CN102198406A - Method for preparing high-content double-transition metal composite molecular sieve - Google Patents
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Abstract
The invention relates to a method for preparing a high-content double-transition metal heteroatom composite molecular sieve. By using a stepwise synthesis method, a a MFI primary structure is firstly synthesized; then a M1-MFI molecular sieve is taken as part of silicon sources wherein M1 is one or two selected from the group consisting of Ni, Co, Cu, Fe, Zn, Cr and the like; M1-MFI is introduced into the hole wall of a mesoporous M2-MCM-41 molecular sieve wherein M2 is one or two selected from the group consisting of Ni, Co, Cu, Fe, Zn, Cr and the like; amorphous substances are guided to arrange in order to change defects of amorphous hole wall of the mesoporous molecular sieve, increase the wall thickness and raise heat stability and hydro-thermal stability of the mesoporous M2-MCM-41 molecular sieve. In the mean time, ion association complex formed by the interaction between a traditional template and a metal coordination compound is taken as a template of the synthesis molecular sieve, and metal ion is directly introduced into the molecular sieve skeleton through the template, successfully designing and synthesizing the double-transition metal heteroatom composite molecular sieve. The above composite molecular sieve material has well-regulated crystal structure, high metal content, two uniform mesoporous apertures, large specific surface area and pore volume, and good heat stability and hydro-thermal stability.
Description
One, technical field
The present invention relates to the preparation method of the two transition metal composite molecular screens of a kind of high-load, specifically, relate to the two transition metal composite molecular screen M of a kind of high-load
1-MFI/M
2-MCM-41 (M
1, M
2One or both of=Ni, Co, Cu, Fe, Zn, Cr etc.) Ni-MFI/Ni-MCM-41, Ni-MFI/Co-MCM-41, Co-MFI/Ni-MCM-41, Co-MFI/Co-MCM-41, Ni-MFI/Fe-MCM-41, Cu-MFI/Fe-MCM-41, Zn-MFI/Cr-MCM-41, the preparation method of composite molecular screens such as Fe-MFI/Cr-MCM-41.
Two, background technology
As everyone knows, ZSM-5 is a micro-pore zeolite molecular sieve shape-selective catalyst important in the modern petroleum industry.Yet because the limitation in its aperture, the product molecule is difficult for spreading out in some reaction, usually causes the generation of side reaction.Along with the heaviness of oil, the catalytic cracking of resolving heavy oil, residual oil becomes the governing factor of petroleum catalytic cracking technical process.Simultaneously, because the needs of Coal Chemical Industry and large biological molecule repercussion study, the large aperture molecular sieve catalyst that developmental research adapts with it is one of current important topic of being badly in need of solution.1992 synthetic first by Mobil company is forerunner's mesopore series material M41S with MCM-41, causes the great attention of international academic community, and MCM-41 has adjustable regular pore passage structure, and pore size is six side's mesoporous molecular sieves of 1.6-10nm.But, be restricted when handling complicated gas component, and restricted its range of application because the aperture of mesopore molecular sieve is evenly single; Mesopore molecular sieve caves under the high temperature, so also limiting it in industrial extensive use always easily because hole wall is thinner.For the limitation of avoiding the ZSM-5 aperture with mesopore molecular sieve is thermally-stabilised and the limitation of hydrothermal stability difference, when synthesising mesoporous molecular sieve, be the silicon source with the micro porous molecular sieve, micro-pore zeolite is directly introduced the hole wall of mesopore molecular sieve, synthetic composite molecular screen has overcome the defective of single molecular sieve structure and application, enlarges its range of application.
The synthetic method of composite molecular screen mainly contains in-situ synthesis, ion-exchange, nanometer self-assembly method.Synthetic being meant of original position can generate micropore and mesoporous two kinds of different materials simultaneously in a reaction system.According to the difference of reaction condition control step, the original position of composite molecular screen is synthetic, and can be divided into a step synthetic and substep is synthetic.Synthetic (CN 1393404A, a kind of step crystallizing process for synthesizing of middle mesoporous-microporous composite molecular sieve composition that patent documentation report composite molecular screen is successively arranged; CN 101186311A, Y/MCM-41 composite molecular screen and preparation method thereof) Kloetstra etc. (Microporous Materials, 1996,6, find in the process of synthetic MCM-41 that 287-293) amount of regulating aluminium and alkali can generate FAU and MCM-41 simultaneously.Find that by transmission electron microscope observing the MCM-41 layer that the major part on FAU surface is had several nanometer thickness covers.(Microporous and Mesoporous Materials such as Karlsson, 1999,27,181～192) utilization softex kw and TTAB are the template agent, by changing reaction temperature, regulate the template agent concentration, original position has been synthesized the MFI/MCM-41 with micropore-mesopore structure, and end product can be by the ratio and the controlling reaction temperature of two kinds of template agent.By tem observation, MFI/MCM-41 is quite complicated aggregation, and MFI type crystal is partially submerged in the MCM-41 aggregation, and the part on MFI crystal surface is covered by the MCM-41 thin layer simultaneously.Ion-exchange is before composite molecular screen forms, and micropore or mesopore molecular sieve have a kind of synthetic, then by the cation replacement Na of ion-exchange with another molecular sieve template agent
+, form template agent cation/molecular screen composite.Exchange to the formation of first kind of second kind of molecular sieve of template agent guiding on the molecular sieve.People such as Kloetstra have carried out the research of outgrowth in the synthetic FAU/MCM-41 of substep.They carry out ion-exchange with NaY or NaX molecular sieve in CTMACl solution, make the part Na on NaY molecular sieve surface
+By CTMA
+Replace, then it joined in the gel of MCM-41 of prepared fresh, with mixed system at a certain temperature crystallization can obtain the FAU/MCM-41 composite molecular screen.Li Fuxiang etc. (the chemistry of fuel journal, 1998,26 (2), 102-106) in ZSM-5, introduced F
-, because of F
-Adding changed the surface electrical properties of ZSM-5, cause its surface to have F
-Thereby, produce electrostatic field, help the gathering of surfactant cation on ZSM-5 micro-pore zeolite interface, thereby promoted the growth of MCM-41 molecular sieve on the micro porous molecular sieve matrix.TEM and electron diffraction diagram show that MCM-41 can grow on the matrix of ZSM-5 preferably.Kloetstra etc. pass through Na
+Ion-exchange, with TPA
+(4-propyl bromide ion) is introduced into the MCM-41 molecular sieve that has obtained Si/Al=30 on the hole wall of MCM-41, and the predecessor of the unformed material in its hole wall when forming ZSM-5 is close.Therefore, work as TPA
+When being distributed in mesoporous wall, can guide that unformed hole wall is partially-crystallized to be the microcellular structure of ZSM-5, generate the MCM-41/ZSM-5 composite molecular screen.The nanometer construction from part is with a kind of method in the primary and secondary structure elementary cell introducing meso-hole structure of micro porous molecular sieve.This method at first synthesizes the sial nano-cluster with molecular sieve primary and secondary construction unit, and then utilizes these nano-clusters and the self assembly of micella template to prepare the regular mesopore molecular sieve with strong acid center and high hydrothermal stability.
Along with the development of composite molecular screen, composite molecular screen is carried out modification then become the focus of research to enlarge its range of application.Wherein, metal ion is introduced the skeleton of molecular sieve, synthetic hetero atom composite molecular screen with more polyacid center and active sites exerts an influence to the activity and the selectivity of acid catalyzed reaction.Maja Mrak (Microporous and Mesoporous Materials95 (2006) 76-85.) synthetic (Ti, Al)-the Beta/MCM-41 molecular sieve has higher catalytic oxidation performance.Its conversion ratio of aromatization of the butane that synthetic Pd-MCM-22/Pt-SAPO-11 such as Narendra Kumar (Applied Catalysis A:General 227 (2002) 97-103) uses improves greatly.
The study on the synthesis of hetero atom composite molecular screen is more in recent years, but the synthetic report of relevant high-load bi-metal atom composite molecular screen is less, the present invention introduces two kinds of a large amount of different metal ions in synthetic microporous-mesoporous composite molecular sieve, improve the acidity of composite molecular screen, select shape selectivity and catalytic activity.
Three, summary of the invention
1, goal of the invention: the invention provides the two transition metal composite molecular screen M of a kind of high-load
1-MFI/M
2-MCM-41 (M
1, M
2One or both of=Ni, Co, Cu, Fe, Zn, Cr etc.) synthetic method, its purpose is to overcome the defective that micro porous molecular sieve is subjected to limited aperture and mesopore molecular sieve heat endurance and hydrothermal stability difference, simultaneously a large amount of metallic atoms is introduced the skeleton of molecular sieve.Improve used catalyst in the petroleum refining industry, improve the acidity of catalyst, strengthen its selectivity and activity.
2, technical scheme: the present invention is achieved through the following technical solutions:
Prepare the ionic associate that a kind of complex that is formed by transition metal (one or both of Ni, Co, Cu, Fe, Zn, Cr etc.) and organic formwork agent associate and form.The used cation constituent of synthetic ionic associate template agent be four butyl bromation amine or CTAB, associating with the EDTA complex of metal ion forms.
A certain amount of metal salt solution and disodium ethylene diamine tetra-acetic acid solution reaction are configured to M[EDTA]
2-Solution dropwise joins it in solution of four butyl bromation amine or CTAB after stirring, and fully stirs, and obtains thick transparency liquid and is respectively [(C
4H
9)
4N]
2 +[M (EDTA)]
2-[C
16H
33(CH
3)
3N]
2 +[M (EDTA)]
2-Template agent as synthetic composite molecular screen.
With silicon source, inorganic base, water, ionic associate template agent [(C
4H
9)
4N]
2 +[M (EDTA)]
2-(R
1) obtaining even colloid according to mixing in proper order, its mole consists of R
1: SiO
2=0.2-0.4, OH
-: SiO
2=0.35-0.5, H
2O: SiO
2=67-135, evenly colloid is under the power hydrothermal condition that boosts certainly, and crystallization obtains described high levels of transition metals hetero-atom molecular-sieve, its crystallization temperature is 150-180 ℃, after crystallization 24-48 hour, reactant is cooled to room temperature is transferred in the there-necked flask, add a certain amount of template agent [C
16H
33(CH
3)
3N]
2 +[M (EDTA)]
2-(R
2), fully stir more than the 3h, mix the back and add ethyl orthosilicate, stir 1h after, be that the mole proportioning of 10. aforesaid each component is R with inorganic adjusting PH with base
1: SiO
2=0.12-0.4, R
2: SiO
2=0.1-0.2, OH
-: SiO
2=0.35-0.7, H
2O: SiO
2The above-mentioned reactant of=70-100. under the power hydrothermal condition that boosts certainly, 110-130 ℃ crystallization 72-96 hour, the product after the crystallization is obtained the molecular sieve finished product through suction filtration, washing, oven dry, roasting.
The used cation constituent of described synthetic ionic associate template agent is one or more in 4-propyl bromide, TBAB and the CTAB etc.
The used hetero atom source of described synthetic ionic associate template agent is one or more soluble metallic salts in nickel, cobalt, copper, iron, zinc, the chromium.
Described and the part coordination of hetero atom source is sodium ethylene diamine tetracetate (Na
2EDTA).
Described silicon source is an aerosil, waterglass, one or more in the ethyl orthosilicate.
Described inorganic base is alkali metal hydroxide or ammoniacal liquor.
Described drying course is to dry 3-8 hour down at 100-130 ℃; Described hydrothermal crystallization process is that substep carries out, and at first at 150-180 ℃ of following hydrothermal crystallizing 24-48 hour, second step was at 100-130 ℃ of following hydrothermal crystallizing 72-96 hour; Described suction filtration, washing process be meant in suction filtration and add the deionized water washing leaching cake, to the pH of filtrate be 7; Described roasting process is ℃ of-700 ℃ insulations of temperature programming to 550 5 hours under the condition of 1 ℃/min.
