CN103100433B - Preparation method of composite carrier material - Google Patents
Preparation method of composite carrier material Download PDFInfo
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- CN103100433B CN103100433B CN201110355794.XA CN201110355794A CN103100433B CN 103100433 B CN103100433 B CN 103100433B CN 201110355794 A CN201110355794 A CN 201110355794A CN 103100433 B CN103100433 B CN 103100433B
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- molecular sieve
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Abstract
The invention discloses a preparation method of a composite carrier material. The composite carrier material comprises a Y-type molecular sieve and an amorphous refractory inorganic oxide. The preparation method comprises that in NaY molecular sieve modification, amorphous refractory inorganic oxide slurry and a surfactant are used so that the molecular sieve and the amorphous refractory inorganic oxide are uniformly dispersed; molecular sieve agglomeration or channel blocking is avoided; a specific surface area and a pore volume of the composite carrier material are greatly improved; and catalyst performances are improved. The composite carrier material is especially suitable for being used as a carrier component of a hydrocracking catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of composite carrier, specifically contain a preparation method for the catalyst carrier material of molecular sieve and amorphous refractory inorganic oxides, especially for the preparation method of the catalyst carrier material containing Y zeolite-amorphous refractory inorganic oxides of hydrocracking catalyst.
Background technology
In general, hydrocracking catalyst is a kind of catalyst simultaneously with cracking function and hydrogenation-dehydrogenation function.Cracking function is provided by acid carrier, and hydrogenation dehydrogenation functionality is provided by active metal, acid carrier major part is for carrier with aluminium oxide or amorphous aluminum silicide, be equipped with a certain amount of molecular sieve, its basic preparation process first aluminium oxide or silicon-containing alumina and molecular sieve and other auxiliary agent is directly mixed, then carry out shaping, dry and roasting, final impregnating metal also activates.Amorphous aluminum silicide, as one of the important component of catalyst carrier, requires that itself must have enough large specific area and pore volume, to carry active metal component; Molecular sieve is mainly acidic cleavage component, and for catalyst, the cooperation of the two is most important, only has the two coordinative role, the catalytic action of competence exertion the best.In prior art, because molecular sieve is added by physical mixed, can not be dispersed in other carrier material of catalyst, affect the reactivity worth of catalyst.
CN1110304A discloses the preparation method of the siliceous and phosphorus oxidation aluminium of a kind of macropore.In the preparation process of this aluminium oxide, silicon and phosphorus substep plastic method add, silicon and phosphorus major part can be made like this to be dispersed in alumina surface, aluminium oxide aperture and pore volume are improved, but owing to adding more phosphorus, make the acid of alumina surface measure particularly B acid amount to greatly reduce, acid strength obviously reduces, and makes it apply and is subject to certain restrictions.CN1184703A discloses a kind of preparation method of silicon-containing alumina.This silicon-containing alumina is a kind of is the alumina globule of 5wt% ~ 15wt% containing silica, its preparation characteristic be shaping after silicon-containing alumina wet bulb in containing the atmosphere of ammonia, carry out low temperature drying, the character of the alumina balls obtained obtains some and improves, but due to some defects of balling-up aspect self, make this forming process complicated, the shortcomings such as product yield is low, and preparation cost is high.EP0339640 discloses a kind of method that coprecipitation prepares titanium-contained aluminum oxide, because coprecipitation itself also exists the problem that body is detained mutually, causes titanium dioxide can not give full play to the facilitation of aluminium oxide.Because co-precipitation requires two or more species co-precipitation under certain condition, this proposes very harsh requirement to the condition of co-precipitation, that is, even if under certain conditions, two kinds of materials can precipitate simultaneously, but this condition may not be also all best to two kinds of materials, and the method has feature and the shortcoming of itself thus.CN1060977A discloses a kind of preparation method of the ultrastable containing amorphous aluminum silicide, is introduced in NaY zeolite by Alusil, then obtains through conventional ammonium ion exchange, hydrothermal calcine process the USY zeolite containing amorphous aluminum silicide.The main deficiency of the method is: part amorphous sial is easy to enter in molecular sieve pore passage, not only block molecular sieve pore passage, decrease pore volume and the specific area of molecular sieve, but also cover part acid site, have impact on the catalytic performance of molecular sieve, also affect the modification process of molecular sieve simultaneously, the catalytic performance of molecular sieve and amorphous aluminum silicide can not be played one's part to the full.
