CN107311201A - The method that nanometer Sn beta-molecular sieves and preparation method thereof and phenol hydroxylation react - Google Patents
The method that nanometer Sn beta-molecular sieves and preparation method thereof and phenol hydroxylation react Download PDFInfo
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Abstract
The present invention relates to beta-molecular sieve technical field, the method that nanometer Sn beta-molecular sieves and preparation method thereof and phenol hydroxylation react is disclosed, the preparation method of the nanometer Sn beta-molecular sieves comprises the following steps：(1) in the presence of aqueous solvent, silicon source, tin source, structure directing agent and alkali source are mixed to get mixed solution, the pH value of mixed solution is adjusted to 9.5~13.8, the mixed solution is subjected to crystallization, separates and is calcined and obtain crystallization product；(2) crystallization product, cobalt salt and/or nickel salt are mixed in proportion in aqueous solvent, obtains reaction solution, the reaction solution is reacted into 2~10h at a temperature of 180~220 DEG C, molecular sieve precursor is obtained；(3) molecular sieve precursor is mixed in aqueous solvent with sulfur-containing medium, carries out hydro-thermal reaction, obtain a nanometer Sn beta-molecular sieves.Composite Nano Sn beta-molecular sieves are prepared for by the above method, the particle size uniformity of the product, specific surface area are big, skeleton defect is few, have good catalytic in phenol hydroxylation reaction.
Description
Technical field
The present invention relates to beta-molecular sieve technical field, and in particular to nanometer Sn- beta-molecular sieves and preparation method thereof and phenol hydroxyl
The method of glycosylation reaction.
Background technology
Hetero-atom molecular-sieve refers to there is non-silicon, the molecular sieve of aluminium element in skeleton structure, and heteroatomic introducing is not only to boiling
The acidity of stone catalyst, surface property play adjustment effect, it is possessed special catalytic performance.Titanium-silicon molecular sieve TS-1 is
The beginning of molecular sieve with four-coordination framework titania, its synthesis for occurring indicating hetero-atom molecular-sieve and application study.
Beta-molecular sieve is by three kinds of structures are different but polymorph that be closely related is constituted stacking fault symbiosis.It has three
Twelve-ring pore passage structure is tieed up, wherein the duct in [100] and [010] direction is all straight hole road, its aperture may each be about 0.66 ×
0.67nm；[001] duct in direction is that the aperture intersected to form by the straight hole road of [100] and [010] both direction is about 0.55
× 0.55nm sinusoidal duct.Due to beta-molecular sieve with unique pore passage structure, good heat and hydrothermal stability and properly
Acidity it is widely used in as catalysis material in petroleum refining and petroleum chemical engineering, such as Alkylation benzene with propylene, alcohol
The amination of class, alkene hydration, the disproportionation of toluene and methylate, be hydrocracked with catalytic dewaxing etc., being a kind of there is wide application
The catalysis material of prospect.Because beta-molecular sieve has a larger pore passage structure, the metal heteroatom such as Ti, Sn is also introduced into its skeleton
Structure.
When Sn to be introduced to the skeleton of beta-molecular sieve, it can effectively be catalyzed BayerVilliger oxidations, Meerwin-
Ponndorf-Verley, Diles-Alder addition and isomerization etc. are reacted, so that in biomass high value added utilization field
Present very well application prospect.But generally, the hetero-atom molecular-sieve of * BEA structures is closed under neutral fluorine-containing system condition
Into [CormaA., NemethL., RenzM., ValenciaS., Nature, 2001,412,423-425].The synthetic method is with HF
For mineralizer, this can not only bring environmental protection and safety problem, moreover it is possible to significantly reduce the basicity of crystallization system, solidification precursor and coagulate
Glue, so as to reduce the diffusion rate of precursor, influence the nucleation and its synthesising stability of molecular sieve.Therefore, the system condition system
The particle size of standby molecular sieve is generally more than 10 microns, and its synthesising stability is unsatisfactory.Therefore, it is necessary to further
Synthesis to Sn-beta molecular sieves is studied to reduce its crystallite dimension, improve its synthesising stability.
Catechol and hydroquinones are the fine chemicals of high added value, are widely used in photographic process, adhesive, resist
The industry such as oxygen agent, additive and dyestuff.Hydoxylating phenol is the main method for preparing catechol and hydroquinones, this method
Mainly using titanium-silicon molecular sieve TS-1 as catalyst, but because its aperture is about only 0.55 nanometer, the diffusion of reaction product by
Suppress, their easy deep oxidation generation quinones.Therefore, research and development are a kind of with excellent phenol hydroxylation activity, and are conducive to reaction
Thing and the molecular sieve catalytic material of reaction product diffusion are very necessary.
The content of the invention
An object of the present invention is to provide a kind of nanometer Sn- beta-molecular sieves, and it has small particle size, size uniform, ratio
The characteristics of surface area is big, and the catalytic performance of Pyrogentisinic Acid's hydroxylating is good.
The second object of the present invention is to provide the preparation method of a kind of nanometer of Sn- beta-molecular sieve, in the basic conditions, passes through
Many one-step hydrothermals synthesize stanniferous high compound beta-molecular sieve.
The third object of the present invention is to provide a kind of method of phenol hydroxylation reaction, using nanometer Sn- beta-molecular sieves as catalysis
Agent, realizes the hydroxylating of phenol, and have higher selectivity to reaction product hydroquinones.
To achieve these goals, the present invention provides the preparation method of a kind of nanometer of Sn- beta-molecular sieve, comprises the following steps：
(1) in the presence of aqueous solvent, silicon source, tin source, structure directing agent and alkali source are mixed to get gel in proportion
Mixed solution, adjust the pH value of mixed solution to 9.5~13.8, by the mixed solution at a temperature of 150~220 DEG C it is brilliant
Change 5~28 days, separate and be calcined and obtain crystallization product；
(2) crystallization product, cobalt salt and/or nickel salt are mixed in proportion in aqueous solvent, obtains reaction solution, will be described
Reaction solution reacts 2~10h at a temperature of 180~220 DEG C, obtains molecular sieve precursor；
(3) molecular sieve precursor is mixed in aqueous solvent with sulfur-containing medium, carried out at a temperature of 80~140 DEG C anti-
1~6h is answered, a nanometer Sn- beta-molecular sieves are obtained.
The present invention also provides a kind of nanometer Sn- beta-molecular sieves according to prepared by the above method, the nanometer Sn- beta-molecular sieves
In each material mol ratio be silicon：Tin：Nickel：Cobalt：Sulphur=1：(0.002~0.014)：(0~0.18)：(0~0.21)：(0.15
~0.5), and cobalt it is different with the mol ratio of nickel when be 0；
And/or the specific surface area of the molecular sieve is 405~639m2/ g, pore volume is 0.22~0.68cm2/ g,
And/or the acid amount of the molecular sieve is 25.5~42.6 μm of ol/g.
The present invention also provides a kind of method for hydroxylation of phenol, according to following steps：, will under conditions of catalyst presence
Phenol and oxidant haptoreaction, obtain hydroquinones, and the catalyst is above-mentioned Sn- beta-molecular sieves.
By above-mentioned technical proposal, the invention provides the preparation method of a kind of nanometer of Sn- beta-molecular sieve, this method is in alkali
Crystallization product has been synthesized by hydro-thermal method under the conditions of property, tin atom is entered inside si molecular sieves, and has replaced the silicon in skeleton,
Tin si molecular sieves are formed, and there is the nickel cobalt sulfide of catalytic performance in the surface continued growth of crystallization product, are combined
Molecular sieve, the particle size of the composite molecular screen is small, specific surface area is big, and skeleton defect is few, in the hydroxylating of phenol
With good catalytic.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the SEM figures of nanometer Sn- beta-molecular sieves in embodiment 1；
Fig. 2 is nanometer Sn- beta-molecular sieves in embodiment 129SiNMR spectrograms；
Fig. 3 is the SEM figures of nanometer Sn- beta-molecular sieves in embodiment 2.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides the preparation method of a kind of nanometer of Sn- beta-molecular sieve, comprise the following steps：
(1) in the presence of aqueous solvent, silicon source, tin source, structure directing agent and alkali source are mixed to get gel in proportion
Mixed solution, adjust the pH value of mixed solution to 9.5~13.8, by the mixed solution at a temperature of 150~220 DEG C it is brilliant
Change 5~28 days, separate and be calcined and obtain crystallization product；
(2) crystallization product, cobalt salt and/or nickel salt are mixed in proportion in aqueous solvent, obtains reaction solution, will be described
Reaction solution reacts 2~10h at a temperature of 180~220 DEG C, obtains molecular sieve precursor；
(3) molecular sieve precursor is mixed in aqueous solvent with sulfur-containing medium, carried out at a temperature of 80~140 DEG C anti-
1~6h is answered, a nanometer Sn- beta-molecular sieves are obtained.
The Sn- beta-molecular sieves crystallite dimension prepared in the prior art is big, synthesis repeated undesirable.The present invention by
Crystallization product has been synthesized under alkalescence condition, and has further been modified on the surface of crystallization product, Sn- beta-molecular sieves are improved
Specific surface area and the size for reducing molecular sieve, so as to improve its catalytic activity.
In the present invention, alkali source provides enough OH for crystallization system-, it is ensured that smoothly completing for crystallization, is improved
Alkali source in the uniformity of crystallization product, the step (1) can be alkali metal hydroxide, ammoniacal liquor, urea, hydrazine hydrate, carbonic acid
Sodium, sodium acid carbonate, sodium fluoride, potassium fluoride, sodium alkoxide, potassium alcoholate, aliphatic amine, alkyl sodium, alkyl potassium, hydrocarbyl lithium, alkyl copper lithium, fat
At least one of fat race hydramine and quaternary ammonium base, preferably ammoniacal liquor, urea, hydrazine hydrate, sodium carbonate, sodium acid carbonate, caustic alcohol, tertiary fourth
At least one of potassium alcoholate and lithium diisopropylamine.
According to the present invention, silicon source of the invention can be at least one in organic silicic acid ester, silica gel, white carbon and Ludox
Kind；Single silicon source is selected in influence of the hetero atom to crystallization product in silicon source, the present invention in order to reduce, it is more preferably organic
One in esters of silicon acis, such as methyl silicate, isopropyl silicate, sub- silester, tetraethoxysilane, tetraethyl orthosilicate
Kind.
According to the present invention, the structure directing agent used in described step (1) can be quaternary ammonium base class, quaternary ammonium salt and fat
At least one of fat amine, wherein, described quaternary ammonium base can be quaternary ammonium base, and described quaternary ammonium salt can be organic
Quaternary ammonium salt, described aliphatic amine can be NH3In at least one hydrogen by aliphatic alkyl (such as alkyl) replace after formed
Compound.
Specifically, the quaternary ammonium that described structure directing agent can represent for the quaternary ammonium base that is represented selected from formula II, general formula III
At least one of aliphatic amine that salt and general formulae IV are represented.
In Formula II, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, for example：R1、R2、R3And R4Can each be each independently methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
Isobutyl group or the tert-butyl group.
In formula III, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, for example：R1、R2、R3And R4Can each be each independently methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
Isobutyl group or the tert-butyl group；X represents halide anion or acid ion, such as can be F-、Cl-、Br-、I-Or HSO4-.
R5(NH2)n(formula IV)
In formula IV, n is 1 or 2 integer.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6
Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, new penta
Base, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6
Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.
Preferably, the structure directing agent described in step (1) is tetraethyl ammonium hydroxide, tetraethyl ammonium fluoride, tetraethyl chlorine
Change at least one of ammonium, tetraethylammonium bromide, tetraethyl ammonium iodide, diethylamine and triethylamine；Further, the structure is led
Can be tetraethyl ammonium hydroxide to agent.
According to the present invention, tin source is to influence the most important element of Sn- beta-molecular sieves, and the pink salt in the present invention can be to have
At least one of machine pink salt and inorganic tin salts.There is toxicity due to organic tin salt, all there is harm, institute to human body and environment
It is preferably tin halides, halogenation stannous, stannous sulfate, STANNOUS SULPHATE CRYSTALLINE, stannate, stannite, nitric acid tin, tin oxide, oxygen to state tin source
Change at least one of stannous.In order that tin element is uniformly distributed in synthesis of molecular sieve, the tin source in the present invention is preferably solvable
Property tin source.In order to ensure that the Sn- beta-molecular sieves of generation have identical crystal habit and crystal morphology, it is to avoid variform
Crystal is produced, and the tin source in the present invention is preferably single tin source, one kind in such as stannic chloride, nitric acid tin, STANNOUS SULPHATE CRYSTALLINE, sodium stannate.
According to the present invention, to improve the efficiency of crystallization, further, and in step (1), each material in the mixed solution
Mol ratio be SiO2：Sn：Structure directing agent：H2O=1：(0.005~0.02)：(0.3~3.5)：(5~200)；Further
Preferably SiO2：Sn：Structure directing agent：H2O=1：(0.01~0.015)：(1.0~2.5)：(10~120).
According to the present invention, in order to promote the crystallization of molecular sieve, the defect in crystallization efficiency, reduction crystal is improved, nothing is reduced
The generation of sizing material, further, 160~200 DEG C of crystallization temperature in the step (1), crystallization time is 10~12 days.
According to the present invention, in order to improve the purity of product, further, the preparation method of the Sn- beta-molecular sieves also includes
Step (4)：The hydro-thermal reaction product of step (3) is centrifuged into 1~3min under 1000~3000 turns/min rotating speed, upper strata is removed
Product after washing, then with water centrifuge washing 2~3 times, is finally placed in vacuum drying chamber and is dried in vacuo, obtain pure by liquid
The nanometer Sn- beta-molecular sieves of change.
According to the present invention, in order to avoid prepared Sn- beta-molecular sieves are oxidized in high temperature drying, the Sn- beta molecules
Sieve is dried under vacuum；Further, the vacuum drying temperature is 50~80 DEG C, and the time is 5~24h.
, according to the invention it is preferred to, in step (2), the cobalt source can be with known to those skilled in the art, such as halogen
Change at least one of cobalt, cobalt nitrate, cobaltous sulfate, cobalt acetate and cobaltous silicate；The nickel source can be those skilled in the art institute
It is known, such as at least one of nickel halogenide, nickel nitrate, nickel sulfate, nickel acetate and silicic acid nickel.
According to the present invention, in order to improve the catalytic efficiency of product, further, mole of each material in the step (2)
Match as crystallization product：Co2+：Ni2+=1：(0~2)：(0~2), and Co2+And Ni2+Quality proportioning it is different when be 0；It is preferred that
, the quality proportioning of each material is crystallization product：Co2+：Ni2+=1：(0.5~1.5)：(0.5~1.5).
According to the present invention, pink colour presoma in the step (2) crystalline substance of pink colour nickel cobalt hydroxide for superficial growth
Change product；To make nickel-cobalt hydroxide complete cure in presoma, further, presoma is situated between with sulfur-bearing in the step (3)
The mass ratio of matter is 1：(1.5~5).
According to the present invention, sulphur source used can such as be vulcanized with known to those skilled in the art in step (3) of the present invention
One or more compositions in sodium, potassium sulfide, thiocarbamide, mercaptan, sulfone, sulfoxide, thioether, sulphonic acid ester, chlorosulfuric acid.
According to the present invention, in hydro-thermal reaction, the pressure of system is to influenceing the crystal formation and crystalline rate of product, and reactant
The self-generated pressure of system depends on the size of void volume in reactor, in order to improve the efficiency of crystallization, further, for step
Suddenly the cumulative volume of mixed solution is the 60~75% of the ptfe autoclave capacity in (1).
The present invention also provides the nanometer Sn- beta-molecular sieves prepared according to the above method, and29Q4/ in SiNMR characterization results
Q3 is not less than 30.
It is described according to the present invention29Q4 signals in SiNMR refer to Si- in molecular sieve (O-Si)4Being total to produced by structure
Shake peak, i.e., the formant that the structure that silicon atom is connected constituted by silicon oxygen bond and four silicon atoms is produced；Q3 signals refer to
HO-Si- (O-Si) in molecular sieve3Formant produced by structure, i.e. silicon atom are connected by silicon oxygen bond with three silicon atoms
And the formant produced with the structure that a hydroxyl is connected constituted.29SiNMR characterization result explanation, nanometer Sn- beta-molecular sieves
Only strong Q4 signals, and Q3 signal is very weak, this illustrates that nanometer Sn- beta-molecular sieves prepared by this method almost lack without skeleton
Fall into.
It is the acid amount of molecular sieve to influence another key factor of molecular sieve catalytic performance, according to the present invention, the nanometer
The acid amount of Sn- beta-molecular sieves is 25.5~42.6 μm of ol/g.
According to the present invention, the mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin：Nickel：Cobalt：Sulphur=1：
(0.002~0.014)：(0~0.18)：(0~0.21)：(0.15~0.5), wherein nickel are when different with the mol ratio of cobalt
Zero, preferably 1：(0.007~0.011)：(0.02~0.09)：(0.05~0.18)：(0.2~0.24).
According to the present invention, an important physical index of molecular sieve is exactly its specific surface area and pore volume, larger ratio surface
Product and pore volume can improve the accessibility of avtive spot in molecular sieve, so as to improve the catalytic effect of molecular sieve, this
The specific surface area of nanometer Sn- beta-molecular sieves is 405~639m in invention2/ g, pore volume is 0.22~0.68cm2/g。
Below will the present invention will be described in detail by specific embodiment.In following embodiment and comparative example, point
The appearance and size of son sieve is determined with HitachiS4800 types SEM, and accelerating potential is 20KV；Molecular sieve29SiNMR spectrograms are determined using BrukerAVANCEIII600WB types nuclear magnetic resonance chemical analyser, and test condition is：
59.588MHz, magic angle rotating speed is 3kHz, wherein, chemical shift represents Q4 for the characteristic peak at -114.9, -112.9 and -109.8 places
Group, chemical shift between -95~-105 for Q3 groups, Q4 and Q3 characteristic peaks area lack than that can represent the skeleton of molecular sieve
Fall into the relative populations of position；Acid amount is analyzed by BIQ-RADFTS3O00 types Fourier infrared spectrograph；Surveyed using nitrogen adsorption methods
The specific surface area and pore volume of molecular sieve are tried, nitrogen adsorption desorption curve uses the 3020-M types of Micromeritics companies tristar II
Number the test of surface analysis instrument, specific surface area and pore volume are calculated by BET and t-plot methods and obtained.
Embodiment 1
Under agitation, by tetraethyl orthosilicate, sodium stannate, tetraethyl ammonium hydroxide and hydrazine hydrate, be mixed in water,
The mol ratio of each material is SiO in the mixed solution of formation2：Sn：Structure directing agent：H2O=1：0.012：1.3：100, stirring
It is gel to solution, the pH value for adding potassium tert-butoxide regulation solution is 12.6, and solution then is transferred into polytetrafluoroethyl-ne alkene reaction
In kettle, the cumulative volume of mixed solution is the 65% of reactor capacity, crystallization 5 days at a temperature of 190 DEG C, separates and is calcined and obtains
Crystallization product；
It is by weight by crystallization product, cobaltous sulfate, nickel nitrate：Crystallization product：Co2+：Ni2+=1：1：1 is dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, is reacted 10h at a temperature of 180 DEG C, is obtained
To the presoma of pink colour；In the aqueous solution that presoma is added to vulcanized sodium, wherein, the mass ratio of presoma and vulcanized sodium is 1：2,
6h is reacted at a temperature of 80 DEG C, obtained hydro-thermal reaction product is centrifuged under 1000 turns/min rotating speed in 3min, removing
Product after washing, then with water centrifuge washing 2 times, is finally placed in 50 DEG C of vacuum drying chamber and is dried in vacuo by layer liquid
24h, the nanometer Sn- beta-molecular sieves purified.
The mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin：Nickel：Cobalt：Sulphur=1：0.01：0.08：0.08：
0.16, its SEM picture as shown in figure 1,29SiNMR spectrograms as shown in Fig. 2 in Fig. 2 chemical shift be -114.9, -112.9 and -
Characteristic peak at 109.8 represents Q4 groups, chemical shift between -95~-105 for Q3 groups, Q4 and Q3 characteristic peaks peak face
Product ratio is as shown in table 1.
Embodiment 2
Under agitation, tetraethoxysilane, STANNOUS SULPHATE CRYSTALLINE, tetraethyl ammonium iodide and caustic alcohol are mixed in water, shape
Into mixed solution in each material mol ratio be SiO2：Sn：Structure directing agent：H2O=1：0.01：1.0：10, stir to molten
Liquid is gel, and the pH value for adding ammoniacal liquor regulation solution is 11.7, and then solution is transferred in ptfe autoclave, mixed
The cumulative volume of solution be reactor capacity 65%, crystallization 10 days at a temperature of 180 DEG C, separate and be calcined obtain crystallization production
Thing；
It is by weight by crystallization product, cobalt nitrate, nickel sulfate：Crystallization product：Co2+：Ni2+=1：0.5：It 1.5 is dissolved in
In water, mixed solution is transferred in ptfe autoclave by obtained mixed solution, is reacted 4h at a temperature of 190 DEG C, is obtained
To the presoma of pink colour；In the aqueous solution that presoma is added to thiocarbamide, the mass ratio of presoma and thiocarbamide is 1：2.5, at 90 DEG C
At a temperature of react 4h, obtained hydro-thermal reaction product is centrifuged into 2min under 2000 turns/min rotating speed, supernatant liquid is removed,
Then use water centrifuge washing 2 times, finally the product after washing is placed in 60 DEG C of vacuum drying chamber and is dried in vacuo 16h, is obtained
The nanometer Sn- beta-molecular sieves of purifying.
The mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin：Nickel：Cobalt：Sulphur is 1：0.007：0.02：
0.11：0.2, its SEM figure are as shown in Figure 3.
Embodiment 3
Under agitation, methyl silicate, stannous sulfate, tetraethyl ammonium iodide and sodium carbonate are mixed in water, shape
Into mixed solution in each material mol ratio be SiO2：Sn：Structure directing agent：H2O=1：0.015：2.5：120, stirring is extremely
Solution is gel, and the pH value for adding isobutyl group lithium regulation solution is 10.2, and solution then is transferred into ptfe autoclave
In, the cumulative volume of mixed solution is the 72% of reactor capacity, crystallization 28 days at a temperature of 200 DEG C, separates and is calcined and obtains
Crystallization product；
It is by weight by crystallization product, cobalt nitrate, nickel acetate：Crystallization product：Co2+：Ni2+=1：1：2 are dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, is reacted 5h at a temperature of 190 DEG C, is obtained
The presoma of pink colour；Presoma is added in the sulfoxide aqueous solution, the mass ratio of presoma and sulfoxide is 1：1.5, in 140 DEG C of temperature
The lower reaction 2h of degree, centrifuges 2min by obtained hydro-thermal reaction product under 2000 turns/min rotating speed, removes supernatant liquid, then
With water centrifuge washing 3 times, finally the product after washing is placed in 80 DEG C of vacuum drying chamber and is dried in vacuo 7h, is purified
Nanometer Sn- beta-molecular sieves.
The mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin：Nickel：Cobalt：Sulphur is 1：0.011：0.09：
0.18：0.28.
Embodiment 4
Under agitation, white carbon, nitric acid tin, etamon chloride and urea ammoniacal liquor are mixed in water in proportion, shape
Into mixed solution in each material mol ratio be SiO2：Sn：Structure directing agent：H2O=1：0.005：0.3：5, stir to molten
Liquid is gel, and the pH value for adding sodium hydrate regulator solution is 9.5, and then solution is transferred in ptfe autoclave,
The cumulative volume of mixed solution is the 60% of reactor capacity, and crystallization 10 days at a temperature of 150 DEG C separate and are calcined and obtain crystallization
Product；
It is by weight by crystallization product, cobalt nitrate, nickel nitrate：Crystallization product：Co2+：Ni2+=1：0.5：1 is dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, is reacted 10h at a temperature of 180 DEG C, is obtained
To the presoma of pink colour；In the aqueous solution that presoma is added to lauryl mercaptan, the mass ratio of presoma and lauryl mercaptan is 1：3,
6h is reacted at a temperature of 80 DEG C, obtained hydro-thermal reaction product is centrifuged under 1000 turns/min rotating speed in 3min, removing
Product after washing, then with water centrifuge washing 2 times, is finally placed in 50 DEG C of vacuum drying chamber and is dried in vacuo by layer liquid
24h, the nanometer Sn- beta-molecular sieves purified.
The mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin：Nickel：Cobalt：Sulphur is 1：0.002：0.01：
0.05：0.15.
Embodiment 5
Under agitation, Ludox, sodium stannite, tetraethyl ammonium hydroxide and ammoniacal liquor are mixed in water in proportion,
The mol ratio of each material is SiO in the mixed solution of formation2：Sn：Structure directing agent：H2O=1：0.02：3.5：200, stirring
It is gel to solution, the pH value for adding caustic alcohol regulation solution is 13.8, and solution then is transferred into ptfe autoclave
In, the cumulative volume of mixed solution is the 75% of reactor capacity, crystallization 10 days at a temperature of 220 DEG C, separates and is calcined and obtains
Crystallization product；
It is by weight by crystallization product, cobaltous sulfate, nickel sulfate：Crystallization product：Co2+：Ni2+=1：2：0.5 is dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, is reacted 2h at a temperature of 220 DEG C, is obtained
The presoma of pink colour；Presoma is added in the ten disulfide aqueous solution, the mass ratio of presoma and sulfur-containing medium is 1：5,140
1h is reacted at a temperature of DEG C, obtained hydro-thermal reaction product is centrifuged into 1min under 3000 turns/min rotating speed, upper liquid is removed
Product after washing, then with water centrifuge washing 3 times, is finally placed in 80 DEG C of vacuum drying chamber and is dried in vacuo 5h, obtain by body
To the nanometer Sn- beta-molecular sieves of purifying.
The mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin：Nickel：Cobalt：Sulphur is 1：0.014：0.17：
0.03：0.5.
Embodiment 6：
Under agitation, by tetraethyl orthosilicate, sodium stannate, tetraethyl ammonium hydroxide and hydrazine hydrate, be mixed in water,
The mol ratio of each material is SiO in the mixed solution of formation2：Sn：Structure directing agent：H2O=1：0.012：1.3：100, stirring
It is gel to solution, the pH value for adding potassium tert-butoxide regulation solution is 12.6, and solution then is transferred into polytetrafluoroethyl-ne alkene reaction
In kettle, the cumulative volume of mixed solution is the 65% of reactor capacity, crystallization 5 days at a temperature of 190 DEG C, separates and is calcined and obtains
Crystallization product；
It is crystallization product by weight by crystallization product, nickel nitrate：Ni2+=1：2 are dissolved in the water, and obtained mixing is molten
Liquid, mixed solution is transferred in ptfe autoclave, and 10h is reacted at a temperature of 180 DEG C, obtains the presoma of green；
In the aqueous solution that presoma is added to vulcanized sodium, the mass ratio of presoma and vulcanized sodium is 1：1.5, reacted at a temperature of 80 DEG C
6h, 3min is centrifuged by obtained hydro-thermal reaction product under 1000 turns/min rotating speed, is removed supernatant liquid, is then centrifuged with water
Product after washing, is finally placed in 50 DEG C of vacuum drying chamber and is dried in vacuo 24h by washing 2 times, the nanometer Sn- purified
Beta-molecular sieve.
The mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin：Nickel：Sulphur is 1：0.01：0.18：0.24.
Embodiment 7：
Under agitation, by tetraethyl orthosilicate, sodium stannate, tetraethyl ammonium hydroxide and hydrazine hydrate, be mixed in water,
The mol ratio of each material is SiO in the mixed solution of formation2：Sn：Structure directing agent：H2O=1：0.012：1.3：100, stirring
It is gel to solution, the pH value for adding potassium tert-butoxide regulation solution is 12.6, and solution then is transferred into polytetrafluoroethyl-ne alkene reaction
In kettle, the cumulative volume of mixed solution is the 65% of reactor capacity, crystallization 5 days at a temperature of 190 DEG C, separates and is calcined and obtains
Crystallization product；
It is by weight by crystallization product, cobaltous sulfate：Crystallization product：Co2+=1：2 are dissolved in the water, and obtained mixing is molten
Liquid, mixed solution is transferred in ptfe autoclave, and 10h is reacted at a temperature of 180 DEG C, obtains the presoma of pink colour；
In the aqueous solution that presoma is added to vulcanized sodium, the mass ratio of presoma and vulcanized sodium is 1：0.6, reacted at a temperature of 80 DEG C
6h, 3min is centrifuged by obtained hydro-thermal reaction product under 1000 turns/min rotating speed, is removed supernatant liquid, is then centrifuged with water
Product after washing, is finally placed in 50 DEG C of vacuum drying chamber and is dried in vacuo 24h by washing 2 times, the nanometer Sn- purified
Beta-molecular sieve.
The mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin：Cobalt：Sulphur is 1：0.01：0.21：0.24.
Comparative example 1
According to the method for embodiment 1, unlike, hydro-thermal reaction system is adjusted to neutrality using hydrofluoric acid, it is specific real
Apply process as follows：
Under agitation, by tetraethyl orthosilicate, sodium stannate, tetraethyl ammonium hydroxide and hydrazine hydrate, be mixed in water,
The mol ratio of each material is SiO in the mixed solution of formation2：Sn：Structure directing agent：H2O=1：0.012：1.3：100, stirring
It is gel to solution, adds hydrofluoric acid and adjust hydro-thermal reaction system to neutrality, be transferred in ptfe autoclave, mix
The cumulative volume of solution is the 65% of reactor capacity, and crystallization 5 days at a temperature of 190 DEG C separate and are calcined and obtain crystallization product；
It is by weight by crystallization product, cobaltous sulfate, nickel nitrate：Crystallization product：Co2+：Ni2+=1：1：1 is dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, is reacted 10h at a temperature of 180 DEG C, is obtained
To the presoma of pink colour；In the aqueous solution that presoma is added to vulcanized sodium, wherein, the mass ratio of presoma and vulcanized sodium is 1：2,
6h is reacted at a temperature of 80 DEG C, obtained hydro-thermal reaction product is centrifuged under 1000 turns/min rotating speed in 3min, removing
Product after washing, then with water centrifuge washing 2 times, is finally placed in 50 DEG C of vacuum drying chamber and is dried in vacuo by layer liquid
24h, the nanometer Sn- beta-molecular sieves purified.
The mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin：Nickel：Cobalt：Sulphur is 1：0.007：0.004：
0.06：0.02.
Comparative example 2
According to the method similar to embodiment 1, the difference is that not in the superficial growth nickel and cobalt of crystallization product, specific implementation
Process is as follows：
Under agitation, by tetraethyl orthosilicate, sodium stannate, tetraethyl ammonium hydroxide and hydrazine hydrate, be mixed in water,
The mol ratio of each material is SiO in the mixed solution of formation2：Sn：Structure directing agent：H2O=1：0.012：1.3：100, stirring
It is gel to solution, adds hydrofluoric acid and adjust hydro-thermal reaction system to neutrality, be transferred in ptfe autoclave, mix
The cumulative volume of solution is the 65% of reactor capacity, and crystallization 5 days at a temperature of 190 DEG C separate and are calcined and obtain a nanometer Sn- β
Molecular sieve.
The mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin is 1：0.008.
Comparative example 3
According to the method similar to embodiment 1, unlike：In step (2), the preparation condition of molecular sieve precursor is
10h is reacted at 160 DEG C, specific implementation process is as follows：
Under agitation, by tetraethyl orthosilicate, sodium stannate, tetraethyl ammonium hydroxide and hydrazine hydrate, be mixed in water,
The mol ratio of each material is SiO in the mixed solution of formation2：Sn：Structure directing agent：H2O=1：0.012：1.3：100, stirring
It is gel to solution, the pH value for adding potassium tert-butoxide regulation solution is 12.6, and solution then is transferred into polytetrafluoroethyl-ne alkene reaction
In kettle, the cumulative volume of mixed solution is 65%, the crystallization 10h at a temperature of 160 DEG C of reactor capacity, separates and is calcined and obtains
Crystallization product；
It is by weight by crystallization product, cobaltous sulfate, nickel nitrate：Crystallization product：Co2+：Ni2+=1：1：1 is dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, is reacted 10h at a temperature of 180 DEG C, is obtained
To the presoma of pink colour；In the aqueous solution that presoma is added to vulcanized sodium, wherein, the mass ratio of presoma and vulcanized sodium is 1：2,
6h is reacted at a temperature of 80 DEG C, obtained hydro-thermal reaction product is centrifuged under 1000 turns/min rotating speed in 3min, removing
Product after washing, then with water centrifuge washing 2 times, is finally placed in 50 DEG C of vacuum drying chamber and is dried in vacuo by layer liquid
24h, the nanometer Sn- beta-molecular sieves purified.
The mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin：Nickel：Cobalt：Sulphur=1：0.003：0.01：
0.02：0.0012.
Nanometer Sn- beta-molecular sieve performance parameters in the embodiment 1-7 of table 1, comparative example 1-2
Catalytic result such as table 1 institute of the embodiment 1-7 and comparative example 1-2 Sn- beta-molecular sieves in phenol hydroxylation reaction
Show, reaction condition includes：Sn- beta-molecular sieves amount is 1g, and phenol amount is 0.1mol, phenol and hydrogen peroxide mol ratio=1：3, normal pressure,
Reaction temperature is 50 DEG C.The composition for the liquid phase mixture that reaction is obtained is determined by using gas chromatography.
Amount × 100% of phenol conversion=(amount of amount-residual reactant of the reactant of addition)/addition reactant；
The amount of the reactant of amount/conversion of target product selectivity=the change into reactant that target product is consumed ×
100%.
Table 2
From upper table data can be seen that according to technical scheme method prepare Sn nano molecular sieves have it is larger
Specific surface area and pore volume, and the glycosylation reaction of Sn nano molecular sieves Pyrogentisinic Acid's hydroxyl has significant catalytic effect.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.It is further to note that described in above-mentioned embodiment
Each particular technique feature, in the case of reconcilable, can be combined by any suitable means.In order to avoid not
Necessary repetition, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. the preparation method of a kind of nanometer of Sn- beta-molecular sieve, it is characterised in that comprise the following steps：
(1) in the presence of aqueous solvent, silicon source, tin source, structure directing agent and alkali source are mixed to get in proportion gelatinous mixed
Close solution, adjust mixed solution pH value to 9.5~13.8, by the mixed solution at a temperature of 150~220 DEG C crystallization 5
~28 days, separate and be calcined and obtain crystallization product；
(2) crystallization product, cobalt salt and/or nickel salt are mixed in proportion in aqueous solvent, obtains reaction solution, by the reaction
Solution reacts 2~10h at a temperature of 180~220 DEG C, obtains molecular sieve precursor；
(3) molecular sieve precursor is mixed in aqueous solvent with sulfur-containing medium, reaction 1 is carried out at a temperature of 80~140 DEG C
~6h, obtains a nanometer Sn- beta-molecular sieves.
2. the preparation method of according to claim 1 nanometer of Sn- beta-molecular sieve, wherein, in step (1), the mixing is molten
The mol ratio of each material is SiO in liquid2：Sn：Structure directing agent：H2O=1：(0.005~0.02)：(0.3~3.5)：(5~
200)。
3. the preparation method of according to claim 1 nanometer of Sn- beta-molecular sieve, wherein, in step (1), the crystallization
160~200 DEG C of crystallization temperature, crystallization time is 10~12 days.
4. the preparation method of according to claim 1 nanometer of Sn- beta-molecular sieve, wherein, in step (2), each material
Quality proportioning be crystallization product：Co2+：Ni2+=1：(0~2)：(0~2), and Co2+And Ni2+Quality proportioning it is different when be 0；
It is preferred that, the quality proportioning of each material is crystallization product：Co2+：Ni2+=1：(0.5~1.5)：(0.5~1.5).
5. the preparation method of according to claim 1 nanometer of Sn- beta-molecular sieve, wherein, in step (3), the presoma
Mass ratio with the sulfur-containing medium is 1：(1.5~5).
6. the preparation method of the nanometer Sn- beta-molecular sieves according to Claims 1 to 5 any one, wherein, the alkali source is
At least one of ammoniacal liquor, urea, hydrazine hydrate, sodium carbonate, sodium acid carbonate, caustic alcohol, potassium tert-butoxide and lithium diisopropylamine.
7. the preparation method of the nanometer Sn- beta-molecular sieves according to Claims 1 to 5 any one, wherein, the tin source is
In tin halides, halogenation stannous, stannous sulfate, STANNOUS SULPHATE CRYSTALLINE, stannate, stannite, nitric acid tin, tin oxide and stannous oxide extremely
Few one kind；
It is preferred that, the tin source is one kind in stannic chloride, nitric acid tin, STANNOUS SULPHATE CRYSTALLINE and sodium stannate.
8. a kind of nanometer Sn- beta-molecular sieves, it is characterised in that the method according to claim 1~7 any one is prepared into
Arrive, the mol ratio of each material is silicon in the nanometer Sn- beta-molecular sieves：Tin：Nickel：Cobalt：Sulphur=1：(0.002~0.014)：(0~
0.18)：(0~0.21)：(0.15~0.5), and cobalt it is different with the mol ratio of nickel when be 0；And/or
The specific surface area of the molecular sieve is 405~639m2/ g, pore volume is 0.22~0.68cm2/g；
And/or the acid amount of the molecular sieve is 25.5~42.6 μm of ol/g.
9. a kind of method of phenol hydroxylation reaction, it is characterised in that according to following steps：Under conditions of catalyst presence,
By phenol and oxidant haptoreaction, hydroquinones is obtained, the catalyst is the Sn- beta molecules according to claim 8
Sieve.
10. method for hydroxylation of phenol according to claim 9, wherein, the reaction condition includes：Phenol and oxidant
Mol ratio be 1：(2~8), reaction temperature is 30~80 DEG C, and the reaction time is 0.5-72h, and the amount of catalyst is total for reactant
The 0.5%-15% of weight.
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