CN110407227A - The method for synthesizing TNU-9 molecular sieve - Google Patents
The method for synthesizing TNU-9 molecular sieve Download PDFInfo
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- CN110407227A CN110407227A CN201810387842.5A CN201810387842A CN110407227A CN 110407227 A CN110407227 A CN 110407227A CN 201810387842 A CN201810387842 A CN 201810387842A CN 110407227 A CN110407227 A CN 110407227A
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- dibromobutane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
This disclosure relates to a kind of method for synthesizing TNU-9 molecular sieve, method includes the following steps: a, by 1,4- dibromobutane, 1- crassitude are mixed with solvent, in 15~90 DEG C of 0.5~96h of pre-reaction, obtain pre-reaction product, the molar ratio of the Isosorbide-5-Nitrae-dibromobutane, 1- crassitude and solvent is 1:(1.8~3): (1~20)；B, pre-reaction product, inorganic base obtained in step a, silicon source, silicon source and water are mixed, is obtained to crystallization mixture, described will carried out hydrothermal crystallizing processing to crystallization mixture, and recycle solid product.Disclosed method, which eliminates, is conventionally synthesized the complicated processes such as TNU-9 Molecular Sieves as Template agent necessary costly separation, purification, avoids a large amount of time loss, energy consumption and material consumption, and it is obvious to reduce cost effectiveness.
Description
Technical field
This disclosure relates to a kind of method for synthesizing TNU-9 molecular sieve.
Background technique
TNU-9 is a kind of molecule of the novel three-dimensional ten-ring intersection construction synthesized by Hong et al. in 2007
Sieve.TNU-9 has the duct (0.52 × 0.6 and 0.51 × 0.55nm) of two sets of ten-rings.In two sets of ten-ring ducts at a distance of relatively narrow
Place, interconnected by another set of ten-ring duct (0.54 × 0.55nm), furthermore also include inside the duct of TNU-9
One biggish basket structure.TNU-9 molecular sieve have extraordinary hydrothermal stability, shown in certain reactions compared with
Good activity and shape selectivity, such as: in toluene disproportionation process, TNU-9 shows higher initial activity, and divides from product
TNU-9 is also demonstrated by certain shape selectivity from the point of view of on cloth；In meta-xylene reforming reaction, TNU-9 also shows higher
Catalytic activity and selectivity.TNU-9 excellent physico-chemical property makes it in the available wider application of petrochemical industry.
Currently, the method for synthesis TNU-9 molecular sieve is at high cost, its extensive use is constrained.Wherein, for synthesizing TNU-
The at high cost of the bi-quaternary ammonium salt template (1,4-MPB) of 9 molecular sieves is one of main reason.
The method of synthesis bis- (N- crassitude) the butane bromides (1,4-MPB) of bi-quaternary ammonium salt template 1,4- generally requires
By two kinds of raw material 1- crassitudes (1-MP) and 1,4- dibromobutane (1,4-DBB) in certain proportion in solvent appropriate
Reaction need to can just obtain purer Isosorbide-5-Nitrae-MPB using crystallization, repeated recrystallize method, and in crystallization, repeated recrystallize process
In need freezing, filtering, organic reagent washing, dry plus organic solvent dissolution appropriate plus organic solvent appropriate to analyse again again
Out, it is filtered, washed, is dried etc. cumbersome operation, consumes a large amount of time, and generate a large amount of energy consumption and material consumption.
In order to avoid synthesizing the above-mentioned unfavorable factor of template, Hong S B is in Journal of the American
It not only reports in Chemical Society, 2007,129:10870-10885 and is synthesized with organic formwork agent 1,4-MPB
TNU-9 molecular sieve also reports predecessor (1-MP) and (1,4-DBB) using synthesis template directly as organic formwork agent
Organic formwork agent Isosorbide-5-Nitrae-MPB is substituted, TNU-9 molecular sieve is also synthesized.But it is under the strong basicity environment of synthesis of molecular sieve and whole
In a reaction mixture system, side reaction or reaction inevitably occur for the raw material for synthesizing template not exclusively, to make
Effective consumption and waste at reaction raw materials, cause undesirable result.
