CN107519922B - Y/Gd2O3/ ZSM-23/ZSM-5/ASA composite material and preparation method - Google Patents
Y/Gd2O3/ ZSM-23/ZSM-5/ASA composite material and preparation method Download PDFInfo
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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
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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
- 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
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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
- 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
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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
- B01J29/08—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
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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
- B01J29/40—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
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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
- B01J29/70—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
- B01J29/7096—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
Abstract
The present invention provides one kind to contain regular mesoporous Y/Gd2O3The preparation method of/ZSM-23/ZSM-5/ASA composite material, comprising: preparation directed agents prepare Gd2O3/ ZSM-23/ZSM-5 presoma synthesizes Y/Gd using hydrothermal crystallization method2O3Then surfactant and alkaline silicon source solution is added in/ZSM-23/ZSM-5 composite molecular screen in the slurries containing molecular sieve, adjust pH value, after precipitating product it is washed, it is dry, roast to get Y/Gd2O3/ ZSM-23/ZSM-5/ASA composite material.The differential thermal fail temperature of Y molecular sieve can be greater than 950 DEG C in the composite material that this method obtains, crystal grain is maintained at 400nm hereinafter, composite material has the characteristics that the pore size distribution of micropore-mesopore, and in surface A SA it is mesoporous for rule it is mesoporous, change synthetic technological condition, mesoporous pore size can be made adjustable.
Description
Technical field
The present invention provides a kind of Y/Gd2O3/ ZSM-23/ZSM-5/ASA composite material and preparation method, specifically, being
One kind is by Y molecular sieve, Gd2O3, ZSM-23/ZSM-5 molecular sieve and amorphous silica-alumina (ASA) be through composite wood made of in-stiu coating
Material.
Background technique
Molecular sieve complex, which refers to, is incorporated in one by molecule, atom or interionic effect by molecular sieve and other materials
The composite material risen.Regular material with meso-hole structure such as MCM-41 mesopore molecular sieve is suitble to because of its biggish cellular structure
In the conversion of organic macromolecule, but its poor thermal stability, hydrothermal stability and weaker acidity limit this kind of materials
In the application of catalytic field.The research of micropore-mesopore composite material 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 is no longer satisfied 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 since micro porous molecular sieve mostly has that 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, can then reduce the utilization rate of acidic site inside micro porous molecular sieve duct in this way, simultaneously
The duct diffusional resistance of narrow elongate is larger, influence reaction product molecule quick diffusion overflow, be easy to cause drastic cracking and
Green coke.Although and mesopore molecular sieve can make up the limitation that micro porous molecular sieve is spread in reactant and reaction product, be situated between
The structural stability of porous molecular sieve is often poor, also limits its catalytic applications.
CN 200810012192 provides a kind of preparation method of Y molecular sieve/silicon dioxide composite material, by Y type molecule
Sieve, sodium hydroxide, distilled water, template and silicon source are uniformly mixed under stirring, and reaction mixture gel, each component is made
Mol ratio are as follows: (0-1.3) Na2O:(34.4-110)H2O: (0.75-11.3)SiO2: (0.046-0.7) R, R is template.
The gel 12~70h of crystallization at 80-180 DEG C, is filtered, is washed, and hud typed composite material is obtained.Y molecular sieve is compound
Content in material is in 10~30wt%, and the partial size of composite material is at 2~10 μm.Y type molecular sieve is not involved in dioxy in this method
The outgrowth of SiClx, without chemical bond between Y type molecular sieve and silica, silica cannot provide acidity, each
It can only play the role of selecting type in kind catalysis reaction, so the acidity of composite material can only be realized by modulation Y molecular sieve.But it is mesoporous
It is irregular multi-stage porous.
Liu et al. is in document Journal of American Chemical Society (2000,122:8791-8792)
In describe a kind of method for preparing mesoporous material using Y molecular sieve secondary structure unit: first by NaOH, NaAlO2、H2O and
Waterglass mixing, is made containing 27wt%SiO2With the Y molecular sieve seed-solution of 14 wt%NaOH, mould is introduced into seed-solution
Plate agent CTAB and dilution heat of sulfuric acid, the pH value for adjusting seed-solution is 9,100 DEG C of crystallization 20h, in crystallization process in seed-solution
Y molecular sieve secondary structure unit be assembled into the composite material with hexagonal mesoporous structure, Al- under the action of template CTAB
MSU-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 amorphous knot
Structure, hydrothermal stability are poor.
Zhang etc. describes one kind in document Applied Catalysis A:General (2008,345:73-79)
Y/MCM-48 is micro--preparation method of mesoporous composite material: NaY crystal seed is added in the precursor sol of MCM-48, presoma is molten
Unclassified stores forms in liquid are as follows: 1TEOS:0.415CTAB:0.48NaOH:55H2O, after mixed liquor stirs 50min, at 110 DEG C
For a period of time, suction filtration, washing obtain solid product to lower hydrothermal crystallizing, and 550 DEG C of roasting 6h obtain Y/MCM-48 in air atmosphere
Composite molecular screen.Although the mesoporous wall thickness of the MCM-48 molecular sieve of this method preparation is increased, its hole wall is still nothing
Amorphous configuration, therefore poor be still of hydrothermal stability restricts its major reason applied.
CN102000604A provides one kind using kaolin as raw material, and inorganic silicate is to add silicon source, microwave method preparation
The method of Y/MCM-41 composite molecular screen.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 screen has micro--mesoporous double-pore structure, and the specific surface area of sample is greater than 550m2/ g, average pore size are about
2.7 nm, sample have regular hexagonal mesoporous structure.Although the MCM-41 molecular sieve hole wall of this method preparation introduces Y type
Molecular sieve secondary structure unit, but thermal stability is still short of, and collapse temperature is lower than 800 DEG C.
CN101172244 provides a kind of preparation method of montmorillonite/Y molecular sieve composite material.By by montmorillonite
Grain is uniformly mixed with Y molecular sieve gel, then carries out crystallization, and is filtered, washed and dried drying and the montmorillonite/Y molecule is made
Sieve composite material.Composite material made from the method for the present invention, while there is the structure feature of montmorillonite and Y molecular sieve, montmorillonite
With Y molecular sieve alternate, Y molecular sieve is grown on montmorillonite microballoon, but this method preparation composite material in Y molecular sieve skeleton
Sial is relatively low, and it is poor to may cause its hydrothermal stability.
CN101172243 provides a kind of preparation method of mesoporous/micropore molecular sieve composite material.The composite material is logical
It crosses to mix adobe isomery material (PCHs) with micro porous molecular sieve gel and carry out made from in-situ crystallization.Invention preparation
In composite material, micro porous molecular sieve is wrapped in adobe isomery surrounding materials, which has micro porous molecular sieve simultaneously
Crystal structure and adobe isomery material meso-hole structure, belong to porosity Composite material.Matched in composite material according to gel
It can be crystallized to obtain the micro porous molecular sieves such as Y type, ZSM-5 type, β type than difference.The stability that this method prepares composite material is poor.
CN200610165597.0 provides a kind of preparation side of nano molecular sieve/sieve and silica-sesquioxide composite catalyzing material
Method first synthesizes nano molecular sieve using directing agent method, and the precipitation step in synthesis is handled using microwave and/or ultrasonic wave,
Then the mixture aqueous solution of waterglass and silicon source is 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 to get the composite catalyzing material, wherein silicon source is selected from sodium metaaluminate or aluminum sulfate,
The particle that this method sieves products molecule is maintained at 100nm or less and nano molecular sieve therein is not easy to assemble, without
Acidic sol process and avoid molecular sieve by acid destroy.The composite material is suitable for the catalytic cracking of heavy oil macromolecular and hydrogen is added to split
Change reaction.
Landau etc. describes one in document Applied Catalysis A:General (1994,115:L7-L14)
The method of kind fabricated in situ nano molecular sieve ZSM-5 in the duct of Silica hydrogel forms 3~5 μm of partial size in the outer surface of silica gel
Zeolite, form 0.5~2 μm of partial size of zeolite in the macropore of silica gel, form partial size 0.02~0.035 in the mesoporous of silica gel
μm zeolite.
Landau etc. described in Chem.Mater (1999,11:2030-2037) it is a kind of by granular size be 10~
The beta-molecular sieve of 15nm is stable at the method in Aluminum sol: being first dispersed in water gel aluminum hydroxide filter cake, pH=is made
9.05 aluminium hydroxide lotion: by the beta-molecular sieve slurries of its pH=12.7 at room temperature according to Al2O3/ molecular sieve=1:1 weight
Than mixing, to pH=11.8, (dust technology is added after described mixing in the preparation of another two batches sample makes the pH for mixing rear slurry to amount
Respectively 11.0 and 10.0)；After stirring 2h, aging is for 24 hours at room temperature；Precipitating is isolated by decantation, and is dried in vacuo at 50 DEG C
It is 70wt% to water content.Extrusion granulation and in 120 DEG C of dry 5h, then temperature-programmed calcination.The disadvantages of the method are as follows preparation
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 technology time is long.CN102000604A introduces microwave processing process during synthesizing Y/MCM-41 composite molecular screen,
Ancillary equipment is increased, the cost for synthesizing composite molecular screen is increased considerably.In addition mentioned in document above or patent it is micro--
Mesoporous silica-alumina materials part in mesoporous composite material is irregular hole.
Summary of the invention
The purpose of the present invention is the preparation processes by improving ASA, obtain the Y/Gd that ASA has rule mesoporous2O3/ZSM-
23/ZSM-5/ASA composite material.
The present invention provides a kind of Y/Gd2O3The preparation method of/ZSM-23/ZSM-5/ASA composite material, includes 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 is added again
Enter silicon source, forms 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 stiring, it is after mixing evenly, static old at 15~50 DEG C
Change 0.5~60h, directed agents are made；The molar ratio of each component is Na in directed agents2O:Al2O3:SiO2: H2O=10~20:1:14
~18:240~440；
(2).Gd2O3The preparation of/ZSM-23/ZSM-5 presoma:
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-23/ZSM-5 molecular sieve pulp；
By gadolinium nitrate: ethyl orthosilicate: ZSM-23/ZSM-5 molecular sieve pulp: aqueous solution mass ratio is 1~5:1~5:
Gadolinium nitrate, ethyl orthosilicate, ZSM-23/ZSM-5 molecular sieve pulp are sequentially added in aqueous solution, are heated to by 1~5:1~10
70~80 DEG C, constant temperature stirs 1~10h, obtains Gd2O3/ ZSM-23/ZSM-5 presoma E, the aqueous solution are 1~5wt% nitre
The mixed aqueous solution of acid and 1~5wt% citric acid；
(3) preparation synthesis Y/Gd2O3The reaction mixture of/ZSM-23/ZSM-5 composite molecular screen:
Silicon source is dissolved in water, Al is formed2O3Content is the solution B of 1~4wt%；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
The presoma E is added to the reaction mixing that synthesis Y/Gd2O3/ZSM-23/ZSM-5 composite molecular screen is made in water glass solution
Object；By the weight of reaction mixture for 100wt% in terms of, the additional amounts of directed agents is 0.5~20wt%, obtains synthesis Y/Gd2O3/
The reaction mixture of ZSM-23/ZSM-5 composite molecular screen, the molar ratio of each component are as follows: Na2O:Al2O3:SiO2:Gd2O3:H2O=
3~10:1:8~18:0.01~0.06:180~320；
(4) hydrothermal crystallizing synthesizes:
The synthesis Y/Gd that step (3) is obtained2O3The reaction mixture of/ZSM-23/ZSM-5 composite molecular screen is 80~140
8~72h of crystallization at DEG C, obtains Y/Gd2O3/ ZSM-23/ZSM-5 composite molecular screen slurries；
(5).Y/Gd2O3The preparation of/ZSM-23/ZSM-5/ASA composite material:
Surfactant is added to Y/Gd2O3In/ZSM-23/ZSM-5 composite molecular screen slurries, alkali is added while stirring
Property silicon source solution, and with the pH value of phosphoric acid regulation system be 7~9, solid mixture matter is obtained, finally by solid obtained above
Compounding substances are filtered, washed, 100~150 DEG C of dry 4~10h, 400~600 DEG C of 2~8h of roasting, obtain Y/Gd2O3/ZSM-
23/ZSM-5/ASA composite material.
Y/Gd of the present invention2O3The preparation method of/ZSM-23/ZSM-5/ASA composite material, in which: in step (5)
The surfactant is preferably one or both of CTAB, P123 and F127.
Y/Gd of the present invention2O3The preparation method of/ZSM-23/ZSM-5/ASA composite material, in which: in step (5)
The additional amount of surfactant preferably accounts for Y/Gd2O31~6wt% of/ZSM-23/ZSM-5/ASA composite material quality.
The present invention also provides a kind of Y/Gd2O3/ ZSM-23/ZSM-5/ASA composite material is above-mentioned Y/Gd2O3/ZSM-
Y/Gd made from the preparation method of 23/ZSM-5/ASA2O3/ ZSM-23/ZSM-5/ASA composite material.
Y/Gd of the present invention2O3/ ZSM-23/ZSM-5/ASA composite material, in which: Y/Gd2O3/ZSM-23/ZSM-
The content of Y molecular sieve is preferably 10~90 wt% in 5/ASA composite material, remaining is sieve and silica-sesquioxide, samarium oxide, ZSM-23
And ZSM-5.
Y/Gd of the present invention2O3/ ZSM-23/ZSM-5/ASA composite material, in which: Y/Gd2O3/ZSM-23/ZSM-
The SiO of sieve and silica-sesquioxide in 5/ASA composite material2With Al2O3Molar ratio be preferably 1~10:1.
Y/Gd of the present invention2O3/ ZSM-23/ZSM-5/ASA composite material, in which: Y/Gd2O3/ZSM-23/ZSM-
Mesoporous preferably rule in 5/ASA composite material is mesoporous, and total pore volume is preferably 0.46~0.58mL/g, and Micropore volume is preferably
0.20~0.30mL/g, it is preferably 0.24~0.33mL/g that mesoporous hole, which holds,.
Y/Gd of the present invention2O3/ ZSM-23/ZSM-5/ASA composite material, in which: Y/Gd2O3/ZSM-23/ZSM-
The regular mesoporous pore size of ASA is preferably between 3~10nm in 5/ASA composite material.
The present invention can be with details are as follows:
Surfactant of the present invention is mainly tri- kinds of nonionic surfactants of CTAB, P123 and F127,
It can be used that one such or two kinds carry out Y/Gd when use2O3The preparation of/ZSM-23/ZSM-5/ASA composite material.
Y/Gd of the present invention2O3Silicon source used in/ZSM-23/ZSM-5/ASA composite material preparation process is ability
Domain is common, such as sodium metaaluminate, boehmite, boehmite, aluminum nitrate, aluminum sulfate, aluminium hydroxide and/or gibbsite,
Alkaline silicon source be it is commonly used in the art, aluminium therein from sodium metaaluminate or can be dissolved in sodium hydroxide solution and intend thin water
Aluminium stone, boehmite, aluminium hydroxide, gibbsite.Acid is acid generally in the art, preferably inorganic acid, such as phosphoric acid.
The Y/Gd prepared using method of the invention2O3The heat of NaY molecular sieve in/ZSM-23/ZSM-5/ASA composite material
Stability is maintained, the product Y/Gd that this method obtains2O3Y type molecular sieve in/ZSM-23/ZSM-5/ASA composite material
Differential thermal fail temperature can be greater than 960 DEG C, even up to 1008~1100 DEG C；Maximum crystal grain is maintained at 400nm or less.
The present invention also provides one kind by Y/Gd obtained by the above method2O3/ ZSM-23/ZSM-5/ASA composite material.
Y/Gd2O3The content of Y molecular sieve is preferably 10~90wt% in/ZSM-23/ZSM-5/ASA composite material, remaining
For sieve and silica-sesquioxide, Al2O3、SiO2, ZSM-23, ZSM-5 and samarium oxide, the SiO of sieve and silica-sesquioxide2With Al2O3Molar ratio most
It is well 1:1~10:1.
Y/Gd of the invention2O3NaY molecular sieve differential thermal fail temperature is reachable in/ZSM-23/ZSM-5/ASA composite material
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 0.24~0.33mL/g of Kong Rongwei.
In conclusion Y/Gd produced by the present invention2O3NaY molecular sieve has in/ZSM-23/ZSM-5/ASA composite material
Crystal grain small (100~400nm), framework si-al ratio are high, thermal stability improves (than the differential thermal fail temperature of corresponding NaY molecular sieve
High 5 DEG C or more) and the mesoporous composition of rule less than the micropore of 1nm and 3~10nm micro--composite mesoporous pore structure the characteristics of.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Analysis test method:
The measurement of the relative crystallinity and framework si-al ratio of NaY molecular sieve: using the production of Bruker company, Germany
D8Advance X-ray diffractometer, determination condition are as follows: CuK α radiation, pipe press 40kV, tube current 40mA.Its measuring method according to
SH/T 0340-92 standard method measurement (see " standard of chemical industry compilation ", China Standards Press publishes for 2000), bone
The measurement of frame silica alumina ratio be by SH/T 0399-92 standard method, (see " standard of chemical industry compilation ", China Standards Press,
2000 publish) measurement and according to the 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 scanning electron microscope of Britain LEO company production, acceleration voltage 20kV, sample
It is gold-plated with physical method before testing.
Thermal stability determination carries out on German Nai Chi instrument company STA 409PC type thermal analyzer.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 hole hold test: the measurement of the specific surface area and pore structure of catalyst and molecular sieve exists
It is carried out in the ASAP2020M specific surface and lacunarity analysis instrument of the production of Micromeritics company, according to BET method calculating ratio table
Area；BJH method calculated pore.
Embodiment 1:
Y/Gd2O3The synthesis of/ZSM-23/ZSM-5/ASA composite material
(1) it the preparation of directed agents: takes 24.7g sodium hydroxide (Beijing Chemical Plant analyzes pure) to be added in 45.9g water, stirs
It mixes to sodium hydroxide and all dissolves, add 6.5g sodium metaaluminate (research institute, Shandong Aluminium Industrial Corp, industrial goods, Al2O3Content
49.1wt%), stirring is all dissolved to sodium metaaluminate, obtains sodium aluminate solution A.By 70g solution A and 100g waterglass (Beijing
Red Star water glass plant, SiO2Content 27.81wt%, Na2O content 8.74wt%) it successively pours into 65.5g deionized water, stirring is equal
After even at 30 DEG C static ageing 22h, obtain directed agents.The molar ratio of directed agents each component are as follows: 16Na2O:Al2O3:16SiO2:
330H2O。
(2)Gd2O3The preparation of/ZSM-23/ZSM-5 presoma: using class solid-phase synthesis (one-pot solid content 60%), with
Silochrom, sodium metaaluminate, deionized water, trimethylamine and hexamethylene diamine are raw material, at 100 DEG C, thermostatic crystallization 48h, synthesize ZSM-
23/ZSM-5 molecular sieve pulp.By gadolinium nitrate: ethyl orthosilicate: ZSM-23/ZSM-5 molecular sieve: water-soluble liquid proportional is 1g:3g:
Gadolinium nitrate, ethyl orthosilicate, ZSM-23/ZSM-5 molecular sieve are sequentially added 1wt% nitric acid and 5wt% citric acid by 4g:10g
In aqueous solution, 70 DEG C are heated to, constant temperature stirs 1h, obtains Gd2O3/ ZSM-23/ZSM-5 presoma E；
(3)Y/Gd2O3The preparation of/ZSM-23/ZSM-5 composite molecular screen: 14.5g aluminum sulfate is dissolved in 50.6g water,
Form Al2O3Content is the aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g meta-aluminic acid
(the same step 1) of specification, stirring form sodium aluminate solution C to being completely dissolved to sodium.By 10.3g directed agents, solution B and solution C and
Presoma E according to conventional NaY molecular sieve preparation step is added sequentially to 75g waterglass, and (specification is stirred evenly in step 1)
Add 48.5g water again afterwards, synthesis Y/Gd is made2O3The reaction mixture of/ZSM-23/ZSM-5 composite molecular screen.Mole of each component
Than for 6.0Na2O:Al2O3:12SiO2:0.01Gd2O3: 260H2O；Reaction mixture is gone in autoclave, it is brilliant at 105 DEG C
Change 22h.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries to get Y/Gd2O3/ ZSM-23/ZSM-5 is multiple
Close zeolite product.
Gained Y/Gd2O3Y molecular sieve relative crystallinity in //ZSM-23/ZSM-5 composite molecular screen is 90%, framework silicon
Aluminium ratio is 5.2, partial size 200nm, and differential thermal fail temperature is 950 DEG C.
(4)Y/Gd2O3The preparation of/ZSM-23/ZSM-5/ASA composite material: 0.8g sodium hydroxide is dissolved in 6.2g water
In, 1g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution D is obtained.The Y/Gd that step (3) is obtained2O3/ZSM-
23/ZSM-5 molecular sieve and mother liquor are cooled to room temperature, and are transferred in beaker, static layering, take out upper layer mother liquor 32mL, then to
Y/Gd2O3It is added in the mix suspending object of/ZSM-23/ZSM-5 molecular sieve and mother liquor and contains 1.3g surfactant P123 aqueous solution
And 30min is stirred at 20 DEG C, solution D is added later, continues to stir 1h after adding, adds phosphoric acid to the mixing of above-mentioned stirring
In object, the pH value of regulation system is 7.Finally solid matter obtained above is filtered, washed, 125 DEG C of dry 7h, 500 DEG C of roastings
4h is burnt, Y/Gd is obtained2O3/ ZSM-23/ZSM-5/ASA composite material, intermediary hole part are sieve and silica-sesquioxide, sieve and silica-sesquioxide
Molar ratio be 8.5:1, mesoporous mesoporous for rule, the content of Y molecular sieve is 62wt%. Y/Gd2O3/ZSM-23/ZSM-5/ASA
The differential thermal fail temperature of NaY molecular sieve is 1010 DEG C in composite material, 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: taking 32.1g sodium hydroxide to be added in 45.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and 112g
Waterglass successively pours into 79g deionized water, and the static ageing 22h at 30 DEG C, obtains directed agents after mixing evenly.Directed agents each group
The molar ratio divided are as follows: 20Na2O:Al2O3:18SiO2:440H2O。
(2)Gd2O3The preparation of/ZSM-23/ZSM-5 presoma: 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-
23/ZSM-5 molecular sieve pulp.By gadolinium nitrate: ethyl orthosilicate: ZSM-23/ZSM-5 molecular sieve: water-soluble liquid proportional is 5g:5g:
Gadolinium nitrate, ethyl orthosilicate, ZSM-23/ZSM-5 molecular sieve are sequentially added 5wt% nitric acid and 1wt% citric acid by 5g:25g
In aqueous solution, 80 DEG C are heated to, constant temperature stirs 10h, obtains Gd2O3/ ZSM-23/ZSM-5 presoma E；
(3)Y/Gd2O3The preparation of/ZSM-23/ZSM-5 composite molecular screen: 14.5g aluminum sulfate is dissolved in 50.6g water,
Form Al2O3Content is the aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g meta-aluminic acid
(the same step 1) of specification, stirring form sodium aluminate solution C to being completely dissolved to sodium.By 10.3g directed agents, solution B and solution C and
Presoma E according to conventional NaY molecular sieve preparation step is added sequentially to 162g waterglass, and (for specification in step 1), stirring is equal
Add 48.5g water after even again, synthesis Y/Gd is made2O3The reaction mixture of/ZSM-23/ZSM-5 composite molecular screen.Each component rubs
You are than being 10Na2O:Al2O3:18SiO2:0.06Gd2O3: 320H2O；Reaction mixture is gone in autoclave, it is brilliant at 80 DEG C
Change 72h.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries to get Y/Gd2O3/ ZSM-23/ZSM-5 is multiple
Close zeolite product.
