CN103055915A - NaY molecular sieve modification method - Google Patents
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- CN103055915A CN103055915A CN2011103185434A CN201110318543A CN103055915A CN 103055915 A CN103055915 A CN 103055915A CN 2011103185434 A CN2011103185434 A CN 2011103185434A CN 201110318543 A CN201110318543 A CN 201110318543A CN 103055915 A CN103055915 A CN 103055915A
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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 the molecular sieve catalytic Material Field, relate to particularly a kind of method of modifying of NaY molecular sieve.
Background technology
The NaY molecular sieve is catalyst or catalyst activity constituent element important in petroleum refining and the chemical process, especially is widely used in fluid catalytic cracking and hydrocracking.In the y-type zeolite that directly synthesizes, Na
+Generally there is negative electrical charge with the balance framework of molecular sieve with the cationic state of non-skeleton.Usually the NaY molecular sieve does not have acidity, must introduce H at non-skeleton cation-bit
+Or just has certain acidity behind the metal ion of high valence state.Therefore, in the acid catalyzed reaction process, Y zeolite must remove most Na
+Rear just have a higher catalytic activity.Usually, the method that molecular sieve removes sodium ion is to use ammonium salt solution or earth solution to carry out ion-exchange, and such as Chinese patent CN1210034A, CN1065844A and US Patent No. 4085069 are described.At present the most frequently used in the industrial production is to use NH
4 +Be swapped out the Na in the molecular sieve
+In exchange process, usually need to add excessive ammonium salt to improve Na
+Removal efficiency, the ammonia nitrogen waste water discharging meeting serious environment pollution of a large amount of high concentrations after exchange is finished.
Usually, the silica alumina ratio that feeds intake during the NaY Zeolite synthesis is generally 8-12, and the silica alumina ratio of product is generally 4.5-5.5.Because the existence of a large amount of framework aluminums, the NaY molecular sieve is not acidproof.Processing can cause serious dealuminzation to the NaY molecular sieve directly to use aqueous acid, to such an extent as to the skeleton avalanche.When pH＜0.4, the framework aluminum of NaY molecular sieve can be removed fully (
J. Chem. Soc., Faraday Trans. I,1987,83,1531-1537).The 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.
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 in addition.For improving the framework si-al ratio of NaY molecular sieve, usually all need to carry out first an ammonium exchange and obtain NH
4Can carry out follow-up modification behind the NaY.Chinese patent CN1048835A, CN1036644C and US Patent No. 4503023 are all reported and are used NH
4NaY is raw material, carries out the liquid phase suction filtration by ammonium fluosilicate solution and mends silicon.Use SiCl
4Directly the NaY molecular sieve is carried out the 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 the process skeleton that a large amount of reaction heat can the heavy damage molecular sieve (
J. Chem. Soc., Faraday Trans. I,1985,81,2889-2901).Hydro-thermal method prepares super steady Y and also needs to use NH
4NaY is raw material, such 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 because the isomorphous substitution reaction of silicon occuring, and the integrality of crystal structure can be destroyed.
The present invention has overcome that framework of molecular sieve avalanche in the above-mentioned prior art, structural intergrity are destroyed, prior art preparation method can not directly process the NaY molecular sieve by acid, under the condition that keeps structural integrity, reach simultaneously the defective of hydrogen proton exchange and dealuminzation, overcome simultaneously and can only use at present inorganic ammonium salt to exchange, can cause the discharging that contains in a large number 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 that the NaY molecular sieve is carried out modification, both can realize Na
+With H
+Between direct exchange make the NaY molecular sieve have acidity, can also improve simultaneously the framework si-al ratio of Y zeolite, and guarantee the structural intergrity of Y zeolite crystal.The inventive method condition is simple, easy and simple to handle, abandoned the process that adopts the standby HY molecular sieve of ammonium salt exchange system, reduces or therefore the discharging of stopping ammonia nitrogen waste water has eco-friendly characteristics.The inventive method can not cause the framework of molecular sieve avalanche, and its principle is that the use of nonaqueous solvents can reduce system acidity, and the present invention is acid by the addition regulation system of control water, thus the control dealumination process.
Summary of the invention
The purpose of this invention is to provide a kind of method of modifying of NaY molecular sieve, comprise the steps:
(1) described NaY molecular sieve and solvent is even, then add acid and silicon species, obtain molecular sieve pulp;
(2) water is added in the described molecular sieve pulp, at 50-130
oReact under the C temperature;
(3) reactant mixture of step (2) gained is filtered, through washing, drying, obtain the Y zeolite after the 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 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
4Described organo-silicon ester comprises tetraethyl orthosilicate, quanmethyl silicate, silicic acid four butyl esters.