Summary of the invention
Purpose of this disclosure is to provide a kind of methods of the synthesis TNU-9 molecular sieve of low cost.
To achieve the goals above, the disclosure provides a kind of method for synthesizing TNU-9 molecular sieve, and this method includes following step
It is rapid:
A, Isosorbide-5-Nitrae-dibromobutane, 1- crassitude are mixed with solvent, in 15~90 DEG C of 0.5~96h of pre-reaction, is obtained
Pre-reaction product, the molar ratio of the Isosorbide-5-Nitrae-dibromobutane, 1- crassitude and solvent are 1:(1.8~3): (1~20)；
B, pre-reaction product, inorganic base obtained in step a, silicon source, silicon source and water are mixed, obtains mixing to crystallization
Object described will carry out hydrothermal crystallizing processing to crystallization mixture, and recycle solid product.
Optionally, in step a, the molar ratio of the Isosorbide-5-Nitrae-dibromobutane, 1- crassitude and solvent be 1:(1.9~
2.5): (2~18).
Optionally, in step a, the condition of the pre-reaction are as follows: 15~60 DEG C, the time is 1~48h.
Optionally, in step a, the solvent be selected from water, the monohydric alcohol of C1~C6, the ether of C4~C6, C3~C6 ketone,
At least one of polyalcohol and the ester of C3~C6 of C2~C4.
Optionally, in step b, mole group to crystallization mixture becomes SiO2: Al2O3: M2O:R:H2O=100:
(0.5~10): (15~50): (8~20): (800~5000), wherein M2O is alkali metal oxide, and R is pre-reaction production
Object, the molal quantity of R is in terms of the molal quantity of the Isosorbide-5-Nitrae-dibromobutane.
Optionally, in step b, the inorganic base is selected from sodium hydroxide, potassium hydroxide, sodium oxide molybdena, potassium oxide, sodium carbonate
At least one of with potassium carbonate.
Optionally, in step b, source of aluminium is selected from sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminium isopropoxide and aluminum acetate
At least one of.
Optionally, in step b, the silicon source is at least one in silica gel, silica solution, white carbon black and ethyl orthosilicate
Kind.
Optionally, in step b, the condition of the hydrothermal crystallizing processing are as follows: temperature is 140~170 DEG C, and the time is 7~14
It.
Optionally, this method further include: the step of being washed, filtered and dried after recycling solid product.
Through the above technical solutions, the disclosure first will synthesize the raw material pre-reaction of template for a period of time, then again by it
It is mixed in certain proportion with other raw materials of synthesis of molecular sieve, hydrothermal crystallizing has synthesized TNU-9 molecular sieve.Disclosed method
It eliminates and is conventionally synthesized the complicated processes such as TNU-9 Molecular Sieves as Template agent necessary costly separation, purification, avoid a large amount of
It is obvious to reduce cost effectiveness for time loss, energy consumption and material consumption；In addition, also overcoming the original that will synthesize template in the prior art
Material directly mixes the drawbacks of raw material brought by crystallization reacts incomplete, need to recycle with other raw materials of synthesis of molecular sieve,
Avoid waste and the effective consumption of resulting reaction raw materials.Using TNU-9 molecular sieve synthesized by disclosed method
Crystallinity it is higher.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Attached drawing is and to constitute part of specification for providing further understanding of the disclosure, with following tool
Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings:
Fig. 1 is the X-ray diffraction spectrogram of the TNU-9 molecular sieve synthesized in embodiment 1.
Specific embodiment
It is described in detail below in conjunction with specific embodiment of the attached drawing to the disclosure.It should be understood that this place is retouched
The specific embodiment stated is only used for describing and explaining the disclosure, is not limited to the disclosure.
