CN107670687A - Molecular sieves of 5@Silicalite of nano crystal ZSM 1 of core shell structure and preparation method thereof - Google Patents
Molecular sieves of 5@Silicalite of nano crystal ZSM 1 of core shell structure and preparation method thereof Download PDFInfo
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- CN107670687A CN107670687A CN201710936872.2A CN201710936872A CN107670687A CN 107670687 A CN107670687 A CN 107670687A CN 201710936872 A CN201710936872 A CN 201710936872A CN 107670687 A CN107670687 A CN 107670687A
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- silicalite
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 143
- 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 143
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 44
- 239000011258 core-shell material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 60
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 229910052681 coesite Inorganic materials 0.000 claims description 24
- 229910052906 cristobalite Inorganic materials 0.000 claims description 24
- 229910052682 stishovite Inorganic materials 0.000 claims description 24
- 229910052905 tridymite Inorganic materials 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 6
- 239000003929 acidic solution Substances 0.000 abstract description 4
- 238000007323 disproportionation reaction Methods 0.000 abstract description 4
- 238000006317 isomerization reaction Methods 0.000 abstract description 4
- 230000011987 methylation Effects 0.000 abstract description 4
- 238000007069 methylation reaction Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- 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 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910020175 SiOH Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- 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
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to molecular sieves of 5@Silicalite of nano crystal ZSM 1 of a kind of core shell structure and preparation method thereof.The present invention is using the molecular sieves of nanometer ZSM 5 as nuclear phase, and crystallite dimension is 50~800nm, and using the molecular sieves of nano Si licalite 1 as shell phase, shell thickness is 5~100nm；After being pre-processed using weakly acidic solution to the molecular sieve outer surfaces of nuclear phase ZSM 5, hydrothermal crystallizing is carried out in shell molecular sieve grows liquid system, the molecular sieves of 5 Silicalite of nano crystal ZSM 1 containing fine and close shell are made.Molecular sieve provided by the invention has the characteristics of continuous duct, diffusional resistance are small, integrated machine intensity is high, selectivity is high；In addition, during it can be effective for catalytic gasoline hydrogenation modifying, and there is excellent catalytic performance in aromatic hydrocarbons selective disproportionation, form selected methylation, selective isomerization and catalytic gasoline hydrogenation modifying etc..
Description
Technical field
The present invention relates to composite catalyzing field of material technology, and in particular to a kind of nano crystal ZSM-5@of core shell structure
Silicalite-1 molecular sieves and preparation method thereof.
Background technology
The typical high-silica zeolite that ZSM-5 molecular sieve is developed as Mobil companies of the U.S., there is three dimensional intersection duct；Its
Specifically there are two types in duct：One is ten-ring straight hole road, and another ten-ring duct for Zigzag types, two kinds of ducts intersect
A diameter of 0.9nm at place.By means of special pore passage structure and acidity, ZSM-5 molecular sieve is used as the catalysis of acid catalyzed reaction
Agent and shape-selective catalyst, in petrochemical industry, fine chemistry industry and environmental protection etc. extensive use.
It is well known that the size of nano particle is generally less than hundreds of nanometers, size between cluster and macro object,
Compared with conventional granulates, the physicochemical properties of nano particle performance are significantly different.Under normal circumstances, little crystal grain zeolite molecular sieve
The catalytic performance showed in catalytic reaction is all more preferable than conventional molecular sieve.The catalytic activity of ZSM-5 molecular sieve also with its crystal grain
Size is closely related, and therefore, the preparation and application of ZSM-5 molecular sieve with small crystal grains, particularly nano-ZSM-5 molecular sieve increasingly cause
Concern.Nano-ZSM-5 molecular sieve has short and regular inner duct, larger external surface area, and reactant and product are in crystal
Interior diffusion rate is very fast, thus coking etc. in improving the utilization rate of catalyst, suppressing course of reaction show it is excellent
Performance more, also there is higher hydrothermal stability, higher catalytic activity.