3, advantage and effect
By the enforcement of technical solution of the present invention, can make to act synergistically two kinds of material advantage complementations well in conjunction with the duct advantage of mesopore molecular sieve and the highly acid and the high hydrothermal stability of micro porous molecular sieve.Improve the defective of the molecular sieve catalyst in single duct used in the petroleum refining industry, increase the content of hetero-atom molecular-sieve skeleton metal simultaneously, improve the acidity of catalyst, strengthen its selectivity and activity.The at first synthetic microporous molecular sieve M of the inventive method
1-MFI (M
1=Ni, Co, Cu, Fe, Zn, Cr etc.) basic structure, with M
1-MFI molecular sieve is as part silicon source, with M
1-MFI introduces mesoporous M
2-MCM-41 (M
2=Ni, Co, Cu, Fe, Zn, Cr etc.) hole wall of molecular sieve, simultaneously in the process of synthetic composite molecular screen because the existence of crystal MFI structure, the orderly arrangement of guiding amorphous substance, thereby change the defective of the amorphous hole wall of mesopore molecular sieve, increase wall thickness, improved the heat endurance and the hydrothermal stability of mesoporous MCM-41 molecular sieve.Simultaneously, make framework of molecular sieve produce more Bronsted acid B acid, acidic zeolite and aperture are produced promotor action, the activity and the selectivity of acid catalyzed reaction exerted an influence because heteroatomic introducing causes the charge unbalance on the skeleton.
The present invention adopts synthetic ionic associate as the template agent, and is big than the molecular diameter of conventional template agent, and therefore, synthetic composite molecular screen has two kinds of mesoporous pore-size distributions at 3nm and 6nm.Because metal heteroatom is by directly introducing framework of molecular sieve with template agent effect, a large amount of metal heteroatoms distributes also comparatively even, in B acid that has increased composite molecular screen and L acid site, make that the acid centre of molecular sieve is dispersed better, the high-load bimetallic hetero-atom molecular-sieve M that this method is synthetic
1-MFI/M
2-MCM-41 (M
1, M
2One or both of=Ni, Co, Cu, Fe, Zn, Cr etc.) has very strong potential using value.
Four, description of drawings
Fig. 1. be the XRD figure of embodiment 1 sample Ni-MFI/Ni-MCM-41.
Fig. 2. be the XRD figure of embodiment 2 sample Ni-MFI/Co-MCM-41.
Fig. 3. be the XRD figure of embodiment 3 sample Co-MFI/Ni-MCM-41.
Fig. 4. be the XRD figure of embodiment 4 sample Co-MFI/Co-MCM-41.
Fig. 5. be the SEM figure of embodiment 1 sample Ni-MFI/Ni-MCM-41.
Fig. 6. be the SEM figure of embodiment 2 sample Ni-MFI/Co-MCM-41.
Fig. 7. be the SEM figure of embodiment 3 sample Co-MFI/Ni-MCM-41.
Fig. 8. be the SEM figure of embodiment 4 sample Co-MFI/Co-MCM-41.
Five, the specific embodiment
Below by embodiment content of the present invention is described in further detail, but not thereby limiting the invention.
A kind of couple of transition metal composite molecular screen M among the present invention
1-MFI/M
2-MCM-41 (M
1, M
2One or both of=Ni, Co, Cu etc.) represent hetero atom composite molecular screen Ni-MFI/Ni-MCM-41, Ni-MFI/Co-MCM-41, Co-MFI/Ni-MCM-41, Co-MFI/Co-MCM-41 etc., the used hetero atom source of used synthetic ionic associate template agent is with nickel nitrate among the embodiment, and cobalt nitrate is an example.Used template agent is an example with the ionic associate template agent of TBAB or CTAB and metal complex formation, used silicon source is an example with aerosil and ethyl orthosilicate, and used inorganic base is example with the alkali metal hydroxide; Used water is deionized water; Used reagent all adopts AR; It is with the test of powder crystal diffraction that the X-ray diffraction of gained finished product is measured, used instrument is a Philips X ' Pert type X-ray diffractometer, voltage 30kV, electric current 30mA, 5 °-70 ° and 0.5 °-10 ° of sweep limits, with Hitachi S-4700 SEM (SEM), measure the size of pattern and crystal grain.
Embodiment 1:
Take by weighing the 2.97g nickel nitrate and be dissolved in 10g deionized water and sodium ethylene diamine tetracetate solution effects, generate metal complex Ni (EDTA)
2-Take by weighing the 12.089g TBAB then, metal complex is mixed with water-soluble cationic surfactant TBAB, the template agent associated matter of generation is as the template agent of experiment.
Take by weighing 0.5g NaOH and be dissolved in the 20g deionized water for stirring, after waiting to dissolve the 3g silica that takes by weighing is dissolved in the solution of NaOH, stir adding template agent [TBA] after 1 hour
+ 2[Ni (EDTA)
2-], continue then to stir 1.5 hours, using sodium hydroxide solution to transfer pH is 9.At last, the total amount of regulating water is 121ml, and above building-up process is at room temperature carried out.Continuous stirring was transferred to the gel that obtains in the teflon-lined retort after 3 hours,, took out and was cooled to room temperature (this solution is designated as A) after 48 hours at 150 ℃ of following static crystallizations, was transferred in the reaction vessel and stirred 3 hours.
The 2.97g nickel nitrate is dissolved in the aqueous solution of 10ml sodium ethylene diamine tetracetate, generates metal complex Ni (EDTA)
2-Take by weighing the 4.93g CTAB then, with metal complex and water-soluble cationic surfactant TBAB association, the template agent associated matter [C of generation
16H
33(CH
3)
3N]
2 +[Ni (EDTA)]
2-(this solution is designated as B).It joins in the reactant A and fully stirs more than the 3h with solution B, mixes the back and adds ethyl orthosilicate, and behind the stirring 1h, transferring pH with inorganic alkali solution is 10.At last, adding the total amount that entry makes water is 90ml, above building-up process is at room temperature carried out, continuous stirring was transferred to the gel that obtains in the teflon-lined retort after 3 hours, at 110 ℃ of following static crystallizations after 48 hours, and suction filtration, wash to filtrate pH be 7,110 ℃ of dryings are after 3 hours, are warming up to 550 ℃ with the speed of 1 ℃/min, are incubated 5 hours and get product.Sample number into spectrum is Ni-MFI/Ni-MCM-41.The X-ray powder diffraction data of gained finished product have the feature of accompanying drawing 1, and the electronic scanner microscope pattern as shown in Figure 5.
Embodiment 2:
The 2.97g nickel nitrate is dissolved in the 10ml disodium ethylene diamine tetra-acetic acid aqueous solution, generates metal complex Ni (EDTA)
2-Take by weighing the 12.089g TBAB then, metal complex is mixed with water-soluble cationic surfactant TBAB, the product of generation is as the template agent of experiment.
Take by weighing 0.5g NaOH and be dissolved in the 20g deionized water for stirring, after waiting to dissolve the 3g silica that takes by weighing is dissolved in the solution of NaOH, stir adding template agent [TBA] after 1 hour
+ 2[Ni (EDTA)
2-], continue then to stir 1.5 hours, using sodium hydroxide solution to transfer pH is 9.At last, the total amount of adjusting water is 121ml.Above building-up process is at room temperature carried out, continuous stirring was transferred to the gel that obtains in the teflon-lined retort after 3 hours, 150 ℃ of following static crystallizations 48 hours, take out and be cooled to room temperature (this solution is designated as A), be transferred in the reaction vessel and stirred 3 hours.
The 2.99g cobalt nitrate is dissolved in the aqueous solution of 10ml sodium ethylene diamine tetracetate, generates metal complex Co (EDTA)
2-Take by weighing the 4.93g CTAB then, metal complex is mixed the template agent associated matter [C of generation with water-soluble cationic surfactant TBAB
16H
33(CH
3)
3N]
2 +[Co (EDTA)]
2-(this solution is designated as B).It joins and fully stirs 3h in the reactant A with solution B, adds ethyl orthosilicate 11.31ml then, and behind the stirring 1h, transferring pH with inorganic alkali solution is 10.At last, the total amount of regulating water is 90ml, and above building-up process is at room temperature carried out.Continuous stirring was transferred to the gel that obtains in the teflon-lined retort after 3 hours, at 110 ℃ of following static crystallizations after 48 hours, and suction filtration, wash to filtrate pH be 7,110 ℃ of dryings are after 3 hours, are warming up to 550 ℃ with the speed of 1 ℃/min, are incubated 5 hours and get product.Sample number into spectrum is Ni-MFI/Co-MCM-41.The X-ray powder diffraction data of gained finished product have the feature of accompanying drawing 2, and the electronic scanner microscope pattern as shown in Figure 6.
Embodiment 3:
Take by weighing the 2.99g cobalt nitrate and be dissolved in 10g deionized water and sodium ethylene diamine tetracetate solution effects, generate metal complex Ni (EDTA)
2-Take by weighing the 12.089g TBAB then, metal complex is mixed with water-soluble cationic surfactant TBAB, the template agent associated matter of generation is as the template agent of experiment.
Take by weighing 0.5g NaOH and be dissolved in the 20g deionized water for stirring, after waiting to dissolve the 3g silica that takes by weighing is dissolved in the solution of NaOH, stir adding template agent [TBA] after 1 hour
+ 2[Co (EDTA)
2-], continue then to stir 1.5 hours, using sodium hydroxide solution to transfer pH is 9.At last, the total amount of regulating water is 121ml, and above building-up process is at room temperature carried out.Continuous stirring was transferred to the gel that obtains in the teflon-lined retort after 3 hours,, took out and was cooled to room temperature (this solution is designated as A) after 48 hours at 150 ℃ of following static crystallizations, was transferred in the reaction vessel and stirred 3 hours.
The 2.97g nickel nitrate is dissolved in the aqueous solution of 10ml sodium ethylene diamine tetracetate, generates metal complex Ni (EDTA)
2-Take by weighing the 4.93g CTAB then, with metal complex and water-soluble cationic surfactant TBAB association, the template agent associated matter [C of generation
16H
33(CH
3)
3N]
2 +[Ni (EDTA)]
2-(this solution is designated as B).It joins in the reactant A and fully stirs more than the 3h with solution B, mixes the back and adds ethyl orthosilicate, and behind the stirring 1h, transferring pH with inorganic alkali solution is 10.At last, adding the total amount that entry makes water is 90ml, above building-up process is at room temperature carried out, continuous stirring was transferred to the gel that obtains in the teflon-lined retort after 3 hours, at 110 ℃ of following static crystallizations after 48 hours, and suction filtration, wash to filtrate pH be 7,110 ℃ of dryings are after 3 hours, are warming up to 550 ℃ with the speed of 1 ℃/min, are incubated 5 hours and get product.Sample number into spectrum is Co-MFI/Ni-MCM-41.The X-ray powder diffraction data of gained finished product have the feature of accompanying drawing 3, and the electronic scanner microscope pattern as shown in Figure 7.
Embodiment 4:
The 2.99g cobalt nitrate is dissolved in the 10ml disodium ethylene diamine tetra-acetic acid aqueous solution, generates metal complex Co (EDTA)
2-Take by weighing the 12.089g TBAB then, metal complex is mixed with water-soluble cationic surfactant TBAB, the product of generation is as the template agent of experiment.
Take by weighing 0.5g NaOH and be dissolved in the 20g deionized water for stirring, after waiting to dissolve the 3g silica that takes by weighing is dissolved in the solution of NaOH, stir adding template agent [TBA] after 1 hour
+ 2[Co (EDTA)
2-], continue then to stir 1.5 hours, using sodium hydroxide solution to transfer pH is 9.At last, the total amount of adjusting water is 121ml.Above building-up process is at room temperature carried out, continuous stirring was transferred to the gel that obtains in the teflon-lined retort after 3 hours, 150 ℃ of following static crystallizations 48 hours, take out and be cooled to room temperature (this solution is designated as A), be transferred in the reaction vessel and stirred 3 hours.
