CN103964461B - A kind of tin si molecular sieves and preparation method thereof - Google Patents
A kind of tin si molecular sieves and preparation method thereof Download PDFInfo
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- CN103964461B CN103964461B CN201310036574.XA CN201310036574A CN103964461B CN 103964461 B CN103964461 B CN 103964461B CN 201310036574 A CN201310036574 A CN 201310036574A CN 103964461 B CN103964461 B CN 103964461B
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Abstract
The invention provides a kind of tin si molecular sieves, it is characterized in that, containing element silicon, tin element and oxygen element, all or part of intra-die 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.Tin si molecular sieves of the present invention has good catalytic oxidation effect.
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 has ZSM-5(MFI) silica zeolite of the framework of molecular sieve of structure.Si molecular sieves directly as the material of membrane sepn, also can be formed hetero-atom molecular-sieve material by utilizing the part silicon in other hybrid atom MCM-41 skeleton, having a extensive future.
Tin metal is incorporated in molecular sieve and forms Sn beta-molecular sieve as being incorporated in β type silica zeolite, for catalyzing and synthesizing in lactone reaction process, has good directional catalyzing performance.
CN1301599A, CN1338427A and CN1338428A etc. disclose the HTS and silica zeolite with hollow structure, but up to now, have no the report that intra-die has the tin si molecular sieves of void structure.
Summary of the invention
The object of this invention is to provide a kind of intra-die tin si molecular sieves with 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 intra-die 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 chamber portion of hollow crystal grain is 0.1 ~ 500nm, is preferably 0.5 ~ 300nm; This material at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is at least 25mg/g, is preferably at least 35mg/g; Hysteresis loop is there is, at relative pressure P/P between the adsorption isothermal line of its nitrogen absorption under low temperature and desorption isotherm
0time near=0.60, during its desorption, when N2 adsorption amount and absorption, N2 adsorption amount difference is greater than 2% of N2 adsorption amount when it adsorbs; The shape of chamber portion is not changeless, can be the different shapes such as rectangle, circle, irregular polygon, or the combination of one or more 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 be gathered into by multiple crystal grain.
Present invention also offers a kind of method preparing above-mentioned tin si molecular sieves, the method comprises:
(1) Xi Yuan and si molecular sieves solid phase mixing are evenly obtained the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of step (1) said Xi Yuan and si molecular sieves, template solution is added;
(3) mixture that above-mentioned steps (2) obtains is proceeded in reactor under hydrothermal crystallizing condition, carry out hydrothermal treatment consists, wherein in reactor containing forming saturated steam at reaction conditions and the water yield being less than 1.2 with the weight ratio of molecular sieve, 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 introducing 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
2/ more than g, and 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, under further preferable case, the external surface area of said tin si molecular sieves is at 35m
2/ more than g.
Generally speaking, the crystal grain of the traditional tin si molecular sieves adopting conventional hydrothermal direct crystallization method to obtain is non-hollow structure, and the ratio that its external surface area accounts for total specific surface area is general also lower than 10%; And traditional HTS is introduced the tin si molecular sieves crystal grain for preparing of Xi Yuan also for non-hollow structure with the form of load, and the ratio that external surface area accounts for total specific surface area is general 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, total the ratio that its external surface area accounts for specific surface area can be greater than 10%, 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, and total specific surface area is by the 472m before load
2/ g drops to the 397m after tin supported
2/ g, external surface area is by the 63m before load
2/ g drops to the 34m after tin supported
2/ g, the i.e. sample that obtains of tin supported, the ratio that its external surface area accounts for total specific surface area is general 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 added can make the structure in si molecular sieves secondary hydrothermal crystallization process change a lot under template exists, make the external surface area of tin si molecular sieves of the present invention account for the ratio of total specific surface area more than 10% thus, and external surface area can reach 35m
2/ more than g.In addition, tin si molecular sieves of the present invention has good catalytic oxidation effect, as reacted for phenol hydroxylation, compared to the si molecular sieves of not stanniferous si molecular sieves or tin supported, tin si molecular sieves of the present invention has higher catalytic oxidation activity, and surprisingly the selectivity of contraposition product Resorcinol is high.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of 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
2/ more than g, is 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
2/ more than g, is 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 referred to as outer surface area.Total specific surface area and external surface area etc. all can record according to ASTMD4222-98 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 diffraction peak at 0.5 ° ~ 9 ° places, and preferably 2 θ have diffraction peak at 5 ° ~ 9 ° places; 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 preceding solution, 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, be more preferably 0.1 ~ 5:100, be particularly preferably 0.2 ~ 2:100.The tin element of ratio like this and element silicon can optimize the catalytic activity of tin si molecular sieves of the present invention further.