The disclosure provides a kind of method for synthesizing TNU-9 molecular sieve, method includes the following steps:
A, Isosorbide-5-Nitrae-dibromobutane, 1- crassitude are mixed with solvent, in 15~90 DEG C of 0.5~96h of pre-reaction, is obtained
Pre-reaction product, the molar ratio of the Isosorbide-5-Nitrae-dibromobutane, 1- crassitude and solvent are 1:(1.8~3): (1~20)；
B, pre-reaction product, inorganic base obtained in step a, silicon source, silicon source and water are mixed, obtains mixing to crystallization
Object described will carry out hydrothermal crystallizing processing to crystallization mixture, and recycle solid product.
The disclosure first will synthesize the raw material pre-reaction of template for a period of time, then again that it is other with synthesis of molecular sieve
Raw material mixes in certain proportion, and hydrothermal crystallizing has synthesized TNU-9 molecular sieve.Disclosed method, which eliminates, is conventionally synthesized TNU-
The complicated processes such as 9 Molecular Sieves as Template agent necessary costly separation, purification, avoid a large amount of time loss, energy consumption and object
It is obvious to reduce cost effectiveness for consumption；In addition, also overcome in the prior art by synthesize template raw material and synthesis of molecular sieve its
Its raw material directly mixes the drawbacks of raw material brought by crystallization reacts incomplete, need to recycle, and avoids resulting anti-
Answer waste and the effective consumption of raw material.Crystallinity using TNU-9 molecular sieve synthesized by disclosed method is higher.
According to the disclosure, the entitled Isosorbide-5-Nitrae-Dibromobutane of English of the Isosorbide-5-Nitrae-dibromobutane, No. CAS is 110-52-
1, structural formula are as follows:
According to the disclosure, the entitled 1-Methylpyrrolidine of English of the 1- crassitude, No. CAS is 120-
94-5, structural formula are as follows:
According to the disclosure, in step a, the molar ratio of the Isosorbide-5-Nitrae-dibromobutane, 1- crassitude and solvent is preferably
1:(1.9~2.5): (2~18), further preferably 1:(2~2.3): (2~14).
According to the disclosure, in step a, the hybrid mode of Isosorbide-5-Nitrae-dibromobutane, 1- crassitude and solvent can be this
Field routine, it is preferable that first 1- crassitude can be mixed with solvent, then Isosorbide-5-Nitrae-dibromobutane is added drop-wise to above-mentioned institute
In the mixed liquor obtained, the speed of the dropwise addition can be 1~60 drop/sec.The pre-reaction in closed reactor or can be taken back
It flows and is carried out in the reaction kettle of device.The condition of the pre-reaction preferably can be with are as follows: 15~60 DEG C, the time is 1~48h.In order to obtain
Ideal effect is obtained, the mixing and the pre-reaction can carry out under stirring conditions.
According to the disclosure, in step a, the solvent can be common organic solvent and water, can be with as long as meeting it
Isosorbide-5-Nitrae-dibromobutane and/or 1- crassitude dissolve each other, for example, the solvent can be the unitary selected from water, C1~C6
At least one of alcohol, the ether of C4~C6, the ketone of C3~C6, the polyalcohol of C2~C4 and ester of C3~C6.Preferably, described molten
Agent is in the ester selected from water, the monohydric alcohol of C1~C4, the ether of C4~C5, the ketone of C3~C4, the polyalcohol of C2~C3 and C3~C4
At least one；Specifically, the solvent can be water, methanol, ethyl alcohol, ether, acetone etc..
