CN103100440A - Preparation method of catalyst carrier material - Google Patents
Preparation method of catalyst carrier material Download PDFInfo
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- CN103100440A CN103100440A CN2011103558321A CN201110355832A CN103100440A CN 103100440 A CN103100440 A CN 103100440A CN 2011103558321 A CN2011103558321 A CN 2011103558321A CN 201110355832 A CN201110355832 A CN 201110355832A CN 103100440 A CN103100440 A CN 103100440A
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Abstract
The invention discloses a preparation method of a catalyst carrier material. 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 alumina in gelling, after gelling of the amorphous alumina, carrying out aging, 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 alumina on the surface of the molecular sieve, improves the binding strength of the molecular sieve and the alumina, avoids agglomeration of the amorphous alumina and the molecular sieve and channel blocking caused by the agglomeration, realizes mutual communication of channels of the alumina and the molecular sieve, fully develops synergism of the alumina and the molecular sieve, and improves catalyst use performances. 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 of catalyst carrier material, especially for the preparation method of the molecular sieve-aluminium oxide composite carrier of hydrogenation catalyst.
Background technology
Developing rapidly and crude oil heaviness and in poor quality progressively of World Economics makes market increase year by year light-end products (aeroamphibious are handed over oil universal, agricultural oils and heating oil etc.) and the demand of industrial chemicals (light aromatics, alkene and ethylene cracking material etc.); For the living environment of to protect mankind self, the progressively appearance of all kinds of environmental regulations is to the requirement that has also proposed increasingly stringent that cleans of all kinds of oil products.Hydrocracking technology is one of important means of crude oil secondary operations, heavy oil lighting.Due to it has that adaptability to raw material is strong, production operation and product solution flexibly and the characteristics such as good product quality, therefore become production high-quality lightweight clear gusoline and solved the important channel in industrial chemicals source.Hydrocracking technology has also obtained increasingly extensive application.
The key of hydrocracking technology is to develop the various hydrocracking catalysts of meeting the need of market.Hydrocracking catalyst is generally 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 the refractory inorganic oxides that consists of carrier.Refractory inorganic oxides generally comprises one or more in amorphous aluminum silicide, amorphous alumina.Between conjugation between molecular sieve in carrier and refractory inorganic oxides and decentralization and its reactivity worth, inseparable relation is arranged, affect to a great extent the active of catalyst and selective to various purpose products.
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 stock yards 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 of catalyst carrier material.Catalyst carrier by the method preparation can combine molecular sieve and aluminium oxide, has good conjugation and decentralization, can avoid molecular sieve and and amorphous alumina between the even clogging that occurs reuniting, have good serviceability.
The preparation method of catalyst carrier material of the present invention 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 alumina 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 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 alumina 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 alumina 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.
In step of the present invention (2), the aluminium oxide plastic is to adopt aluminum soluble salt and acidic precipitation agent or alkaline precipitating agent to carry out the process of neutralization reaction, wherein aluminum soluble salt used is one or more in aluminium chloride, aluminum sulfate, aluminum nitrate, acidic precipitation agent used is generally one or several in hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, carbon dioxide etc., and alkaline precipitating agent used is generally one or several in sodium carbonate, sodium acid carbonate, NaOH, potassium hydroxide, ammoniacal liquor etc.The aluminium oxide plastic also can adopt meta-aluminate (such as sodium metaaluminate and/or potassium metaaluminate) and acid aluminium salt (such as one or more in aluminium chloride, aluminum nitrate, aluminum sulfate) carry out in and the method for plastic.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, is 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 alumina 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.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), the mode of washing of described material is known in those skilled in the art, can select making beating washing, add the modes such as water washing, lower alcohols washing when filtering, the temperature of washing should be in the temperature range of room temperature ~ 90 ℃, 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 the general drying condition that adopts is as follows: under 50 ~ 150 ℃ dry 1 ~ 15 hour.
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 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 aluminium oxide is at 10 wt% ~ 95wt%, and specific area is 200 ~ 800m
2/ g, pore volume are 0.3 ~ 1.8cm
3/ g, the meleic acid amount is 0.1 ~ 2.0 mmol/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, the carrier of hydrocracking catalyst of mink cell focus especially, selective with the activity that improves 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 avoid like this that in aluminium oxide plastic process, fragment enters the duct, stop up aperture or direct plastic in the duct, organic amine has the guide effect to the aluminium oxide duct in aluminium oxide plastic process simultaneously, and match with the hydroxyl that adds or the organic matter of carboxyl in aluminium oxide plastic process, because the organic matter of hydroxyl or carboxyl is water-soluble, make that to have hydrophilic aluminium oxide orderly at the molecular sieve surface alignment, be deposited on equably the surface of molecular sieve, and strengthened the adhesion of molecular sieve and aluminium oxide, avoided amorphous alumina even to stop up the phenomenon in duct with occurring between molecular sieve reuniting, and the duct of aluminium oxide and molecular sieve is connected mutually, make aluminium oxide and molecular sieve give full play to synergy, improved the serviceability of catalyst.Preferably according to requirements adopted suitable method to carry out modification before molecular sieve is introduced, the modification process of molecular sieve can not produce adverse influence to composite carrier like this.
The specific embodiment
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 1500g solid aluminum chloride is joined in 10 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain liquor alumini chloridi (a).Add appropriate distilled water diluting into about 10wt% weak aqua ammonia (b) concentrated ammonia liquor, the 287g 1,5-PD is dissolved in 2L water, forms solution (c).25g1, the 4-butanediamine is dissolved in the 300ml absolute ethyl alcohol, is heated to 60 ℃, stirs half an hour, adds the Modified Zeolite Y Y-1 (SiO after 64g processes
2/ Al
2O
3Mol ratio is 11.0, and lattice constant is 24.42, and relative crystallinity is 95%), continue to stir 2 hours, obtain adsorbing in advance the modified molecular screen (d) of organic amine after filtration.Get the steel retort of one 50 liters, after adding (a) in tank and being heated with stirring to 60 ℃, open the valve of the container that has (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, add (d) this moment in tank, continues to drip (b), open the valve of the container that has (c), in controlling 30 minutes, system in tank is added drop-wise to pH=8.0, controls the valve of the container of (c), guarantee that be added dropwise to complete this moment.Keeping temperature is 60 ℃, pH=8.0, and aging 1 hour, material in tank to be filtered, washing is filtered to without chlorion, with filter cake under 110 ℃ dry 10 hours, pulverizes and sieves and obtains carrier material J-1.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Embodiment 2
1625g solid sulphuric acid aluminium is joined in 10 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a).Add appropriate distilled water diluting into about 10wt% weak aqua ammonia (b) concentrated ammonia liquor, the 242g BDO is dissolved in 1L water, obtains solution (c).The 97g ethylenediamine is dissolved in 5L water, is heated to 60 ℃, stirs half an hour, adds 484g Modified Zeolite Y Y-1 (SiO
2/ Al
2O
3Mol ratio is 11.0, and lattice constant is 24.42, and relative crystallinity is 95%) stir after 2 hours and obtain molecular sieve pulp (d).Get the steel retort of one 50 liters, after adding (a) in tank and being heated with stirring to 60 ℃, open the valve of the container that has (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, open the valve that has (c) and container (d), continue to drip (b), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes, control the valve of (c) and container (d), guarantee that be added dropwise to complete this moment.Keeping temperature is 60 ℃, pH=8.0, and aging 1 hour, material in tank is filtered, wash to the sulfate radical-free ion, filter, with filter cake under 110 ℃ dry 10 hours, pulverize and sieve and obtain carrier material J-2.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Embodiment 3
800g solid sulphuric acid aluminium is joined in 10 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), 238g propane diols are dissolved in 1L water, form solution (c).The 190g diethanol amine is dissolved in 10L water, is heated to 60 ℃, adds 1906g Modified Zeolite Y Y-1 (SiO under stirring
2/ Al
2O
3Mol ratio is 11.0, and lattice constant is 24.42, and relative crystallinity is 95%), continue to keep temperature to stir 2 hours, filter and obtain processing rear molecular sieve (d).Get the steel retort of one 50 liters, insert and add (d) after 2 L deionized water and stirring are heated to 60 ℃, open simultaneously have (a), the valve of (b) and container (c), the pH=8.0 of the hierarchy of control, drip off valve-off in controlling 45 minutes with (a) with (c).Keeping temperature is 60 ℃, pH=8.0, and aging 1 hour, material in tank is filtered, wash to the sulfate radical-free ion, filter, with filter cake under 110 ℃ dry 10 hours, pulverize and sieve and obtain composite J-3.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Embodiment 4
425g solid sulphuric acid aluminium is joined in 4.2 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 228g octylame is dissolved in 5L ethanol, is heated to 60 temperature, and stirring and dissolving adds 2278 g modified HZSM-5 type molecular sieve Z-1 (SiO
2/ Al
2O
3Mol ratio is 38, and specific area is 350m
2/ g, relative crystallinity are 95%) making beating, make slurries (c), the 127g 1, 4-succinic acid is dissolved in 1L water, forms solution (d).Get the steel retort of one 50 liters, after inserting the 2l deionized water and stirring and being heated to 60 ℃, open simultaneously have (a), the valve of (b), (c) and container (d), the pH=8.0 of the hierarchy of control drips off with (a), (c) with (d) in controlling 45 minutes.Keeping temperature is 60 ℃, pH=8.0, and aging 1 hour, material in tank is filtered, wash to the sulfate radical-free ion, filter, with filter cake under 110 ℃ dry 10 hours, pulverize and sieve and obtain carrier material J-4.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Embodiment 5
The 800g solid aluminum chloride is joined in 3L 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, 153g 1, and the 5-glutaric acid is dissolved in 1L water, forms solution (c).6.4g hexamethylene diamine is dissolved in 50ml ethanol, is heated to 60 ℃, adds the Hydrogen β zeolite B-1 (SiO of 16g modification under stirring
2/ Al
2O
3Mol ratio is 30.0, and lattice constant is 12.00, and relative crystallinity is 90%), continue to keep temperature to stir 2 hours, filter and obtain pretreatment molecular sieves (d).Get the steel retort of one 20 liters, after adding (a) in tank and being heated with stirring to 60 ℃, 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 (d) this moment in tank, continues to drip (b), open the valve of the container that has (c), in controlling 30 minutes, system in tank is added drop-wise to pH=8.0, controls the valve of the container of (c), guarantee that be added dropwise to complete this moment.Keeping temperature is 60 ℃, pH=8.0, and aging 1 hour, material in tank to be filtered, washing is filtered to without chlorion, with filter cake under 110 ℃ dry 10 hours, pulverizes and sieves and obtains carrier material J-5.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Comparative Examples 1
