CN107162014A - The method of tin si molecular sieves and preparation method thereof and catalytic oxidation of cyclohexane - Google Patents

The method of tin si molecular sieves and preparation method thereof and catalytic oxidation of cyclohexane Download PDF

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CN107162014A
CN107162014A CN201710535242.4A CN201710535242A CN107162014A CN 107162014 A CN107162014 A CN 107162014A CN 201710535242 A CN201710535242 A CN 201710535242A CN 107162014 A CN107162014 A CN 107162014A
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tin
molecular sieves
crystallization
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CN107162014B (en
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王宝荣
陈飞彪
郭晓红
谢贤清
雷志伟
廖维林
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Jiangxi Normal University
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
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    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
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    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
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Abstract

The present invention relates to beta technical field of molecular sieve, and in particular to the method for tin si molecular sieves and preparation method thereof and catalytic oxidation of cyclohexane, the preparation method of the tin si molecular sieves comprises the following steps：(1) in the presence of aqueous solvent, first silicon source, tin source, structure directing agent, mineralizer are mixed in proportion, it is 9.5~12.5 that alkali source regulation pH value is then added dropwise into system, obtains reactant mixture, reactant mixture is subjected to first crystallization again, first crystallization product is obtained；(2) the second silicon source is dispersed in water, precipitating reagent is then added dropwise, reacted 2~6h, obtain unformed colloidal sol；(3) after first crystallization product is mixed with unformed colloidal sol, secondary crystallization is carried out, secondary crystallization product is obtained；(4) secondary crystallization product is calcined, obtains tin si molecular sieves；The multi-stage porous tin si molecular sieves of surface Silicon-rich are prepared by the above method, the tin si molecular sieves can improve the catalysis oxidation efficiency of hexamethylene.

Description

The method of tin si molecular sieves and preparation method thereof and catalytic oxidation of cyclohexane
Technical field
The present invention relates to beta technical field of molecular sieve, and in particular to tin si molecular sieves and preparation method thereof and catalysis oxidation The method of hexamethylene.
Background technology
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 Acid amount 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.Hetero-atom molecular-sieve refers to the molecular sieve for having non-silicon, aluminium and oxygen element in skeleton structure, heteroatomic to draw Enter and adjustment effect not only is played to the acid of zeolite catalyst, surface property, it is possessed special catalytic performance.Due to β Molecular sieve has bigger pore passage structure, and the metal heteroatom such as Ti, Sn is also introduced into its skeleton structure.It is based on*The miscellaneous original of BEA structures The special Lewis of sub- molecular sieve is acid, they can the oxidant such as effective activation hydrogen peroxide, TBHP, and further It is catalyzed the reaction such as oxidation, oxidation of aromatic hydrocarbons of alkane.
Hexamethylene is always very important process in petrochemical industry and fine chemistry industry, and the selective oxidation of hexamethylene is being changed Have in work production and be of great significance, oxidation reaction generation primary product occurs under catalyst action with air for hexamethylene Cyclohexanol, cyclohexanone, because cyclohexanol, cyclohexanone than hexamethylene are easier oxidation, not only generate adipic acid, also ε-oneself in The accessory substances such as ester, 6 hydroxycaproic acid are generated.In order to reduce the generation of accessory substance, the selectivity and yield of product are improved, it is necessary to control The conversion ratio of preparing cyclohexane.At present, it is industrial that catalyst, the conversion of hexamethylene are mainly used as catalyst or not using cobalt salt Rate is less than 5%, and the overall selectivity of cyclohexanone and cyclohexanol is 78%.The technical resource utilization rate is low, and residue discharge capacity is big.Tradition Catalytic oxidation process due to effect is low, seriously polluted and the need for not meeting human kind sustainable development.In recent years, home and abroad A series of document report Me-ZSM-5 (Me=Cu, Fe, Co, Mn, Ni, Ti etc.) are used for cyclohexane oxidation preparing cyclohexane and hexamethylene The method of ketone.(Appl.Catal.A, 2002,233 such as Tawan Sooknoi：227-237) report direct hydrothermal synthesis legal system Standby Ti-ZSM-5 be used for using acetic acid as the cyclohexane oxidation of solvent in, into skeleton Ti hetero atoms generate it is very high Cyclohexane oxidation activity and selectivity, the conversion ratio of the system cyclohexane is 16%, but selectivity is less than 80%； DanhongYang etc. reports the Co/ZSM-5 prepared with infusion process, Mn/ZSM-5, Ni/ZSM-5, Zn/ZSM-5, Fe/ZSM-5 Molecular sieve catalytic oxidation of cyclohexane under conditions of HP (NHPI) is auxiliary agent, obtains turning for hexamethylene Rate reaches as high as 18.4%, but the selectivity of cyclohexanol and cyclohexanol is also below 70%, at the same above system be required for it is molten The organic solvents such as agent, initiator, catalyst promoter excite oxidation reaction, and to cause very serious environmental pollution increase simultaneously Reaction cost.
