CN103055915B - NaY molecular sieve modification method - Google Patents
NaY molecular sieve modification method Download PDFInfo
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- CN103055915B CN103055915B CN201110318543.4A CN201110318543A CN103055915B CN 103055915 B CN103055915 B CN 103055915B CN 201110318543 A CN201110318543 A CN 201110318543A CN 103055915 B CN103055915 B CN 103055915B
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Abstract
The invention belongs to the molecular sieve catalysis material field, and discloses a NaY molecular sieve modification method, which is characterized in that a NaY molecular sieve and a solvent are uniformly mixed, and then acid and silicon are added, water is added in an obtained molecular sieve slurry, reaction is carried out at the temperature of 50-130 DEG C, and the processes of filtering, washing and drying are carried out to obtain the modified Y-type molecular sieve. The method can realize the direct exchange between Na<+> and H<+> so that the Y-type molecular sieve has acidity, the framework Si/Al ratio of the Y-type molecular sieve can be simultaneously increased, the structural integrity of the Y-type molecular sieve crystal can be guaranteed, the method condition is simple, the operation is simple and the environment is good.
Description
Technical field
The invention belongs to molecular sieve catalytic Material Field, relate to particularly a kind of method of modifying of NaY molecular sieve.
Background technology
NaY molecular sieve is catalyst or catalyst activity constituent element important in petroleum refining and chemical process, especially in fluid catalytic cracking and hydrocracking, is widely used.In direct synthetic y-type zeolite, Na
+generally there is the negative electrical charge with balance framework of molecular sieve with the cationic state of non-skeleton.Conventionally NaY molecular sieve does not have acidity, must introduce H at non-skeleton cation-bit
+or after the metal ion of high valence state, just there is certain acidity.Therefore,, in acid catalyzed reaction process, Y zeolite must remove most Na
+rear just have a higher catalytic activity.Conventionally, the method that molecular sieve removes sodium ion is to use ammonium salt solution or earth solution to carry out ion-exchange, and as Chinese patent CN1210034A, CN1065844A and US Patent No. 4085069 are described.At present the most frequently used in industrial production is to use NH
4 +be swapped out the Na in molecular sieve
+.In exchange process, conventionally need to add excessive ammonium salt to improve Na
+removal efficiency, exchanged the ammonia nitrogen waste water discharge meeting serious environment pollution of rear a large amount of high concentrations.
Conventionally, the silica alumina ratio that feeds intake when NaY Zeolite synthesis is generally 8-12, and the silica alumina ratio of product is generally 4.5-5.5.Due to the existence of a large amount of framework aluminums, NaY molecular sieve is not acidproof.Processing can cause serious dealuminzation to NaY molecular sieve directly to use aqueous acid, to such an extent as to skeleton avalanche.In the time of pH < 0.4, the framework aluminum of NaY molecular sieve can be removed completely (
j. Chem. Soc., Faraday Trans. I,1987,83,1531-1537).CN101823727A report is applied to ceramic membrane technology the modification of NaY molecular sieve, has avoided molecular sieve to contact with the direct of cationic ion-exchange resin, has realized Na
+with H
+between direct exchange.
In addition the ion-exchange capacity of the framework silicon-aluminum of Y zeolite comparison molecular sieve self, heat and hydrothermal stability, acidity and catalytic performance have a significant impact.For improving the framework si-al ratio of NaY molecular sieve, conventionally all need first to carry out an ammonium exchange and obtain NH
4after NaY, can carry out follow-up modification.Chinese patent CN1048835A, CN1036644C and US Patent No. 4503023 are all reported and are used NH
4naY is raw material, carries out liquid phase suction filtration mend silicon by ammonium fluosilicate solution.Use SiCl
4directly NaY molecular sieve is carried out to gas phase aluminium-eliminating and silicon-replenishing, can in the supercage of Y zeolite, form a large amount of Na[AlCl
4], and form Na[AlCl
4] produce in process the skeleton that a large amount of reaction heat can heavy damage molecular sieve (
j. Chem. Soc., Faraday Trans. I,1985,81,2889-2901).Hydro-thermal method is prepared super steady Y and is also needed to use NH
4naY is raw material, as reports such as Chinese patent CN1042523 and US Patent No. 3449370.The super steady Y that hydrothermal treatment consists obtains can use inorganic acid to remove non-framework aluminum, but prepared high silicon Y molecular sieve is not due to the isomorphous substitution reaction of silicon occurring, and the integrality of crystal structure can be destroyed.
The present invention has overcome that framework of molecular sieve avalanche in above-mentioned prior art, structural intergrity are destroyed, prior art preparation method can not directly process NaY molecular sieve by acid, under the complete condition of holding structure, reach the defect of hydrogen proton exchange and dealuminzation simultaneously, overcome simultaneously and can only use at present inorganic ammonium salt to exchange, can cause a large amount of discharges containing high-concentration ammonia nitrogenous wastewater, the problems such as serious environment pollution, the molecular sieve modified new method of a kind of NaY is proposed, directly use acid and silicon species to carry out modification to NaY molecular sieve, both can realize Na
+with H
+between direct exchange make NaY molecular sieve there is acidity, simultaneously can also improve the framework si-al ratio of Y zeolite, and ensure the structural intergrity of Y zeolite crystal.The inventive method condition is simple, easy and simple to handle, abandoned and adopt the process of ammonium salt exchange system for HY molecular sieve, reduces or therefore the discharge of stopping ammonia nitrogen waste water has eco-friendly feature.The inventive method can not cause framework of molecular sieve avalanche, and its principle is that the use of nonaqueous solvents can reduce system acidity, and the present invention passes through to control the addition regulation system acidity of water, thereby controls dealumination process.
Summary of the invention
The method of modifying that the object of this invention is to provide a kind of NaY molecular sieve, comprises the steps:
(1) by even to described NaY molecular sieve and solvent, then add acid and silicon species, obtain molecular sieve pulp;
(2) water is added in described molecular sieve pulp, at 50-130
oat C temperature, react;
(3) reactant mixture of step (2) gained is filtered, through washing, dry, obtain the Y zeolite after modification;
Wherein, described solvent is that boiling point is higher than 50
oc, the solvent molten with water.
In the inventive method, be cycled to repeat described step (1)-(3) molecular sieve is carried out to further modification.
Wherein, described solvent is small molecular alcohol, comprises ethanol, methyl alcohol, isopropyl alcohol, butanols; Or polyalcohol, comprise polyethylene glycol, ethylene glycol, propane diols, glycerine; Or butanone, oxolane.
Wherein, described acid is inorganic acid, H
+type cationic ion-exchange resin or organic carboxyl acid; Described inorganic acid comprises hydrochloric acid, sulfuric acid, nitric acid, sulfuric acid, and described organic carboxyl acid comprises lactic acid, succinic acid, citric acid, tartaric acid.
Wherein, described silicon species is organo-silicon ester and hydrolyzate thereof, or SiCl
4; Described organo-silicon ester comprises tetraethyl orthosilicate, quanmethyl silicate, silicic acid four butyl esters.
In the present invention, acid and silicon species add method for add successively or make in advance add after mixed liquor all can, but must add water and add before in step (2).
Wherein, in described step (2), can disposablely add completely adding of water, or add in batches, or add with the speed of every gram of NaY molecular sieve dropping per hour 0.5-10 ml water.The dropping process adding water can contain a part of period that whole step (2) can be also step (2).
Wherein, the reaction in described step (2) is carried out under standing or stirring, and in step (2), system pressure can be normal pressure or solvent self pressure in closed reactor.The stainless steel cauldron that reaction maybe can be put into sealing under normal pressure adds and thermogeneticly under pressure, carries out.
The present invention, by adopting nonaqueous solvents acid solution to carry out Modified NaY molecular sieve, by controlling the addition of water and adding speed hierarchy of control acidity, and supplements silicon species simultaneously, thereby reach H on the basis that keeps NaY molecular sieve structure integrality
+the object of ion-exchange and raising silica alumina ratio.The discharge that the inventive method innovation is to avoid nitrogen-containing wastewater, realizes H
+ion-exchange, the still taking out aluminium and mend silicon three processes are realized.
The present invention also provides the Y zeolite after a kind of modification obtaining through the inventive method, it is characterized in that, described Y zeolite degree of crystallinity is 50-100%, H
+ion-exchange degree is 30%-96%, silica alumina ratio SiO
2/ Al
2o
3for 6-25, molecular sieve total acid content is 0.8-3.2 mmol H
+/ g molecular sieve.
Detailed description of the invention
In conjunction with following specific embodiment, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Do not deviating under the spirit and scope of inventive concept, variation and advantage that those skilled in the art can expect are all included in the present invention, and taking appending claims as protection domain.
