CN104707648A - Ionothermal post-synthesis for synthesis of functional heteroatomic molecular sieve - Google Patents
Ionothermal post-synthesis for synthesis of functional heteroatomic molecular sieve Download PDFInfo
- Publication number
- CN104707648A CN104707648A CN201310694719.5A CN201310694719A CN104707648A CN 104707648 A CN104707648 A CN 104707648A CN 201310694719 A CN201310694719 A CN 201310694719A CN 104707648 A CN104707648 A CN 104707648A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sieve
- crystallization
- molecular
- synthesis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
An ionthermal post-synthesis method for synthesis of a functional heteroatomic molecular sieve is as follows: a heteroatomic precursor compound, ionic liquid and a parent molecular sieve are mixed evenly according to a certain proportion and feeding method for crystallization for a certain time at a certain temperature, the corresponding functional heteroatomic molecular sieve can be obtained by separating, washing and drying, and the heteroatom content range of the synthesized functional heteroatomic molecular sieve is within 0.001 to 0.1. The crystallization product can be used directly as a catalyst or a catalyst carrier. The method has universality, on the one hand, the method can be used for synthesis of the l heteroatomic molecular sieve difficult to obtain by hydrothermal synthesis, on the other hand, the ionic liquid can be recycled, and the method has the advantages of simple operation, and easy industrial application.
Description
Technical field
The present invention relates to a kind of hot post-synthesis of ion of molecular sieve.Especially, the present invention relates to the method that the hot secondary synthesis of a kind of ion prepares functional hetero-atom molecular-sieve.
Background technology
Molecular sieve, by basic composition classification, is mainly silicate-base molecular sieve and phosphate base molecular sieve two class, and later stage researcher has found again germanate based molecular sieve series.Molecular screen material has special shape selective catalysis performance because of the pore size of its uniform composition, regular structure, adjustable surface acidity and molecular size, and processed at oil and gas as catalysis material, gas separaion and adsorbent, ion-exchanger etc., fine chemistry industry, environmental protection and nuclear waste disposal field be widely applied.
Because different chemical reactions has different requirements to the pore passage structure of porous catalyst material and surface property, therefore, on the one hand the synthesis of novel structure molecular sieve material is the important research contents of material science and catalytic science all the time, on the other hand, the functionalized design of molecular screen material, synthesis and modification expand definition and the category of molecular sieve too.Wherein especially the introducing of transition metal hetero-atom makes molecular sieve have multifunctionality in skeleton, and having further expanded its range of application, is the catalysis material that academia and industrial quarters are paid close attention to jointly.
Framework of molecular sieve introducing hetero-atoms, the hetero-atom molecular-sieve that the transition metal ions same order elements particularly with specific catalytic performance obtains, because metal ion is in isolated high dispersion state on framework of molecular sieve, simultaneously also due to the interaction between molecular sieve precursor skeleton, the unexistent special catalysis of transition metal oxide that they are possessed is conventional, its performance is also obviously different from the original function of parent molecule sieve, not only to the acidity of zeolite catalyst, surface property plays regulating action, be conducive to zeolite catalyst simultaneously and realize multi-functional catalysis.Molecular sieve catalytic function also develops into base catalysis, soda acid double-function catalyzing, oxidation-reduction catalysis and metal catalytic etc. by simple acid catalysis.
In this respect, most typical example is HTS.Nineteen eighty-three, titanium is successfully introduced in MFI topological structure silicate systems by gondola Taramasso, synthesis obtains TS-1 molecular sieve, thus make the application of molecular sieve from traditional acid-base catalysis process spread to catalytic oxidation process, be considered to a milestone of the molecular sieve catalytic research field 1980s.As everyone knows, the production of oxygenatedchemicals is very important process in petrochemical industry and fine chemistry industry always, and traditional catalytic oxidation process does not meet the needs of human kind sustainable development because effect is low, seriously polluted.The catalytic oxidation system developed on HTS basis, because its reaction condition is gentle, selective good, and whole catalytic process only has water byproduct and non-pollution discharge, be considered to eco-friendly green chemistry process, and then cause synthesis and the application study upsurge of HTS for a long time.TS-1 molecular sieve is applied to the Industrial demonstration process of phenol hydroxylation and cyclohexanone oxamidinating by Eni company the earliest, the cyclohexanone oxime that Sinopec is 70,000 tons/year is installed on 2003 and is constructed and put into operation, worldwide first has been carried out the large-scale industrial application of HTS, and Sumitomo, BASF, DOW, Evonik etc. also build up number cover and produce expoxy propane new equipment based on the cyclohexanone oxamidinating of titanium molecular sieve catalysis oxidizing process and epoxidation of propylene subsequently.
In addition, benzene is applied to via N
2the Fe-ZSM-5 catalyst that O catalytic oxidation produces phenol is the hetero-atom molecular-sieve system with unique catalytic performance equally, and research finds that the active sites of catalytic reaction is not merely the acidic site in zeolite molecular sieve, and the Fe in framework of molecular sieve will cause N
2o decomposes and forms active oxygen at catalyst surface, and the active oxygen species formed like this can not pass through O
2simply adsorb at catalyst surface and obtain.With this Fe-ZSM-5(containing Al) for catalyst, phenol selectivity is 100%, phenol yield is 20% ~ 25%, and this result is that one-step synthesis method phenol new technology is laid a good foundation.This technique industrialization already at present, becomes the another example of functional hetero-atom molecular-sieve application.
Remove above-mentioned two molecular sieve analogs, what functional hetero-atom molecular-sieve had research value and application potential most is stanniferous hetero-atom molecular-sieve, especially Sn-Beta hetero-atom molecular-sieve.
