CN106563497B - The preparation method of denatured ethanol olefin hydrocarbon molecules sieve catalysis - Google Patents
The preparation method of denatured ethanol olefin hydrocarbon molecules sieve catalysis Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of denatured ethanol olefin hydrocarbon molecules sieve catalysis, using TEOS as silicon source, aluminum nitrate is as silicon source, and pass through magnetization, oil bath heating synthesizes the H-type Sapo-5/MCM-41 composite molecular screen of new modification, its catalysis ethanol ethylene, ethanol conversion, ethylene selectivity are all very high.
Description
Technical field
The present invention relates to a kind of preparation methods of denatured ethanol olefin hydrocarbon molecules sieve catalysis, belong to catalyst technical field.
Background technique
Molecular sieve can be divided into micro porous molecular sieve (2 nm of <), mesopore molecular sieve (2~50 nm) by its pore size
With large pore molecular sieve (50 nm of >) three classes.Wherein, micro porous molecular sieve (such as HZSM-5) is due to tying in its unique crystal duct
The features such as structure, very strong acid and good hydrothermal stability, makes it have special " shape-selective " catalysis and adsorbing separation
Can, it is widely used during modern oil-refining chemical.But micro porous molecular sieve is due to the limitation in aperture, make macromolecular into
It is all relatively difficult to enter its duct and its duct of diffusion evolution, and diffusional resistance is also larger, to limit it in bulky molecular catalysis
Application in conversion.The invention of M41S race mesopore molecular sieve breaches the limitation of micropore size, can be the catalysis of macromolecular, inhale
It is attached to provide advantageous steric configuration with separating etc., but mesopore molecular sieve limits it because it is acid weaker and hydrothermal stability is poor
Industrial applicability.
Si-Al molecular sieve has stronger acid and special cellular structure, and ethyl alcohol can be realized at a lower temperature
Efficient Conversion.People have carried out extensive work around molecular sieve and its modified catalyst, and the molecular sieve being related to includes ZSM-5 points
Son sieve, 4A and its modified molecular screen.Transition metal or rare-earth metal modified sapo-5 molecular sieve etc..In recent years, people are in molecule
The fields such as sieve catalyst research and development and simulation calculating make great progress.Using sapo-5 molecular sieve as active component
Modified catalyst can show preferable producing ethylene from dehydration of ethanol performance under lower reaction temperature, and in a certain range
To industrial application, but people never stop the application study of molecular sieve ethanol dehydration catalyst.I am not now using
Same silicon source, silicon source, there are also synthetic methods to synthesize Sapo-5/MCM-41 composite molecular screen.
Summary of the invention
In view of the above existing problems in the prior art, the present invention provides a kind of systems of denatured ethanol olefin hydrocarbon molecules sieve catalysis
Preparation Method, using TEOS as silicon source, aluminum nitrate as silicon source synthesis modification H-type Sapo-5/MCM-41 composite molecular screen,
With preferable ethanol conversion.
To achieve the goals above, the technical solution adopted by the present invention is that:
Step 1, first by TEOS, aluminum nitrate, phosphoric acid 50 DEG C of water bath sonicator 2h removal of impurities under ultrasonic oscillation.
Step 2, the TEOS by removal of impurities, aluminum nitrate, deionized water 150 DEG C of stirring 2h under silica gel oil bath under magnetic stirring apparatus
Step 3 pre-processes triethylamine template by ultrasound, is added drop-wise in above-mentioned solution with 20 drop speed per minute,
And 2h is stirred under magnetic agitation
Step 4, phosphoric acid are added dropwise with the speed of 15 drop per minute, and side magnetic agitation, oil bath heating is added dropwise below.It stirs to solidifying
Glue.
Step 5, by coagulant liquid obtained under air atmosphere aging 12h.
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave
330kpa, 700 DEG C are reacted 72h crystallization under argon atmosphere.
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template
Agent obtains sapo-5 molecular sieve
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L are added by the quality of sapo-5 molecular sieve, turn after being sufficiently stirred
It moves to from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature.
A certain amount of template CTMAB and suitable quantity of water is added in step 9 after chilling under vigorous magnetic stirring condition, uses sulphur
Acid for adjusting pH value is to 9.20 h of thermostatic crystallization at 500 DEG C of temperature again, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve.
Step 10 answers prepared Jie's SAPO-5/MCM-5 micropore with ammonium nitrate solution (1 mol/L) using circumfluence method
It closes 1 h of molecular sieve reflux and carries out ion exchange, using filter, drying, roasting, molding is prepared for 50~60 mesh after repeating 2 times
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalyst
Beneficial effects of the present invention: composite molecular screen provided by the invention has following characteristics.SAPO-5 molecular sieve is to ethyl alcohol
The conversion ratio having had, MCM-5 have very high selectivity to ethylene, and the present invention combines the two advantage, have prepared selection
The composite molecular sieve catalyst of the very high producing ethylene from dehydration of ethanol of property.The present invention introduces H element by circumfluence method ammonium nitrate
During the preparation process by magnetic agitation, crystallization under argon atmosphere is calcined under sufficient air, these method of modifying make to be made
Composite catalyst catalytic effect greatly promote and greatly improve ethanol conversion, ethylene selectivity, which also significantly improves, to be matched
For TEOS, aluminum nitrate, phosphoric acid quality ratio is 2:1:1, deionized water 150ml, the hydrogen-oxygen of 2.0 mol/L of triethylamine 5ml, 20ml
Change sodium, composite catalyst catalytic effect obtained is best when 10mlCTMAB.
Specific embodiment
Implementation column 1 produces TEOS, aluminum nitrate, and phosphoric acid quality takes TEOS 10g, aluminum nitrate 10g, phosphorus than the sample for 1:1:1
Sour 10g, deionized water 150ml, 1 0mlCTMAB of sodium hydroxide of 2.0 mol/L of triethylamine 5ml, 20ml；
Step 1, first by 10gTEOS, 10g aluminum nitrate, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, the TEOS by removal of impurities, aluminum nitrate, 100ml deionized water is under magnetic stirring apparatus 150 DEG C under silica gel oil bath
Stir 2h；
Step 3 pre-processes 5ml triethylamine template by ultrasound, is added drop-wise to above-mentioned solution with 20 drop speed per minute
In, and 2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of 15 drop per minute, and side magnetic agitation, oil bath heating is added dropwise below.Stirring
To coagulant liquid；
Step 5, by coagulant liquid obtained under air atmosphere aging 12h；
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave and exists
330kpa, 700 DEG C are reacted 72h crystallization under argon atmosphere；
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template
Agent obtains sapo-5 molecular sieve；
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L of 20ml is added by the quality of sapo-5 molecular sieve, are sufficiently stirred
It is transferred to after mixing from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature；
10ml template CTMAB and 50ml deionized water is added in step 9 after chilling under vigorous magnetic stirring condition,
With sulphur acid for adjusting pH value to 9.20 h of thermostatic crystallization at 500 DEG C of temperature again, obtains compound point of Jie's sapo-5/MCM-41 micropore
Son sieve；
Step 10 answers prepared Jie's SAPO-5/MCM-5 micropore with ammonium nitrate solution (1 mol/L) using circumfluence method
It closes 1 h of molecular sieve reflux and carries out ion exchange, using filter, drying, roasting, molding is prepared for 50~60 mesh after repeating 2 times
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalyst.
Implementation column 2 produces TEOS, and aluminum nitrate, phosphoric acid quality is than the sample for 2:1:1.TEOS 20g, aluminum nitrate 10g are taken,
Phosphatase 11 0g, deionized water 150ml, the sodium hydroxide of 2.0 mol/L of triethylamine 5ml, 20ml, 10mlCTMAB.
Step 1, first by 20gTEOS, 10g aluminum nitrate, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, the TEOS by removal of impurities, aluminum nitrate, 100ml deionized water is under magnetic stirring apparatus 150 DEG C under silica gel oil bath
Stir 2h；
Step 3 pre-processes 5ml triethylamine template by ultrasound, is added drop-wise to above-mentioned solution with 20 drop speed per minute
In, and 2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of 15 drop per minute, and side magnetic agitation, oil bath heating is added dropwise below.Stirring
To coagulant liquid；
Step 5, by coagulant liquid obtained under air atmosphere aging 12h；
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave
330kp, 700 DEG C are reacted 72h crystallization under argon atmosphere；
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template
Agent obtains sapo-5 molecular sieve；
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L of 20ml is added by the quality of sapo-5 molecular sieve, are sufficiently stirred
It is transferred to after mixing from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature；
10ml template CTMAB and 50ml deionized water is added in step, 9 after chilling under vigorous magnetic stirring condition,
With sulphur acid for adjusting pH value to 9.20 h of thermostatic crystallization at 500 DEG C of temperature again, obtains compound point of Jie's sapo-5/MCM-41 micropore
Son sieve；
Step 10 answers prepared Jie's SAPO-5/MCM-5 micropore with ammonium nitrate solution (1 mol/L) using circumfluence method
It closes 1 h of molecular sieve reflux and carries out ion exchange, using filter, drying, roasting, molding is prepared for 50~60 mesh after repeating 2 times
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalyst.
Implementation column 3 produces TEOS, and aluminum nitrate, phosphoric acid quality is than the sample for 3:1:1.TEOS 30g, aluminum nitrate 10g are taken,
Phosphatase 11 0g, deionized water 150ml, 1 0mlCTMAB of sodium hydroxide of 2.0 mol/L of triethylamine 5ml, 20ml.
Step 1, first by 30gTEOS, 10g aluminum nitrate, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, the TEOS by removal of impurities, aluminum nitrate, 100ml deionized water is under magnetic stirring apparatus 150 DEG C under silica gel oil bath
Stir 2h；
Step 3 pre-processes 5ml triethylamine template by ultrasound, is added drop-wise to above-mentioned solution with 20 drop speed per minute
In, and 2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of 15 drop per minute, and side magnetic agitation, oil bath heating is added dropwise below.Stirring
To coagulant liquid；
Step 5, by coagulant liquid obtained under air atmosphere aging 12h；
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave
330kp, 700 DEG C are reacted 72h crystallization under argon atmosphere；
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template
Agent obtains sapo-5 molecular sieve；
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L of 20ml is added by the quality of sapo-5 molecular sieve, are sufficiently stirred
It is transferred to after mixing from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature；
10ml template CTMAB and 50ml deionized water is added in step, 9 after chilling under vigorous magnetic stirring condition,
With sulphur acid for adjusting pH value to 9.20 h of thermostatic crystallization at 500 DEG C of temperature again, obtains compound point of Jie's sapo-5/MCM-41 micropore
Son sieve；
Step 10 answers prepared Jie's SAPO-5/MCM-5 micropore with ammonium nitrate solution (1 mol/L) using circumfluence method
It closes 1 h of molecular sieve reflux and carries out ion exchange, using filter, drying, roasting, molding is prepared for 50~60 mesh after repeating 2 times
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalyst.
Implementation column 4 produces TEOS, and aluminum nitrate, phosphoric acid quality is than the sample for 1:2:1.TEOS 10g, aluminum nitrate 20g are taken,
Phosphatase 11 0g, deionized water 150ml, 1 0mlCTMAB of sodium hydroxide of 2.0 mol/L of triethylamine 5ml, 20ml.
Step 1, first by 10gTEOS, 20g aluminum nitrate, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, the TEOS by removal of impurities, aluminum nitrate, 100ml deionized water is under magnetic stirring apparatus 150 DEG C under silica gel oil bath
Stir 2h；
Step 3 pre-processes 5ml triethylamine template by ultrasound, is added drop-wise to above-mentioned solution with 20 drop speed per minute
In, and 2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of 15 drop per minute, and side magnetic agitation, oil bath heating is added dropwise below.Stirring
To coagulant liquid；
Step 5, by coagulant liquid obtained under air atmosphere aging 12h；
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave
330kp, 700 DEG C are reacted 72h crystallization under argon atmosphere；
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template
Agent obtains sapo-5 molecular sieve；
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L of 20ml is added by the quality of sapo-5 molecular sieve, are sufficiently stirred
It is transferred to after mixing from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature；
10ml template CTMAB and 50ml deionized water is added in step, 9 after chilling under vigorous magnetic stirring condition,
With sulphur acid for adjusting pH value to 9.20 h of thermostatic crystallization at 500 DEG C of temperature again, obtains compound point of Jie's sapo-5/MCM-41 micropore
Son sieve；
Step 10 answers prepared Jie's SAPO-5/MCM-5 micropore with ammonium nitrate solution (1 mol/L) using circumfluence method
It closes 1 h of molecular sieve reflux and carries out ion exchange, using filter, drying, roasting, molding is prepared for 50~60 mesh after repeating 2 times
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalyst.
Implementation column 5 produces TEOS, and aluminum nitrate, phosphoric acid quality is than the sample for 1:3:1.TEOS 10g, aluminum nitrate 10g are taken,
Phosphatase 11 0g, deionized water 150ml, 1 0mlCTMAB of sodium hydroxide of 2.0 mol/L of triethylamine 5ml, 20ml.
Step 1, first by 10gTEOS, 30g aluminum nitrate, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, the TEOS by removal of impurities, aluminum nitrate, 100ml deionized water is under magnetic stirring apparatus 150 DEG C under silica gel oil bath
Stir 2h；
Step 3 pre-processes 5ml triethylamine template by ultrasound, is added drop-wise to above-mentioned solution with 20 drop speed per minute
In, and 2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of 15 drop per minute, and side magnetic agitation, oil bath heating is added dropwise below.Stirring
To coagulant liquid；
Step 5, by coagulant liquid obtained under air atmosphere aging 12h；
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave
330kp, 700 DEG C are reacted 72h crystallization under argon atmosphere；
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template
Agent obtains sapo-5 molecular sieve；
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L of 20ml is added by the quality of sapo-5 molecular sieve, are sufficiently stirred
It is transferred to after mixing from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature；
10ml template CTMAB and 50ml deionized water is added in step, 9 after chilling under vigorous magnetic stirring condition,
With sulphur acid for adjusting pH value to 9.20 h of thermostatic crystallization at 500 DEG C of temperature again, obtains compound point of Jie's sapo-5/MCM-41 micropore
Son sieve；
Step 10 answers prepared Jie's SAPO-5/MCM-5 micropore with ammonium nitrate solution (1 mol/L) using circumfluence method
It closes 1 h of molecular sieve reflux and carries out ion exchange, using filter, drying, roasting, molding is prepared for 50~60 mesh after repeating 2 times
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalyst.
Implementation column 6 produces TEOS, and aluminum nitrate, phosphoric acid quality is than the sample for 1:1:2.TEOS 10g, aluminum nitrate 10g are taken,
Phosphatase 11 0g, deionized water 150ml, 1 0mlCTMAB of sodium hydroxide of 2.0 mol/L of triethylamine 5ml, 20ml.
Step 1, first by 10gTEOS, 10g aluminum nitrate, 20g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, the TEOS by removal of impurities, aluminum nitrate, 100ml deionized water is under magnetic stirring apparatus 150 DEG C under silica gel oil bath
Stir 2h；
Step 3 pre-processes 5ml triethylamine template by ultrasound, is added drop-wise to above-mentioned solution with 20 drop speed per minute
In, and 2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of 15 drop per minute, and side magnetic agitation, oil bath heating is added dropwise below.Stirring
To coagulant liquid；
Step 5, by coagulant liquid obtained under air atmosphere aging 12h；
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave
330kp, 700 DEG C are reacted 72h crystallization under argon atmosphere；
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template
Agent obtains sapo-5 molecular sieve；
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L of 20ml is added by the quality of sapo-5 molecular sieve, are sufficiently stirred
It is transferred to after mixing from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature；
10ml template CTMAB and 50ml deionized water is added in step, 9 after chilling under vigorous magnetic stirring condition,
With sulphur acid for adjusting pH value to 9.20 h of thermostatic crystallization at 500 DEG C of temperature again, obtains compound point of Jie's sapo-5/MCM-41 micropore
Son sieve；
Step 10 answers prepared Jie's SAPO-5/MCM-5 micropore with ammonium nitrate solution (1 mol/L) using circumfluence method
It closes 1 h of molecular sieve reflux and carries out ion exchange, using filter, drying, roasting, molding is prepared for 50~60 mesh after repeating 2 times
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalyst.
Implementation column 7 produces TEOS, and aluminum nitrate, phosphoric acid quality is than the sample for 1:1:3.TEOS 10g, aluminum nitrate 10g are taken,
Phosphoric acid 30g, deionized water 150ml, 1 0mlCTMAB of sodium hydroxide of 2.0 mol/L of triethylamine 5ml, 20ml.
Step 1, first by 10gTEOS, 10g aluminum nitrate, 30g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, the TEOS by removal of impurities, aluminum nitrate, 100ml deionized water is under magnetic stirring apparatus 150 DEG C under silica gel oil bath
Stir 2h；
Step 3 pre-processes 5ml triethylamine template by ultrasound, is added drop-wise to above-mentioned solution with 20 drop speed per minute
In, and 2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of 15 drop per minute, and side magnetic agitation, oil bath heating is added dropwise below.Stirring
To coagulant liquid；
Step 5, by coagulant liquid obtained under air atmosphere aging 12h；
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave
330kp, 700 DEG C are reacted 72h crystallization under argon atmosphere；
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template
Agent obtains sapo-5 molecular sieve；
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L of 20ml is added by the quality of sapo-5 molecular sieve, are sufficiently stirred
It is transferred to after mixing from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature；
10ml template CTMAB and 50ml deionized water is added in step, 9 after chilling under vigorous magnetic stirring condition,
With sulphur acid for adjusting pH value to 9.20 h of thermostatic crystallization at 500 DEG C of temperature again, obtains compound point of Jie's sapo-5/MCM-41 micropore
Son sieve；
Step 10 answers prepared Jie's SAPO-5/MCM-5 micropore with ammonium nitrate solution (1 mol/L) using circumfluence method
It closes 1 h of molecular sieve reflux and carries out ion exchange, using filter, drying, roasting, molding is prepared for 50~60 mesh after repeating 2 times
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalyst.
Implementation column 8 produces TEOS, and aluminum nitrate, phosphoric acid quality is than the sample for 1:1:1.Take TEOS 10g, aluminum nitrate 10g
Phosphatase 11 0g.1 0mlCTMAB of sodium hydroxide of 2.0 mol/L of deionized water 150ml, triethylamine 5ml, 20ml；
Step 1, first by 10gTEOS, 10g aluminum nitrate, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, the TEOS by removal of impurities, aluminum nitrate, the 150 DEG C of stirrings under silica gel oil bath under blender of 100ml deionized water
2h；
Step 3 pre-processes 5ml triethylamine template by ultrasound, is added drop-wise to above-mentioned solution with 20 drop speed per minute
In, and 2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of 15 drop per minute, and side stirring, oil bath heating is added dropwise below.It stirs to solidifying
Glue；
Step 5, by coagulant liquid obtained under air atmosphere aging 12h；
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave
330kpa, 700 DEG C are reacted 72h crystallization under argon atmosphere；
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template
Agent obtains sapo-5 molecular sieve；
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L of 20ml is added by the quality of sapo-5 molecular sieve, are sufficiently stirred
It is transferred to after mixing from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature；
10ml template CTMAB and 50ml deionized water is added in step, 9 after chilling under vigorous magnetic stirring condition,
With sulphur acid for adjusting pH value to 9.20 h of thermostatic crystallization at 500 DEG C of temperature again, obtains compound point of Jie's sapo-5/MCM-41 micropore
Son sieve；
Step 10 answers prepared Jie's SAPO-5/MCM-5 micropore with ammonium nitrate solution (1 mol/L) using circumfluence method
It closes 1 h of molecular sieve reflux and carries out ion exchange, using filter, drying, roasting, molding is prepared for 50~60 mesh after repeating 2 times
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalyst.
Implementation column 9 produces TEOS, and aluminum nitrate, phosphoric acid quality is than the sample for 1:2:1.Take TEOS 10g, aluminum nitrate 20g
Phosphatase 11 0g.1 0mlCTMAB of sodium hydroxide of 2.0 mol/L of deionized water 150ml, triethylamine 5ml, 20ml.
Step 1, first by 10gTEOS, 20g aluminum nitrate, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous;
2h is stirred at room temperature under magnetic stirring apparatus in step 2, the TEOS by removal of impurities, aluminum nitrate, 100ml deionized water;
Step 3 pre-processes 5ml triethylamine template by ultrasound, is added drop-wise to above-mentioned solution with 20 drop speed per minute
In, and 2h is stirred under magnetic stirring;
Step 4,10g phosphoric acid are added dropwise with the speed of 15 drop per minute, side magnetic agitation.It stirs to coagulant liquid;
Step 5, by coagulant liquid obtained under air atmosphere aging 12h;
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave
330kpa, 700 DEG C are reacted 72h crystallization under argon atmosphere;
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template
Agent obtains sapo-5 molecular sieve;
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L of 20ml is added by the quality of sapo-5 molecular sieve, are sufficiently stirred
It is transferred to after mixing from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature;
10ml template CTMAB and 50ml deionized water is added in step 9 after chilling under vigorous magnetic stirring condition,
With sulphur acid for adjusting pH value to 9.20 h of thermostatic crystallization at 500 DEG C of temperature again, obtains compound point of Jie's sapo-5/MCM-41 micropore
Son sieve;
Step 10 answers prepared Jie's SAPO-5/MCM-5 micropore with ammonium nitrate solution (1 mol/L) using circumfluence method
It closes 1 h of molecular sieve reflux and carries out ion exchange, using filter, drying, roasting, molding is prepared for 50~60 mesh after repeating 2 times
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalyst.
Implementation column 10 produces TEOS, and aluminum nitrate, phosphoric acid quality is than the sample for 1:3:1.TEOS 10g, aluminum nitrate 30g are taken,
Phosphatase 11 0g, deionized water 150ml, 1 0mlCTMAB of sodium hydroxide of 2.0 mol/L of triethylamine 5ml, 20ml.
Step 1, first by 10gTEOS, 30g aluminum nitrate, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, the TEOS by removal of impurities, aluminum nitrate, 100ml deionized water is under magnetic stirring apparatus 150 DEG C under silica gel oil bath
Stir 2h；
Step 3 pre-processes 5ml triethylamine template by ultrasound, is added drop-wise to above-mentioned solution with 20 drop speed per minute
In, and 2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of 15 drop per minute, and side magnetic agitation, oil bath heating is added dropwise below.Stirring
To coagulant liquid；
Step 5, by coagulant liquid obtained under air atmosphere aging 12h；
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave
330kpa, 700 DEG C are reacted 72h crystallization under atmosphere；
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template
Agent obtains sapo-5 molecular sieve；
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L of 20ml is added by the quality of sapo-5 molecular sieve, are sufficiently stirred
It is transferred to after mixing from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature；
10ml template CTMAB and 50ml deionized water is added in step 9 after chilling under vigorous magnetic stirring condition,
With sulphur acid for adjusting pH value to 9.20 h of thermostatic crystallization at 500 DEG C of temperature again, obtains compound point of Jie's sapo-5/MCM-41 micropore
Son sieve；
Step 10 answers prepared Jie's SAPO-5/MCM-5 micropore with ammonium nitrate solution (1 mol/L) using circumfluence method
It closes 1 h of molecular sieve reflux and carries out ion exchange, using filter, drying, roasting, molding is prepared for 50~60 mesh after repeating 2 times
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalyst.
The preparation and its performance evaluation of ethanol dehydration catalyst,
Ethanol dehydration reaction carries out in the stainless steel fixed-bed micro-reactor that internal diameter is 14 mm, product gas phase color
Spectrometer on-line analysis.Loaded catalyst is 2.0 g, and nitrogen is diluent, and ethyl alcohol molar fraction and air speed (WHSV) are respectively
30% and 0.5 h-1.
There are also ethylene selectivities for one ethanol conversion of table.
The result shows that when 2 catalytic effect of implementation column is best, it can be found that comparison implementation column 1,2,3. is identical when various operations
When, TEOS, aluminum nitrate, phosphoric acid quality than for 2:1:1 when.H-type SAPO-5/MCM-41 composite molecular sieve catalyst obtained
Catalytic effect is preferably that ethanol conversion is high, and ethylene selectivity is high.Implementation column Isosorbide-5-Nitrae is compared, 5 it can be found that TEOS, aluminum nitrate, phosphorus
H-type SAPO-5/MCM-41 composite molecular sieve catalyst catalytic effect obtained is best when sour mass ratio is 1:2:1, with nitric acid
The increase of aluminium or reduction catalytic effect can all reduce.Compare the increase system that implementation column 1,6,7 can be found that phosphoric acid ratio therewith
The H-type SAPO-5/MCM-41 composite molecular sieve catalyst catalytic effect obtained can reduce.Implementation column 1,8 is compared it can be found that in magnetic
The lower H-type SAPO-5/MCM-41 composite molecular sieve catalyst catalytic effect obtained of power stirring will be got well.Comparing implementation column 2,9 can be with
It was found that H-type SAPO-5/MCM-41 composite molecular sieve catalyst catalytic effect obtained will be significantly better than not existing under silica gel oil bath
It is obtained under silica gel oil bath.It compares implementation column 3,10 and can be found that the H-type made from high pressure reactor reaction under argon atmosphere
SAPO-5/MCM-41 composite molecular sieve catalyst catalytic effect will be got well.
Claims (1)
1. a kind of preparation method of denatured ethanol olefin hydrocarbon molecules sieve catalyst, which is characterized in that specific steps include following step
It is rapid:
Step 1, first by 20gTEOS, 10g aluminum nitrate, the 50 DEG C of water bath sonicator 2h removal of impurities under ultrasonic oscillation of 10g phosphoric acid；
Step 2, the TEOS by removal of impurities, aluminum nitrate, the 150 DEG C of stirrings under silica gel oil bath under magnetic stirring apparatus of 100ml deionized water
2h；
Step 3 pre-processes 5ml triethylamine template by ultrasound, is added drop-wise in above-mentioned solution with 20 drop speed per minute, and
2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of 15 drop per minute, and side magnetic agitation, oil bath heating side is added dropwise, stirring to gel
Liquid；
Step 5, by coagulant liquid obtained under air atmosphere aging 12h；
Step 6 pours into coagulant liquid in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave
330kpa, 700 DEG C are reacted 72h crystallization under argon atmosphere；
Then step 7 filters under vacuum pump, dry, finally calcines 8h under air atmosphere in Muffle furnace, removes template and obtains
To SAPO-5 molecular sieve；
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L of 20ml is added by the quality of SAPO-5 molecular sieve, after being sufficiently stirred
It is transferred to from booster reaction kettle, constant temperature handles 20 h at 150 DEG C of temperature；
10ml template CTMAB and 50ml deionized water is added in step 9 after chilling under vigorous magnetic stirring condition, uses sulphur
Acid for adjusting pH value obtains Jie's SAPO-5/MCM-41 mesoporous-microporous composite molecular to 9, then 20 h of thermostatic crystallization at 500 DEG C of temperature
Sieve；
Step 10, using circumfluence method with the ammonium nitrate solution of 1mol/L to prepared compound point of Jie's SAPO-5/MCM-41 micropore
1 h of son sieve reflux carries out ion exchange, and using filter, drying, roasting, molding is prepared for 50~60 mesh Hydrogens after repeating 2 times
SAPO-5/MCM-41 composite molecular sieve catalyst.
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