CN100422081C - Modified Y zeolite and its preparation method - Google Patents
Modified Y zeolite and its preparation method Download PDFInfo
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- CN100422081C CN100422081C CNB2005100474704A CN200510047470A CN100422081C CN 100422081 C CN100422081 C CN 100422081C CN B2005100474704 A CNB2005100474704 A CN B2005100474704A CN 200510047470 A CN200510047470 A CN 200510047470A CN 100422081 C CN100422081 C CN 100422081C
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Abstract
The invention discloses a modified Y-zeolite and preparing method with molar rate of SiO2/Al2O3 at 7.0-30, wherein the specific area of Y-zeolite is 700-900m2/g with cell constant at 2.425-2.445nm; the relative crystallizing degree is not less than 80% with Na2O content not more than 0.25%; the 1.7-10nm second hole is over 45% in the total hole capacitance; the non-frame aluminium is over 30% in the whole aluminium with infrared acid degree at 0.15-0.55mmol/g; the preparing method adopts NaY as raw material to produce the modified Y-zeolite through ammonia exchanging, hydrothermal disposal, non-frame aluminium stripping, hole expanding and secondary hydrothermal disposal.
Description
Technical field
The present invention relates to a kind of modified Y zeolite and preparation method thereof, in particular as modified Y zeolite of hydrocarbon cracking catalyst acidic components and preparation method thereof.
Background technology
Is the direction of oil refining worker always effort to satisfy people to the demand of the energy with the heavy distillate lighting.Hydrocracking process has become one of important means of light materialization of heavy oil, and the height of hydrocracking catalyst performance then directly influences the effect of light materialization of heavy oil.In order to obtain to have good selectivity and active hydrocracking catalyst, the cracking component of hydrocracking catalyst is used the molecular sieve of modification usually.For the hydrocracking catalyst of voluminous intermediate oil, in order to improve the selectivity of intermediate oil, usually the molecular sieve consumption that requires to use in the catalyzer will lack, the acid site density of molecular sieve is low, in the molecular sieve 〉=pore volume in 1.7nm hole is big as far as possible, to reduce second pyrolysis, when improving catalyst selectivity, also require catalyzer to have higher activity, this just requires modified molecular screen to have higher degree of crystallinity, stronger active centre, more rich secondary pore is to improve the utilising efficiency in acid site.
US4,036,739 discloses the method that light hydrocarbons is produced in a kind of heavy hydrocarbon cracking, discloses a kind of preparation method of Y zeolite in this method, comprises a kind of NH that contains sodium 0.6～5 heavy % of (1) roasting
4NaY zeolite, described roasting under the temperature of 600～1650 (315.6～898.9 ℃), and with the water vapor of 0.5Psi contacts at least condition under carry out, the time of contact is with the structure cell to 2.440 that reduces described zeolite～2.464nm; (2) zeolite after the roasting is carried out ammonium exchange, the condition of exchange makes at least 25% of remaining sodium ion be replaced by ammonium ion, obtains the product of sodium content less than 1 heavy %; (3) product that (2) step of re-baking obtains under the temperature of 600～1650 (315.6～898.9 ℃), the ammonium in enough effective elimination zeolites basically of the time of roasting does not make the lattice constant of zeolite be contracted to below the 2.440nm.Though it is stable with the modified Y zeolite that this method obtains
Be improved, reduced the acid site density of zeolite, produced secondary pore simultaneously, but the decline of the degree of crystallinity of zeolite obviously, the secondary pore of generation is also abundant inadequately.
The LZ-210 zeolite of industrial a large amount of uses at present adopts the chemical method dealumination complement silicon to improve the silica alumina ratio of zeolite, increase the stability of zeolite, reducing the acid site density of zeolite, and do not destroy the degree of crystallinity of zeolite, then is the secondary pore that has only seldom but the zeolite of this method preparation is short of most.
US4,668,649 modified Y zeolites of introducing are twice ammonium salt exchange, twice thermal treatment, and its secondary pore only accounts for 30% of total pore volume.
