CN106563497A - Preparation method for modifying ethyl alcohol to prepare olefin by adopting molecular sieve to catalyze - Google Patents
Preparation method for modifying ethyl alcohol to prepare olefin by adopting molecular sieve to catalyze Download PDFInfo
- Publication number
- CN106563497A CN106563497A CN201610947599.9A CN201610947599A CN106563497A CN 106563497 A CN106563497 A CN 106563497A CN 201610947599 A CN201610947599 A CN 201610947599A CN 106563497 A CN106563497 A CN 106563497A
- Authority
- CN
- China
- Prior art keywords
- sapo
- under
- molecular sieve
- mcm
- teos
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 76
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title abstract description 31
- 235000019441 ethanol Nutrition 0.000 title abstract 4
- 150000001336 alkenes Chemical class 0.000 title abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 41
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 49
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 39
- 238000003760 magnetic stirring Methods 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 28
- 239000000701 coagulant Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000012298 atmosphere Substances 0.000 claims description 25
- 238000002425 crystallisation Methods 0.000 claims description 25
- 230000008025 crystallization Effects 0.000 claims description 25
- 239000003921 oil Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 24
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 24
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 22
- -1 denatured ethanol olefin hydrocarbon Chemical class 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 16
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 13
- 101100236724 Caenorhabditis elegans mcm-5 gene Proteins 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 13
- 239000012300 argon atmosphere Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000741 silica gel Substances 0.000 claims description 13
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229940075894 denatured ethanol Drugs 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 230000005415 magnetization Effects 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 7
- 239000005977 Ethylene Substances 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 20
- 239000002253 acid Substances 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000005864 Sulphur Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 8
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000003292 glue Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a preparation method for modifying ethyl alcohol to prepare olefin by adopting a molecular sieve to catalyze. The preparation method is characterized in that a TEOS is taken as a silicon source, and aluminum nitrate is taken as an aluminum source; and a novel modified H type Sapo-5/MCM-41 composite molecular sieve is synthesized by magnetizing and oil-bath heating. The composite molecular sieve is used for catalyzing alcohol to prepare olefin, so that an ethyl alcohol conversion rate is very high, and ethylene selectivity is very high.
Description
Technical field
The present invention relates to a kind of preparation method of denatured ethanol olefin hydrocarbon molecules sieve catalysis, belongs to catalyst technical field.
Background technology
Molecular sieve can be divided into micro porous molecular sieve (nm of ＜ 2), mesopore molecular sieve (2～50 nm) by its pore size
With large pore molecular sieve (nm of ＞ 50) three classes.Wherein, micro porous molecular sieve (such as HZSM-5) is due to its unique crystal duct knot
The features such as structure, very strong acid and good hydrothermal stability so as to 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 restriction in aperture, enter macromolecular
Enter its duct and its duct of diffusion effusion all relatively difficult, and diffusional resistance is also larger, so as to limit it in bulky molecular catalysis
Application in conversion.The invention of M41S races mesopore molecular sieve breaches the restriction of micropore size, can be the catalysis of macromolecular, inhale
It is attached to provide favourable steric configuration with separating etc., but mesopore molecular sieve limits it because its acidity is weaker and hydrothermal stability is poor
Industrial applicability.
Si-Al molecular sieve has stronger acidity and special pore passage structure, and ethanol is capable of achieving 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 point
Son sieve, 4A and its modified molecular screen.Transition metal or rare-earth metal modified sapo-5 molecular sieves etc..In recent years, people are in molecule
Sieve catalyst researchs and develops and simulates the fields such as calculating and achieves larger progress.With sapo-5 molecular sieves as active component
Modified catalyst can show preferable producing ethylene from dehydration of ethanol performance under relatively low reaction temperature, and obtain within the specific limits
To commercial Application, but application study of the people to molecular sieve ethanol dehydration catalyst never stops.I am not now using
With silicon source, silicon source, also synthetic method are synthesizing Sapo-5/MCM-41 composite molecular screens.
The content of the invention
For the problem that above-mentioned prior art is present, the present invention provides a kind of system of denatured ethanol olefin hydrocarbon molecules sieve catalysis
Preparation Method, by the use of TEOS as silicon source, aluminum nitrate as silicon source synthesis modification H type Sapo-5/MCM-41 composite molecular screens, its
With preferable ethanol conversion.
To achieve these goals, the technical solution used in the present invention is：
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, by the TEOS of removal of impurities, aluminum nitrate, deionized water 150 DEG C of stirring 2h under silica gel oil bath under magnetic stirring apparatus
Step 3, by triethylamine template through ultrasound pretreatment, be added drop-wise in above-mentioned solution with per minute 20 drop speed, and magnetic
The lower stirring 2h of power stirring
Step 4, phosphoric acid are added dropwise with the speed of per minute 15 drops, and side magnetic agitation, oil bath heating is added dropwise below.Stir to gel
Liquid.
Step 5, by obtained coagulant liquid under air atmosphere aging 12h.
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, be then placed in autoclave
330kpa, 700 DEG C are reacted 72h crystallization under argon atmosphere.
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template
Agent obtains sapo-5 molecular sieves
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L are added by the quality of sapo-5 molecular sieves, are transferred to after being sufficiently stirred for
From in booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature.
Step 9, Jing after chilling a certain amount of template CTMAB and suitable quantity of water are added under vigorous magnetic stirring condition, use sulphur
Acid for adjusting pH value is to 9.Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve.
Step 10, using circumfluence method ammonium nitrate solution（1 mol/L）It is multiple to prepared Jie's SAPO-5/MCM-5 micropore
Closing molecular sieve 1 h of backflow carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh
Hydrogen SAPO-5/MCM-41 composite molecular sieve catalysts.
Beneficial effects of the present invention：The composite molecular screen that the present invention is provided has following characteristics.SAPO-5 molecular sieves have to ethanol
Conversion ratio, MCM-5 has very high selectivity to ethene, and the present invention combines the two advantage, prepared it is selective very
The composite molecular sieve catalyst of high producing ethylene from dehydration of ethanol.The present invention is introduced H element and is existed by circumfluence method ammonium nitrate,
By magnetic agitation in preparation process, crystallization under argon atmosphere is calcined under sufficient air, and these method of modifying make obtained compound
Catalyst effect is greatly promoted and greatly improves ethanol conversion, and ethylene selectivity also significantly improves and is in proportioning
TEOS, aluminum nitrate, phosphoric acid quality ratio is 2:1:1, deionized water 150ml, the hydroxide of triethylamine 5ml, 20ml 2.0 mol/L
Sodium, obtained composite catalyst catalytic effect is best during 10mlCTMAB.
Specific embodiment
Implement row 1 and produce TEOS, aluminum nitrate, phosphoric acid quality ratio is 1:1:1 sample, takes TEOS 10g, aluminum nitrate 10g, phosphorus
Sour 10g, deionized water 150ml, the 0mlCTMAB of NaOH 1 of triethylamine 5ml, 20ml 2.0 mol/L；
Step 1, first by 10gTEOS, 10g aluminum nitrates, the 50 DEG C of water bath sonicator 2h removal of impurities under ultrasonic oscillation of 10g phosphoric acid；
Step 2, by the TEOS of removal of impurities, aluminum nitrate, the 150 DEG C of stirrings under silica gel oil bath under magnetic stirring apparatus of 100ml deionized waters
2h；
Step 3, by 5ml triethylamines template through ultrasound pretreatment, with per minute 20 drop speed be added drop-wise in above-mentioned solution, and
2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of per minute 15 drops, and side magnetic agitation, oil bath heating is added dropwise below.Stir to solidifying
Glue；
Step 5, by obtained coagulant liquid under air atmosphere aging 12h；
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in autoclave in 330kpa,
700 DEG C are reacted 72h crystallization under argon atmosphere；
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template and obtain
To sapo-5 molecular sieves；
Step 8, the sodium hydrate aqueous solution that the mol/L of 20ml 2.0 are added by the quality of sapo-5 molecular sieves, after being sufficiently stirred for
It is transferred to from booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature；
Step 9, Jing after chilling under vigorous magnetic stirring condition add 10ml template CTMAB and 50ml deionized waters, use sulphur
Acid for adjusting pH value is to 9.Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve；
Step 10, using circumfluence method ammonium nitrate solution（1 mol/L）It is compound to prepared Jie's SAPO-5/MCM-5 micropore to divide
Son sieve 1 h of backflow carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh Hydrogens
SAPO-5/MCM-41 composite molecular sieve catalysts.
Implement row 2 and produce TEOS, aluminum nitrate, phosphoric acid quality ratio is 2:1:1 sample.TEOS 20g, aluminum nitrate 10g are taken,
Phosphatase 11 0g, deionized water 150ml, the NaOH of triethylamine 5ml, 20ml 2.0 mol/L, 10mlCTMAB.
Step 1, first by 20gTEOS, 10g aluminum nitrates, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, by the TEOS of removal of impurities, aluminum nitrate, the 150 DEG C of stirrings under silica gel oil bath under magnetic stirring apparatus of 100ml deionized waters
2h；
Step 3, by 5ml triethylamines template through ultrasound pretreatment, with per minute 20 drop speed be added drop-wise in above-mentioned solution, and
2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of per minute 15 drops, and side magnetic agitation, oil bath heating is added dropwise below.Stir to solidifying
Glue；
Step 5, by obtained coagulant liquid under air atmosphere aging 12h；
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in 330kp in autoclave,
700 DEG C are reacted 72h crystallization under argon atmosphere；
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template and obtain
To sapo-5 molecular sieves；
Step 8, the sodium hydrate aqueous solution that the mol/L of 20ml 2.0 are added by the quality of sapo-5 molecular sieves, after being sufficiently stirred for
It is transferred to from booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature；
Step, 9 add 10ml template CTMAB and 50ml deionized waters Jing after chilling under vigorous magnetic stirring condition, use sulphur
Acid for adjusting pH value is to 9.Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve；
Step 10, using circumfluence method ammonium nitrate solution（1 mol/L）It is compound to prepared Jie's SAPO-5/MCM-5 micropore to divide
Son sieve 1 h of backflow carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh Hydrogens
SAPO-5/MCM-41 composite molecular sieve catalysts.
Implement row 3 and produce TEOS, aluminum nitrate, phosphoric acid quality ratio is 3:1:1 sample.TEOS 30g, aluminum nitrate 10g are taken,
Phosphatase 11 0g, deionized water 150ml, the 0mlCTMAB of NaOH 1 of triethylamine 5ml, 20ml 2.0 mol/L.
Step 1, first by 30gTEOS, 10g aluminum nitrates, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, by the TEOS of removal of impurities, aluminum nitrate, the 150 DEG C of stirrings under silica gel oil bath under magnetic stirring apparatus of 100ml deionized waters
2h；
Step 3, by 5ml triethylamines template through ultrasound pretreatment, with per minute 20 drop speed be added drop-wise in above-mentioned solution, and
2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of per minute 15 drops, and side magnetic agitation, oil bath heating is added dropwise below.Stir to solidifying
Glue；
Step 5, by obtained coagulant liquid under air atmosphere aging 12h；
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in 330kp in autoclave,
700 DEG C are reacted 72h crystallization under argon atmosphere；
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template and obtain
To sapo-5 molecular sieves；
Step 8, the sodium hydrate aqueous solution that the mol/L of 20ml 2.0 are added by the quality of sapo-5 molecular sieves, after being sufficiently stirred for
It is transferred to from booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature；
Step, 9 add 10ml template CTMAB and 50ml deionized waters Jing after chilling under vigorous magnetic stirring condition, use sulphur
Acid for adjusting pH value is to 9.Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve；
Step 10, using circumfluence method ammonium nitrate solution（1 mol/L）It is compound to prepared Jie's SAPO-5/MCM-5 micropore to divide
Son sieve 1 h of backflow carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh Hydrogens
SAPO-5/MCM-41 composite molecular sieve catalysts.
Implement row 4 and produce TEOS, aluminum nitrate, phosphoric acid quality ratio is 1:2:1 sample.TEOS 10g, aluminum nitrate 20g are taken,
Phosphatase 11 0g, deionized water 150ml, the 0mlCTMAB of NaOH 1 of triethylamine 5ml, 20ml 2.0 mol/L.
Step 1, first by 10gTEOS, 20g aluminum nitrates, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, by the TEOS of removal of impurities, aluminum nitrate, the 150 DEG C of stirrings under silica gel oil bath under magnetic stirring apparatus of 100ml deionized waters
2h；
Step 3, by 5ml triethylamines template through ultrasound pretreatment, with per minute 20 drop speed be added drop-wise in above-mentioned solution, and
2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of per minute 15 drops, and side magnetic agitation, oil bath heating is added dropwise below.Stir to solidifying
Glue；
Step 5, by obtained coagulant liquid under air atmosphere aging 12h；
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in 330kp in autoclave,
700 DEG C are reacted 72h crystallization under argon atmosphere；
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template and obtain
To sapo-5 molecular sieves；
Step 8, the sodium hydrate aqueous solution that the mol/L of 20ml 2.0 are added by the quality of sapo-5 molecular sieves, after being sufficiently stirred for
It is transferred to from booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature；
Step, 9 add 10ml template CTMAB and 50ml deionized waters Jing after chilling under vigorous magnetic stirring condition, use sulphur
Acid for adjusting pH value is to 9.Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve；
Step 10, using circumfluence method ammonium nitrate solution（1 mol/L）It is compound to prepared Jie's SAPO-5/MCM-5 micropore to divide
Son sieve 1 h of backflow carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh Hydrogens
SAPO-5/MCM-41 composite molecular sieve catalysts.
Implement row 5 and produce TEOS, aluminum nitrate, phosphoric acid quality ratio is 1:3:1 sample.TEOS 10g, aluminum nitrate 10g are taken,
Phosphatase 11 0g, deionized water 150ml, the 0mlCTMAB of NaOH 1 of triethylamine 5ml, 20ml 2.0 mol/L.
Step 1, first by 10gTEOS, 30g aluminum nitrates, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, by the TEOS of removal of impurities, aluminum nitrate, the 150 DEG C of stirrings under silica gel oil bath under magnetic stirring apparatus of 100ml deionized waters
2h；
Step 3, by 5ml triethylamines template through ultrasound pretreatment, with per minute 20 drop speed be added drop-wise in above-mentioned solution, and
2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of per minute 15 drops, and side magnetic agitation, oil bath heating is added dropwise below.Stir to solidifying
Glue；
Step 5, by obtained coagulant liquid under air atmosphere aging 12h；
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in 330kp in autoclave,
700 DEG C are reacted 72h crystallization under argon atmosphere；
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template and obtain
To sapo-5 molecular sieves；
Step 8, the sodium hydrate aqueous solution that the mol/L of 20ml 2.0 are added by the quality of sapo-5 molecular sieves, after being sufficiently stirred for
It is transferred to from booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature；
Step, 9 add 10ml template CTMAB and 50ml deionized waters Jing after chilling under vigorous magnetic stirring condition, use sulphur
Acid for adjusting pH value is to 9.Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve；
Step 10, using circumfluence method ammonium nitrate solution（1 mol/L）It is compound to prepared Jie's SAPO-5/MCM-5 micropore to divide
Son sieve 1 h of backflow carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh Hydrogens
SAPO-5/MCM-41 composite molecular sieve catalysts.
Implement row 6 and produce TEOS, aluminum nitrate, phosphoric acid quality ratio is 1:1:2 sample.TEOS 10g, aluminum nitrate 10g are taken,
Phosphatase 11 0g, deionized water 150ml, the 0mlCTMAB of NaOH 1 of triethylamine 5ml, 20ml 2.0 mol/L.
Step 1, first by 10gTEOS, 10g aluminum nitrates, 20g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, by the TEOS of removal of impurities, aluminum nitrate, the 150 DEG C of stirrings under silica gel oil bath under magnetic stirring apparatus of 100ml deionized waters
2h；
Step 3, by 5ml triethylamines template through ultrasound pretreatment, with per minute 20 drop speed be added drop-wise in above-mentioned solution, and
2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of per minute 15 drops, and side magnetic agitation, oil bath heating is added dropwise below.Stir to solidifying
Glue；
Step 5, by obtained coagulant liquid under air atmosphere aging 12h；
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in 330kp in autoclave,
700 DEG C are reacted 72h crystallization under argon atmosphere；
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template and obtain
To sapo-5 molecular sieves；
Step 8, the sodium hydrate aqueous solution that the mol/L of 20ml 2.0 are added by the quality of sapo-5 molecular sieves, after being sufficiently stirred for
It is transferred to from booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature；
Step, 9 add 10ml template CTMAB and 50ml deionized waters Jing after chilling under vigorous magnetic stirring condition, use sulphur
Acid for adjusting pH value is to 9.Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve；
Step 10, using circumfluence method ammonium nitrate solution（1 mol/L）It is compound to prepared Jie's SAPO-5/MCM-5 micropore to divide
Son sieve 1 h of backflow carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh Hydrogens
SAPO-5/MCM-41 composite molecular sieve catalysts.
Implement row 7 and produce TEOS, aluminum nitrate, phosphoric acid quality ratio is 1:1:3 sample.TEOS 10g, aluminum nitrate 10g are taken,
Phosphoric acid 30g, deionized water 150ml, the 0mlCTMAB of NaOH 1 of triethylamine 5ml, 20ml 2.0 mol/L.
Step 1, first by 10gTEOS, 10g aluminum nitrates, 30g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, by the TEOS of removal of impurities, aluminum nitrate, the 150 DEG C of stirrings under silica gel oil bath under magnetic stirring apparatus of 100ml deionized waters
2h；
Step 3, by 5ml triethylamines template through ultrasound pretreatment, with per minute 20 drop speed be added drop-wise in above-mentioned solution, and
2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of per minute 15 drops, and side magnetic agitation, oil bath heating is added dropwise below.Stir to solidifying
Glue；
Step 5, by obtained coagulant liquid under air atmosphere aging 12h；
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in 330kp in autoclave,
700 DEG C are reacted 72h crystallization under argon atmosphere；
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template and obtain
To sapo-5 molecular sieves；
Step 8, the sodium hydrate aqueous solution that the mol/L of 20ml 2.0 are added by the quality of sapo-5 molecular sieves, after being sufficiently stirred for
It is transferred to from booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature；
Step, 9 add 10ml template CTMAB and 50ml deionized waters Jing after chilling under vigorous magnetic stirring condition, use sulphur
Acid for adjusting pH value is to 9.Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve；
Step 10, using circumfluence method ammonium nitrate solution（1 mol/L）It is compound to prepared Jie's SAPO-5/MCM-5 micropore to divide
Son sieve 1 h of backflow carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh Hydrogens
SAPO-5/MCM-41 composite molecular sieve catalysts.
Implement row 8 and produce TEOS, aluminum nitrate, phosphoric acid quality ratio is 1:1:1 sample.Take TEOS 10g, aluminum nitrate 10g
Phosphatase 11 0g.Deionized water 150ml, the 0mlCTMAB of NaOH 1 of triethylamine 5ml, 20ml 2.0 mol/L；
Step 1, first by 10gTEOS, 10g aluminum nitrates, the 50 DEG C of water bath sonicator 2h removal of impurities under ultrasonic oscillation of 10g phosphoric acid；
Step 2, by the TEOS of removal of impurities, aluminum nitrate, 100ml deionized waters 150 DEG C of stirring 2h under silica gel oil bath under agitator；
Step 3, by 5ml triethylamines template through ultrasound pretreatment, with per minute 20 drop speed be added drop-wise in above-mentioned solution, and
2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of per minute 15 drops, and side stirring, oil bath heating is added dropwise below.Stir to coagulant liquid；
Step 5, by obtained coagulant liquid under air atmosphere aging 12h；
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, be then placed in autoclave
330kpa, 700 DEG C are reacted 72h crystallization under argon atmosphere；
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template and obtain
To sapo-5 molecular sieves；
Step 8, the sodium hydrate aqueous solution that the mol/L of 20ml 2.0 are added by the quality of sapo-5 molecular sieves, after being sufficiently stirred for
It is transferred to from booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature；
Step, 9 add 10ml template CTMAB and 50ml deionized waters Jing after chilling under vigorous magnetic stirring condition, use sulphur
Acid for adjusting pH value is to 9.Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve；
Step 10, using circumfluence method ammonium nitrate solution（1 mol/L）It is compound to prepared Jie's SAPO-5/MCM-5 micropore to divide
Son sieve 1 h of backflow carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh Hydrogens
SAPO-5/MCM-41 composite molecular sieve catalysts.
Implement row 9 and produce TEOS, aluminum nitrate, phosphoric acid quality ratio is 1:2:1 sample.Take TEOS 10g, aluminum nitrate 20g
Phosphatase 11 0g.Deionized water 150ml, the 0mlCTMAB of NaOH 1 of triethylamine 5ml, 20ml 2.0 mol/L.
Step 1, first by 10gTEOS, 20g aluminum nitrates, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous;
Step 2, by the TEOS of removal of impurities, aluminum nitrate, 100ml deionized waters are stirred at room temperature 2h under magnetic stirring apparatus;
Step 3, by 5ml triethylamines template through ultrasound pretreatment, with per minute 20 drop speed be added drop-wise in above-mentioned solution, and
2h is stirred under magnetic stirring;
Step 4,10g phosphoric acid are added dropwise with the speed of per minute 15 drops, side magnetic agitation.Stir to coagulant liquid;
Step 5, by obtained coagulant liquid under air atmosphere aging 12h;
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, be then placed in autoclave
330kpa, 700 DEG C are reacted 72h crystallization under argon atmosphere;
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template and obtain
To sapo-5 molecular sieves;
Step 8, the sodium hydrate aqueous solution that the mol/L of 20ml 2.0 are added by the quality of sapo-5 molecular sieves, after being sufficiently stirred for
It is transferred to from booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature;
Step 9, Jing after chilling under vigorous magnetic stirring condition add 10ml template CTMAB and 50ml deionized waters, use sulphur
Acid for adjusting pH value is to 9.Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve;
Step 10, using circumfluence method ammonium nitrate solution（1 mol/L）It is compound to prepared Jie's SAPO-5/MCM-5 micropore to divide
Son sieve 1 h of backflow carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh Hydrogens
SAPO-5/MCM-41 composite molecular sieve catalysts.
Implement row 10 and produce TEOS, aluminum nitrate, phosphoric acid quality ratio is 1:3:1 sample.TEOS 10g, aluminum nitrate 30g are taken,
Phosphatase 11 0g, deionized water 150ml, the 0mlCTMAB of NaOH 1 of triethylamine 5ml, 20ml 2.0 mol/L.
Step 1, first by 10gTEOS, 30g aluminum nitrates, 10g phosphoric acid 50 DEG C of water bath sonicator 2h under ultrasonic oscillation are removed
It is miscellaneous；
Step 2, by the TEOS of removal of impurities, aluminum nitrate, the 150 DEG C of stirrings under silica gel oil bath under magnetic stirring apparatus of 100ml deionized waters
2h；
Step 3, by 5ml triethylamines template through ultrasound pretreatment, with per minute 20 drop speed be added drop-wise in above-mentioned solution, and
2h is stirred under magnetic stirring；
Step 4,10g phosphoric acid are added dropwise with the speed of per minute 15 drops, and side magnetic agitation, oil bath heating is added dropwise below.Stir to solidifying
Glue；
Step 5, by obtained coagulant liquid under air atmosphere aging 12h；
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, be then placed in autoclave
330kpa, 700 DEG C are reacted 72h crystallization under atmosphere；
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template and obtain
To sapo-5 molecular sieves；
Step 8, the sodium hydrate aqueous solution that the mol/L of 20ml 2.0 are added by the quality of sapo-5 molecular sieves, after being sufficiently stirred for
It is transferred to from booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature；
Step 9, Jing after chilling under vigorous magnetic stirring condition add 10ml template CTMAB and 50ml deionized waters, use sulphur
Acid for adjusting pH value is to 9.Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular
Sieve；
Step 10, using circumfluence method ammonium nitrate solution（1 mol/L）It is compound to prepared Jie's SAPO-5/MCM-5 micropore to divide
Son sieve 1 h of backflow carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh Hydrogens
SAPO-5/MCM-41 composite molecular sieve catalysts.
The preparation of ethanol dehydration catalyst and its performance evaluation,
Ethanol dehydration reaction is carried out in the stainless steel fixed-bed micro-reactor that internal diameter is 14 mm, product gas chromatograph
On-line analysis.Loaded catalyst is 2.0 g, and nitrogen is diluent, ethanol molar fraction and air speed（WHSV）Respectively 30% He
0.5 h-1.
The ethanol conversion of table one also has ethylene selectivity.
As a result show best when the catalytic effect of row 2 is implemented, it can be found that row 1,2 are implemented in contrast, 3. when various operations are identical,
TEOS, aluminum nitrate, phosphoric acid quality ratio is 2:1:1 when.Obtained H types SAPO-5/MCM-41 composite molecular sieve catalyst catalysis
Effect is preferably that ethanol conversion is high, and ethylene selectivity is high.Row Isosorbide-5-Nitrae is implemented in contrast, and 5 it can be found that TEOS, aluminum nitrate, phosphoric acid matter
Amount is than being 1:2:Obtained H types SAPO-5/MCM-41 composite molecular sieve catalyst catalytic effect is best when 1, with aluminum nitrate
Increasing or reduce catalytic effect all can reduce.Contrast implements row 1,6,7 and can be found that H obtained in the increase of phosphoric acid ratio therewith
Type SAPO-5/MCM-41 composite molecular sieve catalyst catalytic effect can be reduced.Contrast implements row 1,8 it can be found that stirring in magnetic force
Mixing lower obtained H type SAPO-5/MCM-41 composite molecular sieve catalysts catalytic effect will get well.Contrast is implemented row 2,9 and is can be found that
Obtained H types SAPO-5/MCM-41 composite molecular sieve catalyst catalytic effect will be significantly better than not in silica gel under silica gel oil bath
It is obtained under oil bath.Row 3,10 are implemented in contrast it can be found that autoclave reacts obtained H types SAPO-5/ under argon atmosphere
MCM-41 composite molecular sieve catalysts catalytic effect will get well.
Claims (2)
1. the preparation method that a kind of denatured ethanol olefin hydrocarbon molecules sieve is catalyzed, it is characterised in that using TEOS as silicon source, aluminum nitrate
As silicon source, and by magnetization, oil bath heating synthesizes new modified H type Sapo-5/MCM-41 composite molecular screens.
2. the preparation method that denatured ethanol olefin hydrocarbon molecules sieve according to claim 1 is catalyzed, it is characterised in that concrete step
Suddenly include：
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, by the TEOS of removal of impurities, aluminum nitrate, deionized water 150 DEG C of stirring 2h under silica gel oil bath under magnetic stirring apparatus,
Step 3, by triethylamine template through ultrasound pretreatment, with per minute 20 drop speed be added drop-wise in above-mentioned solution, and
2h is stirred under magnetic agitation,
Step 4, phosphoric acid are added dropwise with the speed of per minute 15 drops, and side magnetic agitation, oil bath heating is added dropwise below,
Stir to coagulant liquid,
Step 5, by obtained coagulant liquid under air atmosphere aging 12h,
Step 6, coagulant liquid is poured in the bottle of polytetrafluoroethylene (PTFE) by flow diverter, is then placed in 330kp in autoclave,
700 DEG C are reacted 72h crystallization under argon atmosphere,
Step 7 and then the filtration under vavuum pump, are dried, and finally calcine 8h under air atmosphere in Muffle furnace, remove template and obtain
To sapo-5 molecular sieves,
Step 8, the sodium hydrate aqueous solution that 2.0 mol/L are added by the quality of sapo-5 molecular sieves, are transferred to after being sufficiently stirred for
From in booster reaction kettle, constant temperature processes 20 h at 150 DEG C of temperature,
Step 9, Jing after chilling a certain amount of template CTMAB and suitable quantity of water are added under vigorous magnetic stirring condition, adjusted with sulfuric acid
PH values are saved to 9,
Again the h of thermostatic crystallization 20 at 500 DEG C of temperature, obtains Jie's sapo-5/MCM-41 mesoporous-microporous composite molecular sieve,
Step 10, using circumfluence method ammonium nitrate solution to prepared Jie's SAPO-5/MCM-5 mesoporous-microporous composite molecular sieve backflow 1
H carries out ion exchange, then Jing filtrations, drying, roasting, repeats 2 aftershapings and is prepared for 50～60 mesh Hydrogen SAPO-5/
MCM-41 composite molecular sieve catalysts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610947599.9A CN106563497B (en) | 2016-10-26 | 2016-10-26 | The preparation method of denatured ethanol olefin hydrocarbon molecules sieve catalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610947599.9A CN106563497B (en) | 2016-10-26 | 2016-10-26 | The preparation method of denatured ethanol olefin hydrocarbon molecules sieve catalysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106563497A true CN106563497A (en) | 2017-04-19 |
| CN106563497B CN106563497B (en) | 2019-05-03 |
Family
ID=58536603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610947599.9A Active CN106563497B (en) | 2016-10-26 | 2016-10-26 | The preparation method of denatured ethanol olefin hydrocarbon molecules sieve catalysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106563497B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172243A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Mesoporous material/micropore molecular sieve composite material and preparation method thereof |
| CN102274748A (en) * | 2011-06-21 | 2011-12-14 | 西北大学 | Catalyst of conversion of ethanol to propylene and propane, preparation method thereof and application thereof |
| CN102380415A (en) * | 2011-09-04 | 2012-03-21 | 西北大学 | Catalyst for preparing methylbenzene by methanol conversion and preparation method and application thereof |
| CN103012035A (en) * | 2012-11-28 | 2013-04-03 | 浙江工业大学 | Method for removing trace hydrocarbon out of aromatic hydrocarbon by utilizing HMCM-41 type mesoporous molecular sieve |
| CN103801386A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of silicalite-1/ZSM-5 composite molecular sieve |
| CN105642342A (en) * | 2014-12-02 | 2016-06-08 | 神华集团有限责任公司 | SAPO-5/SAPO-34 composite molecular sieve, preparation method and application thereof |
-
2016
- 2016-10-26 CN CN201610947599.9A patent/CN106563497B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172243A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Mesoporous material/micropore molecular sieve composite material and preparation method thereof |
| CN102274748A (en) * | 2011-06-21 | 2011-12-14 | 西北大学 | Catalyst of conversion of ethanol to propylene and propane, preparation method thereof and application thereof |
| CN102380415A (en) * | 2011-09-04 | 2012-03-21 | 西北大学 | Catalyst for preparing methylbenzene by methanol conversion and preparation method and application thereof |
| CN103801386A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of silicalite-1/ZSM-5 composite molecular sieve |
| CN103012035A (en) * | 2012-11-28 | 2013-04-03 | 浙江工业大学 | Method for removing trace hydrocarbon out of aromatic hydrocarbon by utilizing HMCM-41 type mesoporous molecular sieve |
| CN105642342A (en) * | 2014-12-02 | 2016-06-08 | 神华集团有限责任公司 | SAPO-5/SAPO-34 composite molecular sieve, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YI WANG ET AL: "Synthesis, characterization and influence parameters on the overgrowth of micro/mesoporous Y-zeolite-MCM-41 composite material under acidic conditions", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| 李岳君等: "《炼油催化剂生产技术》", 31 July 2007, 中国石化出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106563497B (en) | 2019-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105728019A (en) | Application and preparation method of ZSM-5 molecular sieve with mesopores and micropores | |
| CN104495869B (en) | A kind of preparation method of fine grain ZSM-5-35 molecular sieve | |
| CN103495436B (en) | Method for manufacturing ALPO-5/SAPO-34 composite molecular sieve for preparing catalyst of low carbon olefin made of organic oxygenated chemicals | |
| CN102921456B (en) | Heterogeneous catalyst, preparation method of heterogeneous catalyst and application of heterogeneous catalyst | |
| CN106745049A (en) | A kind of molecular sieves of boron modification HZSM 5, preparation method and its usage | |
| CN104556125B (en) | A kind of isomorphous composite molecular screen and its preparation method and application | |
| CN105728013A (en) | Vanadium-doped silicon oxide-based mesoporous molecular sieve catalyst, as well as preparation method and application thereof | |
| CN104043477A (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| CN108128786A (en) | A kind of method that ultrasonic wave added prepares multi-stage porous SAPO-11 molecular sieves | |
| CN105502433A (en) | Preparation method of methanol-to-gasoline catalyst nano Zn-ZSM-5 | |
| CN103447081B (en) | Low-silicon ALPO-5/low-silicon ALPO-18 composite molecular sieve for preparing catalyst for preparing low-carbon alkene from organic oxygen-containing compound and preparation method of composite molecular sieve | |
| CN104591207B (en) | Small-grain NaY-type molecular sieve and preparation method thereof | |
| CN107297224A (en) | A kind of hydrocracking catalyst and preparation method thereof | |
| CN110980759B (en) | Silico-indate molecular sieve and preparation method and application thereof | |
| CN102553650B (en) | Hydrocracking catalyst carrier and preparation method thereof | |
| CN106563497A (en) | Preparation method for modifying ethyl alcohol to prepare olefin by adopting molecular sieve to catalyze | |
| CN105712370A (en) | USY molecular sieve with double meso-structures and preparation method thereof | |
| CN106145133B (en) | A kind of H beta molecular sieves and preparation method thereof | |
| CN108014847B (en) | Cu-SSZ-13/SAPO-11 composite structure molecular sieve and synthetic method thereof | |
| CN103071518B (en) | Catalyst used in production of isobutene through cracking of methyl tert-butyl ether and preparation method thereof | |
| CN108033462A (en) | A kind of multi-stage porous LTL molecular sieves and its synthetic method and application | |
| CN106582798A (en) | Catalyst for MTP (methanol-to-propylene) through conversion and preparation method of catalyst | |
| CN105498829A (en) | Methanol aromatized catalyst as well as preparation method and application thereof | |
| CN106672996A (en) | High-stability nanometer Y molecular sieve and preparation method thereof | |
| CN106466623A (en) | A kind of preparation method of catalyst for hydrogenation de-waxing and the application of the catalyst prepared by the method and this catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190115 Address after: 274500 South Chemical Park, Dongming County, Heze City, Shandong Province Applicant after: Dongming Aoke Fine Chemical Co., Ltd. Address before: 221400 room 9, building 1, San Feng mansion, Xin'an, Xinyi, Xuzhou, Jiangsu. Applicant before: Xinyi CHINO new Mstar Technology Ltd |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |