CN103964461A - Tin-silicon molecular sieve and preparation method thereof - Google Patents
Tin-silicon molecular sieve and preparation method thereof Download PDFInfo
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- CN103964461A CN103964461A CN201310036574.XA CN201310036574A CN103964461A CN 103964461 A CN103964461 A CN 103964461A CN 201310036574 A CN201310036574 A CN 201310036574A CN 103964461 A CN103964461 A CN 103964461A
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Abstract
The invention provides a tin-silicon molecular sieve. The tin-silicon molecular sieve contains silicon, tin and oxygen elements. All or a part of crystal grains have internal cavities or cavity structures, a total specific surface area is greater than or equal to 300m<2>/g, and a ratio of an external specific surface area to the total specific surface area is greater than or equal to 10%. The tin-silicon molecular sieve has good catalytic oxidation effects.
Description
Technical field
The present invention relates to a kind of tin si molecular sieves and preparation method thereof.
Background technology
Si molecular sieves, also referred to as total silicon zeolite, is the molecular sieve that skeleton is all made up of silica element.As Silicalite-1(S-1) molecular sieve is to have ZSM-5(MFI) silica zeolite of the framework of molecular sieve of structure.Si molecular sieves can, directly as the material of membrane sepn, also can form hetero-atom molecular-sieve material by the part silicon that utilizes other heteroatoms to replace in skeleton, has a extensive future.
Tin metal is incorporated in molecular sieve as is incorporated in β type silica zeolite and forms Sn beta-molecular sieve, for catalyzing and synthesizing lactone reaction process, has good directional catalyzing performance.
CN1301599A, CN1338427A and CN1338428A etc. disclose HTS and the silica zeolite with hollow structure, but up to now, have no crystal grain inside and have the report of the tin si molecular sieves of void structure.
Summary of the invention
The object of this invention is to provide a kind of crystal grain inside and there is tin si molecular sieves of void structure and preparation method thereof.
Tin si molecular sieves provided by the invention, wherein, this tin si molecular sieves contains element silicon, tin element and oxygen element, and all or part of crystal grain inside has hole or cavity structure, and total specific surface area>=300m
2/ g, external surface area accounts for ratio>=10% of total specific surface area.
The radical length of the cavity part of hollow crystal grain is 0.1～500nm, is preferably 0.5～300nm; This material is at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recording under the adsorption time condition of 1 hour is 25mg/g at least, is preferably at least 35mg/g; Between the adsorption isothermal line of its nitrogen absorption under low temperature and desorption isotherm, there is hysteresis loop, at relative pressure P/P
0near=0.60 time, when when when its desorption, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference is greater than its absorption 2% of nitrogen adsorptive capacity; The shape of cavity part is not changeless, can be the different shapes such as rectangle, circle, irregular polygon, or one or more combination in these shapes; In this material, the inner crystal grain with hole or cavity structure accounts for 50%～100% of whole crystal grain; Its crystal grain can be single crystal grain or the gathering crystal grain being gathered into by multiple crystal grain.
The present invention also provides a kind of method of preparing above-mentioned tin si molecular sieves, and the method comprises:
(1) Xi Yuan and si molecular sieves solid phase mixing are evenly obtained to the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of the said Xi Yuan of step (1) and si molecular sieves, add template solution;
(3) mixture above-mentioned steps (2) being obtained proceeds to and in reactor, under hydrothermal crystallizing condition, carries out hydrothermal treatment consists, wherein in reactor, contain the water yield that forms saturated steam and be less than 1.2 with the weight ratio of molecular sieve under reaction conditions, the treatment capacity of molecular sieve is at least 10 grams per liter reactors, reclaims product and obtains tin si molecular sieves.
Tin si molecular sieves of the present invention, by introduce Xi Yuan before intermediate water thermal treatment in preparation process, makes total specific surface area of tin si molecular sieves of the present invention at 300m
2more than/g, and the ratio that external surface area accounts for total specific surface area is more than 10%.
According to tin si molecular sieves of the present invention, further, under preferable case, the external surface area of said tin si molecular sieves is at 35m
2more than/g.
Generally speaking, adopting the crystal grain of traditional tin si molecular sieves that traditional hydro-thermal direct crystallization method obtains is non-hollow structure, and its external surface area accounts for the ratio of total specific surface area generally also lower than 10%; And the tin si molecular sieves crystal grain that traditional HTS is prepared taking the form introducing Xi Yuan of load is also as non-hollow structure, and external surface area accounts for the ratio of total specific surface area generally also lower than 10%, and external surface area does not generally reach 35m yet
2/ g; Even if adopt the si molecular sieves of hollow structure (as si molecular sieves prepared by CN1338428A method, can be greater than 10% total its external surface area accounts for the ratio of specific surface area, and external surface area also can be greater than 35m simultaneously
2/ g), but after its tin supported, the data target such as specific surface area changes greatly, the 472m of total specific surface area before by load
2/ g drops to the 397m after tin supported
2/ g, the 63m of external surface area before by load
2/ g drops to the 34m after tin supported
2/ g, the sample that tin supported obtains, its external surface area accounts for the ratio of total specific surface area generally also lower than 10%, and external surface area does not generally reach 35m yet
2/ g(refers to comparative example 4 of the present invention).In the present invention, its special specific surface area character of described tin si molecular sieves, supposition is owing to introducing Xi Yuan before intermediate water thermal treatment in the preparation process of tin si molecular sieves, the Xi Yuan adding can make the structure in si molecular sieves secondary hydrothermal crystallization process change a lot under template exists, make thus ratio that the external surface area of tin si molecular sieves of the present invention accounts for total specific surface area more than 10%, and external surface area can reach 35m
2more than/g.In addition, tin si molecular sieves of the present invention has good catalyzed oxidation effect, as reacted for phenol hydroxylation, than not stanniferous si molecular sieves or the si molecular sieves of tin supported, tin si molecular sieves of the present invention has higher catalytic oxidation activity, and is that the selectivity of contraposition product Resorcinol is high unexpectedly.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of tin si molecular sieves, wherein, this tin si molecular sieves contains silicon, oxygen and tin element, and all or part of crystal grain is non-hollow structure, and its total specific surface area is at 300m
2more than/g, be preferably 310～600m
2/ g, external surface area accounts for the ratio of total specific surface area more than 10%.
According to tin si molecular sieves of the present invention, the external surface area of preferred said tin si molecular sieves is at 35m
2more than/g, be preferably 35～150m
2/ g, more preferably 35～100m
2/ g.
According to tin si molecular sieves of the present invention, the ratio that the external surface area of preferred said tin si molecular sieves accounts for total specific surface area is 10～30%, more preferably 10～25%.
In the present invention, total specific surface area refers to the total specific surface area of BET; And external surface area refers to the surface-area of the outside surface of tin si molecular sieves, also can be referred to as outer surface area.Total specific surface area and external surface area etc. all can record according to ASTM D4222-98 standard method.
According to tin si molecular sieves of the present invention, said crystal grain is the fluorescent property that the tin si molecular sieves of hollow structure has conventional tin si molecular sieves, concrete, 2 θs of said tin si molecular sieves in XRD figure spectrum have located diffraction peak at 0.5 °～9 °, and preferably 2 θ have located diffraction peak at 5 °～9 °; 460cm in FT-IR collection of illustrative plates
-1, 975cm
-1, 800cm
-1, 1080cm
-1near have absorption; There is absorption at 200～300nm place in UV-Vis collection of illustrative plates, preferably has absorption at 200～260nm place.
According to tin si molecular sieves of the present invention, all can realize object of the present invention according to aforementioned techniques scheme, for the present invention, the tin element in preferred said tin si molecular sieves and the mass ratio of element silicon are 0.05～10:100, more preferably 0.1～5:100, is particularly preferably 0.2～2:100.So the tin element of ratio and element silicon can further be optimized the catalytic activity of tin si molecular sieves of the present invention.
According to tin si molecular sieves of the present invention, it is at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recording under the adsorption time condition of 1 hour is 35mg/g at least.Between the adsorption isothermal line of its nitrogen absorption under low temperature and desorption isotherm, there is hysteresis loop.Further, it is at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference is greater than its absorption 2% of nitrogen adsorptive capacity.
According to tin si molecular sieves of the present invention, the crystal grain that its crystal grain inside has hole or cavity structure accounts for 50%～100% of whole crystal grain.The radical length of its crystal grain inner cavity part is 0.5～300nm.
The present invention further provides the method for preparing above-mentioned tin si molecular sieves, the method comprises:
(1) Xi Yuan and si molecular sieves solid phase mixing are evenly obtained to the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of the said Xi Yuan of step (1) and si molecular sieves, add template solution;
(3) mixture above-mentioned steps (2) being obtained proceeds to and in reactor, under hydrothermal crystallizing condition, carries out hydrothermal treatment consists, wherein in reactor, contain the water yield that forms saturated steam and be less than 1.2 with the weight ratio of molecular sieve under reaction conditions, the treatment capacity of molecular sieve is at least 10 grams per liter reactors, reclaims product and obtains tin si molecular sieves.
According to method of the present invention, optional a wider range of the kind of said Xi Yuan, every material that contains tin (can be for example compound and/or the tin simple substance that contains tin element) all can be realized object of the present invention, in the present invention, preferred said Xi Yuan is the compound that contains tin element, can be one or more in inorganic tin compound, organo-tin compound.Inorganic tin compound is as various inorganic salts and the hydrate thereof of tin, as tin chloride, five water tin chlorides, nitric acid tin, tin sulphate, phosphoric acid tin etc.; Organo-tin compound is as the various organic acid salts of tin or organic ligand compound, because the organic ligand compound general toxicity of tin is all larger, thus the various organic acid salts of the preferred tin of organo-tin compound, as acetic acid salt.
In preparation method of the present invention, said si molecular sieves can be at least one in the si molecular sieves (as ZSM-48, MCM-48) of MFI structure (as S-1), MEL structure (as S-2), BEA structure (as Beta), MWW structure (as MCM-22), two-dimentional hexagonal structure (as MCM-41, SBA-15), MOR structure (as MOR), TUN structure (as TUN) and other structures.Under preferable case, said si molecular sieves is one or more in si molecular sieves, the si molecular sieves of MEL structure and the si molecular sieves of BEA structure of MFI structure, the more preferably si molecular sieves of MFI structure.
In the present invention, said si molecular sieves can be commercially available, and also can prepare, and prepares the method for said si molecular sieves for conventionally known to one of skill in the art, does not repeat them here.
In the present invention, said tin si molecular sieves is to introduce mutually tin element by gas-solid under the existence in template in the intermediate water heat treatment process of si molecular sieves to prepare.
According to method of the present invention, in order to improve the catalytic oxidation activity of the tin si molecular sieves preparing according to the inventive method, preferably the said temperature that Xi Yuan is contacted with si molecular sieves solid phase mixing is 20～80 DEG C, more preferably 25～60 DEG C.
According to method of the present invention, according to aforesaid contact conditions, said Xi Yuan and si molecular sieves are carried out to solid phase mixing and contact and all can realize the present invention.Optional a wider range of the time of said mixing contact, in order further to improve the catalytic oxidation activity of tin si molecular sieves of the present invention, for the present invention, it is 1～240min, more preferably 5～120min that further preferred said Xi Yuan mixes with si molecular sieves the time contacting.
According to method of the present invention, in order further to improve the catalytic activity of the tin si molecular sieves preparing according to method of the present invention, in the tin si molecular sieves that the consumption of preferred said si molecular sieves and Xi Yuan makes to prepare, the mass ratio of tin element and element silicon is 0.05～10:100, be preferably 0.1～5:100, more preferably 0.5～2:100.
All can realize object of the present invention according to aforementioned techniques scheme, optional a wider range of the consumption of said si molecular sieves, template, Xi Yuan and water, generally, the consumption mol ratio of said si molecular sieves, template, Xi Yuan and water is 100:0.005～20:0.0005～15:2～1000, be preferably 100:0.005～20:0.001～10:2～500, be particularly preferably 100:1～15:0.1～8:2～50, wherein, si molecular sieves is with SiO
2meter, Xi Yuan is in tin element.In the preferred method of the present invention, the amount proportioning of water does not preferably exceed the saturation vapour amount of its absorption of molecular sieve.In system of the present invention, be all to can be space to provide enough saturation steam amounts substantially, but remaining water is less than molecular sieve saturated extent of adsorption.In other words, want exactly to exceed molecular sieve saturated extent of adsorption, but generally also will meet reaction system in saturated humidity (steam vapour amount).In technical solution of the present invention that Here it is, need to control in reactor and contain the water yield that forms saturated steam and be less than 1.2 with the weight ratio of molecular sieve under reaction conditions, the treatment capacity of molecular sieve is the reason of at least 10 grams per liter reactors.Such as, 100ml container, saturated humidity needs 0.5 gram of water, and reaction can be 20 mol sieves, can be also 1 gram etc.As to add 1 mol sieve adsorpting water quantity be 0.2 gram, 20 mol sieves just can not exceed 4 grams of water at most so, but at least also want more than 0.5 gram.
According to method of the present invention, optional a wider range of the condition of said hydrothermal crystallizing processing, for the present invention, the condition of preferred said crystallization comprises: the temperature of crystallization is 80～200 DEG C in confined conditions, be preferably 100～180 DEG C, more preferably 110～175 DEG C; Time is 6～96h, is preferably 24～96h.
According to method of the present invention, optional a wider range of the kind of said template, specifically can select according to the kind of the tin si molecular sieves that will prepare, and to this, those skilled in the art can know.For the present invention, preferred said template is one or more in tetra-alkyl ammonium hydroxide, hydramine and alkylamine.
According to method of the present invention, optional a wider range of the kind of said tetra-alkyl ammonium hydroxide, the conventional tetra-alkyl ammonium hydroxide in this area all can be realized object of the present invention, for the present invention, preferred said tetra-alkyl ammonium hydroxide is one or more in TPAOH, tetraethyl ammonium hydroxide and TBAH.
As previously mentioned, optional a wider range of the kind of said alkylamine in the present invention, for the present invention, the alkylamine that preferred said alkylamine is C2～C10, to be more preferably selected from general formula be R to said alkylamine
1(NH
2)
nalkylamine, wherein, R
1for alkyl or the alkylidene group of C1～C6, n is 1 or 2, and particularly preferably said alkylamine is one or more in ethamine, n-Butyl Amine 99, butanediamine and hexanediamine.
As previously mentioned, optional a wider range of the kind of said hydramine in the present invention, for the present invention, the hydramine that preferred said hydramine is C2～C5, to be more preferably selected from general formula be (HOR to said hydramine
2)
mnH
(3-m)hydramine, said R
2for the alkyl of C1～C4; M is 1,2 or 3; More preferably said hydramine is one or more in monoethanolamine, diethanolamine and trolamine.
In method provided by the invention, said Xi Yuan is one or more of inorganic tin compound or organo-tin compound.For example preferred, said Xi Yuan is at least one in tin chloride, nitric acid tin, tin acetate.
According to method of the present invention, said recovery is well known to those skilled in the art, when the inventive method reclaims, and can be through filtration step and directly by dry products therefrom, roasting.Said method dry, roasting is well known to the skilled person, for example, generally at the temperature between room temperature to 200 DEG C, carry out dry products therefrom, and all the other conditions are also well known to those skilled in the art, and do not repeat them here.
2 θs of the tin si molecular sieves that the crystal grain preparing according to the aforesaid method of the present invention is hollow structure in XRD figure spectrum have located diffraction peak at 0.5 °～9 °, and preferably 2 θ have located diffraction peak at 5 °～9 °; 460cm in FT-IR collection of illustrative plates
-1, 975cm
-1, 800cm
-1, 1080cm
-1near have absorption; There is absorption at 200～300nm place in UV-Vis collection of illustrative plates, preferably has absorption at 200～260nm place.Prove thus, the tin si molecular sieves that crystal grain of the present invention is hollow structure has the essential characteristic of tin si molecular sieves.
Tin si molecular sieves of the present invention is than not stanniferous si molecular sieves or the si molecular sieves of tin supported, there is better catalytic oxidation activity, and particularly outstanding for phenol hydroxylation reaction performance, in product, the selectivity of Resorcinol improves, and supposition is because its special structure causes.
Following embodiment will be further described the present invention, but therefore not limit the scope of the invention.
In comparative example and embodiment, agents useful for same is commercially available analytical reagent.
In comparative example and embodiment, in the situation without specified otherwise, si molecular sieves used is by the synthetic S-1 sample of prior art (Nature, the method described in the 512nd page of 1978, Vol.271).
In the present invention, X-ray diffraction (XRD) the crystalline phase figure that carries out sample on Siemens D5005 type x-ray diffractometer measures, and gamma ray source is K α (Cu), and test specification 2 θ are at 0.5 ° ~ 30 °.Fourier infrared (FT-IR) spectrogram of sample is measured on Nicolet8210 type Fourier infrared spectrograph, test specification 400～1400cm
-1.Outer～visible diffuse reflection spectrum (UV-vis) of sample solid violet records on SHIMADZU UV-3100 type ultraviolet-visual spectrometer, test specification 200～1000nm.Total specific surface area of sample, external surface area and at relative pressure P/P
0near=0.60 time, the data such as the adsorptive capacity of nitrogen are measured according to ASTM D4222-98 standard method on the static n2 absorption apparatus of the ASAP2405 of Micromeritics company.The transmission electron microscope photo TEM of sample is at the Tecnai G of FEI Co.
2on F20S-TWIN type transmission electron microscope, obtain.
In the present invention, adopt gas-chromatography to carry out the analysis of each composition in activity rating system, undertaken quantitatively, all can carrying out with reference to prior art by proofreading and correct normalization method, calculate on this basis the evaluation index (concrete outcome is in table 1) such as transformation efficiency, the selectivity of product of reactant.
In test case:
Embodiment 1
(1), at 25 DEG C, Xi Yuan and si molecular sieves solid phase mixing 30min are obtained to the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of the said Xi Yuan of step (1) and si molecular sieves, add template solution (in this contact process, according to adding water or not add water, if feeding intake of step (1) can meet the requirement that feeds intake of water, without adding water, if do not meet, can additionally when the mixture stirring that contains TPAOH and tin chloride and si molecular sieves contacts, add water, all the other embodiment are similar, no longer repeat specification); Wherein, ensure that the molar ratio of each material is: silicon source (si molecular sieves): alkali source template (TPAOH): Xi Yuan (crystallization tin tetrachloride): water=100:10:0.5:20, wherein, silicon source is with SiO
2meter, Xi Yuan is in tin element;
(3) mixture above-mentioned steps (2) being obtained proceeds in stainless steel sealed reactor, crystallization 144h under the temperature of 170 DEG C and autogenous pressure, gained crystallization product is filtered, washed with water, and dry 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain tin si molecular sieves.
Through XRF compositional analysis, tin quality percentage composition is 1.8; Characterizing crystal grain through TEM is hollow structure; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, there is absorption at 220nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Comparative example 1
This comparative example is for preparing the process of TS-1 sieve sample by the method described in " Zeolites, 1992, Vol.12:943～950 ".
22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOH, and add 59.8 grams of distilled water, after mixing, at normal pressure and 60 DEG C, be hydrolyzed 1.0 hours, obtain the hydrating solution of tetraethyl orthosilicate, under vigorous stirring, add lentamente by 1.1 grams of tetrabutyl titanates and 5.0 grams of solution that anhydrous isopropyl alcohol forms, gained mixture is stirred 3 hours at 75 DEG C, obtain clear colloid.This colloid is put into stainless steel sealed reactor, and at the temperature of 170 DEG C, constant temperature is placed 3 days, obtains the mixture of crystallization product; This mixture is filtered, is washed with water, and in 110 DEG C dry 60 minutes, obtain the former powder of TS-1, former this TS-1 powder, in 550 DEG C of roasting temperatures 3 hours, is obtained to TS-1 molecular sieve.
Through XRF compositional analysis, its Ti quality percentage composition is 2.6; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is non-hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 960cm
-1, 1080cm
-1near have absorption; In UV-Vis, there is absorption at 210nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Comparative example 2
Prepare tin si molecular sieves with reference to the method for comparative example 1, different, replace titanium source by equimolar tin source stannic chloride pentahydrate, obtain tin si molecular sieves.
Through XRF compositional analysis, Sn quality percentage composition is 3.5; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is non-hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 970cm
-1, 1080cm
-1near have absorption; In UV-Vis, there is absorption at 210nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Comparative example 3
After stannic chloride pentahydrate is mixed with S-1 direct mechanical, roasting (roasting condition is with embodiment 1) obtains the si molecular sieves of tin supported, and in the tin si molecular sieves that wherein consumption of Xi Yuan makes to prepare, Sn quality percentage composition is 1.9.
In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is non-hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 1080cm
-1near have absorption, and at 970cm
-1neighbouring without obviously absorbing; In UV-Vis, there is absorption at 210nm place, and its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Comparative example 4
The si molecular sieves that stannic chloride pentahydrate is mixed to then roasting (roasting condition is with embodiment 1) with the S-1 direct mechanical of preparing according to the method for embodiment in CN1338428A 1 obtains tin supported, in the tin si molecular sieves that wherein consumption of stannic chloride pentahydrate makes to prepare, Sn quality percentage composition is 1.8.
In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 1080cm
-1near have absorption, and at 970cm
-1neighbouring without obviously absorbing; In UV-Vis, there is absorption at 210nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Embodiment 2
(1), at 25 DEG C, Xi Yuan and si molecular sieves solid phase mixing 60min are obtained to the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of the said Xi Yuan of step (1) and si molecular sieves, add template solution; Wherein, ensure that the molar ratio of each material is: silicon source (si molecular sieves): alkali source template (TPAOH): Xi Yuan (crystallization tin tetrachloride): water=100:15:0.1:10, wherein, silicon source is with SiO
2meter, Xi Yuan is in tin element;
(3) said mixture is proceeded in stainless steel sealed reactor, crystallization 120h under the temperature of 160 DEG C and autogenous pressure, filters gained crystallization product, wash with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain tin si molecular sieves.
Through XRF compositional analysis, Sn quality percentage composition is 1.0; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, there is absorption at 220nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Embodiment 3
(1), at 35 DEG C, Xi Yuan and si molecular sieves solid phase mixing 40min are obtained to the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of the said Xi Yuan of step (1) and si molecular sieves, add template solution; Wherein, ensure that the molar ratio of each material is: silicon source (si molecular sieves): alkali source template (TPAOH): Xi Yuan (nitric acid tin): water=100:10:0.2:5, wherein, silicon source is with SiO
2meter, Xi Yuan is in tin element;
(3) mixture above-mentioned steps (2) being obtained proceeds in stainless steel sealed reactor, crystallization 96h under the temperature of 170 DEG C and autogenous pressure, gained crystallization product is filtered, washed with water, and dry 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain tin si molecular sieves.
Through XRF compositional analysis, Sn quality percentage composition is 0.84; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, there is absorption at 230nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Embodiment 4
(1), at 30 DEG C, Xi Yuan and si molecular sieves solid phase mixing 10min are obtained to the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of the said Xi Yuan of step (1) and si molecular sieves, add template solution; Wherein, ensure that the molar ratio of each material is: silicon source (si molecular sieves): alkali source template (TPAOH): Xi Yuan (crystallization tin tetrachloride): water=100:5:1:40, wherein, silicon source is with SiO
2meter, Xi Yuan is in tin element;
(3) mixture above-mentioned steps (2) being obtained proceeds in stainless steel sealed reactor, crystallization 72h under the temperature of 120 DEG C and autogenous pressure, gained crystallization product is filtered, washed with water, and dry 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain tin si molecular sieves.
Through XRF compositional analysis, Sn quality percentage composition is 6.6; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, near 240nm, there is absorption, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Embodiment 5
(1), at 40 DEG C, Xi Yuan and si molecular sieves solid phase mixing 120min are obtained to the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of the said Xi Yuan of step (1) and si molecular sieves, add template solution; Wherein, ensure that the molar ratio of each material is: silicon source (si molecular sieves): alkali source template (TPAOH): Xi Yuan (tin acetate): water=100:18:2:10, wherein, silicon source is with SiO
2meter, Xi Yuan is in tin element;
(3) mixture above-mentioned steps (2) being obtained proceeds in stainless steel sealed reactor, crystallization 24 hours under the temperature of 170 DEG C and autogenous pressure, gained crystallization product is filtered, washed with water, and dry 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain tin si molecular sieves.
Through XRF compositional analysis, its Sn quality percentage composition is 5.3; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, there is absorption at 230nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Embodiment 6
(1), at 25 DEG C, Xi Yuan and si molecular sieves solid phase mixing 180min are obtained to the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of the said Xi Yuan of step (1) and si molecular sieves, add template solution; Wherein, ensure that the molar ratio of each material is: silicon source (si molecular sieves): alkali source template (TPAOH): Xi Yuan (tin tetrachloride): water=100:11:1.5:50, wherein, silicon source is with SiO
2meter, Xi Yuan is in tin element;
(3) mixture above-mentioned steps (2) being obtained proceeds in stainless steel sealed reactor, crystallization 36 hours under the temperature of 170 DEG C and autogenous pressure, gained crystallization product is filtered, washed with water, and dry 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain tin si molecular sieves.
Through XRF compositional analysis, its Sn quality percentage composition is 4.1; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, there is absorption at 220～250nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Embodiment 7
Prepare tin si molecular sieves according to the method for embodiment 6, different, silicon source: alkali source template: Xi Yuan: water=100:1:12:15, obtains tin si molecular sieves.
Through XRF compositional analysis, its Sn quality percentage composition is 9.6; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, there is absorption at 230～260nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Embodiment 8
Prepare tin si molecular sieves according to the method for embodiment 6, different, Xi Yuan is replaced by tin acetate, obtains tin si molecular sieves.
Through XRF compositional analysis, its Sn quality percentage composition is 3.5; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, there is absorption at 230～260nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Embodiment 9
Prepare tin si molecular sieves according to the method for embodiment 6, different, the Contact Temperature of step (1) is 10 DEG C.
Prepare tin si molecular sieves through XRF compositional analysis, its Sn quality percentage composition is 2.8; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, there is absorption at 240nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Comparative example 5
This comparative example is used for illustrating that each material is mixed with tin si molecular sieves simultaneously, specifically carries out as follows:
At 60 DEG C, the TPAOH aqueous solution (concentration is 16 % by weight), Xi Yuan, si molecular sieves mix and blend contact 5h are obtained to gel mixture; Wherein, ensure that the molar ratio of each material is: silicon source (si molecular sieves): alkali source template (TPAOH): Xi Yuan (five water tin chlorides): water=100:10:0.5:200, wherein, silicon source is with SiO
2meter, Xi Yuan is in tin element;
Said mixture is proceeded in stainless steel sealed reactor, crystallization 196h under the temperature of 170 DEG C and autogenous pressure, filters gained crystallization product, wash with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, obtain tin si molecular sieves.
Through XRF compositional analysis, Sn quality percentage composition is 1.4; In XRD crystalline phase figure, be 5 °～9 ° at 2 θ and located diffraction peak; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV～Vis, there is absorption at 230～250nm place, its yield, total specific surface area, external surface area, external surface area account for the ratio of total specific surface area and at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference accounts for its absorption, the data such as the percentage of nitrogen adsorptive capacity are in table 1.
Test case
The molecular sieve that this test case prepares for the method that method of the present invention and prior art be described is for the effect of the catalytic oxidation of phenol hydroxylation.
By the molecular sieve of above-described embodiment and comparative example according to molecular sieve: the weight ratio of phenol: acetone=1:20:16 feeds intake, in a there-necked flask with prolong, mix, be warming up to 80 DEG C, then under whipped state, adding concentration according to the mol ratio of phenol: hydrogen peroxide=3:1 is the aqueous hydrogen peroxide solution of 27.5 % by weight, at this temperature, react 3 hours, products therefrom uses HP-5 capillary column (30m × 0.25mm) to measure phenol conversion on 6890N type gas chromatograph, the results are shown in Table 1.
As can be seen from Table 1: the tin si molecular sieves that the crystal grain that the present invention prepares is hollow structure is than common tin si molecular sieves, the tin si molecular sieves preparing higher than prior art for the Resorcinol selectivity of phenol hydroxylation reaction; The tin si molecular sieves that particularly adopts the preferred method of the present invention to prepare not only has good Resorcinol selectivity, and has the effective rate of utilization of better catalytic oxidation activity and oxygenant.Meanwhile, be to adopt the yield of the tin si molecular sieves that the present invention preferred method prepares higher unexpectedly.
Table 1
Claims (21)
1. a tin si molecular sieves, is characterized in that, contains element silicon, tin element and oxygen element, and all or part of crystal grain inside has hole or cavity structure, and total specific surface area>=300m
2/ g, external surface area accounts for ratio>=10% of total specific surface area.
2. according to the tin si molecular sieves of claim 1, its external surface area>=35m
2/ g.
3. according to the tin si molecular sieves of claim 1 or 2, wherein, said total specific surface area is 310～600m
2/ g, external surface area is 35～100m
2/ g, and the ratio that external surface area accounts for total specific surface area is 10～25%.
4. according to the tin si molecular sieves of claim 1 or 2,2 θ in its XRD figure spectrum have located diffraction peak at 0.5 °～9 °; 460cm in FT-IR collection of illustrative plates
-1, 975cm
-1, 800cm
-1, 1080cm
-1near have absorption; There is absorption at 200～300nm place in UV-Vis collection of illustrative plates.
5. according to the tin si molecular sieves of claim 1 or 2, wherein, the mass ratio of tin element and element silicon is 0.05～10:100.
6. according to the tin si molecular sieves of claim 1, it is at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recording under the adsorption time condition of 1 hour is 35mg/g at least.
7. according to the tin si molecular sieves of claim 1, between the adsorption isothermal line of its nitrogen absorption under low temperature and desorption isotherm, there is hysteresis loop.
8. according to the tin si molecular sieves of claim 1, it is at relative pressure P/P
0when when the desorption of=0.60 o'clock, nitrogen adsorptive capacity is with absorption, nitrogen adsorptive capacity difference is greater than its absorption 2% of nitrogen adsorptive capacity.
