CN1335258A - Synthesis of nanometer size beta-zeolite - Google Patents

Synthesis of nanometer size beta-zeolite Download PDF

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CN1335258A
CN1335258A CN 01109082 CN01109082A CN1335258A CN 1335258 A CN1335258 A CN 1335258A CN 01109082 CN01109082 CN 01109082 CN 01109082 A CN01109082 A CN 01109082A CN 1335258 A CN1335258 A CN 1335258A
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zeolite
crystallization
sio
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nanometer size
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祁晓岚
刘希尧
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Abstract

The synthesis of nanometer size beta-zeolite features that in alkali medium industrial silicon gel or industrial water glass as silicon source and sodium aluminate, aluminum salt or aluminum hydroxide as aluminium source are added under stirring into composite template agent system containing tetraethyl ammonium cation and fluoride for hydrothermal crystallization. After finishing crystallization and through separation, washing and drying, beta-zeolite product with maximum average grain size smaller than 100 nm is obtained. The molar ratio ranges of the material components in the reacted mixture system are also disclosed. Compared with available technology of synthesizing nanometer level beta-zeolite, the present invention has less template agent consumption, shorter crystallization period and lower synthesis cost.

Description

A kind of synthesis of nanometer size beta-zeolite
The invention relates to the novel method of synthesis of nano size beta zeolite molecular sieve, the average maximum particle diameter of this nano-sized molecular sieve is nano level.Technical field belongs to C01B39/00 by International Classification of Patents.
Nanotechnology is a kind of high and new technology that is born the eighties in 20th century, and nanoparticle is meant the particle of particle diameter between 1～100nm.Nano-sized molecular sieve is an important component part of nano material, claims the ultramicron molecular sieve again, is the former subgroup number seldom atom be made of of a class between solid and molecule.The physical properties of nano-sized molecular sieve, chemical property such as thermostability, chemically reactive etc. have a great difference with the regular particle size molecular sieve, and this special nature derives from surface effects and Body Effect.Along with reducing of grain-size, the ratio of surface atom, the specific surface of crystal grain and surface energy increase sharply.The upper layer of nano-sized molecular sieve accounts for very big proportion, and specific surface is big, and the surface atom number is many, and promptly the surfactivity center is many, the catalytic efficiency height.The surface tissue of atom level has significantly changed molecular sieve surface electronic state, helps eliminating diffusional effect, and the aperture is difficult for blocked, and 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.Can be widely used in petroleum catalytic cracking, petrochemical complex and fine chemistry industry aspect as catalyst activity component nano-sized molecular sieve.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.Simultaneously, nano-sized molecular sieve also all has new application prospect in fields such as sorbing material, transmitter, photochromics and stupaliths.
Synthetic (US 3 with classical hydrothermal crystallization method first in 1967 by U.S. Mobil company for the β zeolite, 308,069), 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.
The liquid phase synthesizing method that WO 93/08125 provides, at 70 ℃ of low temperature crystallized nanometer size beta zeolites that prepared 50nm, but crystallization time reaches 25 days, TEAOH/SiO in the raw material 2Mol ratio is up to 0.5, and the template consumption is big, synthetic cost height; People such as Corma (Camblor M A, Corma A, Mifsud A, et al.Stud Surf Sci eatal is 105:341) in the crystallization system of alkali metal-free, by changing system SiO 2/ Al 2O 3Mol ratio, having synthesized grain-size is the β zeolite of 200～10nm, 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.Still there is not at present a kind of low-cost synthesis of nanometer size beta-zeolite that possesses industrial application value.
We have proposed the employing silicon sol and have done the silicon source in Chinese patent CN 1,198,404, the method of synthetic β zeolite can reduce consumption of template agent, zeolite yield height in the alkaline medium that contains tetraethylammonium cation and fluorochemical composite mould plate agent system, and can select different aluminum source (CN 1,249,270), convenient for production, we adopt water glass to do silicon source (CN 1,249,271) in the composite mould plate agent system, can obviously shorten crystallization time, improve β zeolite relative crystallinity.
The present invention is on the basis of the synthetic β zeolite method of our above-mentioned Chinese patents, a kind of synthesis of nanometer size beta-zeolite is provided, characteristics are to use tetraethylammonium cation and fluorochemical composite mould plate agent, industry silicasol or service water glass with cheapness are done the silicon source, organic amine and silicon source are than low, promptly under tetraethyl ammonium ion consumption condition seldom, high yield, low-cost synthesis of high purity (degree of crystallinity) nanometer size beta zeolite.
The present invention adopts tetraethylammonium cation-fluorochemical composite mould plate agent system, synthesis of nano size beta zeolite in alkaline medium.Specifically, method provided by the invention is to do the silicon source with industry silicasol, service water glass, silicon source and aluminium source under agitation join in the composite mould plate agent system that contains tetraethylammonium cation and fluorochemical, and back hydrothermal crystallizing under 50～160 ℃ of conditions stirs.Crystallization process step constant temperature in 1～15 day is finished, and 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 selected from one or more in aluminium hydroxide, Tai-Ace S 150, aluminum nitrate, the aluminum chloride.
According to method provided by the invention, can add a certain amount of mineral alkali and regulate basicity, used mineral alkali can be IA family oxyhydroxide, ammoniacal liquor etc.
According to method provided by the invention, can regulate the particle diameter of nanometer size beta zeolite by the modulation crystallization temperature, crystallization temperature is low more, and grain-size is more little.
According to method provided by the invention, with silicon source, aluminium source, mineral alkali (also can not adding) join contain the tetraethylammonium cation and the fluorochemical composite mould plate agent aqueous solution after, stir, change in the stainless steel cauldron, at 50～160 ℃ of next section of condition thermostatic crystallizations or two sections, 1～15 day synthesis of nano size beta of multistage thermostatic crystallization zeolite.Crystallization finishes, and carries out suction filtration, washing, and drying obtains the nanometer size beta 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 the template consumption obviously to be less than existing nanometer size beta zeolite synthesis technology, and crystallization time obviously shortens, but high yield, low-cost synthesis of high purity (degree of crystallinity) nanometer size beta zeolite.
The used material molar ratio of the inventive method synthesis of nano size beta zeolite scope:
SiO 2/Al 2O 3??????????20～800
(TEA) 2O/SiO 2?????????0.01～0.30
Na 2O/SiO 2????????????0.01～0.50
H 2O/SiO 2?????????????10～25
F -/SiO 2???????????????0～0.30
Nanometer size beta zeolite with the method for the invention provides makes can become Hydrogen through roasting after also can exchanging with ammonium salt solution again through the roasting removed template method after pickling transformation is a Hydrogen.Can be by ion-exchange, dipping or other method with various metals or its compound, as basic metal, alkaline-earth metal, rare earth element, Pt, Pd, Re, Sn, Ni, W, Co, etc. element or its compound introduce the zeolite that wherein makes it to become the different metal modification; The compound that also can introduce elements such as different compounds such as P, Ga, Ti, B makes it to become the zeolite with special purpose; Can also be by method dealuminzations such as pickling, chemical extractings to improve nanometer size beta zeolite silica alumina ratio and to increase secondary pore.Can be used as multiple catalyzer, catalyst adjuvant and sorbent material with present method synthetic nanometer size beta zeolite and modified version thereof.
The following examples will the present invention will be further described, but not thereby limiting the invention.
The preparation of β zeolite standard substance
According to US 3,308, the disclosed method of example in 069 has been synthesized β zeolite standard substance.
(contain Al 26.2g add the 1.05g sodium aluminate among the 25%TEAOH (commercially available product) 2O 343%, contain Na 2O 39%, industrial goods), add the 38.8g silicon sol again and (contain SiO 226%, 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.
Embodiment 1～3
According to method synthesis of nano size beta zeolite provided by the invention
Raw material is
(A), silicon sol: contain SiO 226wt%, industrial goods.
(B), aluminium hydroxide: content 68%, commercially available product.
(C), tetraethyl ammonium hydroxide: content 14.6wt%, industrial goods.
(D), Sodium Fluoride, content 98wt%, commercially available product.
(E), sodium hydroxide: content 96wt%, commercially available product.
Get 24.2g tetraethyl ammonium hydroxide solution, add Sodium Fluoride 1.286g and sodium hydroxide 0.938g under stirring; Add 1.043g aluminium hydroxide and 36g silicon sol successively under stirring, 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 obtains the nanometer size beta zeolite product, adopts X-ray diffraction its degree of crystallinity of technical Analysis and phase structure, and chemical analysis method is analyzed its chemical constitution, and SEM observes grain-size.Relative crystallinity, the median size of crystallization condition and nanometer size beta zeolite product are listed in table 1 among each embodiment.The original constitutive molar ratio that feeds intake is:
1Al 2O 333SiO 22.6 (TEA) 2O5.8Na 2O6.6F -560H 2O table 1
The embodiment numbering ????5 ????6 ????7
Crystallization temperature/℃ ????120 ????100 ????80
Crystallization time/d ????7 ????10 ????15
Product relative crystallinity/% ????101 ????95 ????90
Product S iO 2/Al 2O 3 ????23.3 ????23.2 ????22.6
Median size/nm ????90 ????80 ????70
Embodiment 4
According to method synthesis of nano size beta zeolite provided by the invention
Raw material is
(A), silicon sol: contain SiO 226wt%, industrial goods.
(B), aluminium hydroxide: content 68%, commercially available product.
(C), tetraethyl ammonium hydroxide: content 14.6wt%, industrial goods.
(D), Sodium Fluoride, content 98wt%, commercially available product.
(E), sodium hydroxide: content 96wt%, commercially available product.
Get 45.4g tetraethyl ammonium hydroxide solution, add Sodium Fluoride 1.286g and sodium hydroxide 0.938g under stirring; Add 0.344g aluminium hydroxide and 36g silicon sol successively under stirring, after stirring, change in the stainless steel cauldron, pressed certain temperature programming to 120 ℃ crystallization 6 days.Crystallization finishes and carries out suction filtration, washing, and drying obtains the nanometer size beta zeolite product, 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 3Be 40.8.Median size 95nm.The original constitutive molar ratio that feeds intake is:
1Al 2O 3·100SiO 2·15(TEA) 2O·17.5Na 2O·20F -·2400H 2O
Embodiment 5～7
According to method synthesis of nano size beta zeolite provided by the invention
Raw material is
(A), water glass: contain SiO 226wt% contains Na 2O 8.2wt%, industrial goods.
(B), Tai-Ace S 150: contain Al 2(SO 4) 318H 2O 99%, commercially available product.
(C), tetraethyl ammonium hydroxide: content 18.7wt%, industrial goods.
(D), Sodium Fluoride, content 98wt%, commercially available product.
(E), potassium hydroxide, content 82.0wt%, commercially available product.
Get 9.286g tetraethyl ammonium hydroxide solution, add the 10g deionized water, add Sodium Fluoride 1.030g and potassium hydroxide 1.216g under stirring; Stir down and drip solution and the 69.2g water glass that 1.008g Tai-Ace S 150 is dissolved in 6g water successively, add β zeolite seed crystal 0.27g again.After stirring, change in the stainless steel cauldron, carry out crystallization by certain heating schedule.Crystallization temperature is respectively 140,120,90 ℃.Crystallization finishes and carries out suction filtration, washing, and drying obtains the nanometer size beta zeolite product, adopts X-ray diffraction its degree of crystallinity of technical Analysis and phase structure, and chemical analysis method is analyzed its chemical constitution, and SEM observes grain-size.Relative crystallinity, the median size of crystallization condition and nanometer size beta zeolite product are listed in table 2 among each embodiment.The original constitutive molar ratio that feeds intake is: 1Al 2O 3200SiO 23.9 (TEA) 2O69Na 2O6.2K 2O16F -2560H 2O table 2
The embodiment numbering ????5 ????6 ????7
Crystallization temperature/℃ ????140 ????120 ????90
Crystallization time/d ????3 ????6 ????12
Product relative crystallinity/% ????102 ????97 ????93
Product S iO 2/Al 2O 3 ????58 ????55 ????53
Median size/nm ????90 ????80 ????70
The XRD diffraction of the β zeolite that embodiment 5 makes the results are shown in Table 3, and SEM figure sees accompanying drawing 1.
Table 3
????2θ ????d(nm) ????I/I 0
????7.61 ????1.161 ????16
????11.52 ????0.768 ????3
????16.45 ????0.538 ????3
????18.83 ????0.471 ????2
????21.34 ????0.416 ????18
????22.36 ????0.397 ????100
????25.25 ????0.352 ????8
????26.82 ????0.332 ????14
????28.06 ????0.318 ????4
????28.74 ????0.310 ????7
????29.42 ????0.303 ????15
????30.40 ????0.294 ????6
????30.95 ????0.289 ????4
????33.29 ????0.270 ????5
????34.73 ????0.258 ????2
????36.01 ????0.249 ????2
????43.49 ????0.208 ????7
Adopt the inventive method, the synthetic zeolite does not contain stray crystal.
Embodiment 8～10
According to method synthesis of nano size beta zeolite provided by the invention
Raw material is
(A), water glass: contain SiO 226wt% contains Na 2O 8.2wt%, industrial goods.
(B), sodium aluminate:: contain Al 2O 343wt%, Na 2O39wt%, commercially available product.
(C), tetraethyl ammonium hydroxide: content 18.7wt%, industrial goods.
(D), Neutral ammonium fluoride, content 96wt%, commercially available product.
(E), potassium hydroxide, content 82.0wt%, commercially available product.
Get 18.8g tetraethyl ammonium hydroxide solution, add Neutral ammonium fluoride 0.923g and potassium hydroxide 0.56g under stirring; Stir down and drip solution and the 83.0g water glass of 0.237g sodium aluminate solution successively, add β zeolite seed crystal 0.32g again in 4g water.After stirring, change in the stainless steel cauldron, carry out crystallization by certain heating schedule.Crystallization temperature is respectively 140,120,90 ℃.Crystallization finishes and carries out suction filtration, washing, and drying obtains the nanometer size beta zeolite product, adopts X-ray diffraction its degree of crystallinity of technical Analysis and phase structure, and chemical analysis method is analyzed its chemical constitution, and SEM observes grain-size.Relative crystallinity, the median size of crystallization condition and nanometer size beta zeolite product are listed in table 4 among each embodiment.The original constitutive molar ratio that feeds intake is: 1Al 2O 3360SiO 212 (TEA) 2O1.5Na 2O4.1K 2O24F -4110H 2O table 2
The embodiment numbering ????8 ????9 ????10
Crystallization temperature/℃ ????140 ????120 ????90
Crystallization time/d ????3 ????6 ????12
Product relative crystallinity/% ????105 ????101 ????99
Product S iO 2/Al 2O 3 ????75 ????74 ????72
Median size/nm ????90 ????80 ????60
The SEM figure of the β zeolite that embodiment 8 makes sees accompanying drawing 2.

Claims (6)

1. the synthetic method of a nanometer size beta zeolite, it is characterized in that in alkaline medium, doing the silicon source with industry silicasol or service water glass, under agitation join hydrothermal crystallizing in the composite mould plate agent system that contains tetraethylammonium cation and fluorochemical with the aluminium source, after crystallization finishes after filtration, washing, drying obtain the nanometer size beta zeolite product of maximum median size≤100nm, the molar ratio range of each raw material composition is in its reaction mixture system:
SiO 2/Al 2O 3?????????20～800
(TEA) 2O/SiO 2????????0.01～0.30
Na 2O/SiO 2??????????0.01～0.50
H 2O/SiO 2???????????10～25
F -/SiO 2?????????????0～0.30
2. in accordance with the method for claim 1, it is characterized in that described tetraethylammonium cation can be from halogenide, tetraethyl ammonium hydroxide or its mixture of tetraethyl ammonium.
3. in accordance with the method for claim 1, it is characterized in that described aluminium source is selected from one or more in sodium aluminate, aluminium hydroxide, Tai-Ace S 150, aluminum nitrate, the aluminum chloride.
4. in accordance with the method for claim 1, it is characterized in that can add a certain amount of mineral alkali and regulate basicity, described mineral alkali is IA family oxyhydroxide, ammoniacal liquor etc.
5. in accordance with the method for claim 1, it is characterized in that, crystallization process can be under 50～160 ℃ of conditions 1～15 day one step of constant temperature finish, also can crystallization temperature be divided into two sections or multistage and keep 1～15 day substep to finish 50～160 ℃ of scopes.
6. in accordance with the method for claim 1, it is characterized in that described fluorochemical is one or more in IA family fluorochemical, Neutral ammonium fluoride, the ammonium acid fluoride.
CN 01109082 2001-02-28 2001-02-28 Synthesis of nanometer size beta-zeolite Pending CN1335258A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1325375C (en) * 2004-10-29 2007-07-11 中国石油化工股份有限公司 Beta zeolite granule possessing multiple grade pore passage and its preparation method
CN100384731C (en) * 2005-08-15 2008-04-30 中国石油化工股份有限公司 Method for preparing beta zeolite in small crystal grain
CN100384732C (en) * 2005-08-15 2008-04-30 中国石油化工股份有限公司 Method for synthesizing beta zeolite in small crystal grain
CN101353170B (en) * 2007-07-26 2011-03-30 中国石油化工股份有限公司石油化工科学研究院 Method for synthesis of beta-zeolite
CN101353171B (en) * 2007-07-26 2011-08-10 中国石油化工股份有限公司 Method for synthesis of beta-zeolite
CN102464330A (en) * 2010-11-17 2012-05-23 中国石油化工股份有限公司 Synthesis method for nanometer Beta zeolite
CN106698455A (en) * 2015-11-12 2017-05-24 中国石油化工股份有限公司 Synthetic method for nanometer Beta molecular sieve
CN109876854A (en) * 2017-12-06 2019-06-14 中国科学院大连化学物理研究所 A kind of naphthalene liquid-phase oxidation catalyst, preparation method and application
CN110668459A (en) * 2019-10-25 2020-01-10 吉林大学 Nano Beta molecular sieve with wider silicon-aluminum ratio range and preparation method thereof
US11345605B2 (en) 2019-11-14 2022-05-31 Saudi Arabian Oil Company Systems and methods for preparing nano-sized crystals of BEA zeolite

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1325375C (en) * 2004-10-29 2007-07-11 中国石油化工股份有限公司 Beta zeolite granule possessing multiple grade pore passage and its preparation method
CN100384731C (en) * 2005-08-15 2008-04-30 中国石油化工股份有限公司 Method for preparing beta zeolite in small crystal grain
CN100384732C (en) * 2005-08-15 2008-04-30 中国石油化工股份有限公司 Method for synthesizing beta zeolite in small crystal grain
CN101353170B (en) * 2007-07-26 2011-03-30 中国石油化工股份有限公司石油化工科学研究院 Method for synthesis of beta-zeolite
CN101353171B (en) * 2007-07-26 2011-08-10 中国石油化工股份有限公司 Method for synthesis of beta-zeolite
CN102464330A (en) * 2010-11-17 2012-05-23 中国石油化工股份有限公司 Synthesis method for nanometer Beta zeolite
CN102464330B (en) * 2010-11-17 2014-12-10 中国石油化工股份有限公司 Synthesis method for nanometer Beta zeolite
CN106698455A (en) * 2015-11-12 2017-05-24 中国石油化工股份有限公司 Synthetic method for nanometer Beta molecular sieve
CN106698455B (en) * 2015-11-12 2018-07-20 中国石油化工股份有限公司 A kind of synthetic method of nanometer of Beta molecular sieve
CN109876854A (en) * 2017-12-06 2019-06-14 中国科学院大连化学物理研究所 A kind of naphthalene liquid-phase oxidation catalyst, preparation method and application
CN110668459A (en) * 2019-10-25 2020-01-10 吉林大学 Nano Beta molecular sieve with wider silicon-aluminum ratio range and preparation method thereof
US11345605B2 (en) 2019-11-14 2022-05-31 Saudi Arabian Oil Company Systems and methods for preparing nano-sized crystals of BEA zeolite

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