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 recorded under the adsorption time condition of 1 hour is at least 35mg/g.Hysteresis loop is there is between the adsorption isothermal line of its nitrogen absorption under low temperature and desorption isotherm.Further, it is at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference is greater than 2% of N2 adsorption amount when it adsorbs.
According to tin si molecular sieves of the present invention, the crystal grain that its intra-die has hole or cavity structure accounts for 50% ~ 100% of whole crystal grain.The radical length of its intra-die chamber portion is 0.5 ~ 300nm.
Invention further provides the method for the above-mentioned tin si molecular sieves of preparation, the method comprises:
(1) Xi Yuan and si molecular sieves solid phase mixing are evenly obtained the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of step (1) said Xi Yuan and si molecular sieves, template solution is added;
(3) mixture that above-mentioned steps (2) obtains is proceeded in reactor under hydrothermal crystallizing condition, carry out hydrothermal treatment consists, wherein in reactor containing forming saturated steam at reaction conditions and the water yield being less than 1.2 with the weight ratio of molecular sieve, 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, the range of choices of the kind of said Xi Yuan is wider, every material (can be such as the compound containing tin element and/or tin simple substance) containing tin all can realize object of the present invention, in the present invention, preferred said Xi Yuan is the compound containing tin element, can be one or more in inorganic tin compound, organo-tin compound.Inorganic tin compound as the various inorganic salts of tin and hydrate thereof, as tin chloride, five water tin chlorides, nitric acid tin, tin sulphate, phosphoric acid tin etc.; Organo-tin compound as the various organic acid salt of tin or organic ligand compound, because the organic ligand compound general toxicity of tin is all comparatively large, so the various organic acid salts of the preferred tin of organo-tin compound, as acetic acid salt.
In the preparation process in accordance with 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 the si molecular sieves of the si molecular sieves of MFI structure, the si molecular sieves of MEL structure and BEA 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 the method preparing 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 introduces tin element mutually 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 prepared according to the inventive method, preferably the said temperature contacted with si molecular sieves solid phase mixing by Xi Yuan is 20 ~ 80 DEG C, is more preferably 25 ~ 60 DEG C.
According to method of the present invention, said Xi Yuan and si molecular sieves carried out solid phase mixing according to aforesaid contact conditions and contact and all can realize the present invention.The range of choices of the time of said mixing contact is wider, in order to improve the catalytic oxidation activity of tin si molecular sieves of the present invention further, for the present invention, it is 1 ~ 240min that further preferred said Xi Yuan mixes with si molecular sieves the time contacted, and is more preferably 5 ~ 120min.
According to method of the present invention, in order to improve the catalytic activity of the tin si molecular sieves prepared according to method of the present invention further, the consumption of preferred said si molecular sieves and Xi Yuan makes the mass ratio of tin element and element silicon in the tin si molecular sieves prepared be 0.05 ~ 10:100, be preferably 0.1 ~ 5:100, be more preferably 0.5 ~ 2:100.