CN1179400 has introduced a kind of super-hydrophobic Y zeolite and preparation method thereof, and this method is with Na
2At 550～700 ℃, handled 0.5～10 hour down, and with chemical method selectively removing non-framework aluminum, prepare SiO by 0.01～1.0MPa water vapor pressure less than 0.2% Y zeolite for O content
2/ Al
2O
3Mol ratio is 5.0～25, lattice constant 2.425～2.440nm, specific surface area 600～850m
2/ g, Na
2O content≤0.2w%,＞20 * 10
- 10The secondary pore of m accounts for more than 40% of total pore volume, infrared acidity 0.20～0.60mmol/g.The zeolitic acid center density of this method preparation is low, and the secondary pore pore volume is abundanter, and the degree of crystallinity loss is few, handle VGO heavy oil as the acidic components of hydrocracking catalyst and show good middle distillates oil selectivity and lytic activity, but this preparation method is to the Na of raw material
2The O content requirement is too harsh.
Summary of the invention
At the deficiencies in the prior art, the invention discloses a kind of degree of crystallinity height, secondary pore is abundant, modified Y zeolite of suitable silica alumina ratio and preparation method thereof, intermediate distillate yied increased when this zeolite was used to handle the heavy distillate hydrocracking.
The preparation method of modified Y zeolite provided by the invention comprises: with the NaY zeolite is raw material, carries out ion-exchange with the aqueous solution of ammonium salt, prepares Na
2The O weight content carries out the hydrothermal treatment consists first time then less than 2.7% Y zeolite, product and mineral acid or organic acid and contain NH
4 +The mixing solutions contact formed of salt, the further Na in the exchanging zeolite
+Remove the part non-framework aluminum in the zeolite simultaneously, with expanding agent zeolite is carried out reaming then and handle, carry out the hydrothermal treatment consists second time at last.It is oxalic acid, ammonium oxalate, citric acid, ammonium citrate or their mixing solutions that the expanding agent that adopts is handled in wherein said reaming, the concentration of expanding agent is 0.01～0.3mol/L, 0.03～0.25mol/L preferably, the reaming treatment temp is 70～120 ℃, preferably 80～100 ℃, the concentration that the slurries mesolite is handled in reaming is 0.05～1.0g/ml, preferably 0.1～0.5g/ml, the reaming treatment time is 0.5～3.0 hour, preferably 1.0～2.0 hours.
Other operation steps among the modified Y zeolite preparation method of the present invention is as ammonium salt exchange, hydrothermal treatment consists, take off working method and condition that non-framework aluminum etc. can adopt this area routine.As specifically adopting following condition:
1, ammonium salt exchange: with the NaY zeolite is raw material, the aqueous solution with solubility ammonium salt such as ammonium chloride, volatile salt, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc., the concentration of ammonium salt solution is 0.5～5.0mol/L, 1.0～3.0mol/L preferably, at 70～120 ℃, preferably 80～100 ℃ exchange 0.5～3.0 hour down, the concentration of Y zeolite in the exchange slurries is 0.05～0.5g/ml, 0.1～0.3g/ml preferably, repeated exchanged 1～5 time, the elimination mother liquor, washing, drying makes Na
2O content is less than 2.7%.
2, hydrothermal treatment consists: with the Na that makes
2O content places thermal treatment unit less than 2.7% Y zeolite, less than 3.0 hours, be preferably less than in 2.0 hours system temperature risen to and require temperature, at self water vapor or feeding water vapor, system temperature is controlled at 500～700 ℃, preferably is controlled at 550～650 ℃, system pressure maintains 0.01～0.5MPa, preferably maintain 0.05～0.3MPa, thermal treatment 1.0～8.0 hours, best 2.0～5.0 hours.Hydrothermal treatment consists also can be different with the hydrothermal treatment consists condition can be identical for the second time for the first time.
3, take off non-framework aluminum: for the first time the Y zeolite after the hydrothermal treatment consists is with acid with contain NH
4 +The mixing solutions contact formed of salt, the Na in the exchanging zeolite
+With the part non-framework aluminum that removes in the zeolite, acid wherein can be hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, and the salt that contains ammonium can be the salt that contains above acid, and the concentration of acid is 0.01～0.5mol/L in the mixing solutions, and preferably 0.05～0.3mol/L contains NH
4 +The concentration of salt be 0.5～3.0mol/L, 1.0～2.0mol/L preferably, the exchange temperature is 70～120 ℃, preferably 80～100 ℃, the concentration of exchange slurries mesolite is 0.05～1.0g/ml, 0.1～0.5g/ml preferably, and be 0.5～3.0 hour swap time, preferably 1.0～2.0 hours, the exchange number of times was 1～4 time.