In zeolite molecular sieve shape-selective catalyst preparation process, zeolite grain outer surface and aperture will often be passivated place
Reason, occur and change duct to reactant or the selective activization of product molecule so as to suppress side reaction.Therefore, people in recent years
By various methods modify ZSM-5 outer surface and aperture, as outer surface functional organic, silica chemical gaseous phase deposition and
Chemical liquid deposition etc..But such method inevitably causes the loss of acidic site in duct, and to molecular sieve
Activity and stability bring adverse effect.In addition, Chinese patent CN104556131 is disclosed and has been synthesized ZSM-5/ using microwave
Silicalite-1 core-shell molecular sieves, micron order ZSM-5 molecular sieve is added in Silicalite-1 molecular sieve growth-promoting medias, auxiliary
Heated using microwave, highly shortened the generated time of catalyst.Chinese patent CN101081371A discloses a kind of ZSM-
5/SAPO-11 composite molecular screens, add SAPO-11 synthesis mother liquid in ZSM-5 crystallization product and crystallization is made, for urging
Changing cracking gasoline hydro-upgrading has good Hydrogenation, higher yield of gasoline and certain Aromatization Activity.
Based on this, need badly provide it is a kind of it is new, there is highly effective hydrogenation olefine reducing modification performance for catalytically cracked gasoline
Molecular sieve catalyst.
The content of the invention
For in the prior art the defects of, the present invention is intended to provide a kind of nano crystal ZSM-5 of core shell structure
Silicalite-1 molecular sieves and preparation method thereof.The present invention is using nano-ZSM-5 molecular sieve as nuclear phase, with nanometer
Silicalite-1 molecular sieves are shell phase, after being pre-processed using weakly acidic solution to nuclear phase ZSM-5 molecular sieve outer surface,
Hydrothermal crystallizing is carried out in shell molecular sieve growth liquid system, so as to which the nano crystal nucleocapsid point containing fine and close shell finally be prepared
Son sieve.The monocrystalline core-shell molecular sieve has the spy that continuous duct, diffusional resistance are small, integrated machine intensity is high, selectivity is high
Point, have in aromatic hydrocarbons selective disproportionation, form selected methylation, selective isomerization and catalytic gasoline hydrogenation modifying etc. excellent
Catalytic performance.
Therefore, the present invention provides following technical scheme：
In a first aspect, the present invention provides a kind of nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure, point
Son sieve includes nuclear phase and shell；Wherein, nuclear phase is nano-ZSM-5 molecular sieve, and shell is fine and close Silicalite-1 molecular sieves, and
The weight ratio of ZSM-5 molecular sieve and Silicalite-1 molecular sieves is (1~20)：1.
In the further embodiment of the present invention, in nuclear phase nano-ZSM-5 molecular sieve, SiO2/Al2O3Mol ratio is 20
~400, crystallite dimension is 50~800nm.
In the further embodiment of the present invention, in nuclear phase nano-ZSM-5 molecular sieve, SiO2/Al2O3Mol ratio is 20
~100.
In the further embodiment of the present invention, the thickness of shell Silicalite-1 molecular sieves is 5~100nm.
Second aspect, the present invention provide a kind of system of the nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure
Preparation Method, the outer surface of nuclear phase ZSM-5 molecular sieve is pre-processed using acid solution, afterwards in shell molecular sieve growth-promoting media
Hydrothermal crystallizing is carried out in system, the nano crystal ZSM-5@Silicalite-1 molecular sieves containing fine and close shell are finally prepared.
In the further embodiment of the present invention, preparation method comprises the following steps：S101：Template will not be calcined
Nano-ZSM-5 molecular sieve is placed in acid solution and pre-processed；Wherein, treatment temperature is 40~100 DEG C, and processing time is
0.5~24h；S102：Molecular sieve filtration that S101 is obtained, washing to pH value carry out drying process after being 7, obtain ZSM-5 points
Son sieve；Wherein, drying temperature is 50~110 DEG C, and drying time is 2~12h；S103：Shell growth-promoting media A configuration：Growth-promoting media
It is made up of silicon source, TPAOH, EtOH and water；Wherein, TPAOH/SiO2Mol ratio is 0.02~1, EtOH/SiO2Mol ratio be 1~
20, water/SiO2Mol ratio is 20~300；S104：The ZSM-5 molecular sieve that S102 is obtained is added in the growth-promoting media that S103 is obtained,
2~12h is stirred at room temperature, 5~150h of crystallization at a temperature of being subsequently placed in 120~240 DEG C；Wherein, nuclear phase addition accounts for growth-promoting media A's
Mass fraction is 0.5~10%；S105：Molecular sieve filtration that S104 is obtained, washing to pH value are 7, and ammonium exchanges twice, and in
2~12h is dried at 40~100 DEG C, 2~6h is calcined at last 300~700 DEG C, obtains the nano crystal ZSM-5@of core shell structure
Silicalite-1 molecular sieves.
In the further embodiment of the present invention, in S101, acid solution includes hydrochloric acid, nitric acid, sulfuric acid, formic acid and boron
One or more in acid, and the concentration of acid solution is 0.1~5mol/L；Nuclear phase ZSM-5 is divided using weakly acidic solution
Son sieve outer surface is pre-processed.
The present invention further embodiment in, in S103, silicon source include Ludox, white carbon, tetraethoxysilance and
One or more in silica.
The third aspect, the nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure provided by the invention are being catalyzed
Application in cracking gasoline hydro-upgrading.
In the further embodiment of the present invention, using comprising the following steps：Using catalytically cracked gasoline as raw material, anti-
It is 300~400 DEG C to answer temperature, and reaction pressure is 1~3MPa, and volume space velocity is 1~3h during liquid-1, hydrogen to oil volume ratio be 200~
Under conditions of 500V/V, using nano crystal ZSM-5@Silicalite-1 core-shell molecular sieves, the height of catalytically cracked gasoline is realized
Imitate hydrogenation modification.
The above-mentioned technical proposal of the present invention has advantages below compared with prior art：
(1) applicant has found by many experiments：The present invention uses nano-ZSM-5 molecular sieve as nuclear phase, fine and close monocrystalline
Silicalite-1 molecular sieves are shell, the nano crystal ZSM-5@Silicalite-1 molecular sieves for the core shell structure being prepared
With continuous duct, diffusional resistance is small, integrated machine intensity is high, selectivity it is high the characteristics of；In addition, the present invention is prepared
Molecular sieve be easy to implement core, the flexible modulation of shell composition, and it is in aromatic hydrocarbons selective disproportionation, form selected methylation, selective isomerization
And catalytic gasoline hydrogenation modifying etc. has excellent catalytic performance.
(2) present invention carries out Quick Pretreatment using weakly acidic solution to nuclear phase ZSM-5 molecular sieve outer surface, afterwards in shell
Hydrothermal crystallizing is carried out in layer molecular sieve growth liquid system, effectively prevent aluminium during shell Silicalite-1 molecular sieve symbiosis
The migration of exterior surface, beneficial to compacted zone is formed, simplify preparation technology.
(3) based on pure silicon dioxide phase molecule sieve Silicalite-1 have with ZSM-5 molecular sieve identical MFI structure,
The light base SiOH defects of silicon on surface are less, so as to the purpose realized modification, adjust ZSM-5 zeolite outer surface acidity, so that
Improve ZSM-5 molecular sieve selectivity during the course of the reaction and effectively suppress carbon distribution and inactivate.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram of the nuclear phase ZSM-5 in the embodiment of the present invention one；
Fig. 2 is the scanning electron microscope diagram of the nano crystal core-shell molecular sieve in the embodiment of the present invention one；
Fig. 3 is the transmission electron microscope figure of the nano crystal core-shell molecular sieve in the embodiment of the present invention one.
Embodiment
The embodiment of technical solution of the present invention is described in detail below in conjunction with accompanying drawing.Following examples are only used for
More clearly explanation technical scheme, therefore be only used as example, and the protection model of the present invention can not be limited with this
Enclose.
Experimental method in following embodiments, it is conventional method unless otherwise specified.
Test material used, is to be commercially available from conventional reagent shop unless otherwise specified in following embodiments.
Quantitative test in following examples, it is respectively provided with and repeats to test three times, data is to repeat the average value of experiment three times
Or mean+SD.
The present invention provides a kind of nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure, and molecular sieve includes core
Phase and shell；Wherein, nuclear phase is nano-ZSM-5 molecular sieve, and shell is fine and close Silicalite-1 molecular sieves, and ZSM-5 molecules
The weight ratio of sieve and Silicalite-1 molecular sieves is (1~20)：1；In nuclear phase nano-ZSM-5 molecular sieve, SiO2/Al2O3Mole
Than for 20~400, crystallite dimension is 50~800nm；In nuclear phase nano-ZSM-5 molecular sieve, SiO2/Al2O3Mol ratio be 20~
100；The thickness of shell Silicalite-1 molecular sieves is 5~100nm.
