CN107311201B - The method of nanometer Sn- beta-molecular sieve and preparation method thereof and phenol hydroxylation reaction - Google Patents
The method of nanometer Sn- beta-molecular sieve and preparation method thereof and phenol hydroxylation reaction Download PDFInfo
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Abstract
The present invention relates to beta-molecular sieve technical fields, the method for disclosing nanometer Sn- beta-molecular sieve and preparation method thereof and phenol hydroxylation reaction, the preparation method of the nanometer Sn- beta-molecular sieve, the following steps are included: (1) is 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 roasts to 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 in 180~220 DEG C of at a temperature of 2~10h of reaction, obtain molecular sieve precursor；(3) molecular sieve precursor is mixed in aqueous solvent with sulfur-containing medium, carries out hydro-thermal reaction, obtains a nanometer Sn- beta-molecular sieve.It is prepared for composite Nano Sn- beta-molecular sieve by the above method, the particle size uniformity of the product, large specific surface area, skeleton defect are few, have good catalytic in phenol hydroxylation reaction.
Description
Technical field
The present invention relates to beta-molecular sieve technical fields, and in particular to nanometer Sn- beta-molecular sieve and preparation method thereof and phenol hydroxyl
The method of glycosylation reaction.
Background technique
Hetero-atom molecular-sieve refers to the molecular sieve for having non-silicon, 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 also made to have special catalytic performance.Titanium-silicon molecular sieve TS-1 is
There is the beginning of the synthesis for indicating hetero-atom molecular-sieve and application study in molecular sieve with four-coordination framework titania.
The stacking fault symbiosis that beta-molecular sieve is made of the polymorph that three kinds of structures are different but are closely related.It has three
Twelve-ring cellular structure is tieed up, wherein the duct in [100] and [010] direction is all straight hole road, aperture may each be about 0.66 ×
0.67nm；[001] it is about 0.55 that the duct in direction, which is by the aperture that the straight hole road of [100] and [010] both direction intersects to form,
The sinusoidal duct of × 0.55nm.Due to beta-molecular sieve with unique cellular structure, good heat and hydrothermal stability and properly
Acidity make it can be used as catalysis material to be widely used 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 methylation are hydrocracked with catalytic dewaxing etc., are a kind of to have wide application
The catalysis material of prospect.Since beta-molecular sieve has biggish cellular structure, the metal heteroatoms such as Ti, Sn are also introduced into its skeleton
Structure.
When Sn to be introduced to the skeleton of beta-molecular sieve, it can effectively be catalyzed BayerVilliger oxidation, Meerwin-
The reaction such as Ponndorf-Verley, Diles-Alder addition and isomerization, thus in biomass high value added utilization field
Present very well application prospect.But in general, the hetero-atom molecular-sieve of * BEA structure is closed under neutral fluorine-containing system condition
At [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 which basicity, the solidification precursor for significantly reducing crystallization system are solidifying
Glue, thus the nucleation and its synthesising stability that reduce the diffusion rate of precursor, influence molecular sieve.Therefore, the system condition system
The particle size of standby molecular sieve is usually at 10 microns or more, and its synthesising stability is unsatisfactory.Therefore, it is necessary to further
The synthesis of Sn-beta molecular sieve is studied to reduce its crystallite dimension, improve its synthesising stability.
Catechol and hydroquinone are the fine chemicals of high added value, are widely used in photographic process, adhesive, resist
Oxygen agent, additive and dyestuff etc. are industrial.Hydoxylating phenol is the main method for preparing catechol and hydroquinone, this method
Mainly using titanium-silicon molecular sieve TS-1 as catalyst, but since its aperture is only about 0.55 nanometer, the diffusion of reaction product by
Inhibit, their easy deep oxidations generate quinone.Therefore, it researches and develops a kind of with excellent phenol hydroxylation activity, and is conducive to react
Object and the molecular sieve catalytic material of reaction product diffusion are very necessary.
Summary of the invention
An object of the present invention is to provide a kind of nanometer of Sn- beta-molecular sieve, its, ratio small, of uniform size with particle size
The big feature of surface area, 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, under alkaline condition, pass through
Multistep hydro-thermal method synthesizes stanniferous high compound beta-molecular sieve.
