CN1990381A - Method for preparing middle-aperture material using silicon oxide as main body - Google Patents
Method for preparing middle-aperture material using silicon oxide as main body Download PDFInfo
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- CN1990381A CN1990381A CN 200510136598 CN200510136598A CN1990381A CN 1990381 A CN1990381 A CN 1990381A CN 200510136598 CN200510136598 CN 200510136598 CN 200510136598 A CN200510136598 A CN 200510136598A CN 1990381 A CN1990381 A CN 1990381A
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Abstract
The invention relates to a process of preparing mesopore material, which is characterized by high hydrothermal stability, uniform aperture diameter and applying silicon oxide as main body. The invention is characterized in that it comprises following steps: hydrothermal synthesis of microporous molecular sieve precursor; mixing precursor and template and NaOH and refluxing; then adjusting pH of dissolved substance with inorganic acid; crystallizing under certain condition for a certain period and getting mesopore material of high hydrothermal stability, with grain size being 20-500 nanometer. The specific surface area of this material is 300-1500 m2/ g, the pore capacity is 0.1-1.5 cm3/ g, the pore diameter is 2-10 nm after being baked. 90% of its specific surface area and pore capacity are kept after being dealt with in boiling water of 100 Deg. C for 312 hours.
Description
Technical field
The present invention relates to a kind of high hydrothermal stability, based on the preparation method of the mesopore material of silicon oxide.
Background technology
1992, Mobil company has synthesized the silicon oxide mesopore material, and (U.S.Patent 5057296,1991; U.S.Patent 5098684,1992).This material has high-specific surface area and high thermal stability, and arrange in order in the duct, pore size is adjustable, is with a wide range of applications at aspects such as absorption, separation, macromolecular catalyzed conversion and nano material assemblings, has received much concern since report always.But the hydrothermal stability that the silicon oxide mesopore material is lower is restricted its application.Though having attempted several different methods, people make the hydrothermal stability of silicon oxide mesopore material that raising largely arranged, but compare with traditional micro porous molecular sieve, the hydrothermal stability of this material is still lower, also is difficult to satisfy the harsh requirement of industrial high-temperature catalytic process (as catalytic cracking) at present.
Recently, (U.S.Patent 6702993B2,2004 such as Pinnavaia; U.S.Patent6706169B2,2004; U.S.Patent 6770258B2,2004) and Qiu Shilun etc. (CN1349929A, 2001) reported that the seed-solution with micro porous molecular sieve replaces silicon source commonly used, synthesized the sial mesopore material of high hydrothermal stability.The seed-solution that they adopt is meant when synthetic microporous molecular sieve (as ZSM-5, Y, Beta), when the microtexture unit that occurs molecular sieve in the synthetic system but when also not forming nucleus, interrupt crystallization process by the pH value that reduces reaction pressure, temperature or improve system, the resulting settled solution that contains component such as sial.They think the primary and secondary structural unit that exists micro porous molecular sieve in the seed-solution, these structural units can interact with tensio-active agent, and enter middle hole on framework by the organic and inorganic self assembling process, this is equivalent to introduce the crystallite that is similar to micro porous molecular sieve in unbodied mesopore hole wall, thereby has improved the stability of product.The silica-based mesopore material of gained can be handled in boiling water 300 hours, perhaps handled in the saturated steam under 800 ℃ 2 hours and considerable change does not take place middle hole characteristic.But, should be noted that not all micro porous molecular sieve can obtain seed-solution.Therefore, the range of application of aforesaid method is limited.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the mesopore material based on silicon oxide.
For achieving the above object, technical solution of the present invention is: at first synthetic microporous molecular sieve crystal, dissolve the gained micro porous molecular sieve pH value back crystallization for some time of regulator solution in template and inorganic alkali solution.Characteristics of the present invention also are the hydrothermal stability of resulting mesopore material far above direct synthetic mesopore material, and the granularity of mesopore material is little, can reach 20～500 nanometers.
