CN100512960C - Method for preparing modified MCM-41/aluminium oxide composite carrier - Google Patents
Method for preparing modified MCM-41/aluminium oxide composite carrier Download PDFInfo
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- CN100512960C CN100512960C CNB2006100787402A CN200610078740A CN100512960C CN 100512960 C CN100512960 C CN 100512960C CN B2006100787402 A CNB2006100787402 A CN B2006100787402A CN 200610078740 A CN200610078740 A CN 200610078740A CN 100512960 C CN100512960 C CN 100512960C
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Abstract
The present invention relates to a preparation method of modified MCM-41/aluminium oxide composite carrier material, belonging to the field of composite new material technology. Said invention uses F- modified aluminium oxide as aluminium source, uses water-glass as silicon source, uses hexadecyl trimethyl ammonium bromide as template agent and adopts a hydrothermal synthesis process to prepare the invented MCM-41/aluminium oxide composite material. Said MCM-41/aluminium oxide composite material can be used as carrier of hydrogenation catalyst for diesel oil hydrogenation desulfurisation, hydrogenation denitrification, aromatic hydrocarbon hydrogenation saturation and heavy distillate hydrotreating process.
Description
Technical field
The invention belongs to the composite material technical field, relate to the preparation method of composite carrier, design a kind of especially through F
-The preparation method of MCM-41/ alumina composite material of modified aluminas preparation.
Background technology
By surfactant as the synthetic composite of template direction in big molecule conversion, catalysis, have a wide range of applications and research value as the fields such as separation and purification of catalyst carrier, adsorbing separation and large biological molecule.
U.S. Pat 5098684 provides a kind of method for preparing mesopore molecular sieve MCM-41,100g cetyltrimethylammonium hydroxide solution is mixed with 100g tetramethyl ammonium hydroxide solution (25%), stir, add the silicon oxide hydrate (contain the free water of 6wt.% and 4.5wt.% in conjunction with water) of 25g0.02 micron, mixture 150 ℃ of hydrothermal crystallizings in autoclave spend the night, with solid product separation, washing, drying at room temperature, under 540 ℃ at N
2Middle roasting 1h, roasting 6h in air subsequently.The specific area of mesopore molecular sieve is 993m
2/ g handles down the 2h specific area in 100% water vapour for 676 ℃ and keeps 72%, 788 ℃ and handle the 2h specific area in 100% water vapour down and keep 55%, handles 12 in zeolite
The h structure is destroyed fully, illustrates that hydrothermal stability is poor.Mesopore molecular sieve shrinks at structure cell behind 550 ℃ of roasting 6h that heat treatment structure destroys rapidly more than 25%, 750 ℃, illustrates that heat endurance is also poor.
U.S. Pat 5942208 is in order to overcome the problem of hydrothermal stability difference, adopted the method for regulating pH and adding salt for three times: (1) with ammonium salt aqueous solution, silicate, and aluminate, alkyl trimethyl halo ammonium mixes; (2) carry out the hydrothermal crystallizing reaction with this mixture, regulate the pH value, carry out the hydrothermal crystallizing reaction again; (3) in mixture, add one or more can with the water-soluble organic or inorganic salt of monovalent cation Cheng Jian, comprise CH
3COONa, LiCl, NaCl, KCl, NaNO
3, Na
2SO
4Deng; (4) repeating step (2); (5) hydrothermal crystallizing that carries out appropriate time under suitable temperature reacts, and obtains the middle phase of mesopore molecular sieve; (6) filtration, washing, drying; (7) 500～600 ℃ of roastings.Mesopore molecular sieve is handled 12h in 500 ℃ of roasting 2h or the boiling water in the oxygen that contains the 2.3kPa water vapour, structure is not destroyed, but this complex technical process, poor repeatability, the cycle is long, is difficult to large-scale application.
Gold hero etc. (petrochemical industry, 1999, be silicon source and aluminium source 28:524) with sodium metasilicate, activated alumina, with CTMAB the stay in place form agent, by optimizing synthesis condition, synthesize aperture 3.18nm, specific area 1103m
2The MCM of/g, pore wall thickness 2.82nm-41 mesoporous molecular sieve can improve the stability of MCM-41 mesoporous molecular sieve.