The third object of the present invention is to provide a kind of method of phenol hydroxylation reaction, is catalysis with nanometer Sn- beta-molecular sieve
The hydroxylating of phenol is realized in agent, and to reaction product hydroquinone selectivity with higher.
To achieve the goals above, the present invention provides the preparation method of a kind of nanometer of Sn- beta-molecular sieve, comprising 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 150~220 DEG C at a temperature of it is brilliant
Change 5~28 days, separates and roast to obtain crystallization product；
(2) crystallization product, cobalt salt and/or nickel salt are mixed in proportion in aqueous solvent, obtains reaction solution, it will be described
Reaction solution obtains molecular sieve precursor in 180~220 DEG C of at a temperature of 2~10h of reaction；
(3) molecular sieve precursor is mixed in aqueous solvent with sulfur-containing medium, it is anti-in 80~140 DEG C of at a temperature of progress
1~6h is answered, a nanometer Sn- beta-molecular sieve is obtained.
The present invention also provides a kind of nanometer Sn- beta-molecular sieve according to prepared by the above method, the nanometer Sn- beta-molecular sieve
In each substance molar ratio be silicon: tin: nickel: cobalt: sulphur=1:(0.002~0.014): (0~0.18): (0~0.21): (0.15
~0.5), and the mol ratio of cobalt and nickel is not 0 simultaneously；
And/or the specific surface area of the molecular sieve is 405~639m20.22~0.68cm of/g, Kong Rongwei2/ 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 the following steps:, will under the conditions of existing for the catalyst
Phenol and oxidant haptoreaction, obtain hydroquinone, and the catalyst is above-mentioned Sn- beta-molecular sieve.
Through the above technical solutions, this method is in alkali the present invention provides the preparation method of a kind of nanometer of Sn- beta-molecular sieve
Crystallization product has been synthesized by hydro-thermal method under the conditions of property, has entered tin atom inside si molecular sieves, and replace 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, have been obtained compound
Molecular sieve, the particle size of the composite molecular screen is small, large specific surface area, and skeleton defect is few, in the hydroxylating of phenol
With good catalytic.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of 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 figure of nanometer Sn- beta-molecular sieve in embodiment 1；
Fig. 2 is nanometer Sn- beta-molecular sieve in embodiment 129SiNMR spectrogram；
Fig. 3 is the SEM figure of nanometer Sn- beta-molecular sieve in embodiment 2.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides the preparation methods of a kind of nanometer of Sn- beta-molecular sieve, comprising 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 150~220 DEG C at a temperature of it is brilliant
Change 5~28 days, separates and roast to obtain crystallization product；
(2) crystallization product, cobalt salt and/or nickel salt are mixed in proportion in aqueous solvent, obtains reaction solution, it will be described
Reaction solution obtains molecular sieve precursor in 180~220 DEG C of at a temperature of 2~10h of reaction；
(3) molecular sieve precursor is mixed in aqueous solvent with sulfur-containing medium, it is anti-in 80~140 DEG C of at a temperature of progress
1~6h is answered, a nanometer Sn- beta-molecular sieve is obtained.
The Sn- beta-molecular sieve crystallite dimension prepared in the prior art is big, synthesis repeatability is undesirable.The present invention by
Crystallization product has been synthesized under alkaline condition, and has further been modified on the surface of crystallization product, and Sn- beta-molecular sieve is improved
Specific surface area and the size for reducing molecular sieve, to improve its catalytic activity.
In the present invention, alkali source provides enough OH for crystallization system-, guarantee smoothly completing for crystallization, improve
The uniformity of crystallization product, the alkali source in the step (1) can be alkali metal hydroxide, ammonium hydroxide, urea, hydrazine hydrate, carbonic acid
Sodium, sodium bicarbonate, sodium fluoride, potassium fluoride, sodium alkoxide, potassium alcoholate, aliphatic amine, alkyl sodium, alkyl potassium, hydrocarbyl lithium, alkyl copper lithium, rouge
At least one of fat race hydramine and quaternary ammonium base, preferably ammonium hydroxide, urea, hydrazine hydrate, sodium carbonate, sodium bicarbonate, sodium ethoxide, 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 black and silica solution
Kind；In order to reduce influence of the hetero atom to crystallization product in silicon source, single silicon source is selected in the present invention, it is further preferably organic
One in esters of silicon acis, such as methyl orthosilicate, isopropyl silicate, sub- silester, tetraethoxysilane, tetraethyl orthosilicate
Kind.