Tin due to its acidity moderate, oxidation susceptibility is superior makes its research at catalytic field comparatively active, but the easy inactivation of stanniferous catalyst, and reusability is poor.Tin is introduced framework of molecular sieve, synthesizes stanniferous hetero-atom molecular-sieve, thus utilized the catalytic performance of the uniqueness of tin, become a focus of molecular sieve research field.People's reported first such as the calendar year 2001 Corma synthetic method of Sn-Beta molecular sieve [Corma A., Nemeth L., Renz M., Valencia S., Nature, 2001,412,423-425], by probing into its catalytic performance, find that this catalyst has excellent catalytic performance to Baeyer-Viiliger reaction selective with the product ester or lactone being close to 100%.They have carried out system, lasting and deep research [Corma A., Renz M., Angew.Chem.Int.Ed.2007,46,298 – 300] to the application of Sn-Beta molecular sieve in fields such as fine chemistry industries.
The application progress of nearest stanniferous molecular sieve in biomass conversion and renewable energy utilization allows people attract attention.The energy is the significant problem of international community's common concern, and the conversion preparation as the biomass energy of regenerative resource important component part needs the innovation relying on advanced catalysis material to support.At present, directly utilize living beings or carbohydrate containing the feature enriching functional group, by chemistry and the biological mode transformed, obtain up till now based on the chemicals that fossil resource is produced, become one of worldwide great heat subject.Danish scientist has delivered carbohydrate is catalytically conveted to lactic acid derivative new technology [Holm M., Saravanamurugan S., Taarning E., Science, 2010,328,602-605] via hetero-atom molecular-sieve Sn-Beta on Science.Lactic acid is considered to the important platform chemicals of biomass conversion process equally, can be used for preparing large chemical products such as PLA, acrylic acid, 1,2-PD.Method mainly fermentation method and the chemical synthesis of current industrial production lactic acid, but the fermentation method cycle is long, can only interval or semi-continuous production; The raw material of chemical synthesis generally has toxicity, does not meet Green Chemistry requirement.Therefore, using living beings as raw material, the research being obtained lactic acid by the synthesis of heterogeneous catalysis approach is significant.
Except above-mentioned several functional hetero-atom molecular-sieve, the oxidation catalytic property of the uniqueness such as had because of its hetero atom containing the Si-Al molecular sieve of cobalt, manganese, chromium, zirconium, vanadium etc. or phosphorus aluminium hetero-atom molecular-sieve and obtain extensive concern and research, these molecular sieves are obtained by water heat transfer mostly, but similarly, hetero atom is difficult to enter framework of molecular sieve, and in skeleton heteroatomic amount very few mean the active sites of molecular sieve be not enough to promote reaction carrying out.
As everyone knows, rare earth element is introduced the hydrothermal stability that framework of molecular sieve can significantly improve molecular sieve, strengthen the catalytic activity of molecular sieve, but, the ionic radius of rare earth super large makes it be difficult to enter zeolitic frameworks, and the synthesis of rare-earth heteroatoms zeolite molecular sieve is a difficult problem always.Patent CN1058382, CN1147420, CN1209356 adopt xenocryst guiding method to synthesize ZSM-5 and the Beta molecular sieve containing rare earth respectively.Document J Am Chem Soc, 2010, DOI:10.1021/ja107633j adopts the hydrothermal synthesis method of predecessor cohydrolysis condensation in acid environment, directly rare earth ion is introduced MWW structural zeolite skeleton, obtains the rare-earth heteroatoms MCM-22 molecular sieve that first skeleton replaces.But rare earth ion is very easily hydrolyzed the hydroxide or oxide precipitation that generate indissoluble in the alkaline system of Zeolite synthesis, causes the restive rare earth ion of this synthetic method really to enter framework of molecular sieve.
Except adopting the synthesis of hydrothermal system, the synthesis adopting secondary synthesis method to carry out being difficult to the hetero-atom molecular-sieve synthesized is studied always widely, the gas phase isomorphous substitution method secondary synthesis of such as titaniferous hetero-atom molecular-sieve and stanniferous hetero-atom molecular-sieve, also has the secondary synthesis of the rare-earth Y molecular sieve of industrial extensive use.For stanniferous hetero-atom molecular-sieve, document J.Phys.Chem.C, Beta molecular sieve through nitric acid dealuminzation adopts SnCl4 gas phase same order elements to prepare Sn-Beta molecular sieve by dx.doi.org/10.1021/jp1076966, but the existence of the method for this gas phase same order elements is difficult to operation and unmanageable shortcoming.Document Angew.Chem.Int.Ed., DOI:10.1002/anie.201206193I. then adopt the mode of solid liposome nanoparticle to carry out the research of post-synthesis in the Beta molecular sieve through nitric acid dealuminzation, but the party's rule also exist the distinct disadvantage that Xi Yuan used easily reunites, not easily disperses.
Summary of the invention
In molecular sieve research process, the synthetic method also corresponding development of molecular sieve.The main synthetic method of molecular sieve comprises: hydrothermal synthesis method, solvent-thermal process method, dry glue established law and firm incipient ion thermal synthesis method etc. in recent years, also have secondary synthesis method in addition.
The object of the invention is to overcome the deficiencies in the prior art, by the advantage of coupled ion process for thermosynthesizing and the strong point of secondary synthesis method, provide a kind of hot post-synthesis of ion of complex functionality hetero-atom molecular-sieve.Because the vapour pressure of ionic liquid can be ignored, therefore building-up process can be carried out at ambient pressure, this wants safety many relative to high pressure spontaneous under hydrothermal condition, abandoned the harsh restriction of conventional hydrothermal synthetic method Intermediate High Pressure for synthesis device, and ionic liquid can be recycled.