In addition, the nano crystal ZSM-5@Silicalite-1 molecular sieves of the core shell structure for the present invention, the present invention is specially
Door provides preparation method：
The outer surface of nuclear phase ZSM-5 molecular sieve is pre-processed using acid solution, grown afterwards in shell molecular sieve
Hydrothermal crystallizing is carried out in liquid system, the nano crystal ZSM-5@Silicalite-1 molecules containing fine and close shell are finally prepared
Sieve.
Specifically include following steps：
S101：The nano-ZSM-5 molecular sieve for not being calcined template is placed in acid solution and pre-processed；Wherein, locate
It is 40~100 DEG C to manage temperature, and processing time is 0.5~24h.Wherein, acid solution includes hydrochloric acid, nitric acid, sulfuric acid, formic acid and boron
One or more in acid, and the concentration of acid solution is 0.1~5mol/L.
S102：Molecular sieve filtration that S101 is obtained, washing to pH value carry out drying process after being 7, obtain ZSM-5 molecules
Sieve；Wherein, drying temperature is 50~110 DEG C, and drying time is 2~12h.S103：Shell growth-promoting media A configuration：Growth-promoting media by
Silicon source, TPAOH, EtOH and water composition；Wherein, TPA OH/SiO2Mol ratio is 0.02~1, EtOH/SiO2Mol ratio be 1~
20, water/SiO2Mol ratio is 20~300.
S104：The ZSM-5 molecular sieve that S102 is obtained is added in the growth-promoting media that S103 is obtained, 2~12h is stirred at room temperature, so
After be placed in 120~240 DEG C at a temperature of 5~150h of crystallization；Wherein, nuclear phase addition account for growth-promoting media A mass fraction for 0.5~
10%.
S105：Molecular sieve filtration that S104 is obtained, washing to pH value are 7, and ammonium exchanges twice, and at 40~100 DEG C
2~12h is dried, 2~6h is calcined at last 300~700 DEG C, obtains the nano crystal ZSM-5@Silicalite-1 of core shell structure
Molecular sieve.Wherein, silicon source includes the one or more in Ludox, white carbon, tetraethoxysilance and silica.
In addition, the nano crystal ZSM-5@Silicalite-1 molecular sieves for the core shell structure that the present invention is prepared can have
Effectiveness is during catalytic gasoline hydrogenation modifying；Specifically include following steps：
It it is 300~400 DEG C in reaction temperature using catalytically cracked gasoline as raw material, reaction pressure is 1~3MPa, body during liquid
Product air speed is 1~3h-1, hydrogen to oil volume ratio be 200~500V/V under conditions of, using nano crystal ZSM-5@Silicalite-1
Core-shell molecular sieve, realize the highly effective hydrogenation olefine reducing modification of catalytically cracked gasoline.
Illustrated with reference to embodiment：
Embodiment one
The present invention provides a kind of preparation method of the nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure, bag
Include following steps：
S101：Weigh the nano-ZSM-5 molecular sieve for not being calcined template that silica alumina ratio is 35, crystallite dimension is 150nm
50g, adds the hydrochloric acid solution that 500ml concentration is 5mol/L, stir process 5h, and treatment temperature is 50 DEG C.
S102：Molecular sieve filtration that S101 is obtained, washing are 7,80 DEG C of dry 12h to pH value, obtain outer surface and locate in advance
The ZSM-5 molecular sieve Z-1 of reason.
S103：Weigh TPAOH (25wt%) 2.33g, ethanol 35.23g and water 205g, after mixed dissolution,
Aerosil 2.88g is slowly added under stirring condition, the life of shell Silicalite-1 molecular sieves is obtained after stirring ageing
Long liquid A.
S104：Pretreated nuclear phase Z-1 is added in growth-promoting media A, the mass fraction wherein shared by nuclear phase addition is
2wt%, 10h is stirred at room temperature；It is then charged into the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, is put in quiet in 180 DEG C of baking ovens
Only crystallization 24h.
S105：Be 7 by gained molecular sieve filtration, washing to pH value after crystallization terminates, with 1mol/L ammonium nitrate solution from
Son is exchanged twice, and 6h is dried at 80 DEG C, 550 DEG C of roasting 4h, obtains nano crystal ZSM-5@Silicalite-1 nucleocapsids point
Son sieve ZS-1.
Fig. 1 is the present embodiment nuclear phase ZSM-5 scanning electron microscope diagram；Fig. 2 is sweeping for nano crystal core-shell molecular sieve
Electron microscope picture is retouched, compared with Fig. 1 nuclear phases ZSM-5 scanning electron microscope diagram, the size increase of ZS-1 molecular sieves, particle
It is uniformly dispersed, without twin.Fig. 3 is the transmission electron microscope figure of nano crystal core-shell molecular sieve, as shown in Figure 3：ZS-1 points
Lattice boundary is not found in son sieve, and lattice is continuous, and shell Silicalite-1 molecular sieves grow in nuclear phase ZSM-5 outer surfaces, obtain
To the core-shell molecular sieve of monocrystalline.Silicalite-1 molecular sieve shell thickness is about 12nm.
Embodiment two
The present invention provides a kind of preparation method of the nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure, bag
Include following steps：
S101：Weigh the nano-ZSM-5 molecular sieve for not being calcined template that silica alumina ratio is 35, crystallite dimension is 150nm
50g, adds the hydrochloric acid solution that 500ml concentration is 5mol/L, stir process 5h, and treatment temperature is 50 DEG C.
S102：Molecular sieve filtration that S101 is obtained, washing are 7,80 DEG C of dry 12h to pH value, obtain outer surface and locate in advance
The ZSM-5 molecular sieve Z-1 of reason.
S103：Weigh TPAOH (25wt%) 2.33g, ethanol 35.23g and water 205g, after mixed dissolution,
Aerosil 2.88g is slowly added under stirring condition, the life of shell Silicalite-1 molecular sieves is obtained after stirring ageing
Long liquid A.
S104：Pretreated nuclear phase Z-1 is added in growth-promoting media A, the mass fraction wherein shared by nuclear phase addition is
1wt%, 10h is stirred at room temperature；It is then charged into the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, is put in quiet in 180 DEG C of baking ovens
Only crystallization 24h.
S105：Be 7 by gained molecular sieve filtration, washing to pH value after crystallization terminates, with 1mol/L ammonium nitrate solution from
Son is exchanged twice, and 6h is dried at 80 DEG C, 550 DEG C of roasting 4h, obtains nano crystal ZSM-5@Silicalite-1 nucleocapsids point
Son sieve ZS-2.Silicalite-1 molecular sieve shell thickness is about 22nm.
Embodiment three
The present invention provides a kind of preparation method of the nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure, bag
Include following steps：
S101：Weigh the nano-ZSM-5 molecular sieve for not being calcined template that silica alumina ratio is 70, crystallite dimension is 150nm
50g, adds the hydrochloric acid solution that 500ml concentration is 0.5mol/L, stir process 5h, and treatment temperature is 50 DEG C.
S102：Molecular sieve filtration that S101 is obtained, washing are 7,80 DEG C of dry 12h to pH value, obtain outer surface and locate in advance
The ZSM-5 molecular sieve Z-2 of reason.
S103：Weigh TPAOH (25wt%) 2.33g, ethanol 35.23g and water 205g, after mixed dissolution,
Aerosil 2.88g is slowly added under stirring condition, the life of shell Silicalite-1 molecular sieves is obtained after stirring ageing
Long liquid A.
S104：Pretreated nuclear phase Z-2 is added in growth-promoting media A, the mass fraction wherein shared by nuclear phase addition is
2wt%, 10h is stirred at room temperature；It is then charged into the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, is put in quiet in 180 DEG C of baking ovens
Only crystallization 24h.
S105：Be 7 by gained molecular sieve filtration, washing to pH value after crystallization terminates, with 1mol/L ammonium nitrate solution from
Son is exchanged twice, and 6h is dried at 80 DEG C, 550 DEG C of roasting 4h, obtains nano crystal ZSM-5@Silicalite-1 nucleocapsids point
Son sieve ZS-3.Silicalite-1 molecular sieve shell thickness is about 12nm.
In addition, the advantages of in order to further highlight technical solution of the present invention, set following comparative example：
Comparative example one
It is 35 by silica alumina ratio, the nano-ZSM-5 molecular sieve for not being calcined template that crystallite dimension is 150nm, in 550 DEG C of roastings
Burn 4h.Then, using 1mol/L ammonium nitrate solution ion exchange twice, and at 80 DEG C dry 6h, 550 DEG C roasting 4h, obtain
To nano-ZSM-5 molecular sieve CZ-1.
Comparative example two
It is 70 by silica alumina ratio, the nano-ZSM-5 molecular sieve for not being calcined template that crystallite dimension is 150nm, in 550 DEG C of roastings
Burn 4h.Then, using 1mol/L ammonium nitrate solution ion exchange twice, and at 80 DEG C dry 6h, 550 DEG C roasting 4h, obtain
To nano-ZSM-5 molecular sieve CZ-2.
Above-mentioned three kinds of core-shell molecular sieves (ZS-1, ZS-2 and ZS-3) and reference molecules are sieved using catalytic cracking heavy petrol
(CZ-1 and CZ-2) carries out hydrogenation performance evaluation, and feedstock property is as shown in table 1.
The catalytic cracking heavy petrol main character of table 1
| Project | Raw material 2 |
| Density (20 DEG C), gcm-3 | 0.7525 |
| Sulfur content, μ gg-1 | 1099 |
| Race forms, v% | |
| Alkane | 36.4 |
| Alkene | 38.8 |
| Aromatic hydrocarbons | 18.2 |
| RON | 84.2 |
| Boiling range, DEG C | |
| Initial boiling point | 75 |
| 10% | 95 |
| 50% | 130 |
| 90% | 182 |
| The end point of distillation | 202 |
Specific evaluation procedure is as follows：Using high pressure fixed bed pilot-plant, the loadings of catalyst are all 100ml.First
120 DEG C of dehydration 2h are risen to, then with 2 DEG C of min-1Heating rate rise to 300 DEG C and handle 3h, Hydrogen Vapor Pressure and flow with it is anti-
Answer appreciation condition identical, handled laggard reaction raw materials FCC heavy petrol, reaction evaluating condition is：370 DEG C of temperature, Hydrogen Vapor Pressure
2MPa, liquid hourly space velocity (LHSV) 2h-1, hydrogen-oil ratio 300/1 (V/V), stablize sampling analysis after 12h.After steady running 720h, catalyst is drawn off
And analyze coke content.
The reaction evaluating result of above-mentioned five kinds of catalyst is as shown in table 2.
The reaction evaluating result of 2 six kinds of catalyst of table
| Catalyst | Alkene/v% | Aromatic hydrocarbons/v% | RON loses | Yield of gasoline/weight % | Carbon deposit/weight % |
| ZS-1 | 23.6 | 22.9 | -0.2 | 99.8 | 0.85 |
| ZS-2 | 28.5 | 20.2 | -0.6 | 99.5 | 0.74 |
| ZS-3 | 20.2 | 23.1 | -0.4 | 98.6 | 1.01 |
| CZ-1 | 18.6 | 20.3 | -0.6 | 93.7 | 3.61 |
| CZ-2 | 21.7 | 22.8 | -0.4 | 91.7 | 4.92 |
As seen from the results in Table 2, the nano crystal ZSM-5@Silicalite-1 core-shell molecular sieves prepared by the inventive method
Compared with conventional nano ZSM-5 molecular sieve, active suitable Aromatization Activity, while olefin(e) centent is significantly reduced,
The loss of octane number can be reduced, furthermore it is possible to be greatly enhanced liquid yield, make catalyst that there is stronger carbon accumulation resisting ability.
The present invention is using nano-ZSM-5 molecular sieve as nuclear phase, using nano Si licalite-1 molecular sieves as shell phase, using weak acid
Property solution nuclear phase ZSM-5 molecular sieve outer surface is pre-processed after, it is brilliant in shell molecular sieve grows liquid system to carry out hydro-thermal
Change, so as to which the nano crystal core-shell molecular sieve containing fine and close shell finally be prepared.The monocrystalline core-shell molecular sieve has continuous
Duct, diffusional resistance is small, integrated machine intensity is high, selectivity it is high the characteristics of, in aromatic hydrocarbons selective disproportionation, form selected methylation, select
Shape isomerization and catalytic gasoline hydrogenation modifying etc. have excellent catalytic performance.
In the description of this specification, it is to be understood that reference term " one embodiment ", " some embodiments ", " show
The description of example ", " specific example " or " some examples " etc. mean to combine the specific features of the embodiment or example description, structure,
Material or feature are contained at least one embodiment or example of the present invention.In this manual, above-mentioned term is shown
The statement of meaning property is necessarily directed to identical embodiment or example.Moreover, specific features, structure, material or the spy of description
Point can combine in an appropriate manner in any one or more embodiments or example.In addition, in the case of not conflicting,
Those skilled in the art can be by the different embodiments or example described in this specification and different embodiments or example
Feature is combined and combined.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
- A kind of 1. nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure, it is characterised in that the molecular sieve bag Include nuclear phase and shell；Wherein, the nuclear phase is nano-ZSM-5 molecular sieve, and the shell is fine and close Silicalite-1 molecular sieves, and described The weight ratio of ZSM-5 molecular sieve and the Silicalite-1 molecular sieves is (1~20)：1.
- 2. the nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure according to claim 1, its feature exist In：In the nuclear phase nano-ZSM-5 molecular sieve, SiO2/Al2O3Mol ratio is 20~400, and crystallite dimension is 50~800nm.
- 3. the nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure according to claim 1, its feature exist In：In the nuclear phase nano-ZSM-5 molecular sieve, SiO2/Al2O3Mol ratio is 20~100.
- 4. the nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure according to claim 1, its feature exist In：The thickness of the shell Silicalite-1 molecular sieves is 5~100nm.
- 5. the preparation of the nano crystal ZSM-5@Silicalite-1 molecular sieves of any one of Claims 1 to 4 core shell structure Method, it is characterised in that：The outer surface of the nuclear phase ZSM-5 molecular sieve is pre-processed using acid solution, afterwards in the shell molecular sieve Hydrothermal crystallizing is carried out in growth liquid system, Silicalite-1 points of the nano crystal ZSM-5 containing fine and close shell is finally prepared Son sieve.
- 6. the preparation side of the nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure according to claim 5 Method, it is characterised in that comprise the following steps：S101：The nano-ZSM-5 molecular sieve for not being calcined template is placed in acid solution and pre-processed；Wherein, processing temperature Spend for 40~100 DEG C, processing time is 0.5~24h；S102：Molecular sieve filtration that S101 is obtained, washing to pH value carry out drying process after being 7, obtain ZSM-5 molecular sieve； Wherein, drying temperature is 50~110 DEG C, and drying time is 2~12h；S103：Shell growth-promoting media A configuration：Growth-promoting media is made up of silicon source, TPAOH, EtOH and water；Wherein, TPAOH/SiO2Mole Than for 0.02~1, EtOH/SiO2Mol ratio is 1~20, water/SiO2Mol ratio is 20~300；S104：The ZSM-5 molecular sieve that S102 is obtained is added in the growth-promoting media that the S103 is obtained, 2~12h is stirred at room temperature, so After be placed in 120~240 DEG C at a temperature of 5~150h of crystallization；Wherein, nuclear phase addition account for growth-promoting media A mass fraction for 0.5~ 10%；S105：Molecular sieve filtration that the S104 is obtained, washing to pH value are 7, and ammonium exchanges twice, and at 40~100 DEG C 2~12h is dried, 2~6h is calcined at last 300~700 DEG C, obtains the nano crystal ZSM-5@of the core shell structure Silicalite-1 molecular sieves.
- 7. the preparation side of the nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure according to claim 6 Method, it is characterised in that：In the S101, the acid solution includes the one or more in hydrochloric acid, nitric acid, sulfuric acid, formic acid and boric acid, and described The concentration of acid solution is 0.1~5mol/L.
- 8. the preparation side of the nano crystal ZSM-5@Silicalite-1 molecular sieves of core shell structure according to claim 6 Method, it is characterised in that：In the S103, the silicon source includes the one or more in Ludox, white carbon, tetraethoxysilance and silica.
- 9. the nano crystal ZSM-5@Silicalite-1 molecular sieves of any one of Claims 1 to 4 core shell structure are being catalyzed Application in cracking gasoline hydro-upgrading.
- 10. application according to claim 9, it is characterised in that comprise the following steps：It it is 300~400 DEG C in reaction temperature using catalytically cracked gasoline as raw material, reaction pressure be 1~3MPa, volume sky during liquid Speed is 1~3h-1, hydrogen to oil volume ratio be 200~500V/V under conditions of, using the nano crystal ZSM-5@Silicalite-1 Core-shell molecular sieve, realize the highly effective hydrogenation olefine reducing modification of catalytically cracked gasoline.
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