According to the present invention, structure directing agent used in the step (1) can be quaternary ammonium base class, quaternary ammonium salt and rouge
At least one of fat amine, wherein the 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 structure directing agent can be the quaternary ammonium of the quaternary ammonium base, general formula III expression that indicate selected from general formula II
At least one of the aliphatic amine that salt and general formulae IV indicate.
In Formula II, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as: R1、R2、R3And R4Can respectively be each independently methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
Isobutyl group or tert-butyl.
In formula III, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as: R1、R2、R3And R4Can respectively be each independently methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
Isobutyl group or tert-butyl；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 an integer of 1 or 2.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, tert-butyl, 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, 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
It can be tetraethyl ammonium hydroxide to agent.
According to the present invention, tin source is the most important element for influencing Sn- beta-molecular sieve, 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
Stating tin source is preferably tin halides, halogenation stannous, stannous sulfate, STANNOUS SULPHATE CRYSTALLINE, stannate, stannite, nitric acid tin, tin oxide, oxygen
Change at least one of stannous.In order to be uniformly distributed tin element in synthesis of molecular sieve, the tin source in the present invention is preferably solvable
Property tin source.In order to guarantee the Sn- beta-molecular sieve crystal habit having the same and crystal morphology that generate, variform is avoided
Crystal generates, and the tin source in the present invention is preferably single tin source, such as one of stannic chloride, nitric acid tin, STANNOUS SULPHATE CRYSTALLINE, sodium stannate.
It according to the present invention, is the efficiency for improving crystallization, further, in step (1), each substance 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, crystallization efficiency is improved, the defects of crystal is reduced, reduces nothing
The generation of sizing substance, 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 sieve further includes
Step (4): the hydro-thermal reaction product of step (3) is centrifuged 1~3min under the revolving speed of 1000~3000 turns/min, removes upper layer
Then liquid is used water centrifuge washing 2~3 times, the product after washing is finally placed in a vacuum drying oven vacuum drying, is obtained pure
The nanometer Sn- beta-molecular sieve of change.
According to the present invention, in order to avoid prepared Sn- beta-molecular sieve is oxidized in high temperature drying, the Sn- beta molecule
Sieve is dried under vacuum conditions；Further, the vacuum drying temperature be 50~80 DEG C, the time be 5~for 24 hours.
, according to the invention it is preferred to, in step (2), the cobalt source can be 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 substance in the step (2)
Proportion is crystallization product: Co2+: Ni2+=1:(0~2): (0~2), and Co2+And Ni2+Quality proportioning not simultaneously be 0；It is preferred that
, the quality proportioning of each substance is crystallization product: Co2+: Ni2+=1:(0.5~1.5): (0.5~1.5).
According to the present invention, the pink colour presoma in the step (2) is the crystalline substance that surface grown pink colour nickel cobalt hydroxide
Change product；To make nickel-cobalt hydroxide complete cure in presoma, further, presoma and sulfur-bearing are situated between in the step (3)
The mass ratio of matter is 1:(1.5~5).
According to the present invention, sulphur source used in step (3) of the present invention can be known to those skilled in the art, such as vulcanizes
One of sodium, potassium sulfide, thiocarbamide, mercaptan, sulfone, sulfoxide, thioether, sulphonic acid ester, chlorosulfuric acid or numerous compositions.
According to the present invention, in hydro-thermal reaction, the pressure of system is to the crystal form and crystalline rate for influencing product, and reactant
The self-generated pressure of system depends on the size of void volume in reaction kettle, in order to improve the efficiency of crystallization, further, for step
Suddenly the total 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 result
Q3 is not less than 30.
According to the present invention, described29Q4 signal in SiNMR refers to Si- in molecular sieve (O-Si)4Caused by structure altogether
Shake peak, i.e. the silicon atom formant that is connected composed structure generation with four silicon atoms by silicon oxygen bond；Q3 signal refers to
HO-Si- (O-Si) in molecular sieve3Formant caused by structure, i.e. silicon atom are connected by silicon oxygen bond with three silicon atoms
And the formant that structure composed by being connected with a hydroxyl generates.29The characterization result explanation of SiNMR, nanometer Sn- beta-molecular sieve
Only strong Q4 signal, and the signal of Q3 is very weak, this illustrates that the nanometer Sn- beta-molecular sieve of this method preparation lacks almost without skeleton
It falls into.
Another key factor for influencing molecular sieve catalytic performance is the acid amount of molecular sieve, according to the present invention, the nanometer
The acid amount of Sn- beta-molecular sieve is 25.5~42.6 μm of ol/g.
According to the present invention, the molar ratio of each substance is silicon: tin: nickel: cobalt: sulphur=1 in the nanometer Sn- beta-molecular sieve:
(0.002~0.014): (0~0.18): (0~0.21): (0.15~0.5), wherein the mol ratio of nickel and cobalt be not simultaneously
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 Kong Rong, biggish specific surface
Long-pending and pore volume can improve the accessibility of active site in molecular sieve, so as to improve the catalytic effect of molecular sieve, this
The specific surface area of nanometer Sn- beta-molecular sieve is 405~639m in invention20.22~0.68cm of/g, Kong Rongwei2/g。
It 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 measured with HitachiS4800 type scanning electron microscope, acceleration voltage 20KV；Molecular sieve29SiNMR spectrogram is measured using BrukerAVANCEIII600WB type nuclear magnetic resonance chemical analyser, test condition are as follows:
59.588MHz, magic angle rotating speed 3kHz, wherein chemical shift is that the characteristic peak at -114.9, -112.9 and -109.8 places represents Q4
Group, chemical shift are Q3 group between -95~-105, and the skeleton that the area ratio of Q4 and Q3 characteristic peak can represent molecular sieve lacks
Fall into the relative populations of position；Acid amount is analyzed by BIQ-RADFTS3O00 type Fourier infrared spectrograph；It is surveyed using nitrogen adsorption methods
The specific surface area and Kong Rong of molecular sieve are tried, nitrogen adsorption desorption curve uses II 3020-M type of Micromeritics company tristar
Number surface analysis instrument test, specific surface area and pore volume are calculated by BET and t-plot method.
Embodiment 1
Under agitation, by tetraethyl orthosilicate, sodium stannate, tetraethyl ammonium hydroxide and hydrazine hydrate, be mixed in water,
The mol ratio of each substance 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, it is 12.6 that potassium tert-butoxide, which is added, and adjusts the pH value of solution, and solution is then transferred to polytetrafluoroethyl-ne alkene reaction
In kettle, the total volume of mixed solution is the 65% of reaction kettle capacity, 190 DEG C at a temperature of crystallization 5 days, separate and roast to obtain
Crystallization product；
By weight by crystallization product, cobaltous sulfate, nickel nitrate are as follows: crystallization product: Co2+: Ni2+=1:1:1 is dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, 180 DEG C at a temperature of react 10h, obtain
To the presoma of pink colour；Presoma being added in the aqueous solution of vulcanized sodium, wherein the mass ratio of presoma and vulcanized sodium is 1:2,
80 DEG C at a temperature of react 6h, obtained hydro-thermal reaction product is centrifuged 3min under the revolving speed of 1000 turns/min, in removing
Layer liquid, then uses water centrifuge washing 2 times, is finally placed in the product after washing in 50 DEG C of vacuum oven and is dried in vacuo
For 24 hours, the nanometer Sn- beta-molecular sieve purified.
The molar ratio of each substance is silicon: tin: nickel: cobalt: sulphur=1:0.01:0.08:0.08 in the nanometer Sn- beta-molecular sieve:
0.16, SEM picture as shown in Figure 1,29SiNMR spectrogram as shown in Fig. 2, in Fig. 2 chemical shift be -114.9, -112.9 and -
Characteristic peak at 109.8 represents Q4 group, and chemical shift is Q3 group, the peak face of Q4 and Q3 characteristic peak between -95~-105
Product ratio is as shown in table 1.
Embodiment 2
Under agitation, tetraethoxysilane, STANNOUS SULPHATE CRYSTALLINE, tetraethyl ammonium iodide and sodium ethoxide are mixed in water, shape
At mixed solution in each substance mol ratio be SiO2: Sn: structure directing agent: H2O=1:0.01:1.0:10 is stirred to molten
Liquid is gel, and it is 11.7 that ammonium hydroxide, which is added, and adjusts the pH value of solution, and then solution is transferred in ptfe autoclave, is mixed
The total volume of solution is the 65% of reaction kettle capacity, 180 DEG C at a temperature of crystallization 10 days, separate and roast to obtain crystallization production
Object；
By weight by crystallization product, cobalt nitrate, nickel sulfate are as follows: crystallization product: Co2+: Ni2+=1:0.5:1.5 is dissolved in
In water, mixed solution is transferred in ptfe autoclave by obtained mixed solution, 190 DEG C at a temperature of react 4h, obtain
To the presoma of pink colour；Presoma is added in the aqueous solution of 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 2min under the revolving speed of 2000 turns/min, removes supernatant liquid,
Then it uses water centrifuge washing 2 times, finally the product after washing is placed in 60 DEG C of vacuum oven and is dried in vacuo 16h, obtained
The nanometer Sn- beta-molecular sieve of purifying.
The molar ratio of each substance is silicon: tin: nickel: cobalt: sulphur 1:0.007:0.02 in the nanometer Sn- beta-molecular sieve:
0.11:0.2, SEM figure are as shown in Figure 3.
Embodiment 3
Under agitation, methyl orthosilicate, stannous sulfate, tetraethyl ammonium iodide and sodium carbonate are mixed in water, shape
At mixed solution in each substance mol ratio be SiO2: Sn: structure directing agent: H2O=1:0.015:2.5:120, stirring is extremely
Solution is gel, and it is 10.2 that isobutyl group lithium, which is added, and adjusts the pH value of solution, and solution is then transferred to ptfe autoclave
In, the total volume of mixed solution is the 72% of reaction kettle capacity, 200 DEG C at a temperature of crystallization 28 days, separate and roast to obtain
Crystallization product；
By weight by crystallization product, cobalt nitrate, nickel acetate are as follows: crystallization product: Co2+: Ni2+=1:1:2 is dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, 190 DEG C at a temperature of react 5h, obtain
The presoma of pink colour；Presoma is added in sulfoxide aqueous solution, the mass ratio of presoma and sulfoxide is 1:1.5, in 140 DEG C of temperature
Degree is lower to react 2h, and obtained hydro-thermal reaction product is centrifuged 2min under the revolving speed of 2000 turns/min, removes supernatant liquid, then
With water centrifuge washing 3 times, finally the product after washing is placed in 80 DEG C of vacuum oven and is dried in vacuo 7h, purified
Nanometer Sn- beta-molecular sieve.
The molar ratio of each substance is silicon: tin: nickel: cobalt: sulphur 1:0.011:0.09 in the nanometer Sn- beta-molecular sieve:
0.18:0.28.
Embodiment 4
Under agitation, white carbon black, nitric acid tin, etamon chloride and urea ammonium hydroxide are mixed in water in proportion, shape
At mixed solution in each substance mol ratio be SiO2: Sn: structure directing agent: H2O=1:0.005:0.3:5 is stirred to molten
Liquid is gel, and the pH value that sodium hydrate regulator solution is added is 9.5, and then solution is transferred in ptfe autoclave,
The total volume of mixed solution be reaction kettle capacity 60%, 150 DEG C at a temperature of crystallization 10 days, separate and roast to obtain crystallization
Product；
By weight by crystallization product, cobalt nitrate, nickel nitrate are as follows: crystallization product: Co2+: Ni2+=1:0.5:1 is dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, 180 DEG C at a temperature of react 10h, obtain
To the presoma of pink colour；Presoma being added in the aqueous solution of lauryl mercaptan, the mass ratio of presoma and lauryl mercaptan is 1:3,
80 DEG C at a temperature of react 6h, obtained hydro-thermal reaction product is centrifuged 3min under the revolving speed of 1000 turns/min, in removing
Layer liquid, then uses water centrifuge washing 2 times, is finally placed in the product after washing in 50 DEG C of vacuum oven and is dried in vacuo
For 24 hours, the nanometer Sn- beta-molecular sieve purified.
The molar ratio of each substance is silicon: tin: nickel: cobalt: sulphur 1:0.002:0.01 in the nanometer Sn- beta-molecular sieve:
0.05:0.15.
Embodiment 5
Under agitation, silica solution, sodium stannite, tetraethyl ammonium hydroxide and ammonium hydroxide are mixed in water in proportion,
The mol ratio of each substance 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, it is 13.8 that sodium ethoxide, which is added, and adjusts the pH value of solution, and solution is then transferred to ptfe autoclave
In, the total volume of mixed solution is the 75% of reaction kettle capacity, 220 DEG C at a temperature of crystallization 10 days, separate and roast to obtain
Crystallization product；
By weight by crystallization product, cobaltous sulfate, nickel sulfate are as follows: crystallization product: Co2+: Ni2+=1:2:0.5 is dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, 220 DEG C at a temperature of react 2h, obtain
The presoma of pink colour；Presoma is added in ten disulfide aqueous solutions, the mass ratio of presoma and sulfur-containing medium is 1:5,140
1h is reacted at a temperature of DEG C, and obtained hydro-thermal reaction product is centrifuged 1min under the revolving speed of 3000 turns/min, removes upper liquid
Then body is used water centrifuge washing 3 times, is finally placed in the product after washing in 80 DEG C of vacuum oven and is dried in vacuo 5h, obtain
To the nanometer Sn- beta-molecular sieve of purifying.
The molar ratio of each substance is silicon: tin: nickel: cobalt: sulphur 1:0.014:0.17 in the nanometer Sn- beta-molecular sieve:
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 substance 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, it is 12.6 that potassium tert-butoxide, which is added, and adjusts the pH value of solution, and solution is then transferred to polytetrafluoroethyl-ne alkene reaction
In kettle, the total volume of mixed solution is the 65% of reaction kettle capacity, 190 DEG C at a temperature of crystallization 5 days, separate and roast to obtain
Crystallization product；
It is by weight crystallization product by crystallization product, nickel nitrate: Ni2+=1:2 is dissolved in the water, and obtained mixing is molten
Mixed solution is transferred in ptfe autoclave by liquid, 180 DEG C at a temperature of react 10h, obtain green presoma；
Presoma is added in the aqueous solution of vulcanized sodium, the mass ratio of presoma and vulcanized sodium is 1:1.5,80 DEG C at a temperature of react
Obtained hydro-thermal reaction product is centrifuged under the revolving speed of 1000 turns/min 3min, removes supernatant liquid, be then centrifuged with water by 6h
Product after washing, is finally placed in the nanometer Sn- for being dried in vacuo in 50 DEG C of vacuum oven and for 24 hours, being purified by washing 2 times
Beta-molecular sieve.
The molar ratio of each substance is silicon: tin: nickel: sulphur 1:0.01:0.18:0.24 in the nanometer Sn- beta-molecular sieve.
Embodiment 7:
Under agitation, by tetraethyl orthosilicate, sodium stannate, tetraethyl ammonium hydroxide and hydrazine hydrate, be mixed in water,
The mol ratio of each substance 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, it is 12.6 that potassium tert-butoxide, which is added, and adjusts the pH value of solution, and solution is then transferred to polytetrafluoroethyl-ne alkene reaction
In kettle, the total volume of mixed solution is the 65% of reaction kettle capacity, 190 DEG C at a temperature of crystallization 5 days, separate and roast to obtain
Crystallization product；
By weight by crystallization product, cobaltous sulfate are as follows: crystallization product: Co2+=1:2 is dissolved in the water, and obtained mixing is molten
Mixed solution is transferred in ptfe autoclave by liquid, 180 DEG C at a temperature of react 10h, obtain the presoma of pink colour；
Presoma is added in the aqueous solution of vulcanized sodium, the mass ratio of presoma and vulcanized sodium is 1:0.6,80 DEG C at a temperature of react
Obtained hydro-thermal reaction product is centrifuged under the revolving speed of 1000 turns/min 3min, removes supernatant liquid, be then centrifuged with water by 6h
Product after washing, is finally placed in the nanometer Sn- for being dried in vacuo in 50 DEG C of vacuum oven and for 24 hours, being purified by washing 2 times
Beta-molecular sieve.
The molar ratio of each substance is silicon: tin: cobalt: sulphur 1:0.01:0.21:0.24 in the nanometer Sn- beta-molecular sieve.
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
It is as follows to apply process:
Under agitation, by tetraethyl orthosilicate, sodium stannate, tetraethyl ammonium hydroxide and hydrazine hydrate, be mixed in water,
The mol ratio of each substance 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, hydrofluoric acid is added and is adjusted to neutrality hydro-thermal reaction system, is transferred in ptfe autoclave, mixes
The total volume of solution be reaction kettle capacity 65%, 190 DEG C at a temperature of crystallization 5 days, separate and roast to obtain crystallization product；
By weight by crystallization product, cobaltous sulfate, nickel nitrate are as follows: crystallization product: Co2+: Ni2+=1:1:1 is dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, 180 DEG C at a temperature of react 10h, obtain
To the presoma of pink colour；Presoma being added in the aqueous solution of vulcanized sodium, wherein the mass ratio of presoma and vulcanized sodium is 1:2,
80 DEG C at a temperature of react 6h, obtained hydro-thermal reaction product is centrifuged 3min under the revolving speed of 1000 turns/min, in removing
Layer liquid, then uses water centrifuge washing 2 times, is finally placed in the product after washing in 50 DEG C of vacuum oven and is dried in vacuo
For 24 hours, the nanometer Sn- beta-molecular sieve purified.
The molar ratio of each substance is silicon: tin: nickel: cobalt: sulphur 1:0.007:0.004 in the nanometer Sn- beta-molecular sieve:
0.06:0.02.
Comparative example 2
According to the method for being similar to embodiment 1, the difference is that not growing nickel and cobalt, specific implementation on the surface of crystallization product
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 substance 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, hydrofluoric acid is added and is adjusted to neutrality hydro-thermal reaction system, is transferred in ptfe autoclave, mixes
The total volume of solution be reaction kettle capacity 65%, 190 DEG C at a temperature of crystallization 5 days, separate and roast to obtain a nanometer Sn- β
Molecular sieve.
The molar ratio of each substance is silicon: tin 1:0.008 in the nanometer Sn- beta-molecular sieve.
Comparative example 3
According to the method for being similar to embodiment 1, the difference is that: 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 substance 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, it is 12.6 that potassium tert-butoxide, which is added, and adjusts the pH value of solution, and solution is then transferred to polytetrafluoroethyl-ne alkene reaction
In kettle, the total volume of mixed solution is the 65% of reaction kettle capacity, in 160 DEG C of at a temperature of crystallization 10h, separates and roasts to obtain
Crystallization product；
By weight by crystallization product, cobaltous sulfate, nickel nitrate are as follows: crystallization product: Co2+: Ni2+=1:1:1 is dissolved in water
In, mixed solution is transferred in ptfe autoclave by obtained mixed solution, 180 DEG C at a temperature of react 10h, obtain
To the presoma of pink colour；Presoma being added in the aqueous solution of vulcanized sodium, wherein the mass ratio of presoma and vulcanized sodium is 1:2,
80 DEG C at a temperature of react 6h, obtained hydro-thermal reaction product is centrifuged 3min under the revolving speed of 1000 turns/min, in removing
Layer liquid, then uses water centrifuge washing 2 times, is finally placed in the product after washing in 50 DEG C of vacuum oven and is dried in vacuo
For 24 hours, the nanometer Sn- beta-molecular sieve purified.
The molar ratio of each substance is silicon: tin: nickel: cobalt: sulphur=1:0.003:0.01 in the nanometer Sn- beta-molecular sieve:
0.02:0.0012.
Nanometer Sn- beta-molecular sieve performance parameter in 1 embodiment 1-7 of table, comparative example 1-2
Catalytic result such as table 1 institute of the Sn- beta-molecular sieve of embodiment 1-7 and comparative example 1-2 in phenol hydroxylation reaction
Showing, it is 1g that reaction condition, which includes: Sn- beta-molecular sieve amount, and phenol amount is 0.1mol, phenol and hydrogen peroxide molar ratio=1:3, normal pressure,
Reaction temperature is 50 DEG C.By using the composition for the liquid phase mixture that gas chromatography measurement reaction obtains.
Phenol conversion=(amount-residual reactant amount of the reactant of addition)/addition reactant amount × 100%；
The amount of amount/conversion reactant of target product selectivity=be converted to reactant consumed by target product ×
100%.
Table 2
The Sn nano molecular sieve that can be seen that technical solution method preparation according to the invention from upper table data has larger
Specific surface area and Kong Rong, and the glycosylation reaction of Sn nano molecular sieve Pyrogentisinic Acid's hydroxyl have significant catalytic effect.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.It is further to note that described in above-mentioned specific embodiment
Each particular technique feature can be combined in any appropriate way in the case of no contradiction.In order to avoid not
Necessary repetition, the invention will not be further described in 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 also be regarded as the disclosure of the present invention.
Claims (12)
1. the preparation method of a kind of nanometer of Sn- beta-molecular sieve, which 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 in proportion gelatinous mixed
Solution is closed, at a temperature of crystallization 5 of the pH value of mixed solution to 9.5~13.8, by the mixed solution at 150~220 DEG C is adjusted
It~28 days, separates and roasts to 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 obtains molecular sieve precursor in 180~220 DEG C of at a temperature of 2~10h of reaction；
(3) molecular sieve precursor is mixed in aqueous solvent with sulfur-containing medium, 80~140 DEG C at a temperature of carry out reaction 1
~6h obtains a nanometer Sn- beta-molecular sieve.
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 substance 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 substance
Quality proportioning be crystallization product: Co2+: Ni2+=1:(0~2): (0~2), and Co2+And Ni2+Quality proportioning not simultaneously be 0.
5. the preparation method of according to claim 4 nanometer of Sn- beta-molecular sieve, wherein the quality proportioning of each substance is
Crystallization product: Co2+: Ni2+=1:(0.5~1.5): (0.5~1.5).
6. 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).
7. the preparation method of nanometer Sn- beta-molecular sieve described in any one according to claim 1~6, wherein the alkali source is
At least one of ammonium hydroxide, urea, hydrazine hydrate, sodium carbonate, sodium bicarbonate, sodium ethoxide, potassium tert-butoxide and lithium diisopropylamine.
8. the preparation method of nanometer Sn- beta-molecular sieve described in any one according to claim 1~6, 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.
9. the preparation method of according to claim 8 nanometer of Sn- beta-molecular sieve, wherein the tin source is stannic chloride, nitric acid
One of tin, STANNOUS SULPHATE CRYSTALLINE and sodium stannate.
10. a kind of nanometer of Sn- beta-molecular sieve, which is characterized in that method described in any one is prepared into according to claim 1~9
Arrive, the molar ratio of each substance is silicon: tin: nickel: cobalt: sulphur=1:(0.002~0.014 in the nanometer Sn- beta-molecular sieve): (0~
0.18): (0~0.21): (0.15~0.5), and the mol ratio of cobalt and nickel is not 0 simultaneously；And/or
The specific surface area of the molecular sieve is 405~639m20.22~0.68cm of/g, Kong Rongwei2/g；
And/or the acid amount of the molecular sieve is 25.5~42.6 μm of ol/g.
11. a kind of method of phenol hydroxylation reaction, which is characterized in that according to the following steps: under the conditions of existing for the catalyst,
By phenol and oxidant haptoreaction, hydroquinone is obtained, the catalyst is according to Sn- beta molecule described in any one of claim 10
Sieve.
12. the method for phenol hydroxylation according to claim 11 reaction, wherein the reaction condition include: phenol with
The molar ratio of oxidant is 1:(2~8), reaction temperature is 30~80 DEG C, and reaction time 0.5-72h, the amount of catalyst is anti-
Answer the 0.5%-15% of object total weight.
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