The 2.99g cobalt nitrate is dissolved in the aqueous solution of 10ml sodium ethylene diamine tetracetate, generates metal complex Co (EDTA)
2-Take by weighing the 4.93g CTAB then, metal complex is mixed the template agent associated matter [C of generation with water-soluble cationic surfactant TBAB
16H
33(CH
3)
3N]
2 +[Co (EDTA)]
2-(this solution is designated as B).It joins and fully stirs 3h in the reactant A with solution B, adds ethyl orthosilicate 11.31ml then, and behind the stirring 1h, transferring pH with inorganic alkali solution is 10.At last, the total amount of regulating water is 90ml, and above building-up process is at room temperature carried out.Continuous stirring was transferred to the gel that obtains in the teflon-lined retort after 3 hours, at 110 ℃ of following static crystallizations after 48 hours, and suction filtration, wash to filtrate pH be 7,110 ℃ of dryings are after 3 hours, are warming up to 550 ℃ with the speed of 1 ℃/min, are incubated 5 hours and get product.Sample number into spectrum is Co-MFI/Co-MCM-41.The X-ray powder diffraction data of gained finished product have the feature of accompanying drawing 4, and the electronic scanner microscope pattern as shown in Figure 8.
Claims (7)
1. the preparation method of the two transition metal composite molecular screens of high-load specifically is the composite molecular screen M of the two transition metal of a kind of high-load
1-MFI/M
2-MCM-41 (M
1, M
2One or both of=Ni, Co, Cu, Fe, Zn, Cr etc.) preparation method, the principal character of this molecular sieve analog are that it is with M
1-MFI molecular sieve is as part silicon source, with M
1-MFI introduces the hole wall of mesoporous MCM molecular sieve, simultaneously in the process of synthetic composite molecular screen because the existence of crystal MFI structure, the orderly arrangement of guiding amorphous substance, change the defective of the amorphous hole wall of mesopore molecular sieve, increase wall thickness, formed the heteroatomic composite molecular screen of the high-load with two kinds of apertures simultaneously.
2. according to the described molecular sieve of claim 1, it is characterized in that hetero atom (M in the described molecular sieve
1And M
2) being respectively transition metal such as Ni, Co, Cu, Fe, Zn, Cr, its content is 0wt%-15wt%, composite molecular screen has two kinds of apertures and is respectively 3nm and 6nm.
3. the preparation method of the described molecular sieve of claim 1 is characterized in that the preparation process of the composite molecular screen of the two transition metal of this high-load comprises:
(1) the template agent is synthetic:
Prepare the ionic associate that a kind of complex that is formed by transition metal (Ni, Co, Cu, Fe, Zn, Cr etc.) and organic formwork agent associate and form, the used cation constituent of synthetic ionic associate template agent be the tetrapropyl amine bromide, four butyl bromation amine or CTAB, form with the EDTA complex association of metal ion
A certain amount of metal salt solution and disodium ethylene diamine tetra-acetic acid solution reaction are configured to M[EDTA]
2-Solution dropwise joins it in solution of four butyl bromation amine or CTAB after stirring, and fully stirs, and obtains thick transparency liquid and is respectively [(C
4H
9)
4N]
2+[M (EDTA)]
2-[C
16H
33(CH
3)
3N]
2+[M (EDTA)]
2-As the template agent of synthetic composite molecular screen,
(2) molecular sieve is synthetic:
With silicon source, inorganic base, water, ionic associate template agent [(C
4H
9)
4N]
2+[M (EDTA)]
2-(R
1) mix in a certain order and obtain even colloid, its mole consists of R
1: SiO
2=0.2-0.4, OH
-: SiO
2=0.35-0.5, H
2O: SiO