Ionic liquid, usually also claim ionic liquid at room temperature, refer to the salt combined at the inorganic anion of complete relatively large by volume, organic cation that symmetry is poor in liquid condition of room temperature or near room temperature (lower than 100 DEG C) and small volume.Ionic liquid of a great variety, changes the combination of cation and anion, can the different ionic liquid of design and synthesis.Cation type common in ionic liquid mainly contains quaternary ammonium salt, quaternary phosphine salt, imidazole salt, amidates, pyridine salt, piperidines salt, pyrroles's salt, nafoxidine salt, oxazole class, isoxazole, thiazoles, isothiazole class, pyrazoles, guanidine salt, diazines, triazines, indoles, quinolines, iloquinoline derivative, triazole, pyrrolin class, Thiazoling type, benzotriazole etc., and anion can be then AlCl
4 -, BF
4 -, PF
4 -, CF
3cOO
-, CF
3sO
3 -, (CF
3sO
2)
2n
-, SbF
6 -in organic ion and complex ion, also can be Cl in some cases
-, Br
-, I
-, NO
3 -, ClO
4 -etc. simple inorganic ions.
Ionic liquid is as novel eco-friendly " green solvent " of a class, there is the character of many uniquenesses: (1) ionic liquid body fluid journey is wide, volatility is low, nonflammable, therefore ion thermal synthesis can be carried out at ambient pressure, thus reduces the pressure risk of Zeolite synthesis; (2) the organic amine structure directing agent structure that ionic liquid and Zeolite synthesis are conventional is close, can double as solvent and structure directing agent, and it is of a great variety, molecular structure can design, add the controlled variable of synthesis, for initiative new material provides new platform; (3) ionic liquid is as a kind of ion solvent, new characteristic is dissolved with to inorganic salts, and ion thermal synthesis is carried out in anhydrous system, can avoid the fast hydrolyzing of some transition metal salt under water existence condition and form the phenomenon that precipitation is difficult to enter skeleton, therefore the hot method of ion has very large development space in Zeolite synthesis.
The ion hot post-synthesis main flow of complex functionality hetero-atom molecular-sieve provided by the invention is mixed according to certain ratio and feeding method required hetero atom lead compound, parent molecule sieve and ionic liquid or eutectic mixture, crystallization certain hour at a certain temperature, obtains corresponding functional hetero-atom molecular-sieve through separation, washing, drying.
Its process comprises:
1), by the molecular sieve being used as precursor material via acid treatment, alkali treatment, hydrothermal treatment consists or ion-exchange or be that the combination treatment method of wherein any two kinds, three kinds even all four kinds of methods of aforementioned four kinds of methods obtains parent molecule sieve;
2), by the parent molecule obtained in hetero atom lead compound, ionic liquid and step 1) sieve or unprocessed and directly use precursor molecule sieve raw material be made into the body phase mixed, obtain crystallization mixture;
3), by step 2) in prepared crystallization mixture mix after transfer in reactor, crystallization 2 ~ 240 hours under 100 ~ 280 DEG C of conditions; After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain functional hetero-atom molecular-sieve after drying.
Ionic liquid used in method provided by the invention is the combined system of a kind of of quaternary ammonium salt, quaternary phosphine salt, imidazole salt, amidates, pyridine salt, piperidines salt, pyrroles's salt, nafoxidine salt, oxazole class, isoxazole, thiazoles, isothiazole class, pyrazoles, guanidine salt, diazines, triazines, indoles, quinolines, iloquinoline derivative, triazole, pyrrolin class, Thiazoling type, BTA compounds etc. or its any category.Be preferably the combined system of a kind of or its any category of tetraalkyl ammonium salt class, alkyl imidazole salt compounds etc.Be more preferably R
1r
2r
3r
4n
+x
-(wherein R
1, R
2, R
3, R
4for C1 ~ C4 alkyl substituent, X is Cl, Br), R
1r
2im
+x
-(wherein R
1, R
2for C1 ~ C4 alkyl substituent, Im is imidazole ring, and X is Cl, Br) combined system of a kind of or its any category of compound etc.
Ionic liquid used in method provided by the invention can also be eutectic mixture.Eutectic mixture is the mixture be made up of two or more component, and its fusing point is lower than the fusing point of any component of this mixture of formation.Eutectic mixture belongs to the one of ionic liquid, has the physical and chemical performance being similar to ionic liquid.On the one hand, eutectic mixture shows some solvent properties similar to ionic liquid, as: to inorganic salts, aromatic acid, amino acid and metal oxide, there is good dissolubility; Moreover compared with ionic liquid, eutectic mixture shows again the excellent properties of some uniquenesses not available for ionic liquid, as: be easy to preparation, do not have an effect with water, biodegradable and toxicology is easy to study.Can obviously find out these features, the synthesis that eutectic mixture is used for molecular sieve has more advantage, is a kind of more green and cheap Zeolite synthesis solvent.
The present invention's eutectic mixture used is by quaternary ammonium salt and the composite combined system such as urea and derivative, organic acid or alcohol.The quaternary ammonium salt ionic liquid that can obtain different pH values composite from different organic matter, and the kind of quaternary ammonium salt and the organism kinds composite with it all very abundant, it has more easily prepares, to advantages such as water are insensitive.The present invention's eutectic mixture used is preferably by R
1r
2r
3r
4n
+x
-(wherein R
1, R
2, R
3, R
4for C1 ~ C4 alkyl substituent, X is Cl, Br) or Choline Chloride and the composite combined system of urea, succinic acid, citric acid, oxalic acid or pentaerythrite.
