CN107519921A - Y/Sm2O3/ ZSM 22/ZSM 5/ASA composites and preparation method thereof - Google Patents

Y/Sm2O3/ ZSM 22/ZSM 5/ASA composites and preparation method thereof Download PDF

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CN107519921A
CN107519921A CN201610451095.8A CN201610451095A CN107519921A CN 107519921 A CN107519921 A CN 107519921A CN 201610451095 A CN201610451095 A CN 201610451095A CN 107519921 A CN107519921 A CN 107519921A
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zsm
solution
asa
molecular sieve
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CN107519921B (en
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李海岩
赵晶莹
左艳梅
秦丽红
谢方明
于春梅
孙发民
王甫村
亓荣彬
袁宗胜
张文成
郭金涛
董春明
吕倩
张全国
丛丽茹
靳丽丽
倪术荣
王燕
王亮
杨晓东
李井泉
张凤军
吴昆鹏
李艳晗
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China Petroleum and Natural Gas Co Ltd
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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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
    • 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
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • 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
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—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
    • 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
    • B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7092—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention provides one kind to contain regular mesoporous Y/Sm2O3The preparation method of/ZSM 22/ZSM 5/ASA composites, including：Directed agents are prepared, prepare Sm2O3The presomas of/ZSM 22/ZSM 5, Y/Sm is synthesized using hydrothermal crystallization method2O3The composite molecular screens of/ZSM 22/ZSM 5, surfactant and alkaline silicon source solution are then added in the slurries containing molecular sieve, adjust pH value, after precipitation product it is scrubbed, it is drys, be calcined, produce Y/Sm2O3/ ZSM 22/ZSM 5/ASA composites.The differential thermal fail temperature of Y molecular sieve can be more than 950 DEG C in the composite that this method obtains, crystal grain is maintained at below 400nm, and composite has the pore size distribution feature of micropore-mesopore, and mesoporous to be regular mesoporous in surface A SA, change synthetic technological condition, mesoporous pore size can be made adjustable.

Description

Y/Sm2O3/ ZSM-22/ZSM-5/ASA composites and preparation method thereof
Technical field
The present invention provides a kind of Y/Sm2O3/ ZSM-22/ZSM-5/ASA composites and preparation method thereof, specifically, it is One kind is by Y molecular sieve, Sm2O3, the composite wood that is formed through in-stiu coating of ZSM-22/ZSM-5 molecular sieves and amorphous silica-alumina (ASA) Material.
Background technology
Molecular sieve complex refers to be incorporated in one by molecule, atom or interionic effect by molecular sieve and other materials The composite risen.Regular material with meso-hole structure such as MCM-41 mesopore molecular sieves are adapted to because of its larger pore passage structure In the conversion of organic macromolecule, but its poor heat endurance, hydrothermal stability and weaker acidity limit this kind of material In the application of catalytic field.The research of micropore-mesopore composite based on high stability and highly acid micro porous molecular sieve Then there is important industrial application value.
With molecular sieve catalytic field apply increasingly extensively, the molecular sieve in single duct can not meet a variety of more The catalyst preparation demand of sample.Micro porous molecular sieve is mainly steady with stronger acid and higher structure in heterogeneous catalysis application It is qualitative to be good at, but because micro porous molecular sieve mostly has the problem of aperture is smaller, duct is elongated, it is big in reaction raw materials such as heavy oil Molecule is difficult to diffuse into inside duct, so can then reduce the utilization rate of acidic site inside micro porous molecular sieve duct, simultaneously The duct diffusional resistance of narrow elongate is larger, influence reaction product molecule quick diffusion overflow, easily cause drastic cracking and Green coke.And although mesopore molecular sieve can make up the limitation that micro porous molecular sieve spreads in reactant and reaction product, it is situated between The structural stability of porous molecular sieve is often poor, also limit its catalytic applications.
CN 200810012192 provides a kind of preparation method of Y molecular sieve/silicon dioxide composite material, by Y type molecules Sieve, sodium hydroxide, distilled water, template and silicon source are well mixed under stirring, and reaction mixture gel, each component is made Mol ratio is：(0-1.3)Na2O:(34.4-110)H2O:(0.75-11.3)SiO2:(0.046-0.7) R, R is template.Should Gel 12~70h of crystallization at 80-180 DEG C, through filtering, washing, obtain hud typed composite.Y molecular sieve is in composite wood Content in material is in 10~30wt%, and the particle diameter of composite is at 2~10 μm.Y type molecular sieve is not involved in titanium dioxide in this method The outgrowth of silicon, without chemical bond between Y type molecular sieve and silica, silica can not provide acidity, various It can only be played in catalytic reaction and select type effect, so the acidity of composite can only be realized by modulation Y molecular sieve.It is but mesoporous to be Irregular multi-stage porous.
Liu etc. is in document Journal of American Chemical Society (2000,122:In 8791-8792) Describe a kind of method that mesoporous material is prepared using Y molecular sieve secondary structure unit：First by NaOH, NaAlO2、H2O and water Glass mixes, and is made containing 27wt%SiO2With 14wt%NaOH Y molecular sieve seed-solution, template is introduced into seed-solution CTAB and dilution heat of sulfuric acid, the pH value for adjusting seed-solution are 9,100 DEG C of crystallization 20h, the Y in crystallization process in seed-solution points Son sieve secondary structure unit is assembled into the composite with hexagonal mesoporous structure, Al-MSU- in the presence of template CTAB S.The purpose is to use the assembly mesoporous material of Y type molecular sieve, but the mesoporous wall of micro--mesoporous composite material is impalpable structure, its Hydrothermal stability is poor.
Zhang etc. is in document Applied Catalysis A:General(2008,345:73-79) one kind is described in Y/MCM-48 is micro--preparation method of mesoporous composite material：NaY crystal seeds are added in MCM-48 precursor sol, presoma is molten Unclassified stores composition is in liquid：1TEOS:0.415CTAB:0.48NaOH:55H2After O, mixed liquor stirring 50min, at 110 DEG C Hydrothermal crystallizing for a period of time, filters, washing obtains solid product, and 550 DEG C of roasting 6h obtain Y/MCM-48 and answered in air atmosphere Close molecular sieve.Although the mesoporous wall thickness of MCM-48 molecular sieves prepared by this method is increased, its hole wall is still without fixed Shape structure, therefore poor be still of hydrothermal stability restricts its major reason applied.
CN102000604A provides one kind using kaolin as raw material, and for inorganic silicate to add silicon source, prepared by microwave method The method of Y/MCM-41 composite molecular screens.Before adding a certain amount of sodium metasilicate synthesis Y type molecular sieve as raw material using kaolin first Body is driven, then using cetyl trimethylammonium bromide as template, microwave method prepares composite molecular screen Y/MCM-41.The Y/ of synthesis MCM-41 composite molecular screens have micro--mesoporous double-pore structure, and the specific surface area of sample is more than 550m2/ g, average pore size are about 2.7nm, sample have regular hexagonal mesoporous structure.Although MCM-41 molecular sieves hole wall prepared by this method introduces Y types Molecular sieve secondary structure unit, but heat endurance is still short of, and collapse temperature is less than 800 DEG C.