The method of modifying of NaY molecular sieve of the present invention specifically comprises the following steps:
(1) NaY molecular sieve is mixed with nonaqueous solvents, then add acid and silicon species;
(2) water is added in the molecular sieve pulp of step (1) gained, at 50-130
oat C temperature, under solvent self pressure, react 1-12 hour at normal pressure or in closed reactor;
(3) reactant mixture of step (2) gained is filtered to washing and the dry Y zeolite obtaining after modification;
In the inventive method, be cycled to repeat described step (1)-(3) molecular sieve is carried out to further modification.Be cycled to repeat in process, replace NaY molecular sieve for further modification the Y zeolite of gained after a front modification.
Wherein, step (1) indication nonaqueous solvents comprises the small molecular alcohols such as ethanol, methyl alcohol, isopropyl alcohol and butanols, liquid polyethylene glycol, and the polyalcohols such as ethylene glycol, propane diols and glycerine, the boiling points such as butanone and oxolane are higher than 50
oc and the solvent molten with water.
Step (1) indication acid comprises the inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and sulfuric acid, H
+type cationic ion-exchange resin, and the organic carboxyl acid such as lactic acid, succinic acid, citric acid, tartaric acid.
The silicon species of step (1) indication comprises the organo-silicon esters such as tetraethyl orthosilicate, quanmethyl silicate and silicic acid four butyl esters, the hydrolyzate of above-mentioned organo-silicon ester, and SiCl
4deng.
In step (2), can disposablely add completely adding of water, also can add in batches, also can in reaction overall process, drip completely with the speed of every gram of NaY molecular sieve dropping per hour 0.5-10ml water.
Reaction described in step (2) can be carried out under standing or stirring.The stainless steel cauldron that reaction maybe can be put into sealing under normal pressure adds and thermogeneticly under pressure, carries out.
The inventive method without particular requirement, is generally the former powder of industrial Zeolite synthesis to the type of NaY molecular sieve.The inventive method material rate is that every gram of required acid of NaY molecular sieve is 0.005-0.1mol, and silicon species is 0.001-0.1mol.Required nonaqueous solvents is 5-50ml.According to processing needs, water addition is 0-30ml.Method of modifying gained Y zeolite degree of crystallinity of the present invention is retained in 50-100%, H
+ion-exchange degree reaches 30%-96%, silica alumina ratio SiO
2/ Al
2o
3bring up to 6-25, molecular sieve total acid content is 0.8-3.2 mmol H
+/ g molecular sieve.
embodiment 1
The method of modifying of NaY molecular sieve in the present embodiment, comprises the following steps:
(1) 1 gram of NaY molecular sieve is mixed with ethanol (every gram of NaY joins in 20ml ethanol), then add citric acid and tetraethyl orthosilicate, every gram of NaY adds 0.025mol citric acid and 0.004mol tetraethyl orthosilicate, obtains molecular sieve pulp.Above-mentioned citric acid and tetraethyl orthosilicate also can mixture form add, the result of citric acid, tetraethyl orthosilicate is similar with adding successively.
(2) by 6 grams of disposable molecular sieve pulps that add step (1) gained of water, 80
oc temperature lower seal leaves standstill reaction 6 hours.
(3) reactant mixture of step (2) gained is filtered, through washing, 100
odry 12 hours of C, obtains the Y zeolite 1 after modification.
The solvent that step (1) is used is for boiling point is higher than 50
oc, the nonaqueous solvents molten with water, comprises the small molecular alcohols such as ethanol, methyl alcohol, isopropyl alcohol and butanols, liquid polyethylene glycol, the polyalcohols such as ethylene glycol, propane diols and glycerine, butanone and oxolane etc.
The acid using in step (1) comprises the inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and sulfuric acid, H
+type cationic ion-exchange resin, and the organic carboxyl acid such as lactic acid, succinic acid, citric acid, tartaric acid.
The silicon that step (1) is used comprises the organo-silicon esters such as tetraethyl orthosilicate, quanmethyl silicate and silicic acid four butyl esters, and the hydrolyzate of above-mentioned organo-silicon ester, and SiCl
4deng.
In the present embodiment step (2), under static condition, carrying out.Reaction also can be carried out under stirring.
Gained Y zeolite 1 and the comparison of parent NaY molecular sieve, relative crystallinity is 50%, silica alumina ratio (SiO
2/ Al
2o
3) be 9.4, H
+ion-exchange degree reaches 30%.
comparative example 1
In this comparative example, in the method for modifying of NaY molecular sieve, do not add tetraethyl orthosilicate, other step method are all consistent with embodiment 1.Comprise the following steps:
(1) 1 gram of NaY molecular sieve is mixed with ethanol (every gram of NaY joins in 20ml ethanol), then every gram of NaY adds 0.025mol citric acid, but does not add tetraethyl orthosilicate, obtains molecular sieve pulp.
(2) by 6 grams of disposable molecular sieve pulps that add step (1) gained of water, 80
oc temperature lower seal leaves standstill reaction 6 hours.
(3) reactant mixture of step (2) gained is filtered, through washing, 100
odry 12 hours of C, obtains the Y zeolite 2 after modification.
Gained Y zeolite 2 and the comparison of parent NaY molecular sieve, relative crystallinity is 17%, silica alumina ratio (SiO
2/ Al
2o
3) be 6.2, H
+ion-exchange degree reaches 30%.
Shown in upper table 1, add silicon species after method of modifying gained Y zeolite product quality of the present invention better, all be significantly better than not adding the Y zeolite of silicon species modification at the aspect such as relative crystallinity, silica alumina ratio.
embodiment 2
The method of modifying of NaY molecular sieve in the present embodiment, comprises the following steps:
(1) 1 gram of NaY molecular sieve is mixed with ethanol (every gram of NaY joins in 20ml ethanol), then add respectively tartaric acid and tetraethyl orthosilicate, every gram of NaY adds 0.025mol tartaric acid and 0.004mol tetraethyl orthosilicate, obtains molecular sieve pulp.
(2) 6 grams of water are added in the molecular sieve pulp of step (1) gained, 80 according to the speed of 1 gram of water every gram molecule sieve per hour
onormal pressure stirring reaction 6 hours at C temperature.
(3) reactant mixture of step (2) gained is filtered, through washing, 100
odry 12 hours of C, obtains the Y zeolite after modification one time.
(4), by the Y zeolite after a modification of step (3) gained, repeating step 1-3 twice, obtains the Y zeolite 3 after modification three times.
Y zeolite 3 and the comparison of parent NaY molecular sieve after three modifications of gained, relative crystallinity is 64%, silica alumina ratio (SiO
2/ Al
2o
3) be 25.2, H
+ion-exchange degree reaches 96%.
comparative example 2
In this comparative example, in the method for modifying of NaY molecular sieve, do not use nonaqueous solvents ethanol, directly make water as solvent, other step method are roughly consistent with embodiment 2.Comprise the following steps:
(1) 1 gram of NaY molecular sieve is mixed with 20 ml water, then add respectively tartaric acid and tetraethyl orthosilicate, every gram of NaY adds 0.025mol tartaric acid and 0.004mol tetraethyl orthosilicate, obtains molecular sieve pulp.
(2) by the molecular sieve pulp of step (1) gained 80
onormal pressure stirring reaction 6 hours at C temperature.
(3) reactant mixture of step (2) gained is filtered, through washing, 100
odry 12 hours of C, obtains the product after modification one time, and this product is amorphous products, and FAU structure disappears completely, and relative crystallinity is 0%.
Shown in upper table 2, adopt the method for modifying gained Y zeolite product of the present invention of nonaqueous solvents at relative crystallinity, silica alumina ratio, H
+the aspects such as ion-exchange degree have better quality, adopt aqueous solvent cannot obtain Y zeolite product qualitatively.
embodiment 3
The method of modifying of NaY molecular sieve in the present embodiment, comprises the following steps:
(1) 1 gram of NaY molecular sieve is mixed with 20ml polyethylene glycol, then add respectively concentrated hydrochloric acid and tetraethyl orthosilicate, every gram of NaY adds 0.020mol hydrochloric acid and 0.004mol tetraethyl orthosilicate, obtains molecular sieve pulp.
(2) 6 grams of water are added in the molecular sieve pulp of step (1) gained, 100 according to the speed of 1 gram of water every gram molecule sieve per hour
onormal pressure stirring reaction 6 hours at C temperature.
(3) reactant mixture of step (2) gained is filtered, through washing, 100
odry 12 hours of C, obtains the Y zeolite 4 after modification.
Gained Y zeolite 4 and the comparison of parent NaY molecular sieve, relative crystallinity is 65%, silica alumina ratio (SiO
2/ Al
2o
3) be 11.2, H
+ion-exchange degree reaches 60%.
embodiment 4
The method of modifying of NaY molecular sieve in the present embodiment, comprises the following steps:
(1) 1 gram of NaY molecular sieve is mixed with 20ml ethanol, then add respectively tartaric acid and tetraethyl orthosilicate, every gram of NaY adds 0.030mol hydrochloric acid and 0.004mol tetraethyl orthosilicate, obtains molecular sieve pulp.