According to method provided by the invention, the molecular sieve being used as precursor material in the step 1) described in its process can be have Si-Al molecular sieve, borosilicate zeolite, zinc si molecular sieves or pure silicon molecular sieve component structure and there is the molecular sieve of stable topology framework structure; The molecular sieve of this precursor material also can be have aluminum phosphate Series Molecules sieve component structure and there is the molecular sieve of stable topology framework structure; The molecular sieve of this precursor material can also be have germanate Series Molecules sieve component structure and there is the molecular sieve of stable topology framework structure.
This precursor molecule sieve raw material is via acid treatment, alkali treatment, hydrothermal treatment consists or ion-exchange or be that the combination treatment method of wherein any two kinds, three kinds even all four kinds of methods of aforementioned four kinds of methods obtains parent molecule sieve; And this processing method can adopt traditional conventional heating mode of taking, intensified by ultrasonic wave or microwave reinforced mode of heating can also be selected.The parent molecule sifter device obtained through this processing procedure has abundant hydroxyl, thus is suitable for carrying out secondary synthesis and obtains required functional hetero-atom molecular-sieve.
According to method provided by the invention, other major elements of IIIA ~ VA that the hetero atom of complex functionality hetero-atom molecular-sieve indication is the subgroup element of IIIB ~ IIB, rare earth element and parent molecule of forgoing sieve have existed, are preferably titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, tin, bismuth, lanthanum, cerium.This a series of element all has unique catalytic performance and be able to extensive use in various chemical reaction, but some current catalytic process are easy to inactivation due to active component or are easy to run off or be merely able to adopt homogeneous catalysis process and limit application, and they are fitted in framework of molecular sieve form functional hetero-atom molecular-sieve, it then can be suppressed to run off, and, metal ion is in isolated high dispersion state on framework of molecular sieve, simultaneously also due to the interaction between molecular sieve precursor skeleton, the unexistent special catalysis of metal oxide that they are possessed is conventional, its performance is also obviously different from the original function of parent molecule sieve, thus also may bring brand-new catalytic performance.
According to method provided by the invention, synthesize the content of heteroatoms scope of the functional hetero-atom molecular-sieve skeleton obtained within 0.001 ~ 0.1.
According to method provided by the invention, the step 2 described in its process) intermediate ion liquid can form reaction system together with the polyalcohol of C2 ~ C6, polymer polyol or polyol ethers, is preferably ethylene glycol.This is also the method obviously combining ion thermal synthesis and solvent-thermal process, is conducive to the dissolving of the hetero atom forerunner starting compound that some should not dissolve.
Because ionic liquid body fluid journey is wide, volatility is low, therefore ion thermal synthesis can be carried out at ambient pressure, thus reduces the pressure risk of Zeolite synthesis.Therefore according to method provided by the invention, in the step 3) described in its process, crystallization process can be open, can also be at closure state; Crystallization process can take traditional conventional heating mode, can also select intensified by ultrasonic wave or microwave reinforced mode of heating.Crystallization process is preferably crystallization 2 ~ 120 hours under the condition of 120 ~ 200 DEG C.Crystallization process terminates rear washing can adopt alcohol washing method dissolved ions liquid or eutectic mixture, is preferably the lower alcohol of C1 ~ C6.Mother liquor after washing can reclaim alcohol by separation and ionic liquid recycles.
The present invention synthesizes the functional hetero-atom molecular-sieve that obtains and can directly use as catalyst or catalyst carrier, also or through peracid treatment or alkali treatment or hydrothermal treatment consists to improve the catalytic efficiency of hetero atom active sites in molecular sieve.
The hetero atom functional molecular sieve that the present invention obtains adopts Dutch Philips X ' Pert Pro type X-ray diffractometer to measure the crystal phase structure of synthetic sample.Condition determination: Cu target, K alpha ray (λ=0.15418nm), Ni filtering, voltage 40kV, electric current 40mA, sweep limits 5 ~ 65 °, sweep speed 10 °/min.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of Sn-Beta molecular sieve prepared by embodiment 1.
Fig. 2 is the XRD spectra of Sn-Beta molecular sieve prepared by embodiment 2.
Fig. 3 is the XRD spectra of Ti-MWW molecular sieve prepared by embodiment 3.
Fig. 4 is the UV-Vis spectrogram of Ti-MWW molecular sieve prepared by embodiment 3.
Fig. 5 is the XRD spectra of Sn-MWW molecular sieve prepared by embodiment 4.
Fig. 6 is the XRD spectra of Sn-MWW molecular sieve prepared by embodiment 5.
Fig. 7 is the XRD spectra of La-MWW molecular sieve prepared by embodiment 6.
Fig. 8 is the XRD spectra of Sn-MOR molecular sieve prepared by embodiment 7.
Fig. 9 is the XRD spectra of Zr-MWW molecular sieve prepared by embodiment 8.
Figure 10 is the XRD spectra of TS-1 molecular sieve prepared by embodiment 9.
Figure 11 is the UV-Vis spectrogram of TS-1 molecular sieve prepared by embodiment 9.
Figure 12 is the XRD spectra of Sn-CLO molecular sieve prepared by embodiment 10.
Detailed description of the invention
The present invention is described further for following embodiment, but the present invention is not limited in following embodiment.Any those skilled in the art, are not departing within the scope of technical solution of the present invention, and the technology contents that the present invention can be utilized to disclose is made a little change or is modified to the equivalent case study on implementation of equivalent variations; Every content not departing from technical solution of the present invention, any simple modification done following case study on implementation according to technological core thought of the present invention, equivalent variations and modification, all still belong within the scope of technical solution of the present invention.
Embodiment 1
By Beta molecular sieve (silica alumina ratio=21) 3g adopt red fuming nitric acid (RFNA) (concentration 65%) in liquid: solid be 20 ratio (weight ratio) at 100 DEG C, process 24 hours, obtain the Beta molecular sieve (silica alumina ratio >2000) being rich in Si-OH.
Then in a reactor, take the 1-butyl-3-methyl chloride of dissolving for imidazolium ionic liquid 100g, add butter of tin 1.5g strong agitation and react 4 hours, again the Beta molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.1SnO
2:.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization 20 hours under 200 DEG C of conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain stanniferous Beta hetero-atom molecular-sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, and result as shown in Figure 1, shows that product is consistent with the X-ray diffraction spectrogram of the Beta molecular sieve of standard.
Embodiment 2
Adopt red fuming nitric acid (RFNA) (concentration 65%) in liquid borosilicate Beta molecular sieve (silicon boron than=25) 3g: solid be 20 ratio (weight ratio) under 100 DEG C of heating conditions of intensified by ultrasonic wave, process 10 hours, obtain the Beta molecular sieve (silicon boron is than >1300) being rich in Si-OH.
Then in a reactor, take the 1-ethyl-3-methyl chloride of dissolving for imidazole salts and etamon chloride mixture (weight ratio 1:1) ionic liquid 100g, add butter of tin 0.15g strong agitation and react 4 hours, again the Beta molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.01SnO
2.
Transfer in the reactor of closed type after prepared crystallization mixture is mixed, crystallization 240 hours under 100 DEG C of conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain stanniferous Beta hetero-atom molecular-sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, and result as shown in Figure 2, shows that product is consistent with the X-ray diffraction spectrogram of the Beta molecular sieve of standard.
Embodiment 3
By MCM-22 molecular sieve (silica alumina ratio=25) 3g adopt red fuming nitric acid (RFNA) (concentration 65%) in liquid: solid be 20 ratio (weight ratio) at 100 DEG C, process 24 hours, obtain the MWW molecular sieve (silica alumina ratio >1900) being rich in Si-OH.
Then in a reactor, take the 1-butyl-3-methyl chloride of dissolving for imidazolium ionic liquid 100g, add titanium tetrachloride 0.07g strong agitation and react 4 hours, again the MWW molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.01TiO
2.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization 20 hours under 200 DEG C of conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain Ti-MWW molecular sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, and result as shown in Figure 3, shows that product is consistent with the X-ray diffraction spectrogram of the MWW molecular sieve of standard.UV-Vis characterization result as shown in Figure 4, show that the titanium in product is mostly present in framework of molecular sieve with the form of four-coordination titanium, and these are all the active sites that HTS has oxidation catalysis function, this also and then show the superiority of the hot secondary synthesis method of this ion.
Embodiment 4
Adopt red fuming nitric acid (RFNA) (concentration 65%) in liquid borosilicate MCM-49 molecular sieve (silicon boron than=25) 3g: solid be 20 ratio (weight ratio) under 100 DEG C of heating conditions of intensified by ultrasonic wave, process 10 hours, obtain the MWW molecular sieve (silicon boron is than >800) being rich in Si-OH.
Then in a reactor, take the 1-ethyl-3-methyl chloride of dissolving for imidazole salts and etamon chloride mixture (weight ratio 1:1) ionic liquid 100g, add butter of tin 0.15g strong agitation and react 4 hours, again the MWW molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.01SnO
2.
Transfer in the reactor of closed type after prepared crystallization mixture is mixed, crystallization 240 hours under 100 DEG C of conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain stanniferous MWW hetero-atom molecular-sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, and result as shown in Figure 5, shows that product is consistent with the X-ray diffraction spectrogram of the MWW molecular sieve of standard.
Embodiment 5
MCM-56 molecular sieve (silica alumina ratio=25) 3g is first processed 4 hours under the hydrothermal condition of 550 DEG C, adopt red fuming nitric acid (RFNA) (concentration 65%) in liquid again: solid be 20 ratio (weight ratio) at 80 DEG C, process 4 hours, obtain the MWW molecular sieve (silica alumina ratio >920) being rich in Si-OH.
Then in a reactor, take the 1-heptyl-3-methyl chloride of dissolving for piperidinium salt ionic liquid 100g, add butter of tin 0.33g strong agitation and react 4 hours, again the MWW molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.025SnO
2.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization 10 hours under 150 DEG C of conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain stanniferous MWW hetero-atom molecular-sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, and result as shown in Figure 6, shows that product is consistent with the X-ray diffraction spectrogram of the MWW molecular sieve of standard.
Embodiment 6
By MCM-22 molecular sieve (silica alumina ratio=25) 3g adopt red fuming nitric acid (RFNA) (concentration 65%) in liquid: solid be 20 ratio (weight ratio) at 100 DEG C, process 24 hours, obtain the MWW molecular sieve (silica alumina ratio >1900) being rich in Si-OH.
Then in a reactor, take the 1-butyl-3-methyl chloride of dissolving for imidazolium ionic liquid 100g, add lanthanum trichloride 0.8g strong agitation and react 4 hours, again the MWW molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.033La
2o
3.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization under microwave reinforced 160 DEG C of heating conditions 3 hours.After crystallization terminates, reactant be cooled to room temperature, filter, wash and after drying, obtain the MWW hetero-atom molecular-sieve containing lanthanum.Product has carried out the sign of X-ray diffraction spectrum, and result as shown in Figure 7, shows that product is consistent with the X-ray diffraction spectrogram of the MWW molecular sieve of standard.
Embodiment 7
By mordenite molecular sieve (silica alumina ratio=15) 3g adopt red fuming nitric acid (RFNA) (concentration 65%) in liquid: solid be 20 ratio (weight ratio) at 100 DEG C, process 48 hours, obtain the mordenite molecular sieve (silica alumina ratio >900) being rich in Si-OH.
Then in a reactor, take the 1-butyl-3-bromic ether of dissolving for imidazolium ionic liquid 100g, add butter of tin 0.02g strong agitation and react 4 hours, again the mordenite molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.001SnO
2.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization 5 hours under microwave reinforced 180 DEG C of heating conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain stanniferous modenite hetero-atom molecular-sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, and XRD characterization result as shown in Figure 8, shows that product is consistent with the X-ray diffraction spectrogram of the mordenite molecular sieve of standard.
Embodiment 8
By pure silicon ITQ-1 molecular sieve 3g adopt trimethyl adamantyl ammonium hydroxide (concentration 25%) in liquid: solid be 20 ratio (weight ratio) under microwave reinforced 50 DEG C of heating conditions, process 4 hours, obtain the MWW molecular sieve being rich in Si-OH.
Then in a reactor, take eutectic mixture (Choline Chloride and pentaerythrite form by the weight ratio of 3:1 the is composite) 100g of dissolving, add zirconium chloride 0.75g strong agitation and react 4 hours, again the MWW molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.033ZrO
2.
Transfer to after prepared crystallization mixture is mixed with in teflon-lined reactor, crystallization 48 hours under 175 DEG C of conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and after drying, obtain the MWW hetero-atom molecular-sieve containing zirconium.Product has carried out the sign of X-ray diffraction spectrum, and XRD characterization result as shown in Figure 9, shows that product is consistent with the X-ray diffraction spectrogram of the MWW molecular sieve of standard.
Embodiment 9
Adopt ethylenediamine solution (concentration 40%) in liquid pure silicon S-1 molecular sieve 3g: solid is ratio (weight ratio) process 24 hours under 175 DEG C of heating conditions in a kettle. of 35, obtains the MFI molecular sieve being rich in Si-OH.
Then in a reactor, take the 1-butyl-3-methyl chloride of dissolving for imidazolium ionic liquid 100g, add titanium tetrachloride 0.07g strong agitation and react 4 hours, again the MFI molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.01TiO
2.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization 3 hours under 150 DEG C of heating conditions at intensified by ultrasonic wave.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain TS-1 molecular sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, and XRD characterization result as shown in Figure 10, shows that product is consistent with the X-ray diffraction spectrogram of the MFI molecular sieve of standard.UV-Vis characterization result as shown in figure 11, shows that the titanium in product is mostly present in framework of molecular sieve with the form of four-coordination titanium.
Embodiment 10
According to document Angew.Chem.Int.Ed., 2010,49 (31), 5367 synthesis obtain the 20 ring super big hole CLO aluminium phosphate molecular sieve DNL-1 being rich in P-OH and Al-OH.
Then in a reactor, take the 1-butyl-3-methyl chloride of dissolving for imidazolium ionic liquid 100g, add butter of tin 0.33g strong agitation and react 4 hours, again the CLO aluminium phosphate molecular sieve DNL-1 obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.033SnO
2.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization under microwave reinforced 160 DEG C of heating conditions 2 hours.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain stanniferous CLO aluminium phosphate molecular sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, and XRD characterization result as shown in figure 12, shows that product is consistent with the X-ray diffraction spectrogram of the DNL-1 molecular sieve of standard.
Claims (14)
1. the hot post-synthesis of the ion of a complex functionality hetero-atom molecular-sieve, required hetero atom lead compound, parent molecule sieve and ionic liquid or eutectic mixture are mixed, obtains corresponding functional hetero-atom molecular-sieve through crystallization, separation, washing, drying;
Its process comprises:
1), the molecular sieve being used as precursor material directly used, obtain parent molecule sieve via acid treatment, alkali treatment, hydrothermal treatment consists or ion-exchange process;
2), the parent molecule obtained in hetero atom lead compound, ionic liquid or eutectic mixture and step 1) sieve is made into the body phase mixed, obtain crystallization mixture, molecular sieve and ionic liquid or eutectic mixture are by weight be 1:20 ~ 100, and the amount of hetero atom lead compound is pressed products therefrom silicon/hetero atom ratio (atomic ratio) scope 10 ~ 1000 and measured;
3), by step 2) in prepared crystallization mixture mix after transfer in reactor, crystallization 2 ~ 240 hours under 100 ~ 280 DEG C of conditions; After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain functional hetero-atom molecular-sieve after drying.
2. in accordance with the method for claim 1, it is characterized in that:
Ionic liquid used is the combined system of a kind of or its more than the two kinds any categories in quaternary ammonium salt, quaternary phosphine salt, imidazole salt, amidates, pyridine salt, piperidines salt, pyrroles's salt, nafoxidine salt, oxazole class, isoxazole, thiazoles, isothiazole class, pyrazoles, guanidine salt, diazines, triazines, indoles, quinolines, iloquinoline derivative, triazole, pyrrolin class, Thiazoling type, BTA compounds.
3., according to the method described in claim 1 or 2, it is characterized in that:
Ionic liquid used is preferably the combined system of a kind of or its more than the two kinds any categories in tetraalkyl ammonium salt class, alkyl imidazole salt compounds.
4. in accordance with the method for claim 3, it is characterized in that:
Ionic liquid used is more preferably R
1r
2r
3r
4n
+x
-(wherein R
1, R
2, R
3, R
4for C1 ~ C4 alkyl substituent, X is Cl, Br), R
1r
2im
+x
-(wherein R
1, R
2for C1 ~ C4 alkyl substituent, Im is imidazole ring, and X is Cl, Br) combined system of a kind of or its more than two kinds any categories in compound.
5. in accordance with the method for claim 1, it is characterized in that:
Eutectic mixture used is by the composite combined system such as quaternary ammonium salt and urea, organic acid or alcohol;
Eutectic mixture used is preferably by R
1r
2r
3r
4n
+x
-(wherein R
1, R
2, R
3, R
4for C1 ~ C4 alkyl substituent, X is Cl or Br) or Choline Chloride and the composite combined system of urea, succinic acid, citric acid, oxalic acid or pentaerythrite.
6. in accordance with the method for claim 1, it is characterized in that:
The molecular sieve being used as precursor material in described step 1) be have Si-Al molecular sieve, borosilicate zeolite, zinc si molecular sieves or pure silicon molecular sieve component structure and there is the molecular sieve of stable topology framework structure.
7., according to the method described in claim 1 or 6, it is characterized in that:
The molecular sieve being used as precursor material in described step 1) be have aluminum phosphate Series Molecules sieve component structure and there is the molecular sieve of stable topology framework structure.
8., according to the method described in claim 1 or 6, it is characterized in that:
The molecular sieve being used as precursor material in described step 1) be have germanate Series Molecules sieve component structure and there is the molecular sieve of stable topology framework structure.
9., according to the method described in claim 1 or 6, it is characterized in that:
Required for the molecular sieve being used as precursor material in described step 1), the processing method of process can adopt and take traditional conventional heating mode, can also select intensified by ultrasonic wave or microwave reinforced mode of heating.
10. in accordance with the method for claim 1, it is characterized in that:
Other major elements of IIIA ~ VA that the hetero atom of indication is the subgroup element of IIIB ~ IIB, rare earth element and parent molecule of forgoing sieve have existed, are preferably the one in titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, tin, bismuth, lanthanum, cerium or its more than two kinds;
The content of heteroatoms scope of the functional hetero-atom molecular-sieve skeleton obtained is within 0.001 ~ 0.1.
11. in accordance with the method for claim 1, it is characterized in that:
Described step 2) intermediate ion liquid can form reaction system together with the polyalcohol of C2 ~ C6, polymer polyol or polyol ethers, and be preferably ethylene glycol, reaction system volume ratio is 1:20 ~ 20:1.
12. in accordance with the method for claim 1, it is characterized in that:
In described step 3), crystallization process can be open, can also be at closure state; Crystallization process can take traditional conventional heating mode, can also select intensified by ultrasonic wave or microwave reinforced mode of heating.
13. in accordance with the method for claim 1, it is characterized in that:
In described step 3), crystallization process is preferably crystallization 2 ~ 120 hours under the condition of 120 ~ 200 DEG C.
14. in accordance with the method for claim 1, it is characterized in that:
In described step 3), crystallization process terminates rear washing and can adopt alcohol washing method dissolved ions liquid or eutectic mixture, is preferably the lower alcohol of C1 ~ C6; Mother liquor after washing can reclaim alcohol by separation and ionic liquid recycles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310694719.5A CN104707648B (en) | 2013-12-16 | 2013-12-16 | A kind of ion hot post-synthesis of complex functionality hetero-atom molecular-sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310694719.5A CN104707648B (en) | 2013-12-16 | 2013-12-16 | A kind of ion hot post-synthesis of complex functionality hetero-atom molecular-sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104707648A true CN104707648A (en) | 2015-06-17 |
| CN104707648B CN104707648B (en) | 2018-04-06 |
Family
ID=53407670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310694719.5A Active CN104707648B (en) | 2013-12-16 | 2013-12-16 | A kind of ion hot post-synthesis of complex functionality hetero-atom molecular-sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104707648B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966407A (en) * | 2017-04-07 | 2017-07-21 | 山东科技大学 | A kind of method of the synthesizing small-grain TS 1 in eutectic solvent |
| CN107497395A (en) * | 2017-08-31 | 2017-12-22 | 长沙埃比林环保科技有限公司 | A kind of method that heavy metals sorbing material is prepared under ion hot system |
| CN107519837A (en) * | 2017-08-31 | 2017-12-29 | 长沙埃比林环保科技有限公司 | A kind of method that microwave prepares heavy metals sorbing material |
| CN111437877A (en) * | 2020-04-22 | 2020-07-24 | 陕西延长石油（集团）有限责任公司 | Cu/Zr double-metal-framework type high-silicon β molecular sieve catalyst and preparation method and application thereof |
| CN112495426A (en) * | 2021-01-29 | 2021-03-16 | 山东国瓷功能材料股份有限公司 | Copper molecular sieve catalyst and preparation method and application thereof |
| CN114057549A (en) * | 2020-07-30 | 2022-02-18 | 中国石油化工股份有限公司 | Method for simultaneously preparing phenol and benzenediol |
| CN114516641A (en) * | 2020-11-18 | 2022-05-20 | 中国科学院大连化学物理研究所 | Mordenite molecular sieve and preparation method and application thereof |
| CN114573002A (en) * | 2020-11-18 | 2022-06-03 | 中国科学院大连化学物理研究所 | Mordenite molecular sieve and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1026217C (en) * | 1992-02-22 | 1994-10-19 | 中国石油化工总公司 | Cracking catalyst of super stabilized zeolite containing phosphorus and rare-earth |
| CN100363260C (en) * | 2005-03-18 | 2008-01-23 | 中国科学院大连化学物理研究所 | Synthetic process of SAPO-11 Molecular sieve |
| CN101658791B (en) * | 2008-08-29 | 2012-07-18 | 中国石油化工股份有限公司 | Post-treatment method of titanium silicate molecular sieve material |
| CN102341350B (en) * | 2009-03-03 | 2015-12-02 | 巴斯夫欧洲公司 | Isomorphous substitution silicate |
| CN102153106B (en) * | 2010-07-29 | 2012-12-12 | 兰州理工大学 | Quick reparation method for heteroatom phosphorus aluminum molecular sieve in eutectoid |
| CN102452895B (en) * | 2010-10-29 | 2015-03-18 | 中国石油化工股份有限公司 | Method for catalyzing cycloalkane by utilizing Sn-containing Ti-Si molecular sieve |
| CN102627291B (en) * | 2012-04-09 | 2013-10-30 | 华东师范大学 | Fluorine-containing titanium-silicon molecular sieve with MWW (Manual Wire Wrap) structure and preparation method and application thereof |
-
2013
- 2013-12-16 CN CN201310694719.5A patent/CN104707648B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 王华: "低共熔体在微波离子热法合成杂原子磷酸铝分子筛的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966407A (en) * | 2017-04-07 | 2017-07-21 | 山东科技大学 | A kind of method of the synthesizing small-grain TS 1 in eutectic solvent |
| CN107497395A (en) * | 2017-08-31 | 2017-12-22 | 长沙埃比林环保科技有限公司 | A kind of method that heavy metals sorbing material is prepared under ion hot system |
| CN107519837A (en) * | 2017-08-31 | 2017-12-29 | 长沙埃比林环保科技有限公司 | A kind of method that microwave prepares heavy metals sorbing material |
| CN111437877A (en) * | 2020-04-22 | 2020-07-24 | 陕西延长石油（集团）有限责任公司 | Cu/Zr double-metal-framework type high-silicon β molecular sieve catalyst and preparation method and application thereof |
| CN111437877B (en) * | 2020-04-22 | 2023-03-10 | 陕西延长石油（集团）有限责任公司 | Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst and preparation method and application thereof |
| CN114057549A (en) * | 2020-07-30 | 2022-02-18 | 中国石油化工股份有限公司 | Method for simultaneously preparing phenol and benzenediol |
| CN114057549B (en) * | 2020-07-30 | 2024-02-09 | 中国石油化工股份有限公司 | Method for simultaneously preparing phenol and benzenediol |
| CN114516641A (en) * | 2020-11-18 | 2022-05-20 | 中国科学院大连化学物理研究所 | Mordenite molecular sieve and preparation method and application thereof |
| CN114573002A (en) * | 2020-11-18 | 2022-06-03 | 中国科学院大连化学物理研究所 | Mordenite molecular sieve and preparation method and application thereof |
| CN114516641B (en) * | 2020-11-18 | 2023-06-06 | 中国科学院大连化学物理研究所 | Mordenite molecular sieve and preparation method and application thereof |
| CN113198524A (en) * | 2021-01-29 | 2021-08-03 | 山东国瓷功能材料股份有限公司 | Copper molecular sieve catalyst and preparation method and application thereof |
| CN113198524B (en) * | 2021-01-29 | 2022-06-10 | 山东国瓷功能材料股份有限公司 | Copper molecular sieve catalyst and preparation method and application thereof |
| CN112495426A (en) * | 2021-01-29 | 2021-03-16 | 山东国瓷功能材料股份有限公司 | Copper molecular sieve catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104707648B (en) | 2018-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104707648B (en) | A kind of ion hot post-synthesis of complex functionality hetero-atom molecular-sieve | |
| Zhang et al. | Metal sites in zeolites: synthesis, characterization, and catalysis | |
| Wu et al. | Solvent-free synthesis of zeolites: mechanism and utility | |
| CN101786638B (en) | Titanium silicate molecular sieve modification method | |
| CN104709918B (en) | HTS and its preparation and application with MWW topological structures | |
| CN104707649B (en) | A kind of have the stanniferous molecular sieve of BEA topological structures and its preparation and application | |
| Suib et al. | Recent advances in tetra-(Ti, Sn, Zr, Hf) and pentavalent (Nb, V, Ta) metal-substituted molecular sieve catalysis | |
| CN110203947B (en) | Preparation method of titanium-silicon molecular sieve Ti-MWW | |
| Eilertsen et al. | Synthesis of titanium chabazite: a new shape selective oxidation catalyst with small pore openings and application in the production of methyl formate from methanol | |
| CN104709920B (en) | Tin-containing heteroatomic functional molecular sieve and synthesis and application thereof | |
| CN101757945A (en) | Titanium-silicon molecular sieve TS-1 catalyst for catalyzing ketone oximation reaction | |
| CN102249258A (en) | Method for synthesizing heteroatom Sn-beta zeolite | |
| Wang et al. | Synthesis of TS-1 from an inorganic reactant system and its catalytic properties for allyl chloride epoxidation | |
| CN102757067A (en) | Titanium-silicon molecular sieve, preparation method thereof and method for preparing cyclohexanone oxime by using molecular sieve | |
| CN104556114A (en) | Method for synthesizing titanium-silicon micro-mesoporous composite material | |
| CN104556112A (en) | Titanium-silicon micro-mesoporous molecular sieve composite material and synthetic method thereof | |
| Chen et al. | Gripper-like silicon species for efficient synthesis of crystalline metallosilicates with spatially homogeneous heteroatoms in the framework | |
| CN103818924B (en) | Preparation method of titanium-silicon molecular sieve and application | |
| CN112158856B (en) | Method for preparing Ti-MWW molecular sieve | |
| ZA200507353B (en) | Porous crystalline material (zeolite ITQ-24), preparation method thereof and use of same in the catalytic conversion of organic compounds | |
| CN107032366A (en) | A kind of method for preparing the HTS TS 1 with high skeleton Ti content | |
| CN105728034A (en) | Ti-ECNU-5 titanium silicalite molecular sieve as well as preparation method and application thereof | |
| CN105712371A (en) | USY-Y composite molecular sieve and preparation method thereof | |
| CN104709919B (en) | A kind of stanniferous molecular sieve with MWW topological structure and its preparation and application | |
| Huang et al. | The clean synthesis of small-particle TS-1 with high-content framework Ti by using NH4HCO3 and suspended seeds as an assistant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |