CN1669926A - Method for preparing mesoporous molecular sieve by sepiolite - Google Patents
Method for preparing mesoporous molecular sieve by sepiolite Download PDFInfo
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- CN1669926A CN1669926A CN 200410022996 CN200410022996A CN1669926A CN 1669926 A CN1669926 A CN 1669926A CN 200410022996 CN200410022996 CN 200410022996 CN 200410022996 A CN200410022996 A CN 200410022996A CN 1669926 A CN1669926 A CN 1669926A
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Abstract
The invention relates to the method for preparing mesoporous molecular sieve by sepiolite which consists of fragmenting sepiolite, treating with 2M-6M hydrochloric acid, sulfuric acid or nitric acid for 8-16h, removing magnesium compounds and obtaining non-shaped silicon dioxide, then subjecting aluminium salts and surface active agent to water thermal crystallization in water solution, filtering with crystallized sepiolite, washing with deionized water or extracting with organic solvent to obtain molecular sieve precursor, then burning the precursor for 3-18h in Muffle furnace at the temperature of 300-600 deg. C.
Description
Technical field:
This hair relates to field of inorganic nonmetallic material, is to be raw material with natural layered silicate or silico-aluminate, the preparation mesopore molecular sieve, and especially preparing the aperture with hot-liquid type sepiolite is 3～5nm, specific surface area is greater than 700m
2Six side's molecular sieves (HMS) of/g, contain aluminium six side's molecular sieves (ALHMS), high regular mesoporous silicon oxide (SBA), contain high regular mesoporous silicon oxide (ALSBA) mesopore molecular sieve of aluminium, to be used for the petroleum cracking catalyzer, the Minute Organic Synthesis catalyzer, sorbent material, microelectronic etc.
Background technology:
The preparation of meso-porous molecular sieve material normally is to carry out the skeleton replacement again behind the synthetic pure silicon mesoporous material of raw material to obtain doped mesoporous molecular sieve with the organosilicon, these method complexity, the starting material costliness, organic product behind some organosilicon hydrolyzation also causes environmental pollution, has restricted mesoporous material large-scale industrial production and application.
Summary of the invention:
The objective of the invention is with common natural minerals hot-liquid type sepiolite is raw material, the two-dimentional hexagonal mesoporous molecular sieve of preparation pure silicon skeleton, this material high surface area, wide aperture, it is good to have shape selectivity, diffusibility height, the characteristics of high adsorption capacity, in industrial widespread use, and after the common processing of this type matrix material and Al source, obtaining the hexagonal mesoporous molecular sieve of aluminiferous two dimension, its solid acid is strengthened.
Technical scheme of the present invention is: at first with the sepiolite after the fragmentation, behind hydrochloric acid, sulfuric acid or the nitric acid treatment 8～16h by 2M～6M, deviate from the magnesium compound between lattice layer, become soft silica; In acidity, alkalescence or neutral aqueous solution, carry out the hydrothermal crystallizing reaction then with corresponding aluminium salt and tensio-active agent; Again the sepiolite after the crystallization is filtered: obtain the meso-porous molecular sieve material precursor with deionized water wash or organic solvent extracting; Then with this precursor 1～15 ℃/min of temperature rise rate calcination, 6～18h in retort furnace, calcination time is 3～12h, and calcination temperature is 300～600 ℃, obtains specific surface area after the calcination greater than 700m
2/ g, the aperture is greater than the mesopore molecular sieve of 3.5nm.
Among the present invention, carry out one section hydrothermal crystallizing through pretreated sepiolite, the condition of hydrothermal crystallizing is pH4～12, and solid content is 50～120g/L, and the pressure of crystallization is in 0～100 normal atmosphere (gauge pressure), 90～200 ℃ of temperature, time 12h～12d; Optimum condition is, solid content is 60～100g/L, and crystallization pressure is 1～30 normal atmosphere (gauge pressure), and the crystallization time is 12h～36h, the HMS that obtains, SBA mesopore molecular sieve.Good and a certain proportion of sodium aluminate of its crystallinity, aluminum chloride, aluminium hydroxide etc. are crystallization simultaneously, is contained the aluminium mesopore molecular sieve accordingly, and its solid acid is strengthened.
