CN105460954A - Sn-SCM-3 zeolite molecular sieve and a preparation method therefor - Google Patents
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Abstract
The invention relates to an Sn-SCM-3 zeolite molecular sieve and a preparation method therefor and mainly solves the technical problem in the prior art that a novel zeolite molecular sieve Sn-SCM-3 is not involved. The invention provides a novel Sn-SCM-3 zeolite molecular sieve. The technical problem is better solved by adopting a technical scheme that the Sn-SCM-3 zeolite molecular sieve is composed of chemical compositions in the following molar ratio: SiO2: nSnO2: mX2O3, wherein n is greater than or equal to 0.001 but less than or equal to 0.12, m is less than 0.10, and X is one of two elements Al and B; according to the Sn-SCM-3 zeolite molecular sieve, diffracted intensity maximum values of X ray diffraction peaks appear at d=16.66+/1.7 angstrom, d=8.49+/0.25 angstrom, d=7.24+/0.15 angstrom, d=6.30+/0.12 angstrom, d=5.36+/0.06 angstrom, d=3.68+/0.06 angstrom, d=3.60+/0.06 angstrom and d=3.38+/0.06 angstrom and the relative intensity is greater than 1.0%. The synthesized Sn-SCM-3 zeolite molecular sieve has a relatively good application prospect in the aspect of an organic catalytic reaction.
Description
Technical field
The present invention relates to a kind of Sn-SCM-3 zeolite molecular sieve and preparation method thereof.
Background technology
Zeolite molecular sieve is a kind of porous silicate material of crystallization, its basic structural unit is silicon-oxy tetrahedron, silicon-oxy tetrahedron connects mutually by sharing a Sauerstoffatom and forms the three-dimensional net structure of molecular sieve, wherein silicon-oxy tetrahedron also can be replaced by the tetrahedral portions of other kind, such as aluminum-oxygen tetrahedron and germanium oxygen tetrahedron.Modal zeolite molecular sieve is made up of silicon-oxy tetrahedron and aluminum-oxygen tetrahedron, because aluminum-oxygen tetrahedron is with electronegativity, in the hole of molecular sieve, therefore needs cationic existence with compensation charge, common positively charged ion is alkalimetal ion, also can be H+, NH4+, and organic cation etc.One of main characteristic of zeolite molecular sieve has the arrangement of distinctive duct and pore size, the material matched with duct is only allowed to enter the internal space of molecular sieve, and the material being greater than pore size is left out, thus make it have shape selective, on the other hand, also can by carrying out modulation to the chemical composition of zeolite molecular sieve, thus reach the object changing molecular sieve character, molecular sieve can be made to have acidity or oxidation-reduction quality, it also can be made to change hydrophilic nmature.Because zeolite molecular sieve has some above-mentioned features, therefore impart its widespread use in various fields, such as in absorption, be separated and the field such as catalysis.
Although there is a large amount of natural zeolites in occurring in nature, but these zeolites are difficult to meet industrial all demands, therefore many artificial synthetic zeolites are developed, such as A zeolite (US2882243), X zeolite (US2882244), Y zeolite (US3130007), ZSM-5 zeolite (US3702886) etc.The main method of artificial synthetic zeolite is hydrothermal synthesis method, the key step of a typical hydrothermal synthesis method is first by silicon source, aluminium source, structure directing agent, mineralizer and water Homogeneous phase mixing, obtain starting sol, and then this colloidal sol is placed in reactor, after airtight, at certain temperature and pressure itself, carry out crystallization.Except hydrothermal synthesis method, also have other method also can obtain zeolite molecular sieve, solid phase topology as by stratified material turns crystalline substance to obtain, as US4954325 obtains crystalline molecular sieve MCM-22 by the presoma MCM-22P of roasting stratified material, document (J.Chem.Soc., Chem.Commun., 1995,2187-2188) turn crystalline substance by the high temperature of stratiform persursor material and obtain the zeolite molecular sieve with FER structure.
In addition, also can obtain forming novel novel molecular sieve by the way of existing molecular sieve being carried out to aftertreatment, high silica alumina ratio even the Y zeolite molecular sieve of total silicon can be obtained as by carrying out dealumination treatment to low Y zeolite molecular sieve.Post-treating method is very useful for mixing other tetrahedron in the skeleton be made up of silicon-oxy tetrahedron of molecular sieve, this is because the compound of some metallic elements easily generates the precipitation of oxyhydroxide under the highly basic synthesis condition of molecular sieve, these metallic elements comprise Ti, Sn, Cr etc.
Molecular sieve is applied mainly in acid catalysis in the tradition of catalytic field, based on silicoaluminate salt form zeolite molecular sieve.But research in recent years shows, containing Ti in framework of molecular sieve, Sn, the metallic elements such as Cr can make molecular sieve have the character of catalytic oxidation-reduction reaction, typical example is the application of Ti-beta molecular sieve in the oxidizing reaction of H2O2, the reaction of propylene oxide can be prepared by catalytic epoxidation of propone, realize industrial application at present.
Molecular sieve containing tin element in skeleton also has the ability of catalytic oxidation.As the hydrogen peroxide oxidation reaction of Sn-beta molecular sieve to cyclic ketone and phthalic anhydride has catalytic activity [Nature, 2001, 412, 423] [ChemEurJ, 2002, 8, 4708] [JournalofCatalysis, 2004, 221, 67], to Meerwein-Ponndorf-Verley (MPV) reduction reaction, Oppenauer oxidizing reaction [J.Am.Chem.Soc.2002, 124, 3194] [JournalofCatalysis., 2003, 215, 294], Nulomoline is the reaction [ACSCatal2011 of 5-hydroxymethylfurans (HMF), 1, 408] etc. also all there is certain katalysis, except Sn-beta molecular sieve, Kenyaite containing Sn and the MCM-41 containing Sn can be used for beta pinene and paraformaldehyde Prins condensation generates [CatalysisToday in the reaction of Nopol, 2005, 107-108, 942], stanniferous Silicalite-1 is used for the aspect [JMolecularCatalA:Chemical1996 such as the hydrogen peroxide hydroxylating of phenol, 105, 149], in the middle of the hydrogen peroxide hydroxylating being used for phenol or phenol ester compounds containing the MFI zeolite of Sn [US5399336].Except catalytic selective oxidation reaction, stanniferous molecular sieve also can be used for glucose isomerase being turned to fructose [ACSCatal.2012,2705], for removing the H2S[US5264193 in Sweet natural gas], and be used in [7432406] in dehydrogenation reaction as carrier.
The synthesis of the stanniferous molecular sieve of skeleton has direct hydrothermal synthesis method, and steam assists synthesis method and molecular sieve post treatment method etc.Patent US5110571 and patent US5192519 provides the stanniferous zeolite molecular sieve (PhaseA of Vacuum-assisted method, PhaseB, PhaseL, PhaseG, PhaseK) method, document [StudSurfSci.Catal., 1995, 94, 317] method of Vacuum-assisted method is used to obtain stanniferous MFI, the zeolite molecular sieves such as MEL and MTW, document [ClaysandClayMinerals, 2012, 60, 254] method of a kind of Situ Hydrothermal method synthesis containing the Magadiite material of Sn is provided, the advantage of hydrothermal synthesis method is that synthesis step is simple, but shortcoming is pink salt (being generally tin chloride) is easy to the precipitation generating oxyhydroxide under strongly alkaline conditions, therefore tin is difficult to really to appear in the middle of the skeleton of molecular sieve.
As the improvement to conventional hydrothermal synthesis method, in fluorine-containing system, synthesis of molecular sieve can make the pH value of system significantly reduce, and close to neutrality, therefore can suppress the formation of above-mentioned precipitation of hydroxide to a certain extent.Utilize fluorine-containing system, patent US5399336 has synthesized Sn-MFI, and patent US5968473 and patent US6306364 has synthesized the stanniferous molecular sieve with beta-molecular sieve structure.
