CN104445247B - SCM-4 molecular sieve and preparation method thereof - Google Patents
SCM-4 molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of SCM-4 molecular sieve and preparation method thereof, the problem mainly solving the new molecular sieve SCM-4 being not directed in prior art, the present invention provides a kind of new SCM-4 molecular sieve, by adopting the chemical composition comprising following mol ratio: mM2O:SiO2, wherein M is H, Li, at least one in Na, K, Cs, 0.005 < m < 0.025, is described SCM-4 molecular sieve in interplanar distance d=15.65 �� 1.6?, d=7.79 �� 0.50? d=5.18 �� 0.08? d=3.61 �� 0.06?, d=3.47 �� 0.05?, and d=3.36 �� 0.05? there is the technical scheme of the maximum at X-ray diffraction peak in place, solving above-mentioned technical problem preferably, the SCM-4 molecular sieve of preparation has certain application prospect in the chemisorbed of organic substance.
Description
Technical field
The present invention relates to a kind of SCM-4 molecular sieve and preparation method thereof.
Background technology
Zeolite molecular sieve is the silicate material of a kind of crystallization, element silicon therein can also by other element, particularly some trivalents or quadrivalent element such as Al, B, the part such as Ga, Ge replaces, due to some particularitys in its structure and chemical property, zeolite molecular sieve is in catalysis, and the field such as absorption and ion exchange is all widely applied. One key factor of decision molecular sieve application performance is its duct or cage cave feature, and these are characterized by being determined by the intrinsic crystal structure of molecular sieve, thus obtain the molecular sieve of new crystal structure for open up molecular sieve application have very important significance.
Some molecular sieves can obtain from nature, but, the molecular sieve that major part obtains practical application at catalytic field is all that the method by synthetic obtains. Hydrothermal synthesis method is the method for the most frequently used synthesis of molecular sieve, and some industrially have the molecular sieve of important application, such as A type molecular sieve, X-type molecular sieve, Y type molecular sieve, and ZSM-5 molecular sieve etc. obtains such as through hydrothermal synthesis method. Having main steps that first by silicon source, aluminum source, structure directing agent, alkali and water Homogeneous phase mixing of one typical hydrothermal synthesis method, obtains starting sol, is then placed in reactor by this colloidal sol again, carries out crystallization after airtight at certain temperature and pressure itself.
But also there are document or patent report, converted by stratified material solid at high temperature and can also obtain molecular sieve, as US4954325 obtains crystalline molecular sieve MCM-22 by the presoma MCM-22P of roasting stratified material, this molecular sieve has been observed that the alkylated reaction at aromatic hydrocarbons has the catalytic performance of excellence. Document (J.Chem.Soc., Chem.Commun., 1995,2187-2188) turns crystalline substance by the high temperature of stratiform persursor material and obtains the zeolite molecular sieve with FER structure. Document (MicroporousandMesoporousMaterials., 2008,110,488-500) is by obtaining the zeolite molecular sieve of RWR type after in advance the TMA-RUB-18 of stratiform is carried out acidification.Document (MircoporousandMesoporousMaterials., 2006,90,87-101) reports the roasting in the air of 1000 DEG C of a kind of EU-19 layered silicate material containing piperazine can be converted into EU-20b molecular sieve. Document (MicroporousandMesoporousMaterials., 2005,83,201-211) then finds that the RUB-18 phyllosilicate of roasting alkyl ammonium cation intercalation can obtain RUB-24 molecular sieve.
It is that the amount containing sodium of product is low by one of feature of the synthesis of molecular sieve that is converted of stratified material, therefore it can directly be taken as acidic catalyst and uses without ion-exchange step, the two of feature are that molecular sieve has certain inheritance with its presoma on pattern, generally all there is laminar pattern due to stratified material, the molecular sieve obtained thereby through it also has sheet-like morphology, namely it is nanoscale at a certain specific direction, thus having preferably diffusion, the three of feature are owing to the structure of stratified material is more sensitive for external environment condition, therefore it is carried out different post processing modes and can be easily obtained the crystal structure form that change is various.
Kenyaite is the silicate material of a kind of stratiform, and its molecular formula is Na2O��22SiO2��10H2The structure of O, Kenyaite self is at high temperature not sufficiently stable, thus limiting its practical application. The present invention is by carrying out high-temperature process to after the Kenyaite acidifying of total silicon, it is thus achieved that SCM-4 molecular sieve, at present, not yet finds the material with X ray diffractive crystal structure identical with SCM-4 molecular sieve.
Summary of the invention
One of the technical problem to be solved is to provide the new SCM-4 molecular sieve being not directed in a kind of prior art, and this molecular sieve has bigger micropore size, also has higher heat stability simultaneously.
The two of the technical problem to be solved are to provide the synthetic method of a kind of SCM-4 molecular sieve corresponding with solving one of technical problem.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of SCM-4 molecular sieve, and its chemical composition represented with mol ratio is for mM2O:SiO2, wherein M is H, Li, Na, at least one in the elements such as K, Cs, 0.005 < m < 0.025, described SCM-4 molecular sieve is in interplanar distance d=15.65 �� 1.6, d=7.79 �� 0.50, d=5.18 �� 0.08, d=3.61 �� 0.06, d=3.47 �� 0.05, and there is the maximum at X-ray diffraction peak in d=3.36 �� 0.05 place.
In technique scheme, it is mM that SCM-4 molecular sieve has mol ratio2O:SiO2Chemical composition, wherein m is preferably 0.01 < m < 0.023.
In technique scheme, SCM-4 molecular sieve is further characterized in that it comprises X ray diffracting spectrum as shown in the table:
The line of incidence of X-ray diffraction is CuK �� 1.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: the preparation method of described SCM-4 zeolite molecular sieve:
A) by silicon source, alkaline matter A, Organic substance R, alkali metal salt S and water Homogeneous phase mixing, obtain mole consisting of 10SiO2: (0.2-2.0) A:(0.05-5) R:(0.05-5) S:(100-600) H2The starting sol of O;
B) above-mentioned starting sol is transferred in reactor crystallization under self-generated pressure, and temperature is 150 ~ 210 DEG C, and crystallization time is 12 ~ 140 hours, and the scrubbed separation of product obtains phyllosilicate Kenyaite;
C) acid solution of Kenyaite and 0.05M ~ 5M is stirred 4 ~ 40 hours according to the solid-to-liquid ratio of 1g/ (5 ~ 100) ml at 8 ~ 80 DEG C, be dried after filtration, obtain acid-treated Kenyaite;
D) by acid-treated Kenyaite in 500 ~ 800 DEG C of roastings 2-12 hour, the SCM-4 zeolite molecular sieve obtained;
Wherein, silicon source is selected from Ludox, solid silicone, gas-phase silica, amorphous silica or at least one in organic silicone grease; Alkaline matter A is selected from lithium oxide, sodium oxide, potassium oxide, Cs2O, Lithium hydrate, sodium hydroxide, potassium hydroxide, rubidium hydroxide and at least one in Cesium hydrate.; Alkali metal salt S is selected from the oxalates of alkali metal, sulfate, acetate, nitrate, carbonate, phosphate and at least one in halogenide; Organic substance R is at least one in crown ether, Polyethylene Glycol and multiethylene-glycol dimethyl ether.
In the above-mentioned technical scheme preparing SCM-4 zeolite molecular sieve, Organic substance R mean molecule quantity is between 200 to 1000.
In the above-mentioned technical scheme preparing SCM-4 zeolite molecular sieve, the mol ratio preferred version of starting sol is 10SiO2: (0.4-1.8) A:(0.05-5) R:(0.05-5) S:(120-480) H2O, hydrothermal crystallizing temperature preferably ranges from 155 ~ 190 DEG C, and crystallization time preferably ranges from 16 ~ 100 hours.
In the above-mentioned technical scheme preparing SCM-4 zeolite molecular sieve, the acid treatment temperature of Kenyaite preferably ranges from 10 ~ 60 DEG C, and the process time preferably ranges from 6 ~ 40 hours, and acid is hydrochloric acid, sulphuric acid, acetic acid, nitric acid, oxalic acid and at least one in citric acid. Sintering temperature preferably ranges from 600 ~ 800 DEG C, and roasting time preferably ranges from 2-10 hour.
The SCM-4 molecular sieve obtained by the present invention has remained in that complete crystal structure at 800 DEG C, has higher heat stability, and it has the pore size that about 0.6nm is bigger, has good application prospect in the adsorbing separation to organic substance.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of the Kenyaite that embodiment 1 obtains.
Fig. 2 is X-ray diffraction (XRD) figure of the Kenyaite that embodiment 5 obtains.
The invention will be further elaborated by the examples below, but does not therefore limit the scope of the invention.
Detailed description of the invention
[embodiment 1]
By the NaCl of 0.41 gram, the sodium hydrate aqueous solution of 1.1175 gram 30%, the PEG300 of 10 gram 50% Polyethylene Glycol of 300 (mean molecule quantity be about) solution, the silicon sol solution mix homogeneously of the 40% of the water of 11 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2:1.0NaCl:0.6Na2O:2.5PEG300:175H2O
Said mixture is moved in reactor in 170oC crystallization 24 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material (see figure 1) through XRD.
Mixed in hydrochloric acid by the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.1M, stir 24 hours at 20 DEG C, washing, solid-liquid separation also obtain the solid product that HCl treatment is crossed after drying, by the solid product that obtains through HCl treatment 700 DEG C of roastings 3 hours, obtaining SCM-4 molecular sieve, its x-ray diffraction line is as shown in table 1.
[embodiment 2]
By the NaCl of 0.41 gram, the sodium hydrate aqueous solution of 1.1175 gram 30%, the PEG300 of 10 gram 50% Polyethylene Glycol of 300 (mean molecule quantity be about) solution, the silicon sol solution mix homogeneously of the 40% of the water of 11 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2:1.0NaCl:0.6Na2O:2.5PEG300:175H2O
Said mixture is moved in reactor in 170oC crystallization 24 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material through XRD.
The acetic acid of the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.5M is mixed, stir 24 hours in enclosed system at 80 DEG C, washing, solid-liquid separation also obtain solid product after drying, by this solid product 700 DEG C of roastings 3 hours, obtaining SCM-4 molecular sieve, its x-ray diffraction line is as shown in table 2.
[embodiment 3]
By the NaCl of 0.41 gram, the sodium hydrate aqueous solution of 1.1175 gram 30%, the PEG300 of 10 gram 50% Polyethylene Glycol of 300 (mean molecule quantity be about) solution, the silicon sol solution mix homogeneously of the 40% of the water of 11 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2:1.0NaCl:0.6Na2O:2.5PEG300:175H2O
Said mixture is moved in reactor in 170oC crystallization 24 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material through XRD.
Mixed in hydrochloric acid by the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.1M, stir 24 hours at 20 DEG C, washing, solid-liquid separation also obtain the solid product that HCl treatment is crossed after drying, by the solid product that obtains through HCl treatment 800 DEG C of roastings 3 hours, obtaining SCM-4 molecular sieve, its x-ray diffraction line is as shown in table 3.
[embodiment 4]
By the NaCl of 0.41 gram, the sodium hydrate aqueous solution of 1.1175 gram 30%, the PEG300 of 10 gram 50% Polyethylene Glycol of 300 (mean molecule quantity be about) solution, the silicon sol solution mix homogeneously of the 40% of the water of 11 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2:1.0NaCl:0.6Na2O:2.5PEG300:175H2O
Said mixture is moved in reactor in 170oC crystallization 24 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material through XRD.
The oxalic acid of the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.1M is mixed, stir 24 hours when 80 DEG C airtight, be washed out, solid-liquid separation obtain the solid product that oxalic acid treatment is crossed after drying, by the solid product that obtains through oxalic acid treatment 800 DEG C of roastings 3 hours, obtain SCM-4 molecular sieve.
[embodiment 5]
By the NaCl of 0.41 gram, the sodium hydrate aqueous solution of 1.1175 gram 30%, hexaoxacyclooctadecane-6-6 solution of 10 gram 20%, the silicon sol solution mix homogeneously of the 40% of the water of 8 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2: 1.0NaCl:0.6Na2O:1.0(18-crown ether-6): 175H2O
Said mixture is moved in reactor in 170oC crystallization 24 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material (see figure 2) through XRD.