Repeat the synthetic of embodiment 2, do not add ethylenediamine and BDO, make comparison vehicle material DF-1.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Comparative Examples 2
Repeat the synthetic of embodiment 2, do not add ethylenediamine, make comparison vehicle material DF-2.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Comparative Examples 3
Repeat the synthetic of embodiment 2, do not add Y zeolite and ethylenediamine and BDO, make comparative composite DF-3.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Comparative Examples 4
Repeat the synthetic of embodiment 4, do not add organic amine and organic acid, make comparative composite DF-4.After 5 hours, the Main physical chemical property of gained carrier material sees Table 1 through 500 ℃ of roastings.
Comparative Examples 5
Repeat the synthetic of embodiment 4, do not add HZSM-5 molecular sieve and organic amine and organic acid, make comparison vehicle material 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 5, do not add organic amine and organic acid, make comparison vehicle material 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 Hydrogen beta-molecular sieve and organic amine and organic acid, make comparison vehicle material DF-7.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 | J-1 | J-2 | J-3 | DF-1 | DF-2 | DF-3 | Y-1 |
| Specific area, m 2/g | 371 | 538 | 663 | 430 | 479 | 346 | 786 |
| Pore volume, ml/g | 0.82 | 0.61 | 0.46 | 0.52 | 0.57 | 0.92 | 0.37 |
Table 1 continues the composite carrier 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 | 339 | 268 | 357 | 271 | 355 | 353 | 553 |
| Pore volume, ml/g | 0.26 | 0.85 | 0.22 | 0.95 | 0.72 | 0.91 | 0.20 | 0.40 |
By as seen from Table 1, use the prepared molecular sieve of the inventive method-alumina catalyst carrier material with not adding the prepared Comparative Examples of organic amine and Organic Alcohol (acid) class relatively, specific area and pore volume are greatly improved, the problem that the amorphous alumina that uses the inventive method effectively to solve to cause when plastic even stops up with the reunion between molecular sieve; Relatively can find out with the physico-chemical property of simple molecular sieve with the macroporous aluminium oxide that simple plastic generates, use the prepared composite carrier of the inventive method to follow the data of the physical mixture of macroporous aluminium oxide and molecular sieve to approach on physico-chemical property, more illustrated and used the inventive method in the individual qualitative superiority that keeps molecular sieve and aluminium oxide.Can prepare a kind of macroporous aluminium oxide and the large pore volume molecular sieve organic composite, high degree of dispersion, bigger serface molecular sieve-alumina catalyst carrier material by the inventive method.
Claims (15)
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 alumina 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 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 the method that described organic amine mixes with molecular sieve is as follows: organic amine directly adds 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 alumina 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), the aluminium oxide plastic is to adopt aluminum soluble salt and acidic precipitation agent or alkaline precipitating agent to carry out the process of neutralization reaction, wherein aluminum soluble salt used is one or more in aluminium chloride, aluminum sulfate, aluminum nitrate, acidic precipitation agent used is one or several in hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, carbon dioxide, and alkaline precipitating agent used is one or several in sodium carbonate, sodium acid carbonate, NaOH, potassium hydroxide, ammoniacal liquor.
8. in accordance with the method for claim 1, it is characterized in that in step (2), the aluminium oxide plastic adopt meta-aluminate and acid aluminium salt carry out in the method for plastic.
9. 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.
10. according to the described method of claim 1 or 9, 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 alumina 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 at 100 ℃ ~ 350 ℃; The boiling point of described organic acid is higher than the plastic temperature, and boiling point is at 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.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101172243A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Mesoporous material/micropore molecular sieve composite material and preparation method thereof |
| 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 |
| US20110224067A1 (en) * | 2008-12-18 | 2011-09-15 | Richard Franklin Wormsbecher | Novel ultra stable zeolite y and method for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101172243A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Mesoporous material/micropore molecular sieve composite material and preparation method thereof |
| 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 |
| US20110224067A1 (en) * | 2008-12-18 | 2011-09-15 | Richard Franklin Wormsbecher | Novel ultra stable zeolite y and method for manufacturing the same |
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