CN101172244 provides a kind of preparation method of montmorillonite/Y molecular sieve composite.By by montmorillonite Grain is well mixed with Y molecular sieve gel, then carries out crystallization, and filtered, washing and the dry obtained montmorillonite/Y molecules Sieve composite.Composite made from the inventive method, while there is the architectural feature of montmorillonite and Y molecular sieve, montmorillonite With Y molecular sieve alternate, Y molecular sieve is grown on montmorillonite microballoon, but this method prepare composite in Y molecular sieve skeleton Silica alumina ratio is relatively low, and its hydrothermal stability may be caused poor.
CN101172243 provides a kind of preparation method of mesoporous/micropore molecular sieve composite material.The composite is logical Cross to mix adobe isomery material (PCHs) with micro porous molecular sieve gel and carry out made from in-situ crystallization.Prepared by the invention In composite, micro porous molecular sieve is wrapped in adobe isomery surrounding materials, and the composite has micro porous molecular sieve simultaneously Crystal structure and adobe isomery material meso-hole structure, belong to porosity Composite material.Matched somebody with somebody in composite according to gel It can be crystallized to obtain the micro porous molecular sieves such as Y types, ZSM-5 types, β types than difference.This method prepares the less stable of composite.
CN200610165597.0 provides a kind of preparation side of nano molecular sieve/sieve and silica-sesquioxide composite catalyzing material Method, nano molecular sieve first being synthesized using directing agent method, the precipitation step in synthesis is handled using microwave and/or ultrasonic wave, Then waterglass and the mixture aqueous solution of silicon source are added in the slurries containing nano molecular sieve, it is 7~9.5 that acid adding, which is adjusted to pH, Form gel；Then by gel drying, roasting, the composite catalyzing material is produced, wherein silicon source is selected from sodium metaaluminate or aluminum sulfate, This method make it that the particle that products molecule sieves is maintained at below 100nm and nano molecular sieve therein is not easy to assemble, without Acidic sol process and avoid molecular sieve by acid destroy.The composite is suitable for the catalytic cracking of heavy oil macromolecular and hydrogenation splits Change reaction.
Landau etc. is in document Applied Catalysis A:General(1994,115:L7-L14 one is described in) The method that kind synthesizes nano molecular sieve ZSM-5 in the duct situ of Silica hydrogel, 3~5 μm of particle diameter is formed in the outer surface of silica gel Zeolite, in the macropore of silica gel formed 0.5~2 μm of particle diameter zeolite, in the mesopore of silica gel formed particle diameter 0.02~0.035 μm zeolite.
Landau etc. is in Chem.Mater (1999,11:Described in 2030-2037) it is a kind of by granular size be 10~ 15nm beta-molecular sieve is stable at the method in Alumina gel：Gel aluminum hydroxide filter cake is dispersed in water first, pH=is made 9.05 aluminium hydroxide emulsion：By its pH=12.7 at room temperature beta-molecular sieve slurries according to Al2O3/ molecular sieve=1:1 weight Than mixing, to pH=11.8, (add dust technology after described mixing in the preparation of another two batches sample makes the pH of mixing rear slurry to amount Respectively 11.0 and 10.0)；After stirring 2h, aging 24h at room temperature；Precipitation is isolated by decantation, and in 50 DEG C of vacuum drying It is 70wt% to water content.Extruder grain and in 120 DEG C of dry 5h, then temperature-programmed calcination.The shortcomings that this method is to prepare Time is longer.
The preparation method of the micro--mesoporous composite material referred in above-mentioned document or patent either process it is more complicated or The synthesis technique time is grown.CN102000604A introduces microwave processing process during Y/MCM-41 composite molecular screens are synthesized, Auxiliary equipment is added, increases considerably the cost of synthesis composite molecular screen.Mentioned in other document above or patent it is micro-- Mesoporous silica-alumina materials part in mesoporous composite material is irregular hole.
The content of the invention
The purpose of the present invention is the preparation technology by improving ASA, and obtaining ASA has the mesoporous Y/Sm of rule2O3/ZSM- 22/ZSM-5/ASA composites.
The present invention provides a kind of Y/Sm2O3The preparation method of/ZSM-22/ZSM-5/ASA composites, comprises the following steps：
(1) prepares directed agents：
Sodium hydroxide and silicon source are added to the water, or sodium hydroxide is added to the water to after being completely dissolved and added again Enter silicon source, form sodium aluminate solution A, Al in solution A2O3Content be 2.5~10wt%, Na2O content is 8~35wt%； Solution A and water glass solution are added sequentially in deionized water under agitation, it is static old at 15~50 DEG C after stirring Change 0.5~60h, directed agents are made；The mol ratio of each component is Na in directed agents2O:Al2O3:SiO2:H2O=10~20:1:14 ~18:240~440；
(2).Sm2O3The preparation of/ZSM-22/ZSM-5 presomas：
Using class solid-phase synthesis, one-pot solid content 50%~80%, with silochrom, sodium metaaluminate, deionized water, three Methylamine and hexamethylene diamine are raw material, at 100~180 DEG C, 10~48h of thermostatic crystallization, synthesize ZSM-22/ZSM-5 molecular sieve pulps；
By samaric nitrate：Tetraethyl orthosilicate：ZSM-22/ZSM-5 molecular sieve pulps：Aqueous solution mass ratio is 1~5:1~5: 1~5：1~10, samaric nitrate, tetraethyl orthosilicate, ZSM-22/ZSM-5 molecular sieve pulps are sequentially added in the aqueous solution, are heated to 70~80 DEG C, constant temperature stirs 1~10h, obtains Sm2O3/ ZSM-22/ZSM-5 presomas E, the aqueous solution are 1~5wt% nitric acid With the mixed aqueous solution of 1~5wt% citric acids；
(3) prepares synthesis Y/Sm2O3The reactant mixture of/ZSM-22/ZSM-5 composite molecular screens：
Silicon source is dissolved in water, forms Al2O3Content is 1~4wt% solution B；Sodium hydroxide and silicon source are added to In water, or sodium hydroxide is added to the water to after being completely dissolved and adds silicon source, formation sodium aluminate solution C, in solution C Al2O3Content be 3~9wt%, Na2O content is 1~20wt%；By the directed agents, the solution B, the solution C and institute State presoma E and be added to the reaction mixing that synthesis Y/Sm2O3/ZSM-22/ZSM-5 composite molecular screens are made in water glass solution Thing；Counted using the weight of reactant mixture as 100wt%, the addition of directed agents is 0.5~20wt%, obtains synthesizing Y/Sm2O3/ The reactant mixture of ZSM-22/ZSM-5 composite molecular screens, the mol ratio of each component are：Na2O:Al2O3:SiO2:Sm2O3:H2O= 3~10:1:8~18:0.01~0.06:180~320；
(4) hydrothermal crystallizings synthesize：
The synthesis Y/Sm that step (3) is obtained2O3The reactant mixture of/ZSM-22/ZSM-5 composite molecular screens is 80~140 8~72h of crystallization at DEG C, obtains Y/Sm2O3/ ZSM-22/ZSM-5 composite molecular screen slurries；
(5).Y/Sm2O3The preparation of/ZSM-22/ZSM-5/ASA composites：
Surfactant is added to Y/Sm2O3In/ZSM-22/ZSM-5 composite molecular screen slurries, alkali is added while stirring Property silicon source solution, and be 7~9 with the pH value of phosphoric acid regulation system, solid mixture matter obtained, finally by solid obtained above Compounding substances filtering, washing, 100~150 DEG C of dry 4~10h, 400~600 DEG C of 2~8h of roasting, obtain Y/Sm2O3/ZSM-22/ ZSM-5/ASA composites.