Gained Y/Gd2O3Y molecular sieve relative crystallinity in/ZSM-23/ZSM-5 composite molecular screen is 90%, framework silicon
Aluminium ratio is 5.2, partial size 200nm, and differential thermal fail temperature is 950 DEG C.
(4)Y/Gd2O3The preparation of/ZSM-23/ZSM-5/ASA composite material: 0.8g sodium hydroxide is dissolved in 6.2g water
In, 1g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution D is obtained.The Y/Gd that step (3) is obtained2O3/ZSM-
23/ZSM-5 molecular sieve and mother liquor are cooled to room temperature, and are transferred in beaker, static layering, take out upper layer mother liquor 32mL, then to
Y/Gd2O3It is added in the mix suspending object of/ZSM-23/ZSM-5 molecular sieve and mother liquor and contains 7.8g surfactant P123 aqueous solution
And 30min is stirred at 20 DEG C, solution D is added later, continues to stir 1h after adding, adds phosphoric acid to the mixing of above-mentioned stirring
In object, the pH value of regulation system is 7.Finally solid matter obtained above is filtered, washed, 150 DEG C of dry 4h, 600 DEG C of roastings
2h is burnt, Y/Gd is obtained2O3/ ZSM-23/ZSM-5/ASA composite material, intermediary hole part are sieve and silica-sesquioxide, sieve and silica-sesquioxide
Molar ratio be 8.5:1, mesoporous mesoporous for rule, the content of Y molecular sieve is 62wt%. Y/Gd2O3/ZSM-23/ZSM-5/ASA
The differential thermal fail temperature of NaY molecular sieve is 1010 DEG C in composite material, 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: taking 24.7g sodium hydroxide to be added in 45.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and 100g
Waterglass successively pours into 65.5g deionized water, and the static ageing 22h at 30 DEG C, obtains directed agents after mixing evenly.Directed agents are each
The molar ratio of component are as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2)Gd2O3The preparation of/ZSM-23/ZSM-5 presoma: using class solid-phase synthesis (one-pot solid content 50%), with
Silochrom, sodium metaaluminate, deionized water, trimethylamine and hexamethylene diamine are raw material, at 180 DEG C, thermostatic crystallization 10h, synthesize ZSM-
23/ZSM-5 molecular sieve pulp.By gadolinium nitrate: ethyl orthosilicate: ZSM-23/ZSM-5 molecular sieve pulp: water-soluble liquid proportional is 2g:
Gadolinium nitrate, ethyl orthosilicate, ZSM-23/ZSM-5 molecular sieve are sequentially added 1wt% nitric acid and 1wt% lemon by 4g:3g:10g
In the aqueous solution of acid, 75 DEG C are heated to, constant temperature stirs 10h, obtains Gd2O3/ ZSM-23/ZSM-5 presoma E；
(3)Y/Gd2O3The preparation of/ZSM-23/ZSM-5 composite molecular screen: 14.5g aluminum sulfate is dissolved in 50.6g water,
Form Al2O3Content is the aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g meta-aluminic acid
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 step is added sequentially in 75g waterglass, adds 48.5g water again after mixing evenly, and synthesis Y/ is made
Gd2O3The reaction mixture of/ZSM-23/ZSM-5 molecular sieve.The molar ratio of each component is 6.0Na2O:Al2O3:12SiO2:
0.02Gd2O3:260H2O；Reaction 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, are filtered, washed, dry to get Y/Gd2O3/ ZSM-23/ZSM-5 composite molecular screen product.
Gained Y/Gd2O3Y molecular sieve relative crystallinity in/ZSM-23/ZSM-5 composite molecular screen is 90%, framework silicon
Aluminium ratio is 5.2, partial size 200nm, and differential thermal fail temperature is 950 DEG C.
(4)Y/Gd2O3The preparation of/ZSM-23/ZSM-5/ASA composite material: 7.5g sodium hydroxide is dissolved in 58g water,
9.2g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution D is obtained.The Y/Gd that step (3) is obtained2O3/ZSM-
23/ZSM-5 molecular sieve and mother liquor are cooled to room temperature, and are transferred in beaker, at 25 DEG C, are sequentially added 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 solid matter obtained above is filtered, washed, 100 DEG C of dry 10h, 400 DEG C of roasting 8h, is obtained
Y/Gd2O3/ ZSM-23/ZSM-5/ASA composite material, intermediary hole part are sieve and silica-sesquioxide, and the molar ratio of sieve and silica-sesquioxide is
5:1, mesoporous mesoporous for rule, the content of Y molecular sieve is 35wt%.Y/Gd2O3In/ZSM-23/ZSM-5/ASA composite material
The differential thermal fail temperature of NaY molecular 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: taking 24.7g sodium hydroxide to be added in 45.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and 100g
Waterglass successively pours into 65.5g deionized water, and the static ageing 22h at 30 DEG C, obtains directed agents after mixing evenly.Directed agents are each
The molar ratio of component are as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2)Gd2O3The preparation of/ZSM-23/ZSM-5 presoma: using class solid-phase synthesis (one-pot solid content 65%), with
Silochrom, sodium metaaluminate, deionized water, trimethylamine and hexamethylene diamine are raw material, at 100 DEG C, thermostatic crystallization 48h, synthesize ZSM-
23/ZSM-5 molecular sieve pulp.By gadolinium nitrate: ethyl orthosilicate: ZSM-23/ZSM-5 molecular sieve pulp: water-soluble liquid proportional is 1g:
Gadolinium nitrate, ethyl orthosilicate, ZSM-23/ZSM-5 molecular sieve are sequentially added 1wt% nitric acid and 5wt% lemon by 1g:5g:10g
In the aqueous solution of acid, 100 DEG C are heated to, constant temperature stirs 10h, obtains Gd2O3/ ZSM-23/ZSM-5 presoma E；
(3)Y/Gd2O3The preparation of/ZSM-23/ZSM-5 composite molecular screen: 14.5g aluminum sulfate is dissolved in 50.6g water,
Form Al2O3Content is the aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g meta-aluminic acid
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 step is added sequentially in 75g waterglass, adds 48.5g water again after mixing evenly, and synthesis Y/ is made
Gd2O3The reaction mixture of/ZSM-23/ZSM-5 molecular sieve.The molar ratio of each component is 6Na2O:Al2O3:12SiO2:
0.01Gd2O3:260H2O；Reaction 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, are filtered, washed, dry to get Y/Gd2O3/ ZSM-23/ZSM-5 zeolite product.
