CN107720773A - A kind of method for efficiently synthesizing the molecular sieves of B Al ZSM 5 - Google Patents
A kind of method for efficiently synthesizing the molecular sieves of B Al ZSM 5 Download PDFInfo
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- CN107720773A CN107720773A CN201711037327.6A CN201711037327A CN107720773A CN 107720773 A CN107720773 A CN 107720773A CN 201711037327 A CN201711037327 A CN 201711037327A CN 107720773 A CN107720773 A CN 107720773A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
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Abstract
The invention provides a kind of method for efficiently synthesizing the molecular sieves of B Al ZSM 5, boron source, silicon source, silicon source, alkali source, template, surfactant, crystal seed are used as raw material, the crystallization in stainless steel cauldron, filtered, washing, dry, be calcined to obtain the molecular sieves of B Al ZSM 5.It is characterized in that by adding surfactant, water consumption is reduced, the water silicon ratio that feeds intake is less than 10, combines the synthesis advantage of solid phase and liquid phase, the reaction time is short, molecular sieve product high income, is 3 times or so of conventional hydrothermal method yield, with the SiO that feeds intake2Count product yield and be more than 85%, template dosage is few, and waste water is few, and production cost is low.Gained zeolite product crystal grain is small, and crystallinity is high, and acid strength and acid amount are easily controllable, and specific surface area is big, and pore structure is enriched, and good Propylene Selectivity and catalytic stability are shown in preparing propylene from methanol reaction.
Description
Technical field
The invention belongs to molecular sieve preparation field, and in particular to a kind of method for efficiently synthesizing B-Al-ZSM-5 molecular sieves.
Background technology
Propylene is important basic organic chemical raw material, is widely used in producing polypropylene, expoxy propane, acrylic acid, third
The chemical products with high added-value such as alkene nitrile.At present, propylene demand rapid growth, its production technology depend on petroleum
Steam cracking or catalytic cracking, and China's richness coal, the resources characteristic of few oil so that preparing propylene from methanol skill of the exploitation using coal as raw material
Art has important energy strategy meaning.
It is ZSM-5 molecular sieve that fixed bed preparing propylene from methanol, which reacts the most frequently used catalyst, and ZSM-5 molecular sieve is public by Mobil
Take charge of and successfully develop, there is the three dimensional skeletal structure that five-membered ring is formed, main aperture road contains the pore canal system of two kinds of intersections, and one kind is straight
Tubular duct, aperture are about 0.51nm × 0.55nm；Another kind is zigzag duct, and aperture is about 0.53nm × 0.56nm.
Acidity is too strong when ZSM-5 molecular sieve is directly used in preparing propylene from methanol reaction, there is that Propylene Selectivity is low, catalyst carbon deposition inactivation is fast
The problem of.Boron newtonium is introduced in ZSM-5 molecular sieve skeleton, can effectively change the silica alumina ratio and silicon boron ratio of catalyst, from
And reach regulation catalyst acid intensity and obtain purpose, it can obtain higher Propylene Selectivity and longer for preparing propylene from methanol reaction
Catalytic life.Wherein, it is especially optimal with little crystal grain, the B-Al-ZSM-5 molecular sieve catalytic effects of high silica alumina ratio, but its preparation side
The problem of zeolite product yield is low, and waste liquid is more, and production cost is high in method be present.
Patent CN104098110 discloses a kind of preparation method of the B-Al-ZSM-5 molecular sieves of size tunable, by adding
ZSM-5, B-ZSM-5, Silicalite-1 crystal seed is added to control molecular sieve particle size, grain size can be controlled in the μ of 100nm~15
M, patent CN103708497 disclose the B-Al-ZSM-5 zeolite catalysts that a kind of nano particle for methanol-to-olefins is accumulated
Preparation method, in conventional ZSM-5 synthetic systems introduce boron source, the zeolite seed crystal of MFI type, synthesis particle size is controllable to be received
Rice grain accumulation body B-Al-ZSM-5, available for methanol, dimethyl ether for alkene, but the water silicon that feeds intake, than high, zeolite product is received
Rate is low, and waste liquid amount is big, and processing cost is high.Patent CN102557066 discloses a kind of tetraethyl orthosilicate modified silicon-boron molecular sieve
Preparation method, modified method is impregnated by tetraethyl orthosilicate, reach modulation acid site, modify the mesh of aperture and pore passage structure
, catalyst preparation complex procedures, production cost height.
In published B-Al-ZSM-5 molecular sieves result of study, building-up process feeds intake water silicon than being generally more than 10, point
Son sieve product yield is low, and waste liquid is more, direct exhaust emission environment, and post processing cost is high；Post-modification prepares B-Al-ZSM-5 molecules
It is complicated to be sieved through journey, catalyst preparation flow extends, and production cost is high, and catalytic effect is unstable.
The content of the invention
The technical problems to be solved by the invention are to overcome deficiencies of the prior art, there is provided a kind of efficiently to close
Into the method for B-Al-ZSM-5 molecular sieves.This method reduces water consumption, the water silicon ratio that feeds intake is less than by adding surfactant
10, the synthesis advantage of solid phase and liquid phase is combined, the reaction time is short, molecular sieve product high income, with SiO2It is big to count product yield
In 85%, waste water is few, and production cost is low；By introducing B element into ZSM-5 molecular sieve skeleton, can flexible modulation silica alumina ratio and
Silicon boron ratio, molecular sieve acid strength and acid is effectively controlled to measure.
The present invention is specifically achieved using following technical solution：
A kind of method for efficiently synthesizing B-Al-ZSM-5 molecular sieves, its specific preparation process are as follows：
(1) silicon source, sodium hydroxide, boric acid, template, surfactant are dissolved in deionized water, stirring is equal at room temperature
It is even；
(2) silicon source, crystal seed are added, is sufficiently stirred and is made into mixed glue solution, its total moles ratio of components is SiO2::Al2O3:B2O3：
Na2O:Q:SLS:AEC:H2O=1:(0.001~0.01):(0.005~0.085):(0.005~0.1):(0~0.18):
(0.0015~0.006):(0.0015~0.01):(4~10), wherein Na2O represents basicity, Q represents template, SLS represents ten
Sodium dialkyl sulfate, AEC represent AEO carboxylic acid sodium；The crystal seed be nano-ZSM-5 molecular sieve and
At least one of Silicalite-1 crystal seeds；
(3) mixed glue solution obtained in step (2) is fitted into stainless steel cauldron, the crystallization at 120 DEG C~190 DEG C
24h~84h, reaction terminate after through filtering, washing, drying, being calcined to obtain B-Al-ZSM-5 molecular sieves.
In above-mentioned technical proposal, source of aluminium preferably is selected from least one in aluminum sulfate, aluminum nitrate, aluminium isopropoxide, sodium metaaluminate
Kind.
In above-mentioned technical proposal, the surfactant preferably is selected from lauryl sodium sulfate and AEO carboxylic
Sour sodium.
In above-mentioned technical proposal, the template preferably is selected from 4-propyl bromide, TPAOH, n-butylamine extremely
Few one kind.
In above-mentioned technical proposal, the silicon source preferably is selected from least one of silica gel, white carbon.
In above-mentioned technical proposal, the addition of described crystal seed is SiO in silicon source2The 0.5%-10% of mass fraction, it is excellent
Select 3%~7%.
In above-mentioned technical proposal, mixed glue solution total moles are than preferably SiO2::Al2O3:B2O3:Na2O:Q:SLS:AEC:
H2O
=1:(0.002~0.0067):(0.01~0.065):(0.02~0.07):(0.02~0.14):(0.0018~
0.0045):(0.0025~0.75):(4.5~9).
In above-mentioned technical proposal, step (3) is preferably 160 DEG C~180 DEG C crystallization 36h~60h, filter, wash, drying,
It is calcined routinely condition.
A kind of method for efficiently synthesizing B-Al-ZSM-5 molecular sieves of the present invention has the advantage that as follows：
1) the inventive method can efficiently synthesize B-Al-ZSM-5 molecular sieves, and the water silicon ratio that feeds intake is less than 10, and molecular sieve product is received
Rate is high, is 3 times or so of conventional hydrothermal method yield, with the SiO that feeds intake2Count product yield and be more than 85%, template dosage is few, waste water
Few, production cost is low.
2) zeolite product crystal grain is small made from the inventive method, and crystallinity is high, and specific surface area is big, and pore structure is enriched.
3), can flexible modulation silica alumina ratio and silicon boron ratio, effectively control by introducing B element into ZSM-5 molecular sieve skeleton
Molecular sieve acid strength and acid are measured, and good Propylene Selectivity and catalytic stability are shown in preparing propylene from methanol reaction.
Brief description of the drawings
Fig. 1 is the XRD for the B-Al-ZSM-5 sieve samples that embodiment 1 to embodiment 5 is prepared.
Fig. 2 is the XRD for the B-Al-ZSM-5 sieve samples that embodiment 6 to embodiment 10 is prepared.
The SEM figures for the B-Al-ZSM-5 sieve samples that Fig. 3 is embodiment 1, embodiment 2 is prepared.
The NH for the B-Al-ZSM-5 sieve samples that Fig. 4 is embodiment 1, embodiment 2 is prepared3- TPD schemes.
Specific embodiment：
The present invention is further illustrated with comparative example by the following examples, but not thereby limiting the invention
Content.
Implementation column 1
Weigh 1.01g aluminium isopropoxides to be dissolved in 90.91g deionized waters, sequentially add 3.96g sodium hydroxides, 4.89g boron
Acid, 40.17gTPAOH, stirring make its dissolving；Weigh 0.57gSLS, 1.19gAEC to be dissolved in 38.96g deionized waters, add extremely
In above-mentioned solution, silicon source mixed liquor is sufficiently stirred to obtain.
59.27g white carbons, 4.15g Silicalite-1 crystal seeds are weighed, is added under stirring condition into silicon source mixed liquor,
After being sufficiently mixed uniformly, it is transferred in the reactor of inner liner polytetrafluoroethylene, cools after 180 DEG C of crystallization 48h, product is filtered,
Washing, dry, be calcined to obtain B-Al-ZSM-5 molecular sieves, being designated as BZ-1.
Embodiment 2
Weigh 1.6g aluminium isopropoxides be dissolved in 112g deionized waters, sequentially add 6.62g sodium hydroxides, 8.04g boric acid,
10.4g n-butylamines, stirring make its dissolving；Weigh 0.68gSLS, 1.66gAEC to be dissolved in 48g deionized waters, add to above-mentioned molten
In liquid, silicon source mixed liquor is sufficiently stirred to obtain.
71.12g white carbons, 4.62g Silicalite-1 crystal seeds are weighed, is added under stirring condition into silicon source mixed liquor,
After being sufficiently mixed uniformly, it is transferred in the reactor of inner liner polytetrafluoroethylene, cools after 180 DEG C of crystallization 42h, product is filtered,
Washing, dry, be calcined to obtain B-Al-ZSM-5 molecular sieves, being designated as BZ-2.
Embodiment 3
Weigh 2.01g sodium metaaluminates be dissolved in 128g deionized waters, sequentially add 7.68g sodium hydroxides, 8g boric acid,
35.13gTPABr, stirring make its dissolving；Weigh 1.16gSLS, 2.26gAEC to be dissolved in 32g deionized waters, add to above-mentioned molten
In liquid, silicon source mixed liquor is sufficiently stirred to obtain.
96.98g silica gel, 3.89gZSM-5 crystal seeds are weighed, adds into silicon source mixed liquor, is sufficiently mixed under stirring condition
After even, be transferred in the reactor of inner liner polytetrafluoroethylene, cool after 160 DEG C of crystallization 54h, product is filtered, washing, dry,
B-Al-ZSM-5 molecular sieves are calcined to obtain, are designated as BZ-3.
Embodiment 4
Weigh 2.48g sodium metaaluminates to be dissolved in 96.81g deionized waters, sequentially add 7.56g sodium hydroxides, 6.61g boron
Acid, 28.9gTPABr, stirring make its dissolving；Weigh 1.55gSLS, 3.55gAEC to be dissolved in 41.49g deionized waters, add supreme
State in solution, be sufficiently stirred to obtain silicon source mixed liquor.
106.68g silica gel, 3.73gZSM-5 crystal seeds are weighed, adds into silicon source mixed liquor, is sufficiently mixed under stirring condition
After uniformly, it is transferred in the reactor of inner liner polytetrafluoroethylene, cools after 160 DEG C of crystallization 54h, product is filtered, washs, be dry
It is dry, be calcined to obtain B-Al-ZSM-5 molecular sieves, be designated as BZ-4.
Embodiment 5
Weigh 3.29g sodium metaaluminates be dissolved in 128g deionized waters, sequentially add 8.48g sodium hydroxides, 6.11g boric acid,
42.93gTPABr, stirring make its dissolving；Weigh 2.16gSLS, 5.12gAEC to be dissolved in 32g deionized waters, add to above-mentioned molten
In liquid, silicon source mixed liquor is sufficiently stirred to obtain.
118.67g silica gel, 3.56gZSM-5 crystal seeds are weighed, adds into silicon source mixed liquor, is sufficiently mixed under stirring condition
After uniformly, it is transferred in the reactor of inner liner polytetrafluoroethylene, cools after 160 DEG C of crystallization 60h, product is filtered, washs, be dry
It is dry, be calcined to obtain B-Al-ZSM-5 molecular sieves, be designated as BZ-5.
Embodiment 6
Weigh 1.22g aluminium isopropoxides be dissolved in 112g deionized waters, sequentially add 6.1g sodium hydroxides, 8.38g boric acid,
22.28gTPABr, stirring make its dissolving；Weigh 0.54gSLS, 1.05gAEC to be dissolved in 48g deionized waters, add to above-mentioned molten
In liquid, silicon source mixed liquor is sufficiently stirred to obtain.
62.75g white carbons, 3.77g Silicalite-1 crystal seeds are weighed, is added under stirring condition into silicon source mixed liquor,
After being sufficiently mixed uniformly, it is transferred in the reactor of inner liner polytetrafluoroethylene, cools after 170 DEG C of crystallization 54h, product is filtered,
Washing, dry, be calcined to obtain B-Al-ZSM-5 molecular sieves, being designated as BZ-6.
Implementation column 7
Weigh 1.39g aluminum sulfate be dissolved in 98.6g deionized waters, sequentially add 1.74g sodium hydroxides, 1.23g boric acid,
25.52gTPAOH, stirring make its dissolving；Weigh 1.21gSLS, 2.51gAEC to be dissolved in 42.26g deionized waters, add to above-mentioned
In solution, silicon source mixed liquor is sufficiently stirred to obtain.
62.75g silica gel, 4.39g ZSM-5 crystal seeds are weighed, adds into silicon source mixed liquor, is sufficiently mixed under stirring condition
After uniformly, it is transferred in the reactor of inner liner polytetrafluoroethylene, cools after 180 DEG C of crystallization 48h, product is filtered, washs, be dry
It is dry, be calcined to obtain B-Al-ZSM-5 molecular sieves, be designated as BZ-7.
Embodiment 8
Weigh 2.76g sodium metaaluminates be dissolved in 89.22g deionized waters, sequentially add 6.58g sodium hydroxides, 4.4g boric acid,
43.39gTPAOHr, stirring make its dissolving；Weigh 2.31gSLS, 5.33gAEC to be dissolved in 38.24g deionized waters, add supreme
State in solution, be sufficiently stirred to obtain silicon source mixed liquor.
106.68g silica gel, 3.2g Silicalite-1 crystal seeds are weighed, adds into silicon source mixed liquor, fills under stirring condition
Divide after being well mixed, be transferred in the reactor of inner liner polytetrafluoroethylene, cool after 170 DEG C of crystallization 36h, product is filtered, washes
B-Al-ZSM-5 molecular sieves are washed, dried, being calcined and to obtain, are designated as BZ-8.
Embodiment 9
Weigh 4.78g aluminum nitrates be dissolved in 128g deionized waters, sequentially add 6.52g sodium hydroxides, 6.41g boric acid,
23.67gTPABr, stirring make its dissolving；Weigh 1.28gSLS, 2.37gAEC to be dissolved in 32g deionized waters, add to above-mentioned molten
In liquid, silicon source mixed liquor is sufficiently stirred to obtain.
88.9g silica gel, 4g Silicalite-1 crystal seeds are weighed, is added under stirring condition into silicon source mixed liquor, it is fully mixed
After closing uniformly, it is transferred in the reactor of inner liner polytetrafluoroethylene, cools after 165 DEG C of crystallization 48h, product is filtered, washs, be dry
It is dry, be calcined to obtain B-Al-ZSM-5 molecular sieves, be designated as BZ-9.
Embodiment 10
Weigh 3.66g aluminum sulfate be dissolved in 128g deionized waters, sequentially add 7.03g sodium hydroxides, 6.8g boric acid,
10.05g n-butylamines, stirring make its dissolving；Weigh 1.18gSLS, 2.46gAEC to be dissolved in 32g deionized waters, add to above-mentioned molten
In liquid, silicon source mixed liquor is sufficiently stirred to obtain.
82.06g white carbons, 4.1g Silicalite-1 crystal seeds are weighed, is added under stirring condition into silicon source mixed liquor,
After being sufficiently mixed uniformly, it is transferred in the reactor of inner liner polytetrafluoroethylene, cools after 170 DEG C of crystallization 48h, product is filtered,
Washing, dry, be calcined to obtain B-Al-ZSM-5 molecular sieves, being designated as BZ-10.
Comparative example 1
In embodiment 1, surfactant SLS and AEC are not added, are improved the water silicon ratio that feeds intake, are designated as CZ-1.
Comparative example 2
In example 2, surfactant SLS and AEC are not added, are improved the water silicon ratio that feeds intake, are designated as CZ-2.
Performance test
By embodiment 1, embodiment 2, comparative example 1, the sample of comparative example 2 respectively with 0.5mol/L ammonium sulfates in 90 DEG C of friendships
4h is changed, suction filtration, washing, dry, roasting obtain corresponding HZSM-5 molecular sieves, then obtained after tabletting, sieving (40~60 mesh)
To corresponding catalyst sample.Gained catalyst sample is carried out on fixed-bed reactor respectively after 480 DEG C of hydro-thermal process 24h
Preparing propylene from methanol reacts, loaded catalyst 1.5g, and the mass ratio for feeding methanol and water is 1:1, methanol quality air speed is 3h-1, nitrogen is carrier gas, and reaction temperature is 480 DEG C, and reaction pressure is normal pressure, and product carries out on-line analysis through gas-chromatography.
The catalysis methanol propylene reaction result of table 1
Claims (6)
- A kind of 1. method for efficiently synthesizing B-Al-ZSM-5 molecular sieves, it is characterised in that comprise the following steps：(1) silicon source, sodium hydroxide, boric acid, template, surfactant are dissolved in deionized water, stirred at room temperature；(2) silicon source, crystal seed are added, is sufficiently stirred and is made into mixed glue solution, its total moles ratio of components is SiO2::Al2O3:B2O3： Na2O:Q:SLS:AEC:H2O=1:(0.001~0.01):(0.005~0.085):(0.005~0.1):(0~0.18): (0.0015~0.006):(0.0015~0.01):(4~10), wherein Na2O represents basicity, Q represents template, SLS represents ten Sodium dialkyl sulfate, AEC represent AEO carboxylic acid sodium；Described crystal seed be nano-ZSM-5 molecular sieve or At least one of Silicalite-1 crystal seeds；(3) mixed glue solution obtained in step (2) is fitted into stainless steel cauldron, 120 DEG C~190 DEG C crystallization 24h~84h, Reaction terminate after through filtering, washing, drying, being calcined to obtain B-Al-ZSM-5 molecular sieves.
- 2. preparation method according to claim 1, it is characterised in that described silicon source is aluminum sulfate, aluminum nitrate, isopropanol At least one of aluminium, sodium metaaluminate.
- 3. preparation method according to claim 1, it is characterised in that described surfactant is lauryl sodium sulfate And AEO carboxylic acid sodium.
- 4. preparation method according to claim 1, it is characterised in that described template is 4-propyl bromide, tetrapropyl At least one of ammonium hydroxide, n-butylamine.
- 5. preparation method according to claim 1, it is characterised in that described silicon source is at least one in silica gel, white carbon Kind.
- 6. preparation method according to claim 1, it is characterised in that the addition of described crystal seed is SiO in silicon source2Matter Measure the 0.5%~10% of fraction.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110330030A (en) * | 2019-07-31 | 2019-10-15 | 山东齐鲁华信实业股份有限公司 | The production method of type molecular sieve ZSM-5 is selected with the production of low Crater corrosion sodium metaaluminate |
| CN111348659A (en) * | 2020-04-15 | 2020-06-30 | 鞍山师范学院 | Preparation method of spherical B-Silicalite molecular sieve |
| CN111960429A (en) * | 2020-08-26 | 2020-11-20 | 万华化学集团股份有限公司 | Preparation method of hierarchical porous aluminum phosphate molecular sieve catalyst, catalyst prepared by hierarchical porous aluminum phosphate molecular sieve catalyst and application of hierarchical porous aluminum phosphate molecular sieve catalyst in olefin isomerization |
| CN113979446A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Boron-containing molecular sieve, preparation method and application thereof |
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