Y/Sm of the present invention2O3The preparation method of/ZSM-22/ZSM-5/ASA composites, wherein：In step (5) The surfactant is preferably one or both of CTAB, P123 and F127.
Y/Sm of the present invention2O3The preparation method of/ZSM-22/ZSM-5/ASA composites, wherein：In step (5) The addition of surfactant preferably accounts for Y/Sm2O31~6wt% of/ZSM-22/ZSM-5/ASA composite quality.
The present invention also provides a kind of Y/Sm2O3/ ZSM-22/ZSM-5/ASA composites, it is above-mentioned Y/Sm2O3/ZSM- Y/Sm made from 22/ZSM-5/ASA preparation method2O3/ ZSM-22/ZSM-5/ASA composites.
Y/Sm of the present invention2O3/ ZSM-22/ZSM-5/ASA composites, wherein：Y/Sm2O3/ZSM-22/ZSM- The content of Y molecular sieve is preferably 10~90wt% in 5/ASA composites, remaining be sieve and silica-sesquioxide, samarium oxide, ZSM-22 and ZSM-5。
Y/Sm of the present invention2O3/ ZSM-22/ZSM-5/ASA composites, wherein：Y/Sm2O3/ZSM-22/ZSM- The SiO of sieve and silica-sesquioxide in 5/ASA composites2With Al2O3Mol ratio be preferably 1~10：1.
Y/Sm of the present invention2O3/ ZSM-22/ZSM-5/ASA composites, wherein：Y/Sm2O3/ZSM-22/ZSM- Mesoporous preferably rule in 5/ASA composites is mesoporous, and total pore volume is preferably 0.46~0.58mL/g, and Micropore volume is preferably 0.20~0.30mL/g, mesoporous pore volume are preferably 0.24~0.33mL/g.
Y/Sm of the present invention2O3/ ZSM-22/ZSM-5/ASA composites, wherein：Y/Sm2O3/ZSM-22/ZSM- ASA regular mesoporous pore size is preferably between 3~10nm in 5/ASA composites.
The present invention can be so that details are as follows：
Surfactant of the present invention is mainly tri- kinds of nonionic surfactants of CTAB, P123 and F127, The preparation of Y/Sm2O3/ZSM-22/ZSM-5/ASA composites can be carried out during use using one or two therein.
Y/Sm of the present invention2O3Silicon source used is ability in/ZSM-22/ZSM-5/ASA composite preparation process Domain is conventional, such as sodium metaaluminate, boehmite, boehmite, aluminum nitrate, aluminum sulfate, aluminium hydroxide and/or gibbsite, Alkaline silicon source is commonly used in the art, and aluminium therein can derive from sodium metaaluminate or the thin water of plan being dissolved in sodium hydroxide solution Aluminium stone, boehmite, aluminium hydroxide, gibbsite.Acid is acid generally in the art, preferably inorganic acid, such as phosphoric acid.
The Y/Sm prepared using the method for the present invention2O3The heat of NaY molecular sieve in/ZSM-22/ZSM-5/ASA composites Stability is maintained, the product Y/Sm that this method obtains2O3The difference of Y type molecular sieve in/ZSM-22/ZSM-5/ASA composites Heat damage temperature can be more than 960 DEG C, even up to 1008~1100 DEG C；Maximum crystal grain is maintained at below 400nm.
Present invention also offers a kind of Y/Sm obtained by the above method2O3/ ZSM-22/ZSM-5/ASA composites.
Y/Sm2O3The content of Y molecular sieve is preferably 10~90wt% in/ZSM-22/ZSM-5/ASA composites, and remaining is Sieve and silica-sesquioxide, Al2O3、SiO2, ZSM-22, ZSM-5 and samarium oxide, the SiO of sieve and silica-sesquioxide2With Al2O3Mol ratio it is best For 1：1~10：1.
The Y/Sm of the present invention2O3NaY molecular sieve differential thermal fail temperature is reachable in/ZSM-22/ZSM-5/ASA composites 1008 DEG C~1100 DEG C, the mesoporous average pore size of rule is 3~10nm, and total pore volume is 0.46~0.58mL/g, and Micropore volume is 0.20~0.30mL/g, mesoporous pore volume are 0.24~0.33mL/g.
In summary, Y/Sm produced by the present invention2O3NaY molecular sieve has crystalline substance in/ZSM-22/ZSM-5/ASA composites Grain small (100~400nm), framework si-al ratio are high, heat endurance raising is (higher by 5 than the differential thermal fail temperature of corresponding NaY molecular sieve More than DEG C) and the characteristics of micro--composite mesoporous pore structure of micropore less than 1nm and 3~10nm regular mesoporous composition.
Embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out lower premised on technical solution of the present invention Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation The experimental method of unreceipted actual conditions in example, generally according to normal condition.
Analysis test method：
The relative crystallinity of NaY molecular sieve and the measure of framework si-al ratio：Using the production of German Bruker companies D8Advance X-ray diffractometers, condition determination are：CuK α are radiated, pipe pressure 40kV, tube current 40mA.Its assay method according to SH/T 0340-92 standard methods measure (see《Standard of chemical industry collects》, China Standards Press, publish within 2000), bone The measure of frame silica alumina ratio be by SH/T 0399-92 standard methods, (see《Standard of chemical industry collects》, China Standards Press, Publish within 2000) determine and according to following formula：
Calculate the lattice constant a of NaY molecular sieve.
Then according to Breck-Flanigen formula：
Calculate the framework si-al ratio of NaY molecular sieve.
Sem analysis uses the 435VP type SEM of LEO companies of Britain production, accelerating potential 20kV, sample It is gold-plated with physical method before testing.
Thermal stability determination is carried out on German Nai Chi instrument companies STA 409PC type thermal analyzers.Experiment is in Ar atmosphere Middle progress, heating rate are 10 DEG C/min, temperature range：Room temperature~1200 DEG C.
Specific surface area and pore volume test：The measure of the specific surface area and pore structure of catalyst and molecular sieve exists The ASAP2020M of Micromeritics companies production is calculated according to BET method than being carried out on surface and lacunarity analysis instrument and is compared table Area；BJH method calculated pores.
Embodiment 1：
Y/Sm2O3The synthesis of/ZSM-22/ZSM-5/ASA composites
(1) preparation of directed agents：Take 24.7g sodium hydroxides (Beijing Chemical Plant, analysis are pure) to be added in 45.9g water, stir Mix to sodium hydroxide and all dissolve, add 6.5g sodium metaaluminates (research institute of Shandong Aluminium Industrial Corp, industrial goods, Al2O3Content 49.1wt%), stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A.By 70g solution As and 100g waterglass (Beijing Red Star water glass plant, SiO2Content 27.81wt%, Na2O content 8.74wt%) to pour into successively in 65.5g deionized waters, stirring is equal After even at 30 DEG C static ageing 22h, obtain directed agents.The mol ratio of directed agents each component is：16Na2O:Al2O3:16SiO2: 330H2O。
(2)Sm2O3The preparation of/ZSM-22/ZSM-5 presomas：Using class solid-phase synthesis (one-pot solid content 50%), with Silochrom, sodium metaaluminate, deionized water, trimethylamine and hexamethylene diamine are raw material, at 100 DEG C, thermostatic crystallization 48h, synthesize ZSM- 22/ZSM-5 molecular sieve pulps.By samaric nitrate：Tetraethyl orthosilicate：ZSM-22/ZSM-5 molecular sieves：Water-soluble liquid proportional is 1g：3g： 4g：10g, samaric nitrate, tetraethyl orthosilicate, ZSM-22/ZSM-5 molecular sieves are sequentially added into 1~5wt% nitric acid and 1~5wt% lemons In the aqueous solution of lemon acid, 70 DEG C are heated to, constant temperature stirring 1h, obtains Sm2O3/ ZSM-22/ZSM-5 presomas E；
(3)Y/Sm2O3The preparation of/ZSM-22/ZSM-5 composite molecular screens：14.5g aluminum sulfate is dissolved in 50.6g water, Form Al2O3Content is 3.4wt% aluminum sulfate solution B；4.5g sodium hydroxides are dissolved in 50.4g water, then add 10g meta-aluminic acids (the same step 1) of specification, stirring form sodium aluminate solution C to sodium to being completely dissolved.By 10.3g directed agents, solution B and solution C and Presoma E is added sequentially to 75g waterglass (specification with step 1), after stirring according to conventional NaY molecular sieve preparation process Again plus 48.5g water, synthesis Y/Sm is made2O3The reactant mixture of/ZSM-22/ZSM-5 composite molecular screens.The mol ratio of each component For 6.0Na2O:Al2O3:12SiO2:0.01Sm2O3:260H2O；Reactant mixture is gone in autoclave, the crystallization at 105 DEG C 22h.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, filtering, washing, dries, produce Y/Sm2O3/ ZSM-22/ZSM-5 is compound Zeolite product.
Gained Y/Sm2O3Y molecular sieve relative crystallinity in/ZSM-22/ZSM-5 composite molecular screens is 90%, framework silicon-aluminum Than being 950 DEG C for 5.2, particle diameter 200nm, differential thermal fail temperature.
(4)Y/Sm2O3The preparation of/ZSM-22/ZSM-5/ASA composites：0.8g sodium hydroxides are dissolved in 6.2g water In, 1g sodium metaaluminates are added, stirs to sodium metaaluminate and all dissolves, obtain solution D.The Y/Sm that step (3) is obtained2O3/ZSM- 22/ZSM-5 molecular sieves and mother liquor are cooled to room temperature, are transferred in beaker, static layering, take out upper strata mother liquor 32mL, Ran Houxiang Y/Sm2O3Added in the mix suspending thing of/ZSM-22/ZSM-5 molecular sieves and mother liquor and contain the 1.3g surfactant P123 aqueous solution And 30min is stirred at 20 DEG C, solution D is added afterwards, is continued to stir 1h after adding, is added phosphoric acid to the mixing of above-mentioned stirring In thing, the pH value of regulation system is 7.Finally by solid matter obtained above filtering, washing, 125 DEG C of dry 7h, 500 DEG C of roastings 4h is burnt, obtains Y/Sm2O3/ ZSM-22/ZSM-5/ASA composites, its intermediary hole part are sieve and silica-sesquioxide, sieve and silica-sesquioxide Mol ratio be 8.5：1, mesoporous mesoporous for rule, the content of Y molecular sieve is 62wt%.Y/Sm2O3/ZSM-22/ZSM-5/ASA The differential thermal fail temperature of NaY molecular sieve is 1010 DEG C in composite, and texture property is shown in Table 1.
Embodiment 2：
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents：Take 32.1g sodium hydroxides to be added in 45.9g water, stir all molten to sodium hydroxide Solution, adds 6.5g sodium metaaluminates, stirs to sodium metaaluminate and all dissolves, obtains sodium aluminate solution A.By 70g solution As and 112g Waterglass pours into 113g deionized waters successively, after stirring at 30 DEG C static ageing 22h, obtain directed agents.Directed agents are each The mol ratio of component is：20Na2O:Al2O3:18SiO2:440H2O。
(2)Sm2O3The preparation of/ZSM-22/ZSM-5 presomas：Using class solid-phase synthesis (one-pot solid content 60%), with Silochrom, sodium metaaluminate, deionized water, trimethylamine and hexamethylene diamine are raw material, at 150 DEG C, thermostatic crystallization 24h, synthesize ZSM- 22/ZSM-5 molecular sieve pulps.By samaric nitrate：Tetraethyl orthosilicate：ZSM-22/ZSM-5 molecular sieves：Water-soluble liquid proportional is 5g：5g： 5g：25g, samaric nitrate, tetraethyl orthosilicate, ZSM-22/ZSM-5 molecular sieves are sequentially added into 5wt% nitric acid and 1wt% citric acids In the aqueous solution, 80 DEG C are heated to, constant temperature stirring 10h, obtains Sm2O3/ ZSM-22/ZSM-5 presomas E；
(3)Y/Sm2O3The preparation of/ZSM-22/ZSM-5 composite molecular screens：14.5g aluminum sulfate is dissolved in 50.6g water, Form Al2O3Content is 3.4wt% aluminum sulfate solution B；4.5g sodium hydroxides are dissolved in 50.4g water, then add 10g meta-aluminic acids (the same step 1) of specification, stirring form sodium aluminate solution C to sodium to being completely dissolved.By 10.3g directed agents, solution B and solution C and Presoma E according to conventional NaY molecular sieve preparation process is added sequentially to 162g waterglass, and (specification stirs with step 1) Add 48.5g water again afterwards, synthesis Y/Sm is made2O3The reactant mixture of/ZSM-22/ZSM-5 composite molecular screens.Mole of each component Than for 10Na2O:Al2O3:18SiO2:0.06Sm2O3:320H2O；Reactant mixture is gone in autoclave, the crystallization at 80 DEG C 72h.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, filtering, washing, dries, produce Y/Sm2O3/ ZSM-22/ZSM-5 is compound Zeolite product.
Gained Y/Sm2O3Y molecular sieve relative crystallinity in/ZSM-22/ZSM-5 composite molecular screens is 90%, framework silicon-aluminum Than being 950 DEG C for 5.2, particle diameter 200nm, differential thermal fail temperature.
(4)Y/Sm2O3The preparation of/ZSM-22/ZSM-5/ASA composites：0.8g sodium hydroxides are dissolved in 6.2g water In, 1g sodium metaaluminates are added, stirs to sodium metaaluminate and all dissolves, obtain solution D.The Y/Sm that step (3) is obtained2O3/ZSM- 22/ZSM-5 molecular sieves and mother liquor are cooled to room temperature, are transferred in beaker, static layering, take out upper strata mother liquor 32mL, Ran Houxiang Y/Sm2O3Added in the mix suspending thing of/ZSM-22/ZSM-5 molecular sieves and mother liquor and contain the 7.8g surfactant P123 aqueous solution And 30min is stirred at 20 DEG C, solution D is added afterwards, is continued to stir 1h after adding, is added phosphoric acid to the mixing of above-mentioned stirring In thing, the pH value of regulation system is 7.Finally by solid matter obtained above filtering, washing, 150 DEG C of dry 4h, 600 DEG C of roastings 2h is burnt, obtains Y/Sm2O3/ ZSM-22/ZSM-5/ASA composites, its intermediary hole part are sieve and silica-sesquioxide, sieve and silica-sesquioxide Mol ratio be 8.5：1, mesoporous mesoporous for rule, the content of Y molecular sieve is 62wt%.Y/Sm2O3/ZSM-22/ZSM-5/ASA The differential thermal fail temperature of NaY molecular sieve is 1010 DEG C in composite, and texture property is shown in Table 1.
Embodiment 3
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents：Take 24.7g sodium hydroxides to be added in 45.9g water, stir all molten to sodium hydroxide Solution, adds 6.5g sodium metaaluminates, stirs to sodium metaaluminate and all dissolves, obtains sodium aluminate solution A.By 70g solution As and 100g Waterglass pours into 65.5g deionized waters successively, after stirring at 30 DEG C static ageing 22h, obtain directed agents.Directed agents are each The mol ratio of component is：16Na2O:Al2O3:16SiO2:330H2O。
(2)Sm2O3The preparation of/ZSM-22/ZSM-5 presomas：Using class solid-phase synthesis (one-pot solid content 70%), with Silochrom, sodium metaaluminate, deionized water, trimethylamine and hexamethylene diamine are raw material, at 180 DEG C, thermostatic crystallization 10h, synthesize ZSM- 22/ZSM-5 molecular sieve pulps.By samaric nitrate：Tetraethyl orthosilicate：ZSM-22/ZSM-5 molecular sieve pulps：Water-soluble liquid proportional is 2g： 4g：3g：10g, samaric nitrate, tetraethyl orthosilicate, ZSM-22/ZSM-5 molecular sieves are sequentially added into 1wt% nitric acid and 1wt% lemons In the aqueous solution of acid, 75 DEG C are heated to, constant temperature stirring 10h, obtains Sm2O3/ ZSM-22/ZSM-5 presomas E；
(3)Y/Sm2O3The preparation of/ZSM-22/ZSM-5 composite molecular screens：14.5g aluminum sulfate is dissolved in 50.6g water, Form Al2O3Content is 3.4wt% aluminum sulfate solution B；4.5g sodium hydroxides are dissolved in 50.4g water, then add 10g meta-aluminic acids Sodium, stirring form sodium aluminate solution C to being completely dissolved.By 10.3g directed agents, solution B, solution C and presoma E according to normal Rule NaY molecular sieve preparation process is added sequentially in 75g waterglass, adds 48.5g water after stirring again, and synthesis Y/ is made Sm2O3The reactant mixture of/ZSM-22/ZSM-5/ASA molecular sieves.The mol ratio of each component is 6Na2O:Al2O3:12SiO2: 0.02Sm2O3:260H2O；Reactant mixture is gone in autoclave, the crystallization 22h at 105 DEG C.Hydrothermal crystallizing finishes, and takes out and divides Son sieve and mother liquor, filtering, washing, dry, produce Y/Sm2O3/ ZSM-22/ZSM-5 composite molecular screen products.
Gained Y/Sm2O3Y molecular sieve relative crystallinity in/ZSM-22/ZSM-5 composite molecular screens is 90%, framework silicon-aluminum Than being 950 DEG C for 5.2, particle diameter 200nm, differential thermal fail temperature.
(4)Y/Sm2O3The preparation of/ZSM-22/ZSM-5/ASA composites：7.5g sodium hydroxides are dissolved in 58g water, 9.2g sodium metaaluminates are added, stirs to sodium metaaluminate and all dissolves, obtain solution D.The Y/Sm that step (3) is obtained2O3/ZSM- 22/ZSM-5 molecular sieves and mother liquor are cooled to room temperature, are transferred in beaker, at 25 DEG C, sequentially add while stirring containing P123 3.9g and solution D.Continue to stir 2h at 25 DEG C, phosphoric acid solution is added in the mixture of above-mentioned stirring, finally makes system PH value be 8.5.Finally by solid matter obtained above filtering, washing, 100 DEG C of dry 10h, 400 DEG C of roasting 8h, Y/ is obtained Sm2O3/ ZSM-22/ZSM-5/ASA composites, its intermediary hole part are sieve and silica-sesquioxide, and the mol ratio of sieve and silica-sesquioxide is 5： 1, mesoporous mesoporous for rule, the content of Y molecular sieve is 35wt%.Y/Sm2O3NaY points in/ZSM-22/ZSM-5/ASA composites The differential thermal fail temperature of son sieve is 1008 DEG C, and texture property is shown in Table 1.
