CN106115729A - A kind of synthesis under condition of no solvent has hierarchical porous structure MCM 41 and the method for metal-doped M MCM 41 molecular sieve - Google Patents
A kind of synthesis under condition of no solvent has hierarchical porous structure MCM 41 and the method for metal-doped M MCM 41 molecular sieve Download PDFInfo
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- CN106115729A CN106115729A CN201610471311.5A CN201610471311A CN106115729A CN 106115729 A CN106115729 A CN 106115729A CN 201610471311 A CN201610471311 A CN 201610471311A CN 106115729 A CN106115729 A CN 106115729A
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The invention discloses and a kind of synthesis under condition of no solvent there is hierarchical porous structure MCM 41 and the method for metal-doped M MCM 41 molecular sieve, belong to the synthesis technical field of molecular sieve.Technical scheme main points are: by uniform to solid material silicon source, Tetramethylammonium hydroxide and organic formwork agent ground and mixed, it is then transferred in hydrothermal reaction kettle in 60 100 DEG C of crystallization 12 48h, removes organic formwork agent in 550 DEG C of roastings after having reacted and obtain final products MCM 41 molecular sieve.The invention further particularly discloses the method that synthesis has metal-doped M MCM 41 molecular sieve of hierarchical porous structure under condition of no solvent.The solid phase method of the present invention have simple, environmental pollution is little and single surfactant guides the advantage such as hierarchical porous structure.
Description
Technical field
The invention belongs to the synthesis technical field of molecular sieve, be specifically related to one synthesis under condition of no solvent and have multistage
Pore structure MCM-41 and the method for metal-doped M-MCM-41 molecular sieve.
Background technology
Since M41S mesoporous silicon series material comes out, due to the characteristic of its excellence, such as, big specific surface area, Jie
The easy modulation in aperture, hole, various pattern, big pore volume and bigger absorbability so that mesoporous material enjoys section always
Grind the favor of worker, be one of the important research direction of Material Field.For microporous zeolitic material, mesoporous material is
Big advantage is no more than it has bigger specific surface and bigger aperture, and this makes mesoporous material at the catalysis of macromole, medicine
The adsorbing separation of thing slow release and macromole shows more prominent using value.But, the mesoporous silicon material of MCM-41 series
Material, including after the SBA-15 material (aperture is between 6-10nm) with one-dimensional straight pore passage structure of Stucky et al. report,
Its two-dimensional structure limits their application to a certain extent.
And the synthesising mesoporous material of Conventional solvents by the use of thermal means and multilevel hole material typically require in aqueous solution or alcoholic solution
Completing, the use of a large amount of solvents not only increases synthesis cost, concurrently forms substantial amounts of waste water and waste liquid, also result in environment
It is difficult the injury estimated, belongs to non-green synthetic method.
Nearest domestic Xiao have a good harvest research group report, synthesized the phosphorus with hierarchical porous structure by the method for solid phase synthesis
Aluminum molecular screen, but eco-friendly synthesis can have multi-stage porous and constitutionally stable M41S molecular screen material receives much concern,
This is also the most valuable in actual industrial, however about this face patent and document it is not yet reported that.
Summary of the invention
Present invention solves the technical problem that there is provided a kind of synthesis under condition of no solvent has hierarchical porous structure MCM-
41 and the method for metal-doped M-MCM-41 molecular sieve, this method solve traditional preparation methods synthesis relatively costly and formed
The problem such as a large amount of waste liquid environmental pollutions are heavier.
The present invention solves that above-mentioned technical problem adopts the following technical scheme that, one synthesis under condition of no solvent has many
The method of level pore structure MCM-41 molecular sieve, it is characterised in that concretely comprise the following steps: by solid material silicon source, Tetramethylammonium hydroxide
Uniform with organic formwork agent ground and mixed, it is then transferred in hydrothermal reaction kettle in 60-100 DEG C of crystallization 12-48h, reaction
Removing organic formwork agent in 550 DEG C of roastings after completing and obtain final products MCM-41 molecular sieve, the addition of each raw material should make crystalline substance
Changing the mol ratio of each composition in reaction system is SiO2: TMAOH:R=1.00:0-1.20:0.15-2.15, wherein R is organic
Template.
Further preferably, described silicon source is nine water sodium silicate, silica gel or white carbon.
Further preferably, described organic formwork agent be eight alkyl trimethyl ammonium bromides, ten alkyl trimethyl ammonium bromides, 12
Alkyl trimethyl ammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide or octadecyl trimethyl bromine
Change ammonium.
Further preferably, described crystallization temperature is 60 DEG C, 80 DEG C or 100 DEG C, and the crystallization time is 24h, roasting
Temperature is 550 DEG C.
A kind of method that synthesis has the metal-doped M-MCM-41 molecular sieve of hierarchical porous structure under condition of no solvent, its
It is characterised by concretely comprising the following steps: by solid material silicon source, Tetramethylammonium hydroxide, raw metal and organic formwork agent ground and mixed
Uniformly, it is then transferred in hydrothermal reaction kettle in 60-100 DEG C of crystallization 12-48h, in 500-600 DEG C of roasting after having reacted
Removing organic formwork agent and obtain the MCM-41 molecular sieve that final products are metal-doped, the addition of each raw material should make crystallization body
In system, the mol ratio of each composition is SiO2: TMAOH:M:R=1.00:0-1.20:0.01-0.94:0.15-2.15, wherein M is
Raw metal, R is organic formwork agent.
Further preferably, described silicon source is nine water sodium silicate, silica gel or white carbon.
Further preferably, described raw metal is sodium aluminate, cobalt chloride hexahydrate, Nickel dichloride hexahydrate, six hydration trichlorines
Change ferrum, Hexaaquachromium chloride, zirconyl chloride or gallium chloride.
Further preferably, described organic formwork agent be eight alkyl trimethyl ammonium bromides, ten alkyl trimethyl ammonium bromides, 12
Alkyl trimethyl ammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide or octadecyl trimethyl bromine
Change ammonium.
Further preferably, described crystallization temperature is 60 DEG C, 80 DEG C or 100 DEG C, and the crystallization time is 24h, roasting
Temperature is 550 DEG C.
The present invention, under conditions of not using any solvent (water or organic solvent), utilizes single cation surface activating
Agent just can realize the simple and eco-friendly MCM-41 with hierarchical porous structure preparing different pore size distribution and difference gold
Belong to doping M-MCM-41 molecular sieve, compared with Conventional solvents process for thermosynthesizing, the solid phase method of the present invention have simple,
Environmental pollution is little and single surfactant guides the advantages such as hierarchical porous structure.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the hierarchical porous structure MCM-41 molecular sieve that embodiment 1 prepares；
Fig. 2 is the N of the hierarchical porous structure MCM-41 molecular sieve that embodiment 1 prepares2(wherein illustration is BJH to adsorption-desorption isothermal
With HK pore distribution curve)；
Fig. 3 is the transmission electron microscope picture of the hierarchical porous structure MCM-41 molecular sieve that embodiment 1 prepares；
Fig. 4 is the hierarchical porous structure of the Al doping that embodiment 4 preparesAlThe XRD spectra of-MCM-41 molecular sieve；
Fig. 5 is the hierarchical porous structure of the Al doping that embodiment 4 preparesAlThe transmission electron microscope picture of-MCM-41 molecular sieve；
Fig. 6 is the hierarchical porous structure of the Fe doping that embodiment 6 preparesFeThe XRD spectra of-MCM-41 molecular sieve.
Detailed description of the invention
By the following examples the foregoing of the present invention is described in further details, but this should be interpreted as this
The scope inventing above-mentioned theme is only limitted to below example, and all technology realized based on foregoing of the present invention belong to this
Bright scope.
Embodiment 1
The synthesis of pure silicon MCM-41 molecular sieves
Weigh 0.9g (3.2mmol) nine water sodium silicate and 2.5g (6.8mmol) cetyl trimethylammonium bromide, both are mixed
Uniformly, firmly grind about ten minutes, be then transferred in hydrothermal reaction kettle in 100 DEG C of crystallization 24h, will after having reacted
Sample takes out, and removes cetyl trimethylammonium bromide in 550 DEG C of roastings of high temperature and obtains MCM-41 molecular sieve.
1 can be seen that the MCM-41 molecular sieve of preparation has the highest degree of order under condition of no solvent with reference to the accompanying drawings.
2 show that the final products obtained possess typical IV type isothermal curve with reference to the accompanying drawings, and have two set pore-size distributions
Curve, aperture is respectively 0.5nm and 3.4nm, and then shows that the MCM-41 molecular sieve of preparation has hierarchical porous structure.
3 show that the MCM-41 molecular sieve of preparation has the good degree of order with reference to the accompanying drawings, demonstrate Fig. 1 XRD table further
The result levied.
Embodiment 2
The synthesis of pure silicon MCM-41 molecular sieves
Weigh 0.4g (6.7mmol) white carbon, 1.3g (3.6mmol) cetyl trimethylammonium bromide and 0.1g
(0.551mmol) five hydration Tetramethylammonium hydroxide, by three's mix homogeneously, after firmly grinding about ten minutes, then shifts
In 80 DEG C of crystallization 12h to hydrothermal reaction kettle, after having reacted, sample is taken out, remove 16 in 550 DEG C of roastings of high temperature
Alkyl trimethyl ammonium bromide obtains MCM-41 molecular sieve.
Embodiment 3
The synthesis of pure silicon MCM-41 molecular sieves
Weigh 0.6g (2.1mmol) nine water sodium silicate and 0.2g (0.55mmol) cetyl trimethylammonium bromide, both are mixed
Closing uniformly, after firmly grinding about ten minutes, be then transferred in hydrothermal reaction kettle in 60 DEG C of crystallization 48h, reaction completes
After sample is taken out, remove cetyl trimethylammonium bromide in 550 DEG C of roastings of high temperature and obtain MCM-41 molecular sieve.
Embodiment 4
The synthesis of the MCM-41 molecular sieve of aluminum doping
Weigh 0.4g (6.7mmol) white carbon, 1.3g (3.6mmol) cetyl trimethylammonium bromide, 0.1g (0.551mmol)
Five hydration Tetramethylammonium hydroxide and 0.005g (0.61mmol) sodium metaaluminates, by raw material mix homogeneously, firmly grind about ten
After minute, it is then transferred in hydrothermal reaction kettle in 100 DEG C of crystallization 24h, after having reacted, sample is taken out, at high temperature
550 DEG C of roastings remove cetyl trimethylammonium bromide and obtain the MCM-41 molecular sieve of metal Al doping.
4 can be seen that what the metal Al of preparation adulterated with reference to the accompanying drawingsAl-MCM-41 molecular sieve has the highest degree of order.
5 show what metal Al adulterated with reference to the accompanying drawingsAl-MCM-41 molecular sieve has the good degree of order, demonstrates further
The result that Fig. 4 XRD characterizes.
Embodiment 5
The synthesis of the MCM-41 molecular sieve of aluminum doping
Weigh 0.9g (3.2mmol) nine water sodium silicate, 1.3g (3.6mmol) cetyl trimethylammonium bromide and 0.025g
(3mmol) sodium metaaluminate, by raw material mix homogeneously, after firmly grinding about ten minutes, be then transferred in hydrothermal reaction kettle in
80 DEG C of crystallization 24h, take out sample after having reacted, and remove cetyl trimethylammonium bromide in 550 DEG C of roastings of high temperature
Obtain the MCM-41 molecular sieve of metal Al doping.
Embodiment 6
The synthesis of the MCM-41 molecular sieve of Fe2O3 doping
Weigh 0.4g (6.7mmol) white carbon, 1.3g (3.6mmol) cetyl trimethylammonium bromide, 0.1g (0.551mmol)
Five hydration Tetramethylammonium hydroxide and 0.5g (1.9mmol) Iron(III) chloride hexahydrates, by raw material mix homogeneously, firmly grind about
After ten minutes, it is then transferred in hydrothermal reaction kettle in 100 DEG C of crystallization 24h, after having reacted, sample is taken out, at high temperature
550 DEG C of roastings remove cetyl trimethylammonium bromide and obtain the MCM-41 molecular sieve of metal Fe doping.
6 can be seen that what metal Fe adulterated with reference to the accompanying drawingsFe-MCM-41 sample has the highest degree of order.
In sum, the present invention prepares MCM-41 molecular sieve and metal-doped MCM-41 molecular sieve not only have very well
Order, the advantage such as product structure also with multi-stage porous simultaneously.And the method for Conventional solvents thermal synthesis, it usually needs at water
Completing in solution or organic solvent, the use of a large amount of solvents not only increases synthesis cost, concurrently forms substantial amounts of waste water and gives up
Liquid, also result in the injury being difficult to estimate, belongs to non-green synthetic method to environment, and solid phase synthesis then belongs to eco-friendly
Green synthesis method.
Embodiment above describes the ultimate principle of the present invention, principal character and advantage, the technical staff of the industry should
Understanding, the present invention is not restricted to the described embodiments, and the simply explanation present invention's described in above-described embodiment and description is former
Reason, under the scope without departing from the principle of the invention, the present invention also has various changes and modifications, and these changes and improvements each fall within
In the scope of protection of the invention.
Claims (9)
1. one kind synthesizes the method with hierarchical porous structure MCM-41 molecular sieve under condition of no solvent, it is characterised in that specifically walk
Suddenly it is: solid material silicon source, Tetramethylammonium hydroxide and organic formwork agent ground and mixed is uniform, is then transferred to hydro-thermal reaction
In 60-100 DEG C of crystallization 12-48h in still, remove organic formwork agent in 500-600 DEG C of roasting after having reacted and obtain finally
Product MCM-41 molecular sieve, the addition of each raw material should make the mol ratio of each composition in crystallization system be SiO2:
TMAOH:R=1.00:0-1.20:0.15-2.15, wherein R is organic formwork agent.
The method that synthesis has hierarchical porous structure MCM-41 molecular sieve under condition of no solvent the most according to claim 1,
It is characterized in that: described silicon source is nine water sodium silicate, silica gel or white carbon.
The method that synthesis has hierarchical porous structure MCM-41 molecular sieve under condition of no solvent the most according to claim 1,
It is characterized in that: described organic formwork agent is eight alkyl trimethyl ammonium bromides, ten alkyl trimethyl ammonium bromides, dodecyl front three
Base ammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide or Cetyltrimethylammonium bromide.
The method that synthesis has hierarchical porous structure MCM-41 molecular sieve under condition of no solvent the most according to claim 1,
It is characterized in that: described crystallization temperature is 60 DEG C, 80 DEG C or 100 DEG C, the crystallization time is 24h, and sintering temperature is 550
℃。
5. synthesizing a method with the metal-doped M-MCM-41 molecular sieve of hierarchical porous structure under condition of no solvent, it is special
Levy and be to concretely comprise the following steps: by equal to solid material silicon source, Tetramethylammonium hydroxide, raw metal and organic formwork agent ground and mixed
Even, it is then transferred in hydrothermal reaction kettle, in 60-100 DEG C of crystallization 12-48h, remove in 500-600 DEG C of roasting after having reacted
Going organic formwork agent to obtain the MCM-41 molecular sieve that final products are metal-doped, the addition of each raw material should make crystallization system
In the mol ratio of each composition be SiO2: TMAOH:M:R=1.00:0-1.20:0.01-0.94:0.15-2.15, wherein M is gold
Belonging to raw material, R is organic formwork agent.
The M-MCM-41 that synthesis has hierarchical porous structure metal-doped under condition of no solvent the most according to claim 5 divides
The method of son sieve, it is characterised in that: described silicon source is nine water sodium silicate, silica gel or white carbon.
The M-MCM-41 that synthesis has hierarchical porous structure metal-doped under condition of no solvent the most according to claim 5 divides
The method of son sieve, it is characterised in that: described raw metal is sodium aluminate, cobalt chloride hexahydrate, Nickel dichloride hexahydrate, six hydrations three
Iron chloride, Hexaaquachromium chloride, zirconyl chloride or gallium chloride.
The M-MCM-41 that synthesis has hierarchical porous structure metal-doped under condition of no solvent the most according to claim 5 divides
Son sieve method, it is characterised in that: described organic formwork agent be eight alkyl trimethyl ammonium bromides, ten alkyl trimethyl ammonium bromides,
Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide or octadecyl front three
Base ammonium bromide.
The M-MCM-41 that synthesis has hierarchical porous structure metal-doped under condition of no solvent the most according to claim 5 divides
The method of son sieve, it is characterised in that: described crystallization temperature is 60 DEG C, 80 DEG C or 100 DEG C, and the crystallization time is 24h, roasting
Burning temperature is 550 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587092A (en) * | 2016-12-15 | 2017-04-26 | 河南师范大学 | Novel synthesis method of super-mesoporous/macroporous-crystal wall composite materials |
| CN109111178A (en) * | 2017-06-23 | 2019-01-01 | 高雄医学大学 | Ceramic material with active slow release effect, method for its manufacture and system comprising such ceramic material |
| CN110270368A (en) * | 2018-03-14 | 2019-09-24 | 北京化工大学 | A method of no solwution method synthesis is used for the embedded catalyst material of C-1 chemistry |
| CN111099602A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Iron-containing composite porous molecular sieve |
| CN111215125A (en) * | 2018-11-26 | 2020-06-02 | 北京化工大学 | The target product of the Fischer-Tropsch reaction for the synthesis gas is C5-12And a process for preparing the same |
| CN115707654A (en) * | 2021-08-19 | 2023-02-21 | 中国石油化工股份有限公司 | All-silicon molecular sieve and preparation method and application thereof |
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2016
- 2016-06-27 CN CN201610471311.5A patent/CN106115729B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587092A (en) * | 2016-12-15 | 2017-04-26 | 河南师范大学 | Novel synthesis method of super-mesoporous/macroporous-crystal wall composite materials |
| CN109111178A (en) * | 2017-06-23 | 2019-01-01 | 高雄医学大学 | Ceramic material with active slow release effect, method for its manufacture and system comprising such ceramic material |
| CN109111178B (en) * | 2017-06-23 | 2021-04-02 | 高雄医学大学 | Ceramic material with active slow release effect, method for its manufacture and system comprising such ceramic material |
| CN110270368A (en) * | 2018-03-14 | 2019-09-24 | 北京化工大学 | A method of no solwution method synthesis is used for the embedded catalyst material of C-1 chemistry |
| CN110270368B (en) * | 2018-03-14 | 2020-09-04 | 北京化工大学 | Method for synthesizing carbon-chemical embedded catalyst material by solution-free method |
| CN111099602A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Iron-containing composite porous molecular sieve |
| CN111215125A (en) * | 2018-11-26 | 2020-06-02 | 北京化工大学 | The target product of the Fischer-Tropsch reaction for the synthesis gas is C5-12And a process for preparing the same |
| CN115707654A (en) * | 2021-08-19 | 2023-02-21 | 中国石油化工股份有限公司 | All-silicon molecular sieve and preparation method and application thereof |
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