CN200610134151.1 discloses a kind of preparation method containing the carrier material of molecular sieve and amorphous aluminum silicide.Molecular sieve in carrier is introduced in amorphous aluminum silicide plastic process.The method Middle molecule sieve there will be reunion in silica-alumina supports, or molecular sieve and amorphous aluminum silicide enter mutually the duct of the other side, blocks cell channels and covers a part of acid site, make carrier specific area, pore volume and acid increase limited.
Summary of the invention
For the deficiencies in the prior art part, the invention provides a kind of preparation method with bigger serface, large pore volume, acid suitable composite carrier.The method make molecular sieve and amorphous refractory inorganic oxides dispersion evenly, overcome molecular sieve easily to occur reuniting, or molecular sieve and amorphous refractory inorganic oxides enter mutually the duct of the other side and obstruction duct, make the specific area of carrier, pore volume and acidity be greatly improved.
The preparation method of composite carrier of the present invention, described carrier material comprises Y zeolite and amorphous refractory inorganic oxides, and wherein the content of amorphous refractory inorganic oxides is 40wt% ~ 90wt%, and preparation process is as follows:
L required amorphous refractory inorganic oxides adds water making beating by ();
(2) in NaY molecular sieve modifying process, introduce slurries and the surfactant of step (1) gained, with the weight of final carrier material for benchmark, the addition of surfactant is 2wt% ~ 20wt%;
(3) material of step (2) gained is carried out comprise filtration, washing, dry treatment step, obtain the composite carrier containing Y zeolite and amorphous refractory inorganic oxides.
In step (l) of the present invention, amorphous refractory inorganic oxides can be one or more in aluminium oxide, silica, magnesia, titanium oxide, zirconia, is preferably silica-alumina (i.e. amorphous aluminum silicide).Amorphous aluminum silicide used can be prepared by coprecipitation or grafting copolymerization process, prepares by conventional method in document.SiO in the amorphous aluminum silicide of gained
2weight content be 20% ~ 50%, be preferably 30% ~ 45%.In the slurries of step (1) gained, the content of amorphous refractory inorganic oxides is 5wt% ~ 40wt%.
NaY molecular sieve modifying process of the present invention can carry out modification according to specific needs, comprises one or more in ion-exchange, hydrothermal treatment consists, acid treatment etc.NaY molecular sieve is through modified, and the Y zeolite type obtained can be deep sealumination modified Y type molecular sieve (DAY), super-stable Y molecular sieves (USY), the Y zeolite (SSY) of silicon replacement or the Y zeolite (US-SSY) of super steady silicon replacement.
The surfactant of step of the present invention (2) is preferably nonionic surface active agent, as: one or more in polyglycol ether, APES, AEO, polyoxyethylene carboxylate, polyoxyethylene amine, polyoxyethylate amide, fatty glyceride etc.Described surfactant preferably adds in form of an aqueous solutions, is added to the water the aqueous solution formed containing surfactant by surfactant.
The process that the material of step (2) gained described in step of the present invention (3) carries out comprising filtration, washing, drying and other steps are well known to the skilled person and condition, the processing procedure such as can also comprise pulverizing, sieve.Described drying generally adopts oven drying, and drying condition is as follows: drying 6 ~ 10 hours at 80 ~ 120 DEG C.
In composite carrier prepared by the inventive method, Y zeolite weight content is 10wt% ~ 60wt%, and the content of amorphous refractory inorganic oxides is 40wt% ~ 90wt%, and this carrier material has following character: specific area is 400m
2/ g ~ 1000m
2/ g, pore volume is 0.6cm
3/ g ~ 2.0cm
3/ g, infrared acidity is 0.3 ~ 1.0mmol/g.
Composite carrier prepared by the inventive method is suitable for the carrier component as Cracking catalyst, the suitable especially carrier component as hydrocracking catalyst.
The present invention contains in the preparation process of the composite carrier of molecular sieve and amorphous refractory inorganic oxides, amorphous refractory inorganic oxides is introduced in Y zeolite modifying process, add surfactant simultaneously, not only can make Y zeolite and amorphous refractory inorganic oxides dispersed, both form good coordinative role in catalytic process, to the serviceability improving catalyst, there is good facilitation, and surfactant has the feature of dispersion, surfactant molecule structure has amphipathic: one end is hydrophilic radical, the other end is hydrophobic group, molecular sieve has hydrophobicity, amorphous refractory inorganic oxides has hydrophily, amorphous like this refractory inorganic oxides, surfactant and molecular sieve dispersed, ordered arrangement, avoid Y zeolite and there will be reunion in the carrier, or Y zeolite and amorphous refractory inorganic oxides enter mutually the duct of the other side, obstruction duct and cover part acid centre, make the specific area of carrier material, pore volume and acidity are greatly improved.
Detailed description of the invention
The specific area of product of the present invention and pore volume adopt ASAP2405, and low temperature liquid nitrogen absorption method records.Meleic acid amount, B acid and L sour be adopt infra-red sepectrometry record, use adsorbent for pyridine.Wt% is mass fraction.
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.Embodiment 1
The composite carrier B prepared according to method provided by the invention.
By 1000g amorphous aluminum silicide (dioxide-containing silica is 30wt%), add in 2 liters of distilled water, stirring to pulp, form slurries (a), 100g polyoxyethylate amide is dissolved in 1L water, forms solution (b), gets 250 grams of industrial NaY zeolite (SiO
2/ A1
2o
3=5.0(mol ratio), lattice constant is 2.463nm, Na
2o content is 9wt%), with the NH of 2500ml 10%
4nO
3the aqueous solution exchanges 1 hour at 90 DEG C of temperature, and then is oxalic acid and the NH of 2 by 2500ml pH value
4nO
3mixed liquor carries out secondary exchange, adds slurries (a) and solution (b) solution simultaneously, carries out first time hydrothermal treatment consists 2 hours afterwards, then use the NH of 10% under 0.098 MPa and 550 DEG C condition
4nO
3the aqueous solution exchanges to Na
2after O<0.15wt%, carrying out second time hydrothermal treatment consists 2 hours under 0.12MPa and 650 DEG C condition, is then the HNO of 0.3mol/L by concentration
3the aqueous solution exchanges, and after filtration, washes, then 120 DEG C of dryings 4 hours, obtained composite carrier A.
Embodiment 2
The composite carrier B prepared according to method provided by the invention.
By 1000g amorphous aluminum silicide (dioxide-containing silica is 30wt%), add in 2 liters of distilled water, stirring to pulp, form slurries (a), 120g polyglycol ether is dissolved in 1L water, forms solution (b), gets 250 grams of industrial NaY zeolite (SiO
2/ A1
2o
3=5.0(mol ratio), lattice constant is 2.463nm, Na
2o content is 9wt%), with the NH of 2500ml 10%
4nO
3the aqueous solution exchanges 1 hour at 90 DEG C of temperature, and then is oxalic acid and the NH of 2 by 2500ml pH value
4nO
3mixed liquor carries out secondary exchange, carries out first time hydrothermal treatment consists 2 hours afterwards, then be the NH of 10wt% by concentration under 0.098 MPa and 550 DEG C condition
4nO
3the aqueous solution exchanges to Na
2o<0.15wt%, after adding (a) and (b) solution, carries out second time hydrothermal treatment consists 2 hours simultaneously under 0.12MPa and 650 DEG C condition, is then 0.3 mol/L HNO by concentration
3the aqueous solution exchanges, and after filtration, washes, 120 DEG C of dryings 4 hours, and obtained composite carrier B.
Embodiment 3
The composite carrier C prepared according to method provided by the invention.
By 1000g amorphous aluminum silicide (dioxide-containing silica is 20wt%), add in 2 liters of distilled water, stirring to pulp, form slurries (a), 150g polyoxyethylene amine solvent, in 1L water, forms solution (b), gets 250 grams of industrial NaY zeolite (SiO
2/ A1
2o
3=5.0(mol ratio), lattice constant is 2.463nm, Na
2o content is 9wt%), with the NH of 2500ml 10%
4nO
3the aqueous solution exchanges 1 hour at 90 DEG C of temperature, and then is oxalic acid and the NH of 2 by 2500ml pH value
4nO
3mixed liquor carries out secondary exchange, adds slurries (a) and solution (b) solution simultaneously, carries out first time hydrothermal treatment consists 2 hours afterwards, then use the NH of 10% under 0.098 MPa and 550 DEG C condition
4nO
3the aqueous solution exchanges to Na
2after O<0.15wt%, carrying out second time hydrothermal treatment consists 2 hours under 0.12MPa and 650 DEG C condition, is then the HNO of 0.3mol/L by concentration
3the aqueous solution exchanges, and after filtration, washes, then 120 DEG C of dryings 4 hours, obtained composite carrier C.
Comparative example 1
Reference carrier material C prepared by the method provided according to CN901108741.6 (CN1060977A)
a.
L. 250 grams of industrial NaY zeolite (SiO are got
2/ A1
2o
3=5.0(mol ratio), lattice constant is 2.463nm, Na
2o content is 9wt%), be dispersed in the mother liquor (SiO that 14000g synthesizes NaY gained
2content 5wt%) in, add AlCl while stirring under room temperature
3(A1
2o
3content 3.0 wt%) solution 10000g, slurry pH value is 8.2, filters.
2. the 1st step gained filter cake mixes with moderate amount of sulfuric acid ammonium salt solution, makes zeolite: ammonium sulfate: water=1: 1: 40 (weight ratio), and slurries are warming up to 90 DEG C, carries out ion-exchange reactions 1.0 hours, and then is oxalic acid and the NH of 2 by 2500ml pH value
4nO
3after mixed liquor carries out secondary exchange, under 0.098MPa and 550 DEG C condition, carry out hydrothermal treatment consists 2 hours, obtained reference carrier material C
a.
Comparative example 2
1. get 250 grams of industrial NaY zeolite (SiO
2/ A1
2o
3=5.0(mol ratio), lattice constant is 2.463nm, Na
2o content is 9wt%), be the NH of 10wt% by 2500ml concentration
4nO
3the aqueous solution exchanges 1 hour at 90 DEG C of temperature, and then is oxalic acid and the NH of 2 by 2500ml pH value
4nO
3mixed liquor carries out secondary exchange, carries out first time hydrothermal treatment consists 2 hours afterwards under 0.098 MPa and 550 DEG C condition, then at the NH with 10%
4nO
3the aqueous solution exchanges to Na
2after O<0.15wt%, carrying out second time hydrothermal treatment consists 2 hours under 0.12MPa and 650 DEG C condition, is then 0.3 mol/L HNO by concentration
3the aqueous solution exchanges, through washing, 120 DEG C of dryings 4 hours, and obtained Modified Zeolite Y (by CN02144945.7 preparation).
2. said method is obtained 15g modified Y molecular sieve, 75g amorphous aluminum silicide (dioxide-containing silica is 30wt%), 10g SB aluminium oxide and dust technology kneading, roll, making can the paste of extrusion, extruded moulding, 110 DEG C of dryings 6 hours, obtained reference composite carrier C
b.
Comparative example 3
Reference carrier material C prepared by the method provided according to CN200610134151.1
c.
By the modified Y molecular sieve of 150g comparative example 2 gained, add in 2 liters of distilled water, stirring to pulp, form slurries (a), 4000g Solid aluminum sulfate is joined in 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (b), A1
2o
3concentration is about 4g/100ml.Concentrated ammonia liquor is added appropriate distilled water diluting into about 10% weak aqua ammonia (c).10 liters of distilled water are joined in 4.8L concentrated sodium silicate (technical grade, modulus is 3.0), obtain rare water glass solution (d).Get the steel retort of one 15 liters, 2 liters of distilled water are added and after being heated with stirring to 70 DEG C in tank, open the valve of the container having aluminum sulfate and ammoniacal liquor respectively simultaneously, and slowly (a) is added in retort, by preparing the flow of 750g sial product setting value (b) to make the neutralization reaction time at one hour, what adjust (a) adds speed simultaneously, ensure to add at (a) and (b) simultaneously, and the flow of adjustment (c) rapidly makes the pH value of system remain on 7 ~ 8, and the temperature of the hierarchy of control is at about 65 DEG C.After reacting aluminum sulfate completes, stop adding ammoniacal liquor, after the alumina sol of generation stablizes 20 minutes, by final containing SiO
2amount starts to add metering (d) 3.3 liters, adds, start the ageing process of system in 10 minutes, keeps pH value 8.0, temperature 60 ~ 65 DEG C.After aging 50 minutes, filter colloidal solution and obtain wet cake, by filter cake again adding distil water making beating washing, refilter and obtain filter cake (e).(e) after dry 8 hours, is pulverized, sieve to obtain composite carrier C at 110 DEG C
c.
The physico-chemical property of table 1 complex carrier
| Numbering | A | B | C | C A | C B | C C |
| Specific area, m 2/g | 485 | 482 | 501 | 289 | 380 | 340 |
| Pore volume, ml/g | 0.71 | 0.68 | 0.76 | 0.45 | 0.63 | 0.51 |
| Meleic acid amount, mmol/g | 0.449 | 0.457 | 0.431 | 0.565 | 0.405 | 0.392 |
Claims (8)
1. a preparation method for composite carrier, described carrier material comprises Y zeolite and amorphous refractory inorganic oxides, and wherein the content of amorphous refractory inorganic oxides is 40wt% ~ 90wt%, and preparation process is as follows:
L required amorphous refractory inorganic oxides adds water making beating by ();
(2) in NaY molecular sieve modifying process, introduce slurries and the surfactant of step (1) gained, with the weight of final carrier material for benchmark, the addition of surfactant is 2wt% ~ 20wt%;
(3) material of step (2) gained is carried out comprise filtration, washing, dry treatment step, obtain the composite carrier containing Y zeolite and amorphous refractory inorganic oxides;
The surfactant of step (2) is nonionic surface active agent, is selected from one or more in polyglycol ether, APES, AEO, polyoxyethylene carboxylate, polyoxyethylene amine, polyoxyethylate amide, fatty glyceride.
2. in accordance with the method for claim 1, it is characterized in that in step (2), described surfactant adds in form of an aqueous solutions.
3. in accordance with the method for claim 1, it is characterized in that amorphous refractory inorganic oxides in step (l) is one or more in aluminium oxide, silica, magnesia, titanium oxide, zirconia.
4. in accordance with the method for claim 1, it is characterized in that in step (l), amorphous refractory inorganic oxides is amorphous aluminum silicide, wherein SiO
2weight content be 20% ~ 50%.
5. in accordance with the method for claim 1, it is characterized in that in the slurries of step (1) gained, the content of amorphous refractory inorganic oxides is 5wt% ~ 40wt%.
6. in accordance with the method for claim 1, it is characterized in that described NaY molecular sieve modifying process comprises in ion-exchange, hydrothermal treatment consists, acid treatment one or more.
7. in accordance with the method for claim 1, it is characterized in that described NaY molecular sieve is through modified, the Y zeolite obtained is deep sealumination modified Y type molecular sieve, super-stable Y molecular sieves, the Y zeolite of silicon replacement or the Y zeolite of super steady silicon replacement.
8. in accordance with the method for claim 1, it is characterized in that step (3) described drying is at 80 ~ 120 DEG C dry 6 ~ 10 hours.
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| CN103100433B true CN103100433B (en) | 2015-05-13 |
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| CN106607071B (en) * | 2015-10-26 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of preparation method of high cracking activity Y type molecular sieve |
| CN106669771B (en) * | 2015-11-09 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of compound and preparation method thereof containing nano NaY molecular sieve |
| CN106669772B (en) * | 2015-11-09 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of compound and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172259A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Method for preparing carrier material |
| CN101239328A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Amorphous silica-alumina and its preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172259A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Method for preparing carrier material |
| CN101239328A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Amorphous silica-alumina and its preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 纳米Y型分子筛/无定形硅铝复合材料的制备;何琳琳等;《第15届全国分子筛学术大会论文集》;20091011;295页第2部分 * |
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