Embodiment 4
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents：Take 24.7g sodium hydroxides to be added in 45.9g water, stir all molten to sodium hydroxide Solution, adds 6.5g sodium metaaluminates, stirs to sodium metaaluminate and all dissolves, obtains sodium aluminate solution A.By 70g solution As and 100g Waterglass pours into 65.5g deionized waters successively, after stirring at 30 DEG C static ageing 22h, obtain directed agents.Directed agents are each The mol ratio of component is：16Na2O:Al2O3:16SiO2:330H2O。
(2)Sm2O3The preparation of/ZSM-22/ZSM-5 presomas：Using class solid-phase synthesis (one-pot solid content 80%), with Silochrom, sodium metaaluminate, deionized water, trimethylamine and hexamethylene diamine are raw material, at 100 DEG C, thermostatic crystallization 48h, synthesize ZSM- 22/ZSM-5 molecular sieve pulps.By samaric nitrate：Tetraethyl orthosilicate：ZSM-22/ZSM-5 molecular sieve pulps：Water-soluble liquid proportional is 1g： 1g：5g：10g, samaric nitrate, tetraethyl orthosilicate, ZSM-22/ZSM-5 molecular sieves are sequentially added into 1wt% nitric acid and 5wt% lemons In the aqueous solution of acid, 100 DEG C are heated to, constant temperature stirring 10h, obtains Sm2O3/ ZSM-22/ZSM-5 presomas E；
(3)Y/Sm2O3The preparation of/ZSM-22/ZSM-5 composite molecular screens：14.5g aluminum sulfate is dissolved in 50.6g water, Form Al2O3Content is 3.4wt% aluminum sulfate solution B；4.5g sodium hydroxides are dissolved in 50.4g water, then add 10g meta-aluminic acids Sodium, stirring form sodium aluminate solution C to being completely dissolved.By 10.3g directed agents, solution B, solution C and presoma E according to normal Rule NaY molecular sieve preparation process is added sequentially in 75g waterglass, adds 48.5g water after stirring again, and synthesis Y/ is made Sm2O3The reactant mixture of/ZSM-22/ZSM-5 molecular sieves.The mol ratio of each component is 6Na2O:Al2O3:12SiO2: 0.01Sm2O3:260H2O；Reactant mixture is gone in autoclave, the crystallization 22h at 105 DEG C.Hydrothermal crystallizing finishes, and takes out and divides Son sieve and mother liquor, filtering, washing, dry, produce Y/Sm2O3/ ZSM-22/ZSM-5 zeolite products.
Gained Y/Sm2O3The relative crystallinity of Y molecular sieve in/ZSM-22/ZSM-5 composite molecular screens is 90%, framework silicon Aluminum ratio is 5.2, particle diameter 200nm, and differential thermal fail temperature is 950 DEG C.
(4)Y/Sm2O3The preparation of/ZSM-22/ZSM-5/ASA composites：3.6g sodium hydroxides are dissolved in 27.6g water In, 8.8g sodium metaaluminates are added, stirs to sodium metaaluminate and all dissolves, obtain solution D.The Y/Sm that step (3) is obtained2O3/ ZSM-22/ZSM-5 composite molecular screens and mother liquor are cooled to room temperature, mother liquor 200mL are taken out, then by remaining mother liquor and Y/ The mixture of Sm2O3/ZSM-22/ZSM-5 composite molecular screens is transferred in beaker, is added while stirring at 25 DEG C and is contained P123 After 7.8g, the F127 1.3g aqueous solution stir, then solution D and phosphoric acid successively, the pH value of regulation system is 8.0.Finally will Solid matter filtering obtained above, washing, 120 DEG C of dry 12h, 500 DEG C of roasting 8h, obtain Y/Sm2O3/ZSM-22/ZSM-5/ ASA composite material, its intermediary hole part are sieve and silica-sesquioxide, and the silica alumina ratio of sieve and silica-sesquioxide is 1.5：1, it is mesoporous for rule It is mesoporous, aperture 9.2nm, with Y/Sm2O3On the basis of/ZSM-22/ZSM-5 composites, the content of Y type molecular sieve is 80wt%. Y/Sm2O31027 DEG C of the differential thermal fail temperature of NaY molecular sieve in/ZSM-22/ZSM-5/ASA composites, texture property is shown in Table 1.
Embodiment 5
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents：Take 12.8g sodium hydroxides to be added in 45.9g water, stir all molten to sodium hydroxide Solution, adds 6.5g sodium metaaluminates, stirs to sodium metaaluminate and all dissolves, obtains sodium aluminate solution A.By 70g solution As and 87.5g waterglass pours into 20.5g deionized waters successively, after stirring at 30 DEG C static ageing 22h, obtain directed agents.Lead Mol ratio to agent each component is：10Na2O:Al2O3:14SiO2:240H2O。
(2)Sm2O3The preparation of/ZSM-22/ZSM-5 presomas：Using class solid-phase synthesis (one-pot solid content 80%), with Silochrom, sodium metaaluminate, deionized water, trimethylamine and hexamethylene diamine are raw material, at 100 DEG C, thermostatic crystallization 48h, synthesize ZSM- 22/ZSM-5 molecular sieve pulps.By samaric nitrate：Tetraethyl orthosilicate：ZSM-22/ZSM-5 molecular sieve pulps：Water-soluble liquid proportional is 1g： 1g：5g：10g, samaric nitrate, tetraethyl orthosilicate, ZSM-22/ZSM-5 molecular sieves are sequentially added into 1wt% nitric acid and 5wt% lemons In the aqueous solution of acid, 100 DEG C are heated to, constant temperature stirring 10h, obtains Sm2O3/ ZSM-22/ZSM-5 presomas E；
(3)Y/Sm2O3The preparation of/ZSM-22/ZSM-5 composite molecular screens：14.5g aluminum sulfate is dissolved in 50.6g water, Form Al2O3Content is 3.4wt% aluminum sulfate solution B；4.5g sodium hydroxides are dissolved in 50.4g water, then add 10g meta-aluminic acids Sodium, stirring form sodium aluminate solution C to being completely dissolved.By 10.3g directed agents, solution B, solution C and presoma E according to normal Rule NaY molecular sieve preparation process is added sequentially in 55g waterglass, adds 48.5g water after stirring again, and synthesis Y/ is made Sm2O3The reactant mixture of/ZSM-22/ZSM-5/ASA molecular sieves.The mol ratio of each component is 3Na2O:Al2O3:8SiO2: 0.01Sm2O3:260H2O；Reactant mixture is gone in autoclave, the crystallization 24h at 100 DEG C.Hydrothermal crystallizing finishes, and takes out and divides Son sieve and mother liquor, filtering, washing, dry, produce Y/Sm2O3/ ZSM-22/ZSM-5 zeolite products.
Gained Y/Sm2O3The relative crystallinity of Y molecular sieve in/ZSM-22/ZSM-5 composite molecular screens is 90%, framework silicon Aluminum ratio is 4.2, particle diameter 200nm, and differential thermal fail temperature is 950 DEG C.
(4)Y/Sm2O3The preparation of/ZSM-22/ZSM-5/ASA composites：3.6g sodium hydroxides are dissolved in 27.6g water In, 8.8g sodium metaaluminates are added, stirs to sodium metaaluminate and all dissolves, obtain solution D.The Y/Sm that step (3) is obtained2O3/ ZSM-22/ZSM-5 composite molecular screens and mother liquor are cooled to room temperature, mother liquor 200mL are taken out, then by remaining mother liquor and Y/ Sm2O3The mixture of/ZSM-22/ZSM-5 composite molecular screens is transferred in beaker, is added while stirring at 25 DEG C and is contained P123 After 7.8g, the F127 1.3g aqueous solution stir, then solution D and phosphoric acid successively, the pH value of regulation system is 8.0.Finally will Solid matter filtering obtained above, washing, 120 DEG C of dry 7h, 500 DEG C of roasting 4h, obtain Y/Sm2O3/ZSM-22/ZSM-5/ ASA composite material, its intermediary hole part are sieve and silica-sesquioxide, and the silica alumina ratio of sieve and silica-sesquioxide is 1.5：1, it is mesoporous for rule It is mesoporous, with Y/Sm2O3On the basis of/ZSM-22/ZSM-5 composites, the content of Y type molecular sieve is 80wt%.Y/Sm2O3/ZSM- 1027 DEG C of the differential thermal fail temperature of Y molecular sieve in 22/ZSM-5/ASA composites, texture property is shown in Table 1.
