization, can avoid occurring reuniting between molecular sieve and amorphous aluminum silicide even clogging, has good serviceability.
The present invention contains the preparation method of the catalyst carrier material of molecular sieve and amorphous aluminum silicide, comprising:
(1) molecular sieve is mixed with organic amine, wherein the addition of organic amine accounts for the 1wt% ~ 40wt% of molecular sieve weight;
(2) mixture and the organic matter that add step (1) to obtain in amorphous aluminum silicide plastic process, take the weight of final carrier material as benchmark, the molecular sieve addition is 5wt% ~ 90wt%, organic addition is 1wt% ~ 50wt%, one or more in the organic acid that described organic matter is the organic alcohols that contains two or more hydroxyls, contain two or more carboxyls;
(3) carry out agingly after the described amorphous alumina cemented into bundles of step (2), then carry out hydrothermal treatment consists, more after filtration, washing, drying, obtain catalyst carrier material.
In step of the present invention (1), described organic amine is carbon number less than one or more in the fatty amine of 20, aromatic amine, hydramine.Better suited for containing the amine of chain, be preferably one or more in the fatty amines that contains 2 ~ 10 carbon numbers.For example: ethamine, propylamine, tert-butylamine; Decyl amine, dimethylamine, di-n-propylamine, butylamine, hexylamine, 2 ethyl hexylamine, diethylamine, diisopropylamine, hexamethylene diamine, 1,2-dimethyl propylamine, sec-butylamine, 1,5-dimethylhexylamine, ethylenediamine, 1, one or more in 2-propane diamine, Putriscine, monoethanolamine, diethanol amine, triethanolamine, 3-Propanolamine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, aniline.Organic amine mixes with molecular sieve, can directly add organic amine in molecular sieve, also organic amine can be dissolved in and add in solvent in molecular sieve again, solvent wherein is one or more in water, low-carbon alcohols (being that carbon number is one or more in 1 ~ 5 monohydric alcohol).If the addition of organic amine is larger, needs to filter also and carry out again step (2) after drying.
The plastic process of the amorphous aluminum silicide described in step of the present invention (2) can be undertaken by process well known to those skilled in the art.The plastic process of amorphous aluminum silicide is generally the neutralization reaction process of acid material and alkaline material.The plastic process can adopt the mode of the continuous acid-base titration of soda acid, also can adopt the mode of two kinds of materials and stream neutralization.Silicon components can be to be introduced separately into by the plastic process, carries out plastic after namely aluminium source or precipitant mix are completed again; Also can introduce together with alkaline precipitating agent; It can be also the combination of above-mentioned two kinds of methods.If by introducing together with alkaline precipitating agent, can add together with the mode that alkaline precipitating agent mixes.This preparation process is well known to those skilled in the art.
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.The plastic material generally comprises 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 organic silicon-containing compound etc.), precipitating reagent (NaOH, NH
4OH or CO
2Deng), to use according to the different choice of plastic 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) 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 waterglass add carry out in basic aluminium salt or alkaline precipitating agent in and plastic, Ludox add carry out in acid aluminium salt in and plastic etc.The silicon source also can add after the precipitation of aluminium source in material, also can two or more is combined with aforesaid way.Said method is all well-known to those skilled in the art.Described plastic process is generally carried out under room temperature ~ 85 ℃, is suitably for 40 ~ 80 ℃, is preferably 50 ~ 70 ℃.Described plastic process is generally carried out under certain pH value condition, and typical pH is 6.0 ~ 10.0, is suitably for 7.0 ~ 9.5, is preferably 7.5 ~ 9.0.Step (3) is described aging, and condition is as follows: pH is 6.0 ~ 10.0, is preferably 7.0 ~ 9.5, and ageing time 0.25 ~ 8 hour is adapted at 0.5 ~ 5 hour, is preferably 1 ~ 3 hour, and aging temperature is room temperature ~ 85 ℃, is preferably 40 ~ 80 ℃.Temperature when aging and pH with in and the time temperature and pH preferably identical.
In step of the present invention (1), described molecular sieve is known any or several molecular sieves, preferably one or several in modified molecular screen.These molecular sieves are that those skilled in that art are known, such as faujasite (such as Y zeolite), β zeolite, omega zeolite, modenite, L zeolite, ZSM Series Molecules sieve, SAPO Series Molecules sieve, MCM Series Molecules sieve etc. one or more.For the catalytic performance that obtains to wish, various molecular sieves can carry out suitable modifying process, the process that method of modifying is well known to those skilled in the art is as one or more method modifications in hydrothermal treatment consists, acid treatment, ion-exchange, various solvent processing etc.In step of the present invention (1), the state that adds of described molecular sieve can be that dry powder-shaped adds, and can be also to add with the slurries form.
In step of the present invention (2), the introducing mode of the mixture of step (1) gained adopts the one or more combination of following manner: (1) adds this mixture in plastic cans in plastic neutralization reaction process continuously; (2) this mixture is 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 this mixture are mixed, then in the plastic material and plastic.
Organic alcohols described in step of the present invention (2) is the organic compound that contains two or more hydroxyls, its boiling point is higher than the plastic temperature, generally at 100 ℃ ~ 350 ℃, preferably more than 120 ℃, further preferred more than 150 ℃, for example diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, propane diols, glycerine, 1,4-butanediol, butantriol, 2,2-dimethyl-1,3 propane diols, DPG, xylitol, pentanediol, 1, one or more in 6-hexylene glycol, hexitol, sweet mellow wine.Described organic acid is the organic compound that contains two or more carboxyls, its boiling point is higher than the plastic temperature, generally at 100 ℃ ~ 350 ℃, preferably more than 120 ℃, further preferred more than 150 ℃, one or more in ethanedioic acid (oxalic acid), malonic acid, citric acid, succinic acid, malic acid, tartaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid for example.
In step of the present invention (2), the described organic one or more combination that adds mode can select following manner: (1) is in the plastic initial stage joins plastic cans in advance, (2) be added drop-wise to plastic cans in the plastic process, (3) with one or more mixing of plastic raw material, add in plastic cans with material.Described organic matter can same step (1) gained mixture together add, also can add separately.
In step of the present invention (3), before hydrothermal treatment consists, preferably after filtration or the heating concentration, remove excessive moisture and organic matter.Wherein said heating simmer down to is at 90 ~ 110 ℃ of lower heating stepses (2) products obtained therefrom, and temperature is 95 ~ 105 ℃ preferably, preferably 98 ~ 100 ℃, is heated to immobilising paste shape.
In step of the present invention (3), described hydrothermal treatment consists is carried out in closed container, and the temperature of hydrothermal treatment consists is 90 ~ 300 ℃, preferably 100 ~ 250 ℃, be preferably 150 ~ 210 ℃, described hydrothermal treatment consists is for carrying out under self the pressure condition that produces when the material treatment temperature.The described hydrothermal treatment consists time is 0.5 ~ 48h, is 1 ~ 36h, preferably 2 ~ 24h preferably.
In step of the present invention (3), the mode of washing of described material is known in those skilled in the art, can select the making beating washing, add the modes such as water washing, lower alcohols washing when filtering, the temperature of washing should be in the scope of room temperature ~ 90 ℃ temperature, preferred 50 ~ 70 ℃.The washing of described material is generally carried out in pH is 1.0 ~ 9.0 scope, and preferred pH is 4.0 ~ 8.5.Material described in step of the present invention (3) should not contain or contain the seldom heteroion of amount after washing, filtration, heteroion comprises Na
+, Cl
-, SO
4 2-, NO
3 -, K
+Deng in one or more.
In step of the present invention (3), described material is after washing, filtering, filter cake carries out drying, and that drying mode can adopt is natural drying, oven drying, spray-drying, microwave drying or infra-red drying, and general drying condition is as follows: under 50 ~ 150 ℃ dry 1 ~ 15 hour.
The carrier material of the inventive method preparation is a kind of raw material of Kaolinite Preparation of Catalyst carrier, this carrier material is through 450 ~ 650 ℃ of roastings after 2 ~ 10 hours, the character of gained is as follows: the weight of carrier material is as benchmark after the roasting, the content of molecular sieve is 5wt% ~ 90wt%, the content of amorphous aluminum silicide is at 10wt% ~ 95wt%, in amorphous aluminum silicide, SiO
2Content is generally 10wt% ~ 50wt%, and specific area is 200 ~ 1000m
2/ g, pore volume are 0.3 ~ 1.8cm
3/ g, the meleic acid amount is 0.1 ~ 2.0mmol/g.
The prepared carrier material of the inventive method can be used as acidic components in catalyst, be particularly useful as carrier of hydrocracking catalyst, especially the carrier of hydrocracking catalyst of mink cell focus improves the long period stability of the selective and catalyst of the activity of catalyst and purpose product.
the preparation method of catalyst carrier material of the present invention is that molecular sieve mixes with organic amine in advance, organic amine can be adsorbed onto duct and the place, aperture of molecular sieve in advance, the pore passage structure of molecular sieve is protected in advance, can avoids like this in sial plastic process fragment to enter the duct, stop up aperture or direct plastic in the duct, organic amine has the guide effect to the sial duct in sial plastic process simultaneously, and match with the hydroxyl that adds or the organic matter of carboxyl in sial plastic process, because the organic matter of hydroxyl or carboxyl is water-soluble, make that to have a city, hydrophilic Guilin orderly at the molecular sieve surface alignment, be deposited on equably the surface of molecular sieve, and strengthened the adhesion of molecular sieve and sial, avoided amorphous aluminum silicide even to stop up the phenomenon in duct with occurring between molecular sieve reuniting, and the duct of sial and molecular sieve is connected mutually, make sial and molecular sieve give full play to synergy, the aging amorphous aluminum silicide colloidal sol that helps is assembled gradually, even pore-forming, hydrothermal treatment consists helps the mesopore of amorphous aluminum silicide formation rule, improved the serviceability of catalyst.Molecular sieve can adopt various suitable methods to process according to its instructions for use before introducing, and the modification process of molecular sieve can not produce adverse influence to composite carrier.
Description of drawings
Fig. 1 is the pore size distribution figure of embodiment 2 and Comparative Examples 4 gained carrier materials.
The specific embodiment
Carrier material of the present invention also can add other auxiliary agent as required, as one or more in phosphorus, boron, titanium, zirconium etc.
The specific area of product of the present invention and pore volume are to adopt the low temperature liquid nitrogen physisorphtion to measure, and relative crystallinity and cell parameter adopt X-ray diffraction method to measure.Sodium content adopts By Icp-aes.In the present invention, wt% is mass fraction.
Further illustrate preparation method of the present invention below in conjunction with specific embodiment, but scope of the present invention is not only limited to the scope of these embodiment.
Embodiment 1
The 366g solid aluminum chloride is joined in 1.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain liquor alumini chloridi (a).Add appropriate distilled water diluting into about 10% weak aqua ammonia (b) concentrated ammonia liquor, the 70g xylitol is dissolved in 500ml water, forms solution (c).Get 10L waterglass (technical grade, modulus are 3.0) and be diluted in the 20L deionized water, be configured to solution (d).20.5g diethanol amine is dissolved in 100ml water, is heated to 60 ℃, adds 52g Modified Zeolite Y Y-1 (SiO under stirring
2/ Al
2O
3Mol ratio 11.0, lattice constant are 24.42, and relative crystallinity is 95%) pulled an oar 2 hours, obtain slurries (e).Get a stainless steel reaction tank, after adding (a) in tank and being heated with stirring to 65 ℃, open the valve of the container that has (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.5, continue to drip (b), open the valve that has (c) and container (e), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes, control the valve of (c) and container (e), guarantee that be added dropwise to complete this moment.Keeping temperature is 65 ℃, and pH=8.0 stopped after 20 minutes, added solution (d) in system, adds in 10 minutes according to the content 45wt% calculating of silica in amorphous aluminum silicide.Aging 1 hour, with material in tank under 100 ℃ at the baking oven inner drying to contents on dry basis 15wt%, material is transferred in autoclave, processed 18h under 165 ℃ of conditions, then material is used ethanol to carry out solvent extraction and remove a part of organic matter, filter, washing was filtered to without chlorion, with filter cake under 110 ℃ dry 10 hours, pulverize and sieve, obtain containing the composite carrier S-1 of modification Y molecular sieve 17wt%.After 5 hours, the Main physical chemical property sees Table 1 through 550 ℃ of roastings.
366g solid sulphuric acid aluminium is joined in 1.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a).Add appropriate distilled water diluting into about 10% weak aqua ammonia (b) concentrated ammonia liquor, the 55g adipic acid is dissolved in 500ml water, forms solution (c).Get 10L waterglass (technical grade, modulus are 3.0) and be diluted in the 20L deionized water, be configured to solution (d).The 21g monoethanolamine is dissolved in 100ml water, is heated to 60 ℃, adds 107g Modified Zeolite Y Y-1 (SiO under stirring
2/ Al
2O
3=11.0, lattice constant is 24.42, and relative crystallinity is 95%) pulled an oar 2 hours, obtain slurries (e).Get a stainless steel reaction tank, after adding (a) in tank and being heated with stirring to 65 ℃, open the valve of the container that has (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.5, add this moment in tank, continue to drip (b) and open the valve that has (c) and container (e), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes, control the valve of (c) and container (e), guarantee that be added dropwise to complete this moment.Keeping temperature is 65 ℃, and pH=8.0 stopped after 20 minutes, added solution (d) in system, adds in 10 minutes according to the content 45wt% calculating of silica in amorphous aluminum silicide.Aging 1 hour, with material in tank under 100 ℃ at the baking oven inner drying to contents on dry basis 15wt%, material is transferred in autoclave, processed 4h under 180 ℃ of conditions, use ethanol to carry out a solvent extraction part organic matter material, filter, wash to the sulfate radical-free ion, filter, with filter cake under 110 ℃ dry 10 hours, pulverize and sieve, obtain containing the composite carrier S-2 of Modified Zeolite Y 35wt%.After 5 hours, the Main physical chemical property sees Table 1 through 500 ℃ of roastings, and Fig. 1 is seen in pore size distribution.
Embodiment 3
366g solid sulphuric acid aluminium is joined in 1.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a).It is 20g Al that the solid sodium metaaluminate is mixed with concentration
2O
3/ l sodium aluminate solution (b).109g1,4-succinic acid are dissolved in 1L water, form solution (c).The 119g ethylenediamine is dissolved in 500ml water, is heated to 60 ℃, adds 1189g Modified Zeolite Y Y-1 (SiO under stirring
2/ Al
2O
3=11.0, lattice constant is 24.42, and relative crystallinity is 95%), continue stirring and obtain slurries (d) after 2 hours.Get 10L waterglass (technical grade, modulus are 3.0) and be diluted in the 20L deionized water, be configured to solution (e).Get a steel retort, after inserting the 2l deionized water and stirring and being heated to 65 ℃, open simultaneously have (a), the valve of (b), (c) and container (d), the pH=8.0 of the hierarchy of control (c) He (d) drips off (a) in controlling 45 minutes.Keeping temperature is 65 ℃, and pH=8.0 stopped after 20 minutes, added solution (e) in system, adds in 10 minutes according to the content 45wt% calculating of silica in amorphous aluminum silicide.Aging 1 hour, with material filtering in tank to contents on dry basis 15m%, material is transferred in autoclave, process 4h under 180 ℃ of conditions, filter, wash to the sulfate radical-free ion, filter, with filter cake under 110 ℃ dry 10 hours, pulverize and sieve, obtain containing the composite carrier S-3 of Modified Zeolite Y 75wt%.After 5 hours, the Main physical chemical property sees Table 1 through 500 ℃ of roastings.
