CN1769169A - Beta zeolite particles with hierarchical pores and preparation method thereof - Google Patents
Beta zeolite particles with hierarchical pores and preparation method thereof Download PDFInfo
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- CN1769169A CN1769169A CN 200410050727 CN200410050727A CN1769169A CN 1769169 A CN1769169 A CN 1769169A CN 200410050727 CN200410050727 CN 200410050727 CN 200410050727 A CN200410050727 A CN 200410050727A CN 1769169 A CN1769169 A CN 1769169A
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000002149 hierarchical pore Substances 0.000 title 1
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 61
- 239000010457 zeolite Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 32
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 19
- 238000010306 acid treatment Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 238000002425 crystallisation Methods 0.000 claims description 29
- 230000008025 crystallization Effects 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 17
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 13
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 8
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 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 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- 230000006911 nucleation Effects 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 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 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 9
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 150000007522 mineralic acids Chemical class 0.000 claims 2
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 0.000 claims 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 210000001367 artery Anatomy 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001723 mesolite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000116 mitigating effect Effects 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
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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Abstract
The invention relates to a beta zeolite particle with multistage openings, the mole ratio of SiO2/ Al2O3 being 80-120, the mean particle size being 0.1-0.5um, opening capacity being 0.35-0.50ml/ g, and aperture collectively distributing at three-stage 0.1-1.7nm, 1.7-6.0nm and 10.0-90.0nm. In the beta zeolite preparing process, it uses optimization-condition hydrothermal synthesis method, after synthesis process, firstly proceeding ammonium salt processing procedure to prepare zeolite, then proper-conditioned acid treatment and hydrothermal treatment to prepare final beta zeolite. The prepared beta zeolite having three openings of different aperture, compared with the prior art, it can increase highly the utilization ratio of outer surface of fine grain, decrease diffusion resistance, and improve reaction selectivity. The invented process is simple, the cost is low, and the product repetitiveness is good. The beta zeolite can be used as catalyst for hydrocracking, and so on.
Description
Technical field
The present invention relates to a kind of β zeolite and preparation method thereof, particularly have β zeolite granular of multi-stage artery structure and preparation method thereof.
Background technology
The β zeolite is the supersiliceous zeolite (US3 with three-dimensional open-framework that the U.S. succeeds in developing in the Mobil company sixties; 308; 069); the late nineteen eighties; the various countries scholar is to the research Showed Very Brisk of β zeolite; because the pore passage structure of β zeolite uniqueness and excellent catalytic performance are with a wide range of applications at oil and chemical field.Commercial application shows that the β zeolite has higher hydrogenation cracking activity and hydroisomerization performance, can be used for hydrocracking behind modification and loaded metal, hydro-isomerization, hydrofining, Hydrodewaxing, processes such as diesel oil pour point depression.
The inner arctation of zeolite grain has increased diffusional resistance, has reduced reactivity worth.After crystal grain diminished, outside surface enlarged, and internal diffusion speed improves, to improving catalyst utilization, strengthen the macromole conversion capability, reduce deep reaction, improving aspects such as selectivity and have positively effect.Furtherd investigate fine grain NaY zeolite and big crystal NaY zeolite as EP-02042362, comparative result shows, the former has higher activity and selectivity preferably to heavy oil fluid catalytic cracking.Therefore, little crystal grain prepare zeolite technology more and more is subject to people's attention.
Prior art can synthesize the β zeolite of various different grain sizes.As US3308069 introduction method synthetic β zeolite grain size is 0.3～0.5 μ m, US5164169 synthetic β zeolite grain size is 0.3～1.0 μ m, WO93/08125 synthetic β zeolite grain is 70nm, CN1108213A synthetic β zeolite grain is greater than 0.1 μ m, CN1268545A synthetic β zeolite grain is 0.7～1.5 μ m, and CN1324762A synthetic β zeolite grain is 50～90nm.
In general, the aperture in the zeolite grain is single, and for the bigger zeolite of crystal grain, its diffusion will be seriously influenced, and then the selectivity and the life of catalyst of influence reaction.Reduce the crystal grain of zeolite, can address this problem to a certain extent, this also is that in recent years little crystal grain zeolite (comprising nano zeolite) is subjected to the reason that people pay attention to.But in many cases, the zeolite content in the catalyzer is less, has only 1%～30% as hydrocracking catalyst mesolite content, that is to say, a spot of zeolite quilt " coating " is in a large amount of other materials.As in hydrocracking catalyst, be that a spot of zeolite mixes with a large amount of aluminum oxide of not having cracking activity.Its result must make a large amount of outside surfaces and the aluminum oxide of zeolite bonding, and this is to being difficult to give full play of with the effect that outer area is big, the active centre externalizes the little crystal grain zeolite of characteristics.Therefore, zeolite of the prior art, no matter be big crystal grain, still little crystal grain during as the catalyst member component, all has certain deficiency.In addition, in the β zeolite preparation method, template (tetraethyl ammonium hydroxide) consumption is big in the prior art, and the solid-to-liquid ratio that feeds intake is low, and single-autoclave yield rate is low, the crystallization temperature height, and the time is long, is prone to stray crystal, poor repeatability as a result, filtration difficulty, yield is lower.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of small-particle β zeolite and preparation method thereof with multi-stage artery structure.
The SiO of β zeolite of the present invention
2/ Al
2O
3In 80-120 (mol ratio), mean particle size is 0.1-0.5 μ m, pore volume is 0.35-0.50ml/g, the aperture be the hole of 0.1～1.7nm account for total pore volume 20%～50%, the aperture accounts for 5%～20% of total pore volume for the hole of＞1.7～6.0nm, the aperture be the hole of 10.0～90.0nm account for total pore volume 30%～60%.
β zeolite preparing process of the present invention comprises: silicon source and aluminium source are in the presence of the tetraethyl ammonium hydroxide template, two sections crystallization of hydrothermal method, elder generation's low temperature nucleation, back high temperature crystallization also can adopt a step crystallization, add ammonium salt and handle certain hour, above-mentioned crystallization and handle and to carry out under continuously stirring is filtered, drying then, divides three sections temperature control roastings to remove organic ammonium, acid treatment under the mitigation condition and High Temperature High Pressure hydrothermal treatment consists make the β zeolite product of multistage pore canal.
Detailed process is as follows: the porosu solid silica gel particle is adopted in the silicon source, sodium aluminate is adopted in the aluminium source, template adopts tetraethyl ammonium hydroxide and sodium hydroxide and water to mix, adopt two sections crystallization methods, elder generation's low temperature nucleation, back high temperature crystallization, in crystallizing kettle in 90～130 ℃ of following crystallization 10～40 hours, at 110-170 ℃ of following crystallization 20-50 hour, or 100 ℃-170 ℃ crystallization 10-60 hour.Directly add ammonium salt then and handled 0.2～3.0 hour down at 80～120 ℃, ammonium salt is handled and can be carried out 1～3 time, and the concentration of ammonium salt in mixture is 0.5～3mol/L.Filter after ammonium salt is handled, wash, drying, remove organic ammonium by three sections temperature control roastings, low temperature (150-250 ℃) dehydration 1.0～6.0 hours, middle temperature (250-450 ℃) organic ammonium decomposed 1.0～4.0 hours, and high temperature (450-650 ℃) was removed free charcoal 6.0～20.0 hours.Acid treatment is at 0.1-5.0mol/L (preferred 0.5～1.5mol/L) mineral acid, treatment temp 20-100 ℃, treatment time 1.0-3.0 hour, the High Temperature High Pressure hydrothermal treatment consists is at temperature 500-700 ℃, pressure 0.05-0.5MPa, handled 0.5-5.0 hour, and obtained the beta zeolite with multilevel pore canals particulate product.Each raw material feed ratio (mole) is: Na
2O/Al
2O
3Be 0.5-5.0, be preferably 1.0-2.0; (TEA)
2O/Al
2O
3Be 0.5-5.0, be preferably 1.0-3.0; SiO
2/ Al
2O
3Be 10-100, be preferably 10-50; H
2O/Al
2O
3Be 100-500; Be preferably 100-300.
Said porosu solid silica gel in the inventive method can be gross porosity, mesopore, and the silica gel of pore, said aluminium source can be solid sodium aluminate and liquid sodium aluminate, the sodium source can be the mixture of sodium aluminate or sodium aluminate and sodium hydroxide.Said template tetraethyl ammonium hydroxide is from etamon chloride or tetraethyl-amine bromide.Ammonium salt can be ammonium chloride, ammonium nitrate or ammonium sulfate, also can be mixed-ammonium salt.The mineral acid that acid treatment is used is generally hydrochloric acid, nitric acid or sulfuric acid etc.
β zeolite of the present invention can be used for conversion catalysts such as hydrocracking, hydrotreatment, isomerization, disproportionation, olefin hydration, dehydration of alcohols, dehydrogenation, oxidation, condensation, polymerization.
It is suitable that β zeolite of the present invention has granular size, has multi-stage artery structure.Wherein micropore is the duct of β zeolite itself, is the principal reaction place of material.Mesopore may be the secondary pore that produces in acid treatment and hydrothermal treatment consists process, reduces diffusional resistance, reduces secondary reaction, improves selectivity.Macropore may be that the zeolite primary particle is assembled for behind the final zeolite granular; the duct that forms between primary particle; it mainly acts on the one hand can reduce diffusional resistance; reduce secondary reaction; the more important thing is; this zeolite granular structural defence the outside surface of primary particle fully expose to the open air out, be not subjected to the influence of other catalyst component, can not make full use of the problem of its outside surface when having overcome little crystal grain or nano level zeolite as catalyst component.It is that final suitable particle may be finished in the ammonium salt treating processes that primary particle is assembled.
The inventive method is by the condition of optimization β zeolite crystallization process, and increase by goes on foot the ammonium salt treating processes after crystallization, through appropriate postprocessing, obtains unique β zeolite product.The inventive method is carried out crystallization under conditions such as higher basicity, lower temperature, the crystallization time of lacking, high-speed stirring, then through last handling processes such as ammonium salt processing, obtain final zeolite product.The inventive method silicon source and aluminium source utilization ratio are higher, the single-autoclave yield rate height, and crystallization time is short, and temperature is low, cuts down the consumption of energy, and production cost is low, good repetitiveness.
Description of drawings
Fig. 1 is that the embodiment of the invention 1 gained β zeolite magnification is 20,000 times a transmission electron microscope photo.
Fig. 2 is the X-ray diffraction spectrogram of the embodiment of the invention 1 gained β zeolite.
Embodiment
The following examples will be given and further instruction preparation method provided by the invention.
Embodiment 1
(the laboratory preparation contains Al with the 78g sodium aluminate
2O
319.9m% contains Na
2O 21.44m%), the 435g tetraethyl ammonium hydroxide aqueous solution (industrial product, concentration 1.4N), (Haiyang Chemical Plant, Qingdao produces silochrom particle 288g, contains SiO
295%) and after water purification 120g mixes, fully 100 ℃ of reactions 20 hours in 2 liter stainless steel cauldrons under the continuous stirring condition, rise to 150 ℃ of crystallization 40 hours again, crystallization finishes release, cooling, add ammonium nitrate solution, by ammonium nitrate concn in the system is 2mol/L, stirs at 95 ℃ of constant temperature and filters then in 1 hour, carries out an ammonium salt again by above-mentioned condition and handles.Filter washing, drying then, remove organic ammonium by three sections temperature control roastings, the dehydration in 2 hours of 200 ℃ of constant temperature, 400 ℃ were decomposed organic ammonium 3 hours, 550 ℃ were decomposed free charcoal 12 hours, acid-treated concentration of hydrochloric acid 0.5mol/L, and fully agitation condition was handled 1 hour for following 80 ℃, filter washing, drying then, 650 ℃ of high-temperature high pressure water thermal treatment temps, pressure 0.1MPa handled 2 hours, promptly obtained β zeolite B-1 of the present invention.
Embodiment 2
(the laboratory preparation contains Al with the 80g sodium aluminate
2O
318.90m% contains Na
2O 24.11m%), the 382g tetraethyl ammonium hydroxide aqueous solution (Industrial products, concentration 1.55N), (Haiyang Chemical Plant, Qingdao produces and contains SiO silochrom particle 280g
295.2m%) mix with water purification 158g.Other conditions promptly obtain β zeolite B-2 with embodiment 1.
Embodiment 3
(the industry preparation contains Al with the 80kg sodium aluminate
2O
319.55m% contains Na
2O21.17m%), (Haiyang Chemical Plant, Qingdao produces 459kg tetraethyl ammonium hydroxide (Industrial products, concentration 1.35N) silochrom particle 288kg, contains SiO
297m%) with water purification 140kg, after thorough mixing was even, under the continuous stirring condition, as follows embodiment 1 promptly got the β zeolite, B-3 in 1000 liter stainless steel crystallizing kettles.
Embodiment 4
According to the method for embodiment 1, during crystallization earlier 95 ℃ of crystallization 12 hours, then 155 ℃ of crystallization 25 hours.The ammonium salt concentration adjustment was 1.0mol/L when ammonium salt was handled, and treatment temp is 85 ℃, and the time is 1.5 hours, and number of processes is 3 times.Acid treatment is at 1.5 hydrochloric acid, 90 ℃ of treatment temps, and in 2.0 hours treatment times, other is with embodiment 1, and product is B-4.
Embodiment 5
According to the method for embodiment 2, ammonium salt is handled and used ammonium chloride, the concentration in system is 0.8mol/L, and temperature is 105 ℃, and the time is 2 hours, and number of times is 3 times.Nitric acid is used in acid treatment, and concentration is at 1.2mol/L, 50 ℃ of treatment temps, and in 1.5 hours treatment times, the High Temperature High Pressure hydrothermal treatment consists is 550 ℃ of temperature, and pressure 0.2MPa handled 3.0 hours, and other is with embodiment 1, and getting product is B-5.
Table 1 embodiment of the invention makes β zeolite product character
| Production code member | B-1 | B-2 | B-3 | B-4 | B-5 | |
| Scale L | 2 | 2 | 1000 | 2 | 2 | |
| SiO 2/Al 2O 3 | 102 | 98 | 112 | 115 | 104 | |
| Median size μ m | 0.25 | 0.20 | 0.30 | 0.15 | 0.35 | |
| V Total holeml/g | 0.407 | 0.412 | 0.422 | 0.425 | 0.409 | |
| Product yield % | 85 | 87 | 84 | 88 | 89 | |
| Pore distribution % | ＜1.7nm | 32.2 | 28.9 | 31.8 | 26.2 | 28.4 |
| ＞1.7nm | 67.8 | 71.1 | 68.8 | 67.8 | 71.6 | |
| 1.7-6.0nm | 8.2 | 12.3 | 10.5 | 15.8 | 14.3 | |
| 10.0-90.0nm | 54.5 | 54.4 | 53.2 | 46.3 | 43.4 | |
Claims (10)
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| CN103964458A (en) * | 2013-01-29 | 2014-08-06 | 中国石油大学(北京) | High-silicon-to-aluminum-ratio hierarchical beta zeolite and preparing method thereof |
| CN104671255A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | Beta molecular sieve and preparing method thereof |
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| US11572283B2 (en) | 2017-10-26 | 2023-02-07 | China Petroleum & Chemical Corporation | Molecular sieve having mesopores, preparation method therefor, and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1684101A (en) * | 1999-11-23 | 2001-06-04 | Universite Laval | Mesoporous zeolitic material with microporous crystalline mesopore walls |
| FR2802120B1 (en) * | 1999-12-14 | 2002-02-01 | Inst Francais Du Petrole | MICRO AND MESOPOROUS SILICOALUMINATE SOLID, PROCESS FOR PREPARATION, USE AS A CATALYST AND IN CONVERSION OF HYDROCARBONS |
| CN1100004C (en) * | 2000-05-19 | 2003-01-29 | 中国石油化工集团公司 | Synthesis of small-crystallite beta zeolite |
| CN1335258A (en) * | 2001-02-28 | 2002-02-13 | 刘希尧 | Synthesis of nanometer size beta-zeolite |
| CN1176017C (en) * | 2001-08-24 | 2004-11-17 | 复旦大学 | Process for preparing multi-class sequential macroreticular-micropore material |
| CN1226096C (en) * | 2001-09-24 | 2005-11-09 | 复旦大学 | Method for preparing multi-level pore structure zeolite material by zeolization of diatomite |
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2004
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| CN108069437A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of Beta molecular sieves and its synthetic method and application |
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| CN109704357A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of Beta molecular sieve and its preparation method and application |
| CN109704357B (en) * | 2017-10-26 | 2021-01-15 | 中国石油化工股份有限公司 | Preparation method of Beta molecular sieve |
| US11572283B2 (en) | 2017-10-26 | 2023-02-07 | China Petroleum & Chemical Corporation | Molecular sieve having mesopores, preparation method therefor, and application thereof |
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