Comparative example 1
Using the condition of embodiment 4, but surfactant is not added with when preparing Y/ASA composites.
(1) preparation of directed agents：Take 24.7g sodium hydroxides (Beijing Chemical Plant, analysis are pure) to be added in 45.9g water, stir Mix to sodium hydroxide and all dissolve, add 6.5g sodium metaaluminates (research institute of Shandong Aluminium Industrial Corp, industrial goods, Al2O3Content 49.1wt%), stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A.By 70g solution As and 100g waterglass (Beijing Red Star water glass plant, SiO2Content 27.81wt%, Na2O content 8.74wt%) to pour into successively in 65.5g deionized waters, stirring is equal After even at 30 DEG C static ageing 22h, obtain directed agents.The mol ratio of directed agents each component is：16Na2O:Al2O3:16SiO2: 330H2O。
(2) preparation of NaY types molecular sieve：14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3Content is 3.4wt% aluminum sulfate solution B；4.5g sodium hydroxides are dissolved in 50.4g water, then add 10g sodium metaaluminates (the same step of specification 1), stirring forms sodium aluminate solution C to being completely dissolved.By 10.3g directed agents, solution B and solution C according to conventional NaY molecules Sieve preparation process is added sequentially to 75g waterglass, and (specification adds 48.5g water, synthesis is made again with step 1) after stirring The reactant mixture of NaY molecular sieve.The mol ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；By reactant mixture Go in autoclave, the crystallization 22h at 105 DEG C.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, filtering, washing, dries, i.e., Obtain NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, particle diameter 200nm, and differential thermal destroys Temperature is 950 DEG C.
(3) preparation of Y/ASA composites：In addition to surfactant is not added with, with (4) the step of embodiment 4.Mesoporous hole Footpath is 3.3~5.2nm.910 DEG C of the differential thermal fail temperature of NaY molecular sieve in Y/ASA composites, texture property is shown in Table 1.
Comparative example 2
Small crystal grain NaY molecular sieve is prepared by the method for CN 1033503C embodiment 4 and prepares Y/ASA composites.
(1) preparation of directed agents：Take 29.5g sodium hydroxides to be added in 75g water, stir to sodium hydroxide and all dissolve, 4.78g boehmites are added, stirs to boehmite and all dissolves, obtain sodium metaaluminate.200g waterglass is added to The sodium metaaluminate and 12g deionized waters of above-mentioned preparation mix 1h at 35 DEG C, are then made and rub in 35 DEG C of static aging 6h Your ratio is 16Na2O:Al2O3:15SiO2:320H2O, light transmittance<30% conventional directed agents.
189g specifications waterglass same as described above is added in conventional directed agents, after placing 1.5h at 30 DEG C, is made Light transmittance is 90%, and a mole composition is 20.6Na2O:Al2O3:30SiO2:495H2Improvement directing agent solution as clear as crystal O, Room temperature uses after placing 24h.
(2) preparation of NaY types molecular sieve：According to mol ratio 3.84Na2O:Al2O3:12SiO2:220H2O synthesizing formula, By 250g specifications waterglass same as described above, the improvement directed agents of the above-mentioned preparations of 510g, 160g Al2O3Content is 6.8wt% Aluminum sulfate solution and 9.7g sodium aluminate solutions (Al2O3Content 7.5wt%, Na2O content is 15wt%) 1h is mixed, so After be warming up to 97 DEG C, crystallization 26h, filtering, dry.
The relative crystallinity of gained NaY molecular sieve is 79%, framework si-al ratio 5.8, particle diameter 100nm, and differential thermal destroys Temperature is 935 DEG C.
(3) preparation of Y/ASA composites：In addition to surfactant is not added with, with (4) the step of embodiment 4.Mesoporous part For sieve and silica-sesquioxide, silica alumina ratio 5.5:1, mesoporous aperture is 3.2~6.5nm, NaY molecular sieve in Y/ASA composites 1050 DEG C of differential thermal fail temperature, texture property is shown in Table 1.
Comparative example 3
The method provided by CN 201010514225.0 synthesizes NaY molecular sieve and prepares Y/ASA composites.
(1) directed agents are synthesized：Take 48g waterglass (modulus 3.0), add 8g polyethylene glycol PEG-2000, at 15 DEG C with 200 turns/r/min mixing speed stirring 1h, obtains solution A；7.8g sodium hydroxides are dissolved in 24mL water, add meta-aluminic acid Sodium 1.6g, stir to sodium metaaluminate and all dissolve, obtain solution B；Solution A is stirred under 3000 turns/r/min mixing speed, Solution B is poured into solution A, continues to stir 1.5h under 3000 turns/r/min mixing speeds, finally at 15 DEG C with 200 turns/ R/min mixing speeds stir aging 12h, and 20.4mL water is supplemented after aging, continue to stir speed at 15 DEG C with 200 turns/r/min Degree stirring 0.5h.In addition to PEG-2000, the mol ratio of remaining each component is 18Na2O:Al2O3:22SiO2:426H2O.Place 10h It is standby.
(2) NaY type molecular sieves are synthesized：3g sodium hydroxides are dissolved in 23.3mL water, 3.7g sodium metaaluminates is added, stirs Mix to sodium metaaluminate and all dissolve, add 10.5g polyethylene glycol 2000s (PEG-2000) under agitation to whole dissolvings, obtain solution C；15g aluminum sulfate is dissolved in 25mL water, obtains solution D.C solution is stirred with 3000r/min mixing speed, sequentially adds water Glass solution 90g, directed agents 10.6g, solution D and solution C, obtain colloidal sol E.Colloidal sol E is stirred at 15 DEG C with 3000r/min clocks Speed stirs 20min, then stirs 1h with 200 turns/min mixing speeds, obtains colorless gel.Obtained colorless gel is transferred to In the synthesis reactor of inner liner polytetrafluoroethylene, the hydrothermal crystallizing 32h at 104 DEG C, NaY type molecular sieves are obtained.
The relative crystallinity of gained nano NaY molecular sieve is 82%, framework si-al ratio 5.0, particle diameter are 20~100nm, Differential thermal fail temperature is 900 DEG C.
(3) preparation of Y/ASA composites：In addition to surfactant is not added with, with (4) the step of embodiment 4.Mesoporous part For sieve and silica-sesquioxide, silica alumina ratio 5:1, mesoporous aperture is 6.2~8.2nm, the difference of NaY molecular sieve in Y/ASA composites 985 DEG C of heat damage temperature, texture property is shown in Table 1.