According to the disclosure, in step b, the pre-reaction product, inorganic base, silicon source, the hybrid mode of silicon source and water can be with
Conventional for this field, it is preferable that it can be first soluble in water by the pre-reaction product, inorganic base and silicon source, it obtains mixing molten
Liquid；Again under agitation, the mixed solution is contacted with silicon source, is obtained to crystallization mixture.It is described to crystallization mixture
A mole composition can be SiO2: Al2O3: M2O:R:H2O=100:(0.5~10): (15~50): (8~20): (800~
5000), preferably 100:(0.8~8): (20~40): (8~15): (1000~4000), wherein M2O is alkali metal oxidation
Object, R are the pre-reaction product, and the molal quantity of R is in terms of the molal quantity of the Isosorbide-5-Nitrae-dibromobutane.
According to the disclosure, in step b, the inorganic base, silicon source, silicon source can be for for synthesizing the normal of TNU-9 molecular sieve
Advise type.For example, the inorganic base can be for selected from sodium hydroxide, potassium hydroxide, sodium oxide molybdena, potassium oxide, sodium carbonate and carbonic acid
At least one of potassium.Source of aluminium can be in sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminium isopropoxide and aluminum acetate
It is at least one.The silicon source is can be for selected from least one of silica gel, silica solution, white carbon black and ethyl orthosilicate.
According to the disclosure, in step b, the condition of the hydrothermal crystallizing processing can be with are as follows: temperature is 140~170 DEG C, the time
It is 7~14 days.In order to obtain ideal effect, the hydrothermal crystallizing can carry out under stirring conditions.
According to the disclosure, this method can also include: the step of washed, filtered and dried after recycling solid product.
Wherein, the washing, filtering and drying are the conventional steps of synthesis of molecular sieve, and the disclosure does not have special limitation to its condition.
For example, the condition of the drying can be with are as follows: temperature is 80~120 DEG C, the time is 8~for 24 hours.
The disclosure is described further below by embodiment, but does not therefore limit content of this disclosure.
The relative concept and calculation of " relative crystallinity " in embodiment and comparative example are as follows: point synthesized with comparative example 1
Son sieve product Z0 is calculated as on the basis of 2 sections θ of XRD spectra are the sum of the peak area in 21.0-27.5 ° with percentage
100%；The product synthesized in following embodiment and comparative example on XRD spectra 2 sections θ be 21.0-27.5 ° in peak area it
Ratio (in terms of percentage) with the sum of the peak area of XRD spectra with Z0 is the relative crystallinity value of corresponding product
(R.C.%).
In embodiment and comparative example, XRD analysis uses III A type diffractometer of Rigaku D/MAX-, test condition: Cu target, K
α radiation, Ni filter plate, tube voltage 35kV, tube current 35mA, 2 θ of scanning range are 4-55 °.
In embodiment and comparative example, the specification of used various reagents and source are as follows:
NaOH、Al(NO3)39H2O, dehydrated alcohol, methanol, acetone, ether are that analysis is pure, Beijing Chemical Plant's production；
Bis- (N- crassitude) butane bromide (Isosorbide-5-Nitrae-MPB) aqueous solutions of Isosorbide-5-Nitrae-, 58 weight % of solid content are had greatly by Guangzhou
Fine Chemical Works production；
1- crassitude (1-MP), > 98.0 weight %, Tokyo chemical conversion industry strain commercial firm；
Isosorbide-5-Nitrae-dibromobutane (Isosorbide-5-Nitrae-DBB), > 98.0 weight %, Tokyo chemical conversion industry strain commercial firm；
White carbon black, SiO2Content is 97 weight %, Zhuzhou prosperity company；
In embodiment and comparative example, the Cost Estimation of synthesis of molecular sieve are as follows: the valence of all raw materials of synthesis of molecular sieve
The weight ratio of lattice summation and products therefrom.
Comparative example 1
This comparative example is for illustrating document Synthesis, crystal structure, characterization, and
catalytic properties of TNU-9.Journal of the American Chemical Society,2007,
The method of TNU-9 molecular sieve is synthesized disclosed in 129:10870-10885, the specific steps are as follows:
By bis- (N- crassitude) butane bromide (1,4-MPB) aqueous solutions of 9.98g1,4- and 2.92g NaOH, 1.5gAl
(NO3)3·9H2O dissolves in appropriate amount of deionized water, is uniformly mixed, and 6.19g white carbon black is added under stirring conditions, milky is made
Colloidal waits for crystallization mixture, and mole group becomes 4.5 (Isosorbide-5-Nitrae-MPB): 11Na2O:0.6Al2O3: 30SiO2: 1200H2O.By institute
It must be transferred in the crystallizing kettle of 100ml polytetrafluoroethyllining lining, be rotated hydrothermal crystallizing 14 days at 160 DEG C, revolving speed 100rpm.
Then stop crystallization, product is washed, filters, and 80 DEG C of drying 12h obtain molecular screen primary powder Z0.
By the XRD determining result of molecular screen primary powder Z0 and document Synthesis, crystal structure,
characterization,and catalytic properties of TNU-9.Journal of the American
Chemical Society, the comparison of TNU-9 molecular sieve XRD spectra disclosed in 2007,129:10870-10885, determines that Z0 is
TNU-9 molecular sieve.The relative crystallinity for setting molecular screen primary powder Z0 is listed in table 1 as 100% and synthesis cost.
Comparative example 2
This comparative example is used to illustrate the predecessor 1- crassitude (1-MP) and 1,4- dibromo fourth using synthesis template
The method that alkane (1,4-DBB) substitution organic formwork agent 1,4-MPB directly synthesizes TNU-9 molecular sieve.
TNU-9 molecular sieve is synthesized according to the method for comparative example 1, difference is, using 3.91g1- crassitude (1-MP)
And 3.305g1,4- dibromobutane (Isosorbide-5-Nitrae-DBB) substitute bis- (N- crassitude) the butane bromides (Isosorbide-5-Nitrae-MPB) of Isosorbide-5-Nitrae-, 1- methyl
The molar ratio of pyrrolidines and 1,4- dibromobutane is 3:1.Synthesis obtains molecular screen primary powder Z1.
XRD test is carried out to molecular screen primary powder Z1, and by measurement result and document Synthesis, crystal
structure,characterization,and catalytic properties of TNU-9.Journal of the
American Chemical Society, the comparison of TNU-9 molecular sieve XRD spectra disclosed in 2007,129:10870-10885, warp
Comparison can determine that Z1 is TNU-9 molecular sieve, calculates its relative crystallinity and synthesis cost is listed in table 1.
The method that embodiment 1-7 is used to illustrate the synthesis TNU-9 molecular sieve of the disclosure.
Embodiment 1
Under agitation, 29.32g1- crassitude and 36mL dehydrated alcohol are mixed, then by 33.05g1,4- bis-
Bromobutane is added drop-wise in above-mentioned mixed liquor with 5 drops/sec of speed, and the pre-reaction 8h at 50 DEG C obtains pre-reaction product A1.1,4- bis-
The molar ratio of bromobutane, 1- crassitude and etoh solvent is 1:2.25:4.12.
By pre-reaction product A1,15g Al (NO3)3·9H2O, 29.2gNaOH solution is dissolved in appropriate amount of deionized water, mixing
Uniformly, under stirring conditions, it is slowly added to 61.9g white carbon black, opalescent colloidal shape is made and waits for its mole of group of crystallization mixture
As SiO2: Al2O3: Na2O:A1:H2O=100:2:36.7:15:4000 continues to stir 1h, be transferred to churned mechanically 1L
In autoclave, after stirring hydrothermal crystallizing 14 days at 160 DEG C, stopping crystallization, product is washed, after filtering, and 80 DEG C
Drying 12h obtains molecular screen primary powder B1.
XRD test is carried out to molecular screen primary powder B1, spectrogram is as shown in Figure 1.By gained XRD spectra and document Synthesis,
crystal structure,characterization,and catalytic properties of TNU-9.Journal
The XRD of TNU-9 molecular sieve disclosed in of the American Chemical Society, 2007,129:10870-10885
Spectrogram can determine that B1 is TNU-9 molecular sieve after comparing, calculate its relative crystallinity and synthesis cost is listed in table 1.