Preparation method of the present invention is:
A) preparation Si: aAl: bNaOH: cNaCl: dH
2The initial gel reaction thing of O: eHMI, wherein:
HMI is a hexamethylene imine, and a is the mol ratio in Al source and silicon source, and b is the mol ratio in NaOH and silicon source, and c is the mol ratio in NaCl and silicon source, and d is H
2The mol ratio in O and silicon source, e is the mol ratio in MHI and silicon source;
0≤a≤0.2，0.05≤(b+c)≤0.5，10≤d≤500，0.2≤e≤2.0；
Preferably be 0≤a≤0.05,0.1≤(b+c)≤0.3,20≤d≤50,0.4≤e≤1.0;
Wherein, silicon source material is white carbon black, water glass, silicon sol, orthosilicic acid and/or positive silicon ester; Aluminium source material is Wickenol CPS 325, nitric hydrate aluminium, hydrazine aluminum sulfate and/or sodium metaaluminate;
B) (preferably crystallization temperature was 135～150 ℃ in 2～15 days in 100～160 ℃ of following crystallization with the reactant of step a; Crystallization time is 4～10 days), crystallization product obtains the micro porous molecular sieve presoma, called after P after washing, drying;
C) presoma P that step b is obtained and template, NaOH, H
2O mixes, and is mixed with P: xR: yNaOH: zH
2The compound of O, wherein R represents template, is segmented copolymer EO
20PO
70EO
20, cetyl trimethylammonium bromide (CTAB), hexadecylamine and/or octadecylamine; , x, y, z be R, NaOH, H respectively
2The mol ratio of O and presoma P, wherein: 0.6≤x≤5.0,0.8≤y≤5.0,50≤z≤100, preferably, 0.6≤x≤5.0,0.8≤y≤5.0,50≤z≤100;
D) mixture that step c is obtained is reduced to room temperature in 80～120 ℃ reflux down 2～50 hours (preferably being 90～100 ℃ refluxed 6～24 hours);
E) pH with inorganic acid solution regulating step d backflow back gained mixture is 0.5～11 (preferably pH is 3～9), in 10～80 ℃ reflux down 2～100 hours (preferably being 20～40 ℃ refluxed 6～50 hours), at last solid product separation, washing, drying are obtained the former powder of mesopore material then;
F) the former powder that step e is obtained to remove template, obtains the mesopore material of high order high hydrothermal stability in 350～850 ℃ of following roastings 6～20 hours.
Again specifically, its preparation method is:
1) in proportion with silicon source material, aluminium source material, NaOH, NaCl, H
2O and HMI under agitation mix, and obtain initial gel reaction thing.It is transferred to have in the teflon-lined stainless steel cauldron crystallization under autogenous pressure.The reactor rotating speed is 10～150r/min, and crystallization temperature is 100～160 ℃, and crystallization time is 2～15 days.After the solid product that obtains separated with mother liquor and washing, drying obtains the micro porous molecular sieve presoma.
2) in proportion with presoma and template, NaOH, H
2O mixes, and the mixture that obtains was refluxed 2～50 hours down at 80～120 ℃.After mixture reduced to room temperature, with pH value to 0.5～11 of the mineral acid regulation system of 0.1～10M, mineral acid can be hydrochloric acid, sulfuric acid, phosphoric acid etc., stirs 2～100 hours down at 10～80 ℃ then.After solid-liquid separation, washing, drying, obtain the former powder of mesopore sample.Comprise template in this sample, for removing template, with it in 350～850 ℃ of roastings 6～20 hours, obtain high hydrothermal stability, the aperture is uniformly based on the mesopore material of silicon oxide.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of the former powder of mesopore material of embodiment 1 preparation;
Curve A, B, C, D, E are respectively the XRD figure of the former powder of mesopore material of embodiment 2,3,4,5,6 preparations among Fig. 2;
Curve A, B, C, D are respectively the XRD figure of the former powder of mesopore material of embodiment 7,8,9,10 preparations among Fig. 3;
Fig. 4 is the mesopore material XRD figure of embodiment 11 preparations;
Fig. 5 is the scanning electron photomicrograph of the former powder of mesopore material of embodiment 8 preparations;
Fig. 6 is the XRD figure of the mesopore material of Comparative Examples 1 and Comparative Examples 2 preparations.
Embodiment
Below by object lesson in detail the present invention is described in detail, but the present invention is not limited to these embodiment.
Embodiment 1
The white carbon black of 40 grams, 0.5 gram sodium metaaluminate, 2.5 gram sodium hydroxide, 2.7 gram NaCl were mixed also stirring at room after 30 minutes with 540 gram deionized waters and 47.5 gram HMI, the gel that forms is transferred in the band teflon-lined stainless steel cauldron, crystallization is 8 days under 150 ℃, 90r/min, the gained solid product after centrifugal, deionized water wash and 100 ℃ of dryings the former powder UTM-1 of presoma, its XRD figure is seen Fig. 1.
The white carbon black of 40 grams, 2.5 gram sodium hydroxide, 2.7 gram NaCl were mixed also stirring at room after 30 minutes with 540 gram deionized waters and 40 gram HMI, the gel that forms is transferred in the band teflon-lined stainless steel cauldron, crystallization is 8 days under 150 ℃, 90r/min, product after centrifugal, deionized water wash and 100 ℃ of dryings the former powder kenyaite of presoma, its XRD figure is seen Fig. 1.
Get the former powder of 1.8 gram UTM-1, after 4.5 gram cetyl trimethylammonium bromides (CTAB) and 4 gram NaOH mix, add 190 ml deionized water, place 100 ℃ of backflows of oil bath after 8 hours gained suspension, the HCl to pH=9 of cooling and adding 2M, stirring at room is 12 hours again, after the XRD figure of washing, dry back gained sample is seen Fig. 2 A.
Get the former powder of 1.8 gram UTM-1, after 4.5 gram CTAB and 4 gram NaOH mix, add 190 ml deionized water, place 100 ℃ of backflows of oil bath after 8 hours gained suspension, the HCl to pH=7 of cooling and adding 2M, stirring at room is 12 hours again, after the XRD figure of washing, dry back gained sample is seen Fig. 2 B.
In embodiment 3, mixture cooling back adds the HCl to pH=3 of 2M, keeps all the other conditions constant, and the XRD figure of gained sample is seen Fig. 2 C.
In embodiment 3, be 1.44 grams with the quantitative change of CTAB, keep other condition constant, the XRD figure of gained sample is seen Fig. 2 D.
In embodiment 3, be 1.82 grams with the quantitative change of NaOH, keep other condition constant, the XRD figure of gained sample is seen Fig. 2 E.
Get the former powder of 1.8 gram kenyaite, after 4.5 gram CTAB and 4 gram NaOH mix, add 190 ml deionized water, place 100 ℃ of backflows of oil bath after 8 hours gained suspension, the HCl to pH=9 of cooling and adding 2M, stirring at room is 12 hours again, sees Fig. 3 A after obtain the XRD figure of sample after the washing, drying.
In embodiment 7, mixture cooling back adds the HCl to pH=7 of 2M, keeps other condition constant, and the XRD figure of gained sample is seen Fig. 3 B.
In embodiment 7, mixture cooling back adds the HCl to pH=5 of 2M, keeps all the other conditions constant, and the XRD figure of gained sample is seen Fig. 3 C.
In embodiment 7, mixture cooling back adds the HCl to pH=3 of 2M, keeps all the other conditions constant, and the XRD figure of gained sample is seen Fig. 3 D.
Embodiment 11
With the sample that obtains among the embodiment 3 through 550 ℃ of roastings after 10 hours with H
2O mixes back (control water and solid ratio are 100 milliliters of every grams), places for some time then in 100 ℃ of baking ovens, isolates solid at last and carries out structural analysis.Through different treatment after the time XRD figure of sample see Fig. 4, its typical structure parameter is listed in table 1.XRD result shows that prepared material has regular pore passage structure among Fig. 4.Fig. 4 shows also that simultaneously the sample that obtains among the embodiment 3 through after 312 hours boiling water treating, still can keep good long-range order; Table 1 shows that the specific surface area of sample is 922m
2/ g, pore volume are 1.08cm
3/ g is respectively 92% and 90% before the boiling water treating.XRD result and nitrogen adsorption result show that the gained sample has high hydrothermal stability.
Embodiment 12
The SEM of embodiment 8 the results are shown in Figure 5, and as can be seen from Figure 5 this sample has uniform particle diameter, and its granularity is about 200nm.
Comparative Examples 1
With tetraethoxy (TEOS) is the synthetic MCM-41 of raw material.With proportioning is TEOS: Al
2O
3: CTAB: NaOH: H
2O=1: 0.01: 0.12: 0.2: 100 gel is transferred in the band teflon-lined stainless steel cauldron, in 100 ℃ of following crystallization 3 days, the gained solid product after centrifugal, deionized water wash and 100 ℃ of dryings the former powder of MCM-41, through 550 ℃ of roastings after 10 hours its XRD figure see Fig. 6.
Comparative Examples 2
With MCM-41 and the H after 550 ℃ of roastings
2O places for some time after mixing (control water and solid ratio are 100 milliliters of every grams) in 100 ℃ of baking ovens, isolate solid at last, carries out structural analysis.Through different treatment after the time XRD figure of sample see Fig. 6 (ordinate zou is identical with Fig. 4), its typical structure parameter is listed in table 1.After Fig. 6 showed that the MCM-41 material was handled through 24 hours, its order reduced greatly.Table 1 shows that the specific surface area of sample is 150m
2/ g, pore volume are 0.35cm
3/ g is respectively 17% and 51% before the boiling water treating.Further the prolongation treatment time can cause caving in of central hole structure.
Table 1 through 550 ℃ of roastings after the structures of samples parameter
| Sample | Treatment condition | Specific surface area (m 2/g) | Pore volume (cm 3/g) | Aperture (nm) |
| | 550 ℃ of roastings, 550 ℃ of roastings in 10 hours and boiling water treating 550 ℃ of roastings in 312 hours 550 ℃ of roastings in 10 hours and boiling water treating 24 hours | 1003 922(92％) 858 150(17％) | 1.20 1.08(90％) 0.68 0.35(51％) | 2.4 2.2 2.2 3.8 |
Numeric representation parameter of sample after boiling water treating in the bracket accounts for the per-cent before its processing
Claims (10)
1. preparation method based on the mesopore material of silicon oxide, the synthetic microporous molecular sieve presoma of first hydro-thermal mixes presoma and refluxes with template and NaOH, utilize pH value that mineral acid regulates solute crystallization afterwards then; Its concrete steps are:
A) preparation Si:aAl:bNaOH:cNaCl:dH
2The initial gel reaction thing of O:eHMI, wherein:
HMI is a hexamethylene imine, and a is the mol ratio in Al source and silicon source, and b is the mol ratio in NaOH and silicon source, and c is the mol ratio in NaCl and silicon source, and d is H
2The mol ratio in O and silicon source, e is the mol ratio in MHI and silicon source;
0≤a≤0.2，0.05≤b+c≤0.5，10≤d≤500，0.2≤e≤2.0；
B) with the reactant of step a in 100～160 ℃ of following crystallization 2～15 days, crystallization product obtains the micro porous molecular sieve presoma, called after P after washing, drying;
C) presoma P that step b is obtained and template, NaOH, H
2O mixes, and is mixed with P:xR:yNaOH:zH
2The compound of O, wherein R represents template, is segmented copolymer EO
20PO
70EO
20, cetyl trimethylammonium bromide, hexadecylamine and/or octadecylamine; X, y, z be R, NaOH, H respectively
2The mol ratio of O and presoma P, wherein: 0.6≤x≤5.0,0.8≤y≤5.0,50≤z≤100;
D) mixture that step c is obtained refluxed 2～50 hours down in 80～120 ℃, reduced to room temperature;
E) pH with inorganic acid solution regulating step d backflow back gained mixture is 0.5～11, refluxes 2～100 hours down in 10～80 ℃ then, at last solid product separation, washing, drying is obtained the former powder of mesopore material;
F) the former powder that step e is obtained to remove template, obtains the mesopore material of high order high hydrothermal stability in 350～850 ℃ of following roastings 6～20 hours.
2, preparation method as claimed in claim 1 is characterized in that, the mesopore material particle diameter of preparation is 20～500 nanometers.
3. preparation method as claimed in claim 1 is characterized in that, silicon source material is white carbon black, water glass, silicon sol, orthosilicic acid and/or positive silicon ester.
4. preparation method as claimed in claim 1 is characterized in that, aluminium source material is Wickenol CPS 325, nitric hydrate aluminium, hydrazine aluminum sulfate and/or sodium metaaluminate.
5. preparation method as claimed in claim 1 is characterized in that Si:aAl:bNaOH:cNaCl:dH
2In the initial gel reaction thing of O:eHMI, 0≤a≤0.05,0.1≤b+c≤0.3,20≤d≤50,0.4≤e≤1.0.
6. preparation method as claimed in claim 1 is characterized in that, the crystallization temperature among the step b is 135～150 ℃; Crystallization time is 4～10 days.
7. preparation method as claimed in claim 1 is characterized in that, presoma and template, NaOH, H among the step c
2In the O mixture, 0.6≤x≤5.0,0.8≤y≤5.0,50≤z≤100.
8. preparation method as claimed in claim 1 is characterized in that, presoma mixes the back in 90～100 ℃ of backflows 6～24 hours in the steps d with template and NaOH.
9. preparation method as claimed in claim 1 is characterized in that, the pH among the step e is 3～9.
10. preparation method as claimed in claim 1 is characterized in that, the crystallization temperature among the step e is 20～40 ℃, and the time is 6～50 hours.
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