CN106925340A - Methanol-to-olefin catalyst and preparation method thereof - Google Patents
Methanol-to-olefin catalyst and preparation method thereof Download PDFInfo
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- CN106925340A CN106925340A CN201511021643.5A CN201511021643A CN106925340A CN 106925340 A CN106925340 A CN 106925340A CN 201511021643 A CN201511021643 A CN 201511021643A CN 106925340 A CN106925340 A CN 106925340A
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- methanol
- gallium
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- olefin catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010457 zeolite Substances 0.000 claims abstract description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 239000010703 silicon Substances 0.000 claims abstract description 37
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 33
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 31
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 229910002651 NO3 Inorganic materials 0.000 claims description 15
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 229940044658 gallium nitrate Drugs 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000009849 deactivation Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 10
- 230000008569 process Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002796 Si–Al Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- -1 methyl alcohol alkene Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 241001281643 Solus Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012546 transfer Methods 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/06—Propene
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- 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
-
- 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
- Y02P20/584—Recycling of catalysts
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention proposes a kind of methanol-to-olefin catalyst and preparation method.Catalyst is silicon gallium SSZ-13 zeolites, and silicon source, the silicon gallium zeolite of one-step synthesis method little crystal grain are substituted with gallium source, and micropore volume is 0.15~0.25mL/g, and specific surface area is 450~550m2/ g, average mesopore size is 3.0~18.0nm, and average particle size particle size is 100~500 μm.Zeolite catalyst crystal grain of the invention is small, specific surface area is larger, diffusion is excellent, with resistance to deactivation higher and catalyst regenerating stability.
Description
Technical field
The present invention relates to a kind of methanol-to-olefin catalyst and preparation method thereof, belong to petrochemical technology neck
Domain.
Background technology
Especially low-carbon alkene is the important organic base stock of modern industry to alkene.At present, domestic and international low-carbon (LC)
The acquisition of alkene is relied primarily on carries out steam cracking to petroleum hydrocarbons such as naphtha and light diesel fuels.Due to the whole world
Petroleum resources it is increasingly in short supply, promote with biomass, coal, natural gas is the methyl alcohol alkene of basic carbon source
Hydrocarbon technology has obtained more extensive concern.
The key of methanol-to-olefins technology commercialization is that synthesis has high selectivity, high activity and high stability
Catalyst.SAPO-34 molecular sieves with CHA topological structures are because of its special pore passage structure, weaker acid
Center and selectivity of light olefin higher and turn into the optimum catalyst of methanol to olefins reaction.And it is same
The SSZ-13 zeolites for possessing CHA topological structures also have industrialized potential, but compared to SAPO-34
Molecular sieve, SSZ-13 but has stronger acidity and inactivates faster.If its inactivation can be controlled effectively
System, the optimum temperature of methanol to olefins reaction just can be less than SAPO-34, have benefited from this, its decaying catalyst
Regenerator size can design it is smaller, to save more investments.
In order to slow down the inactivation of catalyst, by reducing zeolite size, processed using soda acid or various
Pore-foaming agent produces mesoporous in zeolite molecular sieve, is to increase the diffusion in zeolite of reactant or product molecule
The important channel of efficiency.The use of Bis-quaternary Ammonium Salt Surfactant is successfully synthesized with single cell thickness
ZSM-5 zeolite, the activity of catalytic reaction is greatly improved, and this has benefited from the molecule of the zeolite for improving
Diffuser efficiency.Then, the method is applied in SSZ-13 zeolites, is lived by using bi-quaternary ammonium salt surface
Property agent be successfully introduced into mesoporous, carbon accumulation resisting ability of the gained catalyst in methanol to olefins reaction is big greatly
By force.But the synthesis of above-mentioned mesoporous SSZ-13 zeolites must use expensive surfactant so that industry
Change hindered.The mode of alkali process also can carry out pore-creating to SSZ-13 zeolites, however, gained is mesoporous
The reactivity of SSZ-13 catalyst is but substantially reduced, and further sign proves, in alkali process desiliconization
During along with substantial amounts of dealuminzation phenomenon, the reduction of highly acid position causes drastically reducing for catalyst activity.
On the other hand, little crystal grain zeolite is similarly subjected to concern.It both maintains high product selectivity, and there is provided very
Good mass transfer ability, therefore exploitation little crystal grain methanol-to-olefin catalyst has great importance.
The content of the invention
It is an object of the invention to provide a kind of little crystal grain methanol-to-olefin catalyst；Another object of the present invention exists
In the method that offer prepares above-mentioned catalyst.
The present invention provides a kind of preparation method of methanol-to-olefin catalyst, comprises the following steps：
(1) template TMAdaOH is weighed, NaOH and water is added, quick stirring is well mixed；
(2) gallium nitrate is added to (1) resulting solution, continues to stir until the dissolving of gallium source；
(3) silicon source is added to (2) resulting solution, continues to stir；
(4) step (3) gained colloidal sol is transferred in stainless steel water heating kettle, crystallization temperature is 150~180 DEG C,
Crystallization time 5~8 days, crystallization takes out kettle after terminating, water-cooled to room temperature, suction filtration, is washed to neutrality, and
It is dried overnight in 100~120 DEG C of baking ovens；
(5) calcination stepses (4) gained zeolite is obtained for 6~10 hours with removing template at 550~580 DEG C
To silicon gallium zeolite；
(6) in 1M NH4NO3Effects of ion exchange step (5) gained silicon gallium zeolite, obtains silicon after roasting
Gallium SSZ-13 zeolites, i.e. methanol-to-olefin catalyst.
The preparation method of methanol-to-olefin catalyst of the present invention, wherein, silicon source described in step (3)
Preferably tetraethyl orthosilicate, Ludox AS40 or Ludox HS30, its feed postition for disposable quick plus
Enter.
The preparation method of methanol-to-olefin catalyst of the present invention, wherein, the crystallization in step (4) is excellent
Elect static crystallization as.
The preparation method of methanol-to-olefin catalyst of the present invention, these, it is preferred to, in step (5)
Sintering temperature rises to 220 DEG C with 5 DEG C/min of speed, constant temperature 2~3 hours, then with 5 DEG C/min of speed
Rise to 550~580 DEG C of simultaneously constant temperature 6~10 hours.
The preparation method of methanol-to-olefin catalyst of the present invention, wherein, silicon gallium described in step (6)
Zeolite and NH4NO3The consumption of solution is preferably：Per 100mL NH4NO3Solution boils corresponding to 1g silicon gallium
Stone.
The preparation method of methanol-to-olefin catalyst of the present invention, wherein, ion described in step (6)
Exchange preferably in triplicate.
The preparation method of methanol-to-olefin catalyst of the present invention, wherein, template TMAdaOH,
NaOH, gallium nitrate, silicon source and water are according to mol ratio TMAdaOH:Na2O:Ga2O3:SiO2:H2O
=(10~20):(5~10):(1~5):(50~100):(2200~5000).
The present invention also provides a kind of methanol-to-olefin catalyst, and it is the preparation of above-mentioned methanol-to-olefin catalyst
Methanol-to-olefin catalyst obtained in method.Wherein, the silicon-gallium molar ratio of silicon gallium SSZ-13 zeolites is 10~50,
Micropore volume is 0.15~0.25mL/g, and specific surface area is 450~550m2/ g, average mesopore size is 3.0~18.0
Nm, average particle size particle size is 100~500 μm.
Catalyst of the invention can be used in methanol to olefins reaction, and silicon gallium zeolite is by compressing tablet and screens
200 μm~300 μm particles of particle diameter, 50mg is in quartzy fixed bed reaction pipe for filling.Before reaction,
Need to pre-process catalyst, kept for 2 hours after being warming up to 550 DEG C with 2 DEG C/min of speed, with
After be cooled to 350 DEG C of reaction temperature, methyl alcohol brings reactor into by helium.Gaseous product is detected by chromatogram.Instead
The test condition is answered to be：Mass space velocity 1h-1, reaction time 24h, 350 DEG C of reaction temperature, pressure 1.07 × 105
Pa。
Compared with existing SSZ-13 zeolite preparation methods, beneficial effects of the present invention：
Gained zeolite grain is small, and specific surface area is big, and the accumulation hole of generation is mesoporous, and average-size is distributed as
3.0~18.0nm.Silicon gallium zeolite acidity is weaker than Si-Al zeolite, and reaction temperature is relatively low, and resistance to deactivation is stronger.
Brief description of the drawings
Fig. 1：The scanning electron microscope (SEM) photograph of Si-Al zeolite and silicon gallium zeolite, left figure is sial SSZ-13 zeolites, right
Figure is silicon gallium SSZ-13 zeolites；
Fig. 2：The XRD spectra of sial SSZ-13 and silicon gallium SSZ-13；
Fig. 3：The nitrogen adsorption isotherm and mesoporous distribution of Si-Al zeolite and silicon gallium zeolite, nitrogen thermostatic absorption
Desorption curve (left side) and mesoporous distribution map (right side), (a) sial SSZ-13, (b) silicon gallium SSZ-13；
Fig. 4：Catalyst methanol to olefins reaction is evaluated.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is premised on technical solution of the present invention
Under implemented, give detailed implementation method and process, but protection scope of the present invention be not limited to it is following
Embodiment.
Embodiment 1
The preparation of sial SSZ-13 zeolites and silicon gallium SSZ-13 zeolites
NaOH (50wt%) 0.24g is weighed, deionized water 11.4g is added, template is added
TMAdaOH (25wt%) 3.38g, is uniformly mixed.Gallium nitrate 0.26g add previous solu in,
Stirring 30 minutes, is subsequently adding silicon source Ludox AS40 (40wt%) 3g.It is stirred vigorously 2 hours, gained
Colloidal sol is transferred in stainless steel water heating kettle, and static crystallization temperature is 150 DEG C, crystallization time 8 days.Sial
The building-up process of SSZ-13 zeolites is consistent with silicon gallium zeolite.Crystallization takes out kettle after terminating, water-cooled to room temperature,
Suction filtration, neutrality is washed to, and is dried overnight in 120 DEG C of baking ovens；Sample is calcined afterwards, and temperature is with 5
DEG C/min speed rise to 220 DEG C, constant temperature 2~3 hours, then 570 DEG C are risen to 5 DEG C/min of speed
And constant temperature 10 hours is removing template；Sample after roasting is in 1M NH4NO3Effects of ion is exchanged
Three times, h-type zeolite is obtained after being calcined again.NH4NO3The consumption of solution is：Per 100mL NH4NO3
Solution corresponds to 1g silicon gallium zeolites.
Embodiment 2
NaOH (50wt%) 0.20g is weighed, deionized water 12.8g is added, template is added
TMAdaOH (25wt%) 2.5g, is uniformly mixed.Gallium nitrate 0.12g add previous solu in,
Stirring 30 minutes, is subsequently adding tetraethyl orthosilicate 4.2g.It is stirred vigorously 2 hours, gained colloidal sol is transferred to
In stainless steel water heating kettle, static crystallization temperature is 180 DEG C, crystallization time 6 days.Crystallization is taken out after terminating
Kettle, water-cooled to room temperature, is washed to neutrality at suction filtration, and is dried overnight in 110 DEG C of baking ovens；Roast afterwards
Sample is burnt, temperature rises to 220 DEG C with 5 DEG C/min of speed, constant temperature 2~3 hours, then with 5 DEG C/min
Speed rises to 580 DEG C and constant temperature 8 hours to remove template；Sample after roasting is in 1M NH4NO3
Effects of ion is exchanged three times, and h-type zeolite is obtained after being calcined again.NH4NO3The consumption of solution is：Often
100mL NH4NO3Solution corresponds to 1g silicon gallium zeolites.
Embodiment 3
NaOH (50wt%) 0.3g is weighed, deionized water 12.4g is added, template TMAdaOH is added
(25wt%) 4g, is uniformly mixed.In gallium nitrate 0.3g addition previous solus, stir 30 minutes,
It is subsequently adding Ludox HS30 (30wt%) 4g.It is stirred vigorously 2 hours, gained colloidal sol is transferred to stainless steel
In water heating kettle, static crystallization temperature is 160 DEG C, crystallization time 5 days.Crystallization takes out kettle, water after terminating
It is cooled to room temperature, suction filtration, is washed to neutrality, and is dried overnight in 100 DEG C of baking ovens；Sample is calcined afterwards,
Temperature rises to 220 DEG C with 5 DEG C/min of speed, constant temperature 2~3 hours, then is risen to 5 DEG C/min of speed
550 DEG C and constant temperature 6 hours are removing template；Sample after roasting is in 1M NH4NO3Effects of ion
Exchange three times, h-type zeolite is obtained after being calcined again.NH4NO3The consumption of solution is：Per 100mL
NH4NO3Solution corresponds to 1g silicon gallium zeolites.
The pore structure property that roasting removes the zeolite sample after template is shown in Table 1.
Embodiment 4
Methanol to olefins reaction active appraisal experiment uses fixed-bed micro-reactor-gas phase chromatographic device.Instead
Raw material is answered for methyl alcohol, conveying gas is helium, first, zeolite catalyst is by 200 μm -300 of compressing tablet and screening
The particle of μm particle diameter, 50mg is in quartzy fixed bed reaction pipe for filling., it is necessary to catalysis before reaction
Agent is pre-processed, and is kept for 2 hours after being warming up to 550 DEG C with 2 DEG C/min of speed, is then cooled to anti-
350 DEG C of temperature is answered, methyl alcohol brings reactor into by helium.Gaseous product is detected by chromatogram.Reaction test condition
For：Mass space velocity 1h-1, reaction time 24h, 350 DEG C of reaction temperature, pressure 1.07 × 105Pa.Often
Check that product is constituted by gas-chromatography within 20 minutes.Evaluation result is shown in Table 2 and Fig. 4.
Embodiment 5
This example is the physicochemical property and Activity evaluation of above catalyst.
The physicochemical property of catalyst is shown in Table 1.As shown in Table 1, silicon gallium SSZ-13 catalyst of the present invention compares table
Area increases because particle diameter diminishes, and its micropore volume is more or less the same with sial SSZ-13 zeolites, shows that it is high
Crystallinity.Its average mesopore diameter be 3~18nm, and sial SSZ-13 zeolites have no it is mesoporous.
When evaluating catalyst, catalyst fixed bed layer is passed through after helium and material benzenemethanol mixing.Comment
The process conditions all same that each example catalyst of valency is used, respectively：Mass space velocity 1h-1, reaction time 24h,
350 DEG C of reaction temperature, pressure 1.07 × 105Pa.Evaluation result is shown in Table 2.
From this example, the silicon gallium SSZ-13 catalyst that the inventive method is obtained resists carbon distribution with higher
Ability and good reactivity stability.
The catalyst physicochemical property of table 1
The catalyst methanol to olefins reaction evaluation result of table 2
aThe life-span of catalyst when methanol conversion is 50%.
Claims (8)
1. a kind of preparation method of methanol-to-olefin catalyst, comprises the following steps：
(1) template TMAdaOH is weighed, NaOH and water is added, quick stirring is well mixed；
(2) gallium nitrate is added to (1) resulting solution, continues to stir until the dissolving of gallium source；
(3) silicon source is added to (2) resulting solution, continues to stir；
(4) step (3) gained colloidal sol is transferred in stainless steel water heating kettle, crystallization temperature is 150~180 DEG C,
Crystallization time 5~8 days, crystallization takes out kettle after terminating, water-cooled to room temperature, suction filtration, is washed to neutrality, and
It is dried overnight in 100~120 DEG C of baking ovens；
(5) at 550~580 DEG C calcination stepses (4) gained 6~10 hours of zeolite to remove template,
Obtain silicon gallium zeolite；
(6) in 1 M NH4NO3Effects of ion exchange step (5) gained silicon gallium zeolite, obtains silicon after roasting
Gallium SSZ-13 zeolites, i.e. methanol-to-olefin catalyst.
2. according to the preparation method of the methanol-to-olefin catalyst described in claim 1, wherein, step (3)
Described in silicon source be tetraethyl orthosilicate, Ludox AS40 or Ludox HS30, its feed postition is disposable
Rapidly join.
3. according to the preparation method of the methanol-to-olefin catalyst described in claim 1, wherein, step (4)
In crystallization be static crystallization.
4. according to the preparation method of the methanol-to-olefin catalyst described in claim 1, wherein, step (5)
Middle sintering temperature rises to 220 DEG C with 5 DEG C/min of speed, constant temperature 2~3 hours, then with 5 DEG C/min of speed
Degree rises to 550~580 DEG C of simultaneously constant temperature 6~10 hours.
5. according to the preparation method of the methanol-to-olefin catalyst described in any one of Claims 1 to 4, wherein,
Silicon gallium zeolite and NH described in step (6)4NO3The consumption of solution is：Every 100 mL NH4NO3Solution pair
Should be in 1g silicon gallium zeolites.
6. according to the preparation method of the methanol-to-olefin catalyst described in any one of Claims 1 to 4, wherein,
Ion exchange described in step (6) is in triplicate.
7. according to the preparation method of the methanol-to-olefin catalyst described in any one of Claims 1 to 4, wherein,
Template TMAdaOH, NaOH, gallium nitrate, silicon source and water are according to mol ratio TMAdaOH:Na2O:
Ga2O3:SiO2:H2O=10~20:5~10:1~5:50~100:2200~5000.
8. a kind of methanol-to-olefin catalyst, it is the methanol-to-olefins described in any one of claim 1~7
Methanol-to-olefin catalyst obtained in the preparation method of catalyst, wherein, the silicon gallium of silicon gallium SSZ-13 zeolites
Mol ratio is 10~50, and micropore volume is 0.15~0.25mL/g, and specific surface area is 450~550m2/ g, averagely
Mesopore size is 3.0~18.0nm, and average particle size particle size is 100~500 μm.
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Citations (4)
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|---|---|---|---|---|
| US4544538A (en) * | 1982-07-09 | 1985-10-01 | Chevron Research Company | Zeolite SSZ-13 and its method of preparation |
| CN101573293A (en) * | 2006-12-27 | 2009-11-04 | 雪佛龙美国公司 | Preparation of molecular sieve SSZ-13 |
| CN102451749A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing olefin by conversion of methanol as well as preparation and application thereof |
| CN103601211A (en) * | 2013-12-04 | 2014-02-26 | 北京化工大学 | Synthesis method of molecular sieve SSZ-13 |
-
2015
- 2015-12-31 CN CN201511021643.5A patent/CN106925340A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4544538A (en) * | 1982-07-09 | 1985-10-01 | Chevron Research Company | Zeolite SSZ-13 and its method of preparation |
| CN101573293A (en) * | 2006-12-27 | 2009-11-04 | 雪佛龙美国公司 | Preparation of molecular sieve SSZ-13 |
| CN102451749A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing olefin by conversion of methanol as well as preparation and application thereof |
| CN103601211A (en) * | 2013-12-04 | 2014-02-26 | 北京化工大学 | Synthesis method of molecular sieve SSZ-13 |
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| QINGJUN ZHU ET AL: "Methanol-to-olefin over gallosilicate analogues of chabazite zeolite", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
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