CN111097486A - Y molecular sieve and preparation method and application thereof - Google Patents
Y molecular sieve and preparation method and application thereof Download PDFInfo
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- CN111097486A CN111097486A CN201811264078.9A CN201811264078A CN111097486A CN 111097486 A CN111097486 A CN 111097486A CN 201811264078 A CN201811264078 A CN 201811264078A CN 111097486 A CN111097486 A CN 111097486A
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- molecular sieve
- dealumination
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- type molecular
- sodium
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 200
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005342 ion exchange Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims abstract description 11
- -1 molecular sieve ammonium salt Chemical class 0.000 claims abstract description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 10
- ADSOSINJPNKUJK-UHFFFAOYSA-N 2-butylpyridine Chemical compound CCCCC1=CC=CC=N1 ADSOSINJPNKUJK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 29
- 239000011734 sodium Substances 0.000 claims description 28
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 19
- 150000003863 ammonium salts Chemical class 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229940104869 fluorosilicate Drugs 0.000 claims description 9
- IZHYRVRPSNAXGV-UHFFFAOYSA-M potassium;naphthalene-1-sulfonate Chemical compound [K+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 IZHYRVRPSNAXGV-UHFFFAOYSA-M 0.000 claims description 8
- 229910001415 sodium ion Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 14
- 238000005336 cracking Methods 0.000 abstract description 9
- 230000002378 acidificating effect Effects 0.000 abstract description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 5
- 235000010344 sodium nitrate Nutrition 0.000 abstract 2
- 239000007787 solid Substances 0.000 description 22
- 238000002156 mixing Methods 0.000 description 16
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- GDCCFQMGFUZVKK-UHFFFAOYSA-N 1-butyl-2h-pyridine Chemical compound CCCCN1CC=CC=C1 GDCCFQMGFUZVKK-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 8
- 238000010335 hydrothermal treatment Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IEYSWVWNWSRECJ-UHFFFAOYSA-N C(CCC)C1=NC=CC=C1.N1=CC=CC=C1 Chemical compound C(CCC)C1=NC=CC=C1.N1=CC=CC=C1 IEYSWVWNWSRECJ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a modified Y-type molecular sieve, which contains 2.0-6.0 wt% of Na2O by mass based on the total amount of the modified Y-type molecular sieve; the ratio of the pyridine infrared acid amount to the butylpyridine infrared acid amount of the Y-type molecular sieve is 5-60; the pyridine infrared acid content is 0.05-0.6 mmol/g, and the preparation method of the modified Y-type molecular sieve comprises the following steps: (1) pretreating a NaY molecular sieve to obtain a sodium-removed and aluminum-removed Y-type molecular sieve; (2) treating the pretreated Y molecular sieve obtained in the step (1) with NaNO3 aqueous solution; (3) adding the Y molecular sieve treated by the NaNO3 aqueous solution in the step (2) into a naphthalene sulfonate aqueous solution for dipping treatment; (4) and (3) carrying out ion exchange reaction on the treated molecular sieve ammonium salt, and then drying and roasting to obtain the modified Y molecular sieve. The acidic central position of the molecular sieve is intensively distributed in the small holes of the molecular sieve, so that the secondary cracking efficiency of the hydrocracking reaction can be effectively improved.
Description
Technical Field
The invention relates to a Y molecular sieve and a preparation method and application thereof, in particular to a modified Y molecular sieve and a preparation method and application thereof.
Background
The hydrocracking technology has the characteristics of strong raw material adaptability, large product scheme flexibility, high target product selectivity, good product quality, high added value and the like, can directly convert various heavy and poor raw materials into clean fuel oil and high-quality chemical raw materials, becomes one of the most important heavy oil deep processing technologies in modern oil refining and petrochemical industries, and is increasingly widely applied at home and abroad. Although the processing capacity of the existing hydrocracking device in China exceeds 50.0Mt/a, the quality of the crude oil in China is gradually deteriorated, the import quantity of the high-sulfur crude oil is greatly increased, the requirements of environmental protection on the quality of an oil refining process and a petroleum product are strict day by day, and the demand of the market on clean fuel oil and chemical raw materials is continuously increased. Therefore, the hydrocracking technology can be more widely applied, and simultaneously, higher requirements are put on the hydrocracking technology.