The Y/Sm of table 12O3The texture property of/ZSM-22/ZSM-5/ASA composites
The Y/Sm prepared it can be seen from the result of table 1 using the method for the present invention2O3/ ZSM-22/ZSM-5/ASA is compound The differential thermal fail temperature of NaY molecular sieve in material is improved.Y/Sm prepared by the present invention2O3/ZSM-22/ZSM-5/ ASA composite material has larger total pore volume and mesoporous pore volume, and mesoporous average pore size is 3~10nm and is the mesoporous knot of rule Structure, open space is provided for organic macromolecule conversion, is advantageous to the Efficient Conversion of heavy oil molecules.And prepared in composite During, the random distribution of mesoporous pore size for the composite for being not added with surface-active and preparing.

Claims (8)

  1. A kind of 1. Y/Sm2O3The preparation method of/ZSM-22/ZSM-5/ASA composites, comprises the following steps：
    (1) prepares directed agents：
    Sodium hydroxide and silicon source are added to the water, or sodium hydroxide is added to the water to after being completely dissolved and adds aluminium Source, sodium aluminate solution A is formed, Al in solution A2O3Content be 2.5~10wt%, Na2O content is 8~35wt%；Stirring Mix it is lower solution A and water glass solution are added sequentially in deionized water, after stirring, the static ageing at 15~50 DEG C 0.5~60h, directed agents are made；The mol ratio of each component is Na in directed agents2O:Al2O3:SiO2:H2O=10~20:1:14~ 18:240~440；
    (2).Sm2O3The preparation of/ZSM-22/ZSM-5 presomas：
    First, using class solid-phase synthesis, one-pot solid content 50%~80%, with silochrom, sodium metaaluminate, deionized water, Trimethylamine and hexamethylene diamine are raw material, at 100~180 DEG C, 10~48h of thermostatic crystallization, synthesize ZSM-22/ZSM-5 molecular sieve pulps；
    Secondly, by samaric nitrate：Tetraethyl orthosilicate：ZSM-22/ZSM-5 molecular sieve pulps：Aqueous solution mass ratio is 1~5:1~ 5:1~5：1~10, samaric nitrate, tetraethyl orthosilicate, ZSM-22/ZSM-5 molecular sieve pulps are sequentially added in the aqueous solution, heated To 70~80 DEG C, constant temperature stirs 1~10h, obtains Sm2O3/ ZSM-22/ZSM-5 presomas E, the aqueous solution are 1~5wt% nitre The mixed aqueous solution of acid and 1~5wt% citric acids；
    (3) prepares synthesis Y/Sm2O3The reactant mixture of/ZSM-22/ZSM-5 composite molecular screens：
    Silicon source is dissolved in water, forms Al2O3Content is 1~4wt% solution B；Sodium hydroxide and silicon source are added to water In, or sodium hydroxide is added to the water to after being completely dissolved and adds silicon source, forms sodium aluminate solution C, Al in solution C2O3 Content be 3~9wt%, Na2O content is 1~20wt%；By the directed agents, the solution B, the solution C and it is described before Drive body E, which is added in water glass solution, is made synthesis Y/Sm2O3The reactant mixture of/ZSM-22/ZSM-5 composite molecular screens；With anti- The weight of mixture is answered to be counted for 100wt%, the addition of directed agents is 0.5~20wt%, obtains synthesizing Y/Sm2O3/ZSM-22/ The reactant mixture of ZSM-5 composite molecular screens, the mol ratio of each component are：Na2O:Al2O3:SiO2:Sm2O3:H2O=3~10: 1:8~18:0.01~0.06:180~320；
    (4) hydrothermal crystallizings synthesize：
    The synthesis Y/Sm that step (3) is obtained2O3The reactant mixture of/ZSM-22/ZSM-5 composite molecular screens is at 80~140 DEG C 8~72h of crystallization, obtains Y/Sm2O3/ ZSM-22/ZSM-5 composite molecular screen slurries；
    (5).Y/Sm2O3The preparation of/ZSM-22/ZSM-5/ASA composites：
    Surfactant is added to Y/Sm2O3In/ZSM-22/ZSM-5 composite molecular screen slurries, alkaline aluminium is added while stirring Source solution, and be 7~9 with the pH value of phosphoric acid regulation system, solid mixture matter is obtained, finally mixes solid obtained above Material filtering, washing, 100~150 DEG C of dry 4~10h, 400~600 DEG C of 2~8h of roasting, obtain Y/Sm2O3/ZSM-22/ZSM- 5/ASA composites.
  2. 2. Y/Sm according to claim 12O3The preparation method of/ZSM-22/ZSM-5/ASA composites, its feature exist In：Surfactant described in step (5) is one or both of CTAB, P123 and F127.
  3. 3. Y/Sm according to claim 12O3The preparation method of/ZSM-22/ZSM-5/ASA composites, its feature exist In：The addition of surfactant accounts for Y/Sm in step (5)2O3The 1 of/ZSM-22/ZSM-5/ASA composite quality~ 6wt%.
  4. A kind of 4. Y/Sm2O3/ ZSM-22/ZSM-5/ASA composites, it is the Y/Sm described in any one of claims 1 to 32O3/ Y/Sm made from ZSM-22/ZSM-5/ASA preparation method2O3/ ZSM-22/ZSM-5/ASA composites.
  5. 5. Y/Sm according to claim 42O3/ ZSM-22/ZSM-5/ASA composites, it is characterised in that：Y/Sm2O3/ The content of Y molecular sieve is 10~90wt% in ZSM-22/ZSM-5/ASA composites, remaining be sieve and silica-sesquioxide, samarium oxide, ZSM-22 and ZSM-5.
  6. 6. Y/Sm according to claim 42O3/ ZSM-22/ZSM-5/ASA composites, it is characterised in that：Y/Sm2O3/ The SiO of sieve and silica-sesquioxide in ZSM-22/ZSM-5/ASA composites2With Al2O3Mol ratio be 1~10：1.
  7. 7. Y/Sm according to claim 42O3/ ZSM-22/ZSM-5/ASA composites, it is characterised in that：Y/Sm2O3/ Mesoporous mesoporous for rule in ZSM-22/ZSM-5/ASA composites, total pore volume is 0.46~0.58mL/g, and Micropore volume is 0.20~0.30mL/g, mesoporous pore volume are 0.24~0.33mL/g.
  8. 8. Y/Sm according to claim 42O3/ ZSM-22/ZSM-5/ASA composites, it is characterised in that：Y/Sm2O3/ ASA regular mesoporous pore size is between 3~10nm in ZSM-22/ZSM-5/ASA composites.
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CN101239325A (en) * 2007-02-09 2008-08-13 中国石油化工股份有限公司 Montmorillonite/ZSM-5 molecular sieve composite material and preparation thereof
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