CN101186311B - Y/MCM-48 composite molecular screen and preparation method thereof - Google Patents
Y/MCM-48 composite molecular screen and preparation method thereof Download PDFInfo
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- CN101186311B CN101186311B CN2007101708008A CN200710170800A CN101186311B CN 101186311 B CN101186311 B CN 101186311B CN 2007101708008 A CN2007101708008 A CN 2007101708008A CN 200710170800 A CN200710170800 A CN 200710170800A CN 101186311 B CN101186311 B CN 101186311B
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Abstract
The invention relates to a catalytic material of a composite molecular sieve containing micropore Y-zeolite phase and mediated hole MCM- 48 phase, which is produced by taking mixed cationic and non-ion surfactant as template; the invention also relates to a preparation method of the catalytic material. By adopting a method of overgrowth and employing mixed aqueous solution of cationic surfactant: cetyl trimethyl ammonium bromide(CTAB) and nonionic surfactant: p -octyl polyethylene phenyl ether OP-10 as template, under the alkaline hydrothermal condition the invention synthesizes composite molecular sieve which is provided with Y/MCM-48 with micropore and two-mode mediated holes. The framework ratio Si/Al of microporous phase Y-zeolite of the composite molecular sieve is higher than traditional Y-zeolite, and the ratio Si/Al and the content of the framework of microporous phase can be adjusted by changing synthesis conditions. The method of the invention has simple operation and good repeatability, which provides with optional materials for developing novel catalyst with industrial application prospect, and the synthesis has practical application value.
Description
Technical field
The present invention relates to one type is that the template preparation contains micropore Y zeolite facies and mesoporous MCM-48 composite molecular screen catalysis material mutually and preparation method thereof simultaneously with mixed-cation-non-ionic surface active agent.
Background technology
Since the sixties in last century, artificial synthetic microporous molecular sieve came out; Micro porous molecular sieve has the pore structure of homogeneous and stronger acidity because of it; In acid catalyzed reaction, playing crucial effect, for the mankind have created great riches, is the pillar of petrochemical industry development; But along with the heaviness of oil product and the demand of medicine, large biological molecule reaction, its application has been limited in the narrow and small duct of micro porous molecular sieve.Mesopore molecular sieve appear as heavy oil and macromolecular application has brought dawn, but faintly acid that its hole wall randomness causes and hydro-thermal unstability make its not industrialization so far.Deficiency to micropore and mesopore molecular sieve; Scientists has competitively developed the new material that several different methods attempts to prepare both advantages; As: (1) is through chemical method pore-creating in micropore; Perhaps adopt the method for hard template to make the mesoporous or large pore material that hole wall is a micro porous molecular sieve, but the shortcoming of this type material be mesoporous or the pore-size distribution of macropore inhomogeneous, influence it in adsorbing separation with select the application aspect the catalysis; (2) through surfactant with micro porous molecular sieve is nanocrystalline or the secondary structure unit supermolecule is assembled; Synthetic one type of hole wall contains the mesopore molecular sieve of the nanocrystalline or secondary structure unit of micro porous molecular sieve; Though increased the order of mesoporous wall; Improved the acidity and the hydrothermal stability of mesopore molecular sieve, but because the shortrange order of nanocrystalline or secondary structure unit, its acid strength is not enough to satisfy the needs of strong acid reaction.In order to overcome in the micropore pore-creating sample; The limitation of mesoporous uneven shortcoming and SBU (secondary structure unit) mesopore molecular sieve, people try to explore one type of micropore/mesoporous composite molecular sieve with bimodulus (micropore, mesoporous) pore structure and dual acidity (strong acid, weak acid) of uniform