CN108928832A - Preparation method without germanium IWR zeolite molecular sieve - Google Patents
Preparation method without germanium IWR zeolite molecular sieve Download PDFInfo
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- CN108928832A CN108928832A CN201710361946.4A CN201710361946A CN108928832A CN 108928832 A CN108928832 A CN 108928832A CN 201710361946 A CN201710361946 A CN 201710361946A CN 108928832 A CN108928832 A CN 108928832A
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- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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Abstract
The present invention relates to a kind of preparation method of no germanium IWR zeolite molecular sieve, there is template used dose of IWR zeolite molecular sieve of synthesis and the problems such as Ge element be expensive and gained IWR zeolite molecular sieve structural stability is poor in the prior art of being solved.By the present invention in that use it is cheap, can be from the bursine of commercially available acquisition as organic formwork agent, according to bursine/SiO2=0.1~1.5, SiO2/B2O3=0.5~100, oxide/SiO of hetero atom metal W2=0~0.2, F‑/SiO2=0.1~1.5, H2O/SiO2=1~50 mole composition, obtains porous crystalline IWR zeolite molecular sieve for mixture hydrothermal crystallizing.The IWR zeolite molecular sieve stable structure that the present invention synthesizes；Synthesis range is wide, and operation is simple, is convenient for promoting.
Description
Technical field
The present invention relates to a kind of preparation methods of zeolite molecular sieve, more specifically to a kind of no germanium IWR zeolite point
The preparation method of son sieve.
Technical background
Zeolite molecular sieve is a kind of crystalline, porous silicate material, is widely used as adsorbent, ion-exchanger and industry
Catalyst.Currently, the topology molecular sieve structure checked and approved through International Molecular sieve association has had reached 231 kinds.
The molecular sieve of multidimensional cellular structure has diffusion advantage in catalysis reaction, and when the duct of all directions has difference
Pore size when, molecular sieve can show unique shape selective catalysis ability.From the point of view of petrochemical industry, 12 member rings ×
The molecular sieve of 10 membered ring channel structures has excellent catalytic properties in aromatic alkylated reaction.
The molecular sieves such as IWR zeolite molecular sieve and CIT, SSZ-26, SSZ-33 have identical periodical construction unit or
Stack layer, but the interlayer accumulation mode of several molecular sieves is different.In IWR molecular sieve, the accumulation mode of interlayer is AAA ...,
Produce 10 member ring straight hole roads along b axis direction with along c-axis direction 12 member ring straight hole roads, along a axis direction 12 member rings " word
The cross one another 3 D pore canal system in shape " duct.First IWR structure molecular screen being reported is ITQ-24, by Corma project
Group synthesizes to obtain (US 7344696B) by using hexamethylene bis (trimethylammonium) dication template, needs to introduce in synthesis
A large amount of Ge stablizes double four-membered ring (D4R) structural units present in IWR structure.Wu Peng et al. is disclosed using dimethyl six
The templates such as benzylidene amino synthesize the method (CN1328164C) of IWR structural zeolite molecular sieve ECNU-3, in the method equally
Introduce backbone element of a large amount of Ge as zeolite molecular sieve.
It has been used in the method for the above synthesis IWR zeolite molecular sieve and has been difficult to from commercially available acquisition, expensive template；
A large amount of Ge is introduced as backbone element, increases synthesis cost；The presence of Ge makes the structural stability of zeolite molecular sieve, especially
It is that hydrothermal stability substantially reduces, and is unfavorable for commercial introduction.
Summary of the invention
It is at high cost in the presence of template used dose of IWR zeolite molecular sieve of synthesis that the purpose of the present invention is to solve the prior arts
The problems such as high, Ge usage amount is big and gained IWR zeolite molecular sieve structural stability is poor provides a kind of IWR zeolite molecular sieve
Synthetic method, this method using it is cheap, can synthesize from the organic formwork agent of commercially available acquisition without germanium IWR zeolite molecular sieve, gained
IWR zeolite molecular sieve structural stability is good, the use of bursine is specifically that template is synthesized without germanium IWR zeolite molecules
Sieve.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
A kind of preparation method of no germanium IWR zeolite molecular sieve, includes the following steps：By silicon source, boron source, bursine,
Oxide, fluoride and the water of hetero atom metal elements W are according to bursine/SiO2=0.1~1.5, SiO2/B2O3=0.5
~100, oxide/SiO of hetero atom metal elements W2=0~0.2, F-/SiO2=0.1~1.5, H2O/SiO2=1~50
Molar ratio is uniformly mixed and obtains mixture；By said mixture hydrothermal crystallizing, crystallization product is obtained；To above-mentioned crystallization product into
Row washing, separation, drying and calcination operation.
In above-mentioned technical proposal, organic formwork agent bursine and SiO2Between molar ratio be bursine/
SiO2=0.2~1.0, more preferably ratio is bursine/SiO2=0.3~0.8.
In above-mentioned technical proposal, it is fixed that silicon source is selected from sodium metasilicate, waterglass, silica solution, solid silicone, gas-phase silica, nothing
At least one of shape silica, zeolite molecular sieve or organo-silicon ester.
In above-mentioned technical proposal, SiO2With B2O3Molar ratio be SiO2/B2O3=2~60, more preferably ratio is SiO2/
B2O3=10~50.
In above-mentioned technical proposal, boron source is selected from boric acid, sodium tetraborate, amorphous boron, potassium borate, kodalk, five
At least one of ammonium borate and organic boron ester.
In above-mentioned technical proposal, the oxide and SiO of hetero atom metal elements W2Between molar ratio be W oxidation
Object/SiO2=0~0.1, more preferably ratio is oxide/SiO of W2=0~0.05.
In above-mentioned technical proposal, hetero atom metallic element M include in Mg, Al, Ga, Fe, Zn, Sn, Ti, Zr, V extremely
Few one kind.
In above-mentioned technical proposal, the source of the oxide of hetero atom metal element A l include selected from sodium metaaluminate, aluminum sulfate,
At least one of aluminum nitrate, aluminium chloride, aluminium isopropoxide, boehmite, molecular sieve or amorphous alumina, the present invention one are real
It applies in example, zeolite molecular sieve is Beta molecular sieve；The source of the oxide of hetero atom metal element Ti includes being selected from titanium sulfate, nothing
Shape at least one of titanium dioxide, butyl titanate.
In above-mentioned technical proposal, fluoride and SiO2Between molar ratio be F-/SiO2=0.2~1.0, more preferably compare
Value is F-/SiO2=0.3~0.8.
In above-mentioned technical proposal, fluoride is selected from least one of hydrofluoric acid, ammonium fluoride, sodium fluoride, potassium fluoride.
In above-mentioned technical proposal, H in synthesis2O and SiO2Molar ratio be H2O/SiO2=2~20, more preferably ratio be
H2O/SiO2=3~15.
In above-mentioned technical proposal, crystallization temperature is 100~200 DEG C, and more preferably crystallization temperature is 135~180 DEG C；When crystallization
Between be 24~350 hours, more preferably crystallization time be 40~240 hours.
In above-mentioned technical proposal, above-mentioned crystallization product is washed, is separated, drying and calcination it is normal using this field
The washing of rule, separation, drying and calcination means.
Present invention firstly provides use the synthesis of bursine template to have organic formwork agent knot without germanium IWR molecular sieve
Structure is simple, raw material is easy to get, cheap advantage, and the prior art that compares has saved synthesis cost.Ge member is replaced using B element
Element plays the role of double quaternary ring structures in stable IWR molecular sieve, so as to avoid expensive Ge member is introduced in synthesis
Element.Use bursine for template, gained IWR zeolite molecular sieve structural stability is good.In addition, in bursine structure
Hydroxyl be conducive to the introducings of heteroatom elements, meet the needs of different catalysis reactions.Synthesis step of the present invention is simple, can operate
Property it is strong, synthesis range it is wide, be convenient for promoting.
Detailed description of the invention
Fig. 1 is obtained X-ray diffraction (XRD) figure of calcining sample by embodiment 1；
Fig. 2 is obtained scanning electron microscope (SEM) photo of calcining sample by embodiment 1；
Fig. 3 is obtained X-ray diffraction (XRD) figure of calcining sample by comparative example 3；
Fig. 4 is obtained X-ray diffraction (XRD) figure of calcining sample by comparative example 4；
Fig. 5 obtains X-ray diffraction (XRD) figure of calcining sample after water impregnates by comparative example 4.
Specific embodiment
In conjunction with following specific embodiments, the present invention is described in further detail, and of the invention protects content not limit to
In following embodiment.
【Embodiment 1】
By in the molten 2.693g 45wt% bursine aqueous solution of 0.25g boric acid, it is added 3g Ludox (HS-40,40%)
It stirs evenly, is eventually adding 1g 37%NH4F aqueous solution.Container opening is stirred overnight with volatile fraction water, until reaction is mixed
Close mole composition that object reaches final.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 168 in 170 DEG C of baking ovens
When.Solid is filtered, is washed with distilled water and obtains original powder solid after dry at 100 DEG C after reaction.Original powder solid is placed in horse
Not final products are obtained within roasting temperature 5 hours at 550 DEG C in furnace.Sample shows stable IWR structure, XRD after calcining
Map is as shown in Figure 1, SEM photograph is as shown in Figure 2.
The stability of IWR zeolite molecular sieve is analyzed as follows：Go the IWR molecular sieve after template agent removing normal 1g calcining
It is soaked under temperature in 30g water, soaking time is for 24 hours, to obtain solid through filtering and after 100 DEG C of dryings.Solid after water immersion
Compared with before immersion, crystal retention 95%.
【Embodiment 2】
By in the molten 2.693g 45wt% bursine aqueous solution of 0.6g boric acid, it is added 3g Ludox (HS-40,40%)
It stirs evenly, is eventually adding 1g 37%NH4F aqueous solution.Container opening is stirred overnight with volatile fraction water, until reaction is mixed
Close mole composition that object reaches final.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 120 in 170 DEG C of baking ovens
When.Obtained solid is IWR molecular sieve after solid is filtered, washed, is dried, calcined after reaction.
【Embodiment 3】
0.9g boric acid is dissolved in 2.693g 45wt% bursine aqueous solution, 4.16g tetraethyl orthosilicate is added
(TEOS) 1.2g 37%NH is added after hydrolysis completely4F aqueous solution.Container opening is stirred overnight with ethyl alcohol and the part water of volatilizing,
Until reaction mixture reaches final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 192 in 160 DEG C of baking ovens
When.Obtained solid is IWR molecular sieve after solid is filtered, washed, is dried, calcined after reaction.
【Embodiment 4】
0.05g boric acid is dissolved in 2.693g 45wt% bursine aqueous solution, it is equal that the stirring of 1.2g white carbon black is added
It is even, it is eventually adding 0.65g 37%NH4F aqueous solution.Container opening is stirred overnight with volatile fraction water, until reaction mixture
Reach final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 120 in 150 DEG C of baking ovens
When.Obtained solid is the IWR molecule of the molecular sieve impurity containing about 5%CDO after solid is filtered, washed, is dried, calcined after reaction
Sieve.
【Embodiment 5】
0.25g boric acid is dissolved in 4.31g 45wt% bursine aqueous solution, addition 3g Ludox (HS-40,
40%) it stirs evenly, container opening is stirred overnight with volatile fraction water.0.8g 40%HF solution is added, and regulating pondage is extremely
Reaction mixture reaches final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 120 in 170 DEG C of baking ovens
When.Obtained solid is IWR molecular sieve after solid is filtered, washed, is dried, calcined after reaction.
【Embodiment 6】
0.124g boric acid is dissolved in 1.616g 45wt% bursine aqueous solution, addition 3g Ludox (HS-40,
40%) it stirs evenly, container opening is stirred overnight with volatile fraction water.0.3g 40%HF solution is added, and regulating pondage is extremely
Reaction mixture reaches final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 192 in 170 DEG C of baking ovens
When.Obtained solid is IWR molecular sieve after solid is filtered, washed, is dried, calcined after reaction.
【Embodiment 7】
0.25g boric acid is dissolved in 2.693g 45wt% bursine aqueous solution, addition 3g Ludox (HS-40,
40%) it stirs evenly, is eventually adding 0.5g 37%NH4F aqueous solution and 0.25g 40%HF solution.Container opening is stirred
Night is with volatile fraction water, until reaction mixture reaches final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 72 in 170 DEG C of baking ovens
When.Obtained solid IWR molecular sieve after solid is filtered, washed, is dried, calcined after reaction.
【Embodiment 8】
0.381g sodium tetraborate is dissolved in 2.693g 45wt% bursine aqueous solution, 3g Ludox (HS- is added
40,40%) it stirs evenly, it is eventually adding 1g 37%NH4F aqueous solution.Container opening is stirred overnight with volatile fraction water, directly
Reach final mole composition to reaction mixture.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 192 in 180 DEG C of baking ovens
When.Obtained solid is IWR points of the molecular sieve impurity containing about 10%AST after solid is filtered, washed, is dried, calcined after reaction
Son sieve.
【Embodiment 9】
0.25g boric acid is dissolved in 2.693g 45wt% bursine aqueous solution, 4.16g tetraethyl orthosilicate is added
(TEOS) and the hydrolysis of 0.163g aluminium isopropoxide is complete, is eventually adding 1g 37%NH4F aqueous solution.By container opening be stirred overnight with
Volatilize ethyl alcohol, propyl alcohol and part water, until reaction mixture reaches final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 196 in 170 DEG C of baking ovens
When.Obtained solid is the molecular sieve of IWR containing aluminium, product SiO after solid is filtered, washed, is dried, calcined after reaction2/Al2O3=
60。
【Embodiment 10】
0.25g boric acid is dissolved in 2.693g 45wt% bursine aqueous solution, 1.2g white carbon black and 0.045g is added
Boehmite stirs evenly, and is eventually adding 1g 37%NH4F aqueous solution.Container opening is stirred overnight with volatile fraction water,
Until reaction mixture reaches final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 240 in 185 DEG C of baking ovens
When.Obtained solid is the molecular sieve of IWR containing aluminium, product SiO after solid is filtered, washed, is dried, calcined after reaction2/Al2O3=
75。
【Embodiment 11】
0.25g boric acid is dissolved in 2.693g 45wt% bursine aqueous solution, addition 1.6g Ludox (HS-40,
And 1.5g Beta molecular sieve (SiO 40%)2/Al2O3=25) it stirs evenly, is eventually adding 1g 37%NH4F aqueous solution.It will hold
Device opening is stirred overnight with volatile fraction water, until reaction mixture reaches final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 240 in 170 DEG C of baking ovens
When.Obtained solid is the molecular sieve of IWR containing aluminium, product SiO after solid is filtered, washed, is dried, calcined after reaction2/Al2O3=
34。
【Embodiment 12】
0.05g boric acid is dissolved in 2.693g 45wt% bursine aqueous solution, 1.2g white carbon black and 0.06g is added
Made calcined IWR molecular sieve in embodiment 1.It is stirring evenly and then adding into 1g 37%NH4F aqueous solution.Container opening is stirred
It mixes overnight with volatile fraction water, until reaction mixture reaches final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 168 in 170 DEG C of baking ovens
When.Obtained solid is the IWR molecular sieve without CDO molecular sieve impurity after solid is filtered, washed, is dried, calcined after reaction.
【Embodiment 13】
0.25g boric acid is dissolved in 2.693g 45wt% bursine aqueous solution, addition 3g Ludox (HS-40,
40%) it hydrolyzes and stirs evenly with 0.034g butyl titanate (TBOT), be eventually adding 1g 37%NH4F aqueous solution.By container
Opening is stirred overnight with butanol and the part water of volatilizing, until reaction mixture reaches final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 168 in 150 DEG C of baking ovens
When.Obtained solid is titaniferous IWR molecular sieve, Si/Ti=in product after solid is filtered, washed, is dried, calcined after reaction
240。
【Embodiment 14】
0.25g boric acid is dissolved in 3.232g 45wt% bursine aqueous solution, 4.16g tetraethyl orthosilicate is added
(TEOS) it hydrolyzes and stirs evenly with 0.085g butyl titanate (TBOT), be eventually adding 0.6g 37%NH4F aqueous solution and
0.3g 40%HF solution.Container opening is stirred overnight with the ethyl alcohol that volatilizees, butanol and part water, until reaction mixture reaches
Final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 168 in 150 DEG C of baking ovens
When.Obtained solid is titaniferous IWR molecular sieve, Si/Ti=in product after solid is filtered, washed, is dried, calcined after reaction
88。
【Comparative example 1】
0.25g boric acid is dissolved in 5.89g 25wt% tetraethyl ammonium hydroxide aqueous solution, addition 3g Ludox (HS-40,
40%) it stirs evenly, is eventually adding 1g 37%NH4F aqueous solution.Container opening is stirred overnight with volatile fraction water, until anti-
Mixture is answered to reach final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 168 in 170 DEG C of baking ovens
When.Obtained solid is BEC molecular sieve after solid is filtered, washed, is dried, calcined after reaction.
【Comparative example 2】
0.25g boric acid is dissolved in 3.65g 25wt% tetramethylammonium hydroxide aqueous solution, addition 3g Ludox (HS-40,
40%) it stirs evenly, is eventually adding 1g 37%NH4F aqueous solution.Container opening is stirred overnight with volatile fraction water, until anti-
Mixture is answered to reach final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 168 in 170 DEG C of baking ovens
When.Obtained solid is AST molecular sieve after solid is filtered, washed, is dried, calcined after reaction.
【Comparative example 3】
0.1g boric acid is dissolved in 10ml 0.5M hydroxide hexamethonium C6 solution, 4.16g tetraethyl orthosilicate is added
(TEOS) it stirs evenly, is eventually adding 1g 37%NH4F aqueous solution.Container opening is stirred overnight with ethyl alcohol and the part of volatilizing
Water, until reaction mixture reaches final mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 336 in 175 DEG C of baking ovens
When.Obtained solid is EUO molecular sieve after solid is filtered, washed, is dried, calcined after reaction, and XRD spectrum is as shown in Figure 3.
【Comparative example 4】
1.046g germanium oxide is dissolved in 30ml 0.5M hydroxide hexamethonium C6 solution, 4.16g tetraethyl orthosilicate is added
(TEOS), container opening is stirred overnight after hydrolysis completely with ethyl alcohol and the part water of volatilizing, until reaction mixture reaches final
Mole composition.
Said mixture is fitted into the crystallizing kettle with polytetrafluoroethyllining lining, it is small to be placed in crystallization 336 in 170 DEG C of baking ovens
When.Obtained solid is IWR molecular sieve after solid is filtered, washed, is dried, calcined after reaction, and XRD spectrum is as shown in Figure 4；Water
After middle immersion for 24 hours, framework of molecular sieve collapses, crystal retention<1%, XRD spectrum is as shown in Figure 5.
Claims (10)
1. a kind of preparation method of no germanium IWR zeolite molecular sieve, includes the following steps：
A) by silicon source, boron source, bursine, the oxide of hetero atom metal elements W, fluoride and water according to hydroxide gallbladder
Alkali/SiO2=0.1~1.5, SiO2/B2O3=0.5~100, oxide/SiO of hetero atom metal elements W2=0~0.2, F-/
SiO2=0.1~1.5, H2O/SiO2=1~50 molar ratio is uniformly mixed and obtains mixture；
B) said mixture hydrothermal crystallizing obtains crystallization product；
C) above-mentioned crystallization product washed, separated, drying and calcination operation.
2. the preparation method of no germanium IWR zeolite molecular sieve according to claim 1, it is characterised in that organic formwork agent hydrogen-oxygen
Change choline and SiO2Between molar ratio be bursine/SiO2=0.2~1.0.
3. the preparation method of no germanium IWR zeolite molecular sieve according to claim 1, it is characterised in that silicon source is selected from silicic acid
In sodium, waterglass, silica solution, solid silicone, gas-phase silica, amorphous silica, zeolite molecular sieve or organo-silicon ester
It is at least one；Boron source is selected from boric acid, sodium tetraborate, amorphous boron, potassium borate, kodalk, ammonium pentaborate and organic
At least one of boron ester.
4. the preparation method of no germanium IWR zeolite molecular sieve according to claim 1, it is characterised in that SiO2With B2O3Rub
Your ratio is SiO2/B2O3=2~60.
5. the preparation method of no germanium IWR zeolite molecular sieve according to claim 1, it is characterised in that hetero atom metallic element
W is selected from least one of Mg, Al, Ga, Fe, Zn, Sn, Ti, Zr, V.
6. the preparation method of no germanium IWR zeolite molecular sieve according to claim 1, it is characterised in that fluoride and SiO2It
Between molar ratio be F-/SiO2=0.2~1.0.
7. the preparation method of no germanium IWR zeolite molecular sieve according to claim 1, it is characterised in that fluoride is selected from hydrogen fluorine
At least one of acid, ammonium fluoride, sodium fluoride, potassium fluoride.
8. the preparation method of no germanium IWR zeolite molecular sieve according to claim 1, it is characterised in that H in synthesis2O and SiO2
Molar ratio be H2O/SiO2=2~20.
9. the preparation method of no germanium IWR zeolite molecular sieve according to claim 1, it is characterised in that reaction mixture exists
Hydrothermal crystallizing 20~350 hours at a temperature of 100~200 DEG C.
10. the synthesis of any one of claim 1-9 the method is used as catalytic cracking of hydrocarbon plus hydrogen without germanium IWR zeolite molecular sieve
Cracking, alkylating aromatic hydrocarbon, alkane isomerization, toluene disproportionation, dewaxing reaction, methanol-to-olefins, methanol aromatic hydrocarbons, esterification, acyl group
Change, alkene epoxidation, Baeyer-Villiger oxidation, Meerwein-Ponndorf-Verley reaction process catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710361946.4A CN108928832B (en) | 2017-05-22 | 2017-05-22 | Preparation method of germanium-free IWR zeolite molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710361946.4A CN108928832B (en) | 2017-05-22 | 2017-05-22 | Preparation method of germanium-free IWR zeolite molecular sieve |
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