Mixed in hydrochloric acid by the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.1M, stir 24 hours at 20 DEG C, washing, solid-liquid separation also obtain the solid product that HCl treatment is crossed after drying, by the solid product that obtains through HCl treatment 700 DEG C of roastings 3 hours, obtaining SCM-4 molecular sieve, its x-ray diffraction line is as shown in table 4.
[embodiment 6]
By the NaCl of 0.41 gram, the sodium hydrate aqueous solution of 1.1175 gram 30%, hexaoxacyclooctadecane-6-6 solution of 10 gram 20%, the silicon sol solution mix homogeneously of the 40% of the water of 8 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2: 1.0NaCl:0.6Na2O:1.0(18-crown ether-6): 175H2O
Said mixture is moved in reactor in 170oC crystallization 24 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material through XRD.
Mixed in hydrochloric acid by the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.1M, stir 24 hours at 20 DEG C, washing, solid-liquid separation also obtain the solid product that HCl treatment is crossed after drying, by the solid product that obtains through HCl treatment 800 DEG C of roastings 3 hours, obtaining SCM-4 molecular sieve, its x-ray diffraction line is as shown in table 5.
[embodiment 7]
By the NaCl of 0.41 gram, the sodium hydrate aqueous solution of 1.1175 gram 30%, hexaoxacyclooctadecane-6-6 solution of 10 gram 20%, the silicon sol solution mix homogeneously of the 40% of the water of 8 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2: 1.0NaCl:0.6Na2O:1.0(18-crown ether-6): 175H2O
Said mixture is moved in reactor in 170oC crystallization 24 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material through XRD.
The acetic acid of the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.5M is mixed, airtight stirring 24 hours at 80 DEG C, washing, solid-liquid separation also obtain acetated solid product after drying, by processing the solid product obtained 800 DEG C of roastings 3 hours through acetic acid, obtain SCM-4 molecular sieve.
[embodiment 8]
By the NaCl of 0.41 gram, the sodium hydrate aqueous solution of 1.6762 gram 30%, the PEG300 of 10 gram 50% Polyethylene Glycol of 300 (mean molecule quantity be about) solution, the silicon sol solution mix homogeneously of the 40% of the water of 11 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2:1.0NaCl:0.9Na2O:2.5PEG300:175H2O
Said mixture is moved in reactor in 170oC crystallization 24 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material through XRD.
Mixed in hydrochloric acid by the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.1M, stir 24 hours at 20 DEG C, washing, solid-liquid separation also obtain the solid product that HCl treatment is crossed after drying, by the solid product that obtains through HCl treatment 700 DEG C of roastings 3 hours, obtain SCM-4 molecular sieve.
[embodiment 9]
By the NaCl of 0.41 gram, the sodium hydrate aqueous solution of 0.8381 gram 30%, the PEG300 of 10 gram 50% Polyethylene Glycol of 300 (mean molecule quantity be about) solution, the silicon sol solution mix homogeneously of the 40% of the water of 11 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2:1.0NaCl:0.45Na2O:2.5PEG300:175H2O
Said mixture is moved in reactor in 180oC crystallization 30 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material through XRD.
Mixed in hydrochloric acid by the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.1M, stir 24 hours at 20 DEG C, washing, solid-liquid separation also obtain the solid product that HCl treatment is crossed after drying, by the solid product that obtains through HCl treatment 700 DEG C of roastings 3 hours, obtain SCM-4 molecular sieve.
[embodiment 10]
By the NaCl of 0.41 gram, the sodium hydrate aqueous solution of 1.1175 gram 30%, the PEG300 of 10 gram 50% Polyethylene Glycol of 300 (mean molecule quantity be about) solution, the silicon sol solution mix homogeneously of the 40% of the water of 11 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2:0.5NaCl:0.6Na2O:2.5PEG300:175H2O
Said mixture is moved in reactor in 170oC crystallization 30 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material through XRD.
Mixed in hydrochloric acid by the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.1M, stir 24 hours at 20 DEG C, washing, solid-liquid separation also obtain the solid product that HCl treatment is crossed after drying, by the solid product that obtains through HCl treatment 700 DEG C of roastings 3 hours, obtain SCM-4 molecular sieve.
[embodiment 11]
By the NaCl of 0.41 gram, the potassium hydroxide aqueous solution of 1.54 gram 30%, the PEG300 of 10 gram 50% Polyethylene Glycol of 300 (mean molecule quantity be about) solution, the silicon sol solution mix homogeneously of the 40% of the water of 11 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2:1.0NaCl:0.6K2O:2.5PEG300:175H2O
Said mixture is moved in reactor in 180oC crystallization 30 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material through XRD.
Mixed in hydrochloric acid by the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.1M, stir 24 hours at 20 DEG C, washing, solid-liquid separation also obtain the solid product that HCl treatment is crossed after drying, by the solid product that obtains through HCl treatment 700 DEG C of roastings 3 hours, obtain SCM-4 molecular sieve.
[embodiment 12]
By the KCl of 0.52 gram, the potassium hydroxide aqueous solution of 1.54 gram 30%, the PEG600 of 10 gram 50% Polyethylene Glycol of 600 (mean molecule quantity be about) solution, the silicon sol solution mix homogeneously of the 40% of the water of 11 grams and 8.1 milliliters, the mol ratio of gained mixture is:
10SiO2:1.0KCl:0.6K2O:1.25PEG600:175H2O
Said mixture is moved in reactor in 180oC crystallization 30 hours, reaction terminate after through washing, dried, be accredited as Kenyaite material through XRD.
Mixed in hydrochloric acid by the above-mentioned Kenyaite material of 1 gram and 20 milliliters of 0.1M, stir 24 hours at 20 DEG C, washing, solid-liquid separation also obtain the solid product that HCl treatment is crossed after drying, by the solid product that obtains through HCl treatment 700 DEG C of roastings 3 hours, obtain SCM-4 molecular sieve.
Table 1
| Interplanar distance (d value), | Relative intensity (I/I0), % |
| 15.88 | 74.6 |
| 7.93 | 53.8 |
| 7.64 | 2.1 |
| 7.05 | 1.6 |
| 6.36 | 4.8 |
| 5.82 | 7.2 |
| 5.33 | 84.6 |
| 4.40 | 14.3 6 --> |
| 4.11 | 13.3 |
| 3.90 | 14.4 |
| 3.71 | 4.3 |
| 3.62 | 10.3 |
| 3.52 | 11.5 |
| 3.34 | 100 |
Table 2
| Interplanar distance (d value), | Relative intensity (I/I0), % |
| 15.61 | 90 |
| 7.76 | 77 |
| 7.30 | 2.1 |
| 6.91 | 1.6 |
| 6.30 | 4.9 |
| 5.68 | 7.8 |
| 5.24 | 93 |
| 4.22 | 12.1 |
| 4.06 | 18.6 |
| 3.88 | 13.0 |
| 3.65 | 4.9 |
| 3.58 | 9.8 |
| 3.51 | 13.6 |
| 3.37 | 100 |
Table 3
| Interplanar distance (d value), | Relative intensity (I/I0), % |
| 15.69 | 82.1 |
| 7.82 | 59.8 |
| 7.44 | 2.7 |
| 6.98 | 2.0 |
| 6.41 | 4.9 |
| 5.74 | 7.8 |
| 5.23 | 89.9 |
| 4.31 | 14.7 |
| 4.12 | 13.6 |
| 3.89 | 17.6 |
| 3.69 | 7.1 |
| 3.65 | 18.7 |
| 3.49 | 13.2 7 --> |
| 3.38 | 100.0 |
Table 4
| Interplanar distance (d value), | Relative intensity (I/I0), % |
| 15.78 | 71.3 |
| 7.90 | 42.9 |
| 7.29 | 3.6 |
| 7.08 | 2.4 |
| 6.44 | 8.6 |
| 5.77 | 9.9 |
| 5.13 | 79.8 |
| 4.28 | 16.2 |
| 4.13 | 15.5 |
| 3.91 | 18.6 |
| 3.68 | 4.5 |
| 3.61 | 15.2 |
| 3.49 | 16.7 |
| 3.35 | 100 |
Table 5
| Interplanar distance (d value), | Relative intensity (I/I0), % |
| 15.71 | 61.2 |
| 7.83 | 48.4 |
| 7.43 | 5.1 |
| 7.02 | 3.3 |
| 6.38 | 4.2 |
| 5.71 | 7.7 |
| 5.19 | 70.0 |
| 4.31 | 13.6 |
| 4.09 | 13.7 |
| 3.97 | 15.6 |
| 3.68 | 8.1 |
| 3.61 | 12.3 |
| 3.49 | 9.6 |
| 3.39 | 100.0 |
Claims (9)
1. a SCM-4 molecular sieve, the chemical composition represented with mol ratio is for mM2O:SiO2, wherein M is at least one in H, Li, Na, K and Cs element, 0.005 < m < 0.025, and described SCM-4 molecular sieve is in interplanar distance AndThere is the maximum at X-ray diffraction peak in place.
2. SCM-4 molecular sieve according to claim 1, it is characterised in that having mol ratio is mM2O:SiO2SCM-4 molecular sieve in, 0.01 < m < 0.023.
3. SCM-4 molecular sieve according to claim 1, it is characterised in that SCM-4 molecular sieve comprises X ray diffracting spectrum as shown in the table:
The line of incidence of X-ray diffraction is CuK �� 1.
4. the preparation method of the SCM-4 molecular sieve described in claim 1, including following several steps:
A) by silicon source, alkaline matter A, Organic substance R, alkali metal salt S and water Homogeneous phase mixing, obtain mole consisting of 10SiO2:(0.2-2.0)A:(0.05-5)R:(0.05-5)S:(100-600)H2The starting sol of O;
B) above-mentioned starting sol is transferred in reactor crystallization under self-generated pressure, and temperature is 150��210 DEG C, and crystallization time is 12��140 hours, and the scrubbed separation of product obtains phyllosilicate Kenyaite;
C) acid solution of Kenyaite and 0.05M��5M is stirred 4��40 hours according to the solid-to-liquid ratio of 1g/ (5��100) ml at 8��80 DEG C, be dried after filtration, obtain acid-treated Kenyaite;
D) by acid-treated Kenyaite in 500��800 DEG C of roastings 2-12 hour, the SCM-4 zeolite molecular sieve obtained;
Wherein, silicon source is selected from Ludox, solid silicone, gas-phase silica, amorphous silica or at least one in organic silicone grease; Alkaline matter A is selected from lithium oxide, sodium oxide, potassium oxide, Cs2O, Lithium hydrate, sodium hydroxide, potassium hydroxide, rubidium hydroxide and at least one in Cesium hydrate.; Alkali metal salt S is selected from the oxalates of alkali metal, sulfate, acetate, nitrate, carbonate, phosphate and at least one in halogenide; Organic substance R is at least one in crown ether, Polyethylene Glycol and multiethylene-glycol dimethyl ether, and the mean molecule quantity of Organic substance R is between 200 to 1000.
5. the preparation method of SCM-4 molecular sieve according to claim 4, it is characterised in that the mol ratio of starting sol is 10SiO2:(0.4-1.8)A:(0.05-5)R:(0.05-5)S:(120-480)H2O��
6. the preparation method of SCM-4 molecular sieve according to claim 4, it is characterised in that starting sol is hydrothermal crystallizing 16��100 hours at 155��190 DEG C.
7. the preparation method of SCM-4 molecular sieve according to claim 4, it is characterised in that the acid treatment temperature of Kenyaite is 10��60 DEG C, the process time is 6��40 hours.
8. the preparation method of SCM-4 molecular sieve according to claim 7, it is characterised in that the acid of acid treatment is hydrochloric acid, sulphuric acid, acetic acid, nitric acid, oxalic acid and at least one in citric acid.
9. the preparation method of SCM-4 molecular sieve according to claim 4, it is characterised in that sintering temperature is 600��800 DEG C, roasting time is 2-10 hour.
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| US5063039A (en) * | 1988-09-19 | 1991-11-05 | Mobil Oil Corp. | Synthesis of kenyaite-type layered silicate material and its polymeric chalcogenide intercalates |
| KR100544730B1 (en) * | 2003-04-16 | 2006-01-24 | 한국화학연구원 | A nobel process for preparing magadiite and kenyaite |
| CN103204505B (en) * | 2012-01-13 | 2015-03-18 | 中国石油化工股份有限公司 | Preparation method of aluminum-containing layered kenyaite |
| CN103072990A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Preparation method of two-dimensional layered-structure material kenyaite |
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