CN103100435B - Preparation method of catalyst carrier dry gel powder - Google Patents
Preparation method of catalyst carrier dry gel powder Download PDFInfo
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- CN103100435B CN103100435B CN201110355820.9A CN201110355820A CN103100435B CN 103100435 B CN103100435 B CN 103100435B CN 201110355820 A CN201110355820 A CN 201110355820A CN 103100435 B CN103100435 B CN 103100435B
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Abstract
The invention discloses a preparation method of catalyst carrier dry gel powder. 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, and then carrying out filtration, washing and drying to obtain the catalyst carrier dry gel powder. 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, fully develops synergism of the silica-alumina and the molecular sieve, and improves catalyst use performances. The catalyst carrier dry gel powder 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 of catalyst carrier for hydrgenating dry glue powder, especially for the preparation method of the molecular sieve-amorphous aluminum silicide complex carrier dry glue powder of hydrogenation catalyst.
Background technology
Developing rapidly of World Economics is progressively deteriorated with crude oil, and the demand of market to light-end products and industrial chemicals is increased year by year.Hydrocracking technology is crude oil secondary operations, one of the important means of heavy oil lighting obtains 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 provided respectively by the acidic components in catalyst and hydrogenation active component.Acidic components in catalyst are generally provided by molecular sieve contained in catalyst and/or amorphous aluminum silicide.The features such as molecular sieve has stronger acidity, is the major cleavage component in catalyst, has reaction temperature low, and activity is strong.Amorphous aluminum silicide catalyst reaction temperatures is higher, but reaction comparatively relaxes, and middle distillates oil selectivity is good.It is the Main way that hydrocracking catalyst develops that molecular sieve uses with amorphous aluminum silicide and molecular sieve combination.And by the catalyst obtained by molecular sieve and amorphous aluminum silicide, there is good activity, selective and stability, be suitable for long-term operation.
Molecular sieve in carrier has inseparable relation with the conjugation between amorphous aluminum silicide with between decentralization and its reactivity worth, and the acid site of good dispersion then carrier is evenly distributed, and reaction mass reacts comparatively even in the catalyst; Affect the activity of catalyst and selective to various object product to a great extent.The dispersiveness how solved between molecular sieve and amorphous silicon alumina supporter is the key that preparation has sound response performance catalyst.
Hydrocracking catalyst disclosed in the patents such as CN201010197869.1, CN200810117102.6, CN00105235.7 is all prepared after mechanical mixture by raw material single to molecular sieve, aluminium oxide etc.Catalyst prepared by the method can be uneven because of various raw material mixing, affects the performance of each component property.
CN1060976A discloses a kind of preparation method of the ultrastable containing amorphous alumina.The method is that in aluminum sulfate solution, add ammoniacal liquor adjust ph be 3.5 ~ 7.5, then NaY zeolite or HNaY zeolite is added, 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 the ultrastable containing amorphous alumina.The method is after aluminium oxide plastic, adds zeolite materials, then the composite of modification gained according to a conventional method.There is amorphous alumina and easily occur agglomeration in the method, make amorphous alumina skewness over a molecular sieve, even block the duct of molecular sieve, the specific area of catalyst and pore volume are significantly reduced, and the patency in molecular sieve and aluminium oxide duct is poor, affect the performance of catalyst.The method carries out hydrothermal treatment consists and ammonium exchange process by NaY zeolite again with after amorphous alumina compound, increases treating capacity, reduces the efficiency of process, and in processing procedure, amorphous alumina can be processed together, easily produces ill effect to aluminium oxide.
CN200610134151.1 discloses a kind of preparation method of carrier material, and the method is prepared by the method directly adding molecular sieve in amorphous aluminum silicide plastic process.In the method easily there is agglomeration in amorphous aluminum silicide, also easily enter the duct of the other side or the aperture of blocking molecular sieve, affect amorphous aluminum silicide distribution over a molecular sieve, the connectivity in molecular sieve and amorphous aluminum silicide duct is poor, the specific area of catalyst and pore volume are reduced, affects 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 of catalyst carrier dry gel powder.Molecular sieve and amorphous aluminum silicide can combine by the catalyst carrier prepared by the method, there is good conjugation and decentralization, can avoid molecular sieve and and macropore amorphous aluminum silicide between to occur reuniting even clogging, there is good serviceability.