All object of the present invention can be realized according to preceding solution, the range of choices of the consumption of said si molecular sieves, template, Xi Yuan and water is wider, 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.Be all can be the saturation steam amount that space provides enough substantially in system of the present invention, but the water of remainder 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 is in saturated humidity (steam vapour amount).Need in technical solution of the present invention that Here it is to control containing forming saturated steam at reaction conditions and the water yield being less than 1.2 with the weight ratio of molecular sieve in reactor, 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, also can be 1 gram etc.As add 1 mol sieve adsorpting water quantity be 0.2 gram, so 20 mol sieve just more than 4 grams of water, but can not at least also want more than 0.5 gram at most.
According to method of the present invention, the range of choices of the condition of said hydrothermal crystallizing process is wider, and 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, be more preferably 110 ~ 175 DEG C; Time is 6 ~ 96h, is preferably 24 ~ 96h.
According to method of the present invention, the range of choices of the kind of said template is wider, and specifically can select according to the kind of the tin si molecular sieves that will prepare, 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, the range of choices of the kind of said tetra-alkyl ammonium hydroxide is wider, the tetra-alkyl ammonium hydroxide that this area is commonly used all can realize 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, in the present invention, the range of choices of the kind of said alkylamine is wider, and for the present invention, preferred said alkylamine is the alkylamine of C2 ~ C10, and more preferably said alkylamine is selected from general formula is R
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, in the present invention, the range of choices of the kind of said hydramine is wider, and for the present invention, preferred said hydramine is the hydramine of C2 ~ C5, and more preferably said hydramine is selected from general formula is (HOR
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.Such as 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, and when the inventive method reclaims, can require no filtration step and directly products therefrom is dry, roasting.The method of said drying, roasting is well known to the skilled person, and such as generally carry out dry for products therefrom at the temperature between room temperature to 200 DEG C, all the other conditions are also well known to those skilled in the art, and do not repeat them here.
The crystal grain prepared according to the aforesaid method of the present invention is that 2 θs of tin si molecular sieves in XRD figure spectrum of hollow structure have diffraction peak at 0.5 ° ~ 9 ° places, and preferably 2 θ have diffraction peak at 5 ° ~ 9 ° places; 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, crystal grain of the present invention is the essential characteristic that the tin si molecular sieves of hollow structure has tin si molecular sieves.
Tin si molecular sieves of the present invention is compared to the si molecular sieves of not stanniferous si molecular sieves or tin supported, there is better catalytic oxidation activity, and particularly outstanding for showing in phenol hydroxylation reaction, 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, when without specified otherwise, si molecular sieves used is the S-1 sample synthesized by prior art (method described in Nature, 1978, Vol.271 the 512nd page).
In the present invention, X-ray diffraction (XRD) the crystalline phase figure that SiemensD5005 type x-ray diffractometer carries out sample measures, and gamma ray source is K α (Cu), and test specification 2 θ is at 0.5 ° ~ 30 °.Fourier infrared (FT-IR) spectrogram of sample measures on Nicolet8210 type Fourier infrared spectrograph, test specification 400 ~ 1400cm
-1.Outer ~ visible diffuse reflection spectrum (UV-vis) of sample solid violet records on SHIMADZUUV-3100 type ultraviolet-visual spectrometer, test specification 200 ~ 1000nm.Total specific surface area of sample, Extra specific surface area sum are at relative pressure P/P
0time near=0.60, the data such as adsorptive capacity of nitrogen measure according to ASTMD4222-98 standard method on the static n2 absorption apparatus of Micromeritics company ASAP2405.The transmission electron microscope photo TEM of sample is at FEI Co. TecnaiG
2f20S-TWIN type transmission electron microscope obtains.
In the present invention, gas-chromatography is adopted to carry out the analysis of each composition in activity rating system, being undertaken quantitatively, all can refer to prior art and carrying out by correcting normalization method, calculating the evaluation index (concrete outcome is in table 1) such as the transformation efficiency of reactant, the selectivity of product on this basis.
In test case:
Embodiment 1
(1) at 25 DEG C, Xi Yuan and si molecular sieves solid phase mixing 30min is obtained the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of step (1) said Xi Yuan and si molecular sieves, template solution is added (in this contact process, according to needing to add water or do not add water, if feeding intake of step (1) can meet the requirement that feeds intake of water, then without the need to adding water, if do not meet, then can additionally stir containing TPAOH and tin chloride and the mixture of si molecular sieves contact in add water, all the other embodiments 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 (stannic chloride pentahydrate): water=100:10:0.5:20, wherein, silicon source is with SiO
2meter, Xi Yuan is in tin element;
(3) mixture that above-mentioned steps (2) obtains is proceeded in stainless steel sealed reactor, crystallization 144h at the temperature of 170 DEG C and autogenous pressure, gained crystallization product is filtered, washes with water, and dry 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, tin si molecular sieves is obtained.
Through XRF compositional analysis, tin mass percentage is 1.8; Characterizing crystal grain through TEM is hollow structure; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, have absorption at 220nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs 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, at normal pressure and 60 DEG C, 1.0 hours are hydrolyzed after mixing, obtain the hydrating solution of tetraethyl orthosilicate, add the solution be made up of 1.1 grams of tetrabutyl titanates and 5.0 grams of anhydrous isopropyl alcohols with vigorous stirring lentamente, gained mixture is stirred 3 hours at 75 DEG C, obtains clear colloid.This colloid is put into stainless steel sealed reactor, and at the temperature of 170 DEG C, constant temperature places 3 days, obtains the mixture of crystallization product; This mixture is filtered, washes with water, and in 110 DEG C of dryings 60 minutes, obtains the former powder of TS-1, by former for this TS-1 powder in 550 DEG C of roasting temperatures 3 hours, obtain TS-1 molecular sieve.
Through XRF compositional analysis, its Ti mass percentage is 2.6; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; 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, have absorption at 210nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Comparative example 2
Method with reference to comparative example 1 prepares tin si molecular sieves, unlike, replace titanium source by equimolar tin source stannic chloride pentahydrate, obtain tin si molecular sieves.
Through XRF compositional analysis, Sn mass percentage is 3.5; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; 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, have absorption at 210nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Comparative example 3
After being mixed with S-1 direct mechanical by stannic chloride pentahydrate, roasting (roasting condition is with embodiment 1) obtains the si molecular sieves of tin supported, and wherein the consumption of Xi Yuan makes Sn mass percentage in the tin si molecular sieves prepared be 1.9.
In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; 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, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Comparative example 4
S-1 direct mechanical prepared by stannic chloride pentahydrate and the method according to embodiment in CN1338428A 1 is mixed the si molecular sieves that then roasting (roasting condition is with embodiment 1) obtains tin supported, wherein the consumption of stannic chloride pentahydrate makes Sn mass percentage in the tin si molecular sieves prepared be 1.8.
In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; 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, have absorption at 210nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Embodiment 2
(1) at 25 DEG C, Xi Yuan and si molecular sieves solid phase mixing 60min is obtained the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of step (1) said Xi Yuan and si molecular sieves, template solution is added; Wherein, ensure that the molar ratio of each material is: silicon source (si molecular sieves): alkali source template (TPAOH): Xi Yuan (stannic chloride pentahydrate): 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 at the temperature of 160 DEG C and autogenous pressure, filters gained crystallization product, washes with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, tin si molecular sieves is obtained.
Through XRF compositional analysis, Sn mass percentage is 1.0; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, have absorption at 220nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Embodiment 3
(1) at 35 DEG C, Xi Yuan and si molecular sieves solid phase mixing 40min is obtained the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of step (1) said Xi Yuan and si molecular sieves, template solution is added; 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 that above-mentioned steps (2) obtains is proceeded in stainless steel sealed reactor, crystallization 96h at the temperature of 170 DEG C and autogenous pressure, gained crystallization product is filtered, washes with water, and dry 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, tin si molecular sieves is obtained.