pore size.This molecular sieve analog has mesoporously can improve the accessibility in activated centre and the diffusivity of reactant molecule; And the stronger acidity of micromolecular cracking needs in the reaction intermediate and suitable micropore also can be provided, can realize " relay-type " catalytic cracking that the big molecule of heavy oil is descending.The research of this respect has in recent years obtained considerable progress, and composite molecular screens such as β/MCM-41, β/MCM-48, ZSM-5/MCM-41, ZSM-5/MCM-48, Y/MCM-41 are synthesized in succession.But be confined to MCM-41 and micropore compound in one dimension straight hole road mostly, and be to be that template is synthesized, only solved the problem that has or not, do not realize the controlledly synthesis of micropore phase content and skeleton Si/Al in the composite molecular screen with single surfactant.Another important member in the MCM41S series-three-dimensional double helix duct MCM-48 has diffusion preferably than the MCM-41 in one dimension straight hole road, but since its to generate phase region very narrow; Formation condition is harsh; Be difficult to syntheticly, in addition the synthesis condition of Y and MCM-48 differs bigger again, and it is big to adopt single cationic surfactant to synthesize desired concn; Reason such as uneconomical; So do not see the report of relevant Y/MCM-48 composite molecular screen so far as yet, and at present catalyst for cracking heavy oil usually with Y zeolite as main active component, content and the skeleton Si/Al that realize Y component in the composite molecular screen are than adjustable; Satisfying the needs of different catalytic reactions, so controlledly synthesis Y/MCM-48 composite molecular screen will have more important realistic meaning.
Summary of the invention
The objective of the invention is to obtain a kind of micropore/mesoporous composite molecular sieve that contains micropore Y zeolite facies and mesoporous MCM-48 (micropore, the mesoporous) pore structure of the bimodulus with uniform pore size and dual acidity (strong acid, weak acid) mutually and simple to operate, the preparation method of favorable reproducibility.
This method adopts the outgrowth method, promptly at first that the Y zeolite molecular sieve is surperficial sodium ion (Na
+) or hydrogen ion (H
+) with cetyltrimethyl ammonium (CTA
+) cation exchanges, and nonionic polyethylene octyl phenyl ether (OP-10) inserts cation CTA
+Between, form the mixed surfactant micella, replenish the silicon source then, under the condition of hydrothermal crystallizing, forming with the Y zeolite through the surfactant self assembly at the Y zeolite surface is nuclear, mesoporous MCM-48 is the composite molecular screen of shell core-shell type.Step is following: a certain proportion of CTAB, OP-10 and water stir into settled solution under 20 ℃～40 ℃, in this solution, add a certain amount of Y zeolite powder, under same temperature, stir 15～60min, make the Na on Y zeolite molecular sieve surface
+Perhaps H
+With CTA
+Cation exchanges, and adds waterglass then, continues to stir 1～3h, and the mixed sols that obtains is regulated PH between 9.0～12.0 with hydrochloric acid or NaOH, 75 ℃～125 ℃ crystallization 12～96h in the stainless steel cauldron of packing into then.After crystallization finished, solid product promptly got the former powder of synthesis type through filtering, wash, drying;
Used material should reach following molar ratio range in above-mentioned synthesizing: 1 SiO
2: 0.12～0.17 CTAB:0.020～0.027OP-10:0.20～0.35 Na
2O:59 H
2O, Y zeolite molecular sieve/SiO
2(mass ratio)=0.22～1.98.
Among the above-mentioned preparation method, require the Na on Y zeolite molecular sieve surface
+Perhaps H
+Should be fully and CTA
+Cation exchanges, and swap time, 30～60min was better.
Among the above-mentioned preparation method, 30 ℃ of the whipping temps behind the adding waterglass, mixing time 1～2h is more suitable.
Among the above-mentioned preparation method, synthesis condition is better in following ranges: molar ratio of material is 1 SiO
2: 0.15 CTAB:0.025OP-10:0.28 Na
2O:59 H
2O, Y zeolite molecular sieve/SiO
2(mass ratio)=0.22～1.98, PH is controlled at 10.5～11.5, and crystallization temperature is 90～110 ℃, and crystallization time is 24～72h.
Among the above-mentioned preparation method, control raw material Y zeolite addition, as: Y/SiO
2(g/g)=0.22～1.98, can make the content of micropore phase in the composite molecular screen controlled, content is from 0%～50%.
The former powder of synthesis type is flowed down in 350～650 ℃ of roasting 1～3h at nitrogen earlier, and roasting 3～7h again under the same temperature in air atmosphere promptly obtains roasting type sample after the roasting then.
The Y/MCM-48 composite molecular screen material that the present invention synthesized is a kind of catalysis material.
The formation condition of using the synthetic Y/MCM-48 composite molecular screen of outgrowth method can overcome Y and MCM-48 differs big and is difficult to synthetic difficulty under unified system; And the content and the framework si-al ratio of Y zeolite facies in can the modulation composite molecular screen, thereby satisfy the needs of different catalytic reactions.
Use mixed-cation-anion surfactant can enlarge the synthetic phase region of MCM-48; Make synthesizing easily of MCM-48; Can overcome simultaneously the restriction that the synthetic composite molecular screen requirement micro-pore zeolite of outgrowth method has lower silica alumina ratio, mixed surfactant can also reduce the consumption of total surfactant greatly.
The cheap waterglass that uses technical grade greatly reduces production cost as the silicon source.
This method uses finished product Y zeolite as raw material, has simplified operating process greatly.And the kind of Y zeolite can modulation, can make the skeleton Si/Al ratio of Y zeolite in the composite molecular screen be higher than conventional Y zeolite, as the overstable gamma zeolite DY that selects silica alumina ratio=13 for use is as precursor, and the porous skeleton Si/Al in the Y/MCM-48 composite molecular screen is than up to 5.9.
Since this material be a kind of be nuclear with micropore Y zeolite, mesoporous MCM-48 is the core-shell type structure of shell, can realize " relay-type " catalytic cracking that the big molecule of heavy oil is descending, thereby show good catalytic perfomance.As comparing with corresponding mechanical impurity, in the time of 400 ℃, the Y/MCM-48 composite molecular screen is the former 1.6 times to the lytic activity of normal heptane, and such composite molecular screen has potential industrial application value.
Description of drawings:
The prepared Y/MCM-48 composite molecular screen catalysis material of the present invention has the characterization result of typical Fig. 1-5.
Fig. 1 is the low angle part (left side) of the Y/MCM-48 composite molecular screen that synthesizes and the XRD figure on high angle part (right side).Low bight component demonstrates the several characteristic diffraction maximum of typical cubic mesoporous phase, that is: [211], [220], [321], [400], [420], [322] [, 421], [431].Angle of elevation partial graph demonstrates typical Y zeolite characteristic diffraction peak, as: [111], [220], [311], [331], [511], [333] etc.The mesoporous MCM-48 that Fig. 1 show sample includes Y zeolite facies and high regularity mutually.
Fig. 2 is the nitrogen adsorption (left side) and the pore size distribution curve (right side) of Y/MCM-48 composite molecular screen.The nitrogen adsorption is p/p at relative pressure
0=0.20-0.40 demonstrates N in the zone
2Adsorbance suddenly increase, corresponding to N
2Capillary condensation phenomenon in the MCM-48 mesopore orbit; At p/p
0There is a hysteresis loop between the=0.45-1.0, corresponding to the absorption of secondary pore in the DY sample.The pore size distribution curve show sample has 2.6nm and the 3.9nm bimodulus is mesoporous.
Fig. 3 is (a) pure Y zeolite, (b) pure MCM-48, (c) Y/MCM-48 composite molecular screen, (d) sem photograph of the mechanical impurity of Y and MCM-48.Show among the figure that the composite molecular screen sample is the particle that the Y zeolite surface closely is wrapped in MCM-48, and mechanical impurity is two mutually loose being deposited in together that separate, one is the Y zeolite granular mutually, and one is the MCM-48 particle mutually.