Gained Y/Gd2O3The relative crystallinity of Y molecular sieve in/ZSM-23/ZSM-5 composite molecular screen is 90%, framework silicon
Aluminium ratio is 5.2, partial size 200nm, and differential thermal fail temperature is 950 DEG C.
(4)Y/Gd2O3The preparation of/ZSM-23/ZSM-5/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water
In, 8.8g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution D is obtained.The Y/Gd that step (3) is obtained2O3/
ZSM-23/ZSM-5 composite molecular screen and mother liquor are cooled to room temperature, and mother liquor 200mL are taken out, then by remaining mother liquor and Y/
Gd2O3The mixture of/ZSM-23/ZSM-5 composite molecular screen is transferred in beaker, is added while stirring at 25 DEG C and is contained P123
7.8g, F127 1.3g aqueous solution after mixing evenly, then successively solution D and phosphoric acid, the pH value of regulation system is 8.0.Finally
Solid matter obtained above is filtered, washed, 120 DEG C of dry 12h, 500 DEG C of roasting 8h, obtains Y/Gd2O3/ZSM-23/
ZSM-5/ASA composite material, intermediary hole part are sieve and silica-sesquioxide, and the silica alumina ratio of sieve and silica-sesquioxide is 1.5:1, mesoporous
It is mesoporous for rule, with Y/Gd2O3On the basis of/ZSM-23/ZSM-5 composite material, the content of Y type molecular sieve is 80wt%.Y/
Gd2O31027 DEG C of the differential thermal fail temperature of NaY molecular sieve in/ZSM-23/ZSM-5/ASA composite material, 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: taking 12.8g sodium hydroxide to be added in 45.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and
87.5g waterglass successively pours into 20.5g deionized water, and the static ageing 22h at 30 DEG C, obtains directed agents after mixing evenly.It leads
To the molar ratio of agent each component are as follows: 10Na2O:Al2O3:14SiO2:240H2O。
(2)Gd2O3The preparation of/ZSM-23/ZSM-5 presoma: 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-
23/ZSM-5 molecular sieve pulp.By gadolinium nitrate: ethyl orthosilicate: ZSM-23/ZSM-5 molecular sieve pulp: water-soluble liquid proportional is 1g:
Gadolinium nitrate, ethyl orthosilicate, ZSM-23/ZSM-5 molecular sieve are sequentially added 5wt% nitric acid and 5wt% lemon by 1g:5g:10g
In the aqueous solution of acid, 100 DEG C are heated to, constant temperature stirs 10h, obtains Gd2O3/ ZSM-23/ZSM-5 presoma E；
(3)Y/Gd2O3The preparation of/ZSM-23/ZSM-5 composite molecular screen: 14.5g aluminum sulfate is dissolved in 50.6g water,
Form Al2O3Content is the aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g meta-aluminic acid
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 step is added sequentially in 55g waterglass, adds 48.5g water again after mixing evenly, and synthesis Y/ is made
Gd2O3The reaction mixture of/ZSM-23/ZSM-5 molecular sieve.The molar ratio of each component is 3Na2O:Al2O3:8SiO2:
0.01Gd2O3:260H2O；Reaction mixture is gone in autoclave, crystallization is for 24 hours at 100 DEG C.Hydrothermal crystallizing finishes, and takes out and divides
Son sieve and mother liquor, are filtered, washed, dry to get Y/Gd2O3/ ZSM-23/ZSM-5 zeolite product.
Gained Y/Gd2O3The relative crystallinity of Y molecular sieve in/ZSM-23/ZSM-5 composite molecular screen is 90%, framework silicon
Aluminium ratio is 4.2, partial size 200nm, and differential thermal fail temperature is 950 DEG C.
(4)Y/Gd2O3The preparation of/ZSM-23/ZSM-5/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water
In, 8.8g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution D is obtained.The Y/Gd that step (3) is obtained2O3/
ZSM-23/ZSM-5 composite molecular screen and mother liquor are cooled to room temperature, and mother liquor 200mL are taken out, then by remaining mother liquor and Y/
Gd2O3The mixture of/ZSM-23/ZSM-5 composite molecular screen is transferred in beaker, is added while stirring at 25 DEG C and is contained P123
After mixing evenly, then successively solution D and phosphoric acid, the pH value of regulation system is 8.0 to the aqueous solution of 1.3g, F1277.8g.Finally will
Solid matter obtained above is filtered, washed, 120 DEG C of dry 7h, 500 DEG C of roasting 4h, obtains Y/Gd2O3/ZSM-23/ZSM-5/
ASA composite material, intermediary hole part are sieve and silica-sesquioxide, and the silica alumina ratio of sieve and silica-sesquioxide is 1.5:1, mesoporous for rule
It is mesoporous, with Y/Gd2O3On the basis of/ZSM-23/ZSM-5 composite material, the content of Y type molecular sieve is 80wt%.Y/Gd2O3/ZSM-
1027 DEG C of the differential thermal fail temperature of Y molecular sieve in 23/ZSM-5/ASA composite material, texture property is shown in Table 1.
