CN103771439A - Method for preparing Beta zeolite molecular sieve from diatomite - Google Patents
Method for preparing Beta zeolite molecular sieve from diatomite Download PDFInfo
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Abstract
The invention relates to a method for preparing a Beta zeolite molecular sieve from diatomite. The method comprises following steps of (1) mixing diatomite, silica sol, an NaOH solution, a tetraethyl ammonium hydroxide solution and a certain amount of distilled water according to a proportion of SiO2:aAl2O3:bNa2O:cTEAOH(a=0.03-0.2; b=0.01-0.12; c=0.01-0.50), and stirring for 1-3 hours so as to obtain a gel product; (2) stirring the gel product for 2-6 hours at 60-80 DEG C till dry glue forms; (3) extruding the dry glue into powder, putting the powder into a high pressure hydro-thermal synthesis reaction kettle, and crystallizing for 48-240 hours at 110-170 DEG C so as to obtain the crystallizing product; and (4) carrying out suction filtering, washing and stoving on the crystallizing product, and roasting to remove template agent so as to obtain the Beta zeolite molecular sieve. According to the method, the diatomite is taken as a main raw material for main silicon source and aluminum source, and the zeolite molecular sieve with the Beta structure is prepared through a novel crystallizing method, namely 'dry glue conversion technology'.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, be specifically related to a kind of method of utilizing diatomite to prepare Beta zeolite molecular sieve.
Background technology
Zeolite molecular sieve is due to its unique pore passage structure and stronger surface acidity, has that hydrothermal stability is high, selectivity is high, an outstanding advantages such as renewable, environmentally safe, aspect petroleum refining industry and fine chemicals synthetic, has consequence.Beta zeolite molecular sieve belongs to macropore supersiliceous zeolite, the 3 D pore canal system of being intersected by an one dimension twelve-ring duct (7.6 × 6.4) and two two-dimensional drape shape ducts (5.5 × 5.5) forms, in structure, there are two kinds of skeleton arrangement, three kinds of crystallographic systems, in many acid catalyzed reactions, present unique catalytic performance.
Diatomite is a kind of biogenic silicastone, and the diatom remains that mainly formed by the Geological Evolution period of history form, and chemical formula is SiO
2: nH
2o.Diatomite has the microvoid structure of unique ordered arrangement, and porosity is high, and density is little, specific surface area is large, absorption property, acid-proof alkaline and good insulation preformance, this has determined that diatomite can be used as good support of the catalyst, also can be used as the ideal material of preparation Beta zeolite molecular sieve.
U.S. Pat 3308069 (1964) reported first the synthetic method of Beta zeolite, it is characterized in that: will contain Na
2o, Al
2o3, TEAOH, SiO
2make slurries with the mixture of water, in autoclave at 75～200 ℃ crystallization 3～60 days, its feed molar composition is counted with oxide compound: SiO
2/ Al
2o
3=10～200, Na
2o/TEAOH=0.0～0.1, TEAOH/SiO
2=0.1～1.0 (is TEA
2o/SiO
2=0.05～0.5), H
2o/TEAOH=20～75.The subject matter of the method is the expensive of tetraethyl ammonium hydroxide template used, and consumption is large, and crystallization time is longer.
Up to now, the method for practical synthesizing of Beta zeolite is still using tetraethyl ammonium hydroxide (TEAOH) as template, and large usage quantity (as: EP164939, EP187522A2).For reducing Beta zeolite synthesis cost, following discloses document and patent documentation attempt to adopt non-tetraethyl ammonium hydroxide template, as: adopt relatively inexpensive tetraethyl-ammonium halide (EP164939, and dimethyl benzylamine-benzyl halide (EP 159846) US4847055), dibenzyl-1, 4-diazabicyclo [2, 2, 2] octane (EP159847, US 4554145, EP 5171556), dibenzyl dimethylamine (US4642226), diethylenetriamine (US7704487B2) and 4, 4 '-cyclopropyl, two piperidines substitute tetraethyl-oxyammonia, or adopt contain TEAOH composite shuttering system, as TEAOH-TEAX (X=F, Cl, Br)-trolamine (US 5164169, US 5164170, EP523829A1), TEAOH-diethanolamine (US 5139759) etc.But when all not overcoming synthetic Beta zeolite, above-mentioned technology needs a large amount of organic formwork agents and the higher problem of cost.