The preparation method of catalyst carrier dry gel powder of the present invention, comprises following preparation process:
(1) mixed with organic amine by molecular sieve, wherein the addition of organic amine accounts for the 1wt% ~ 40wt% of molecular sieve;
(2) in amorphous aluminum silicide plastic process, add mixture and organic matter that step (1) obtains, with the weight of final carrier dry gel powder for benchmark, molecular sieve addition is 5wt% ~ 90wt%, organic addition is 1wt% ~ 50wt%, and described organic matter is containing the organic alcohols of two or more hydroxyls, containing one or more in the organic acid of two or more carboxyls;
(3) carry out aging after the amorphous aluminum silicide cemented into bundles described in step (2), then after filtration, washing, dry, obtain catalyst carrier dry gel powder.
In step of the present invention (1), described organic amine is fatty amine, aromatic amine, one or more in hydramine that carbon number is less than 20.Better suited is the amine containing chain, is preferably containing one or more in the fatty amines of 2 ~ 10 carbon numbers.Such as: 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, organic amine directly can be added in molecular sieve, also organic amine can be dissolved in solvent and add again in molecular sieve, solvent is wherein water, one or more in low-carbon alcohols (namely carbon number is one or more in the monohydric alcohol of 1 ~ 5).If the addition of organic amine is comparatively large, needs to filter and carry out step (2) again after drying.
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 plastic process generally adopts two kinds of materials and flows plastic mode of operation, or a kind of material is placed on another kind of material in plastic cans and adds the mode of operation of plastic continuously.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 (in waterglass, Ludox and organic silicon-containing compound etc. one or more), precipitating reagent (NaOH, NH
4oH or CO
2deng), the different choice according to plastic process uses, and 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 silicon source in 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.Silicon source also can add after the precipitation of aluminium source in material, also can two or more is combined by aforesaid way.Said method is all well-known to those skilled in the art.Described plastic process is generally carried out at room temperature ~ 85 DEG C, is comparatively suitably for 40 ~ 80 DEG C, is preferably 50 ~ 70 DEG C.Described plastic process is generally carried out under certain pH value condition, and typical pH is 6.0 ~ 10.0, is comparatively suitably for 7.0 ~ 9.5, is preferably 7.5 ~ 9.0.Aging described in step (3), condition is as follows: pH is 6.0 ~ 10.0, and be preferably 7.0 ~ 9.5, ageing time 0.25 ~ 8 hour, is comparatively adapted at 0.5 ~ 5 hour, and be preferably 1 ~ 3 hour, aging temperature is room temperature ~ 85 DEG C, is preferably 40 ~ 80 DEG C.Temperature time aging and pH with in time temperature preferably identical with pH.
In step of the present invention (1), described molecular sieve is known any one or several molecular sieve, one or several in best 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.In order to obtain the catalytic performance of hope, various molecular sieve can carry out suitable modifying process, the process that method of modifying is well known to those skilled in the art, as one or more method modifications in hydrothermal treatment consists, acid treatment, ion-exchange, various solvent process etc.In step of the present invention (1), the state that adds of described molecular sieve can be that dry powder-shaped adds, and also can be add with slurries form.
In step of the present invention (2), the incorporation way of the mixture of step (1) gained adopts the one or more combination of following manner: this mixture, in plastic neutralization reaction process, adds in plastic cans by (1) 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 plastic material of this mixture are mixed, then in plastic material and plastic.
Organic alcohols described in step of the present invention (2) is the organic compound containing two or more hydroxyls, its boiling point is higher than gelling temperature, general at 100 DEG C ~ 350 DEG C, preferably more than 120 DEG C, preferably more than 150 DEG C further, such as diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, propane diols, glycerine, 1,4-butanediol, butantriol, 2, one or more in 2-dimethyl-1,3 propane diols, DPG, xylitol, pentanediol, 1,6-hexylene glycol, hexitol, sweet mellow wine.Described organic acid is the organic compound containing two or more carboxyls, its boiling point is higher than gelling temperature, general at 100 DEG C ~ 350 DEG C, preferably more than 120 DEG C, preferably more than 150 DEG C further, such as, in ethanedioic acid (oxalic acid), malonic acid, citric acid, succinic acid, malic acid, tartaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid one or more.
In step of the present invention (2), described organic feed postition can select the one or more combination of following manner: (1) joined in plastic cans in advance at the plastic initial stage, (2) be added drop-wise in plastic cans in plastic process, (3) with one or more mixing of plastic raw material, add in plastic cans with material.Described organic matter can the mixture of same step (1) gained together add, and also can add separately.
