CN103979574B - The method of solid phase synthesis molecular sieve - Google Patents
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- CN103979574B CN103979574B CN201410246562.4A CN201410246562A CN103979574B CN 103979574 B CN103979574 B CN 103979574B CN 201410246562 A CN201410246562 A CN 201410246562A CN 103979574 B CN103979574 B CN 103979574B
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Abstract
The invention discloses a kind of method of solid phase synthesis molecular sieve, it is using Neutral ammonium fluoride as mineralizer, using bromination organic formwork agent as directed agents; Synthetic method comprises the following steps: after being mixed with anhydrous sodium metasilicate by a certain amount of water, and recrystallization forms the Starso containing crystal water; Then at room temperature by a certain amount of Starso containing crystal water, white carbon black, bromination organic formwork agent, Neutral ammonium fluoride and/aluminum nitrate, the mixture material after grinding to mixing, then is put into Glass tubing, with flame sealing by mixed grinding; The Glass tubing sealed is placed in 180 DEG C of baking oven crystallization after 4 weeks, reaction product is washed, is placed in 60 DEG C of baking ovens to complete drying; The present invention is by using F
?as mineralizer, obtain this molecular sieve that cannot obtain in alkaline synthetic route of ITQ-13 and F-ZSM-5 zeolite molecular sieve, and maintain good degree of crystallinity and purity; Reactant cost reduces; Energy consumption reduces; Product purity is high.
Description
Technical field
The present invention relates to a kind of molecular sieve preparation method, particularly one is with NH
4f is as the method for mineralizer solid phase synthesis ITQ-13 and ZSM-5 molecular sieve.
Background technology
Zeolite molecular sieve due to have larger specific surface area, higher hydrothermal stability, can the surface acidic-basic property of modulation and duct selectivity, and be widely used in the absorption of petrochemical complex, separation and various catalytic process.The synthesis of zeolite molecular sieve and catalytic applications are the focuses of industrial application and academic research always.Wherein, ITQ-13 (T.Boix, M.Puche, M.A.Camblor, A.Corma, USPatent6471941B1, 2002) molecular sieve is a kind of synthesizing porous crystalline material with three-dimensional channel system, there is ITH topological framework, this structure comprises first group of usually parallel duct, the wherein ten-ring that formed by tetrahedral coordination atom of each duct, and second group also forms parallel duct by the ten-ring of tetrahedral coordination atom usually, and intersect with first group of duct, also comprise the 3rd group of parallel channels usually formed by the nonatomic ring of tetrahedral coordination atom, it intersects with described first and second groups of ducts.Due to its special pore passage structure, can be applicable to the selective conversion process of hydro carbons, such as oil catalytic pyrolysis generates the conversion etc. of propylene and compound fragrant hydrocarbon, therefore industrially has a good application prospect.In addition, ZSM-5 molecular sieve (R.JArgauer, G.RLandolt, Mobiloilcorp, US3702886A, 1972), due to thermostability and hydrothermal structural stability that it has higher silica alumina ratio, unique pore passage structure, larger specific surface area and excellence, have also been obtained in the petrochemical process such as shape slective cracking, alkylation, isomerization, disproportionation, catalytic dewaxing, etherificate of hydro carbons and apply extremely widely.
Use organic ammonium to become as Organic structure directing agent (structuredirectingagent) and obtain zeolite structured very effective ways.Multiple organic ammonium has been successfully used in the synthesis of molecular sieve.Before the eighties in last century, synthesis of molecular sieve mainly takes water heat transfer under the condition of alkalescence, since F
-reaction system is introduced into replace the OH group of alkalescence as mineralizer, the synthesis of molecular sieve has a great development, this method is the unique method of some special construction molecular sieve of synthesis in some sense, and can obtain the less molecular sieve crystal of skeleton defect point.On skeleton, the minimizing of lattice defect position can increase the hydrophobicity of molecular screen material effectively, meanwhile, and F
-as mineralizer, can introducing hetero-atoms more effectively, as Ti, Fe, Al or B etc. enter the catalytic performance that framework of molecular sieve carrys out Molecular regulator sieve.
2012, Zhejiang University Xiao Fengshou taught study group and develops a kind of directly by the method (Xiao Fengshou etc., CN102627287) of synthesis of molecular sieve under Solid raw materials grinding condition of no solvent.This synthetic method simplifies traditional hydrothermal synthesis method greatly, improves productive rate, reduces production cost, has saved the energy, decreases the pollution to environment, has very large industrial application potentiality.This method adopts traditional ammonium salt to provide alkalescence source (i.e. OH
-group is as mineralizer) the molecular sieve structure that obtains of synthetic route still there is limitation; And under traditional alkaline condition in hydro-thermal gel synthesis ITQ-13 and F-ZSM-5 zeolite molecular sieve process, bromination organic formwork agent needs to use silver suboxide or ion exchange column to be converted into hydroxide organic formwork agent, reaction cost increases; Silicon source and aluminium source hydrolytic process in basic solution is consuming time very long, and efficiency is low and energy consumption is larger; The water yield cannot accurately control, so very easily obtain mix products; Simultaneously because needs add hydrofluoric acid to introduce fluorion mineralizer, bring again the harm in the health of experimenter, therefore seek applicable reducing costs, it is very necessary for raising the efficiency with safer synthetic method.
Summary of the invention
Main purpose of the present invention is the deficiency overcoming synthesis ITQ-13 and ZSM-5 molecular sieve technology, provides one to reduce costs, raises the efficiency the method with safer solid phase synthesis molecular sieve.
For solving the problems of the technologies described above, the technical solution used in the present invention realizes in the following manner:
A method for solid phase synthesis molecular sieve, it is using Neutral ammonium fluoride as mineralizer, using bromination organic formwork agent as directed agents; Synthetic method comprises the following steps: after being mixed with anhydrous sodium metasilicate by a certain amount of water, and recrystallization forms the Starso containing crystal water; Then at room temperature by a certain amount of Starso containing crystal water, white carbon black, bromination organic formwork agent, Neutral ammonium fluoride and/aluminum nitrate, the mixture material after grinding to mixing, then is put into Glass tubing, with flame sealing by mixed grinding; The Glass tubing sealed is placed in 180 DEG C of baking oven crystallization after 4 weeks, reaction product is washed, is placed in 60 DEG C of baking ovens to complete drying;
Described bromination organic formwork agent is hexamethyl bromination two ammonium, 4-propyl bromide or tetraethylammonium bromide;
The mol ratio of reaction raw materials is:
1.0Na
2siO
3xH
2o:1.0SiO
2(white carbon black): 0.15-0.25HMBr
2: 1.2-1.8NH
4f
1.0Na
2siO
3xH
2o:1.0SiO
2(white carbon black): 0.15-0.25TPABr:1.0-1.8NH
4f.
1.0Na
2siO
3xH
2o:1.0SiO
2(white carbon black): 0.05-0.2Al (NO
3)
39H
2o:0.15-0.25TPABr:1.0-1.8NH
4f.
1.0Na
2siO
3xH
2o:1.0SiO
2(white carbon black): 0.4-0.8TEABr:1.0-1.8NH
4f.
1.0Na
2siO
3xH
2o:1.0SiO
2(white carbon black): 0.05-0.2Al (NO
3)
39H
2o:0.4-0.8TEABr:1.0-1.8NH
4f.
Described white carbon black is unbodied white carbon black, and in the Starso of recrystallization, the mole number of water is x=3-9.
During described grinding, raw material is placed in agate mortar, grinding 5-10 minute.
In 60 DEG C of baking ovens to the time of complete drying be 8-12 hours.
The present invention is by using NH
4f realizes F
-as another important synthesis path of mineralizer (non-alkaline synthetic method), successfully synthesize ITQ-13, because F
-directed agents required in ITQ-13 crystallization process, formed two tetra-atomic ring structure (D4R,
19a specified chemical displacement-38ppm is had in F spectrum), and in the synthesis of traditional alkalescence, be two tetra-atomic ring structures that cannot obtain this pure silicon; Meanwhile, F is used
-as the non-alkaline synthetic method of mineralizer, also obtain different crystal size, different catalytic performance (F
-be conducive to heteroatoms such as Al, Zn, Ti, B etc. as mineralizer and enter into framework of molecular sieve) molecular sieve.
Can be successfully used in the organic ammonium of Zeolite synthesis numerous, the present invention has selected hexamethyl bromination two ammonium as directed agents to synthesize ITQ-13; For ZSM-5, the present invention have selected 4-propyl bromide and the representative organic ammonium of tetraethylammonium bromide these two kinds to realize synthesis path.Because F
-as mineralizer, can introducing hetero-atoms more effectively, so the present invention enters framework of molecular sieve to illustrate compared to alkaline synthesis path by introducing Al atom, F
-more effectively can introduce Al atom as mineralizer and enter framework of molecular sieve.At F
-as in the synthesis path of mineralizer, the water yield generally needs accurate control, so the present invention contains crystal water Starso by water being introduced anhydrous sodium metasilicate formation controls the water yield.F
-be generally by adding HF in colloidal sol as mineralizer, and the present invention use NH
4f, instead of the HF acid that corrodibility is very strong, the security that improve experiment and the pollution reduced environment.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention is by using F
-as mineralizer, obtain this molecular sieve that cannot obtain in alkaline synthetic route of ITQ-13 and F-ZSM-5 zeolite molecular sieve, and maintain good degree of crystallinity and purity, and experimental result shows F
-enter the amount in framework of molecular sieve, directly affect the amount that Al atom enters into framework of molecular sieve, indicate F
-as the impact that mineralizer is introduced as aluminium heteroatoms.
Use bromination organic formwork agent, thus do not need to use silver suboxide or ion exchange column to be converted into hydroxide organic formwork agent, so reactant cost reduces; Do not need very long hydrolytic process consuming time, improve efficiency and decrease energy consumption; The water yield can accurately control again, so can obtain single product.
Accompanying drawing explanation
The XRD spectrum of Fig. 1 to be hexamethyl bromination two ammonium be ITQ-13 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase;
The SEM photo of Fig. 2 to be hexamethyl bromination two ammonium be ITQ-13 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase;
The NMR of Fig. 3 to be hexamethyl bromination two ammonium be ITQ-13 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase
19f composes;
The XRD spectrum of Fig. 4 to be 4-propyl bromide be F-ZSM-5 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase;
The SEM photo of Fig. 5 to be 4-propyl bromide be F-ZSM-5 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase;
The NMR of Fig. 6 to be 4-propyl bromide be F-ZSM-5 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase
19f composes;
The XRD spectrum of Fig. 7 to be tetraethylammonium bromide be F-ZSM-5 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase;
The SEM photo of Fig. 8 to be tetraethylammonium bromide be F-ZSM-5 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase;
The NMR of Fig. 9 to be tetraethylammonium bromide be F-ZSM-5 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase
19f composes;
Figure 10 is 4-propyl bromide is the XRD spectrum of directed agents solventless method solid phase synthesis containing the F-ZSM-5 molecular sieve of aluminium;
Figure 11 is 4-propyl bromide is the SEM photo of directed agents solventless method solid phase synthesis containing the F-ZSM-5 molecular sieve of aluminium;
Figure 12 is 4-propyl bromide is the NMR of directed agents solventless method solid phase synthesis containing the F-ZSM-5 molecular sieve of aluminium
19f composes;
Figure 13 is 4-propyl bromide is the NMR of directed agents solventless method solid phase synthesis containing the F-ZSM-5 molecular sieve of aluminium
27al composes;
Figure 14 is tetraethylammonium bromide is the XRD spectrum of directed agents solventless method solid phase synthesis containing the F-ZSM-5 molecular sieve of aluminium;
Figure 15 is tetraethylammonium bromide is the SEM photo of directed agents solventless method solid phase synthesis containing the F-ZSM-5 molecular sieve of aluminium;
Figure 16 is tetraethylammonium bromide is the NMR of directed agents solventless method solid phase synthesis containing the F-ZSM-5 molecular sieve of aluminium
19f composes;
Figure 17 is tetraethylammonium bromide is the NMR of directed agents solventless method solid phase synthesis containing the F-ZSM-5 molecular sieve of aluminium
27al composes;
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention is described in detail:
Embodiment 1: hexamethyl bromination two ammonium is the ITQ-13 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase.
After being mixed with 1.22g Starso by the water of 0.54g, recrystallization forms the Starso containing three crystal water; Then under room temperature by 1.76g tri-hydrated sodium metasilicate and 0.56g white carbon black, 0.52g hexamethyl bromination two ammonium, 0.59g Neutral ammonium fluoride mixing be placed in agate mortar, grinding 5-10 minute, to mixing, then the mixture material after grinding is put into Glass tubing, with flame sealing; Finally the Glass tubing sealed is placed in 180 DEG C of baking oven crystallization after 4 weeks, reaction product is washed, is placed in 12,60 DEG C of baking ovens little of complete drying, finally obtains product.
The proportioning of reaction raw materials is as follows:
1.0Na
2siO
33H
2o:1.0SiO
2(white carbon black): 0.15HMBr
2: 1.6NH
4f
Analyzing its structure through X-ray diffraction (Fig. 1) is ITQ-13 zeolite molecular sieve, and can find out that what obtain is the block crystal grain of rectangular parallelepiped by stereoscan photograph (Fig. 2).Solid-state nuclear magnetic resonance
19f composes the feature that zeolite molecular sieve that (Fig. 3) (chemical shift is-38ppm) also demonstrate synthesis has ITQ-13 topology molecular sieve structure.
Embodiment 2: 4-propyl bromide is the F-ZSM-5 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase.
After being mixed with 1.22g anhydrous sodium metasilicate by the water of 0.54g, recrystallization forms the Starso containing three crystal water; Then under room temperature by 1.76g tri-hydrated sodium metasilicate and 0.56g white carbon black, 0.53g 4-propyl bromide, 0.59g Neutral ammonium fluoride mixing be placed in agate mortar, grinding 5-10 minute, to mixing, then the mixture material after grinding is put into Glass tubing, with flame sealing; Finally the Glass tubing sealed is placed in 180 DEG C of baking oven crystallization after 4 weeks, reaction product is washed, is placed in 11,60 DEG C of baking ovens little of complete drying, finally obtains product.
The proportioning of reaction raw materials is as follows:
1.0Na
2siO
33H
2o:1.0SiO
2(white carbon black): 0.2TPABr:1.6NH
4f.
Analyzing its structure through X-ray diffraction (Fig. 4) is F-ZSM-5 zeolite molecular sieve, and clearly can find out the block crystal grain of the well-regulated hexagonal octahedron of the spined tool of band of to be typical with F the be mineralizer growth obtained by stereoscan photograph (Fig. 5).Solid-state nuclear magnetic resonance
19f composes the feature that zeolite molecular sieve that (Fig. 6) (chemical shift is-63ppm) also demonstrate synthesis has F-ZSM-5 topology molecular sieve structure.
Embodiment 3: tetraethylammonium bromide is the F-ZSM-5 molecular sieve of directed agents solventless method solid phase synthesis pure silicon phase
After being mixed with 1.22g anhydrous sodium metasilicate by the water of 1.08g, recrystallization forms the Starso containing six crystal water; Then under room temperature by 2.30g six hydrated sodium metasilicate and 0.56g white carbon black, 0.88g tetraethylammonium bromide, 0.59g Neutral ammonium fluoride mixing be placed in agate mortar, grinding 5-10 minute, to mixing, then the mixture material after grinding is put into Glass tubing, with flame sealing; Finally the Glass tubing sealed is placed in 180 DEG C of baking oven crystallization after 4 weeks, reaction product is washed, be placed in 10,60 DEG C of baking ovens about a day little of complete drying, finally obtain product.The proportioning of reaction raw materials is as follows:
1.0Na
2siO
36H
2o:1.0SiO
2(white carbon black): 0.60TEABr:1.6NH
4f.
Analyzing its structure through X-ray diffraction (Fig. 7) is F-ZSM-5 zeolite molecular sieve, and clearly can find out that what obtain is the block crystal grain of rectangular parallelepiped by stereoscan photograph (Fig. 8).Solid-state nuclear magnetic resonance
19the zeolite molecular sieve that F spectrum (Fig. 9) also demonstrates synthesis has the feature of F-ZSM-5 topology molecular sieve structure.
Embodiment 4: 4-propyl bromide is the F-ZSM-5 molecular sieve of directed agents solventless method solid phase synthesis containing aluminium
After being mixed with 1.22g anhydrous sodium metasilicate by the water of 0.54g, recrystallization forms the Starso containing three crystal water; Then under room temperature by 1.76g tri-hydrated sodium metasilicate and 0.56g white carbon black, 0.21g aluminum nitrate, 0.53g 4-propyl bromide, the mixing of 0.59g Neutral ammonium fluoride is placed in agate mortar, and grinding 5-10 minute, to mixing, again the mixture material after grinding is put into Glass tubing, with flame sealing; Finally the Glass tubing sealed is placed in 180 DEG C of baking oven crystallization after 4 weeks, reaction product is washed, be placed in 9,60 DEG C of baking ovens about a day little of complete drying, finally obtain product.The proportioning of reaction raw materials is as follows:
1.0Na
2siO
33H
2o:1.0SiO
2(white carbon black): 0.2Al (NO
3)
3: 0.2TPABr:1.6NH
4f.
Be F-ZSM-5 zeolite molecular sieve through X-ray diffraction analysis (Figure 10) its structure.And clearly can find out that what obtain is typical in F by stereoscan photograph (Figure 11)
-for the block crystal grain of the well-regulated hexagonal octahedron of the spined tool of band of mineralizer growth.Solid-state nuclear magnetic resonance
19the zeolite molecular sieve that F spectrum (Figure 12) also demonstrates synthesis has the feature of F-ZSM-5 topology molecular sieve structure.Solid-state nuclear magnetic resonance
27al spectrum (Figure 13) also demonstrates Al atom and well enters in framework of molecular sieve.
Embodiment 5: tetraethylammonium bromide is the F-ZSM-5 molecular sieve of directed agents solventless method solid phase synthesis containing aluminium
After being mixed with 1.22g Starso by the water of 0.54g, recrystallization forms the Starso containing three crystal water; Then under room temperature by 1.76g tri-hydrated sodium metasilicate and 0.56g white carbon black, 0.21g aluminum nitrate, 0.88g tetraethylammonium bromide, the mixing of 0.59g Neutral ammonium fluoride is placed in agate mortar, and grinding 5-10 minute, to mixing, again the mixture material after grinding is put into Glass tubing, with flame sealing; Finally the Glass tubing sealed is placed in 180 DEG C of baking oven crystallization after 4 weeks, reaction product is washed, be placed in 8,60 DEG C of baking ovens about a day little of complete drying, finally obtain product.The proportioning of reaction raw materials is as follows:
1.0Na
2siO
33H
2o:1.0SiO
2(white carbon black): 0.2Al (NO
3)
3: 0.6TEABr:1.6NH
4f.
Be F-ZSM-5 zeolite molecular sieve through X-ray diffraction analysis (Figure 14) its structure.And clearly can find out that what obtain is the block crystal grain of rectangular parallelepiped by stereoscan photograph (Figure 15).Solid-state nuclear magnetic resonance
19f spectrum (Figure 16) also illustrate that little F
-enter into the skeleton of molecular sieve; And at solid-state nuclear magnetic resonance
27it is also fewer that Al spectrum (Figure 17) also sees the amount that Al atom enters in the skeleton of molecular sieve, and this well describes F
-as the impact that mineralizer is introduced heteroatoms (as aluminium).
The above is only several embodiment of the present invention, not does any pro forma restriction to the present invention, although the present invention discloses as above with preferably case study on implementation, but and is not used to limit the present invention.According to any simple modification that technical spirit of the present invention is done case study on implementation, equivalent variations and modification, all still belong within the scope of technical solution of the present invention.
Claims (4)
1. a method for solid phase synthesis molecular sieve, it is using Neutral ammonium fluoride as mineralizer, using bromination organic formwork agent as directed agents; Synthetic method comprises the following steps: after being mixed with anhydrous sodium metasilicate by a certain amount of water, and recrystallization forms the Starso containing crystal water; Then at room temperature by a certain amount of Starso containing crystal water, white carbon black, Neutral ammonium fluoride, hexamethyl bromination two ammonium and/or aluminum nitrate, the mixture material after grinding to even, then is put into Glass tubing, with flame sealing by mixed grinding; The Glass tubing sealed is placed in 180 DEG C of baking oven crystallization at least 4 weeks, reaction product is washed, is placed in 60 DEG C of baking ovens to complete drying;
The mol ratio of reaction raw materials is:
1.0Na
2SiO
3·xH
2O：1.0SiO
2：0.15-0.25HMBr
2：1.2-1.8NH
4F
Above-mentioned SiO
2for white carbon black.
2. the method for solid phase synthesis molecular sieve according to claim 1, is characterized in that: described white carbon black is unbodied white carbon black, and in the Starso of recrystallization, the mole number of water is x=3-9.
3. the method for solid phase synthesis molecular sieve according to claim 1 and 2, is characterized in that: during grinding, raw material is placed in agate mortar, grinding 5-10 minute.
4. the method for solid phase synthesis molecular sieve according to claim 1 and 2, is characterized in that: in 60 DEG C of baking ovens to the complete drying time be 8-12 hours.
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| US10301185B2 (en) | 2014-10-15 | 2019-05-28 | Basf Se | Solidothermal synthesis of zeolitic materials and zeolites obtained therefrom |
| CN105271295A (en) * | 2015-11-25 | 2016-01-27 | 中国科学院武汉物理与数学研究所 | Method for preparing ITQ-13 molecular sieve by solvent-free synthesis |
| CN106082265B (en) * | 2016-06-24 | 2018-04-27 | 云南大学 | A kind of method with lignite synthesis in solid state ZSM-5 molecular sieve |
| CN106185974B (en) * | 2016-07-07 | 2019-02-05 | 昆明理工大学 | A kind of preparation method of titanium-silicon molecular sieve TS-1 |
| CN106185979B (en) * | 2016-07-07 | 2019-02-19 | 昆明理工大学 | A kind of preparation method of multi-stage porous ZSM-5 molecular sieve |
| CN106166500A (en) * | 2016-07-07 | 2016-11-30 | 昆明理工大学 | A kind of preparation method of the catalyst of catalytic decomposition methanthiol |
| KR20190052706A (en) * | 2016-09-27 | 2019-05-16 | 바스프 에스이 | High-efficiency solid-state thermal synthesis of zeolite materials |
| CN106698456B (en) * | 2017-01-06 | 2018-09-21 | 浙江大学 | The method of the line style polyquaternary amine alkali organic formwork agent one-step synthesis method molecular sieves of ITQ-13 containing aluminium |
| CN110270368B (en) * | 2018-03-14 | 2020-09-04 | 北京化工大学 | Method for synthesizing carbon-chemical embedded catalyst material by solution-free method |
| CN108163870B (en) * | 2018-03-16 | 2019-08-23 | 淮阴工学院 | It is the method that the agent of raw material slightly soluble prepares ZSM-5 zeolite with recessed soil |
| CN113526518B (en) * | 2020-04-17 | 2022-10-21 | 中国石油化工股份有限公司 | All-silicon molecular sieve with ITH structure and synthesis method thereof |
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