(2) 6 grams of water are added in the molecular sieve pulp of step (1) gained, pack teflon-lined autoclave into, 100
oat C temperature, leave standstill reaction 6 hours.
(3) reactant mixture of step (2) gained is filtered, through washing, 100
odry 12 hours of C, obtains the Y zeolite 5 after modification.
Gained Y zeolite 5 and the comparison of parent NaY molecular sieve, relative crystallinity is 75%, silica alumina ratio (SiO
2/ Al
2o
3) be 12.2, H
+ion-exchange degree reaches 65%.
embodiment 5
The method of modifying of the present embodiment NaY molecular sieve is substantially the same manner as Example 1, and the reaction of the present embodiment is carried out at 50 DEG C, obtains the Y zeolite 6 after modification.The present embodiment gained Y zeolite 6 and the comparison of parent NaY molecular sieve, relative crystallinity is 81%, silica alumina ratio (SiO
2/ Al
2o
3) be 5.6, H
+ion-exchange degree reaches 30%.
embodiment 6
The method of modifying of the present embodiment NaY molecular sieve is substantially the same manner as Example 1, and the reaction of the present embodiment is carried out in closed reactor at 130 DEG C, obtains the Y zeolite 7 after modification.The present embodiment gained Y zeolite 7 and the comparison of parent NaY molecular sieve, relative crystallinity is 45%, silica alumina ratio (SiO
2/ Al
2o
3) be 10.1, H
+ion-exchange degree reaches 35%.
embodiment 7
The method of modifying of the present embodiment NaY molecular sieve is substantially the same manner as Example 1, and nonaqueous solvents that the present embodiment uses is butanone.The present embodiment gained Y zeolite 8 and the comparison of parent NaY molecular sieve, its relative crystallinity is 55%, silica alumina ratio (SiO
2/ Al
2o
3) be 9.1, H
+ion-exchange degree is 34%.
comparative example 1
The present embodiment illustrates the method for modifying of prior art NaY molecular sieve.
1 g NaY molecular sieve adds in 20 ml water, adds 1 g ammonium sulfate, stirs 1 hour, after filtration, washing, the dry Y zeolite 9 obtaining after modification at 80 DEG C.
Y zeolite 9 relative crystallinities are 85%, silica alumina ratio (SiO
2/ Al
2o
3) be 5.3, NH
4 +ion-exchange degree reaches 50%.
Original technique is used a large amount of ammonium salts, causes the discharge of ammonia nitrogen waste water; And need can change into H type through roasting rear, and cannot improve significantly framework si-al ratio.
embodiment 8
The present embodiment is that the Y zeolite 9 that obtains taking comparative example 1 modification is as reference, to utilizing the NH of Y zeolite of method of modifying gained of the present invention
3the acid evaluation experimental of-TPD.
By above-described embodiment, comparative example, the prepared Modified Zeolite Y 1-9 compressing tablet of comparative example and grind to form 40-60 object particle and be placed in quartz ampoule, with 10
othe heating rate of C/min is warmed up to 500
oc also keeps 60min, is then cooled to room temperature, passes into NH
3absorption 30min, this passes into argon gas with 10 subsequently
othe heating rate of C/min is warmed up to 100, keeps about 60min to treat that baseline is steady, with 10
othe heating rate of C/min is warmed up to 700
oc also keeps 60min to stop.
From table 3, through acid and the common modification gained of silicon species Y zeolite total acid content of the present invention and middle strong acid (250-550 DEG C) in nonaqueous solvents with H
+ion-exchange degree increases and increases.Compared with aqueous solvent gained sample 2, the reservation of degree of crystallinity has ensured the acid strength of molecular sieve.And the amount of Y zeolite strong acid of the present invention (more than 550 DEG C) is higher than obtaining Y zeolite 9 by art methods ammonium salt clearing house, show to abandon ammonium salt exchange process acid and the common modification of silicon species in nonaqueous solvents through the inventive method, can reach directly exchange of acid, make Y zeolite there is acidity, can also improve the framework si-al ratio of Y zeolite, and ensure the structural intergrity of Y zeolite crystal simultaneously.
In acid catalysis, total acid content is larger, and respective acids density is also larger, can cause bimolecular reaction and secondary response to increase.After Y zeolite aluminium-eliminating and silicon-replenishing of the present invention, silica alumina ratio raises, and therefore, Y zeolite total acid content of the present invention diminishes compared with 9 total acid contents of Y zeolite in art methods, and the molecular sieve that modification of the present invention is prepared meets acid catalyzed requirement.