The core of the hydrocracking technology is a hydrocracking catalyst which is a bifunctional catalyst with cracking and hydrogenation activities, wherein the cracking function is provided by acidic carrier materials such as molecular sieves, the hydrogenation function is provided by active metals of a VI group and a VIII group in the periodic table of elements loaded on the catalyst, and different reaction requirements are met by modulating the cracking and hydrogenation double-functional sites. The molecular sieve is used as a cracking component of the hydrocracking catalyst, and the performance of the molecular sieve plays a decisive role in the reaction performance of the catalyst. At present, the molecular sieve type used by the hydrocracking catalyst is mainly a Y molecular sieve. The number and distribution of the acid centers of the Y molecular sieve directly determine the reaction characteristics of the molecular sieve, particularly the size of the pore channel where the acid centers of the Y molecular sieve are located directly determines the cracking reaction selectivity of the molecular sieve to a certain class of reactants and reaction products, so that the allocation of the acid center distribution is an important direction of the modification treatment process of the Y molecular sieve. The modification technology of the Y-type molecular sieve generally comprises a hydrothermal modification method, a chemical dealumination modification method such as inorganic acid, organic acid, salt and complexing agent, a modification method combining hydrothermal modification and chemical dealumination, and the like. For example, patent CN96119840.0 adopts a hydrothermal desulfurization combined with buffer solution treatment to modify the Y molecular sieve; however, in the modified Y-type molecular sieve obtained by the current modification method, acid centers are distributed in different pore channels (micropores and secondary pores) of the molecular sieve.
The patent CN96119840.0 adopts a mode of combining hydrothermal desulfurization with buffer solution treatment to carry out modification treatment on the Y molecular sieve; chinese patent CN96120016.2 discloses a high-silicon crystallinity Y-type molecular sieve and a preparation method thereof, and NH is used4NaY is used as a reaction raw material, ammonium hexafluorosilicate is firstly used for dealuminizing and silicon supplementing, then hydro-thermal treatment is carried out, finally an aluminum salt solution is used for treatment, and the obtained Y molecular sieve keeps higher crystallinity while deeply dealuminizing; U.S. patent US4036739 discloses a hydrocracking process wherein a Y-type molecular sieve is modified by contacting with at least 0.5psi steam at a temperature of 315 to 899 ℃ for a period of time. However, the modification processes all have the problems that the acid centers of the modified Y-type molecular sieve are distributed in the molecular sieve pore canals with different sizes, and the dispersity of the acid sites of the molecular sieve is large.
Disclosure of Invention
Aiming at the defects in the prior art, the first aspect of the invention provides a modified Y-type molecular sieve.
The modified Y-type molecular sieve takes the total amount of the modified Y-type molecular sieve as a reference, and the Y-type molecular sieve contains Na2The mass content of O is 2.0-6.0 wt%; the ratio of the pyridine infrared acid amount to the butylpyridine infrared acid amount of the Y-type molecular sieve is 5-60; the amount of the pyridine infrared acid is 0.05-0.6 mmol/g.
Preferably, the specific surface area of the modified Y-type molecular sieve is 600-900 m2(ii)/g; the pore volume is 0.30-0.60 ml/g; the relative crystallinity is 60% -140%, and the unit cell parameter is 2.430-2.450; the molar ratio of silicon to aluminum (5-50): 1.
a second aspect of the present invention provides a process for preparing the modified Y-type molecular sieve of the present invention, comprising the steps of:
(1) pretreating a NaY molecular sieve to obtain a sodium-removed and aluminum-removed Y-type molecular sieve;
(2) NaNO for the pretreated Y molecular sieve obtained in the step (1)3Treating the aqueous solution;
(3) to the step (2) through NaNO3Adding the Y molecular sieve treated by the aqueous solution into a naphthalene sulfonate aqueous solution for dipping treatment;
(4) and (3) carrying out ion exchange reaction on the treated molecular sieve ammonium salt, and then drying and roasting to obtain the modified Y molecular sieve.
Preferably, the pretreatment in step (1) comprises: ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination, and acid dealumination.
Preferably, the pretreatment in step (1) comprises:
(a) carrying out ammonium ion exchange reaction on the NaY molecular sieve and an ammonium salt water solution to obtain a sodium-removed Y-type molecular sieve;
(b) carrying out hydrothermal dealumination on the sodium-removed Y-shaped molecular sieve to obtain a hydrothermal dealumination product;
(c) and carrying out chemical dealumination on the hydrothermal dealumination product to obtain the sodium-removed and dealuminated Y-shaped molecular sieve, wherein the chemical dealumination is aluminum salt dealumination, fluorosilicate dealumination or acid dealumination.
Through the technical scheme, the invention provides the modified Y-type molecular sieve with the acidic central sites intensively distributed in micropores. The acid center of the mesoporous pore channel (secondary pore) of the modified Y-type molecular sieve is basically occupied by Na ions, and only the acid center in the microporous pore channel is left. The infrared acid content on the modified Y-type molecular sieve is measured by using basic organic matters with different molecular sizes, such as pyridine and n-butylpyridine, and when the ratio of the pyridine infrared acid content to the butylpyridine infrared acid content can reflect the distribution of acid centers in micropores and secondary pore channels.