Modified Y zeolite of the present invention has following feature: SiO
2/ Al
2O
3Mol ratio is 7.0～30, specific surface area 700～900m
2/ g, lattice constant 2.425～2.445nm, relative crystallinity 〉=80% is generally 85%～105%, Na
2O content≤0.25w%, the secondary pore of 1.7～10nm account for total pore volume more than 45%, are generally 45%～65%, and non-framework aluminum accounts for more than 30% of whole alumiunum amount, is generally 30%～50%.The infrared acidity of zeolite is generally 0.15～0.55mmol/g.
Preparation method provided by the invention has following advantage:
Modified Y zeolite with method preparation provided by the invention is obtaining higher SiO
2/ Al
2O
3The high-specific surface area and the high-crystallinity that have kept zeolite in the time of mol ratio adopt simple reaming to handle, and can obtain higher secondary pore ratio, and not destroy the degree of crystallinity of zeolite, and acid site density is low, Heat stability is good.
Modified Y zeolite with method preparation provided by the invention contains abundant non-framework aluminum.
Its physico-chemical property of modified Y zeolite provided by the invention has determined it to be suitable as the acidic cleavage component of middle oil type hydrocracking catalyst, and has good catalytic performance.Be that the middle oil type hydrocracking catalyst of acidic components preparations shows existing catalyzer when being used to handle heavy distillate and has better middle distillates oil selectivity and activity stability for example with modified Y zeolite of the present invention.
The following examples will the present invention will be further described.
Example 1
(1) with NaY zeolite (relative crystallinity 95%, lattice constant 2.470nm, SiO
2/ Al
2O
3Mol ratio is 5.1, Na
2O content is 11.0w%, and Wenzhou catalyst plant is produced) be that the ammonium chloride solution of 2.5mol/L mixes with concentration, the solid-liquid weight ratio is 10, be warming up to 100 ℃, under agitation carried out ion-exchange 1.5 hours, the elimination mother liquor, repeated exchanged 1 time is filtered, with the deionized water wash filter cake to there not being Cl
-Be detected, it is moisture 15% that filter cake places baking oven to dry to filter cake in 110 ℃, obtains Na
2O content is the Y zeolite sample I of 2.4w%
1
(2) with sample I
1Place heat treatment furnace, the heating schedule of design temperature is: rose to 580 ℃ in 1.2 hours, constant temperature 4 hours.The per hour flow of water vapor is 20% of an example weight, and Controlling System pressure is 0.05MPa, finishes until constant temperature, obtains Y zeolite sample I
2
(3) with sample I
2The mixing solutions of forming with nitric acid and volatile salt contacts and stirs, and the concentration of nitric acid is 0.15mol/L in the mixing solutions, and concentration of ammonium carbonate is 1.0mol/L, and other conditions are identical with step (1), obtain Y zeolite sample I
3
(4) with sample I
3The mixing solutions of forming with oxalic acid and ammonium oxalate contacts and stirs, and the concentration of mixing solutions mesoxalic acid is 0.10mol/L, and the concentration of ammonium oxalate is 1.5mol/L, and other conditions are identical with step (1), obtain Y zeolite sample I
4
(5) with sample I
4Place heat treatment furnace, the heating schedule of design temperature is: rose to 620 ℃ in 2.0 hours, and constant temperature 2 hours, the pressure of keeping system with the water vapor of sample self is 0.1MPa, obtains sample A.Its physico-chemical property sees Table 1.
Example 2
(1) gets NaY zeolite 100g, use the ammonium acetate 750ml of 1.5mol/L to stir exchange 2.0 hours, elimination mother liquor down at 82 ℃, repeated exchanged 2 times, filter cake 2500ml deionized water wash, it is moisture 20% to place baking oven to dry under 110 ℃ to filter cake then, obtains sample II
1
(2) with sample II
1Place heat treatment furnace, in 1 hour temperature is risen to 600 ℃, inject water vapor, Controlling System pressure is 0.15MPa, constant temperature 4 hours.Obtain Y zeolite sample II
2
(3) with sample II
2The mixing solutions 1000ml that forms with oxalic acid and ammonium oxalate contacted and stirs 1.0 hours at 90 ℃, the concentration of mixing solutions mesoxalic acid is 0.22mol/L, and the concentration of ammonium oxalate is 2.0mol/L, repeats 2 times, filter cake 2500ml deionized water wash obtains zeolite sample II
3
(4) with sample II
390 ℃ of following stir process 0.5 hour, suction filtration, washing obtained Y zeolite sample II with the citric acid 500ml of 0.2mol/L
4
(5) with sample II
4Place heat treatment furnace, in 1 hour temperature is risen to 650 ℃, inject water vapor, Controlling System pressure is 0.10MPa, constant temperature 3 hours.Obtain Y zeolite sample B.Its physico-chemical property sees Table 1.
Example 3
(1) in enamel still, adds 160kg industry NH
4NO
3(chemical plant, Dalian product, purity＞99.9%) and 910L H
2O is heated to 75 ℃, adds 125kg NaY zeolite, stirs 2 hours down at 92 ℃, repeats this step 2 time, filters and be washed to neutrality, and it is moisture 10% to be dried to filter cake at 110 ℃, obtains Na
2O content is the Y zeolite sample III of 2.0w%
1
(2) zeolite sample III
1Press in the external-heat rotary heat treatment furnace in packing into, be warming up to 610 ℃ in 1.5 hours, and inject water vapor, steam rates is 30kg/h, system pressure control 0.08MPa, and system temperature maintains 610 ℃, and thermal treatment 3.5 hours obtains Y zeolite sample III
2
(3) zeolite sample III
2Pack in the enamel still, add the mixing solutions 1000L that contains nitric acid 0.15mol/L and contain ammonium nitrate 1.5mol/L, be warming up to 95 ℃, stirred 2 hours, the elimination mother liquor repeats this step 1 time, be washed to neutrality, it is moisture 25% to be dried to filter cake at 110 ℃, obtains Y zeolite sample III
3
(4) with sample III
395 ℃ of following stir process 1.0 hours, suction filtration, washing obtained Y zeolite sample III with the citric acid 1000L of 0.12mol/L
4
(5) zeolite sample III
4Press in the external-heat rotary heat treatment furnace in packing into, be warming up to 640 ℃ in 1.5 hours, keep system pressure 0.18MPa with the water vapor of self, system temperature maintains 640 ℃, and thermal treatment 3.0 hours obtains modified Y zeolite sample C.Its physico-chemical property sees Table 1.
Reference example 4
The method of introducing according to CN1179400 prepares.
(1) NH that the 2.0kgNaY zeolite is added to 160 liters of concentration is 3mol/L
4NO
3In the solution, stir ion-exchange 0.5 hour down at 150 ℃, co-ion exchange 12 times obtains Na
2O content is 0.17% Y zeolite, and oven dry obtains product IV
1
(2) with product IV
1Put into the high-pressure rotary stove, at 700 ℃, roasting is 4 hours under the 0.01MPa water vapor pressure, obtains product IV
2
(3) get product IV
2400g, putting into concentration is the 4L hydrochloric acid soln of 0.4mol/L, handles 2 hours, filters, washs to neutral, oven dry obtains product D.Its physico-chemical property sees Table 1.
Reference example 5
(1) get the ammonium chloride solution 1000ml of NaY zeolite 100g, stir exchange 1.0 hours down at 90 ℃ with 2mol/L, the elimination mother liquor, repeated exchanged 1 time, washing, drying obtain Na
2O content is the Y zeolite sample V of 2.8w%
1
(2) with sample V
1Place thermal treatment unit, at 650 ℃, the water vapor contact conditions of 0.5Psi was handled 3.0 hours down, obtained sample V
2
(3) with sample V
2Ammonium chloride solution 1500ml with 1mol/L stirs exchange 2 hours down at 90 ℃, and the elimination mother liquor is washed to and detects no Cl
-, drying obtains sample V
3
(4) sample V
3At 650 ℃, re-baking is 3.0 hours under the water vapor contact conditions of 0.5Psi, obtains product E.Its physico-chemical property sees Table 1.
The physico-chemical property of table 1 modified Y zeolite A～E
Example 6～10
Zeolite A, B, C, D, E with example 1～5 are the acidic cleavage component, with the amorphous silicon aluminium is carrier, with group vib metal W and the metal Ni of VIII family is the hydrogenation activity component, with the metallic Z r of IVB family is auxiliary agent, adopts conventional coprecipitation method to be prepared into middle oil type hydrocracking catalyst CA, CB, CC and reference agent CD, CE.Zeolite A, B, C, D, the E content in catalyzer is 20w%.Coprecipitation method can prepare according to a conventional method, the method preparation of being introduced as adopting among the ZL98114489.6.
The specific surface area of the catalyzer CA of example 6 preparations is 240m
2/ g, pore volume are 0.34ml/g, and the weight composition is: WO
322.0%, NiO 9.0%, ZrO
27.0%, SiO
233.0%, Al
2O
329.0%.
The specific surface area of the catalyzer CB of example 7 preparations is 260m
2/ g, pore volume are 0.36ml/g, and the weight composition is: WO
321.0%, NiO 7.5%, ZrO
26.5%, SiO
230.0%, Al
2O
335.0%.
The specific surface area of the catalyzer CC of example 8 preparations is 270m
2/ g, pore volume are 0.31ml/g, and the weight composition is: WO
323.6%, NiO 7.4%, ZrO
27.0%, SiO
231.0%, Al
2O
331.0%.
The specific surface area of the reference agent CD of example 9 preparations is 254m
2/ g, pore volume are 0.31ml/g, and the weight composition is: WO
322.0%, NiO 9.0%, ZrO
27.0%, SiO
233.0%, Al
2O
329.0%.
The specific surface area of the reference agent CE of example 10 preparations is 212m
2/ g, pore volume are 0.29ml/g, and the weight composition is: WO
323.10%, NiO 7.9%, ZrO
27.2%, SiO
233.0%, Al
2O
329.0%.
Middle oil type hydrocracking catalyst CA, CB, CC and reference agent CD, CE evaluation result on packaged unit are compared.Estimate and adopt single hop once by flow process, stock oil is high nitrogen heavy distillate with isolated island VGO, and its main character is as follows: density 0.9249g/ml, 337～539 ℃ of boiling ranges, sulphur 0.77w%, nitrogen 0.18w%, carbon residue 0.01w%, 26 ℃ of condensation points, BMCI value 46.1.Table 2 has been listed comparing result.
Table 2 catalyzer CA, CB, CC and reference agent CD, CE evaluation result
From the evaluation result of table 2 as can be seen, modified Y zeolite of the present invention is as the acidic cleavage component of middle oil type hydrocracking catalyst, and catalyst activity is suitable with reference agent CD, is better than reference agent CE, and middle distillates oil selectivity is better than reference agent CD and CE.
Claims (10)
1. the preparation method of a modified Y zeolite, comprising: with the NaY zeolite is raw material, carries out ion-exchange with the aqueous solution of ammonium salt, prepares Na
2The O weight content carries out the hydrothermal treatment consists first time then less than 2.7% Y zeolite, product and mineral acid or organic acid and contain NH
4 +The mixing solutions contact formed of salt, the further Na in the exchanging zeolite
+Remove the part non-framework aluminum in the zeolite simultaneously, with expanding agent zeolite is carried out reaming then and handle, carry out the hydrothermal treatment consists second time at last; It is oxalic acid, ammonium oxalate, citric acid, ammonium citrate or their mixing solutions that the expanding agent that adopts is handled in wherein said reaming, the concentration of expanding agent is 0.01～0.3mol/L, the reaming treatment temp is 70～120 ℃, and the reaming treatment time is 0.5～3.0 hour.
2. in accordance with the method for claim 1, it is characterized in that it is 0.05～1.0g/ml that the concentration of slurries mesolite is handled in reaming.
3. in accordance with the method for claim 1, the concentration that it is characterized in that described expanding agent is 0.03～0.25mol/L, and the concentration that the slurries mesolite is handled in reaming is 0.1～0.5g/ml.
4. in accordance with the method for claim 1, it is characterized in that described reaming treatment temp is 80～100 ℃, the reaming treatment time is 1.0～2.0 hours.
5. in accordance with the method for claim 1, it is characterized in that it is ammonium chloride, volatile salt, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate or ammonium citrate that described NaY zeolite raw material carries out the employed solubility ammonium salt of ion-exchange with ammonium salt aqueous solution, the concentration of ammonium salt solution is 0.5～5.0mol/L, at 70～120 ℃, under exchange 0.5～3.0 hour, the concentration of Y zeolite in the exchange slurries is 0.05～0.5g/ml, exchanges 1～5 time.
6. in accordance with the method for claim 5, it is characterized in that described ammonium salt concentration is 1.0～3.0mol/L, the exchange temperature is 80～100 ℃, and the concentration of Y zeolite in the exchange slurries is 0.1～0.3g/ml.
7. in accordance with the method for claim 1, it is characterized in that described first time hydrothermal treatment consists and for the second time the hydrothermal treatment consists condition under 500～700 ℃ of water vapor conditions, to handle 1.0～8.0 hours.
8. in accordance with the method for claim 1, it is characterized in that described hydrothermal treatment consists temperature is 550～650 ℃, pressure is 0.01～0.5MPa, and the hydrothermal treatment consists time is 2.0～5.0 hours.
9. in accordance with the method for claim 1, it is characterized in that the non-framework aluminum method of taking off of Y zeolite is after described first time of the hydrothermal treatment consists: the Y zeolite after the hydrothermal treatment consists is with acid with contain NH for the first time
4 +The mixing solutions contact formed of salt, the Na in the exchanging zeolite
+With the part non-framework aluminum that removes in the zeolite, acid wherein is selected from hydrochloric acid, carbonic acid, nitric acid or sulfuric acid, and the salt that contains ammonium is the salt that contains above acid, and the concentration of acid is 0.01～0.5mol/L in the mixing solutions, contains NH
4 +The concentration of salt be 0.5～3.0mol/L, temperature is 70～120 ℃, the concentration of exchange slurries mesolite is 0.05～1.0g/ml, the time is 0.5～3.0 hour, the exchange number of times is 1～4 time.
10. in accordance with the method for claim 9, the ammonium salt concentration that it is characterized in that described acid is 0.05～0.3mol/L, NH
4 +Concentration be 1.0～2.0mol/L, temperature is 80～100 ℃, the concentration of exchange slurries mesolite is 0.1～0.5g/ml, the time is 1.0～2.0 hours.
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| CN101570334B (en) * | 2008-04-30 | 2011-06-22 | 中国石油天然气股份有限公司 | NaY molecular sieve modification method |
| CN101823727B (en) * | 2009-03-04 | 2012-03-07 | 中国石油天然气股份有限公司 | Modification method of molecular sieve |
| MX2010005333A (en) * | 2010-05-14 | 2011-11-23 | Mexicano Inst Petrol | Process for altering the physico-chemical properties of faujasite y-type zeolites. |
| CN102442685B (en) * | 2010-10-13 | 2013-11-06 | 中国石油化工股份有限公司 | Modification method of in-situ Y zeolite |
| CN102442684A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Modification method of in-situ Y zeolite |
| CN102895988A (en) * | 2011-07-25 | 2013-01-30 | 中国石油天然气股份有限公司 | Preparation method of in-situ crystallization catalyst |
| CN103058217B (en) * | 2011-10-21 | 2015-04-01 | 中国石油化工股份有限公司 | Preparation method of rare-earth-containing Y molecular sieve |
| CN103073024B (en) * | 2011-10-26 | 2014-12-31 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| CN103100402B (en) * | 2011-11-09 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| CN103100401B (en) * | 2011-11-09 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst containing in-situ Y zeolite |
| WO2013072809A1 (en) * | 2011-11-18 | 2013-05-23 | Basf Se | Process for ion exchange on zeolites |
| CN103508467B (en) | 2012-06-27 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of rare-earth Y molecular sieve and preparation method thereof |
| JP6232058B2 (en) | 2012-06-27 | 2017-11-15 | 中国石油化工股▲ふん▼有限公司 | Catalytic cracking catalyst containing modified Y-type zeolite and process for its preparation |
| TWI568495B (en) | 2012-09-14 | 2017-02-01 | China Petrochemical Technology Co Ltd | Catalytic cracking catalyst with rare earth Y type molecular sieve and preparation method thereof |
| US11179705B2 (en) | 2017-11-29 | 2021-11-23 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve and preparation method thereof, hydrocracking catalyst and preparation method thereof, and method for hydrocracking hydrocarbon oil |
| CN112403499B (en) * | 2019-08-22 | 2023-07-21 | 中国石油化工股份有限公司 | Preparation method and application of vanadium phosphorus oxide catalyst |
| EP4137458A1 (en) * | 2020-04-16 | 2023-02-22 | JGC Catalysts and Chemicals Ltd. | Faujasite type zeolite and method for producing same |
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| CN1058358A (en) * | 1990-07-18 | 1992-02-05 | 中国科学院大连化学物理研究所 | A kind of preparation method of type-Y high silicon zeolite |
| CN1179400A (en) * | 1996-10-15 | 1998-04-22 | 中国石油化工总公司 | Super-hydrophobic Y zeolite and its preparing process |
| CN1415704A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Cracking catalyst with hydrogen being added for noble metal and its prepn. method |
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