(chemistry of fuel journal, 1998,26 (3): 243) synthesized pure silicon MCM-41 mesoporous molecular sieve material with surfactant 1631 and 1831, employing room temperature method and hydrothermal crystallization method respectively such as Dou Tao.With 1831 the effect under compare, utilize the sieve sample of 1631 preparations to have crystallization velocity and heat endurance faster preferably, adopt 1831 then can obtain having bigger cell parameter and good hydrothermal stability and acid proof pure silicon MCM-41 product.
The MCM of pure silicon-41 molecular sieve stable fine, but acidity is very weak.Adding aluminium is to improve acid main method, but adds after the aluminium, and the stability of AlMCM-41 molecular sieve can descend a lot.It is that aluminium source, waterglass are the silicon source that Chinese patent CN 03134883.1 has introduced with aluminium oxide, and 1831 have synthesized stable high MCM-41/ alumina composite material for the template agent.But the structural stability of MCM-41 also is not fine.In order further to improve the stability of the AlMCM-41 that contains aluminium, have good acidity simultaneously, it is the effective means that addresses this problem that aluminium oxide is carried out surface treatment.
The present invention carries out F with aluminium oxide
-Ion modification, and mix the MCM of hydro-thermal synthesizing high-stability-41/ alumina composite material with waterglass and template agent.The structural stability of synthetic MCM-41 molecular sieve improves manyly.
Summary of the invention
The average pore size of MCM of the present invention-41/ alumina composite material is 3～10nm, and pore volume is 0.5～1.1ml/g, specific area 180～500m
2/ g, the purpose of preparation MCM-41/ alumina composite material provides a kind of hydrofinishing and carrier of hydrogenating catalyst with higher stability, be more suitable in as diesel hydrogenation for removal sulphur, hydrodenitrogeneration, aromatic hydrogenation is saturated and the carrier of the hydrotreating catalyst of heavy distillate.
The Composite Preparation general thought: the present invention is the aluminium oxide that floods certain order number (20～100 order) with the aqueous solution of fluoride, adds silicon sources such as waterglass again, adds the template agent, uses rare acid for adjusting pH value, the hydrothermal crystallizing after washing, and drying, roasting, screening forms.
Implementation step of the present invention is as follows:
1. aluminium oxide preliminary treatment: 20～100 order aluminium oxide are flooded with fluoride aqueous solution,, help the crystallization of MCM-41 at its surface fluorination sodium layer.Dipping temperature is room temperature～80 ℃, and dip time is 2～48h, needs in the dipping process to stir, and stir speed (S.S.) is 50～500rap/min.
2. with 20～100 order aluminium oxide and the silicon source aqueous solution of step 1, constitute the predecessor of composite.
3. the acquisition of composite gel: the mixture that step 2 is obtained joins the template agent and water is mixed in the jelly system, and adding rare acid for adjusting pH value is 9～13.
4. the acquisition of composite carrier: the product that step 3 is obtained is at 90～150 ℃ of hydrothermal crystallizing 12～144h after washings, 90～130 ℃ of down dry 5～40h, and 450～650 ℃ of following roasting 3～20h promptly obtain the composite of white powder.
Concrete summary of the invention is as follows:
The preparation method of a kind of modified MC M-41/ aluminium oxide composite carrier is with F
-Modified aluminas as aluminium source, waterglass as silicon source, softex kw as the template agent, hydro-thermal is synthesized MCM-41/ alumina composite material.
Modified aluminas is that aluminium oxide makes by infusion process in the solution of soluble fluoride.Soluble fluoride is a sodium fluoride.The weight concentration of fluorine is 0.05～0.15g/mL in the described soluble fluoride solution.The granularity of aluminium oxide is 20～200 orders.
Its preparation method may further comprise the steps,
A) aluminium oxide of modification and silicon source aqueous solution join in the gluey system that template agent and water is mixed into again, form the slurries of composite, and wherein the mol ratio of each component is (3.0～6.0) Na in the slurries
2O:(7.0～25) SiO
2: (1) Al
2O
3: (0.85～2.5) F:(0.01～0.1) CTAB:(350～400) H
2O adds acid and regulates pH value to 9～13;
B) slurries that step a) is obtained are at 90～150 ℃ of following crystallization 12～144h, and the material that obtains after filtration, after the washing, at 80～130 ℃ of down dry 5～40h, at 450～650 ℃ of following roasting 3～20h, obtain described material.