Embodiment 2
TNU-9 molecular sieve is synthesized according to the method for embodiment 1, and difference is, under agitation, by 29.32g1- methyl
Pyrrolidines and the mixing of 43mL ether, then by 33.05g1,4- dibromobutane is added drop-wise in above-mentioned mixed liquor with 10 drops/sec of speed,
The pre-reaction 16h at 35 DEG C obtains pre-reaction product A2.The molar ratio of 1,4- dibromobutane, 1- crassitude and solvent ether
For 1:2.0:2.76.A1 is substituted with pre-reaction product A2, obtains molecular screen primary powder B2, XRD spectra and embodiment 1 are consistent, meter
It calculates its relative crystallinity and synthesis cost is listed in table 1.
Embodiment 3
TNU-9 molecular sieve is synthesized according to the method for embodiment 1, and difference is, under agitation, by 27.37g1- methyl
Pyrrolidines is mixed with 35mL deionized water, then by 33.05g1,4- dibromobutane is added drop-wise in above-mentioned mixed liquor, at 60 DEG C
Pre-reaction 48h obtains pre-reaction product A3.The molar ratio of 1,4- dibromobutane, 1- crassitude and aqueous solvent is 1:2.1:
12.96.A1 is substituted with pre-reaction product A3, obtains molecular screen primary powder B3, XRD spectra and embodiment 1 are consistent, and it is opposite to calculate it
Crystallinity and synthesis cost are listed in table 1.
Embodiment 4
TNU-9 molecular sieve is synthesized according to the method for embodiment 1, and difference is, under agitation, by 32.58g1- methyl
Pyrrolidines is mixed with 160mL methanol, then by 33.05g1,4- dibromobutane is added drop-wise to above-mentioned mixed liquor with 30 drops/sec of speed
In, pre-reaction for 24 hours, obtains pre-reaction product A4 at 50 DEG C.Mole of 1,4- dibromobutane, 1- crassitude and solvent methanol
Than substituting A1 for 1:2.5:14.5 with pre-reaction product A4, molecular screen primary powder B4 is obtained, XRD spectra and embodiment 1 are consistent, meter
It calculates its relative crystallinity and synthesis cost is listed in table 1.
Embodiment 5
TNU-9 molecular sieve is synthesized according to the method for embodiment 1, and difference is, under agitation, by 24.76g1- methyl
Pyrrolidines is mixed with 155mL acetone, then by 33.05g1,4- dibromobutane is added drop-wise to above-mentioned mixed liquor with 20 drops/sec of speed
In, the pre-reaction 4h at 40 DEG C obtains pre-reaction product A6.Mole of 1,4- dibromobutane, 1- crassitude and solvent acetone
Than for 1:1.9:14.1.A1 is substituted with pre-reaction product A5, obtains molecular screen primary powder B5, XRD spectra and embodiment 1 are consistent,
It calculates its relative crystallinity and synthesis cost is listed in table 1.
Embodiment 6
Synthesize TNU-9 molecular sieve according to the method for embodiment 1, difference is, under agitation, by 160mL ethyl alcohol with
The mixed liquor of 33.05g1,4- dibromobutane is added drop-wise in 33.89g1- crassitude with 40 drops/sec of speed, pre- at 50 DEG C
10h is reacted, pre-reaction product A6 is obtained.The molar ratio of 1,4- dibromobutane, 1- crassitude and etoh solvent is 1:2.6:
18.32.A1 is substituted with pre-reaction product A6, obtains molecular screen primary powder B5, XRD spectra and embodiment 1 are consistent, and it is opposite to calculate it
Crystallinity and synthesis cost are listed in table 1.
Embodiment 7
Synthesize TNU-9 molecular sieve according to the method for embodiment 1, difference is, under agitation, by 16mL ethyl alcohol with
The mixed liquor of 33.05g1,4- dibromobutane is added drop-wise in 23.46g1- crassitude with 3 drops/sec of speed, pre- anti-at 75 DEG C
60h is answered, pre-reaction product A7 is obtained.The molar ratio of 1,4- dibromobutane, 1- crassitude and etoh solvent is 1:1.8:1.83.
A1 is substituted with pre-reaction product A7, obtains molecular screen primary powder B7, XRD spectra and embodiment 1 are consistent, calculate its relative crystallinity
Table 1 is listed in synthesis cost.
Table 1
Seen from table 1, disclosed method can significantly reduce the synthesis cost of TNU-9 molecular sieve, and prepared
TNU-9 molecular sieve relative crystallinity with higher.
The preferred embodiment of the disclosure is described in detail in conjunction with attached drawing above, still, the disclosure is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure
Monotropic type, these simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (10)
1. a kind of method for synthesizing TNU-9 molecular sieve, which is characterized in that method includes the following steps:
A, Isosorbide-5-Nitrae-dibromobutane, 1- crassitude are mixed with solvent, in 15~90 DEG C of 0.5~96h of pre-reaction, is obtained pre- anti-
Product is answered, the molar ratio of the Isosorbide-5-Nitrae-dibromobutane, 1- crassitude and solvent is 1:(1.8~3): (1~20)；
B, pre-reaction product, inorganic base obtained in step a, silicon source, silicon source and water are mixed, is obtained to crystallization mixture, it will
It is described to carry out hydrothermal crystallizing processing to crystallization mixture, recycle solid product.
2. according to the method described in claim 1, wherein, in step a, the Isosorbide-5-Nitrae-dibromobutane, 1- crassitude with it is molten
The molar ratio of agent is 1:(1.9~2.5): (2~18).
3. according to the method described in claim 1, wherein, in step a, the condition of the pre-reaction are as follows: 15~60 DEG C, the time is
1~48h.
4. according to the method described in claim 1, wherein, in step a, the solvent is selected from water, the monohydric alcohol of C1~C6, C4
At least one of the ether of~C6, the ketone of C3~C6, the polyalcohol of C2~C4 and ester of C3~C6.
5. according to the method described in claim 1, wherein, in step b, mole group to crystallization mixture becomes SiO2:
Al2O3: M2O:R:H2O=100:(0.5~10): (15~50): (8~20): (800~5000), wherein M2O is alkali metal oxygen
Compound, R are the pre-reaction product, and the molal quantity of R is in terms of the molal quantity of the Isosorbide-5-Nitrae-dibromobutane.
6. according to the method described in claim 1, wherein, in step b, the inorganic base be selected from sodium hydroxide, potassium hydroxide,
At least one of sodium oxide molybdena, potassium oxide, sodium carbonate and potassium carbonate.
7. according to the method described in claim 1, wherein, in step b, source of aluminium is selected from sodium metaaluminate, aluminum nitrate, sulfuric acid
At least one of aluminium, aluminium isopropoxide and aluminum acetate.
8. according to the method described in claim 1, wherein, in step b, the silicon source be selected from silica gel, silica solution, white carbon black and
At least one of ethyl orthosilicate.
9. according to the method described in claim 1, wherein, in step b, the condition of the hydrothermal crystallizing processing are as follows: temperature 140
~170 DEG C, the time is 7~14 days.
10. according to the method described in claim 1, wherein, this method further include: washed, filtered after recycling solid product
The step of with drying.
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| CN201810387842.5A CN110407227B (en) | 2018-04-26 | 2018-04-26 | Method for synthesizing TNU-9 molecular sieve |
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| CN115279493A (en) * | 2020-02-18 | 2022-11-01 | 环球油品有限责任公司 | Toluene disproportionation using enhanced UZM-39 aluminosilicate zeolite |
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