The pH regulator agent of being adopted among the present invention is mineral acid such as sulfuric acid, hydrochloric acid or organic acid such as acetic acid, phenylformic acid and inorganic or organic mixing acid; Or adopting alkali lye to regulate as sodium hydroxide, potassium hydroxide, the reaction system pH after the adjusting is 4～12.
The anion surfactant that is adopted among the present invention is quaternary ammonium salt such as chlorination or Cetrimide, chlorination or cetrimonium bromide, chlorination or octadecyl trimethyl ammonium bromide etc., or the mixture of above-mentioned quaternary ammonium salt and short chain alkanes based quaternary ammonium salt.Cats product such as sodium laurylsulfonate or Sodium dodecylbenzene sulfonate etc.; Neutral surface active agent such as amino dodecane, cetylamine etc., these tensio-active agents help to form template, for the formation in mesoporous aperture creates conditions.
The present invention compares with existing Technology and has the following advantages:
(1) meso-porous molecular sieve material high surface area, the wide aperture of the present invention preparation, it is good to have a shape selectivity, the diffusibility height, the characteristics of high adsorption capacity are used widely industrial.(2) product of the present invention is two dimension six side's ordered mesoporous molecular sieve materials, changes different crystallization conditions and obtains HMS, SBA mesopore molecular sieve; Obtain ALHMS, ALSBA mesopore molecular sieve with the common crystallization in aluminium source, its solid acid is strengthened.
(3) the present invention can also obtain fire retardant Mg (OH) except the preparation pore size distribution is the meso-porous molecular sieve material of 3～5nm
2Accessory substance.
(4) all to adopt organosilicon and silicon sol be raw material to prior art, the method of process hydro-thermal reaction or microwave crystallization prepares mesoporous molecule and must sieve, its starting material costliness, with natural scpiolitc is after raw material carries out the pre-treatment crystallization, make mesopore molecular sieve through pyroprocessing again, its production cost will descend 20%.
Description of drawings:
The X-diffractogram of synthetic HMS under Fig. 1 alkaline condition
The X-diffractogram of synthetic SBA under Fig. 2 alkaline condition
The X-diffractogram of synthetic ALHMS under Fig. 3 alkaline condition
The X-diffractogram of the down synthetic ALSBA of Fig. 4 alkaline condition
The X-diffractogram of comprehensive HMS under Fig. 5 acidic conditions
The X-diffractogram of synthetic HMS under Fig. 6 neutrallty condition
Embodiment:
Embodiment 1
Sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
NaOH is dissolved in the solution that obtains pH12 in the distilled water, adds CTAB and 4 bromide, CTAB: SiO
2Be 0.1～0.5: 1, CTAB: 4 bromide is 1: 1～5; Add the sepiolite after handling in this solution, solid-to-liquid ratio is 15: 100, and strong mixing disperses 1h, obtains suspension;
This suspension is poured in the autoclave, be warming up to 120 ℃, step-down cooling behind the pressure 15atm reaction 36h, cooling vacuum filters washing and obtains white solid;
This white solid calcination 8h under the temperature of 823K obtains the meso-porous molecular sieve material of white;
The XRD figure of this meso-porous molecular sieve material is indicated as the HMS mesopore molecular sieve as shown in Figure 1, and specific surface area is 648.8m
2/ g, mean pore size 4.2nm.
Embodiment 2
Sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
NaOH is dissolved in the solution that obtains pH12 in the distilled water, adds the content of CTAB and 4 bromide, CTAB: SiO
2Be 0.5～1.2: 1, CTAB: 4 bromide is 1: 0.2～0.8;
Add the sepiolite after handling in this solution, solid-to-liquid ratio is 15: 100, and strong mixing disperses 1h, obtains suspension;
This suspension is poured in the autoclave, be warming up to 120 ℃, step-down cooling behind the pressure 15atm reaction 36h, cooling vacuum filters washing and obtains white solid;
This white solid calcination 8h under the temperature of 823K obtains the meso-porous molecular sieve material of white;
Obtain XRD figure mesopore molecular sieve as shown in Figure 2 after the crystallization, its structure is the SBA mesopore molecular sieve, and specific surface area is 783.9m
2/ g, mean pore size is 3.9nm.