9. according to the tin si molecular sieves of claim 1, the crystal grain that its crystal grain inside has hole or cavity structure accounts for 50%～100% of whole crystal grain.
10. according to the tin si molecular sieves of claim 1, the radical length of its crystal grain inner cavity part is 0.5～300nm.
11. according to the tin si molecular sieves of claim 1, and the shape that it is characterized in that the cavity part of this material grains inside is selected from one or several the combination in rectangle, circle and irregular polygon.
12. according to the tin si molecular sieves of claim 1, it is characterized in that this material grains is single crystal grain or the gathering crystal grain that is gathered into by multiple crystal grain.
Prepare the method for tin si molecular sieves for 13. 1 kinds, it is characterized in that the method comprises:
(1) Xi Yuan and si molecular sieves solid phase mixing are evenly obtained to the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of the said Xi Yuan of step (1) and si molecular sieves, add template solution;
(3) mixture above-mentioned steps (2) being obtained proceeds to and in reactor, under hydrothermal crystallizing condition, carries out hydrothermal treatment consists, wherein in reactor, contain the water yield that forms saturated steam and be less than 1.2 with the weight ratio of molecular sieve under reaction conditions, the treatment capacity of si molecular sieves is at least 10 grams per liter reactors, reclaims product and obtains tin si molecular sieves.
14. according to the method for claim 13, wherein, said Xi Yuan is comprised with the condition of si molecular sieves solid phase mixing: the temperature of mixing is 20～80 DEG C, and the time of mixing is 1～240min.
15. according to the method for claim 13, and wherein, said si molecular sieves is at least one being selected from MFI, MEL, BEA, MWW, two-dimentional hexagonal structure, MOR, TUN structure si molecular sieves.
16. according to the method for claim 13, and wherein, in the tin si molecular sieves that the consumption of said si molecular sieves and Xi Yuan makes to prepare, the mass ratio of tin element and element silicon is 0.05～10:100.
17. according to the method for claim 13, and wherein, the consumption mol ratio of said si molecular sieves, template, Xi Yuan and water is 100:1～15:0.1～8:2～50, and si molecular sieves is with SiO
2meter, Xi Yuan is in tin element.
18. according to the method for claim 13, and wherein, said hydrothermal crystallizing condition comprises: the temperature of processing is in confined conditions 80～200 DEG C, and the time is 6～96h.
19. according to the method for any one in claim 13～17, and wherein, said Xi Yuan is one or more of inorganic tin compound or organo-tin compound.
20. according to the method for claim 19, and wherein, said Xi Yuan is at least one in tin chloride, five water tin chlorides, nitric acid tin, tin sulphate, phosphoric acid tin, tin acetate.
21. according to the method for claim 13, and wherein, said template is one or more in tetra-alkyl ammonium hydroxide, hydramine and alkylamine.
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| CN108998090A (en) * | 2018-09-25 | 2018-12-14 | 浙江绿保再生资源科技有限公司 | A kind of recovery and treatment method of used oil |
| CN109205639A (en) * | 2017-06-29 | 2019-01-15 | 中国石油化工股份有限公司 | Modified with noble metals si molecular sieves and its preparation method and application and the method for producing hydrogen peroxide |
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| CN112744832A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Tin-containing molecular sieve, preparation method thereof and phenol hydroxylation reaction method |
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| CN109205639A (en) * | 2017-06-29 | 2019-01-15 | 中国石油化工股份有限公司 | Modified with noble metals si molecular sieves and its preparation method and application and the method for producing hydrogen peroxide |
| CN109205639B (en) * | 2017-06-29 | 2020-08-18 | 中国石油化工股份有限公司 | Noble metal modified silicon molecular sieve, preparation method and application thereof, and method for producing hydrogen peroxide |
| CN108998090A (en) * | 2018-09-25 | 2018-12-14 | 浙江绿保再生资源科技有限公司 | A kind of recovery and treatment method of used oil |
| CN111253364A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing ketal and/or acetal glycerol by catalyzing glycerol |
| CN112744832A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Tin-containing molecular sieve, preparation method thereof and phenol hydroxylation reaction method |
| CN112744832B (en) * | 2019-10-30 | 2023-07-11 | 中国石油化工股份有限公司 | Tin-containing molecular sieve, preparation method thereof and phenol hydroxylation reaction method |
| CN114105164A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Sn-MEL molecular sieve and preparation method and application thereof |
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