Claims (7)
1. a method of modifying for NaY molecular sieve, is characterized in that, comprises the following steps:
(1) by even to described NaY molecular sieve and solvent, then add acid and silicon species, obtain molecular sieve pulp;
(2) water is added in described molecular sieve pulp, at 50-130 DEG C of temperature, react;
(3) reactant mixture of step (2) gained is filtered, through washing, dry, obtain the Y zeolite after modification;
Wherein, described solvent be boiling point higher than 50 DEG C, the nonaqueous solvents molten with water; Described solvent is small molecular alcohol, comprises ethanol, methyl alcohol, isopropyl alcohol, butanols; Or polyalcohol, comprise polyethylene glycol, ethylene glycol, propane diols, glycerine; Or butanone, oxolane;
Disposable add completely adding of water in described step (2), or add in batches, or add with the speed of every gram of NaY molecular sieve dropping per hour 0.5-10ml water;
Described method material rate is that every gram of required acid of NaY molecular sieve is 0.005-0.1mol, and silicon species is 0.001-0.1mol; Required nonaqueous solvents is 5-50ml; Water addition is 6-30ml.
2. the method for modifying of NaY molecular sieve as claimed in claim 1, is characterized in that, is cycled to repeat described step (1)-(3) molecular sieve is carried out to modification.
3. the method for modifying of NaY molecular sieve as claimed in claim 1, is characterized in that, described acid is inorganic acid, H
+type cationic ion-exchange resin or organic carboxyl acid; Described inorganic acid comprises hydrochloric acid, sulfuric acid, nitric acid, and described organic carboxyl acid comprises lactic acid, succinic acid, citric acid, tartaric acid.
4. the method for modifying of NaY molecular sieve as claimed in claim 1, is characterized in that, described silicon species is organo-silicon ester and hydrolyzate thereof, or SiCl
4; Described organo-silicon ester comprises tetraethyl orthosilicate, quanmethyl silicate, silicic acid four butyl esters.
5. the method for modifying of NaY molecular sieve as claimed in claim 1, is characterized in that, the reaction in described step (2) is carried out under standing or stirring.
6. utilize the Y zeolite that method of modifying prepares as claimed in claim 1, it is characterized in that, described Y zeolite degree of crystallinity is 50-100%, H
+ion-exchange degree is 30%-96%, silica alumina ratio SiO
2/ Al
2o is 6-25.
7. Y zeolite as claimed in claim 6, is characterized in that, described Y zeolite total acid content is 0.8-3.2mmol H
+/ g molecular sieve.
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| CN105621442B (en) * | 2014-11-27 | 2018-12-14 | 中国海洋石油集团有限公司 | Modified NaY molecular sieve and its preparation method and application and hydrotreating catalyst carrier and application |
| CN106467308B (en) * | 2015-08-21 | 2018-08-28 | 中国石油化工股份有限公司 | A kind of preparation method of high silica alumina ratio Y type molecular sieve |
| CN106467307B (en) * | 2015-08-21 | 2018-08-28 | 中国石油化工股份有限公司 | A kind of method of modulation Y type molecular sieve acidity |
| CN106608641B (en) * | 2015-10-26 | 2019-02-01 | 中国石油化工股份有限公司 | A method of improving Y type molecular sieve stability |
| CN106608644B (en) * | 2015-10-26 | 2018-09-28 | 中国石油化工股份有限公司 | Method that is a kind of while improving Y type molecular sieve silica alumina ratio and acid amount |
| CN106608640B (en) * | 2015-10-26 | 2019-02-01 | 中国石油化工股份有限公司 | It is a kind of that obtained molecular sieve is modified by NaY |
| CN106608643B (en) * | 2015-10-26 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of method of modifying of Y type molecular sieve |
| CN112808298B (en) * | 2019-11-18 | 2023-07-11 | 中国石油化工股份有限公司 | Catalyst containing hierarchical pore Y-type molecular sieve and preparation method thereof |
| CN112808297B (en) * | 2019-11-18 | 2023-07-14 | 中国石油化工股份有限公司 | Solid acid alkylation catalyst and preparation method thereof |
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| US4738940A (en) * | 1984-03-30 | 1988-04-19 | Institut Francais Du Petrole | Novel hydrocracking or cracking catalyst for hydrocarbon charges |
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