Embodiment 3
Sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
In the suspension of pH12, add NaAlO
2Stir 1h, this suspension is poured in the autoclave, be warming up to 120 ℃, step-down cooling behind the pressure 15atm reaction 36h, cooling vacuum filters washing and obtains white solid;
This white solid calcination 8h under the temperature of 723K obtains the meso-porous molecular sieve material of white;
The XRD figure of this meso-porous molecular sieve material is indicated as the ALHMS mesopore molecular sieve as shown in Figure 3, and specific surface area is 570m
2/ g, mean pore size 4.2nm.
Embodiment 4
Sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
NaOH is dissolved in the solution that obtains pH12 in the distilled water, adds the content of CTAB and 4 bromide, CTAB: SiO
2Be 0.5～1.2: 1, CTAB: 4 bromide is 1: 0.2～0.8; Add the sepiolite after handling in this solution, solid-to-liquid ratio is 15: 100, and strong mixing disperses 1h, obtains suspension and carries out crystallization; Obtain mesopore molecular sieve after the crystallization.The XRD figure of this meso-porous molecular sieve material is indicated as the ALSBA mesopore molecular sieve as shown in Figure 4, and specific surface area is 673m
2/ g, mean pore size 3.9nm.
Embodiment 5
Sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
HCl is dissolved in the solution that obtains pH6 in the distilled water, and the amino dodecane of adding adds the sepiolite after handling in this solution, and solid-to-liquid ratio is 10: 100, and strong mixing disperses 1h, obtains suspension;
This suspension is poured in the autoclave, be warming up to 120 ℃, step-down cooling behind the pressure 15atm reaction 36h, cooling vacuum filters washing and obtains white solid;
This white solid calcination 8h under the temperature of 823K obtains the meso-porous molecular sieve material of white;
The XRD figure of this meso-porous molecular sieve material is indicated as the HMS mesopore molecular sieve as shown in Figure 5, and specific surface area is 982m
2/ g, mean pore size 4.2nm.
Embodiment 6
Sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
With the sepiolite after handling, the preparation solid-to-liquid ratio is 15: 100 a PH7 suspension, adds an amount of Sodium dodecylbenzene sulfonate, obtains suspension; This suspension is poured in the autoclave, be warming up to 120 ℃, step-down cooling behind the pressure 15atm reaction 36h; Cooling vacuum filters washing and obtains white solid;
This white solid calcination 8h under the temperature of 823K obtains the meso-porous molecular sieve material of white;
The XRD figure of this meso-porous molecular sieve material is indicated as the HMS mesopore molecular sieve as shown in Figure 6, and specific surface area is 932m
2/ g, mean pore size 4.2nm.
Claims (10)
1. one kind prepares the method for mesopore molecular sieve with sepiolite, it is characterized in that: at first with the sepiolite after the fragmentation, behind hydrochloric acid, sulfuric acid or the nitric acid treatment 8～16h by 2M～6M, deviate from the magnesium compound between lattice layer, become soft silica; In acidity, alkalescence or neutral aqueous solution, carry out the hydrothermal crystallizing reaction then with corresponding aluminium salt and tensio-active agent; Again the sepiolite after the crystallization is filtered: obtain the meso-porous molecular sieve material precursor with deionized water wash or organic solvent extracting; Then with this precursor 1～15 ℃/min of temperature rise rate calcination, 6～18h in retort furnace, calcination time is 3～12h, and calcination temperature is 300～600 ℃, obtains specific surface area after the calcination greater than 700m
2/ g, the aperture is greater than the mesopore molecular sieve of 3.5nm.
2. the method for preparing mesopore molecular sieve with sepiolite according to claim 1, it is characterized in that: carry out one section hydrothermal crystallizing through pretreated sepiolite, the condition of hydrothermal crystallizing is pH4～12, solid content is 50～120g/L, the pressure of crystallization is in 0～100 normal atmosphere (gauge pressure), 90～200 ℃ of temperature, time 12h～12d; Optimum condition is, solid content is 60～100g/L, and crystallization pressure is 1～30 normal atmosphere (gauge pressure), and the crystallization time is 12h～36h, the HMS that obtains, SBA mesopore molecular sieve.Good and a certain proportion of sodium aluminate of its crystallinity, aluminum chloride, aluminium hydroxide etc. are crystallization simultaneously, is contained the aluminium mesopore molecular sieve accordingly, and its solid acid is strengthened.
3. according to claim 1ly prepare the method for mesopore molecular sieve with sepiolite, it is characterized in that: the pH regulator agent of employing is mineral acid such as sulfuric acid, hydrochloric acid or organic acid such as acetic acid, phenylformic acid and inorganic or organic mixing acid; Or adopting alkali lye to regulate as sodium hydroxide, potassium hydroxide, the reaction system pH after the adjusting is 4～12.
4. the method for preparing mesopore molecular sieve with sepiolite according to claim 1, it is characterized in that: the anion surfactant of employing is quaternary ammonium salt such as chlorination or Cetrimide, chlorination or cetrimonium bromide, chlorination or octadecyl trimethyl ammonium bromide etc., or the mixture of above-mentioned quaternary ammonium salt and short chain alkanes based quaternary ammonium salt; Cats product such as sodium laurylsulfonate or Sodium dodecylbenzene sulfonate; Neutral surface active agent such as amino dodecane, cetylamine.
5. according to claim 1ly prepare the method for mesopore molecular sieve with sepiolite, it is characterized in that: sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
NaOH is dissolved in the solution that obtains pH12 in the distilled water, adds CTAB and 4 bromide, CTAB: SiO
2Be 0.1～0.5: 1, CTAB: 4 bromide is 1: 1～5; Add the sepiolite after handling in this solution, solid-to-liquid ratio is 15: 100, and strong mixing disperses 1h, obtains suspension;
This suspension is poured in the autoclave, be warming up to 120 ℃, step-down cooling behind the pressure 15atm reaction 36h, cooling vacuum filters washing and obtains the HMS mesopore molecular sieve, and specific surface area is 648.8m
2/ g, mean pore size 4.2nm.
6. according to claim 1ly prepare the method for mesopore molecular sieve with sepiolite, it is characterized in that: sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
NaOH is dissolved in the solution that obtains pH12 in the distilled water, adds the content of CTAB and 4 bromide, CTAB: SiO
2Be 0.5～1.2: 1, CTAB: 4 bromide is 1: 0.2～0.8;
Add the sepiolite after handling in this solution, solid-to-liquid ratio is 15: 100, and strong mixing disperses 1h, obtains suspension;
This suspension is poured in the autoclave, be warming up to 120 ℃, step-down cooling behind the pressure 15atm reaction 36h, cooling vacuum filters washing and obtains white solid;
This white solid is calcination 8h under the temperature of 823K, obtains mesopore molecular sieve after the crystallization, and its structure is the SBA mesopore molecular sieve, and specific surface area is 783.9m
2/ g, mean pore size is 3.9nm.
7. according to claim 1ly prepare the method for mesopore molecular sieve with sepiolite, it is characterized in that: sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
In the suspension of pH12, add NaAlO
2Stir 1h, this suspension is poured in the autoclave, be warming up to 120 ℃, step-down cooling behind the pressure 15atm reaction 36h, cooling vacuum filters washing and obtains white solid;
This white solid is calcination 8h under the temperature of 723K, obtains the ALHMS mesopore molecular sieve, and specific surface area is 570m
2/ g, mean pore size 4.2nm.
8. according to claim 1ly prepare the method for mesopore molecular sieve with sepiolite, it is characterized in that: sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
NaOH is dissolved in the solution that obtains pH12 in the distilled water, adds the content of CTAB and 4 bromide, CTAB: SiO
2Be 0.5～1.2: 1, CTAB: 4 bromide is 1: 0.2～0.8; Add the sepiolite after handling in this solution, solid-to-liquid ratio is 15: 100, and strong mixing disperses 1h, obtains suspension and carries out crystallization; Obtain the ALSBA mesopore molecular sieve after the crystallization, specific surface area is 673m
2/ g, mean pore size 3.9nm.
9. according to claim 1ly prepare the method for mesopore molecular sieve with sepiolite, it is characterized in that: sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
HCl is dissolved in the solution that obtains pH6 in the distilled water, and the amino dodecane of adding adds the sepiolite after handling in this solution, and solid-to-liquid ratio is 10: 100, and strong mixing disperses 1h, obtains suspension;
This suspension is poured in the autoclave, be warming up to 120 ℃, step-down cooling behind the pressure 15atm reaction 36h, cooling vacuum filters washing and obtains white solid;
This white solid calcination 8h under the temperature of 823K obtains the HMS mesopore molecular sieve, and specific surface area is 982m
2/ g, mean pore size 4.2nm.
10. according to claim 1ly prepare the method for mesopore molecular sieve with sepiolite, it is characterized in that: sepiolite obtains the low sepiolite of Mg content behind 2M salt acid treatment 12h, it consists of: SiO
264.5%, CaO 0.26%, and MgO 1.7%, H
2O 33.2%;
With the sepiolite after handling, the preparation solid-to-liquid ratio is 15: 100 a PH7 suspension, adds an amount of Sodium dodecylbenzene sulfonate, obtains suspension; This suspension is poured in the autoclave, be warming up to 120 ℃, step-down cooling behind the pressure 15atm reaction 36h; Cooling vacuum filters washing and obtains white solid;
This white solid calcination 8h under the temperature of 823K obtains the HMS mesopore molecular sieve, and specific surface area is 932m
2/ g, mean pore size 4.2nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101934234A (en) * | 2010-09-13 | 2011-01-05 | 中南大学 | Mesoporous molecular sieve catalyst for catalytic cracking of waste plastics as well as preparation method and application thereof |
| CN101623624B (en) * | 2009-08-10 | 2011-05-25 | 浙江理工大学 | Preparation method of organic sepiolite |
| CN104248988A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical mesoporous sepiolite composite carrier, catalyst and preparation method and application thereof and preparation method of ethyl acetate |
| CN106669593A (en) * | 2016-12-28 | 2017-05-17 | 长沙理工大学 | Framework modified sepiolite as well as preparation method and application thereof |
-
2004
- 2004-03-19 CN CN 200410022996 patent/CN1669926A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101623624B (en) * | 2009-08-10 | 2011-05-25 | 浙江理工大学 | Preparation method of organic sepiolite |
| CN101934234A (en) * | 2010-09-13 | 2011-01-05 | 中南大学 | Mesoporous molecular sieve catalyst for catalytic cracking of waste plastics as well as preparation method and application thereof |
| CN101934234B (en) * | 2010-09-13 | 2012-07-04 | 中南大学 | Mesoporous molecular sieve catalyst for catalytic cracking of waste plastics as well as preparation method and application thereof |
| CN104248988A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical mesoporous sepiolite composite carrier, catalyst and preparation method and application thereof and preparation method of ethyl acetate |
| CN104248988B (en) * | 2013-06-28 | 2016-03-30 | 中国石油化工股份有限公司 | The preparation method of spherical mesoporous sepiolite complex carrier and Catalysts and its preparation method and application and ethyl acetate |
| CN106669593A (en) * | 2016-12-28 | 2017-05-17 | 长沙理工大学 | Framework modified sepiolite as well as preparation method and application thereof |
| CN106669593B (en) * | 2016-12-28 | 2019-09-27 | 长沙理工大学 | A kind of framework modification sepiolite and its preparation method and application |
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