Comparative example 1
Surfactant is not added using the condition of embodiment 4, but when preparing Y/ASA composite material.
(1) it the preparation of directed agents: takes 24.7g sodium hydroxide (Beijing Chemical Plant analyzes pure) to be added in 45.9g water, stirs
It mixes to sodium hydroxide and all dissolves, add 6.5g sodium metaaluminate (research institute, Shandong Aluminium Industrial Corp, industrial goods, Al2O3Content
49.1wt%), stirring is all dissolved to sodium metaaluminate, obtains sodium aluminate solution A.By 70g solution A and 100g waterglass (Beijing
Red Star water glass plant, SiO2Content 27.81wt%, Na2O content 8.74wt%) it successively pours into 65.5g deionized water, stirring is equal
After even at 30 DEG C static ageing 22h, obtain directed agents.The molar ratio of directed agents each component are as follows: 16Na2O:Al2O3:16SiO2:
330H2O。
(2) preparation of NaY type molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3Content is
The aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate (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 molecule
Sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g water again after mixing evenly, synthesis is made in step 1)
The reaction mixture of NaY molecular sieve.The molar ratio of each component is 6.2Na2O:Al2O3: 12SiO2:260H2O；By reaction mixture
It goes in autoclave, the crystallization 22h at 105 DEG C.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries, i.e.,
Obtain NaY type zeolite product.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, partial size are 200 nm, and differential thermal destroys
Temperature is 950 DEG C.
(3) preparation of Y/ASA composite material: in addition to surfactant is not added, with (4) the step of embodiment 4.Mesoporous hole
Diameter is 3.3~5.2nm.910 DEG C of the differential thermal fail temperature of NaY molecular sieve in Y/ASA composite material, texture property is shown in Table 1.
Comparative example 2
Small crystal grain NaY molecular sieve is prepared by the method for the embodiment 4 of CN 1033503C and prepares Y/ASA composite material.
(1) preparation of directed agents: taking 29.5g sodium hydroxide to be added in 75g water, and stirring to sodium hydroxide is all dissolved,
4.78g boehmite is added, stirring to boehmite is all dissolved, and sodium metaaluminate is obtained.200g waterglass is added to
1h is mixed in the sodium metaaluminate and 12g deionized water of above-mentioned preparation at 35 DEG C, is then made and rubs in 35 DEG C of static aging 6h
You are than being 16Na2O: Al2O3:15SiO2:320H2O, the conventional directed agents of light transmittance < 30%.
189g specification 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 mole group becomes 20.6Na2O:Al2O3:30SiO2:495H2O as clear as crystal improvement directing agent solution,
It is placed at room temperature for and uses afterwards for 24 hours.
(2) preparation of NaY type molecular sieve: according to molar ratio 3.84Na2O:Al2O3:12SiO2: 220H2The synthesizing formula of O,
By 250g specification waterglass same as described above, the improvement directed agents of the above-mentioned preparation of 510g, 160g Al2O3Content is 6.8wt%
Aluminum sulfate solution and 9.7g sodium aluminate solution (Al2O3Content 7.5wt%, Na2O content is 15wt%) 1h is mixed, so
After be warming up to 97 DEG C, crystallization 26h, it is filtering, dry.
The relative crystallinity of gained NaY molecular sieve is 79%, framework si-al ratio 5.8, partial size are 100 nm, and differential thermal destroys
Temperature is 935 DEG C.
(3) preparation of Y/ASA composite material: in addition to surfactant is not added, 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 composite material
1050 DEG C of differential thermal fail temperature, texture property is shown in Table 1.
Comparative example 3
By the method synthesis NaY molecular sieve that CN 201010514225.0 is provided and prepare Y/ASA composite material.
(1) directed agents are synthesized: taking 48g waterglass (modulus 3.0), adds 8g polyethylene glycol PEG -2000, at 15 DEG C
1h is stirred with the mixing speed of 200 turns/r/min, obtains solution A；7.8g sodium hydroxide is dissolved in 24mL water, is added partially
Sodium aluminate 1.6g, stirring to sodium metaaluminate are all dissolved, and solution B is obtained；Solution A is stirred under the mixing speed of 3000 turns/r/min
It mixes, solution B is poured into solution A, continuation stirs 1.5h under 3000 turns/r/min mixing speed, finally with 200 at 15 DEG C
Turn/r/min mixing speed stirring aging 12h, 20.4mL water is supplemented after aging, continuation is stirred at 15 DEG C with 200 turns/r/min
Mix speed stirring 0.5h.In addition to PEG-2000, the molar ratio of remaining each component is 18Na2O:Al2O3:22SiO2:426H2O.It places
10h is spare.
(2) it synthesizes NaY type molecular sieve: 3g sodium hydroxide being dissolved in 23.3mL water, 3.7g sodium metaaluminate is added, stirs
It mixes to sodium metaaluminate and all dissolves, 10.5g polyethylene glycol 2000 (PEG-2000) is added under stiring to whole dissolutions, obtains solution
C；15g aluminum sulfate is dissolved in 25mL water, solution D is obtained.C solution is stirred with the mixing speed of 3000r/min, is sequentially added
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 clock
Speed stirring 20min is mixed, then 1h is stirred with 200 turns/min mixing speed, obtains colorless gel.Obtained colorless gel is shifted
Into the synthesis reactor of inner liner polytetrafluoroethylene, the hydrothermal crystallizing 32h at 104 DEG C obtains NaY type molecular sieve.
The relative crystallinity of gained nano NaY molecular sieve is 82%, framework si-al ratio 5.0, partial size are 20~100nm,
Differential thermal fail temperature is 900 DEG C.
(3) preparation of Y/ASA composite material: in addition to surfactant is not added, 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 composite material
985 DEG C of heat damage temperature, texture property is shown in Table 1.
1 Y/Gd of table2O3The texture property of/ZSM-23/ZSM-5/ASA composite material
The Y/Gd prepared it can be seen from the result of table 1 using method of the invention2O3/ ZSM-23/ZSM-5/ASA is multiple
The differential thermal fail temperature of NaY molecular sieve in condensation material is improved.Y/Gd prepared by the present invention2O3/ZSM-23/ZSM-
5/ASA composite material has biggish total pore volume and mesoporous Kong Rong, and mesoporous average pore size is 3~10nm and is the mesoporous knot of rule
Structure provides open space for organic macromolecule conversion, is conducive to the Efficient Conversion of heavy oil molecules.And it is prepared in composite material
In the process, the random distribution of mesoporous pore size of composite material for being not added with surface-active and preparing.
Claims (7)
1. a kind of Y/ Gd2O3The preparation method of/ZSM-23/ZSM-5/ASA composite material, includes 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 forms sodium aluminate solution A, Al in solution A2O3Content be 2.5~10wt%, Na2O content is 8~35wt%；It is stirring
It is lower that solution A and water glass solution are added sequentially in deionized water, after mixing evenly, the static ageing 0.5 at 15~50 DEG C
Directed agents are made in~60h；The molar ratio of each component is Na in directed agents2O:Al2O3:SiO2: H2O=10~20:1:14~18:240
~440；
(2). Gd2O3The preparation of/ZSM-23/ZSM-5 presoma:
Firstly, using class solid-phase synthesis, one-pot solid content 50% ~ 80%, with silochrom, sodium metaaluminate, deionized water, front three
Amine and hexamethylene diamine are raw material, at 100 ~ 180 DEG C, 10 ~ 48h of thermostatic crystallization, synthesize ZSM-23/ZSM-5 molecular sieve pulp；
Secondly, pressing gadolinium nitrate: ethyl orthosilicate: ZSM-23/ZSM-5 molecular sieve pulp: aqueous solution mass ratio is 1 ~ 5:1 ~ 5:1
~ 5:1 ~ 10 sequentially add gadolinium nitrate, ethyl orthosilicate, ZSM-23/ZSM-5 molecular sieve pulp in aqueous solution, it is heated to 70 ~
80 DEG C, constant temperature stirs 1 ~ 10h, obtains Gd2O3/ ZSM-23/ZSM-5 presoma E, the aqueous solution be 1 ~ 5wt% nitric acid and 1 ~
The mixed aqueous solution of 5wt% citric acid；
(3) preparation synthesis Y/ Gd2O3The reaction mixture of/ZSM-23/ZSM-5 composite molecular screen:
Silicon source is dissolved in water, Al is formed2O3Content is the solution B of 1~4wt%；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 silicon source, forms sodium aluminate solution C, Al in solution C2O3's
Content is 3~9 wt%, Na2O content is 1~20wt%；By the directed agents, the solution B, the solution C and the forerunner
Body E, which is added in water glass solution, is made synthesis Y/ Gd2O3The reaction mixture of/ZSM-23/ZSM-5 composite molecular screen；With anti-
Answer the weight of mixture for 100wt% meter, the additional amount of directed agents is 0.5 ~ 20 wt%, obtains synthesis Y/ Gd2O3/ZSM-23/
The reaction mixture of ZSM-5 composite molecular screen, the molar ratio of each component are as follows: Na2O:Al2O3:SiO2: Gd2O3:H2O=3~10:1:
8~18:0.01~0.06:180~320；
(4) hydrothermal crystallizing synthesizes:
The synthesis Y/ Gd that step (3) is obtained2O3The reaction mixture of/ZSM-23/ZSM-5 composite molecular screen is at 80~140 DEG C
8~72h of lower crystallization, obtains Y/ Gd2O3/ ZSM-23/ZSM-5 composite molecular screen slurries；
(5). Y/ Gd2O3The preparation of/ZSM-23/ZSM-5/ASA composite material:
Surfactant is added to Y/ Gd2O3In/ZSM-23/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
Substance is filtered, washed, 100~150 DEG C of 4~10 h of drying, 400~600 DEG C of 2~8 h of roasting, obtains Y/ Gd2O3/ZSM-23/
ZSM-5/ASA composite material, the surfactant are one or both of CTAB, P123 and F127.
2. Y/Gd according to claim 12O3The preparation method of/ZSM-23/ZSM-5/ASA composite material, feature exist
In: the additional amount of surfactant accounts for Y/ Gd in step (5)2O3The 1 of/ZSM-23/ZSM-5/ASA composite material quality~
6wt%。
3. a kind of Y/Gd2O3/ ZSM-23/ZSM-5/ASA composite material is the described in any item Y/Gd of claim 1 ~ 22O3/
Y/Gd made from the preparation method of ZSM-23/ZSM-5/ASA composite material2O3/ ZSM-23/ZSM-5/ASA composite material.
4. Y/Gd according to claim 32O3/ ZSM-23/ZSM-5/ASA composite material, it is characterised in that: Y/Gd2O3/
In ZSM-23/ZSM-5/ASA composite material the content of Y molecular sieve be 10~90 wt%, remaining for sieve and silica-sesquioxide, gadolinium oxide,
ZSM-23 and ZSM-5.
5. Y/Gd according to claim 42O3/ ZSM-23/ZSM-5/ASA composite material, it is characterised in that: Y/Gd2O3/
The SiO of sieve and silica-sesquioxide in ZSM-23/ZSM-5/ASA composite material2With Al2O3Molar ratio be 1~10:1.
6. Y/Gd according to claim 32O3/ ZSM-23/ZSM-5/ASA composite material, it is characterised in that: Y/Gd2O3/
Mesoporous mesoporous for rule in ZSM-23/ZSM-5/ASA composite material, total pore volume is 0.46~0.58 mL/g, and Micropore volume is
0.20~0.30 mL/g, mesoporous 0.24 ~ 0.33 mL/g of Kong Rongwei.
7. Y/Gd according to claim 62O3/ ZSM-23/ZSM-5/ASA composite material, it is characterised in that: Y/Gd2O3/
The regular mesoporous pore size of ASA is between 3 ~ 10 nm in ZSM-23/ZSM-5/ASA composite material.
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