The load capacity of the fluoride of modified MC M-41/ aluminium oxide composite carrier is weight percentage 1.0～5.0%.Average pore size is 3～10nm, and pore volume is 0.5～1.1ml/g, and specific area is 180～500m
2/ g.
At F
-In the aluminium oxide of modification, by mixing with waterglass and template agent, hydro-thermal is synthesized MCM-41/ alumina composite material, can further improve the structural stability of MCM-41, regulate the surface acid basicity of composite, make MCM-41/ alumina composite material be more suitable in as diesel hydrogenation for removal sulphur, hydrodenitrogeneration, aromatic hydrogenation is saturated and the carrier of the hydrotreating catalyst of heavy distillate.Meet the needs of production.
Description of drawings
Fig. 1. the XRD spectra of composite 1
Fig. 2. the XRD spectra of composite 2
Fig. 3. the XRD spectra of composite 3
Fig. 4. the XRD spectra of composite 4
Fig. 5. the XRD spectra of composite 5
Fig. 6. the XRD spectra of composite 6
Fig. 7. the XRD spectra of sample 7 (pure MCM-41)
Fig. 8 does not adsorb the MCM-41/Al of the aluminium oxide preparation of F
2O
3The XRD spectra of composite
Fig. 9. the XRD spectra of composite 1 after 900 ℃ of roastings
Figure 10. the XRD spectra of pure MCM-41 after 900 ℃ of roastings
Figure 11. do not adsorb the MCM-41/Al of the aluminium oxide preparation of F
2O
3XRD spectra after 900 ℃ of roastings
The specific embodiment
Get the 6.6g sodium fluoride and be dissolved in the 50ml water, add 24g γ-Al
2O
3, soak 24h, get the aluminium oxide of F-modification.(modulus is 3.0, SiO to add 352ml waterglass again
2Content be 26m%) in the γ-Al of above-mentioned F modification
2O
3In, dipping 6h.Get the 6g CTAB and mix, stir into slurry, the two is mixed, stir that the dilute sulfuric acid adjusting pH value with 2mol/L is 11.0 behind the 1h, the consisting of of this mixture: 4.5Na with 100ml water
2O:8.3SiO
2: Al
2O
3: 0.67F:0.07CTAB:380H
2O.140 ℃ of following hydrothermal crystallizing 24h in the autoclave of being with polytetrafluoroethylene (PTFE) to serve as a contrast take out product, with 100ml distilled water washing 5 times, and dry 12h under 110 ℃, 550 ℃ of following roasting 5h obtain white MCM-41/ γ-Al
2O
3Composite 1.XRD the results are shown in Figure 1.
Get the 6.6g sodium fluoride and be dissolved in the 50ml water, add 24g γ-Al
2O
3, soak 24h, get F
-The aluminium oxide of modification.(modulus is 3.0, SiO to add 352ml waterglass again
2Content be 26m%) in the γ-Al of above-mentioned F modification
2O
3In, dipping 6h.Get the 6g CTAB and mix, stir into slurry, the two is mixed, stir that the dilute sulfuric acid adjusting pH value with 2mol/L is 12.0 behind the 1h, the consisting of of this mixture: 4.5Na with 100ml water
2O:8.3SiO
2: Al
2O
3: 0.67F:0.07CTAB:380H
2O.140 ℃ of following hydrothermal crystallizing 48h in the autoclave of being with polytetrafluoroethylene (PTFE) to serve as a contrast take out product, with 100ml distilled water washing 5 times, and dry 12h under 110 ℃, 550 ℃ of following roasting 5h obtain white MCM-41/ γ-Al
2O
3Composite 2.XRD the results are shown in Figure 2.
Get the 6.6g sodium fluoride and be dissolved in the 50ml water, add 24g γ-Al
2O
3, soak 24h, get F
-The aluminium oxide of modification.(modulus is 3.0, SiO to add 704ml waterglass again
2Content be 26m%) in the γ-Al of above-mentioned F modification
2O
3In, dipping 6h.Get the 6g CTAB and mix, stir into slurry, the two is mixed, stir that the dilute sulfuric acid adjusting pH value with 2mol/L is 12.0 behind the 1h, the consisting of of this mixture: 4.5Na with 100ml water
2O:16.6SiO
2: Al
2O
3: 0.67F:0.07CTAB:380H
2O.140 ℃ of following hydrothermal crystallizing 24h in the autoclave of being with polytetrafluoroethylene (PTFE) to serve as a contrast take out product, with 100ml distilled water washing 5 times, and dry 12h under 110 ℃, 550 ℃ of following roasting 5h obtain white MCM-41/ γ-Al
2O
3Composite 3.XRD the results are shown in Figure 3.
Get the 6.6g sodium fluoride and be dissolved in the 50ml water, add 24g γ-Al
2O
3, soak 24h, get F
-The aluminium oxide of modification.(modulus is 3.0, SiO to add 704ml waterglass again
2Content be 26m%) in the γ-Al of above-mentioned F modification
2O
3In, dipping 6h.Get the 2.57g CTAB and mix, stir into slurry, the two is mixed, stir that the dilute sulfuric acid adjusting pH value with 2mol/L is 12.0 behind the 1h, the consisting of of this mixture: 4.5Na with 100ml water
2O:16.6SiO
2: Al
2O
3: 0.67F:0.03CTAB:380H
2O.140 ℃ of following hydrothermal crystallizing 24h in the autoclave of being with polytetrafluoroethylene (PTFE) to serve as a contrast take out product, with 100ml distilled water washing 5 times, and dry 12h under 110 ℃, 550 ℃ of following roasting 5h obtain white MCM-41/ γ-Al
2O
3Composite 4, XRD the results are shown in Figure 4.
Get the 13g sodium fluoride and be dissolved in the 50ml water, add 24g γ-Al
2O
3, soak 24h, get F
-The aluminium oxide of modification.(modulus is 3.0, SiO to add 704ml waterglass again
2Content be 26m%) in the γ-Al of above-mentioned F modification
2O
3In, dipping 6h.Get the 2.57g CTAB and mix, stir into slurry, the two is mixed, stir that the dilute sulfuric acid adjusting pH value with 2mol/L is 12.0 behind the 1h, the consisting of of this mixture: 4.5Na with 100ml water
2O:16.6SiO
2: Al
2O
3: 1.3F:0.03CTAB:380H
2O.140 ℃ of following hydrothermal crystallizing 24h in the autoclave of being with polytetrafluoroethylene (PTFE) to serve as a contrast take out product, with 100ml distilled water washing 5 times, and dry 12h under 110 ℃, 550 ℃ of following roasting 5h obtain white MCM-41/ γ-Al
2O
3Composite 5.XRD the results are shown in Figure 5.
Get the 25g sodium fluoride and be dissolved in the 100ml water, add 24g γ-Al
2O
3, soak 24h, get F
-The aluminium oxide of modification.(modulus is 3.0, SiO to add 1018ml waterglass again
2Content be 26m%) in the γ-Al of above-mentioned F modification
2O
3In, dipping 6h.Get the 7.62g CTAB and mix, stir into slurry, the two is mixed, stir that the dilute sulfuric acid adjusting pH value with 2mol/L is 12.0 behind the 1h, the consisting of of this mixture: 6.0Na with 100ml water
2O:24.0SiO
2: Al
2O
3: 2.5F:0.09CTAB:400H
2O.140 ℃ of following hydrothermal crystallizing 24h in the autoclave of being with polytetrafluoroethylene (PTFE) to serve as a contrast take out product, with 100ml distilled water washing 5 times, and dry 12h under 110 ℃, 550 ℃ of following roasting 5h obtain white MCM-41/ γ-Al
2O
3Composite 5.XRD the results are shown in Figure 6.
Comparative example 1
Getting the 6g CTAB mixes with 100ml water, stir into jelly, get 352ml waterglass and join in CTAB and the aqueous mixtures, regulate pH to 12.0 with the dilute sulfuric acid of 2mol/L after stirring 1h, the consisting of of this mixture: 4.5Na
2O:8.3SiO
20.07CTAB:380H
2O.140 ℃ of following hydrothermal crystallizing 24h in the autoclave of being with polytetrafluoroethylene (PTFE) to serve as a contrast take out product, with 100ml distilled water washing 5 times, and dry 12h under 110 ℃, 550 ℃ of following roasting 5h obtain white MCM-41, and XRD the results are shown in Figure 7.