The method comprises the steps of firstly carrying out Na ion exchange on an acid center of a modified Y molecular sieve, then, selecting naphthalenesulfonate with larger molecular size for adsorption treatment, selectively adsorbing naphthalenesulfonate anions to sodium ions which are distributed in macropores and have good accessibility, then carrying out ammonium exchange on the molecular sieve adsorbing the naphthalenesulfonate anions to remove the sodium ions which are not protected by the naphthalenesulfonate anions and exposed in the micropores of the molecular sieve, and finally roasting to remove the adsorbed ammonium ions and sulfonate ions so as to expose acid sites distributed in the positions of the micropores of the molecular sieve. The acidic central position of the molecular sieve is intensively distributed in the small holes of the molecular sieve, so that the secondary cracking efficiency of the hydrocracking reaction can be effectively improved.
In the process technology for producing naphtha by two-stage hydrocracking, when the molecular sieve is used as an acidic component to prepare a hydrocracking catalyst which is used as a second-stage cracking catalyst to process middle distillate oil generated by a first-stage reaction, the naphtha yield can be improved, particularly the reaction selectivity of light naphtha is improved, and the method has a good application prospect.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a modified Y-type molecular sieve, which is characterized in that the modified Y-type molecular sieve preferably contains Na based on the total amount of the modified Y-type molecular sieve2The mass content of O is 2.2-5.0 wt%, more preferably 2.5-4.0 wt%; preferably, the ratio of the pyridine infrared acid amount to the n-butylpyridine infrared acid amount of the Y-type molecular sieve is 10-40, and more preferably 15-30; preferably, the infrared acid content of the modified Y-type molecular sieve pyridine is 0.08-0.5 mmol/g, and more preferably 0.1-0.4 mmol/g.
Preferably, the specific surface area of the modified Y-type molecular sieve is 620-850 m2A specific ratio of 650 to 800 m/g2(ii)/g; preferably, the pore volume of the modified Y-type molecular sieve is 0.32-0.55 ml/g, more preferably 0.35-0.50 ml/g;
preferably, the relative crystallinity of the modified Y-type molecular sieve is 70-130%, more preferably 80-120%; the unit cell parameter is 2.435-2.450, preferably 2.436-2.445;
preferentially, the mole ratio of silicon to aluminum of the modified Y-type molecular sieve is (6-30): 1, more preferably (8 to 15): 1.
the modified Y-type molecular sieve provided by the invention has the advantages that the acidic centers are mainly distributed in the microporous pore channels, and a small amount of even no acidic centers are distributed in the mesopores, so that the secondary cracking efficiency in the hydrocracking reaction process can be obviously improved.
The characteristic of the distribution of the acid centers in the pore channels of the modified Y-type molecular sieve provided by the invention can be embodied by using pyridine and n-butylpyridine as two probe molecules to respectively perform acid measurement on the modified Y-type molecular sieve. The molecular diameter of n-butylpyridine is about 0.8nm, and can only enter the large pore channel of the modified Y-type molecular sieve provided by the invention to reflect the total amount of acid centers in the large pore channel. The molecular diameter of pyridine is about 0.6nm, and the pyridine can enter micropores and macropores of the modified Y-type molecular sieve to reflect the total amount of acid centers in all the pores of the modified Y-type molecular sieve. The specific test process may be: by pyridine and n-butylpyridine absorption infrared spectroscopy, a Nicolet 6700 Fourier infrared spectrometer of the Nicolet company in America is adopted,
taking 20mg of a ground sample (the granularity is less than 200 meshes), pressing into a sheet with the diameter of 20mm, and mounting the sheet on a sample rack of an absorption cell; a 200mg sample (sheet) was loaded into a beaker at the lower end of the quartz spring (the spring length was recorded before the sample was loaded,x 1mm), connecting the absorption cell with an adsorption tube, and starting to evacuate and purify to reach a vacuum degree of 4 multiplied by 10-2At Pa, the temperature was raised to 500 ℃ and maintained for 1 hour to remove adsorbed substances on the surface of the sample (in this case, the length of the spring after sample purification is recorded,x 2mm). Then cooling to room temperature, adsorbing pyridine (or n-butylpyridine) to saturation, heating to 160 ℃, balancing for 1 hour, desorbing the physically adsorbed pyridine (at this time, the length of the spring after adsorbing the pyridine,x 3mm), the total acid amount was determined by a pyridine (or n-butylpyridine) gravimetric adsorption method.