Fig. 4 is Y/MCM-48 composite molecular screen and corresponding mechanical impurity catalytic pyrolysis conversion ratio figure to normal heptane under different temperatures.Be presented among the figure under the different reaction temperatures, the catalytic pyrolysis activity of composite molecular screen all is higher than corresponding mechanical impurity.
Fig. 5 is low angle 2 θ parts (left side) and the angle of elevation 2 θ XRD figure on (right side) partly of the Y/MCM-48 composite molecular screen of the different micropore phase contents that synthesize, and the content of micropore is respectively (a) 6.7% in the composite molecular screen, (b) 14.5%, (c) 22.8%, (d) 32.1%.
The specific embodiment
Further describe characteristic of the present invention through instance below, the present invention is not limited to following instance.
0.88g is ground in the mixed solution that thin Y zeolite powder joins CTAB and θ P-10, stir 30min fast, in above-mentioned mixed liquor, add 5.7ml waterglass (25.4wt%SiO then
2, 7.47wt%NaO
2, 67.29wt%H
2O), stir 2h down at 30 ℃, the initial gel that obtains mixing, its mole ratio of components are 1 SiO
2: 0.15 CTAB:0.025 OP-10:0.28Na
2O:59 H
2O, Y zeolite/SiO
2(mass ratio)=0.44.Regulate PH ≈ 10.6, this colloidal sol is packed in the 40ml agitated reactor, 100 ℃ of crystallization 72h, end product promptly gets the Y/MCM-48 composite molecular screen through filtering, wash, drying.
1.76g is ground thin Y zeolite powder join in the mixed solution of CTAB and OP-10, stir 30min fast, in above-mentioned mixed liquor, add 5.7ml waterglass (25.4wt%SiO then
2, 7.47wt%NaO
2, 67.29wt%H
2O), stir 1h down at 40 ℃, the initial gel that obtains mixing, its mole ratio of components are 1 SiO
2: 0.15 CTAB:0.025 OP-10:0.28Na
2O:59 H
2O, Y zeolite/SiO
2(mass ratio)=0.88.Regulate PH ≈ 9, this colloidal sol is packed in the 40ml agitated reactor, 125 ℃ of crystallization 12h, end product promptly gets the Y/MCM-48 composite molecular screen through filtering, wash, drying.
Instance 3
0.88g is ground thin Y zeolite powder join in the mixed solution of CTAB and OP-10, stir 30min fast, in above-mentioned mixed liquor, add 5.7ml waterglass (25.4wt%SiO then
2, 7.47wt%NaO
2, 67.29wt%H
2O), stir 3h down at 20 ℃, the initial gel that obtains mixing, its mole ratio of components are 1 SiO
2: 0.17 CTAB:0.020 OP-10:0.20Na
2O:59 H
2O, Y zeolite/SiO
2(mass ratio)=0.44.Regulate PH ≈ 12, this colloidal sol is packed in the 40ml agitated reactor, 75 ℃ of crystallization 96h, end product promptly gets the Y/MCM-48 composite molecular screen through filtering, wash, drying.
Instance 4
0.88g is ground thin Y zeolite powder join in the mixed solution of CTAB and OP-10, stir 20min fast, in above-mentioned mixed liquor, add 5.7ml waterglass (25.4wt%SiO then
2, 7.47wt%NaO
2, 67.29wt%H
2O), stir 2h down at 30 ℃, the initial gel that obtains mixing, its mole ratio of components are 1 SiO
2: 0.12 CTAB:0.027 OP-10:0.35Na
2O:59 H
2O, Y zeolite/SiO
2(g/g)=0.44.Regulate PH ≈ 10.6, this colloidal sol is packed in the 40ml agitated reactor, 100 ℃ of crystallization 48h, end product promptly gets the Y/MCM-48 composite molecular screen through filtering, wash, drying.