In step of the present invention (3), the mode of washing of described material is known in those skilled in the art, can select to add the mode such as water washing, lower alcohols washing when making beating washing, filtration, the temperature of washing should in the scope of room temperature ~ 90 DEG C temperature, preferably 50 ~ 70 DEG C.The washing of described material is generally carried out in the scope that pH is 1.0 ~ 9.0, and preferred pH is 4.0 ~ 8.5.Material described in step of the present invention (3) should not contain or contain the heteroion of seldom amount after washing, filtration, and 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 drying mode can adopt natural drying, oven drying, spraying dry, microwave drying or infra-red drying, and general drying condition is as follows: drying 1 ~ 15 hour at 50 ~ 150 DEG C.
Carrier dry gel powder of the present invention also can add other auxiliary agent as required, as one or more in phosphorus, boron, titanium, zirconium etc.
Carrier dry gel powder prepared by the inventive method is a kind of raw material of Kaolinite Preparation of Catalyst carrier, through 450 ~ 650 DEG C of roastings after 2 ~ 10 hours, the character of gained is as follows: with the weight of carrier after roasting for benchmark, the content of molecular sieve is 5wt% ~ 90wt%, the content of amorphous aluminum silicide is at 10 wt% ~ 95wt%, in amorphous aluminum silicide, SiO
2content is generally 10wt% ~ 50wt%, and after roasting, the character of carrier is as follows: specific area is 200 ~ 1000m
2/ g, pore volume is 0.3 ~ 1.8cm
3/ g, meleic acid amount is 0.1 ~ 2.0mmol/g.
Carrier dry gel powder prepared by the inventive method can be used as acidic components in the 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 activity of catalyst and the selective and catalyst of object product.
The preparation method of catalyst carrier dry gel powder of the present invention is that molecular sieve mixes with organic amine in advance, organic amine can be adsorbed onto duct and the aperture place of molecular sieve in advance, the pore passage structure of molecular sieve is protected in advance, fragment in sial plastic process can be avoided like this to enter duct, blocking aperture or direct plastic in duct, organic amine has the guide effect to sial duct in sial plastic process simultaneously, and match with the organic matter of the hydroxyl added in sial plastic process or carboxyl, because the organic matter of hydroxyl or carboxyl is water-soluble, make to there is hydrophilic sial in molecular sieve surface arrangement in order, be deposited on the surface of molecular sieve equably, and enhance the adhesion of molecular sieve and sial, avoid amorphous aluminum silicide and even block the phenomenon in duct with occurring between molecular sieve reuniting, and make the duct of sial and molecular sieve mutually through, sial and molecular sieve is made to give full play to synergy, improve the serviceability of catalyst.Molecular sieve can adopt various suitable method to process according to its instructions for use before being introduced, and the modification process of molecular sieve can not produce adverse influence to composite carrier.
Detailed description of the invention
The specific area of product of the present invention and pore volume adopt 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 embodiments.
embodiment 1
486g solid aluminum chloride is joined in 1 liter of distilled water, heat simultaneously and be stirred to dissolving, obtaining liquor alumini chloridi (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10% weak aqua ammonia (b), 93g Xylitol dissolves, in 500ml water, forms solution (c).Get 10L waterglass (technical grade, modulus is 3.0) to be diluted in 20L deionized water, be configured to solution (d).15g monoethanolamine is dissolved in 100ml water, is heated to 60 DEG C, adds 38g Modified Zeolite Y Y-1 (SiO under stirring
2/ Al
2o
3=11.0, lattice constant is 24.42, and relative crystallinity is 95%) pull an oar 2 hours, obtain slurries (e).Get a stainless steel reaction tank, (a) is added and after being heated with stirring to 65 DEG C in tank, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.5, continue to drip (b), open the valve of the container having (c) and (e), control, in 30 minutes, system in tank is added drop-wise to pH=8.0, control the valve of the container of (c) and (e), ensure now to be added dropwise to complete.Keep temperature to be 65 DEG C, pH=8.0, stops after 20 minutes, in system, adds solution (d), is that 45wt% calculating added in 10 minutes according to the content of silica in amorphous aluminum silicide.Aging 1 hour, filtered by material in tank, washing to without chlorion, is filtered, and by filter cake drying 10 hours at 110 DEG C, pulverize and sieve and obtain catalyst carrier dry gel powder J-1, through 550 DEG C of roastings after 10 hours, the Main physical chemical property of gained is in table 1.
embodiment 2
120g Solid aluminum sulfate is joined in 1 liter of distilled water, heat simultaneously and be stirred to dissolving, obtaining aluminum sulfate solution (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10% weak aqua ammonia (b), 18g BDO is dissolved in 500ml water, forms solution (c).Get 10L waterglass (technical grade, modulus is 3.0) to be diluted in 20L deionized water, be configured to solution (d).13g monoethanolamine is dissolved in 100ml water, is heated to 60 DEG C, adds 65g Modified Zeolite Y Y-1 (SiO under stirring
2/ Al
2o
3=11.0, lattice constant is 24.42, and relative crystallinity is 95%) pull an oar 2 hours, obtain slurries (e).Get a stainless steel reaction tank, (a) is added and after being heated with stirring to 65 DEG C in tank, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.5, now add in tank, continue to drip the valve that (b) opens the container having (c) and (e), control, in 30 minutes, system in tank is added drop-wise to pH=8.0, control the valve of the container of (c) and (e), ensure now to be added dropwise to complete.Keep temperature to be 65 DEG C, pH=8.0, stops after 20 minutes, in system, adds solution (d), is that 45wt% calculating added in 10 minutes according to the content of silica in amorphous aluminum silicide.Aging 1 hour, filtered by material in tank, wash to sulfate radical-free ion, filter, by filter cake at 110 DEG C dry 10 hours, pulverize and sieve and obtain catalyst carrier dry gel powder J-2, through 500 DEG C of roastings after 5 hours, the Main physical chemical property of gained was in table 1.
embodiment 3
120g Solid aluminum sulfate is joined in 1 liter of distilled water, heat simultaneously and be stirred to dissolving, obtaining aluminum sulfate solution (a).Solid sodium metaaluminate being mixed with concentration is 20g Al
2o
3/ l sodium aluminate solution (b).36g 1, 4-succinic acid is dissolved in 1L water, forms solution (c).57g ethylenediamine is dissolved in 500ml water, is heated to 60 DEG C, adds 572g 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 is 3.0) to be diluted in 20L deionized water, be configured to solution (e).Get a steel retort, insert after 2l deionized water and stirring is heated to 65 DEG C, open the valve of container having (a), (b), (c) and (d) simultaneously, the pH=8.0 of the hierarchy of control, controls (a) (c) and (d) to be dripped off in 45 minutes.Keep temperature be 65 DEG C, pH=8.0, stops after 20 minutes, in system, adds solution (e), according to amorphous aluminum silicide in silica content 50wt% calculating added in 10 minutes.Aging 1 hour, material in tank is filtered, wash to sulfate radical-free ion, filter, by filter cake at 110 DEG C dry 10 hours, pulverize and sieve and obtain catalyst carrier dry gel powder J-3, through 500 DEG C of roastings after 5 hours, pulverizing and sieving of gained obtains carrier material J-3.Main physical chemical property is in table 1.
embodiment 4
120g Solid aluminum sulfate is joined in 1 liter of distilled water, heat simultaneously and be stirred to dissolving, obtaining aluminum sulfate solution (a).Solid sodium aluminate being mixed with concentration is 20g Al
2o
3/ l sodium aluminate solution (b), 117g octylame is dissolved in 5L ethanol, is heated to 60 DEG C, adds 1170g modified HZSM-5 type molecular sieve (SiO under stirring
2/ Al
2o
3=38, specific area is 350m
2/ g, relative crystallinity is 95%) continuing stirring 2 hours, obtained slurries (c), 36g 1,3-PD is dissolved in 1L water, forms solution (d).Get 10L waterglass (technical grade, modulus is 3.0) to be diluted in 20L deionized water, be configured to solution (e).Get a steel retort, insert after 2l deionized water and stirring is heated to 65 DEG C, open the valve of container having (a), (b), (c) and (d) simultaneously, the pH=8.0 of the hierarchy of control, controls (a) (c) and (d) to be dripped off in 45 minutes.Keep temperature to be 65 DEG C, pH=8.0, stops after 20 minutes, in system, adds solution (e), calculates added in 10 minutes according to the content 45wt% of silica in amorphous aluminum silicide.Aging 1 hour, filtered by material in tank, wash to sulfate radical-free ion, filter, by filter cake at 110 DEG C dry 10 hours, pulverize and sieve and obtain catalyst carrier dry gel powder J-4, through 500 DEG C of roastings after 5 hours, the Main physical chemical property of gained was in table 1.
embodiment 5
654g solid aluminum chloride is joined in 1 liter of distilled water, heat simultaneously and be stirred to dissolving, obtaining liquor alumini chloridi (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10% weak aqua ammonia (b), 125g sweet mellow wine is dissolved in 1L water, forms solution (c).Get 10L waterglass (technical grade, modulus is 3.0) to be diluted in 20L deionized water, be configured to solution (d).9.5g1,4-butanediamine is dissolved in 100ml water, is heated to 60 DEG C, adds the Hydrogen β zeolite (SiO of 24g modification
2/ Al
2o
3=30.0, lattice constant is 12.00, and relative crystallinity is 90%) continue stirring 2 hours, obtain slurries (e).Get a steel retort, (a) is added and after being heated with stirring to 65 DEG C in tank, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.0, continue to drip (b), open the valve of the container having (c) and (e), control, in 30 minutes, system in tank is added drop-wise to pH=8.0, control the valve of the container of (c) and (e), ensure now to be added dropwise to complete.Keep temperature to be 65 DEG C, pH=8.0, stops after 20 minutes, in system, adds solution (d), calculates added in 10 minutes according to the content 45wt% of silica in amorphous aluminum silicide.Aging 1 hour, filtered by material in tank, washing to without chlorion, is filtered, and by filter cake drying 10 hours at 110 DEG C, pulverize and sieve and obtain catalyst carrier dry gel powder J-5, through 500 DEG C of roastings after 5 hours, the Main physical chemical property of gained is in table 1.
comparative example 1
Repeat the synthesis of embodiment 2, do not add monoethanolamine and BDO, obtained comparison vehicle dry glue powder DF-1.Through 500 DEG C of roastings after 5 hours, the Main physical chemical property of gained is in table 1.
comparative example 2
Repeat the synthesis of embodiment 2, do not add monoethanolamine, obtained comparison vehicle dry glue powder material DF-2.Through 500 DEG C of roastings after 5 hours, the Main physical chemical property of gained is in table 1.
comparative example 3
Repeat the synthesis of embodiment 2, do not add Y zeolite and monoethanolamine and BDO, obtained comparison vehicle dry glue powder DF-3.Through 500 DEG C of roastings after 5 hours, the Main physical chemical property of gained is in table 1.
comparative example 4
Repeat the synthesis of embodiment 4, do not add organic amine and Organic Alcohol, obtained comparison vehicle dry glue powder DF-4.Through 500 DEG C of roastings after 5 hours, the Main physical chemical property of gained is in table 1.
comparative example 5
Repeat the synthesis of embodiment 4, do not add HZSM-5 molecular sieve and organic amine and Organic Alcohol, obtained comparison vehicle dry glue powder DF-5.Through 500 DEG C of roastings after 5 hours, the Main physical chemical property of gained is in table 1.
comparative example 6
Repeat the synthesis of embodiment 5, do not add organic amine and Organic Alcohol, obtained comparison vehicle dry glue powder DF-6.Through 500 DEG C of roastings after 5 hours, the Main physical chemical property of gained is in table 1.
comparative example 7
Repeat the synthesis of embodiment 5, do not add Hydrogen beta-molecular sieve and organic amine and Organic Alcohol, obtained comparison vehicle dry glue powder DF-7.Through 500 DEG C of roastings after 5 hours, the Main physical chemical property of gained is in table 1.
Table 1 carrier dry gel powder main character
| Bearer number | J-1 | J-2 | J-3 | DF-1 | DF-2 | DF-3 | Y-1 |
| Specific area, m 2/g | 368 | 536 | 663 | 429 | 477 | 343 | 786 |
| Pore volume, ml/g | 0.72 | 0.56 | 0.43 | 0.47 | 0.52 | 0.80 | 0.37 |
Table 1 continues carrier dry gel powder main character
| Bearer number | J-4 | J-5 | DF-4 | DF-5 | DF-6 | DF-7 | Z-1 | B-1 |
| Specific area, m 2/g | 334 | 336 | 267 | 347 | 269 | 345 | 353 | 553 |
| Pore volume, ml/g | 0.25 | 0.74 | 0.21 | 0.82 | 0.63 | 0.81 | 0.20 | 0.40 |
Can be found out by table 1 Data Comparison, use molecular sieve-amorphous aluminum silicide complex carrier dry glue powder specific area obtained by the inventive method and pore volume to be greatly improved, effectively can solve the problem that the amorphous aluminum silicide that causes when plastic even blocks with the reunion between molecular sieve; Use the carrier dry gel powder obtained by the inventive method on physico-chemical property, follow the data of the physical mixture of amorphous aluminum silicide and molecular sieve close, more describe and use the inventive method in the qualitative superiority of individuality retaining molecular sieve and amorphous aluminum silicide.By the inventive method can prepare a kind of amorphous aluminum silicide and molecular sieve organic composite, the catalyst carrier dry gel powder of the large pore volume bigger serface of high degree of dispersion.