The research work that reduces Beta zeolite synthesis cost recent years has turned to from finding relatively inexpensive alternate template agent aspect the consumption aspect that how to reduce expensive tetraethyl ammonium hydroxide.External relevant Beta synthetic method mainly contains following several.(1) European patent EP 187522A2 (1985) has reported the new technology of " single solution is synthetic " synthetic Beta zeolite.It is characterized in that: by Na
2o, SiO
2, Al
2o
3after mixing with Beta zeolite seed crystal, mix again 6～10 days synthetic Beta zeolites of crystallization at 75～150 ℃ with tetraethyl ammonium hydroxide solution.The method has been avoided introducing too much water, improved the degree of supersaturation of each reactive material in solution, and then has reduced the consumption of the required tetraethyl ammonium hydroxide of synthetic system.The molar ratio of system is SiO
2/ Al
2o
3=10～200, Na
2o/TEA
2o=0.3～1.0, TEA
2o/SiO
2=0.01～0.1, H
2o/TEA
2o=25～150, crystal seed add-on is 0.1～1.0wt% of reaction mixture butt, grain fineness number is about 3 μ m, but crystal seed used need be that template is synthetic with TEAOH.(2) U.S. Pat 5427765 (1994) has been reported a kind of method of synthetic Beta zeolite.It is characterized in that: after first processing for some time by alkali metal silicate solutions with containing the aqueous solution of aluminium in 0～55 ℃, PH=5～9 scope through filtering, washing obtains SiO
2/ Al
2o
3=10～200 silica-alumina gel, then gel is mixed with alkali metal hydroxide, tetraethyl ammonium hydroxide, crystallization 24～120 hours at 70～160 ℃, the molar ratio of this system is SiO
2/ Al
2o
3=10～200, M
2o/SiO
2=0.01～1, TEA
2o/SiO
2=0.05～0.7, H
2o/TEA
2o=8～30, in the time having crystal seed to exist in synthesized gel rubber, its add-on is 0.01～10wt% of preparation gel, crystal seed is synthetic by TEAOH template.(3) U.S. Pat 7141232B2 (2005) has reported the molecular sieve preparation method by spray-drying process, comprising synthesizing of Beta zeolite.It is characterized in that: the slurries that contain silicon source, aluminium source and a small amount of tetraethyl ammonium hydroxide solution are added to tetraethyl ammonium hydroxide solution after spray drying treatment again.Gained mixture crystallization under certain temperature, pressure obtains Beta zeolite product.In said slurries, can add crystal seed, also can not add crystal seed, molar ratio is SiO
2/ Al
2o
3=12～∞, M
2o/SiO
2=0.04～0.7, TEA
2o/SiO
2=0.01～0.03, H
2o/TEA
2o=1～4.In the time adopting crystal seed synthetic, its add-on accounts for the 0.01-10wt% of SiO2 in gel, and crystal seed used is NH4-Beta zeolite.Adopt the method to greatly reduce the system water yield, the TEA+/SiO2 mol ratio that adds crystal seed in embodiment can be down to the complete required time of 0.13, Beta zeolite crystallization and be shortened to 48 hours.But the method gel preparation course complexity, exists solid gel viscosity large, be unfavorable for stirring the problem that industrial implementation difficulty is large.
The domestic study on the synthesis about zeolite molecular sieve mainly contains following methods.(1) Chinese invention patent (application number 94102212.9,1994; 94102213.7,1994) and report the method for the synthetic Beta zeolite of Surface-wetting method.It is characterized in that: using any aperture solid silicone as silicon source, joined in the solution being formed by aluminium source, sodium source, tetraethylammonium cation, water and mixed, make silica gel particle by solution-wet, 10～60 hours synthetic Beta zeolites of crystallization at 140～170 ℃.The molar ratio that its Patent 94102213.7 adopts is SiO
2/ Al
2o
3=10～100, Na
2o/SiO
2=0.01～0.1, TEA
2o/SiO
2=0.025～0.075, H
2o/SiO
2=1～3.The method greatly reduces the consumption of water and tetraethylammonium cation, has reduced production cost.But the reduction of the system water yield has directly caused again the increase of reactant viscosity simultaneously, be difficult for stirring, be therefore unfavorable for industrial application.(2) Chinese invention patent (application number 96100045.7,1996 years) has been reported the method for the synthetic Beta zeolite of fractional crystallization.It is characterized in that: on the Surface-wetting method basis of patent 94102212.9, crystallization condition is optimized, in two steps or multistep carry out crystallization, effectively utilize template.The molar ratio of this patent is SiO
2/ Al
2o
3=20～600, Na
2o/SiO
20.01～0.1, TEA
2o/SiO
2=0.015～0.10, H
2o/SiO
2=2～10.There is equally the problem that reactant viscosity is large in this synthetic method.(3) Chinese invention patent (application number 98122007.X, 1998) has been reported a kind of method of synthetic Beta zeolite.It is characterized in that: first He Na source, pulverous aluminium source is dissolved in the tetraethylammonium cation aqueous solution, then join silica gel or and silicon sol in, at 140-160 ℃, crystallization 10-80 hour synthetic Beta zeolite, regulates grain size by regulation system basicity.The molar ratio of system is: SiO
2/ Al
2o
3=10～55, Na
2o/SiO
2=0.04～0.25, TEA
2o/SiO
2=0.01～0.06, H
2o/SiO
2=2～6.The method is the low wash water reactant system adopting take solid silicone as silicon source equally, SiO
2/ Al
2o
3synthetic narrow range, crystallization time is longer.(4) Chinese invention patent (application number 99119034.3,1999 years) has been reported a kind of synthetic method of Beta zeolite.It is characterized in that: adopt Surface-wetting method, in the initial gel of preparation, add organic viscosity depressant, i.e. fiber-like compound, lignin compound, polyacrylate compounds, alcamine compound, amides or their mixture.The consumption of viscosity-depression agent is SiO in reactant
20.01～15wt%.This has improved the large problem of low wash water synthetic system medium viscosity to a certain extent.But the use of organic viscosity-depression agent has caused the environmental pollution in cost increase and last handling process.(5) Chinese invention patent (application number 00107486.5,2000 year) has been reported a kind of synthetic method of little crystal grain Beta zeolite.It is characterized in that: adopt Surface-wetting method, in the initial gel of preparation, add organic additive, i.e. polyol-based non-ionic surfactant, polyether class lubricating oil or their mixture, consumption is SiO in reaction mixture
20.05-8wt%, for improve reactant system viscosity large, stir difficult problem.But the introducing of organic additive causes environmental pollution in cost increase and last handling process to increase the weight of.(6) Chinese invention patent (application number 97111745.4,1997 years) has been reported a kind of method of synthetic Beta zeolite.It is characterized in that: to adding industry silicasol, sodium aluminate and crystal seed, 4～15 days synthetic Beta zeolites of crystallization at 90～200 ℃ containing in the basic solution of composite mould plate agent.Composite mould plate agent is made up of halogenide, tetraethyl ammonium hydroxide or its mixture and the fluorochemical of tetraethyl ammonium.The molar ratio of system is: SiO
2/ Al
2o
3=10～400, Na
2o/SiO
2=0.005～0.6, (TEA)
2o/SiO
2=0.03～0.5, H
2o/SiO
2=10～30, (NH
4)
2o/SiO
2=0～0.1, TEA
+/ F
-=0.25～4, crystal seed add-on is the SiO that feeds intake
20～5wt%.It is the consumption that reduces organic amine template that this method adds the effect of fluorochemical, has expanded the SiO of Beta zeolite synthesis
2/ Al
2o
3compare scope.But the method gel crystallization required time is long, and F
-use equipment is caused to larger corrosion.(7) Chinese invention patent (application number 98119974.7,1998 years) improves synthetic method in patent 97111745.4.Feature after improvement is: in employing Tai-Ace S 150, aluminum chloride, aluminum nitrate and pseudo-boehmite, any one is as aluminium source, to adding aluminium source, silicon source and crystal seed, 30 hours～10 days synthetic Beta zeolites of crystallization at 90～200 ℃ containing in the basic solution of composite mould plate agent.Composite mould plate agent is made up of halogenide, tetraethyl ammonium hydroxide or its mixture and the fluorochemical of tetraethyl ammonium.The molar ratio of system is: SiO
2/ Al
2o
3=10～200, Na
2o/SiO
2=0.005～0.6, (TEA)
2o/SiO
2=0.03～0.20, H
2o/SiO
2=10～30, (NH
4)
2o/SiO
2=0～1.0, TEA
+/ F
-=0.25～4, crystal seed add-on is the SiO that feeds intake
20～5wt%.There is equally F in the method
-to the problem of equipment corrosion.(8) Chinese invention patent (application number 98119975.5,1998 years) has carried out again improving to the synthetic method in patent 97111745.4.It is characterized in that: adopting industrial-grade sodium silicate is silicon source, to adding aluminium source, silicon source and crystal seed containing in the basic solution of composite mould plate agent, 20 hours～7 days synthetic Beta zeolites of crystallization at 90～200 ℃, composite mould plate agent is made up of halogenide, tetraethyl ammonium hydroxide or its mixture and the fluorochemical of tetraethyl ammonium.The molar ratio of system is: SiO
2/ Al
2o
3=10～800, Na
2o/SiO
2=0.27～0.8, (TEA)
2o/SiO
2=0.02～0.25, H
2o/SiO
2=10～30, F
-/ SiO
2=0.01～0.30, crystal seed add-on is the SiO that feeds intake
20～5wt%.The method still requires to add fluorochemical.(9) Chinese invention patent (application number 00131432.7,2000 year) has been reported a kind of synthetic method of Beta zeolite.It is characterized in that: after water glass is mixed with aluminium source, regulate PH value to make it to reach 2～12, at 180～240 ℃, mist projection granulating makes microspheroidal silica-alumina gel, then joined in the basic solution containing template, at 80～200 ℃, hydrothermal crystallizing synthesizes Beta zeolite for 6～144 hours.The molar ratio adopting is: SiO
2/ Al
2o
3=10～∞, Na
2o/SiO
2=0.01～0.50, (TEA)
2o/SiO
2=0.01～0.50, H
2o/SiO
2=2～12, F
-/ SiO
2=0～0.30.(10) Chinese invention patent (application number 02123599.6,2002 year) has been reported the method for the synthetic Beta zeolite of the even distribution of template density unevenness.It is characterized in that: synthetic system is divided into main and auxiliary two portions, feeds intake respectively, main part SiO
2/ Al
2o
3=20～100, (TEA)
2o/SiO
2=0.03～0.075, Na
2o/SiO
2=0.04～0.11, H
2o/SiO
2=2～8; Slave part SiO
2/ Al
2o
3=20～60, FZMB/SiO
2=0～0.25, Na
2o/SiO
2=0.04～0.11, H
2o/SiO
2=2～6, auxiliary template agent (FZMB) adopts triethylamine, trolamine, diethanolamine, di-n-propylamine or Di-n-Butyl Amine.Major-minor two portions mix 24-48 hour synthetic Beta zeolite product of rear segmentation crystallization.The advantage of the method has been to reduce the consumption of master module agent, has shortened crystallization time, but exists gel preparation course complexity simultaneously, and need add the shortcoming of auxiliary template agent.(11) Chinese invention patent (application number 200610115385.1,2006 years) has been reported the method for preparing Beta zeolite take kaolin as raw material.It is characterized in that: using the kaolin after 600～800 ℃ of roastings, acid treatment as silicon and aluminum source, joined in the aqueous solution of sodium source and tetraethylammonium cation and mix, crystallization 26～60 hours at 120～185 ℃.The molar ratio of system is: SiO
2/ Al
2o
3=60～100, Na
2o/SiO
2=0.019～0.095, (TEA)
2o/SiO
2=0.015～0.05, H
2o/SiO
2=1.3～5.3.The method is used cheap kaolin as silicon and aluminum source, although low price kaolin early stage complex disposal process, limited the silica alumina ratio (60～100) of initial gel.That this synthetic method adopts in addition is also super dense reaction system (H
2o/SiO
2=1.3～5.3), reactant viscosity large, be unfavorable for large-scale production.(12) Chinese invention patent (application number 200810050456.3,2008 years) has been reported a kind of method without the synthetic Beta zeolite of template.It is characterized in that: be respectively silicon source, aluminium source with white carbon black, sodium aluminate, by add the Beta zeolite seed crystal after roasting in initial gel, gel crystallization at 100～180 ℃ obtains Beta zeolite for 12～24 hours.The molar ratio of system is: SiO
2/ Al
2o
3=31.4～40.3, Na
2o/SiO
2=0.260～0.342, H
2o/SiO
2=13～50; Beta zeolite seed crystal SiO
2/ Al2O
3=22～25, add-on is SiO
25～20wt%.The method has broken through Beta zeolite synthesis and must use the restriction of organic formwork agent, and crystallization time is short, is expected to reduce production costs, and omits follow-up calcination steps, alleviate environmental pollution.But be not difficult to find out, it is narrow that the method also exists synthetic phase region, the large limitation with needing specific crystal seed of amount of seed.
In sum, the searching of the alternate template agent of synthetic Beta zeolite is not simple and easy to, and research shows that the guide effect of alternate template agent is also undesirable, and consumption is large, crystallization time is long.These problems make the alternate template agent progress of failing to make a breakthrough in Beta zeolite synthesis.Meanwhile, above research shows, relies on the silicon source of solid or high density can realize the reduction of template consumption, therefore finds cheap suitable solid or high density silicon source, and for realizing, the synthetic Beta zeolite molecular sieve of low cost is significant.
Summary of the invention
The technical problem that will solve required for the present invention is in above-mentioned prior art problem, a kind of method of utilizing diatomite to prepare Beta zeolite molecular sieve is provided, the method and additive method difference are to realize cheap diatomite and substitute He Lv source, traditional silicon source, and effectively reduce template consumption, and then reduce costs, realize the synthetic new way of Beta zeolite molecular sieve.
The present invention is in order to solve the problems of the technologies described above, and the technical scheme adopting is:
Utilize diatomite to prepare the method for Beta zeolite molecular sieve, it comprises the following steps:
(1) Purification of Diatomite pre-treatment;
(2) according to SiO
2:
aal
2o
3:
bna
2o:
ctEAOH(
a=0.03～0.2;
b=0.01～0.12;
c=0.01～0.50) ratio, obtains gel product by diatomite, silicon sol, NaOH solution, tetraethyl ammonium hydroxide solution and a certain amount of distilled water mix and blend 1～3h;
(3) gel product is stirred to 2～6h at 60～80 ℃ of temperature, until form dry glue;
(4) dry glue is squeezed into after powder, in high pressure water thermal synthesis reactor, at 110～170 ℃ of crystallization 48～240h, obtains crystallization product;
(5) by after crystallization product suction filtration, washing, oven dry, template is removed in roasting, obtains Beta zeolite molecular sieve.The main raw material of the present invention using diatomite as He Lv source, main silicon source, has prepared the zeolite molecular sieve with Beta structure by new crystallization method " Dry gel conversion method technology ".
Compared with prior art, the invention has the beneficial effects as follows:
(1) adopt diatomite as the synthetic main raw material of Beta zeolite molecular sieve, effectively utilized the SiO in diatomite
2and Al
2o
3composition substitutes He Lv source, traditional silicon source, has reduced raw materials cost, has widened diatomaceous application, has realized the new way of Beta Zeolite synthesis.(2) adopt the synthetic Beta zeolite molecular sieve of diatomite, effectively reduced the consumption of template tetraethyl ammonium hydroxide.(3) technological operation is simple, loose operation condition, and the Beta zeolite product epigranular preparing, degree of crystallinity is high.
Accompanying drawing explanation
Fig. 1 is diatomaceous powder x ray diffraction (XRD) collection of illustrative plates; Fig. 2 is powder x ray diffraction (XRD) collection of illustrative plates of the Beta zeolite molecular sieve prepared of embodiment 1; Fig. 3 is diatomaceous scanning electron microscope (SEM) photo; Fig. 4 is scanning electron microscope (SEM) photo of the Beta zeolite molecular sieve prepared of embodiment 1.
Embodiment
In order to understand better the present invention, further set forth content of the present invention in conjunction with following instance, but content of the present invention is not only confined to the following examples.
Comparative example 1
Take silicon sol as silicon source, Tai-Ace S 150 is as aluminium source, employing TEAOH is template, the method for synthetic Beta zeolite molecular sieve authentic specimen, it comprises the following steps: (1) takes 0.342 g Tai-Ace S 150 and makes alum liquor be dissolved in distilled water at 80 ℃ in.(2) take 8 mol/L NaOH solution and the 5.450 g 20 % tetraethyl ammonium hydroxides of 0.55 mL, under magnetic agitation, mix 5 min, after mixing, join 3.004 g 40 % silicon sol Ludox HS-40, continue to stir 30 min.(3) alum liquor of being prepared by above-mentioned (1) adds in colloidal solution (2), then adds the distilled water that measures ratio, stirs 2 h, obtains consisting of of coagulant liquid: SiO
2: TEAOH: Al
2o
3: NaOH: H
2o mol ratio=1: 0.37: 0.05: 0.22:22.(4) gelating soln is heated to 80 ℃ and constant temperature, stirs lower transpiring moisture, adopts tetrafluoroethylene stirring rod hand operated mixing in the time that gelating soln becomes thickness.Until form dry glue.(5) dry glue is squeezed into powder, is positioned in high pressure water thermal synthesis reactor crystallization 72 h at 170 ℃.Deionized water wash, filtration for crystallization product, 80 ℃ of dry 12 h, under air, at temperature programming to 550 ℃, roasting 6 h remove organic formwork agent, make BEA molecular sieve.The degree of crystallinity of comparative example of the present invention and embodiment sample all with its characteristic diffraction peak therewith authentic specimen compare, represent with relative crystallinity.
Embodiment 1
Take diatomite as He Lv source, silicon source, employing TEAOH is template, the method of synthetic Beta zeolite molecular sieve sample, it comprises the following steps: (1) joins 1.758 g diatomite powders in the mixing solutions of 0.47 mL 8 mol/L NaOH solution and 13.251 g 25 % tetraethyl ammonium hydroxides, magnetic agitation 30 min.(2) consisting of according to coagulant liquid: SiO
2: TEAOH: Al
2o
3: NaOH: H
2o mol ratio=1: 0.37: 0.11: 0.17:22 adds the distilled water of residue metering ratio, stirs 2 h.(3) gelating soln is heated to 80 ℃ and constant temperature, stirs lower transpiring moisture, adopts tetrafluoroethylene stirring rod hand operated mixing in the time that gelating soln becomes thickness.Until form dry glue.(4) dry glue is squeezed into powder, is positioned in high pressure water thermal synthesis reactor crystallization 72 h at 140 ℃.Deionized water wash, filtration for crystallization product, 80 ℃ of dry 12 h, under air, at temperature programming to 550 ℃, roasting 6 h remove organic formwork agent, make BEA molecular sieve, and recording the wherein relative crystallinity of Beta zeolite with powder X-ray diffractometry is 88.9%.
Embodiment 2
Take diatomite as He Lv source, silicon source, employing TEAOH is template, the method of synthetic Beta zeolite molecular sieve sample, it comprises the following steps: (1) joins 2.344 g diatomite powders in the mixing solutions of 0.29 mL 8 mol/L NaOH solution and 8.838 g 25 % tetraethyl ammonium hydroxides, magnetic agitation 30 min.(2) consisting of according to coagulant liquid: SiO
2: TEAOH: Al
2o
3: NaOH: H
2o mol ratio=1: 0.50: 0.11: 0.078:22 adds the distilled water of residue metering ratio, stirs 2 h.(3) gelating soln is heated to 80 ℃ and constant temperature, stirs lower transpiring moisture, adopts tetrafluoroethylene stirring rod hand operated mixing in the time that gelating soln becomes thickness.Until form dry glue.(4) dry glue is squeezed into powder, is positioned in high pressure water thermal synthesis reactor crystallization 72 h at 140 ℃.Deionized water wash, filtration for crystallization product, 80 ℃ of dry 12 h, under air, at temperature programming to 550 ℃, roasting 6 h remove organic formwork agent, make BEA molecular sieve, and recording the wherein relative crystallinity of Beta zeolite with powder X-ray diffractometry is 87.2%.
Embodiment 3
Take silica gel as, diatomite is as silicon source, diatomite doubles as aluminium source, employing TEAOH is template, the method of synthetic Beta zeolite molecular sieve sample, it comprises the following steps: (1) joins 0.325 g diatomite powder and 5.180 g 30% silica gel in the mixing solutions of 0.31 mL 8 mol/L NaOH solution and 6.312 g 35 % tetraethyl ammonium hydroxides, magnetic agitation 30 min.(2) consisting of according to coagulant liquid: SiO
2: TEAOH: Al
2o
3: NaOH: H
2o mol ratio=1: 0.37: 0.03: 0.076:22 adds the distilled water of residue metering ratio, stirs 2 h.(3) gelating soln is heated to 80 ℃ and constant temperature, stirs lower transpiring moisture, adopts tetrafluoroethylene stirring rod hand operated mixing in the time that gelating soln becomes thickness.Until form dry glue.(4) dry glue is squeezed into powder, is positioned in high pressure water thermal synthesis reactor crystallization 72 h at 140 ℃.Deionized water wash, filtration for crystallization product, 80 ℃ of dry 12 h, under air, at temperature programming to 550 ℃, roasting 6 h remove organic formwork agent, make BEA molecular sieve, and recording the wherein relative crystallinity of Beta zeolite with powder X-ray diffractometry is 84.5%.
Embodiment 4
Take silica gel as, diatomite is as silicon source, diatomite doubles as aluminium source, employing TEAOH is template, the method of synthetic Beta zeolite molecular sieve sample, it comprises the following steps: (1) joins 0.844 g diatomite powder and 8.040 g 30% silica gel in the mixing solutions of 0.63 mL 8 mol/L NaOH solution and 8.417 g 35 % tetraethyl ammonium hydroxides, magnetic agitation 30 min.(2) consisting of according to coagulant liquid: SiO
2: TEAOH: Al
2o
3: NaOH: H
2o mol ratio=1: 0.40: 0.03: 0.10:22 adds the distilled water of residue metering ratio, stirs 2 h.(3) gelating soln is heated to 80 ℃ and constant temperature, stirs lower transpiring moisture, adopts tetrafluoroethylene stirring rod hand operated mixing in the time that gelating soln becomes thickness.Until form dry glue.(4) dry glue is squeezed into powder, is positioned in high pressure water thermal synthesis reactor crystallization 72 h at 140 ℃.Deionized water wash, filtration for crystallization product, 80 ℃ of dry 12 h, under air, at temperature programming to 550 ℃, roasting 6 h remove organic formwork agent, make BEA molecular sieve, and recording the wherein relative crystallinity of Beta zeolite with powder X-ray diffractometry is 86.3%.
Claims (6)
1. utilize diatomite to prepare the method for Beta zeolite molecular sieve, its feature with comprise the following steps:
(1) Purification of Diatomite pre-treatment;
(2) according to SiO
2: aAl
2o
3: bNa
2o:cTEAOH(a=0.03～0.2; B=0.01～0.12; C=0.01～0.50) ratio, diatomite, silicon sol, NaOH solution, tetraethyl ammonium hydroxide solution and a certain amount of distilled water mix and blend 1～3h are obtained to gel product;
(3) gel product is stirred to 2～6h at 60～80 ℃ of temperature, until form dry glue;
(4) dry glue is squeezed into after powder, in high pressure water thermal synthesis reactor, at 110～170 ℃ of crystallization 48～120h, obtains crystallization product;
(5) by after crystallization product suction filtration, washing, oven dry, template is removed in roasting, obtains Beta zeolite molecular sieve.
2. according to the synthetic method of a kind of Beta zeolite molecular sieve described in claim 1, it is characterized in that He Lv source, said silicon source is diatomite.
3. according to the synthetic method of a kind of Beta zeolite molecular sieve described in claim 1, it is characterized in that organic formwork agent is TEAOH or its haloid.
4. according to the synthetic method of a kind of Beta zeolite molecular sieve described in claim 1, it is characterized in that crystallization temperature scope is 110～170 ℃; Crystallization time is for changing 48～240h; The present invention allows made silica-alumina gel mixture to have following mole of composition: SiO
2/ Al
2o
3=5～50, Na
2o/SiO
2=0.01～0.12, TEA
2o/SiO
2=0.02～1.0, H
2o/SiO
2=10～25.
5. according to the synthetic method of a kind of Beta zeolite molecular sieve described in claim 1, it is characterized in that crystallization temperature scope is 110～170 ℃; Crystallization time is 48～240h.
6. according to the synthetic method of a kind of Beta zeolite molecular sieve described in claim 4, it is characterized in that different silica alumina ratios: SiO
2/ Al
2o
3>=5.0; There is different granularities: select grain fineness number≤1 μ m.
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| CN113694961A (en) * | 2021-09-26 | 2021-11-26 | 吉林化工学院 | Nano hierarchical pore BEA structure molecular sieve catalyst and preparation method and application thereof |
| CN114146724A (en) * | 2021-12-01 | 2022-03-08 | 南宁师范大学 | Preparation method of modified ZSM-5 molecular sieve |
| CN114455602A (en) * | 2022-03-08 | 2022-05-10 | 福州大学 | Preparation method of hierarchical porous nanometer TS-1 molecular sieve |
| CN114920261A (en) * | 2022-06-14 | 2022-08-19 | 延边大学 | Method for preparing illite clay-based integral hierarchical porous nano H-Beta zeolite by utilizing two-stage temperature-changing crystallization technology |
| CN115385353A (en) * | 2022-09-14 | 2022-11-25 | 青岛惠城环保科技集团股份有限公司 | Method for preparing Beta molecular sieve by using green low-template agent |
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| CN101125662A (en) * | 2006-08-15 | 2008-02-20 | 中国石油大学(北京) | Method for preparing beta zeolite from kaolin |
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| CN1346795A (en) * | 2001-09-24 | 2002-05-01 | 复旦大学 | Process for preparing zeolite material with multi-class pore canal by zeolitizing diatomite |
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| CN113694961A (en) * | 2021-09-26 | 2021-11-26 | 吉林化工学院 | Nano hierarchical pore BEA structure molecular sieve catalyst and preparation method and application thereof |
| CN113694961B (en) * | 2021-09-26 | 2023-11-10 | 吉林化工学院 | Nano hierarchical pore BETA structure molecular sieve catalyst, and preparation method and application thereof |
| CN114146724A (en) * | 2021-12-01 | 2022-03-08 | 南宁师范大学 | Preparation method of modified ZSM-5 molecular sieve |
| CN114146724B (en) * | 2021-12-01 | 2024-01-30 | 南宁师范大学 | Preparation method of modified ZSM-5 molecular sieve |
| CN114455602A (en) * | 2022-03-08 | 2022-05-10 | 福州大学 | Preparation method of hierarchical porous nanometer TS-1 molecular sieve |
| CN114920261A (en) * | 2022-06-14 | 2022-08-19 | 延边大学 | Method for preparing illite clay-based integral hierarchical porous nano H-Beta zeolite by utilizing two-stage temperature-changing crystallization technology |
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