Instance 5
The former powder of the synthesis type of Y/MCM-48 composite molecular screen is flowed down in 500 ℃ of roasting 2h at nitrogen earlier, and roasting 5h again under the same temperature in air atmosphere promptly obtains roasting type sample then.
Claims (7)
1. one kind is that nuclear, mesoporous MCM-48 are the preparation method of composite molecular screen Y/MCM-48 of the core-shell type structure of shell with the Y zeolite; It is characterized in that softex kw CTAB is a cationic surfactant, Triton X-100 OP-10 is a non-ionic surface active agent, is template with both mixed solution; With the Y zeolite as the micropore precursor; As replenishing the silicon source, prepare microporous mesoporous composite molecular screen Y/MCM-48 with waterglass, said microporous mesoporous composite molecular screen Y/MCM-48 includes micropore Y zeolite facies and mesoporous MCM-48 mutually; Has the mesoporous pore passage structure of micropore and bimodulus; And when content is all adjustable for the skeleton Si/Al of micropore phase in the composite molecular screen, and said material is higher than corresponding mechanical impurity catalytic activity, and its concrete steps are following:
A certain proportion of CTAB, OP-10 and water stir into settled solution under 20 ℃～40 ℃, in this solution, add a certain amount of Y zeolite powder, under same temperature, stir 15～60min; Add waterglass then, continue to stir 1～3h, the mixed sols that obtains is regulated pH between 9.0～12.0 with hydrochloric acid or NaOH; 75 ℃～125 ℃ crystallization 12～96h then in the stainless steel cauldron pack into; After crystallization finished, solid product promptly got the former powder of synthesis type through suction filtration, washing, oven dry;
Used molar ratio of material is at following scope: 1SiO in above-mentioned synthesizing
2: 0.12～0.17CTAB: 0.020～0.027OP-10: 0.20～0.35Na
2O: 59H
2O, Y zeolite and SiO
2Mass ratio be 0.22～1.98.
2. the preparation method of composite molecular screen Y/MCM-48 according to claim 1 is characterized in that selecting for use different Y zeolites as the micropore phase, realizes that the skeleton Si/Al of micropore phase in the composite molecular screen is adjustable.
3. the preparation method of composite molecular screen Y/MCM-48 according to claim 1 is characterized in that the content of micropore phase in the composite molecular screen is controlled, content greater than zero smaller or equal to 50%.
4. the preparation method of composite molecular screen Y/MCM-48 according to claim 1 is characterized in that consisting of of employed waterglass: 25.4%SiO
2, 7.4%Na
2O, 67.2%H
2O.
5. the preparation method of composite molecular screen Y/MCM-48 according to claim 1, it is characterized in that the synthesis condition of optimizing is better in following ranges: molar ratio of material is 1SiO
2: 0.15CTAB: 0.025OP-10: 0.28Na
2O: 59H
2O, Y zeolite molecular sieve and SiO
2Mass ratio be 0.22～1.98, pH is 10.5～11.5, crystallization temperature is 90～110 ℃, crystallization time is 24～72h.
6. the preparation method of composite molecular screen Y/MCM-48 according to claim 1; It is characterized in that the former powder of synthesis type is flowed down in 350～650 ℃ of roasting 1～3h at nitrogen earlier; Roasting 3～7h again under the same temperature in air atmosphere promptly obtains roasting type sample then.
7. the preparation method of composite molecular screen Y/MCM-48 according to claim 1 is characterized in that selecting for use high silica alumina ratio Y zeolite as the micropore phase, and the skeleton Si/Al ratio of Y zeolite facies is higher than conventional Y zeolite in the resulting composite molecular screen.
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| CN102198406A (en) * | 2010-03-26 | 2011-09-28 | 北京化工大学 | Method for preparing high-content double-transition metal composite molecular sieve |
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