Claims (13)
1. a preparation method for catalyst carrier dry gel powder, comprising:
(1) mixed with organic amine by molecular sieve, wherein the addition of organic amine accounts for the 1wt% ~ 40wt% of molecular sieve; Described organic amine is fatty amine, aromatic amine, hydramine, one or more in acid amides that carbon number is less than 20;
(2) in amorphous aluminum silicide plastic process, add mixture and organic matter that step (1) obtains, with the weight of final carrier dry gel powder for benchmark, molecular sieve addition is 5wt% ~ 90wt%, organic addition is 1wt% ~ 50wt%, and described organic matter is containing the organic alcohols of two or more hydroxyls, containing one or more in the organic acid of two or more carboxyls; The boiling point of described organic alcohols is higher than gelling temperature, and boiling point is 100 DEG C ~ 350 DEG C; The boiling point of described organic acid is higher than gelling temperature, and boiling point is 100 DEG C ~ 350 DEG C;
(3) carry out aging after the amorphous aluminum silicide cemented into bundles described in step (2), then after filtration, washing, dry, 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 containing one or more in the fatty amines of 2 ~ 10 carbon numbers.
3. in accordance with the method for claim 1, it is characterized in that described organic amine and molecular sieve mixed method: directly added in molecular sieve by organic amine, or be dissolved in by organic amine in solvent and add in molecular sieve again, solvent is wherein one or more in water, low-carbon alcohols; Described low-carbon alcohols to be carbon number be in the monohydric alcohol of 1 ~ 5 one or more.
4. in accordance with the method for claim 1, after it is characterized in that step (1) molecular sieve mixes with organic amine, after filtration and drying after carry out step (2) again.
5. in accordance with the method for claim 1, it is characterized in that the plastic process of the amorphous aluminum silicide described in step (2) is the neutralization reaction process of acid material and alkaline material, plastic process adopts the mode of the continuous acid-base titration of soda acid, or adopts two kinds of materials and the mode of stream neutralization.
6. 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, plastic process adopts two kinds of materials and flows plastic mode of operation, or a kind of material is placed on another kind of material in plastic cans and adds the mode of operation of plastic continuously.
7. in accordance with the method for claim 6, it is characterized in that, in step (2), it is Al that plastic material comprises aluminium source
2(SO
4)
3, AlCl
3, Al (NO
3)
3and NaAlO
2in one or more, silicon source is one or more in waterglass, Ludox and organic silicon-containing compound, and precipitating reagent is NaOH, NH
4oH, CO
2in one or more.
8. in accordance with the method for claim 1, it is characterized in that in step (1), described molecular sieve is one or more in 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.
9. 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 slurries form.
10. in accordance with the method for claim 1, it is characterized in that in step (2), the incorporation way of the mixture of step (1) gained adopts the one or more combination of following manner: this mixture, in plastic neutralization reaction process, adds in plastic cans by (1) 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 plastic material of this mixture are mixed, then in plastic material and plastic.
11. 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, one or more in 3 propane diols, DPG, xylitol, pentanediol, 1,6-hexylene glycol, hexitol.
12. 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.
13. in accordance with the method for claim 1, it is characterized in that in step (2), described organic feed postition selects the one or more combination of following manner: (1) joined in plastic cans in advance at the plastic initial stage, (2) be added drop-wise in plastic cans in plastic process, (3) with one or more mixing of plastic raw material, add in plastic cans with material.
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| CN101172260A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst |
| 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 |
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| CN101172260A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst |
| 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 |
Non-Patent Citations (1)
| Title |
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| MCM-22分子筛的合成与引用研究;牛雄雷;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20070815;46页倒数第5-8行 * |
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