366g solid sulphuric acid aluminium is joined in 1.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a).It is 20g Al that solid sodium aluminate is mixed with concentration
2O
3/ l sodium aluminate solution (b), the 158g octylame is dissolved in 3.5L ethanol, is heated to 60 ℃, adds 1586g modified HZSM-5 type molecular sieve (SiO under stirring
2/ Al
2O
3Mol ratio 38, specific area are 350m
2/ g, relative crystallinity are 95%) continue to stir 2 hours, make slurries (c), the 109g 1,3-PD is dissolved in 1L water, forms solution (d).Get 10L waterglass (technical grade, modulus are 3.0) and be diluted in the 20L deionized water, be configured to solution (e).Get a steel retort, after inserting the 2l deionized water and stirring and being heated to 65 ℃, open simultaneously have (a), the valve of (b), (c) and container (d), the pH=8.0 of the hierarchy of control (c) He (d) drips off (a) in controlling 45 minutes.Keeping temperature is 65 ℃, pH=8.0, stop after 20 minutes, add solution (e) in system, content 45wt% calculating according to silica in amorphous aluminum silicide added in 10 minutes, aging 1 hour, material filtering in tank to contents on dry basis 15wt%, is transferred to material in autoclave, processed 4h under 180 ℃ of conditions, filter, wash to the sulfate radical-free ion, filter, with filter cake under 110 ℃ dry 10 hours, pulverize and sieve, obtain containing the composite carrier S-4 of modified HZSM-5 molecular sieve 80wt%.After 5 hours, the Main physical chemical property sees Table 1 through 500 ℃ of roastings.
Embodiment 5
The 366g solid aluminum chloride is joined in 1.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain liquor alumini chloridi (a).Add appropriate distilled water diluting into about 10% weak aqua ammonia (b) concentrated ammonia liquor, 70g sweet mellow wine is dissolved in 1L water, forms solution (c).Get 10L waterglass (technical grade, modulus are 3.0) and be diluted in the 20L deionized water, be configured to solution (d).8.8 g1, the 4-butanediamine is dissolved in 100ml water, is heated to 60 ℃, adds the Hydrogen β zeolite (SiO of 22g modification
2/ Al
2O
3Mol ratio 30.0, lattice constant are 12.00, and relative crystallinity is 90%) continue to stir 2 hours, obtain slurries (e).Get a steel retort, after adding (a) in tank and being heated with stirring to 65 ℃, open the valve of the container that has (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, continue to drip (b), open the valve that has (c) and container (e), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes, control the valve of (c) and container (e), guarantee that be added dropwise to complete this moment.Keeping temperature is 65 ℃, and pH=8.0 stopped after 20 minutes, added solution (d) in system, adds in 10 minutes according to the content 45wt% calculating of silica in amorphous aluminum silicide.Aging 1 hour, with material in tank under 100 ℃ at the baking oven inner drying to contents on dry basis 15wt%, material is transferred in autoclave, processed 18h under 165 ℃ of conditions, use ethanol to carry out a solvent extraction part organic matter material, filter, washing was filtered to without chlorion, with filter cake under 110 ℃ dry 10 hours, pulverize and sieve, obtain containing the composite carrier S-5 of modified beta zeolite 8wt%.After 5 hours, the Main physical chemical property sees Table 1 through 500 ℃ of roastings.
Comparative Examples 1
Repeat the synthetic of embodiment 2, do not add monoethanolamine and adipic acid, make comparative composite DF-1.After 5 hours, the Main physical chemical property sees Table 1 through 500 ℃ of roastings.
Comparative Examples 2
Repeat the synthetic of embodiment 2, do not add monoethanolamine, make comparative composite DF-2.After 5 hours, the Main physical chemical property sees Table 1 through 500 ℃ of roastings.
