CN1291915C - Method for synthesizing molecular sieve in media pores - Google Patents
Method for synthesizing molecular sieve in media pores Download PDFInfo
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- CN1291915C CN1291915C CN 200410004482 CN200410004482A CN1291915C CN 1291915 C CN1291915 C CN 1291915C CN 200410004482 CN200410004482 CN 200410004482 CN 200410004482 A CN200410004482 A CN 200410004482A CN 1291915 C CN1291915 C CN 1291915C
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- molecular sieve
- mesopore molecular
- water glass
- silicon
- modulus
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 54
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 239000011148 porous material Substances 0.000 title description 3
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 37
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 239000002210 silicon-based material Substances 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000009415 formwork Methods 0.000 claims description 9
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 150000002602 lanthanoids Chemical class 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- -1 molecular sieve alkali-metal Chemical class 0.000 claims 2
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000012736 aqueous medium Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 238000013019 agitation Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 206010013786 Dry skin Diseases 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 8
- 229910001948 sodium oxide Inorganic materials 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical class [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical class [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
一种介孔分子筛的合成方法，该方法包括在水介质中将一种含硅化合物、一种有机模板剂和一种酸混合并晶化，其特征在于，所述的含硅化合物为水玻璃，其模数小于3.5；所谓模数是指水玻璃中硅(以氧化物计)的摩尔数与碱金属(以氧化物计)的摩尔数之比。与现有方法相比，本发明提供的方法采用廉价水玻璃为硅源，可合成出低成本、高结晶度的介孔分子筛。A method for synthesizing mesoporous molecular sieves, the method comprising mixing and crystallizing a silicon-containing compound, an organic template and an acid in an aqueous medium, characterized in that the silicon-containing compound is water glass , and its modulus is less than 3.5; the so-called modulus refers to the ratio of the moles of silicon (calculated as oxides) to the moles of alkali metals (calculated as oxides) in water glass. Compared with the existing method, the method provided by the invention adopts cheap water glass as a silicon source, and can synthesize mesoporous molecular sieves with low cost and high crystallinity.
Description
Technical field
The invention relates to a kind of synthetic method of mesopore molecular sieve.
Background technology
Mesopore molecular sieve (mesoporous molecular sieves) is the molecular screen material that a class has the regular pore canal structure, its aperture big (＞2 nanometer), and can in micron-scale, keep duct order highly.Wherein, be representative with MCM-41, people have carried out broad research to its application in fields such as catalyzer, support of the catalyst.
For MCM-41 mesopore molecular sieve with the close pile structure of six sides, prior art mainly is to be template with chain alkyl trimethyl quaternary ammonium salt (or alkali) cats product, (pH=9-14) adopts hydrothermal method synthetic (U.S.Pat.5,057,296 under alkaline condition; 5,108,725; 5,098,684; 5,102,643; 5,110,572; 5,300,277; 5,215,737; 6,190,639).Under above-mentioned synthesis condition, positively charged cats product micella (S
+) and electronegative silicon species (I
-), pass through S
+I
-Electrostatic interaction mutually combines, and silicon species through hydrothermal crystallizing, calcination steps, forms the MCM-41 mesopore molecular sieve with regular pore canal structure under base catalysis.In addition, people such as Huo have reported with the quaternary ammonium salt to be template, at SiO
2Near (Nature (368 (1994) 317) and the strong acid media (method for preparing the MCM-41 mesopore molecular sieve among the Chem.Mater. (6 (1994) 1176) iso-electric point.The synthesising mesoporous molecular sieve pattern of this method is by S
+I
-Widen to S
+X
-I
+, X
-Represent Cl
-, Br
-Or OH
-In negative ion.
Existing synthesising mesoporous molecular sieve method is the silicon source with silicoorganic compound, and its shortcoming is the cost height.
Summary of the invention
The objective of the invention is at existing be the high shortcoming of silicon source synthesising mesoporous molecular sieve method cost with silicoorganic compound, the synthetic method of the low mesopore molecular sieve of a kind of new cost is provided.
The preparation method of mesopore molecular sieve provided by the invention is included in the water medium a kind of silicon-containing compound, a kind of organic formwork agent and a kind of acid is mixed and crystallization, it is characterized in that described silicon-containing compound is a water glass, and its modulus is less than 3.5; So-called modulus is meant the ratio of the mole number of the mole number of silicon in the water glass (in oxide compound) and basic metal (in oxide compound).
Compare with existing method, it is the silicon source that method provided by the invention adopts cheap water glass, can synthesize the mesopore molecular sieve of low cost, high-crystallinity.
For example, the mesopore molecular sieve that 2 water glass synthesizes under 40 ℃ of conditions according to the method that the invention provides with modulus, through 600 ℃ of roasting degree of crystallinity 96% mesopore molecular sieve; Adopting modulus is the mesopore molecular sieve that 0.49 water glass at room temperature synthesizes, and is 110% through 600 ℃ of roasting degree of crystallinity.
Embodiment
According to method provided by the invention, described modulus is preferably less than 2.5, more preferably 0.2-2.
Described organic formwork agent is existing synthesising mesoporous molecular sieve template commonly used, and preferred formula is: C
nH
2n+1N (Me)
3X or C
nH
2n+1N (C
5H
5) in the X compound one or more, wherein n=10-18 is preferably 12-16, X
-Represent Cl
-, Br
-Or OH
-In negative ion.
Described acid is selected from one or more in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, the oxalic acid, is preferably hydrochloric acid, acetic acid or their mixture.
According to method provided by the invention, be preferably in the consumption of each component of mole number: the organic formwork agent of one mole water glass (in silicon oxide) 0.2-20 mole, the acid of 5-60 mole, the water of 50-250 mole.
The condition of described crystallization comprises: temperature is a room temperature-80 ℃, is preferably 25-65 ℃, and crystallization time is 2-24 hour, is preferably 4-24.
According to method provided by the invention, also comprise before described crystallization or in the crystallization process and introduce one or more metal components that are selected from IIB, IVB, VB, VIB, VIII family and the lanthanide series metal, one or more metal components among preferred Ti, Ni, W, Nb, V, Fe, Zn, La or the Ce wherein.Its method can be to be selected from IIB with containing, IVB, VB, VIB, the solution of the precursor of one or more metal components and described water glass in VIII family and the group of the lanthanides, organic formwork agent and acid directly mix, crystallization, also can be at described water glass, in the process of organic formwork agent and acid mixing and crystallization, to contain and be selected from IIB, IVB, VB, VIB, the solution of the precursor of VIII family and lanthanide series metal component is introduced, in oxide compound and with the mesopore molecular sieve total amount is benchmark, described metal group IVB, VB, VIB, the introducing amount of one or more branches is 0.5-20 weight % in VIII family and the group of the lanthanides, is preferably 1-5 weight %.
Describedly contain in vitriol, nitrate, muriate or the acetate that the precursor that is selected from IIB, IVB, VB, VIB, VIII family and lanthanide series metal component is selected from them one or more.
According to method provided by the invention, also comprise at least one washing step, method conventional in the prior art is adopted in described washing, and in oxide compound, described washing makes alkali metal content in the final mesopore molecular sieve less than 3 weight %, preferably less than 2.5 weight %.
According to method provided by the invention, can also comprise a calcination steps, described roasting can be carried out before described washing, also can carry out after described washing, described maturing temperature is 400-750 ℃, is preferably 450-650 ℃, roasting time is 0.5-5 hour, is preferably 2-4 hour.
In the embodiment preferred, the preparation method of described mesopore molecular sieve may further comprise the steps:
(1) mixed aqueous solution of preparation organic formwork agent and acid under agitation generates precipitation with this mixing solutions and water glass reaction;
(2) stir the precipitation crystallization that down step (1) is generated, crystallization condition is: temperature is that 20-80 ℃, crystallization time are 10-24 hour;
(3) washing of the crystallization product that obtains of step (2), in oxide compound, described washing makes alkali metal content in the final mesopore molecular sieve less than 3 weight %;
According to method provided by the invention, in another embodiment preferred, the preparation method of described mesopore molecular sieve may further comprise the steps:
(1) mixed aqueous solution of preparation organic formwork agent and acid, under agitation with this mixing solutions and water glass, contain the solution reaction that is selected from the precursor of one or more metal components in IIB, IVB, VB, VIB, VIII family and the group of the lanthanides and generate to precipitate
(2) stir the precipitation crystallization that down step (1) is generated, crystallization condition is: temperature is that 20-80 ℃, crystallization time are 10-24 hour;
The washing of the crystallization product that (3) obtains, in oxide compound, described washing makes alkali metal content in the final mesopore molecular sieve less than 3 weight %;
Molecular sieve crystallinity height, Heat stability is good by method provided by the invention is synthesized can keep Stability Analysis of Structures at 600 ℃, and have very high specific surface area and (be about 1000m
2/ g).This mesopore molecular sieve can be used as uses such as catalyzer, support of the catalyst, sorbent material.
Following example will the present invention is further illustrated.
Agents useful for same in the example except that specifying, is chemically pure reagent.
The content using plasma emission spectrographic determination of each metal component.
Wherein, the degree of crystallinity of described molecular sieve is relative crystallinity, diffracted intensity [Lin (CPS)] with the main diffraction peak in the described mesopore molecular sieve x-ray diffraction spectra (100 diffraction peaks) calculates, according to document (the synthesising mesoporous molecular sieve of method among the Nature (368 (1994) 317), with it is Comparative Examples, and to define its degree of crystallinity be 100%.
The degree of crystallinity that with water glass is the synthesising mesoporous molecular sieve in silicon source is calculated by following formula: the degree of crystallinity of mesopore molecular sieve=with water glass is the Lin (CPS)/with the Lin (CPS) * 100% of the synthesising mesoporous molecular sieve in organosilicon source of the synthesising mesoporous molecular sieve in silicon source.The X-ray diffraction experiment carries out on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44KV, 40mA, sweep velocity are 2 °/minute.
Comparative Examples
This Comparative Examples explanation is mesopore molecular sieve synthetic in silicon source with the organosilicon.
Under the room temperature condition 10.94 gram cetyl trimethylammonium bromides are added in the 585 gram water, add (37%) 71.1 milliliter of hydrochloric acid then, under agitation condition, obtain the solution S X0 of clear.
Taking by weighing tetraethoxy 52.05 slowly adds in the SX0 solution under agitation condition, continue under the room temperature to stir 20 hours, its pH value＜0.5[pH value adopts pH precision test paper qualitative test (down together)], filter, and with 10 times deionized water wash 3 times, 120 ℃ of dryings 3 hours, the mesopore molecular sieve D1 that obtains having the MCM-41 crystalline phase.In 550 ℃ of roastings after 3 hours, the degree of crystallinity of D1, aperture and specific surface are listed in the table 1 in the air atmosphere.
Example 1
Under the room temperature condition 17 gram cetyl trimethylammonium bromides are added in the 185 gram water, add (37%) 28.22 milliliter of hydrochloric acid then, under agitation condition, obtain the solution S X1 of clear.
(Chang Ling refinery product, silica content is 279.8 grams per liters, Na to measure 34.35 ml water glass
2O 87.3 grams per liters, modulus of water glass are 3.3).Slowly add under agitation condition in the SX1 solution, continue under the room temperature to stir 20 hours, filter its pH value＜2, and with 10 times deionized water wash 6 times, 120 ℃ of dryings 3 hours, the mesopore molecular sieve B1 that obtains having the MCM-41 crystalline phase.In 550 ℃ of roastings after 3 hours, the degree of crystallinity of B1, aperture and specific surface are listed in the table 1 in the air atmosphere.
Example 2
Under the room temperature condition 17 gram cetyl trimethylammonium bromides are added in the 185 gram water, add (37%) 106.65 milliliter of hydrochloric acid then, under agitation condition, obtain the solution S X2 of clear.
Measure 1000 ml water glass (with example 1), add 647.6 gram sodium hydroxide in this water glass solution, dissolving back thin up to 3400 milliliter obtains modulus and is 0.49 water glass solution I1.
Under the stirring at room condition, 116.8ml I1 water glass solution is slowly added in the SX2 solution, continue to stir its pH value＜2 18 hours, filter, and with 10 times deionized water wash 6 times, 120 ℃ of dryings 3 hours, the mesopore molecular sieve B2 that obtains having the MCM-41 crystalline phase.In 600 ℃ of roastings after 3 hours, the degree of crystallinity of B2, aperture, specific surface and sodium oxide content are listed in the table 1 in the air atmosphere.
Example 3
Under 40 ℃ of conditions 15 gram Tetradecyl Trimethyl Ammonium Bromide are added in the 150 gram water, add (37%) 68.2 milliliter of hydrochloric acid then, under agitation condition, obtain the solution S X3 of clear.
Measure 1000 ml water glass (with example 1), add 74.64 gram sodium hydroxide in this water glass solution, dissolving back thin up to 1500 milliliter obtains modulus and is 2.0 water glass solution I2.
Under 40 ℃ of agitation conditions 109.2ml I2 water glass solution is slowly added in the SX3 solution, continue to stir 18 hours, its pH value＜1, filtration, and with 10 times deionized water wash 6 times, 120 ℃ of dryings 3 hours, the mesopore molecular sieve B3 that obtains having the MCM-41 crystalline phase.In 600 ℃ of roastings after 3 hours, the degree of crystallinity of B3, aperture, specific surface and sodium oxide content are listed in the table 1 in the air atmosphere.
Example 4
Under the room temperature condition 19 gram bromohexadecane yl pyridines are added in the 172 gram water, add (37%) 108.18 milliliter of hydrochloric acid then, under agitation condition, obtain the solution S X4 of clear.
Measure 1000 ml water glass (with example 1), add 135.7 gram sodium hydroxide in this water glass solution, dissolving back thin up to 1200 milliliter obtains modulus and is 1.5 water glass solution I3.
Under 60 ℃ of agitation conditions, 92.5ml I3 water glass solution is slowly added in the SX4 solution, continue to stir its pH value＜1 16 hours, filter, and with 10 times deionized water wash 6 times, 120 ℃ of dryings 3 hours, the mesopore molecular sieve B4 that obtains having the MCM-41 crystalline phase.In 600 ℃ of roastings after 3 hours, the degree of crystallinity of B4, aperture, specific surface and sodium oxide content are listed in the table 1 in the air atmosphere.
Example 5
Under the room temperature condition 17 gram bromotetradecane yl pyridines are added in the 165 gram water, add (37%) 4201.2 milliliter of hydrochloric acid then, under agitation condition, obtain the solution S X5 of clear.
Measure 1000 ml water glass (with example 1), add 1129.2 gram sodium hydroxide in this water glass solution, dissolving back thin up to 1200 milliliter obtains modulus and is 0.3 water glass solution I4.
Under 60 ℃ of agitation conditions 116.8ml I4 water glass solution is slowly added in the SX5 solution, continue to stir its pH value＜05 16 hours, filter, and with 10 times deionized water wash 6 times, 120 ℃ of dryings 3 hours, the mesopore molecular sieve B5 that obtains having the MCM-41 crystalline phase.In 600 ℃ of roastings after 3 hours, the degree of crystallinity of B5, aperture, specific surface and sodium oxide content are listed in the table 1 in the air atmosphere.
Example 6
Under the room temperature condition 17 gram cetyl trimethylammonium bromides are added in the 185 gram water, add (37%) 106.65 milliliter of hydrochloric acid then, under agitation condition, obtain the solution S X6 of clear.
Take by weighing 10 gram tetrabutyl titanates and be dissolved in the propyl alcohol of 90 grams, the concentration that obtains tetrabutyl titanate is the propanol solution M1 of 10 weight %.
Under room temperature, stirring, 116.8ml I1 and 5.27 gram M1 solution are slowly joined in the SX6 solution in the mode that also flows, continue stirring 16 hours, its pH value＜2, filter, and with 8 times deionized water wash 6 times, 120 ℃ of dryings 3 hours, the mesopore molecular sieve B6 that obtains having the MCM-41 crystalline phase.In 480 ℃ of roastings after 3 hours, the sodium oxide of B6, titanium oxide content, degree of crystallinity, aperture and specific surface are listed in the table 1 in the air atmosphere.
Example 7
Under the room temperature condition 17 gram cetyl trimethylammonium bromides are added in the 185 gram water, add (37%) 106.65 milliliter of hydrochloric acid then, under agitation condition, obtain the solution S X7 of clear.
Take by weighing 20 gram iron nitrates and be dissolved in the 80ml water, the concentration that obtains iron nitrate is the aqueous solution M2 of 20 weight %.
Under room temperature, stirring, 116.8ml I1 and 6.9 gram M2 solution are slowly joined in the SX7 solution in the mode that also flows, continue stirring 18 hours, its pH value＜2, filter, and with 8 times deionized water wash 6 times, 120 ℃ of dryings 3 hours, the mesopore molecular sieve B7 that obtains having the MCM-41 crystalline phase.In 500 ℃ of roastings after 3 hours, the sodium oxide of B7, iron oxide content, degree of crystallinity, aperture and specific surface are listed in the table 1 in the air atmosphere.
Example 8
Under the room temperature condition 17 gram cetyl trimethylammonium bromides are added in the 185 gram water, add (37%) 106.65 milliliter of hydrochloric acid then, under agitation condition, obtain the solution S X8 of clear.
Take by weighing 25 gram cerous nitrates and be dissolved in the 75ml water, the concentration that obtains cerous nitrate is the aqueous solution M3 of 25 weight %.
Under room temperature, stirring, 116.8ml I1 and 7.1 gram M3 solution are slowly joined in the SX8 solution in the mode that also flows, continue stirring 20 hours, its pH value＜2, filter, and with 8 times deionized water wash 6 times, 120 ℃ of dryings 3 hours, the mesopore molecular sieve B8 that obtains having the MCM-41 crystalline phase.500 ℃ of roastings are 3 hours in the air atmosphere, and the sodium oxide of B8, cerium oxide content, degree of crystallinity, aperture and specific surface are listed in the table 1.
Table 1
| Example | Mesopore molecular sieve | Sodium oxide weight % | Degree of crystallinity % | Bore dia footpath nanometer | Specific surface m 2/g | Metal oxide weight % |
| Comparative Examples | D1 | / | 100 | 2.5 | 1152 | / |
| 1 | B1 | 2.2 | 58 | 2.4 | 1021 | / |
| 2 | B2 | 1.9 | 110 | 2.6 | 1078 | / |
| 3 | B3 | 1.8 | 96 | 2.5 | 1028 | / |
| 4 | B4 | 1.8 | 93 | 2.6 | 1076 | / |
| 5 | B5 | 1.6 | 113 | 2.5 | 1038 | / |
| 6 | B6 | 1.9 | 107 | 2.3 | 973 | TiO 2：1.22 |
| 7 | B7 | 1.8 | 104 | 2.4 | 1002 | Fe 2O 3：2.45 |
| 8 | B8 | 1.7 | 110 | 2.5 | 1025 | CeO 2：4.01 |
Data declaration in example and the table 1 the invention provides the mesopore molecular sieve stable performance that method adopts cheap water glass to synthesize for the silicon source, the degree of crystallinity height.
Claims (8)
1, a kind of synthetic method of mesopore molecular sieve, this method is included in the water medium mixes a kind of silicon-containing compound, a kind of organic formwork agent and a kind of acid and crystallization, it is characterized in that, described silicon-containing compound is a water glass, its modulus is less than 3.5, and the consumption of described each component is counted in mole number: 1 mole of organic formwork agent with the water glass 0.2-20 mole of silicon oxide, the acid of 5-60 mole, the water of 50-250 mole; So-called modulus is meant in the mole number of silicon in the water glass of oxide compound and ratio in the alkali-metal mole number of oxide compound.
2, method according to claim 1 is characterized in that, described modulus is less than 2.5.
3, method according to claim 2 is characterized in that, described modulus is 0.2-2.
4, method according to claim 1 is characterized in that, the condition of described crystallization: temperature is that room temperature-80 ℃, time are 2-24 hour.
5, method according to claim 1, it is characterized in that, described method also is included in before the crystallization or introduces one or more metal components that are selected from IIB, IVB, VB, VIB, VIII family and the lanthanide series metal in the crystallization process, in oxide compound and with the mesopore molecular sieve total amount is benchmark, and the introducing amount of described metal component is 0.5-20 weight %.
6, method according to claim 5, it is characterized in that, described metal component is selected from one or more among Ti, Ni, W, Nb, V, Fe, Zn, La or the Ce, is benchmark in oxide compound and with the mesopore molecular sieve total amount, and the introducing amount of described metal component is 1-5 weight %.
7, method according to claim 1 is characterized in that, described method also comprises the step of at least one washing, is benchmark in oxide compound and with the mesopore molecular sieve total amount, and described washing makes in the final mesopore molecular sieve alkali-metal content less than 3 weight %.
8, method according to claim 7 is characterized in that, is benchmark in oxide compound and with the mesopore molecular sieve total amount, and described washing makes in the final mesopore molecular sieve alkali-metal content less than 2.5 weight %.
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| US10888852B2 (en) | 2015-07-23 | 2021-01-12 | Albemarle Corporation | FCC catalyst additive and binder |
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| CN100500564C (en) * | 2007-04-13 | 2009-06-17 | 中国科学院山西煤炭化学研究所 | A kind of method for preparing mesoporous material by non-surfactant method |
| CN103848435A (en) * | 2014-03-18 | 2014-06-11 | 山东理工大学 | Method for preparing hexagonal phase MCM-41 mesoporous molecular sieve from rice hull as silicon source |
| CN111151291A (en) * | 2020-01-21 | 2020-05-15 | 山东玉皇化工有限公司 | Preparation method and application of mesoporous molecular sieve catalyst |
| CN112811436A (en) * | 2021-01-11 | 2021-05-18 | 洛阳理工学院 | Method for synthesizing MCM-41 mesoporous material by using waste glass |
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| US10888852B2 (en) | 2015-07-23 | 2021-01-12 | Albemarle Corporation | FCC catalyst additive and binder |
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