2=67-135, evenly colloid is under the power hydrothermal condition that boosts certainly, crystallization obtains described high levels of transition metals hetero-atom molecular-sieve precursor slurries, its crystallization temperature is 150-180 ℃, after crystallization 24-48 hour, reactant is cooled to room temperature is transferred in the there-necked flask, add a certain amount of template agent [C
16H
33(CH
3)
3N]
2+[M (EDTA)]
2-(R
2), fully stir more than the 3h, mix the back and add ethyl orthosilicate, stir 1h after, be 10 to obtain even colloid with inorganic adjusting PH with base, the mole proportioning of aforesaid each component is R
1: SiO
2=0.12-0.4, R
2: SiO
2=0.1-0.2, OH
-: SiO
2=0.35-0.7, H
2O: SiO
2=70-100, above-mentioned reactant are under the power hydrothermal condition that boosts certainly, and crystallization obtains the two transition metal hetero-atom composite molecular screens of described high-load, and its crystallization temperature is 110-130 ℃, and crystallization 72-96 hour,
(3) after crystallization process finishes, will generate the product suction filtration, wash to filtrate pH be 7, drying under 100-120 ℃ of condition, 550 ℃ of-760 ℃ of roastings obtain target product.
4. high-load bimetallic composite molecular screen M as claimed in claim 3
1-MFI/M
2-MCM-41 Preparation of catalysts method, the silicon source that it is characterized in that the above is aerosil or ethyl orthosilicate.
5. high-load bimetallic composite molecular screen M as claimed in claim 3
1-MFI/M
2-MCM-41 Preparation of catalysts method is characterized in that described template agent is four butyl bromation amine, four third class amine bromide or CTABs.
6. high-load bimetallic composite molecular screen M as claimed in claim 3
1-MFI/M
2-MCM-41 Preparation of catalysts method is characterized in that described inorganic base is NaOH or ammoniacal liquor.
7. high-load bimetallic composite molecular screen M as claimed in claim 3
1-MFI/M
2-MCM-41 Preparation of catalysts method is characterized in that described slaine is solubility nitrate, sulfate or the chloride of Ni, Co, Cu, Fe, Zn, Cr etc.
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|---|---|---|---|
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| CN102838129A (en) * | 2012-09-14 | 2012-12-26 | 北京化工大学 | Mesoporous molecular sieves with crystal structures and preparation method of mesoporous molecular sieves |
| CN106887608A (en) * | 2015-12-16 | 2017-06-23 | 中国海洋大学 | The preparation method and application of inexpensive hollow carbon sphere base oxygen reduction catalyst |
| CN106887608B (en) * | 2015-12-16 | 2019-04-30 | 中国海洋大学 | The preparation method and application of inexpensive hollow carbon sphere base oxygen reduction catalyst |
| CN106083509A (en) * | 2016-06-20 | 2016-11-09 | 中国石油大学(北京) | The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins |
| CN106770557A (en) * | 2017-01-09 | 2017-05-31 | 广西民族大学 | A kind of preparation method of highly sensitive Bezafibrate molecular imprinting electrochemical sensor |
| CN107176613A (en) * | 2017-07-12 | 2017-09-19 | 天津工业大学 | A kind of multi-stage porous zeolite crystal embeds the preparation method of Fe nanoparticle catalysts |
| CN108262006A (en) * | 2018-01-22 | 2018-07-10 | 四川大学 | A kind of MCM-41 molecular sieves of skeleton incorporation metal and preparation method thereof |
| CN108262006B (en) * | 2018-01-22 | 2020-11-27 | 四川大学 | MCM-41 molecular sieve with metal doped in framework and preparation method thereof |
| CN114534770A (en) * | 2022-01-06 | 2022-05-27 | 深圳大学 | Preparation of catalyst with wave-absorbing-catalyzing function and application of microwave pyrolysis of sludge |
| CN114534770B (en) * | 2022-01-06 | 2024-01-30 | 深圳大学 | Catalyst with wave-absorbing-catalytic function and preparation and sludge microwave pyrolysis application thereof |
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