Comparative Examples 3
Repeat the synthetic of embodiment 2, do not add Y zeolite and monoethanolamine and adipic acid, make comparative composite DF-3.After 5 hours, the Main physical chemical property sees Table 1 through 500 ℃ of roastings.
Comparative Examples 4
Repeat the synthetic of embodiment 2, do not carry out hydrothermal treatment consists, make comparative composite DF-4.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings, and pore size distribution is shown in Fig. 1.
Comparative Examples 5
Repeat the synthetic of embodiment 4, do not add organic amine and Organic Alcohol, make comparative composite DF-5.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Comparative Examples 6
Repeat the synthetic of embodiment 4, do not carry out hydrothermal treatment consists, make comparative composite DF-6.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Comparative Examples 7
Repeat the synthetic of embodiment 5, do not add organic amine and Organic Alcohol, make comparative composite DF-7.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Comparative Examples 7
Repeat the synthetic of embodiment 5, do not carry out hydrothermal treatment consists, make comparative composite DF-8.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Table 1 composite carrier main character
| Bearer number | S-1 | S-2 | S-3 | DF-1 | DF-2 | DF-3 | DF-4 | Y-1 |
| Specific area, m 2/g | 402 | 478 | 648 | 383 | 426 | 340 | 473 | 786 |
| Pore volume, ml/g | 0.70 | 0.62 | 0.46 | 0.53 | 0.58 | 0.78 | 0.62 | 0.37 |
Table 1 continues the composite carrier main character
| Bearer number | S-4 | S-5 | DF-4 | DF-5 | DF-6 | DF-7 | Z-1 | B-1 |
| Specific area, m 2/g | 337 | 345 | 271 | 333 | 276 | 342 | 353 | 553 |
| Pore volume, ml/g | 0.31 | 0.74 | 0.26 | 0.30 | 0.63 | 0.73 | 0.21 | 0.40 |
Find out by table 1 Data Comparison, use the prepared molecular sieve of the inventive method-amorphous aluminum silicide composite carrier specific surface and pore volume to obtain improving greatly, can effectively solve the problem that the amorphous aluminum silicide that causes even stops up with the reunion between molecular sieve when plastic; Can find out that by the pore size distribution of Fig. 1 hydrothermal treatment consists helps to form mesopore and pore distribution concentration.Can prepare the composite catalyst carrier material of a kind of amorphous aluminum silicide and the large pore volume molecular sieve organic composite, high degree of dispersion, bigger serface by the inventive method.
Claims (18)
1. the preparation method of a catalyst carrier material comprises:
(1) molecular sieve is mixed with organic amine, wherein the addition of organic amine accounts for the 1wt% ~ 40wt% of molecular sieve weight;
(2) mixture and the organic matter that add step (1) to obtain in amorphous aluminum silicide plastic process, take the weight of final carrier material as benchmark, the molecular sieve addition is 5wt% ~ 90wt%, organic addition is 1wt% ~ 50wt%, one or more in the organic acid that described organic matter is the organic alcohols that contains two or more hydroxyls, contain two or more carboxyls;
(3) carry out agingly after the described amorphous aluminum silicide cemented into bundles of step (2), then carry out hydrothermal treatment consists, after filtration, washing, drying, obtain catalyst carrier material.
2. in accordance with the method for claim 1, it is characterized in that in step (1), described organic amine is carbon number less than one or more in the fatty amine of 20, aromatic amine, hydramine, acid amides, naphthylamines.
3. in accordance with the method for claim 1, it is characterized in that in step (1), described organic amine is for containing one or more in the fatty amines of 2 ~ 10 carbon numbers.
4. in accordance with the method for claim 1, it is characterized in that described organic amine mixes with molecular sieve, directly add in molecular sieve, perhaps be dissolved in and add in solvent in molecular sieve again, solvent wherein is one or more in water, low-carbon alcohols; Described low-carbon alcohols is that carbon number is one or more in 1 ~ 5 monohydric alcohol.