The invention adjusts the concentrated distribution of the acid center in the micropores of the Y-shaped molecular sieve, thereby realizing the control of the reaction of hydrocarbon oil molecules on the molecular sieve. And the distribution of the acid center position is represented by the infrared acid total amount measurement of pyridine and n-butylpyridine. For a conventional Y-type molecular sieve which is not subjected to acid center position adjustment in a pore channel, the ratio of the infrared total acid amount of pyridine to the infrared total acid amount of n-butylpyridine is generally between 1.2 and 2.0. Therefore, whether the acid center position in the mesopores of the Y-type molecular sieve is controlled or not can be distinguished.
When the total acid amount of the modified Y-type molecular sieve measured by using pyridine and n-butylpyridine is far larger than the conventional ratio, namely the ratio of the infrared total acid amount of pyridine of the modified Y-type molecular sieve to the infrared total acid amount of n-butylpyridine of the modified Y-type molecular sieve is 5-60, the modified Y-type molecular sieve is proved to have the acid centers mainly concentrated in the microporous pore channels.
A second aspect of the present invention provides a process for preparing the modified Y-type molecular sieve of the present invention, comprising the steps of:
(1) pretreating a NaY molecular sieve to obtain a sodium-removed and aluminum-removed Y-type molecular sieve;
(2) NaNO for the pretreated Y molecular sieve obtained in the step (1)3Treating the aqueous solution;
(3) to the step (2) through NaNO3Adding the Y molecular sieve treated by the aqueous solution into a naphthalene sulfonate aqueous solution for dipping treatment;
(4) and (3) carrying out ion exchange reaction on the treated molecular sieve ammonium salt, and then drying and roasting to obtain the modified Y molecular sieve.
Preferably, the pretreatment in step (1) comprises: ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination, and acid dealumination.
Preferably, the pretreatment in step (1) comprises: ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination, and acid dealumination. In the present invention, the NaY molecular sieve may be subjected to one or more steps of ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination and acid dealumination, and the order between the steps may not be limited as long as the sodium dealumination can be providedY-type molecular sieves, e.g. Na, of said sodium-and aluminium-removed Y-type molecular sieves2O content less than 3 wt%, SiO2/Al2O3The molar ratio is (5-50): 1. unit cell constant 2.430-2.450. Generally, the NaY molecular sieve is first sodium-removed by ammonium ion exchange, and then the sodium-removed product is dealuminized, which may be one or a combination of hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination and acid dealumination.
In a preferred embodiment of the present invention, the pretreatment in step (1) comprises:
(a) carrying out ammonium ion exchange reaction on the NaY molecular sieve and an ammonium salt water solution to obtain a sodium-removed Y-type molecular sieve;
(b) carrying out hydrothermal dealumination on the sodium-removed Y-shaped molecular sieve to obtain a hydrothermal dealumination product;
(c) carrying out chemical dealumination on the hydrothermal dealumination product to obtain the sodium and aluminum removed Y-shaped molecular sieve,
wherein the chemical dealumination is aluminum salt dealumination, fluorosilicate dealumination or acid dealumination.
According to the invention, the step (a) is used for removing Na ions in the NaY molecular sieve, so that the subsequent dealumination process can be smoothly carried out. Preferably, the process of the ammonium salt ion exchange reaction in step (a) is as follows: exchanging the NaY molecular sieve with an ammonium salt aqueous solution for 1-3h at 60-120 ℃, preferably 60-90 ℃, wherein the exchange times are 1-4 times, and obtaining the sodium-removed Y-type molecular sieve.
Preferably, Na of the sodium-removed Y-type molecular sieve2The O content is less than 3 wt.%.
Preferably, the SiO of the NaY molecular sieve2/Al2O3The molar ratio is (3-6): 1, Na2The O content is 6-12 wt%.
Preferably, the ammonium salt is selected from one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate and ammonium oxalate, and the molar concentration of the ammonium salt aqueous solution is 0.3-6mol/L, preferably 1-3 mol/L.
According to the invention, step (b) is used for dealuminating the sodium-removed Y-type molecular sieve to form macropores. Preferably, the hydrothermal dealumination in step (b) is carried out by: contacting the sodium-removed Y-type molecular sieve with steam for 1-6h at the temperature of 520-700 ℃ and the pressure of 0.01-0.5 MPa.
Preferably, the number of times of the hydrothermal dealumination is 1 to 3 times.
According to the invention, step (c) is used for the chemical dealumination of molecular sieves, forming macropores. Preferably, the chemical dealumination in step (c) is performed by: and (3) carrying out constant-temperature reaction on the product of the hydrothermal dealumination and an aluminum salt solution, an ammonium fluosilicate solution or a nitric acid solution at the temperature of 50-120 ℃ for 0.5-3 h.
Preferably, the aluminum salt solution is an aqueous solution of at least one of aluminum chloride, aluminum sulfate, and aluminum nitrate.
Preferably, the molar concentration of the aluminum salt solution, the ammonium fluosilicate solution or the nitric acid solution is 0.05-2 mol/L. And (3) carrying out the constant temperature reaction on the product of the hydrothermal dealumination and the aluminum salt solution to obtain the aluminum salt dealumination. And when the product of the hydrothermal dealumination and the ammonium fluosilicate solution are subjected to the constant temperature reaction, the dealumination of the fluosilicate is obtained. And when the product of the hydrothermal dealumination and the nitric acid solution are subjected to the constant temperature reaction, the acid dealumination is obtained.
Preferably, the Na (NO 3) aqueous solution treatment process in the step (2) is that the Y molecular sieve treated by the aluminum salt treatment in the step (3) is added into a Na (NO 3) aqueous solution with the concentration of 0.1-3.0 wt%, and the mixture is heated to 40-80 ℃ for constant-temperature reaction for 1-4 hours;
preferably, the naphthalenesulfonate used in the naphthalenesulfonate treatment process in step (3) may be alkali metal salts such as sodium naphthalenesulfonate and potassium naphthalenesulfonate, the concentration of the naphthalenesulfonate in the solution is 0.2-1 mol/L by K or Na ion concentration, the treatment condition is stirring treatment at normal temperature, and the treatment time is 2-6 h.
Preferably, the ammonium salt ion exchange reaction step in the step (4) is to exchange the molecular sieve obtained in the step (3) with an ammonium salt aqueous solution for 1 to 3 hours at the temperature of between 60 and 120 ℃, preferably between 60 and 90 ℃, and the exchange times are 1 to 4 times. Preferably, the ammonium salt in the step (4) is one or more selected from ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate and ammonium oxalate, and the molar concentration of the ammonium salt aqueous solution is 0.3-6mol/L, preferably 1-3 mol/L.
Preferably, the drying condition in the step (4) is 100-150 ℃, and the drying time is 1-4 hours; the roasting condition is 500-700 ℃ roasting treatment for 2-6 h.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the amounts of pyridine and n-butylpyridine in infrared are determined by pyridine and n-butylpyridine absorption infrared spectroscopy, using Nicolet 6700 Fourier transform infrared spectrometer of Nicolet, USA, and the procedure is as follows:
20mg of a ground sample (the granularity is less than 200 meshes) is pressed into a sheet with the diameter of 20mm, the sheet is arranged on a sample frame of an absorption cell, 200mg of the sample (the sheet) is arranged in a hanging cup at the lower end of a quartz spring (the length of the spring is recorded before the sample is added, x1 mm), the absorption cell and an absorption tube are connected well, evacuation and purification are started, when the vacuum degree reaches 4 x 10 < -2 > Pa, the temperature is increased to 500 ℃ and kept for 1h, and the surface adsorbate of the sample is removed (at this time, the length of the spring after the sample is purified is recorded as x2 mm). Then, the temperature was decreased to room temperature, pyridine (n-butylpyridine) was adsorbed to saturation, the temperature was increased to 160 ℃ again, the temperature was equilibrated for 1 hour, and the physically adsorbed pyridine (in this case, the length of the spring after adsorption of pyridine, x3, mm) was desorbed, and the total acid amount was determined by a pyridine (n-butylpyridine) weight adsorption method.
The surface area and pore volume were measured by using a low-temperature nitrogen adsorption method (BET method);
na in molecular sieve2O content, molecular Sieve SiO2/Al2O3The molar ratio was determined by fluorimetry;
the unit cell parameters and the relative crystallinity of the molecular sieve are determined by an XRD method, the instrument is a Rigaku Dmax-2500X-ray diffractometer, Cuk α radiation is adopted, graphite single crystal filtering is carried out, the operating tube voltage is 35KV, the tube current is 40mA, the scanning speed (2 theta) is 2 DEG/min, the scanning range is 4 DEG-35 DEG, and a standard sample is the Y-type molecular sieve raw powder used in the embodiment 1 of the invention.
Example 1
Modification treatment process of the molecular sieve:
(1) taking testMixing the NaY molecular sieve raw powder prepared in the room with ammonium nitrate with the concentration of 0.5mol/L according to the liquid-solid ratio of 3:1, exchanging for 3 hours at 70 ℃, repeating the process for 3 times, wherein the Na content in the exchanged Y molecular sieve is Na2O is 2.5%;
(2) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (1) at 550 ℃ and 0.1MPa for 2 hours; repeating the process once;
(3) stirring and mixing the molecular sieve obtained in the step (2) with distilled water according to the liquid-solid ratio of 5:1, then heating to 80 ℃, adding 400ml of 0.5mol/L aluminum sulfate solution in the stirring process, and reacting for 2 hours at constant temperature;
(4) adding the Y molecular sieve treated by the aluminum salt obtained in the step (3) into 2mol/L NaNO3Treating with water solution at 60 deg.C for 2 hr;
(5) step (4) passing through NaNO3Adding the treated Y molecular sieve into sodium naphthalenesulfonate aqueous solution with the concentration of 0.3mol/L, and stirring for 3 hours at room temperature;
(6) and (3) mixing the molecular sieve treated by the sodium naphthalenesulfonate in the step (5) with ammonium nitrate with the concentration of 2.0mol/L according to the liquid-solid ratio of 3:1, exchanging for 1 hour at 80 ℃, repeating the process for 3 times, drying for 4 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to obtain the modified Y molecular sieve of the example 1, wherein the serial number of the molecular sieve is Y-1.
Example 2
(1) Mixing NaY molecular sieve raw powder prepared in a laboratory with 2.0mol/L ammonium nitrate according to a liquid-solid ratio of 3:1, exchanging at 80 ℃ for 2h, repeating the process for 1 time, wherein the Na content in the exchanged Y molecular sieve is 2.7 percent calculated by Na 2O.
(2) And (2) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (1) at 580 ℃ and 0.1Mpa for 2h, and repeating the process once.
(3) Treating the molecular sieve obtained in the step (2) with an ammonium fluosilicate solution with the concentration of 0.4mol/L at 90 ℃ for 2h according to the liquid-solid ratio of 5: 1;
(4) adding the Y molecular sieve treated by the ammonium fluosilicate obtained in the step (3) into 0.8mol/L of Na (NO)3) Treating with water solution at 70 deg.C for 2 hr;
(5) step (4) passing through NaNO3The treated Y molecular sieve is added with the concentration of 0.5mol/LStirring and processing the mixture for 3 hours at room temperature in a potassium naphthalene sulfonate aqueous solution;
(6) and (3) mixing the molecular sieve treated by the sodium naphthalenesulfonate in the step (5) with ammonium nitrate with the concentration of 1.5mol/L according to the liquid-solid ratio of 3:1, exchanging for 2 hours at 60 ℃, repeating the process for 2 times, drying for 4 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to obtain the modified Y molecular sieve of the example 2, wherein the serial number of the modified Y molecular sieve is Y-2.
Example 3
(1) Mixing NaY molecular sieve raw powder prepared in a laboratory with 2.0mol/L ammonium nitrate according to a liquid-solid ratio of 3:1, exchanging at 80 ℃ for 2 hours, repeating the process for 2 times, wherein the Na content in the exchanged Y molecular sieve is Na22.3 percent of O;
(2) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (1) at 630 ℃ and 0.1MPa for 2 hours.
(3) And (3) mixing the molecular sieve obtained in the step (2) with 0.6mol/L dilute nitric acid solution according to the liquid-solid ratio of 5:1, heating to 95 ℃, and reacting at constant temperature for 2 hours.
(4) Adding the Y molecular sieve treated by the dilute nitric acid obtained in the step (3) into 1.5mol/L of Na (NO)3) Treating with water solution at 70 deg.C for 2 hr;
(5) step (4) passing through Na (NO)3) Adding the treated Y molecular sieve into 0.5mol/L potassium naphthalenesulfonate aqueous solution, and stirring at room temperature for 2 hours;
(6) and (3) mixing the molecular sieve treated by the potassium naphthalene sulfonate in the step (5) with ammonium nitrate with the concentration of 1.5mol/L according to the liquid-solid ratio of 3:1, exchanging for 3 hours at 80 ℃, repeating the process for 2 times, drying for 4 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to obtain the modified Y molecular sieve of the example 3, wherein the serial number of the modified Y molecular sieve is Y-3.
Example 4
(1) Mixing NaY molecular sieve raw powder prepared in a laboratory with ammonium nitrate with the concentration of 0.5mol/L according to the liquid-solid ratio of 3:1, exchanging for 3 hours at 70 ℃, repeating the process for 3 times, wherein the Na content in the exchanged Y molecular sieve is Na2O is 2.5%;
(2) treating the Y molecular sieve obtained in the step (1) with 0.2mol/L ammonium fluosilicate treatment solution according to the liquid-solid ratio of 6:1 at the constant temperature of 80 ℃ for 2 h;
(3) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (2) at 520 ℃ for 2h under 0.2MPa, and repeating the process for 1 time;
(4) and (4) stirring and mixing the molecular sieve obtained in the step (3) with 0.6mol/L aluminum sulfate solution according to the liquid-solid ratio of 5:1, heating to 75 ℃, and reacting for 2 hours at constant temperature.
(5) Adding the Y molecular sieve treated by the aluminum salt obtained in the step (4) into 0.6mol/L of Na (NO)3) Treating with water solution at 50 deg.C for 2 hr;
(6) subjecting step (5) to Na (NO)3) Adding the treated Y molecular sieve into 0.3mol/L potassium naphthalenesulfonate aqueous solution, and stirring at room temperature for 4 hours;
(7) and (3) mixing the molecular sieve treated by the potassium naphthalene sulfonate in the step (6) with ammonium nitrate with the concentration of 2.0mol/L according to the liquid-solid ratio of 3:1, exchanging for 2 hours at 80 ℃, repeating the process for 2 times, drying for 4 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to obtain the modified Y molecular sieve of the example 4, wherein the serial number of the modified Y molecular sieve is Y-4.
Example 5
(1) Mixing NaY molecular sieve raw powder prepared in a laboratory with ammonium nitrate with the concentration of 1.5mol/L according to the liquid-solid ratio of 3:1, exchanging for 3 hours at 80 ℃, repeating the process for 1 time, wherein the Na content in the exchanged Y molecular sieve is Na22.9 percent of O;
(2) treating the Y molecular sieve obtained in the step (1) with 0.2mol/L ammonium fluosilicate treatment solution according to the liquid-solid ratio of 6:1 at the constant temperature of 80 ℃ for 2 h;
(3) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (2) at 550 ℃ for 3h under 0.1MPa, and repeating the process for 1 time;
(4) and (4) stirring and mixing the molecular sieve obtained in the step (3) with 0.6mol/L aluminum sulfate solution according to the liquid-solid ratio of 5:1, heating to 75 ℃, and reacting for 2 hours at constant temperature.
(5) Adding the Y molecular sieve treated by the aluminum salt obtained in the step (4) into 0.5mol/L of Na (NO)3) Treating with water solution at 50 deg.C for 2.5 h;
(6) subjecting step (5) to Na (NO)3) Adding the treated Y molecular sieve into sodium naphthalenesulfonate water solution with the concentration of 0.4mol/L, and stirring at room temperature for 4 hours;
(7) and (3) mixing the molecular sieve treated by the potassium naphthalene sulfonate in the step (6) with ammonium nitrate with the concentration of 2.0mol/L according to the liquid-solid ratio of 3:1, exchanging for 2 hours at 80 ℃, repeating the process for 2 times, drying for 4 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to obtain the modified Y molecular sieve of the example 5, wherein the serial number of the modified Y molecular sieve is Y-5.
Comparative example 1
(1) Mixing NaY molecular sieve raw powder prepared in a laboratory with ammonium nitrate with the concentration of 0.5mol/L according to the liquid-solid ratio of 3:1, exchanging for 3 hours at 70 ℃, repeating the process for 3 times, wherein the Na content in the exchanged Y molecular sieve is Na2O is 2.5%;
(2) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (1) at 550 ℃ and 0.1MPa for 2 hours; this process was repeated once.
(3) And (3) mixing the molecular sieve obtained in the step (2) with 0.5mol/L aluminum sulfate solution according to the liquid-solid ratio of 5:1, and reacting for 2 hours at a constant temperature of 80 ℃.
And (3) drying the molecular sieve treated by the aluminum salt at 120 ℃ for 4h and roasting at 550 ℃ for 4h to obtain the modified Y molecular sieve of the comparative example 1, wherein the molecular sieve is numbered as B-1.
Comparative example 2
(1) 200g of NaY molecular sieve raw powder prepared in a laboratory is taken, ammonium nitrate with the concentration of 0.5mol/L is mixed according to the liquid-solid ratio of 3:1, the exchange is carried out for 3 hours at 70 ℃, the process is repeated for 3 times, and the Na content in the exchanged Y molecular sieve is Na2O is 2.5%;
(2) treating the Y molecular sieve obtained in the step (1) with 0.2mol/L ammonium fluosilicate treatment solution according to the liquid-solid ratio of 6:1 at the constant temperature of 80 ℃ for 2 h;
(3) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (2) at 520 ℃ for 2h under 0.2MPa, and repeating the process for 1 time;
(4) and (4) mixing the molecular sieve obtained in the step (3) with 0.6mol/L aluminum sulfate solution according to the liquid-solid ratio of 5:1, and reacting for 2 hours at a constant temperature of 75 ℃. The modified Y molecular sieve of comparative example 2, numbered B-2, was obtained after drying at 120 ℃ for 4h and calcining at 550 ℃ for 4 h.
The properties of the molecular sieves prepared in the above examples and comparative examples are shown in Table 1.
TABLE 1 comparison of physicochemical Properties of molecular sieves for examples and comparative examples
Claims (11)
1. A modified Y-type molecular sieve, characterized in that: based on the total amount of the modified Y-type molecular sieve, the Y-type molecular sieve contains Na2The mass content of O is 2.0-6.0 wt%; the ratio of the pyridine infrared acid amount to the butylpyridine infrared acid amount of the Y-type molecular sieve is 5-60; the amount of the pyridine infrared acid is 0.05-0.6 mmol/g.
2. The preferable selection of claim 1, wherein the specific surface area of the modified Y-type molecular sieve is 600-900 m2(ii)/g; the pore volume is 0.30-0.60 ml/g; the relative crystallinity is 60% -140%, and the unit cell parameter is 2.430-2.450; 5-50 of molar ratio of silicon to aluminum: 1.
3. a preparation method of a modified Y-type molecular sieve is characterized by comprising the following steps:
(1) pretreating a NaY molecular sieve to obtain a sodium-removed and aluminum-removed Y-type molecular sieve;
(2) NaNO for the pretreated Y molecular sieve obtained in the step (1)3Treating the aqueous solution;
(3) to the step (2) through NaNO3Adding the Y molecular sieve treated by the aqueous solution into a naphthalene sulfonate aqueous solution for dipping treatment;
(4) and (3) carrying out ion exchange reaction on the treated molecular sieve ammonium salt, and then drying and roasting to obtain the modified Y molecular sieve.
4. The method of claim 3, wherein: the pretreatment process in the step (1) comprises the following steps: ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination, and acid dealumination.
5. The method of claim 4, wherein: the pretreatment process in the step (1) comprises the following steps:
(a) carrying out ammonium ion exchange reaction on the NaY molecular sieve and an ammonium salt water solution to obtain a sodium-removed Y-type molecular sieve;
(b) carrying out hydrothermal dealumination on the sodium-removed Y-shaped molecular sieve to obtain a hydrothermal dealumination product;
(c) and carrying out chemical dealumination on the hydrothermal dealumination product to obtain the sodium-removed and dealuminated Y-shaped molecular sieve, wherein the chemical dealumination is aluminum salt dealumination, fluorosilicate dealumination or acid dealumination.
6. The method of claim 5, wherein: the process of the ammonium salt ion exchange reaction in the step (a) is as follows: exchanging the NaY molecular sieve with an ammonium salt aqueous solution for 1-3h at the temperature of 60-120 ℃ for 1-4 times to obtain the sodium-removed Y-type molecular sieve.
7. The method of claim 5, wherein: the process of the hydrothermal dealumination in the step (b) is as follows: contacting the sodium-removed Y-type molecular sieve with steam for 1-6h at the temperature of 520-700 ℃ and the pressure of 0.01-0.5 MPa.
8. The method of claim 5, wherein: the chemical dealumination process in the step (c) comprises the following steps: and (3) carrying out constant-temperature reaction on the product of the hydrothermal dealumination and an aluminum salt solution, an ammonium fluosilicate solution or a nitric acid solution at the temperature of 50-120 ℃ for 0.5-3 h.
9. The method of claim 3, wherein: and (3) adding the Y molecular sieve treated by the aluminum salt in the step (3) into a Na (NO 3) aqueous solution with the concentration of 0.1-3.0 wt%, heating to 40-80 ℃, and reacting at constant temperature for 1-4 hours.
10. The method of claim 3, wherein: the naphthalenesulfonate used in the naphthalenesulfonate treatment process in the step (3) is sodium naphthalenesulfonate or potassium naphthalenesulfonate, the concentration of the naphthalenesulfonate in the solution is 0.2-1 mol/L by K or Na ion concentration, the treatment condition is stirring treatment at normal temperature, and the treatment time is 2-6 hours.
11. The method of claim 3, wherein: and (4) performing an ammonium salt ion exchange reaction step, namely exchanging the molecular sieve obtained in the step (3) with an ammonium salt aqueous solution at the temperature of 60-120 ℃ for 1-3h, wherein the exchange times are 1-4.
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