Comparative example 2
Get and add 24g γ-Al in the 100ml water
2O
3, stir into pulpous state.(modulus is 3.0, SiO to add 1018ml waterglass again
2Content be 26m%) in above-mentioned γ-Al
2O
3In, dipping 6h.Get the 7.62g CTAB and mix, stir into slurry, the two is mixed, stir that the dilute sulfuric acid adjusting pH value with 2mol/L is 12.0 behind the 1h, the consisting of of this mixture: 6.0Na with 100ml water
2O:24.0SiO
2: Al
2O
3: 0.09CTAB:400H
2O.140 ℃ of following hydrothermal crystallizing 24h in the autoclave of being with polytetrafluoroethylene (PTFE) to serve as a contrast take out product, with 100ml distilled water washing 5 times, and dry 12h under 110 ℃, 550 ℃ of following roasting 5h obtain white MCM-41/ γ-Al
2O
3Composite 5.XRD the results are shown in Figure 8.
Comparative example 3
The material of embodiment 1 and comparative example 1 and comparative example 2 behind 900 ℃ of following roasting 1h, is measured XRD result, see Fig. 9, Figure 10 and Figure 11.The material of embodiment 1 still keeps very high degree of crystallinity (see figure 9), and the XRD degree of crystallinity of the material of comparative example 1 and comparative example 2 reduces very big (see figure 10), shows through the aluminium oxide of the F modification synthetic MCM-41/ γ-Al that obtains of hydro-thermal again
2O
3Composite has good heat endurance.
Table 1 preparation MCM-41/ γ-Al
2O
3The physical parameter of composite
| Composite | Specific area m 2/g | Pore volume ml/g | Average |
| 1 | 400.0 | 0.82 | 3.12 |
| 2 | 180.5 | 0.54 | 4.55 |
| 3 | 320.4 | 0.78 | 4.79 |
| 4 | 192.8 | 0.59 | 4.27 |
| 5 | 290.6 | 0.57 | 3.23 |
| 6 | 498.2 | 0.84 | 3.15 |
Claims (8)
1, the preparation method of a kind of modified MC M-41/ aluminium oxide composite carrier is characterized in that: with F
-Modified aluminas as aluminium source, waterglass as silicon source, softex kw as the template agent, hydro-thermal is synthesized MCM-41/ alumina composite material.
2, preparation method according to claim 1 is characterized in that: described modified aluminas is that aluminium oxide makes by infusion process in the solution of soluble fluoride.
3, preparation method according to claim 2 is characterized in that: described soluble fluoride is a sodium fluoride.
4, preparation method according to claim 2 is characterized in that: the weight concentration of fluorine is 0.05～0.15g/mL in the described soluble fluoride solution.
5, preparation method according to claim 1 is characterized in that: F
-Adopting the granularity of aluminium oxide before the modified aluminas modification is 20～200 orders.
6, preparation method according to claim 1 is characterized in that: may further comprise the steps,
A) aluminium oxide of modification and silicon source aqueous solution join in the gluey system that template agent and water is mixed into again, form the slurries of composite, and wherein the mol ratio of each component is (3.0～6.0) Na in the slurries
2O:(7.0～25) SiO
2: (1) Al
2O
3: (0.85～2.5) F:(0.01～0.1) softex kw: (350～400) H
2O adds acid for adjusting pH value to 9～13;
B) slurries that step a) is obtained are at 90～150 ℃ of following crystallization 12～144h, and the material that obtains after filtration, after the washing, at 80～130 ℃ of down dry 5～40h, at 450～650 ℃ of following roasting 3～20h, obtain described material.
7, according to claim 1 or 6 described preparation methods, it is characterized in that: the load capacity of the fluoride of described modified MC M-41/ aluminium oxide composite carrier is weight percentage 1.0～5.0%.
8, according to claim 1 or 6 described preparation methods, it is characterized in that: described modified MC M-41/ aluminium oxide composite carrier average pore size is 3～10nm, and pore volume is 0.5～1.1ml/g, and specific area is 180～500m
2/ g.
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