5. in accordance with the method for claim 1, after it is characterized in that step (1) molecular sieve and organic amine mixing, carry out again step (2) after filtration and after drying.
6. in accordance with the method for claim 1, the plastic process that it is characterized in that the amorphous aluminum silicide described in step (2) is the neutralization reaction process of acid material and alkaline material, the plastic process adopts the mode of the continuous acid-base titration of soda acid, perhaps adopts the mode of two kinds of materials and stream neutralization.
7. in accordance with the method for claim 1, it is characterized in that in step (2), amorphous aluminum silicide plastic process 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.
8. in accordance with the method for claim 7, it is characterized in that in step (2), the plastic material comprises that the aluminium source is Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3And NaAlO
2In one or more, the silicon source be in waterglass, Ludox and organic silicon-containing compound one or more, precipitating reagent is NaOH, NH
4OH, CO
2In one or more.
9. in accordance with the method for claim 1, it is characterized in that in step (1) one or more in described molecular sieve faujasite, β zeolite, omega zeolite, modenite, L zeolite, ZSM Series Molecules sieve, SAPO Series Molecules sieve, MCM Series Molecules sieve and above-mentioned modified molecular screen.
10. in accordance with the method for claim 1, it is characterized in that in step (1), the state that adds of described molecular sieve is that dry powder-shaped adds, or adds with the slurries form.
11. in accordance with the method for claim 1, it is characterized in that in step (2), the introducing mode of the mixture of step (1) gained adopts the one or more combination of following manner: (1) adds this mixture in plastic cans in plastic neutralization reaction process continuously; (2) this mixture is 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 this mixture are mixed, then in the plastic material and plastic.
12. in accordance with the method for claim 1, it is characterized in that the boiling point of the organic alcohols described in step (2) higher than the plastic temperature, boiling point is 100 ℃ ~ 350 ℃; The boiling point of described organic acid is higher than the plastic temperature, and boiling point is 100 ℃ ~ 350 ℃.
13. in accordance with the method for claim 1, it is characterized in that the organic alcohols described in step (2) is diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, propane diols, glycerine, 1,4-butanediol, butantriol, 2,2-dimethyl-1,3 propane diols, DPG, xylitol, pentanediol, 1, one or more in 6-hexylene glycol, hexitol, sweet mellow wine.
14. in accordance with the method for claim 1, it is characterized in that the organic acid described in step (2) is one or more in ethanedioic acid, malonic acid, citric acid, succinic acid, malic acid, tartaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid.
15. in accordance with the method for claim 1, it is characterized in that in step (2), the described organic mode that adds is selected the one or more combination of following manner: (1) is in the plastic initial stage joins plastic cans in advance, (2) be added drop-wise to plastic cans in the plastic process, (3) with one or more mixing of plastic raw material, add in plastic cans with material.
16. it is characterized in that in step (3), before hydrothermal treatment consists in accordance with the method for claim 1,, after filtration or the heating concentration, remove excessive moisture and organic matter, described heating simmer down to is heated to immobilising paste shape at 90 ~ 110 ℃ of lower heating stepses (2) products obtained therefrom.
17. in accordance with the method for claim 1, it is characterized in that in step (3), described hydrothermal treatment consists is carried out in closed container, the temperature of hydrothermal treatment consists is 90 ~ 300 ℃, described hydrothermal treatment consists is for carrying out under self the pressure condition that produces when the material treatment temperature, and the described hydrothermal treatment consists time is 0.5 ~ 48h.
18. in accordance with the method for claim 1, it is characterized in that in step (3), described hydrothermal treatment consists is carried out in closed container, the temperature of hydrothermal treatment consists is 100 ~ 250 ℃, described hydrothermal treatment consists is for carrying out under self the pressure condition that produces when the material treatment temperature, and the described hydrothermal treatment consists time is 1 ~ 36h.
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