The content of the invention
An object of the present invention is to provide a kind of tin si molecular sieves, and the tin si molecular sieves divide for the multi-stage porous of surface Silicon-rich Son sieve, has good catalytic activity and selecting catalytic performance to the oxidation reaction of hexamethylene.
The second object of the present invention is to provide a kind of preparation method of tin si molecular sieves, by preparing knot in the basic conditions The tin si molecular sieves that brilliant degree is high, uniformity is good.
The third object of the present invention is to provide a kind of method of catalytic oxidation of cyclohexane.
To achieve these goals, the present invention provides a kind of tin si molecular sieves, and the tin si molecular sieves include micropore Sn- β Molecular sieve and the micropore SiO for being grown in micropore Sn- beta-molecular sieves surface2, and in the tin si molecular sieves silicon and tin mol ratio For 1：(0.005~0.016), molecular sieve acid amount is 37.6~59.1 μm of ol/g, and the specific surface area of the tin si molecular sieves is 694 ~734m2/ g, pore volume is 0.31~0.6cm2/g。
A kind of preparation method of tin si molecular sieves, comprises the following steps：
(1) in the presence of aqueous solvent, the first silicon source, tin source, structure directing agent, mineralizer are mixed in proportion, then It is 9.5~12.5 that alkali source regulation pH value is added dropwise into system, obtains mol ratio for SiO2：Sn：Mineralizer：Structure directing agent： H2O=1：(0.01~0.1)：(0.003~2.8)：(1.8~5.5)：The reactant mixture of (10~200), then reaction is mixed Thing carries out first crystallization, obtains first crystallization product；
(2) the second silicon source is dispersed in water, precipitating reagent is then added dropwise, react 2~6h, obtain mol ratio for SiO2： Precipitating reagent=1：The unformed colloidal sol of (10~25)；
(3) after first crystallization product is mixed with unformed colloidal sol, secondary crystallization is carried out, secondary crystallization product is obtained；
(4) secondary crystallization product is calcined, obtains tin si molecular sieves.
It is a further object to provide a kind of method of catalytic oxidation of cyclohexane, methods described is：In catalyst In the presence of under conditions of, by hexamethylene and oxidant haptoreaction, the catalyst is the tin silicon prepared according to the above method Molecular sieve.
By above-mentioned technical proposal, the invention provides a kind of preparation method of nanometer tin si molecular sieves, by alkalescence Under the conditions of Hydrothermal Synthesiss micropore Sn- beta-molecular sieves, then the again mesoporous silica in its superficial growth, obtains surface Silicon-rich Multistage porous molecular sieve, the characteristics of molecular sieve has size uniformity, specific surface area is big, and catalytic oxidation of cyclohexane reaction In there is good catalytic efficiency and there is higher selectivity to product adipic acid.
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 XRD of tin si molecular sieves in embodiment 1；
Fig. 2 is the SEM figures of tin si molecular sieves in embodiment 1；
Fig. 3 is the XRD of tin si molecular sieves in embodiment 2；
Fig. 4 is the SEM figures of tin si 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 a kind of tin si molecular sieves, the tin si molecular sieves include micropore Sn- beta-molecular sieves and are grown in this The micropore SiO on micropore Sn- beta-molecular sieves surface2, the tin si molecular sieves are multistage porous molecular sieve, significantly increase the ratio of molecular sieve Surface area.
Wherein, the molar ratio and molecular sieve of silicon and tin acid amount be influence molecular sieve catalytic performance important parameter it One, further, the mol ratio of silicon and tin is 1 in the Sn- β：(0.005~0.016), molecular sieve acid amount for 37.6~ 59.1μmol/g。
According to the present invention, an important physical index of molecular sieve is exactly its specific surface area, and larger specific surface area is sieve Son sieve provides more avtive spot in catalytic reaction, so as to improve the catalytic effect of molecular sieve, further, institute The specific surface area for stating tin si molecular sieves is 694~734m2/ g, pore volume is 0.31~0.6cm2/g。
Present invention also offers a kind of preparation method of tin si molecular sieves, comprise the following steps：
(1) in the presence of aqueous solvent, the first silicon source, tin source, structure directing agent, mineralizer are mixed in proportion, then It is 9.5~12.5 that alkali source regulation pH value is added dropwise into system, obtains mol ratio for SiO2：Sn：Mineralizer：Structure directing agent： H2O=(0.01~0.1)：(0.003~2.8)：(1.8~5.5)：The reactant mixture of (10~200), then by reactant mixture First crystallization is carried out, first crystallization product is obtained；
(2) the second silicon source is dispersed in water, precipitating reagent is then added dropwise, react 2~6h, obtain mol ratio for SiO2： Precipitating reagent=1：The unformed colloidal sol of (10~25)；
(3) after first crystallization product is mixed with unformed colloidal sol, secondary crystallization is carried out, secondary crystallization product is obtained；
(4) secondary crystallization product is calcined, obtains tin si molecular sieves.
According to the present invention, the specific surface area of molecular sieve is to influence one of key factor of molecular sieve performance, it is preferred that in step Suddenly in the reactant mixture of (1), foaming agent is also contained, in crystallization process, foaming agent can promote being internally formed for molecular sieve Uniform loose structure, so that the effect for improving molecular sieve specific surface area is reached, it is further preferred that first silicon source and institute The mol ratio for stating foaming agent is 1：(0.03~0.15).
Foaming agent can be azo-compound, sulfonyl hydrazines compound, nitroso compound and hydrogenation fluothane in the present invention One or more compositions in hydrocarbon, it is preferred that the foaming agent is 4- aminobphenyls, N-nitrosodimethylamine, 4,4- oxos pair At least one of this sulfohydrazide and unifor.
According to the present invention, in step (1), first silicon source can be molten for organic silicic acid ester, silica gel, white carbon and silicon At least one of glue；Further, in order to reduce influence of the hetero atom to crystallization product in silicon source, the silicon source is preferably to have Machine esters of silicon acis, the organosilicon acid esters can be methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, silicic acid At least one of isopropyl ester.
According to the present invention, the structure directing agent used in described step (1) can be with known to those skilled in the art Synthesis Sn- beta-molecular sieves when conventional structure directing agent, the present invention has no particular limits to it, such as structure directing agent Can at least one of for quaternary ammonium base class, quaternary ammonium salt and fatty amines, wherein, described quaternary ammonium base can be organic quaternary ammonium Alkali, described quaternary ammonium salt can be organic quaternary ammonium salt class, and described aliphatic amine can be NH3In at least one hydrogen by fat The compound formed after fat race alkyl (such as alkyl) substitution.
Specifically, described structure directing agent can be the quaternary ammonium salt that quaternary ammonium base, the formula 2 represented selected from formula 1 is represented At least one of aliphatic amine represented with formula 3.
In formula 1, 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 2, 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 3)
In formula 3, n is 1 or 2 integer.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6's Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, Isopentyl, tertiary pentyl and n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6Branch Chain 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.
Mineralizer can be sodium salt, sylvite in the present invention, be more specifically sodium halide, potassium halide, sodium sulphate, potassium sulfate, Sodium sulfite, potassium sulfite, potassium sulfide, vulcanized sodium, sodium nitrate, potassium nitrate, natrium nitrosum, potassium nitrite, sodium carbonate, carbonic acid Potassium；It is preferred that mineralizer to contain at least one of sodium halide and potassium halide；It is further preferred that mineralizer be sodium fluoride and At least one of potassium fluoride.
In the present invention, alkali source provides enough OH for crystallization system-, it is ensured that crystallization smoothly completing anyway, improve Alkali source in the uniformity of crystallization product, the step (1) is alkali metal hydroxide, alkaline earth metal hydroxide, ammoniacal liquor, At least one of urea, hydrazine hydrate, sodium carbonate, sodium acid carbonate, aliphatic amine, aliphatic hydramine and quaternary ammonium base, further institute It is at least one in ammoniacal liquor, urea, hydrazine hydrate, sodium carbonate, sodium acid carbonate, aliphatic amine, aliphatic hydramine and quaternary ammonium base to state alkali source Kind.
According to the present invention, tin source is to influence the most important element of Sn-beta molecular sieves, and the tin source can be organotin Salt and inorganic tin salts, have toxicity due to organic tin salt, all have harm, further, the tin source to human body and environment For in tin halides, halogenation stannous, stannous sulfate, STANNOUS SULPHATE CRYSTALLINE, stannate, stannite, nitric acid tin, tin oxide and stannous oxide At least one, in order to ensure that the Sn-beta molecular sieves of generation have identical crystal habit and crystal morphology, it is to avoid a variety of shapes The crystal of state is produced, and the tin source in the present invention is preferably single tin source, in stannic chloride, nitric acid tin, STANNOUS SULPHATE CRYSTALLINE and sodium stannate It is a kind of.
According to the present invention, the mol ratio of each material is SiO in reactant mixture in the step (1)2：Sn：Mineralizer： Structure directing agent：H2O=1：(0.036~0.06)：(0.04~1.6)：(2.2~5.0)：(20~100), more preferably 1： 0.06：0.15：0.04：2.2：20.
According to the present invention, the temperature and time of hydro-thermal reaction is influence hydrothermal product crystal habit, crystal size and production One of key factor of thing pattern, further, first 120~160 DEG C of crystallization temperature in the step (1), crystallization time is 1 ~3 days, more preferably first 120~140 DEG C of crystallization temperature, crystallization time was 2~3 days.
According to the present invention, in step (2), the present invention does not have special limitation to the second silicon source, can be organic silicic acid At least one of ester, silica gel, white carbon and Ludox.
According to the present invention, further, the mol ratio of each material is SiO in mixture in the step (2)2：Precipitation Agent=1：(12~20).
According to the present invention, the content of tin and silicon is entered than being also one of important parameter of influence molecular sieve performance in the present invention One step, the mass ratio of pre- crystallization product and unformed colloidal sol is 1 in the step (3)：(10~40).
According to the present invention, the present invention to colloidal sol by carrying out secondary crystallization reaction, it is to avoid occurs product reunion in sintering Phenomenon so that product has good dispersiveness and uniformity, further, the temperature of the secondary crystallization is 90~180 DEG C, The time of secondary crystallization is 5~10 days.
According to the present invention, the structure directing agent and other impurity in product can be removed by roasting, it is heretofore described The temperature of roasting needs to reach structure directing agent decomposition temperature in step (4), but will not saboteur's sieve structure, further , the temperature of roasting is 350~700 DEG C in the step (4), and roasting time is 0.5~6h；More preferably, the step (4) The temperature of middle roasting is 450~550 DEG C, and roasting time is 2~4h.
According to the present invention, precipitating reagent can promote silicon source to hydrolyze in the present invention, generate silica, precipitating reagent of the invention Can be alkaline matter, because the species and consumption of precipitating reagent influence silicon source hydrolysis rate, further, the precipitating reagent is At least one of aminated compounds and/or ammonium salt, such as fatty amine, hydramine, quaternary ammonium base, quaternary ammonium base are further, described heavy Shallow lake agent is ethylenediamine, diethylamine, triethylamine, hydroxide (2- ethoxys), the isopropyl ammonium of iodate four, cyclohexylamine, N, N- dimethyl benzenes In amine, tetramethyl ammonium hydroxide, cetyl trimethylammonium bromide, Variquat B 200, TMAH extremely Few one kind.
According to the present invention, in hydro-thermal reaction, the pressure of system be influence product crystal formation and crystalline rate another Key factor, and the self-generated pressure of reaction system depends on the size of void volume in reactor, in order to improve crystallization Efficiency, further, in step (1), during first crystallization, the cumulative volume of mixed solution is the reactor capacity 60~85%, in step (3), in secondary crystallization course of reaction, the cumulative volume of colloidal sol is the 70~88% of reactor capacity.
In addition, present invention also offers a kind of method of catalytic oxidation of cyclohexane, methods described is：Exist in catalyst Under the conditions of, by hexamethylene and oxidant haptoreaction, wherein haptoreaction condition is the mass ratio of tin si molecular sieves and hexamethylene For 1：(0.5~3), hexamethylene and hydrogen peroxide mol ratio=1：(2~8), normal pressure, reaction temperature is 30~100 DEG C, reaction time For 4~8h.
The present invention will be described in detail by way of examples below.In following embodiment and comparative example, X-ray is spread out The crystalline phase figure for penetrating (XRD) is to be determined to obtain with Philips Panalytical X'pert, and test condition is：Cu targets, K α radiation, Ni filter plates, super detector, tube voltage 30KV, tube current 40mA；The appearance and size of molecular sieve is to use Hitachi S4800 types Number SEM determine, accelerating potential is 20KV；Acid amount passes through BIQ-RAD FTS3O00 type Fourier infrared spectrums Instrument is analyzed；The specific surface area and pore volume sieved using nitrogen adsorption methods test molecule, nitrogen adsorption desorption curve are used The surface analysis instrument test of the 3020-M models of Micromeritics companies tristar II, specific surface area and pore volume pass through BET and t-plot methods are calculated and obtained.
Embodiment 1
Under agitation, by butyl silicate, nitric acid tin, this double sulfohydrazide of 4,4- oxos, tetraethyl ammonium hydroxide and Potassium fluoride mixed dissolution is in water, after being well mixed, and it is 11.6 to add urea regulation pH value, obtains mol ratio for SiO2：Sn：Hair Infusion：Mineralizer：Structure directing agent：Water=1：0.06：0.15：0.04：2.2：100 reactant mixture, by reactant mixture It is transferred in reactor, the cumulative volume of reactant mixture is the 75% of the reactor capacity, crystallization 2 days at 140 DEG C are obtained just Secondary crystallization product；
By colloidal silica dispersion in water, the matter of hydroxide (2- ethoxys), silica gel and hydroxide (2- ethoxys) is then added dropwise Amount is than being 1：15,3h is reacted, unformed colloidal sol is obtained, first crystallization product is added in unformed colloidal sol, first crystallization product Mass ratio with unformed colloidal sol is 1：20, after being well mixed, it is transferred in reactor, carries out secondary crystallization, the temperature of secondary crystallization Spend for 120 DEG C, the time is 6 days, obtains secondary crystallization product；
3h under secondary crystallization product is calcined at 500 DEG C, obtains tin si molecular sieves.
The XRD of the tin si molecular sieves is as shown in figure 1, SEM figures are as shown in Figure 2.
Embodiment 2
Under agitation, tetraethyl orthosilicate, stannic chloride, 4- aminobphenyls, tetraethyl ammonium hydroxide and sodium fluoride are mixed Conjunction is dissolved in the water, after being well mixed, and it is 10 to add ammoniacal liquor regulation pH value, obtains mol ratio for SiO2：Sn：Foaming agent：Ore deposit Agent：Structure directing agent：Water=1：0.036：0.03：1.6：5.0：200 reactant mixture, reaction is transferred to by reactant mixture In kettle, the cumulative volume of reactant mixture is the 85% of the reactor capacity, crystallization 3 days at 120 DEG C, obtains first crystallization production Thing；
By colloidal silica dispersion in water, ethylenediamine is then added dropwise, the mass ratio of silica gel and ethylenediamine is 1：16,3h is reacted, is obtained To unformed colloidal sol, first crystallization product is added in unformed colloidal sol, the mass ratio of first crystallization product and unformed colloidal sol For 1：30, after being well mixed, it is transferred in reactor, carries out secondary crystallization, the temperature of secondary crystallization is 110 DEG C, and the time is 6 days, Obtain secondary crystallization product；
Secondary crystallization product is calcined 4h at 450 DEG C, tin si molecular sieves are obtained.
The XRD of the tin si molecular sieves is as shown in figure 3, SEM figures are as shown in Figure 4.
Embodiment 3
Under agitation, tetraethyl orthosilicate, stannic chloride, 4- aminobphenyls, tetraethyl ammonium hydroxide and sodium fluoride are mixed Conjunction is dissolved in the water, after being well mixed, and it is 12 to add ammoniacal liquor regulation pH value, obtains mol ratio for SiO2：Sn：Foaming agent：Ore deposit Agent：Structure directing agent：Water=1：0.04：0.08：0.8：2.5：150 reactant mixture, reaction is transferred to by reactant mixture In kettle, the cumulative volume of reactant mixture is the 60% of the reactor capacity, crystallization 1 day at 160 DEG C, obtains first crystallization production Thing；
By colloidal silica dispersion in water, cetyl trimethylammonium bromide, silica gel and cetyl trimethyl bromine is then added dropwise The mass ratio for changing ammonium is 1：18,4h is reacted, unformed colloidal sol is obtained, first crystallization product is added in unformed colloidal sol, for the first time The mass ratio of crystallization product and unformed colloidal sol is 1：25, after being well mixed, it is transferred in reactor, carries out secondary crystallization, it is secondary The temperature of crystallization is 150 DEG C, and the time is 8 days, obtains secondary crystallization product；
Secondary crystallization product is calcined 4h at 350 DEG C, tin si molecular sieves are obtained.
Embodiment 4
Under agitation, will there are silica gel, sodium stannate, tetraethylammonium bromide and sodium fluoride mixed dissolution in water, mix After uniform, it is 9.5 to add sodium acid carbonate regulation pH value, obtains mol ratio for SiO2：Sn：Mineralizer：Structure directing agent：H2O= 1：0.01：2.8：5.5：20 reactant mixture, reactant mixture is transferred in reactor, and the cumulative volume of reactant mixture is institute The 65% of reactor capacity is stated, crystallization 5 days at 100 DEG C obtain first crystallization product；
By colloidal silica dispersion in water, the matter of Variquat B 200, silica gel and Variquat B 200 is then added dropwise Amount is than being 1：12,2h is reacted, unformed colloidal sol is obtained, first crystallization product is added in unformed colloidal sol, first crystallization product Mass ratio with unformed colloidal sol is 1：10, after being well mixed, it is transferred in reactor, carries out secondary crystallization, the temperature of secondary crystallization Spend for 90 DEG C, the time is 10 days, obtains secondary crystallization product；
Secondary crystallization product is calcined 6h at 350 DEG C, tin si molecular sieves are obtained.
Embodiment 5
Under agitation, by white carbon, stannous sulfate, diethylamine and sodium sulfite mixed dissolution in water, mixing is equal After even, it is 12.5 to add sodium carbonate regulation reactant mixture pH value, obtains mol ratio for SiO2：Sn：Mineralizer：Structure directing Agent：H2O=1：0.1：0.003：1.8：10 reactant mixture, reactant mixture is transferred in reactor, reactant mixture Cumulative volume is the 85% of the reactor capacity, and crystallization 1 day at 200 DEG C obtains first crystallization product；
By colloidal silica dispersion in water, the mass ratio of tetramethyl ammonium hydroxide, silica gel and tetramethyl ammonium hydroxide is then added dropwise For 1：12,6h is reacted, unformed colloidal sol is obtained, first crystallization product is added in unformed colloidal sol, first crystallization product and nothing The mass ratio of sizing colloidal sol is 1：40, after being well mixed, it is transferred in reactor, carries out secondary crystallization, the temperature of secondary crystallization is 180 DEG C, the time is 5 days, obtains secondary crystallization product；
Secondary crystallization product is calcined 0.5h at 700 DEG C, tin si molecular sieves are obtained.
Comparative example 1
According to the method for embodiment 3, unlike, hydro-thermal reaction system is adjusted to neutrality using hydrofluoric acid, it is specific real Apply process as follows：
Under agitation, by butyl silicate, nitric acid tin, this double sulfohydrazide of 4,4- oxos, tetraethyl ammonium hydroxide and Potassium fluoride mixed dissolution is in water, after being well mixed, and obtains mol ratio for SiO2：Sn：Foaming agent：Mineralizer：Structure directing Agent：Water=1：0.04：0.08：0.8：2.5：150 reactant mixture, hydrofluoric acid regulation reactant mixture pH is added into system It is worth for 7, reactant mixture is transferred in reactor, the cumulative volume of reactant mixture is the 75% of the reactor capacity, 140 Reacted 2 days at a temperature of DEG C, obtain first crystallization product；
By colloidal silica dispersion in water, the matter of hydroxide (2- ethoxys), silica gel and hydroxide (2- ethoxys) is then added dropwise Amount is than being 1：15,3h is reacted, unformed colloidal sol is obtained, first crystallization product is added in unformed colloidal sol, first crystallization product Mass ratio with unformed colloidal sol is 1：20, after being well mixed, it is transferred in reactor, carries out secondary crystallization, the temperature of secondary crystallization Spend for 120 DEG C, the time is 6 days, obtains secondary crystallization product；
3h under secondary crystallization product is calcined at 500 DEG C, obtains tin si molecular sieves.
Comparative example 2
Tin molecular sieve is synthesized according to synthetic method similar to Example 3, its difference is：Step (2) is not contained：By silicon Source is dispersed in water, and precipitating reagent is then added dropwise, and is reacted 2~6h, is obtained unformed colloidal sol, specific implementation process is as follows：
Under agitation, by butyl silicate, nitric acid tin, tetraethyl ammonium hydroxide, potassium fluoride, urea mixed dissolution in water In, mol ratio is obtained for SiO2：Sn：Mineralizer：Structure directing agent：H2O=1：0.04：0.8：2.5：150 reaction mixing Thing, regulation reactant mixture pH value is 11.6, reactant mixture is transferred in reactor, the cumulative volume of reactant mixture is described The 75% of reactor capacity, reacts 2 days at a temperature of 140 DEG C, obtains first crystallization product；
Crystallization product is calcined 3h at 500 DEG C, after cooling, tin silicon compound is obtained.
Comparative example 3
According to the method for embodiment 3, unlike, the mol ratio of each material is SiO in regulation reactant mixture2：Sn： Foaming agent：Mineralizer：Structure directing agent：H2O=1：0.09：2.8：0.8：2.5：150, specific implementation process is as follows：
Under agitation, by butyl silicate, nitric acid tin, this double sulfohydrazide of 4,4- oxos, tetraethyl ammonium hydroxide and Potassium fluoride mixed dissolution is in water, after being well mixed, and it is 11 to add urea regulation pH value, obtains mol ratio for SiO2：Sn：Foaming Agent：Mineralizer：Structure directing agent：Water=1：0.09：2.8：0.8：2.5：150 reactant mixture, reactant mixture is transferred to In reactor, the cumulative volume of reactant mixture is the 75% of the reactor capacity, crystallization 2 days at 140 DEG C, obtains just para-crystal Change product；
By colloidal silica dispersion in water, the matter of hydroxide (2- ethoxys), silica gel and hydroxide (2- ethoxys) is then added dropwise Amount is than being 1：15,3h is reacted, unformed colloidal sol is obtained, first crystallization product is added in unformed colloidal sol, first crystallization product Mass ratio with unformed colloidal sol is 1：20, after being well mixed, it is transferred in reactor, carries out secondary crystallization, the temperature of secondary crystallization Spend for 120 DEG C, the time is 6 days, obtains secondary crystallization product；
3h under secondary crystallization product is calcined at 500 DEG C, obtains tin si molecular sieves.
Comparative example 4
According to the method for embodiment 3, unlike, the mol ratio of each material is SiO in regulation reactant mixture2：Sn： Foaming agent：Mineralizer：Structure directing agent：H2O=1：0.04：0.08：0.8：2.5：150, specific implementation process is as follows：
Under agitation, by butyl silicate, nitric acid tin, 4,4- oxos double this sulfohydrazide, tetraethyl ammonium hydroxide, fluorine Change potassium, urea mixed dissolution in water, it is 11 to add hydrazine hydrate regulation pH value, obtains mol ratio for SiO2：Sn：Mineralizer：Knot Structure directed agents：H2O=1：0.04：0.08：0.8：2.5：50 reactant mixture, reactant mixture is transferred in reactor, instead The cumulative volume for answering mixture is the 75% of the reactor capacity, and crystallization 2 days at 140 DEG C obtain first crystallization product；
By colloidal silica dispersion in water, the matter of hydroxide (2- ethoxys), silica gel and hydroxide (2- ethoxys) is then added dropwise Amount is than being 1：15,3h is reacted, unformed colloidal sol is obtained, first crystallization product is added in unformed colloidal sol, first crystallization product Mass ratio with unformed colloidal sol is 1：20, after being well mixed, it is transferred in reactor, carries out secondary crystallization, the temperature of secondary crystallization Spend for 120 DEG C, the time is 6 days, obtains secondary crystallization product；
3h under secondary crystallization product is calcined at 500 DEG C, obtains tin si molecular sieves.
Comparative example 5
According to the method for embodiment 3, unlike, the mol ratio of silica gel and precipitating reagent is 1 in step (2):5.
Under agitation, by butyl silicate, nitric acid tin, this double sulfohydrazide of 4,4- oxos, tetraethyl ammonium hydroxide and Potassium fluoride mixed dissolution is in water, after being well mixed, and it is 11.6 to add urea regulation pH value, obtains mol ratio for SiO2：Sn：Hair Infusion：Mineralizer：Structure directing agent：Water=1：0.04：0.08：0.8：2.5：150 reactant mixture, reactant mixture is turned Enter in reactor, the cumulative volume of reactant mixture is the 75% of the reactor capacity, crystallization 2 days at 140 DEG C, obtain first Crystallization product；
By colloidal silica dispersion in water, the matter of hydroxide (2- ethoxys), silica gel and hydroxide (2- ethoxys) is then added dropwise Amount is than being 1：5, react 3h, obtain unformed colloidal sol, first crystallization product is added in unformed colloidal sol, first crystallization product with The mass ratio of unformed colloidal sol is 1：20, after being well mixed, it is transferred in reactor, carries out secondary crystallization, the temperature of secondary crystallization For 120 DEG C, the time is 6 days, obtains secondary crystallization product；
3h under secondary crystallization product is calcined at 500 DEG C, obtains tin si molecular sieves.
The performance parameter of tin si molecular sieves described in embodiment 1-5, comparative example 1-2 is summarized in table 1.
Table 1
Influence knot of the embodiment 1-5 and comparative example 1-5 Sn-beta molecular sieves in the efficiency to catalytic oxidation of cyclohexane As shown in table 2, reaction condition includes fruit：Sn-beta molecular sieves amount is 1g, and hexamethylene is 2g, hexamethylene and hydrogen peroxide mol ratio =1：5, normal pressure 0.1MPa, reaction temperature are 50 DEG C.The liquid phase mixture that reaction is obtained is determined by using gas chromatography Composition.
The amount of cyclohexane conversion=(amount of amount-residual reactant of the reactant of addition)/addition reactant × 100%；
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 this method be under alkaline environment it is anti-by hydro-thermal The Sn-beta molecular sieves with MULTIPLE COMPOSITE structure should be synthesized, the present invention adds the ratio of molecular sieve by MULTIPLE COMPOSITE structure Surface area, improves selecting catalytic performance of the molecular sieve to organic matter, and Sn-beta molecules of the present invention improve the catalysis oxygen of hexamethylene Change performance.
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 (11)

1. a kind of tin si molecular sieves, it is characterised in that the tin si molecular sieves include micropore Sn- beta-molecular sieves and to be grown in this micro- The micropore SiO on hole Sn- beta-molecular sieves surface2；
It is preferred that, the mol ratio of silicon and tin is 1 in the tin si molecular sieves：(0.005~0.016), molecular sieve acid amount is 37.6 ~59.1 μm of ol/g；
It is further preferred that the specific surface area of the tin si molecular sieves is 694~734m2/ g, pore volume is 0.31~0.6cm2/g。
2. a kind of preparation method of tin si molecular sieves, it is characterised in that comprise the following steps：
(1) in the presence of aqueous solvent, the first silicon source, tin source, structure directing agent, mineralizer are mixed in proportion, then to body It is 9.5~12.5 that alkali source regulation pH value is added dropwise in system, obtains mol ratio for SiO2：Sn：Mineralizer：Structure directing agent：H2O= 1：(0.01~0.1)：(0.003~2.8)：(1.8~5.5)：The reactant mixture of (10~200), then reactant mixture is entered The first crystallization of row, obtains first crystallization product；
(2) the second silicon source is dispersed in water, precipitating reagent is then added dropwise, react 2~6h, obtain mol ratio for SiO2：Precipitating reagent =1：The unformed colloidal sol of (10~25)；
(3) after first crystallization product is mixed with unformed colloidal sol, secondary crystallization is carried out, secondary crystallization product is obtained；
(4) secondary crystallization product is calcined, obtains tin si molecular sieves.
3. the preparation method of tin si molecular sieves according to claim 2, wherein, in step (1), the reactant mixture In also include foaming agent；
It is preferred that, the mol ratio of first silicon source and the foaming agent is 1：(0.03~0.15)；
It is preferred that, the foaming agent is azo-compound, sulfonyl hydrazines compound, nitroso compound and hydrogenated in fluothane hydrocarbon It is at least one.
4. the preparation method of the tin si molecular sieves according to Claims 2 or 3, wherein, in step (1), the reaction is mixed The mol ratio of each material is SiO in compound2：Sn：Mineralizer：Structure directing agent：H2O=1：(0.036~0.06)：(0.04~ 1.6)：(2.2~5.0)：(20~100).
5. the preparation method of the tin si molecular sieves according to Claims 2 or 3, wherein, in step (1), the just para-crystal It is 100~200 DEG C to change temperature, and first crystallization time is 1~5 day；
It is preferred that, first 120~160 DEG C of the crystallization temperature, first crystallization time is 1~3 day.
6. the preparation method of the tin si molecular sieves according to Claims 2 or 3, wherein, it is described unformed in step (2) The mol ratio of each material is SiO in gel2：Precipitating reagent=1：(12~20).
7. the preparation method of the tin si molecular sieves according to Claims 2 or 3, wherein, the precipitating reagent is ethylenediamine, diethyl Amine, triethylamine, hydroxide (2- ethoxys), the isopropyl ammonium of iodate four, cyclohexylamine, N, accelerine, tetramethyl ammonium hydroxide, At least one of cetyl trimethylammonium bromide, Variquat B 200 and TMAH.
8. the preparation method of the tin si molecular sieves according to Claims 2 or 3, wherein, in step (3), the crystallization production The mass ratio of thing and unformed colloidal sol is 1：(10~40).
9. the preparation method of the tin si molecular sieves according to Claims 2 or 3, wherein, in step (3), two para-crystal The temperature of change is 90~180 DEG C, and the time of secondary crystallization is 5~10 days；And/or
The sintering temperature is 350~700 DEG C, and roasting time is 0.5~6h；
It is preferred that, the sintering temperature is 450~550 DEG C, and roasting time is 2~4h.
10. the preparation method of the tin si molecular sieves according to Claims 2 or 3, wherein,
The alkali source be alkali metal hydroxide, alkaline earth metal hydroxide, ammoniacal liquor, urea, hydrazine hydrate, sodium carbonate, sodium acid carbonate, At least one of aliphatic amine, aliphatic hydramine and quaternary ammonium base；
The tin source be tin halides, halogenation stannous, stannous sulfate, STANNOUS SULPHATE CRYSTALLINE, stannate, stannite, nitric acid tin, tin oxide and At least one of stannous oxide；It is preferred that, the tin source is one kind in stannic chloride, nitric acid tin, STANNOUS SULPHATE CRYSTALLINE and sodium stannate；
The mineralizer is sodium salt and/or sylvite；
First silicon source and the second silicon source are respectively at least one of organosilicon acid esters, silica gel, white carbon and Ludox；
The structure directing agent is at least one of quaternary ammonium bases, quaternary ammonium salt and fatty amines.
11. a kind of method of catalytic oxidation of cyclohexane, it is characterised in that methods described includes：Under conditions of catalyst presence, By hexamethylene and oxidant haptoreaction, the catalyst is according to claim 1 or 2 or any according to claim 2~11 The tin si molecular sieves that method described in one is prepared；
It is preferred that, the catalytic reaction condition includes：The mass ratio of tin si molecular sieves and hexamethylene is 1：(0.5~3), Hexamethylene and oxidant mol ratio=1：(2~8), reaction temperature is 30~100 DEG C, and the reaction time is 4~8h.
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