Through XRF compositional analysis, Sn mass percentage is 0.84; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, have absorption at 230nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Embodiment 4
(1) at 30 DEG C, Xi Yuan and si molecular sieves solid phase mixing 10min is obtained the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of step (1) said Xi Yuan and si molecular sieves, template solution is added; Wherein, ensure that the molar ratio of each material is: silicon source (si molecular sieves): alkali source template (TPAOH): Xi Yuan (stannic chloride pentahydrate): water=100:5:1:40, wherein, silicon source is with SiO
2meter, Xi Yuan is in tin element;
(3) mixture that above-mentioned steps (2) obtains is proceeded in stainless steel sealed reactor, crystallization 72h at the temperature of 120 DEG C and autogenous pressure, gained crystallization product is filtered, washes with water, and dry 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, tin si molecular sieves is obtained.
Through XRF compositional analysis, Sn mass percentage is 6.6; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; 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, have absorption, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Embodiment 5
(1) at 40 DEG C, Xi Yuan and si molecular sieves solid phase mixing 120min is obtained the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of step (1) said Xi Yuan and si molecular sieves, template solution is added; 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 that above-mentioned steps (2) obtains is proceeded in stainless steel sealed reactor, crystallization 24 hours at the temperature of 170 DEG C and autogenous pressure, gained crystallization product is filtered, washes with water, and dry 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, tin si molecular sieves is obtained.
Through XRF compositional analysis, its Sn mass percentage is 5.3; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, have absorption at 230nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Embodiment 6
(1) at 25 DEG C, Xi Yuan and si molecular sieves solid phase mixing 180min is obtained the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of step (1) said Xi Yuan and si molecular sieves, template solution is added; 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 that above-mentioned steps (2) obtains is proceeded in stainless steel sealed reactor, crystallization 36 hours at the temperature of 170 DEG C and autogenous pressure, gained crystallization product is filtered, washes with water, and dry 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, tin si molecular sieves is obtained.
Through XRF compositional analysis, its Sn mass percentage is 4.1; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, have absorption at 220 ~ 250nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Embodiment 7
Tin si molecular sieves is prepared according to the method for embodiment 6, unlike, silicon source: alkali source template: Xi Yuan: water=100:1:12:15, obtains tin si molecular sieves.
Through XRF compositional analysis, its Sn mass percentage is 9.6; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, have absorption at 230 ~ 260nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Embodiment 8
Tin si molecular sieves is prepared according to the method for embodiment 6, unlike, Xi Yuan is replaced by tin acetate, obtains tin si molecular sieves.
Through XRF compositional analysis, its Sn mass percentage is 3.5; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, have absorption at 230 ~ 260nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Embodiment 9
Tin si molecular sieves is prepared according to the method for embodiment 6, unlike, the Contact Temperature of step (1) is 10 DEG C.
Prepare tin si molecular sieves through XRF compositional analysis, its Sn mass percentage is 2.8; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV-Vis, have absorption at 240nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Comparative example 5
This comparative example is mixed with tin si molecular sieves for illustration of each material 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 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 at the temperature of 170 DEG C and autogenous pressure, filters gained crystallization product, washes with water, and dries 120 minutes in 110 DEG C, then 550 DEG C of roasting temperatures 3 hours, tin si molecular sieves is obtained.
Through XRF compositional analysis, Sn mass percentage is 1.4; In XRD crystalline phase figure, be that 5 ° ~ 9 ° places have diffraction peak at 2 θ; Characterizing crystal grain through TEM is hollow structure; In FT-IR, 460cm
-1, 800cm
-1, 975cm
-1, 1080cm
-1near have absorption; In UV ~ Vis, have absorption at 230 ~ 250nm place, its yield, total specific surface area, external surface area, external surface area account for total specific surface area ratio and at relative pressure P/P
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference accounts for the data such as the percentage of N2 adsorption amount when it adsorbs in table 1.
Test case
The molecular sieve that this test case prepares for illustration of the method for method of the present invention and prior art 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: phenol: the weight ratio of acetone=1:20:16 feeds intake, mix in the there-necked flask of a band prolong, be warming up to 80 DEG C, then under whipped state, according to phenol: the mol ratio of hydrogen peroxide=3:1 adds the aqueous hydrogen peroxide solution that concentration is 27.5 % by weight, react 3 hours at this temperature, 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 crystal grain that the present invention prepares be the tin si molecular sieves of hollow structure compared to common tin si molecular sieves, for the tin si molecular sieves for preparing higher than prior art of Resorcinol selectivity in phenol hydroxylation reaction; The tin si molecular sieves particularly adopting 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, the yield of the tin si molecular sieves surprisingly adopting the preferred method of the present invention to prepare is higher.
Table 1
Claims (21)
1. a tin si molecular sieves, is characterized in that, containing element silicon, tin element and oxygen element, all or part of intra-die 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 diffraction peak at 0.5 ° ~ 9 ° places; 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 recorded under the adsorption time condition of 1 hour is at least 35mg/g.
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
0during desorption when=0.60, when N2 adsorption amount and absorption, N2 adsorption amount difference is greater than 2% of N2 adsorption amount when it adsorbs.
9., according to the tin si molecular sieves of claim 1, the crystal grain that its intra-die 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 intra-die chamber portion is 0.5 ~ 300nm.
11., according to the tin si molecular sieves of claim 1, is characterized in that the shape of the chamber portion 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, is characterized in that the gathering crystal grain that this material grains is single crystal grain or is gathered into by multiple crystal grain.
13. 1 kinds of methods preparing the tin si molecular sieves of one of claim 1-12, is characterized in that the method comprises:
(1) Xi Yuan and si molecular sieves solid phase mixing are evenly obtained the mixture of Xi Yuan and si molecular sieves;
(2) in the mixture of step (1) said Xi Yuan and si molecular sieves, template solution is added;
(3) mixture that above-mentioned steps (2) obtains is proceeded in reactor under hydrothermal crystallizing condition, carry out hydrothermal treatment consists, wherein in reactor containing forming saturated steam at reaction conditions and the water yield being less than 1.2 with the weight ratio of molecular sieve, 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, saidly to be comprised with the condition of si molecular sieves solid phase mixing by Xi Yuan: the temperature mixed 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 be selected from least one in MFI, MEL, BEA, MWW, two-dimentional hexagonal structure, MOR, TUN structure si molecular sieves.
16. according to the method for claim 13, and wherein, the consumption of said si molecular sieves and Xi Yuan makes the mass ratio of tin element and element silicon in the tin si molecular sieves prepared be 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 processed in confined conditions is 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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| 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 |
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| 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 |
| CN114105164B (en) * | 2020-08-28 | 2023-08-08 | 中国石油化工股份有限公司 | Sn-MEL molecular sieve and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314348A (en) * | 2001-03-30 | 2001-09-26 | 清华大学 | Method for synthesizing hexanolactam by using titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime |
| CN102451733A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method of catalytic oxidization of cyclic ketone by using tin supported molecular sieve |
-
2013
- 2013-01-30 CN CN201310036574.XA patent/CN103964461B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314348A (en) * | 2001-03-30 | 2001-09-26 | 清华大学 | Method for synthesizing hexanolactam by using titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime |
| CN102451733A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method of catalytic oxidization of cyclic ketone by using tin supported molecular sieve |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and CHaracterization of Crystalline ,Tin-silicate Molecular Sieves with MFI Structure;Nawal Kishor Mal et al.;《J.CHEM.SOC.,CHEM.COMMUN.》;19941231;第1933-1934页 * |
| Synthesis of tin-silicalite molecular sieves with MEL structure and their catalytic activity in oxidation reactions;Nawal Kishor Mal et al.;《Applied Catalysis A: General》;19951231;第125卷;第233-245页 * |
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