Water vapour assists synthesis method to be a kind of method of newer synthesis zeolite, also bibliographical information is had at present for the report containing heteroatoms zeolite molecular sieve synthesis, as the synthesis [MaterialsChemistryandPhysics for stanniferous beta-molecular sieve, 2013,141,, but application example is still less 519].
Zeolite molecular sieve post-treating method (secondary synthesis) is traditional a kind of method for the synthesis of hybrid atom MCM-41 zeolite molecular sieve.As US Patent No. 4933161 provides a kind of synthetic method of stanniferous FAU molecular sieve, use tin tetrachloride or tindichloride as Xi Yuan, carry out process with (more than 100 DEG C) under certain temperature FAU zeolite to FAU zeolite or dealuminzation in acid condition and can obtain stanniferous FAU molecular sieve.Patent US5401488 utilizes secondary synthesis method to have also been obtained multiple stanniferous molecular sieve; the stanniferous compound wherein used in building-up process had both served the effect of dealuminzation; again can as the source of tin; a problem of two-step fabrication to produce more waste liquid amount, is unfavorable for environment protection.
Improve as to the one of secondary synthesis method, document [AngewChemIntEd., 2012,51,11736] a kind of solid state synthesis method of stanniferous molecular sieve has been delivered, namely be Xi Yuan with tin oxalate, sufficient mixed grinding is carried out with the beta-molecular sieve of pre-dealuminzation, and then calcination at a certain temperature, the method accurately can control the content of tin, do not produce waste liquid, be adapted at industrial amplification and produce.
The molecular sieve that SCM-3 molecular sieve is a kind of conversion by stratified material and obtains, still directly can not obtain from Hydrothermal Synthesis system.Can a certain amount of boron or a small amount of aluminium be contained in the chemical constitution of SCM-3, but there is not yet SCM-3 molecular sieve skeleton being mixed tin.
Summary of the invention
One of technical problem to be solved by this invention is to provide the new Sn-SCM-3 molecular sieve do not related in a kind of prior art, and this molecular sieve has the structure of SCM-3 molecular sieve, contains element tin in skeleton simultaneously.
Two of technical problem to be solved by this invention is to provide a kind of synthetic method of the molecular sieve corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the invention provides a kind of Sn-SCM-3 molecular sieve, comprising the chemical constitution of following mol ratio: SiO
2: nSnO
2: mX2O3, wherein 0.001≤n≤0.12, m<0.10, X are the one in Al and B two kinds of elements, and described Sn-SCM-3 molecular sieve exists
and
there is the X-ray diffraction peak that relative intensity is greater than 1.0% in place.
It is SiO that above-mentioned Sn-SCM-3 molecular sieve has mol ratio
2: nSnO
2: the chemical constitution of mX2O3, wherein 0.005≤n≤0.10, m<0.08, X are the one in Al and B two kinds of elements.
Above-mentioned Sn-SCM-3 molecular sieve comprises X ray diffracting data as follows:
Wherein, the incident ray of X-ray diffraction is CuK α 1.
The preparation method of above-mentioned Sn-SCM-3 molecular sieve, comprises following several step:
A) by layered silicate Kenyaite and 0.05 ~ 10mol/L, preferably the acid solution A of 0.1 ~ 10mol/L according to the solid-to-liquid ratio of 1g/ (5 ~ 100) ml at 8 ~ 150 DEG C, lower stirring 4 ~ 80 hours, stir 6 ~ 40 hours at being more preferably 10 ~ 120 DEG C, carry out drying after filtration, obtain acid-treated Kenyaite; Wherein acid is hydrochloric acid, sulfuric acid, acetic acid, nitric acid, at least one in oxalic acid and citric acid.
B) by above-mentioned acid-treated Kenyaite and pink salt according to (100 ~ 10): the mass ratio of 1 carries out mixing and grinding, and obtains solid mixture, and wherein pink salt is stannous oxalate, at least one in stannous acetate.
C) by above-mentioned solid mixture roasting 2-12 hour at 500 ~ 800 DEG C, to be maturing temperature be preferred condition
500 ~ 700 DEG C, roasting time is 2-10 hour, obtains Sn-SCM-3 zeolite molecular sieve;
In the preparation method of above-mentioned Sn-SCM-3 molecular sieve, the X in layered silicate material used
2o
3/ SiO
2mol ratio between 0.005 to 0.1, wherein X is at least one in boron and aluminium.
Layered silicate Kenyaite can obtain from occurring in nature, but because natural Kenyaite material contains more impurity, and generally do not contain or only contain a small amount of aluminium or boron, therefore the Kenyaite containing aluminium or boron obtains preferably by synthetic, and the Kenyaite containing aluminium or boron used in the present invention can obtain respectively by following experimental procedure synthesis:
(1) the Kenyaite material of boracic
By the boric acid of 0.863 gram, the NaCl of 0.41 gram, 1.1175 the aqueous sodium hydroxide solution of gram 30%, PEG300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 gram 50%, the water of 11 grams and 8.1 milliliters 40% silicon sol solution mix, the mol ratio of gained mixture is:
10SiO
2：0.4B
2O
3：1.0NaCl:0.6Na
2O:2.5PEG300:175H
2O
Said mixture is moved in 180 DEG C of crystallization 40 hours in reactor, after reaction terminates after washing, drying, be accredited as Kenyaite material through XRD, see Fig. 1.
(2) containing the Kenyaite material of aluminium
By the sodium metaaluminate of 0.0572 gram, the NaCl of 0.41 gram, 1.88 the aqueous sodium hydroxide solution of gram 30%, PEG300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 gram 50%, the water of 11 grams and 8.1 milliliters 40% silicon sol solution mix, the mol ratio of gained mixture is:
10SiO2：0.1Al2O3：1.0NaCl:0.9Na
2O:2.5PEG300:175H2O
Said mixture is moved in 170 DEG C of crystallization 40 hours in reactor, after reaction terminates after washing, drying, be accredited as Kenyaite material through XRD.
Be present in the middle of the skeleton of molecular sieve containing aluminium or containing the form that Al or B in the Kenyaite material of B is the position replacing Si, but after peracid treatment, Al and B of part can separate out from skeleton, thus leaves room.The material leaving tetrahedral vacancy by this and pink salt admixed together, at high temperature there is migration and fill up the room that this Al and B stay in tin atom, thus the position occupied on skeleton, there is topology turn crystalline substance in stratified material simultaneously, three-dimensional molecular sieve structure is become from laminate structure, namely become SCM-3 from Kenyaite, thus obtain stanniferous SCM-3 molecular sieve.The Sn-SCM-3 molecular sieve formed remains the interlayer characteristic of SCM-3 molecular sieve spaciousness, brings again the redox property of metal simultaneously, therefore estimates to have broad application prospects in macromolecular organic catalytic reaction.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction result of the Kenyaite containing B.
The scanning electron microscopic picture of the Sn-SCM-3 molecular sieve that Fig. 2 obtains for embodiment 1.
Below by embodiment, the invention will be further elaborated, but therefore do not limit the scope of the invention.
Embodiment
[embodiment 1]
Be the Kenyaite material of 0.04 and the mixed in hydrochloric acid of 20 milliliters of 0.1M by the mol ratio of 1 gram of B2O3/SiO2, stir 24 hours at 20 DEG C, washing, solid-liquid separation obtain the solid product that HCl treatment crosses after drying, the Kenyaite that 2 grams obtain through HCl treatment is mixed with 0.045 gram of stannous oxalate and grinds, solid mixture after grinding was in 600 DEG C of roastings 5 hours, obtain Sn-SCM-3 molecular sieve, its x-ray diffraction line is as shown in table 1, and in product, the mol ratio of Sn/Si is 0.006.
[embodiment 2]
Be the Kenyaite material of 0.04 and the mixed in hydrochloric acid of 20 milliliters of 10M by the mol ratio of 1 gram of B2O3/SiO2, stir 24 hours at 20 DEG C, washing, solid-liquid separation obtain the solid product that HCl treatment crosses after drying, the Kenyaite that 2 grams obtain through HCl treatment is mixed with 0.089 gram of stannous oxalate and grinds, solid mixture after grinding was in 600 DEG C of roastings 5 hours, obtain Sn-SCM-3 molecular sieve, its x-ray diffraction line and table one similar, in product, the mol ratio of Sn/Si is 0.009.
[embodiment 3]
Be the Kenyaite material of 0.04 and the mixed in hydrochloric acid of 20 milliliters of 10M by the mol ratio of 1 gram of B2O3/SiO2, airtight stirring 24 hours at 100 DEG C, washing, solid-liquid separation obtain the solid product that HCl treatment crosses after drying, the Kenyaite that 2 grams obtain through HCl treatment is mixed with 0.089 gram of stannous oxalate and grinds, solid mixture after grinding was in 600 DEG C of roastings 5 hours, obtain Sn-SCM-3 molecular sieve, its x-ray diffraction line and table one similar, in product, the mol ratio of Sn/Si is 0.013.
[embodiment 4]
Be the Kenyaite material of 0.04 and the mixed in hydrochloric acid of 20 milliliters of 10M by the mol ratio of 1 gram of B2O3/SiO2, airtight stirring 24 hours at 100 DEG C, washing, solid-liquid separation obtain the solid product that HCl treatment crosses after drying, the Kenyaite that 2 grams obtain through HCl treatment is mixed with 0.193 gram of stannous oxalate and grinds, solid mixture after grinding was in 600 DEG C of roastings 5 hours, obtain Sn-SCM-3 molecular sieve, its x-ray diffraction line and table one similar, in product, the mol ratio of Sn/Si is 0.022.
[embodiment 5]
Be the Kenyaite material of 0.04 and the mixed in hydrochloric acid of 20 milliliters of 10M by the mol ratio of 1 gram of B2O3/SiO2, airtight stirring 24 hours at 100 DEG C, washing, solid-liquid separation obtain the solid product that HCl treatment crosses after drying, the Kenyaite that 2 grams obtain through HCl treatment is mixed with 0.387 gram of stannous oxalate and grinds, solid mixture after grinding was in 600 DEG C of roastings 5 hours, obtain Sn-SCM-3 molecular sieve, its x-ray diffraction line and table one similar, in product, the mol ratio of Sn/Si is 0.049.
[embodiment 6]
Be the Kenyaite material of 0.04 and the mixed in hydrochloric acid of 20 milliliters of 0.1M by the mol ratio of 1 gram of B2O3/SiO2, stir 24 hours at 20 DEG C, washing, solid-liquid separation obtain the solid product that HCl treatment crosses after drying, the Kenyaite that 2 grams obtain through HCl treatment is mixed with 0.0045 gram of stannous oxalate and grinds, solid mixture after grinding was in 700 DEG C of roastings 5 hours, obtain Sn-SCM-3 molecular sieve, its x-ray diffraction line and table one similar, in product, the mol ratio of Sn/Si is 0.006.
[embodiment 7]
Be the Kenyaite material of 0.02 and the mixed in hydrochloric acid of 20 milliliters of 0.1M by the mol ratio of 1 gram of B2O3/SiO2, stir 24 hours at 20 DEG C, washing, solid-liquid separation obtain the solid product that HCl treatment crosses after drying, the Kenyaite that 2 grams obtain through HCl treatment is mixed with 0.045 gram of stannous oxalate and grinds, solid mixture after grinding was in 600 DEG C of roastings 5 hours, obtain Sn-SCM-3 molecular sieve, its x-ray diffraction line and table one similar, in product, the mol ratio of Sn/Si is 0.0051.
[embodiment 8]
Be the Kenyaite material of 0.1 and the mixed in hydrochloric acid of 20 milliliters of 0.1M by the mol ratio of 1 gram of B2O3/SiO2, stir 24 hours at 20 DEG C, washing, solid-liquid separation obtain the solid product that HCl treatment crosses after drying, the Kenyaite that 2 grams obtain through HCl treatment is mixed with 0.045 gram of stannous oxalate and grinds, solid mixture after grinding was in 600 DEG C of roastings 5 hours, obtain Sn-SCM-3 molecular sieve, its x-ray diffraction line and table one similar, in product, the mol ratio of Sn/Si is 0.008.
Table 1
Claims (10)
1. a Sn-SCM-3 molecular sieve, comprises the chemical constitution of following mol ratio: SiO
2: nSnO
2: mX2O3, wherein 0.001≤n≤0.12, m<0.10, X are the one in Al and B two kinds of elements, and described Sn-SCM-3 molecular sieve exists
and
there is the X-ray diffraction peak that relative intensity is greater than 1.0% in place.
2. Sn-SCM-3 molecular sieve according to claim 1, it is characterized in that described Sn-SCM-3 molecular sieve has mol ratio is SiO
2: nSnO
2: the chemical constitution of mX2O3, wherein 0.005≤n≤0.10, m<0.08, X are the one in Al and B two kinds of elements.
3. Sn-SCM-3 molecular sieve according to claim 1, is characterized in that described Sn-SCM-3 molecular sieve comprises X ray diffracting data as follows:
Wherein, the incident ray of X-ray diffraction is CuK α 1.
4. the preparation method of Sn-SCM-3 molecular sieve according to claim 1, comprises following several step:
A) the acid solution A of layered silicate Kenyaite and 0.05 ~ 10mol/L is stirred 4 ~ 80 hours according to the solid-to-liquid ratio of 1g/ (5 ~ 100) ml at 8 ~ 150 DEG C, after filtration, carry out drying, obtain acid-treated Kenyaite;
B) by above-mentioned acid-treated Kenyaite and pink salt according to (100 ~ 10): the mass ratio of 1 carries out mixing and grinding, and obtains solid mixture.
C) by above-mentioned solid mixture roasting 2-12 hour at 500 ~ 800 DEG C, Sn-SCM-3 zeolite molecular sieve is obtained.
5. the preparation method of Sn-SCM-3 molecular sieve according to claim 4, it is characterized in that the acid treatment temperature of Kenyaite is 10 ~ 120 DEG C, the treatment time is 6 ~ 40 hours.
6. the preparation method of Sn-SCM-3 molecular sieve according to claim 7, is characterized in that acid-treated acid is hydrochloric acid, sulfuric acid, acetic acid, nitric acid, at least one in oxalic acid and citric acid.
7. the preparation method of Sn-SCM-3 molecular sieve according to claim 7, is characterized in that used acid concentration is 0.1 ~ 10mol/l.
8. the preparation method of Sn-SCM-3 molecular sieve according to claim 7, is characterized in that pink salt is stannous oxalate, at least one in stannous acetate.
9. the preparation method of Sn-SCM-3 molecular sieve according to claim 4, it is characterized in that the maturing temperature of solid mixture is 500 ~ 700 DEG C, roasting time is 2-10 hour.
10. the preparation method of Sn-SCM-3 molecular sieve according to claim 4, is characterized in that the X in layered silicate material
2o
3/ SiO
2mol ratio between 0.005 to 0.1, wherein X is at least one in boron and aluminium.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107777701A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | Molecular sieves of SCM 12 and preparation method thereof |
| CN113831238A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Method for preparing methyl lactate by catalytic conversion of carbohydrate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4933161A (en) * | 1987-02-04 | 1990-06-12 | Exxon Research And Engineering Company | Tin substitution into zeolite frameworks |
| CN102659133A (en) * | 2012-04-20 | 2012-09-12 | 华东师范大学 | Preparation method for P type zeolite molecular sieve with core-shell structure |
-
2014
- 2014-09-09 CN CN201410455050.9A patent/CN105460954B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4933161A (en) * | 1987-02-04 | 1990-06-12 | Exxon Research And Engineering Company | Tin substitution into zeolite frameworks |
| CN102659133A (en) * | 2012-04-20 | 2012-09-12 | 华东师范大学 | Preparation method for P type zeolite molecular sieve with core-shell structure |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107777701A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | Molecular sieves of SCM 12 and preparation method thereof |
| CN113831238A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Method for preparing methyl lactate by catalytic conversion of carbohydrate |
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