Among the present invention, acid and the adding method of silicon species for add successively or make in advance add after the mixed liquor all can, but must add before adding of water in step (2).
Wherein, the adding of water can disposablely add fully in the described step (2), or adds in batches, or the speed dropping that per hour drips 0.5-10 ml water with every gram NaY molecular sieve adds.The dropping process that adds water can contain a part of period that whole step (2) also can be step (2).
Wherein, the reaction in the described step (2) leave standstill or stirring under carry out, system pressure can be normal pressure or solvent self pressure in closed reactor in the step (2).Reaction maybe can be put into sealing under normal pressure stainless steel cauldron adds and thermogeneticly carries out under pressure.
The present invention is by adopting the nonaqueous solvents acid solution to come the Modified NaY molecular sieve, and is acid by addition and the adding speed hierarchy of control of control water, and replenishes simultaneously silicon species, thereby reaches H on the basis that keeps NaY molecular sieve structure integrality
+The purpose of ion-exchange and raising silica alumina ratio.The inventive method innovation is to avoid the discharging of nitrogen-containing wastewater, realizes H
+Ion-exchange, the still taking out aluminium and mend three processes of silicon are realized.
The present invention also provides a kind of Y zeolite after the modification that the inventive method obtains, and 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
3Be 6-25, the molecular sieve total acid content is 0.8-3.2 mmol H
+/ g molecular sieve.
The specific embodiment
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.Under the spirit and scope that do not deviate from inventive concept, variation and advantage that those skilled in the art can expect all are included in the present invention, and take appending claims as protection domain.
The method of modifying of NaY molecular sieve of the present invention specifically may further comprise the steps:
(1) NaY molecular sieve and nonaqueous solvents are mixed, then add acid and silicon species;
(2) water is added in the molecular sieve pulp of step (1) gained, at 50-130
oReacted 1-12 hour under solvent self pressure at normal pressure or in closed reactor under the C temperature;
(3) reactant mixture with step (2) gained filters, and washing and drying obtain the Y zeolite after the modification;
In the inventive method, be cycled to repeat described step (1)-(3) molecular sieve is carried out further modification.Be cycled to repeat in the process, replace the NaY molecular sieve to be used for further modification the Y zeolite of gained after the 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.
The adding of water can disposablely add fully in the step (2), also can add in batches, and the speed that also can per hour drip 0.5-10ml water with every gram NaY molecular sieve in the reaction overall process drips fully.
Described in the step (2) reaction can leave standstill or stirring under carry out.Reaction maybe can be put into sealing under normal pressure stainless steel cauldron adds and thermogeneticly carries out under pressure.
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 the required acid of every gram 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, the 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, the 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 may further comprise the steps:
(1) 1 gram NaY molecular sieve and ethanol (every gram NaY joins in the 20ml ethanol) are mixed, then add citric acid and tetraethyl orthosilicate, every gram 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, similar with the result who adds successively citric acid, tetraethyl orthosilicate.
(2) in the molecular sieve pulp with the 6 gram disposable adding step of water (1) gained, 80
oC temperature lower seal leaves standstill reaction 6 hours.
(3) reactant mixture with step (2) gained filters, through washing, 100
oDry 12 hours of C obtains the Y zeolite 1 after the modification.
The employed solvent of step (1) is that 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.
Employed acid comprises the inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and sulfuric acid, H in the step (1)
+Type cationic ion-exchange resin, and the organic carboxyl acid such as lactic acid, succinic acid, citric acid, tartaric acid.
The employed silicon of step (1) 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.
Under static condition, carrying out in the present embodiment step (2).Reaction also can be carried out under stirring.
Gained Y zeolite 1 compares with parent NaY molecular sieve, and relative crystallinity is 50%, silica alumina ratio (SiO
2/ Al
2O
3) be 9.4, H
+Ion-exchange degree reaches 30%.
Comparative example 1
Do not add tetraethyl orthosilicate in this Comparative Examples in the method for modifying of NaY molecular sieve, other step method are all consistent with embodiment 1.May further comprise the steps:
(1) 1 gram NaY molecular sieve and ethanol (every gram NaY joins in the 20ml ethanol) are mixed, then every gram NaY adds the 0.025mol citric acid, but does not add tetraethyl orthosilicate, obtains molecular sieve pulp.
(2) in the molecular sieve pulp with the 6 gram disposable adding step of water (1) gained, 80
oC temperature lower seal leaves standstill reaction 6 hours.
(3) reactant mixture with step (2) gained filters, through washing, 100
oDry 12 hours of C obtains the Y zeolite 2 after the modification.
Gained Y zeolite 2 compares with parent NaY molecular sieve, and 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, method of modifying gained Y zeolite product quality of the present invention is better behind the adding silicon species, all significantly is better than not adding the Y zeolite of silicon species modification at aspects such as relative crystallinity, silica alumina ratios.
Embodiment 2
The method of modifying of NaY molecular sieve in the present embodiment may further comprise the steps:
(1) 1 gram NaY molecular sieve and ethanol (every gram NaY joins in the 20ml ethanol) are mixed, then add respectively tartaric acid and tetraethyl orthosilicate, every gram NaY adds 0.025mol tartaric acid and 0.004mol tetraethyl orthosilicate, obtains molecular sieve pulp.
(2) with 6 gram water according to 1 gram water per hour the speed of every gram molecule sieve add in the molecular sieve pulp of step (1) gained, 80
oThe normal pressure stirring reaction is 6 hours under the C temperature.
(3) reactant mixture with step (2) gained filters, through washing, 100
oDry 12 hours of C obtains the Y zeolite after the modification one time.
(4) with the Y zeolite after the modification of step (3) gained, repeating step 1-3 twice obtains the Y zeolite 3 after the modification three times.
Y zeolite 3 compares with parent NaY molecular sieve after three modifications of gained, and relative crystallinity is 64%, silica alumina ratio (SiO
2/ Al
2O
3) be 25.2, H
+Ion-exchange degree reaches 96%.
Comparative example 2
Do not use nonaqueous solvents ethanol in this Comparative Examples in the method for modifying of NaY molecular sieve, directly make water as solvent, other step method are roughly consistent with embodiment 2.May further comprise the steps:
(1) 1 gram NaY molecular sieve and 20 ml water are mixed, then add respectively tartaric acid and tetraethyl orthosilicate, every gram NaY adds 0.025mol tartaric acid and 0.004mol tetraethyl orthosilicate, obtains molecular sieve pulp.
(2) with the molecular sieve pulp of step (1) gained 80
oThe normal pressure stirring reaction is 6 hours under the C temperature.
(3) reactant mixture with step (2) gained filters, through washing, 100
oDry 12 hours of C obtains the product after the modification one time, and this product is amorphous products, the complete obiteration of FAU structure, 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 then can't obtain qualitatively Y zeolite product.
Embodiment 3
The method of modifying of NaY molecular sieve in the present embodiment may further comprise the steps:
(1) 1 gram NaY molecular sieve and 20ml polyethylene glycol are mixed, then add respectively concentrated hydrochloric acid and tetraethyl orthosilicate, every gram NaY adds 0.020mol hydrochloric acid and 0.004mol tetraethyl orthosilicate, obtains molecular sieve pulp.
(2) with 6 gram water according to 1 gram water per hour the speed of every gram molecule sieve add in the molecular sieve pulp of step (1) gained, 100
oThe normal pressure stirring reaction is 6 hours under the C temperature.
(3) reactant mixture with step (2) gained filters, through washing, 100
oDry 12 hours of C obtains the Y zeolite 4 after the modification.
Gained Y zeolite 4 compares with parent NaY molecular sieve, and 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 may further comprise the steps:
(1) 1 gram NaY molecular sieve and 20ml ethanol are mixed, then add respectively tartaric acid and tetraethyl orthosilicate, every gram NaY adds 0.030mol hydrochloric acid and 0.004mol tetraethyl orthosilicate, obtains molecular sieve pulp.
(2) 6 gram water are added in the molecular sieve pulp of step (1) gained, the teflon-lined autoclave of packing into is 100
oLeave standstill reaction 6 hours under the C temperature.
(3) reactant mixture with step (2) gained filters, through washing, 100
oDry 12 hours of C obtains the Y zeolite 5 after the modification.
Gained Y zeolite 5 compares with parent NaY molecular sieve, and 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 under 50 ℃, obtains the Y zeolite 6 after the modification.The present embodiment gained Y zeolite 6 compares with parent NaY molecular sieve, and 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 130 ℃ of lower closed reactors, obtains the Y zeolite 7 after the modification.The present embodiment gained Y zeolite 7 compares with parent NaY molecular sieve, and 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 parent NaY molecular sieve relatively, its relative crystallinity is 55%, silica alumina ratio (SiO
2/ Al
2O
3) be 9.1, H
+Ion-exchange degree is 34%.
Comparative Examples 1
The present embodiment illustrates the method for modifying of prior art NaY molecular sieve.
1 g NaY molecular sieve adds in the 20 ml water, adds 1 g ammonium sulfate, stirs under 80 ℃ 1 hour, after filtration, washing, drying obtain the Y zeolite 9 after the modification.
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 discharging of ammonia nitrogen waste water; And need to change into the H type through the roasting rear, and can't improve significantly framework si-al ratio.
Embodiment 8
The present embodiment is that the Y zeolite 9 that obtains take Comparative Examples 1 modification is as reference, to the NH of the Y zeolite that utilizes method of modifying gained of the present invention
3The acid evaluation experimental of-TPD.
With above-described embodiment, comparative example, the prepared Modified Zeolite Y 1-9 compressing tablet of Comparative Examples and grind to form 40-60 purpose particle and place quartz ampoule, with 10
oThe heating rate of C/min is warmed up to 500
oC also keeps 60min, then is 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 approximately that 60min treats that baseline is steady, with 10
oThe heating rate of C/min is warmed up to 700
oC also keeps 60min to stop.
By as seen 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 ℃) in nonaqueous solvents with H
+Ion-exchange degree increases and increases.Compare with aqueous solvent gained sample 2, the reservation of degree of crystallinity has guaranteed the acid strength of molecular sieve.And the amount of Y zeolite strong acid of the present invention (more than 550 ℃) is higher than by art methods ammonium salt clearing house and gets Y zeolite 9, show through the inventive method and abandon ammonium salt exchange process acid and the common modification of silicon species in nonaqueous solvents, can reach directly exchange of acid, make Y zeolite have acidity, can also improve simultaneously the framework si-al ratio of Y zeolite, and guarantee the structural intergrity of Y zeolite crystal.
In acid catalysis, total acid content is larger, and respective acids density is also larger, can cause bimolecular reaction and secondary response to increase.Silica alumina ratio raises behind the Y zeolite aluminium-eliminating and silicon-replenishing of the present invention, and therefore, Y zeolite total acid content of the present invention is compared with Y zeolite 9 total acid contents in the art methods and diminished, so that the molecular sieve that modification of the present invention prepares meets acid catalyzed requirement.
Claims (9)
1. the method for modifying of a NaY molecular sieve is characterized in that, may further comprise the steps:
(1) described NaY molecular sieve and solvent is even, then add acid and silicon species, obtain molecular sieve pulp;
(2) water is added in the described molecular sieve pulp, at 50-130
oReact under the C temperature;
(3) reactant mixture of step (2) gained is filtered, through washing, drying, obtain the Y zeolite after the modification;
Wherein, described solvent is that boiling point is higher than 50
oC, the nonaqueous solvents molten with water.
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 modification.
3. the method for modifying of NaY molecular sieve as claimed in claim 1 is characterized in that, 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.
4. 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, sulfuric acid, and described organic carboxyl acid comprises lactic acid, succinic acid, citric acid, tartaric acid.
5. 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
4Described organo-silicon ester comprises tetraethyl orthosilicate, quanmethyl silicate, silicic acid four butyl esters.
6. the method for modifying of NaY molecular sieve as claimed in claim 1 is characterized in that, the adding of water can disposablely add fully in the described step (2), or adds in batches, or the speed dropping that per hour drips 0.5-10ml water with every gram NaY molecular sieve adds.
7. the method for modifying of NaY molecular sieve as claimed in claim 1 is characterized in that, the reaction in the described step (2) leave standstill or stirring under carry out.
8. the Y zeolite that utilizes method of modifying as claimed in claim 1 to prepare 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.
9. Y zeolite as claimed in claim 8 is characterized in that, described Y zeolite total acid content is 0.8-3.2 mmol H
+/ g molecular sieve.
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| CN105621442A (en) * | 2014-11-27 | 2016-06-01 | 中国海洋石油总公司 | Modified NaY molecular sieve, preparation method and application thereof, carrier for hydrotreatment catalyst, and application of carrier |
| CN106608644A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Method for simultaneously improving silicon-aluminum ratio and acid content of Y type molecular sieve |
| CN106608640A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Molecular sieve obtained by NaY modification |
| CN106608643A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Y type molecular sieve modification method |
| CN106608641A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Method for improving stability of 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 |
| 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 |
| CN112808297A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Solid acid alkylation catalyst and preparation method thereof |
| CN112808298A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Catalyst containing hierarchical pore Y-type molecular sieve and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105621442A (en) * | 2014-11-27 | 2016-06-01 | 中国海洋石油总公司 | Modified NaY molecular sieve, preparation method and application thereof, carrier for hydrotreatment catalyst, and application of carrier |
| 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 |
| 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 |
| CN106608643A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Y type molecular sieve modification method |
| CN106608641A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Method for improving stability of Y-type molecular sieve |
| CN106608640A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Molecular sieve obtained by NaY modification |
| CN106608644A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Method for simultaneously improving silicon-aluminum ratio and acid content of Y type molecular sieve |
| 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 |
| 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 |
| CN112808297A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Solid acid alkylation catalyst and preparation method thereof |
| CN112808298A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Catalyst containing hierarchical pore Y-type molecular sieve and preparation method thereof |
| 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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| CN103055915B (en) | 2014-12-10 |
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