CN1915816A - Method for preparing beta zeolite in small crystal grain - Google Patents
Method for preparing beta zeolite in small crystal grain Download PDFInfo
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- CN1915816A CN1915816A CN 200510028772 CN200510028772A CN1915816A CN 1915816 A CN1915816 A CN 1915816A CN 200510028772 CN200510028772 CN 200510028772 CN 200510028772 A CN200510028772 A CN 200510028772A CN 1915816 A CN1915816 A CN 1915816A
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- zeolite
- sio
- crystal grain
- beta zeolite
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Abstract
This invention relates to a method for preparing beta-zeolite with fine grains. The method comprises: (1) adopting silica sol with high SiO2 content as the Si source, sodium aluminate as the Al source, and tetraethyl ammonium cations as the templating agent; (2) performing hydrothermal crystallization at 80-160 deg.C for 1-8 days to obtain beta-zeolite with fine grains. The method solves the problems of low yield of molecular sieve and large amount of templating agent consumption caused by large amount of water consumption, and can be used in industrial manufacture of beta-zeolite.
Description
Technical field
The present invention relates to a kind of method for preparing beta zeolite in small crystal grain.
Background technology
Ultrafine particle typically refers to the small solid particulate of size less than the hundreds of nanometer, be that the Jie of a class between cluster and macro object sees material, its surface atom number and body be ratio the reducing and sharply increase with grain size of total atom number mutually, demonstrate tangible volume effect, surface effects and quantum size effect, thereby ultrafine particle is become have the novel material of unique physicochemical property.Along with reducing of zeolite crystal size, the ratio of surface atom, the specific surface of crystal grain and surface energy increase sharply.Specific surface is big, and the surface atom number is many, and promptly the surfactivity center is many, and the catalytic efficiency height helps eliminating diffusional effect, and the aperture is difficult for blocked.In some specific catalyzed reaction, nano-sized molecular sieve can effectively be improved the reactivity worth of same composition regular particle size molecular sieve.Aspect physical strength,, thereby have higher-strength and wear resistance because particle is little.Small crystal grain molecular sieve is owing to have bigger outer specific surface and higher intracrystalline rate of diffusion, make reactant molecule be easy to arrive catalytic active site, and product spreads out from the duct easily, all shows than the more superior performance that manys of big grain-size molecular sieve improving the utilization ratio of catalyzer, strengthen macromolecular conversion capability, reduce deep reaction, improve target product selectivity and reduce aspects such as catalyzer coking deactivation rate.Can be used as the catalyst activity component and be widely used in petroleum catalytic cracking, petrochemical complex and fine chemistry industry aspect.Nano-scale NaY molecular sieve as high silica alumina ratio can significantly improve the heavy oil cracking rate, improves gasoline octane rating, shows higher cracking activity and cracking selectivity.
Zeolite with nanometer-size die size (particle diameter is below 100 nanometers) exists with two states usually: a class is to be scattered in the solvent with discrete colloidal particle form, forms stable molecular sieve colloidal sol, and the lower crystallization temperature of main employing synthesizes; Another kind ofly then exist with the accumulation bodily form formula of nano zeolite, its crystallization temperature is higher relatively.
The β zeolite synthesized (US3308069) with classical hydrothermal crystallization method by U.S. Mobil company first in 1967, it is supersiliceous zeolite with three-dimensional staggered twelve-ring pore passage structure, very big using value is arranged at aspects such as catalysis and absorption, behind modification or some metal constituent element of load, can be used for refining of petroleum and petrochemical process such as catalytic cracking, hydrocracking, alkylation, hydro-isomerization, hydrofining, Hydrodewaxing, olefin hydration, and multiple fine chemicals building-up process such as nitrated, ammonification, esterification.In the patented technology of Mobil company, the consumption of template tetraethyl ammonium hydroxide is very big, so cost is higher, is unfavorable for large-scale commercial production, and crystallization time is long.
WO93/08125 provides a kind of liquid-phase synthesis process of nanometer size beta zeolite, and at 70 ℃ of low temperature crystallized β zeolites that prepare about 50 nanometers of grain-size, but crystallization time reaches 25 days, TEAOH/SiO in the raw material
2Mol ratio is up to 0.5 (TEA is a tetraethyl ammonium), and the template consumption is big, synthetic cost height; People such as Corma (Camblor M A, Corma A, Mifsud A, et al.Stud SurfSci catal in the crystallization system that the alkali metal-free positively charged ion exists, is the silicon source with the white carbon black 105:341), metallic aluminium is the aluminium source, by changing system SiO
2/ Al
2O
3Mol ratio, having synthesized grain-size is the β zeolite of 200～10 nanometers, because basicity is provided TEAOH/SiO fully in the crystallization system by template
2Mol ratio is up to 0.52, and synthetic cost is higher, and crystallization time also reaches 8～15 days, and the regulating measure of product grains size is also limited.(LandauM V such as Landau, Tavor D, Regev O, et al.Chem Mater, 1999,11 (8): 2030) then be the silicon source with the silicon sol, aluminum isopropylate is the aluminium source, at low sodium ions content, synthesizing particle diameter under the high template concentration is the β zeolite accumulation body of 60～100 nanometers, and finds that it is formed by littler primary particle gathering.
Chinese patent CN1335258 uses tetraethylammonium cation and fluorochemical composite mould plate agent, does the silicon source with silicon sol or water glass, synthesis of high purity (degree of crystallinity) nanometer size beta zeolite.But in the document, the large usage quantity of water cause the template consumption big, and the molecular sieve yield is low.
Summary of the invention
Technical problem to be solved by this invention be in the prior art since raw mix in water consumption bigger, cause the template consumption big, the problem that the molecular sieve yield is low provides a kind of new method for preparing beta zeolite in small crystal grain.This method have feed molar form in the water yield few, the synthetic high advantage of molecular sieve yield that obtains.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing beta zeolite in small crystal grain, with the tetraethylammonium cation is template, with weight percentage is that 30～50% silicon sol is the silicon source, sodium aluminate is the aluminium source, in temperature is the β zeolite that 80～160 ℃ of following hydrothermal crystallizings got maximum median size≤200 nanometers in 1～8 day, and the molar ratio range of each material component is as follows in its reaction mixture system:
SiO
2/ Al
2O
3Be 10～800;
(TEA)
2O/SiO
2Be 0.01～0.25;
Na
2O/SiO
2Be 0.01～0.50;
H
2O/SiO
2Be 3～9.8.
The tetraethylammonium cation preferred version is selected from halogenide, tetraethyl ammonium hydroxide or its mixture of tetraethyl ammonium in the technique scheme.Silicon source preferred version is selected from SiO
2Weight content is 35～45% industry silicasol.In the reaction mixture (TEA)
2O/SiO
2The mol ratio preferable range is 0.1～0.2; H
2O/SiO
2The mol ratio preferable range is 5～8.5.
The present invention adopts high density tetraethyl ammonium solution template, SiO
2The industry silicasol that content is high is the silicon source, and sodium aluminate constitutes close phase system for the aluminium source.The present invention is owing to use close phase system, and water silicon is than low, organic amine template actual concentrations height, thus improved the service efficiency of organic amine template; Under the alkali metal cation existence condition, synthesize, overcome the limitation of existing patent, reduced production cost; Simultaneously, use close phase system that single-autoclave yield rate is improved greatly, obtained better technical effect.
Specifically, method provided by the invention is with high density tetraethyl ammonium basic solution template, SiO
2The industry silicasol that content is high is the silicon source, and sodium aluminate is close phase system synthesizing beta zeolite in small crystal grain for the aluminium source constitutes.Under agitation respectively aluminium source and silicon source are joined in the composite mould plate agent system of tetraethyl ammonium basic solution and fluorochemical, back hydrothermal crystallizing under 80～160 ℃ of conditions stirs.Crystallization process can be in 1～8 day a step constant temperature finish, also can be divided into two sections or multistage and finish step by step.
According to method provided by the invention, used aluminium source is a sodium aluminate.
According to method provided by the invention, can add a certain amount of mineral alkali and regulate basicity, used mineral alkali can be LA family oxyhydroxide, ammoniacal liquor etc.
According to method provided by the invention, can regulate the grain-size of β zeolite by the modulation crystallization temperature, crystallization temperature is low more, and grain-size is more little.
According to method provided by the invention, silicon source, aluminium source, mineral alkali (also can not adding) are joined in the tetraethyl ammonium basic solution, change over to after stirring in the stainless steel cauldron, at 80～160 ℃ of next section of condition thermostatic crystallizations or two sections, 1～8 day synthesizing beta zeolite in small crystal grain of multistage thermostatic crystallization.Crystallization finishes, and carries out suction filtration, washing, and drying obtains the β zeolite product.Utilize its phase structure of X-ray diffraction technical Analysis and degree of crystallinity, analyze its chemical constitution with chemical analysis method.
Characteristics of the present invention are to use close phase system, the single-autoclave yield rate height, and the template consumption is low, and crystallization time shortens, and synthetic cost is low.
The invention will be further elaborated below by embodiment.
Embodiment
The preparation of β zeolite standard substance
According to the disclosed method of example among the US3308069, synthesized β zeolite standard substance.
Adding 1.05 gram sodium aluminates (contain Al among the 25% weight TEAOH (commercially available product) 26.2 restrain
2O
343% weight contains Na
2O 39% weight, industrial goods), add 38.8 gram silicon sol again and (contain SiO
226% weight, industrial goods), continue to stir 1 hour.Change in the stainless steel cauldron, take out cooling after 3 days 150 ℃ of following crystallization, after filtration, the washing after, under 140 ℃, be drying to obtain the β zeolite.
The mol ratio of each component that feeds intake is:
1Al
2O
3·38SiO
2·5(TEA)
2O·1.5Na
2O·532H
2O
With this sample is the benchmark sample, and its XRD measures degree of crystallinity as 100%, the degree of crystallinity of the embodiment of the invention and comparative example all with its feature diffraction therewith the benchmark sample contrast, represent with relative crystallinity.
[comparative example 1]
Method synthesis of nano size beta zeolite according to the CN1335258 disclosure
Raw material is
(A), silicon sol: contain SiO
226 weight %, industrial goods.
(B), aluminium hydroxide: content 68 weight %, commercially available product.
(C), tetraethyl ammonium hydroxide: content 14.6 weight %, industrial goods.
(D), Sodium Fluoride, content 98 weight %, commercially available product.
(E), sodium hydroxide: content 96 weight %, commercially available product.
Get 24.2 gram tetraethyl ammonium hydroxide solution, add Sodium Fluoride 1.286 grams and sodium hydroxide 0.938 gram under stirring; Add 1.043 gram aluminium hydroxides and 36 gram silicon sol under stirring successively, after stirring, change in the stainless steel cauldron, carry out crystallization by certain heating schedule.Crystallization temperature is 120 ℃.Crystallization finishes and carries out suction filtration, washing, and drying obtains the nanometer size beta zeolite product of median size 90 nanometers, and the X-ray diffraction technical Analysis is indicated as pure β zeolite, and degree of crystallinity is 98%, and chemical analysis method is analyzed its product S iO
2/ Al
2O
3Mol ratio is 23.3.The original constitutive molar ratio that feeds intake is:
1Al
2O
3·33SiO
2·2.6(TEA)
2O·5.8Na
2O·6.6F
-·560H
2O
[comparative example 2]
Raw material is:
(A), water glass: contain SiO
226 weight % contain Na
2O 8.2 weight %, industrial goods.
(B), sodium aluminate: contain Al
2O
343 weight %, Na
2O 39 weight %, commercially available product.
(C), tetraethyl ammonium hydroxide: content 18.7 weight %, industrial goods.
(D), Neutral ammonium fluoride, content 96 weight %, commercially available product.
(E), potassium hydroxide, content 82.0 weight %, commercially available product.
Get 18.8 gram tetraethyl ammonium hydroxide solution, add Neutral ammonium fluoride 0.923 gram and potassium hydroxide 0.56 gram under stirring; Stir and drip solution and the 83.0 gram water glass of 0.237 gram sodium aluminate solution down successively, add β zeolite seed crystal 0.32 gram again in 4 gram water.After stirring, change in the stainless steel cauldron, carry out crystallization by certain heating schedule.140 ℃ of crystallization 3 days, crystallization finishes and carries out suction filtration, washing, and drying obtains the β zeolite product of median size 90 nanometers, adopts the X-ray diffraction technical Analysis to be indicated as pure β zeolite, and degree of crystallinity is 98%.Zeolite yield (refer in the product in the sial and raw material the ratio of sial) 40%.The original constitutive molar ratio that feeds intake is:
1Al
2O
3·360SiO
2·12(TEA)
2O·1.5Na
2O·4.1K
2O·24F
-·4110H
2O
[embodiment 1～3]
According to method synthesis of nano size beta zeolite provided by the invention
Raw material is
(A), silicon sol: contain SiO
240 weight %, industrial goods.
(B), sodium aluminate: contain Al
2O
343 weight %, commercially available product.
(C), tetraethyl ammonium hydroxide: content 35 weight %, industrial goods.
Get 42.1 gram tetraethyl ammonium hydroxide solution, stir 2.372 gram sodium aluminates of adding down and 75 gram silicon sol, after stirring, change in the stainless steel cauldron, carry out crystallization by certain heating schedule.Crystallization temperature is respectively 120,100,80 ℃.Crystallization finishes and carries out suction filtration, washing, and drying, X-ray diffraction technical Analysis show that product is pure β zeolite, and chemical analysis method is analyzed its chemical constitution, and SEM observes grain-size.Crystallization condition and β zeolite product average grain size and relative crystallinity are listed in table 1 among each embodiment.The original constitutive molar ratio that feeds intake is:
1Al
2O
3·50SiO
2·5(TEA)
2O·1.5Na
2O·400H
2O
Table 1
| The embodiment numbering | 1 | 2 | 3 |
| Crystallization temperature/℃ | 120 | 100 | 80 |
| Crystallization time/sky | 3 | 6 | 10 |
| Product relative crystallinity/% | 97 | 93 | 90 |
| Product S iO 2/Al 2O 3Mol ratio | 43.3 | 42.1 | 40.9 |
| Median size/nanometer | 160 | 110 | 90 |
| The zeolite yield, % | 75 | 80 | 86 |
The XRD diffraction of the β zeolite that embodiment 1 makes the results are shown in Table 2.
Table 2
| 2θ | D (nanometer) | I/I 0 |
| 7.66 | 1.154 | 20 |
| 11.52 | 0.768 | 3 |
| 16.45 | 0.538 | 3 |
| 18.26 | 0.486 | 3 |
| 21.30 | 0.417 | 17 |
| 22.32 | 0.398 | 100 |
| 25.24 | 0.353 | 7 |
| 26.66 | 0.334 | 14 |
| 28.50 | 0.313 | 5 |
| 29.34 | 0.304 | 12 |
| 30.42 | 0.294 | 5 |
| 31.12 | 0.287 | 4 |
| 31.94 | 0.280 | 2 |
| 33.36 | 0.269 | 6 |
| 34.42 | 0.261 | 3 |
| 35.84 | 0.251 | 3 |
| 37.52 | 0.240 | 3 |
| 43.54 | 0.208 | 6 |
Adopt the inventive method, the synthetic zeolite does not contain stray crystal.
[embodiment 4～6]
According to method synthesis of nano size beta zeolite provided by the invention
Raw material is
(A), silicon sol: contain SiO
240 weight %, industrial goods.
(B), sodium aluminate: contain Al
2O
343 weight %, commercially available product.
(C), tetraethyl ammonium hydroxide: content 35 weight %, industrial goods.
By a certain percentage, get a certain amount of tetraethyl ammonium hydroxide solution, add a certain amount of sodium aluminate and 75 gram silicon sol under stirring respectively, after stirring, change in the stainless steel cauldron, carry out crystallization by certain heating schedule.120 ℃ of crystallization are carried out suction filtration, washing after 3 days, drying, X-ray diffraction technical Analysis show that product is pure β zeolite, and chemical analysis method is analyzed its chemical constitution, and SEM observes grain-size.Crystallization condition and β zeolite product average grain size and relative crystallinity are listed in table 3 among each embodiment.
The original constitutive molar ratio that feeds intake is:
1Al
2O
3·xSiO
2·y(TEA)
2O·1.5Na
2O·zH
2O。
Table 3
| The embodiment numbering | 4 | 5 | 6 |
| The original X Y Z tetraethyl ammonium hydroxide that feeds intake, the gram sodium aluminate, gram | 20 1.5 146 31.6 5.930 | 100 12.5 880 52.6 1.186 | 200 30 1911 63.1 0.593 |
| Product relative crystallinity/% product S iO 2/Al 2O 3Mol ratio median size/nano zeolite yield, % | 95 17.5 150 80 | 88 68.5 130 76 | 85 91.0 100 70 |
Claims (5)
1, a kind of method for preparing beta zeolite in small crystal grain, with the tetraethylammonium cation is template, with weight percentage is that 30～50% silicon sol is the silicon source, sodium aluminate is the aluminium source, in temperature is the β zeolite that 80～160 ℃ of following hydrothermal crystallizings got maximum median size≤200 nanometers in 1～8 day, and the molar ratio range of each material component is as follows in its reaction mixture system:
SiO
2/ Al
2O
3Be 10～800;
(TEA)
2O/SiO
2Be 0.01～0.25;
Na
2O/SiO
2Be 0.01～0.50;
H
2O/SiO
2Be 3～9.8.
2,, it is characterized in that tetraethylammonium cation is selected from the halogenide of tetraethyl ammonium, tetraethyl ammonium hydroxide or its mixture according to the described method for preparing beta zeolite in small crystal grain of claim 1.
3,, it is characterized in that the silicon source is selected from SiO according to the described method for preparing beta zeolite in small crystal grain of claim 1
2Weight content is 35～45% industry silicasol.
4, according to the described method for preparing beta zeolite in small crystal grain of claim 1, it is characterized in that (TEA) in the reaction mixture
2O/SiO
2Mol ratio is 0.1～0.2.
5, according to the described method for preparing beta zeolite in small crystal grain of claim 1, it is characterized in that H in the reaction mixture
2O/SiO
2Mol ratio is 5～8.5.
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|---|---|---|---|
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|---|---|---|---|
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|---|---|
| CN1915816A true CN1915816A (en) | 2007-02-21 |
| CN100384731C CN100384731C (en) | 2008-04-30 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288098A (en) * | 2013-05-28 | 2013-09-11 | 辽宁工业大学 | Preparation method of nano-beta zeolite molecular sieve |
| CN112707409A (en) * | 2020-12-30 | 2021-04-27 | 中海油天津化工研究设计院有限公司 | Green preparation method of nano all-silicon Beta molecular sieve |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11345605B2 (en) | 2019-11-14 | 2022-05-31 | Saudi Arabian Oil Company | Systems and methods for preparing nano-sized crystals of BEA zeolite |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232579A (en) * | 1991-06-14 | 1993-08-03 | Mobil Oil Corporation | Catalytic cracking process utilizing a zeolite beta catalyst synthesized with a chelating agent |
| CN1035668C (en) * | 1994-03-11 | 1997-08-20 | 中国石油化工总公司 | Method No.1 for synthesizing beta zealite |
| CN1268545A (en) * | 1999-03-30 | 2000-10-04 | 中国石油化工集团公司 | Method for synthesizing beta-zeolite |
| CN1335258A (en) * | 2001-02-28 | 2002-02-13 | 刘希尧 | Synthesis of nanometer size beta-zeolite |
| CN1139537C (en) * | 2001-04-04 | 2004-02-25 | 中国石油化工股份有限公司 | Process for preparing beta-zeolite |
-
2005
- 2005-08-15 CN CNB2005100287727A patent/CN100384731C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288098A (en) * | 2013-05-28 | 2013-09-11 | 辽宁工业大学 | Preparation method of nano-beta zeolite molecular sieve |
| CN103288098B (en) * | 2013-05-28 | 2015-05-20 | 辽宁工业大学 | Preparation method of nano-beta zeolite molecular sieve |
| CN112707409A (en) * | 2020-12-30 | 2021-04-27 | 中海油天津化工研究设计院有限公司 | Green preparation method of nano all-silicon Beta molecular sieve |
| CN112707409B (en) * | 2020-12-30 | 2022-11-15 | 中海油天津化工研究设计院有限公司 | Green preparation method of nano all-silicon Beta molecular sieve |
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