CN101274764B - Preparation for nanometer allitic beta-zeolite - Google Patents
Preparation for nanometer allitic beta-zeolite Download PDFInfo
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- CN101274764B CN101274764B CN2007100649799A CN200710064979A CN101274764B CN 101274764 B CN101274764 B CN 101274764B CN 2007100649799 A CN2007100649799 A CN 2007100649799A CN 200710064979 A CN200710064979 A CN 200710064979A CN 101274764 B CN101274764 B CN 101274764B
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Abstract
The invention discloses a method for preparing Al-rich Beta zeolite. The method is characterized in that a silicon source which is easy to be dissolved in alcohols and a hydrolytic reagent are mixed to be gel which is then treated with aging and drying to obtain silica gel; the silica gel is then evenly mixed with hydrated alumina and acid to obtain mixed silicon-aluminum gel; after being aged, the prepared mixed silicon-aluminum gel is evenly mixed with tetraethyl ammonium cation compound, ionic compound containing F<-> and water to carry out crystallization and recover products of the crystallization.
Description
Technical field
The invention relates to a kind of crystalline silicate prepare zeolite method, more specifically say so about a kind of nanometer β prepare zeolite method.
Background technology
Nano aluminum-rich beta-zeolite generally is meant the allitic beta-zeolite of particle diameter less than 100nm.
The β zeolite is U.S. Mobile company 1967 be synthesized first (Wadlinger R.L, Kerr G.T, Rosinski E.J.USP3,308,069).This zeolite has unique three-dimensional open-framework, have higher hydrocracking and hydro-isomerization catalytic activity, behind modification or some metal constituent element of load, can be used for petroleum refining and petrochemical process such as hydrocracking, hydro-isomerization, hydrofinishing and Hydrodewaxing, diesel oil pour point depression.According to the method for this patent disclosure, the β zeolite is to contain Na
2O, Al
2O
3, TEAOH, SiO
2Make slurries with the mixture of water, obtained in 3～60 days in 75～200 ℃ of crystallizations in autoclave, the molar ratio of reaction system is: SiO
2/ Al
2O
3=10～200, Na
2O/TEAOH=0.0～0.1, TEAOH/SiO
2=0.1～1.0, H
2O/TEAOH=20～75, the silica alumina ratio of the β zeolite that obtains is all 20～250.
In " Vaudry F., Renzo F.D., et al., Zeolites, 1997,19:253-258 " the β zeolite that contains 6 aluminium atoms in the unit cell is defined as the stoichiometry zeolite, corresponding its silica alumina ratio (SiO
2/ Al
2O
3) be 19.3, and then silica alumina ratio is lower than 19.3 β zeolite allitic beta-zeolite (Aluminum-rich β zeolite).
" Ramesh B.Borade and Abraham Clearfield.Chem.Commun., 1996,625 " by earlier being prepared into the dry powder method of crystallization again with reaction mass, at the silica alumina ratio that feeds intake is to have prepared allitic beta-zeolite (SiO under 9 the condition
2/ Al
2O
3=9).This reaction system adopts be fuming silica gel, sodium metaaluminate, tetraethyl ammonium hydroxide and deionized water to make raw material.Its mole that feeds intake consists of: 1Na
2O:Al
2O
3: 9SiO
2: 1.6TEAOH:60H
2O was 170 ℃ of following crystallization 2 days.But, be easy to generate stray crystal such as Gismondine, Analcime during this method amplification test.
The CN1086792A disclosed method is to adopt directing agent method to synthesize allitic beta-zeolite under the very low situation of template agent TEAOH consumption, and silica alumina ratio scope narrower (silica alumina ratio 8～15) approaches ultrastable.This method at first needs to prepare directed agents, then respectively with sodium aluminate, NaOH, silicon source, aluminium source, deionized water and homemade β guiding agent for zeolite (add directed agents amount account for the synthetic mixture cumulative volume 0.5%～10%) mix by a certain percentage, crystallization is 2 days under 413K.Although the used template agent consumption of this method is lower, crystallization time is also shorter, and the utilization rate of silicon is lower than 30%, and roasting easily causes framework dealumination.
" M.Matsukata, M.Ogura, T.Osaki, E.Kikuchi, A.Mitra.Microporous andMesoporous Materials48 (2001) 23～29 " reported and utilized water vapour auxiliary crystallization method to synthesize allitic beta-zeolite, and minimum silica alumina ratio is 7.This method adopts aluminium hydroxide and silester to make silicon and aluminum source, and tetraethyl ammonium hydroxide is done the template agent, at first forms with NaOH, tetraethyl ammonium hydroxide solution, aluminium hydroxide and silester preparation mole: SiO
2: xAl
2O
3: TEAOH:0.098Na
2O:33.3H
2O, the gel of (x〉0.033).Before crystallization gel need in 15 ℃ aging 24 hours, then in 60 ℃ of dried overnight; Crystallization in the reactor of inner liner polytetrafluoroethylene 55ml again, the dried glue of crystallization 1.5g needs 0.5g water, feed intake minimum that crystallization needs lower temperature (373K) and long crystallization time (at least 10 days) during silica alumina ratio 7, product then is unformed when in higher temperature 413K crystallization.The template dosage that adopts this method to use is very big, and crystallization time is longer, has therefore limited industrialization.
In WO97/33830, disclose first and contained F
-Ion and TEA
+Under the condition of ion near neutrality, very wide silica alumina ratio scope (SiO
2/ Al
2O
3The β zeolite that synthesizes pure phase in=12.286～∞).This method is a raw material with silester and metallic aluminium powder, does the template agent with tetraethyl ammonium hydroxide, the minimum SiO that reaches of gel silica alumina ratio
2/ Al
2O
3=12, the minimum SiO that reaches of β zeolite silica alumina ratio of preparation
2/ Al
2O
3=14.4, but crystallization time reaches 62 days, therefore, industrial synthesizing aluminum-enriched β zeolite to have little significance.
The disclosed a kind of synthesis of nanometer size beta-zeolite of CN1335258A, but silica alumina ratio is 20～800, is not allitic beta-zeolite.
Up to now, do not see the report of fluorine-containing system synthesis of nano allitic beta-zeolite.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, the method for synthesis of nano allitic beta-zeolite in a kind of fluorine-containing system is provided.
The preparation method of nano aluminum-rich beta-zeolite provided by the invention is characterized in that this method comprises the steps:
(1) the silicon source that will be soluble in alcohols is mixed in 15～150 ℃ with hydrolytic reagent and becomes glue, and is aging dry, obtains silica gel, and wherein hydrolytic reagent is selected from ammoniacal liquor, ammonium fluoride, organic acid, inorganic acid or its mixture;
(2) silica gel that step (1) is obtained and hydrated alumina, acid mix and obtain sial and mix glue, 20～220 ℃ after aging at least 12 hours with the tetraethylammonium cation compound, contain F
-Ionic compound and water mix, and obtain mole and consist of: SiO
2/ Al
2O
3=5～20, Na
2O/SiO
2=0～0.01, H
2O/SiO
2=1.0～8.0, TEA
+/ SiO
2=0.1～1.0, F
-/ SiO
2=0.1～1.0 mixture, and control pH is 6～9, TEA wherein
+The expression tetraethylammonium cation;
(3), and reclaim crystallization product with mixture crystallization under 75～200 ℃ of temperature, closed container self-generated pressure of step (2).
Preparation method provided by the invention is at very low raw silicon aluminum ratio SiO
2/ Al
2O
3=5～20, with tetraethylammonium cation (TEA
+) do the template agent, contain F
-Synthesize zeolite under the condition of ion, low water, low silica-alumina ratio.Prepared zeolite detects mutually through the XRD thing, has identical feature with the XRD spectra of standard industry β 30 zeolites, does not contain other crystalline phases; Determine that through TEM or Scherrer formula sign synthetic sample is the nanoscale scope, be lower than 19.3, prove allitic beta-zeolite through the icp analysis silica alumina ratio.This method is especially at low silica-alumina ratio scope SiO
2/ Al
2O
3=6～15, obtain the nano aluminum-rich beta-zeolite of high-crystallinity and high yield, and crystallization time is short.
Above-mentioned said Scherrer formula is used to measure the zeolite grain size.
The Scherrer formula is: D=0.90 λ/B (2 θ) cos θ
In the formula: D---crystal grain diameter, nm; θ---Bragg angle, degree; λ---incident wavelength, nm; B (2 θ)---the intrinsic of main peak half-peak breadth diffracted ray adds width, rad; B=(B
m 2-B
s 2)
1/2, Bm is meant the main peak half-peak breadth (FWHM) of testing sample, Bs is meant the standard specimen main peak half-peak breadth (FWHM) greater than 200nm of appointment.B
sGet the half-peak breadth 0.145 of crystal grain greater than the allitic beta-zeolite of 1 μ m.Diffraction maximum gets 302, and this peak half-peak breadth and beta-zeolite molecular sieve fault of construction are irrelevant.
Among the preparation method provided by the invention, the preferred facile hydrolysis in step (1) said silicon source, be dissolved in alcohol methyl silicate or silester; Said hydrolytic reagent is selected from ammoniacal liquor, ammonium fluoride, organic acid, inorganic acid or its mixture, said organic acid such as formic acid, tartaric acid etc., said inorganic acid such as nitric acid, hydrochloric acid etc., said silicon source and hydrolytic reagent mix and are preferable over 25～80 ℃ and become glue, and gelation time is controlled at 0.3h～24h.
Among the preparation method provided by the invention, said hydrated alumina is a boehmite in the step (2), ageing time is preferably 12～48 hours, said acid is selected from one or more in formic acid, acetate, nitric acid and the hydrochloric acid, and said silica gel and hydrated alumina, acid mix under ultrasonic wave and obtains the mixed glue of sial.
Among the preparation method provided by the invention, the process of the said recovery crystallization product of step (3) is well known to those skilled in the art, and the present invention there is no special feature at this, typically refers to the process with crystallization product washing, drying and roasting.
Among the preparation method provided by the invention, after step (3), can also obtain containing the nano aluminum-rich beta-zeolite of above-mentioned element again with ion-exchange method with the compound that is selected from alkaline-earth metal, rare earth element, Pt, Pd, Re, Sn, Ni, W, Co.
Preparation method provided by the invention, directly synthetic allitic beta-zeolite with nanoscale, have following characteristics: the silica gel for preparing alkali metal content very low (or not containing) earlier, then silicon source and aluminium source are mixed into the mixed glue of more uniform solid-state sial, when the preparation sial mixes glue, do not introduce template agent cation, handle through proper temperature; When crystallization, just introduce template agent cation and F
-Ion.
Adopt method provided by the invention can go out nano aluminum-rich beta-zeolite than crystallization under the condition at lower silica alumina ratio and water silicon, product output per single reactor height.The big I of zeolite crystal by regulate the cogelled preparation parameter of sial, initially feed intake condition, crystallization process come modulation control.
Nano aluminum-rich beta-zeolite with method preparation provided by the invention can not need through overpickling and ammonium ion exchange, can directly be transformed into the Hydrogen nano aluminum-rich beta-zeolite through behind the roasting removed template method.
Nano aluminum-rich beta-zeolite (silica alumina ratio is below 19.3) the useful as catalysts constituent element or the carrier of method preparation provided by the invention, Yin Qifu aluminium and have more highdensity acid site, because of its nanoscale has bigger external surface area, make more activated centre obtain exposing, in catalytic reaction, can effectively eliminate diffusion effect, catalytic efficiency is not fully exerted, thereby has a better benzene alkylation (as benzene and ethene or propylene synthesizing ethyl benzene or isopropylbenzene), hydrocracking and hydro-isomerization, catalytic activitys such as etherificate can be used for hydrocracking and hydro-isomerization behind modification or some metal constituent element of load, petroleum refining such as hydrofinishing and Hydrodewaxing and petroleum refining process.In addition, can also be used as ion-exchanger and adsorbent, at industrial bavin, the gasoline desulfur of can be used for, perhaps as vehicle exhaust desulfurization, denitrification catalyst, auxiliary agent etc.
Description of drawings
Fig. 1 is the XRD spectra of standard industry β 30 zeolites.
Fig. 2 is the XRD spectra of the zeolite sample of embodiment 1 preparation.
Fig. 3 is the TEM figure of the β zeolite sample of embodiment 1 preparation.
The specific embodiment
Below by embodiment the present invention is further described, but content not thereby limiting the invention.
Embodiment 1
(1) silester, nitric acid and water are mixed 60 ℃ and become glue, 110 ℃ are aging dry, obtain silica gel;
(2) silica gel that step (1) is obtained and boehmite, formic acid mix and obtain sial and mix glue, mix with tetraethyl ammonium fluoride and water after aging 15 hours at 130 ℃, obtain mole and consist of: SiO
2/ Al
2O
3=10, Na
2O/SiO
2=0.0, H
2O/SiO
2=1.5, TEA
+/ SiO
2=0.28, F
-/ SiO
2=0.28 mixture, and control pH is 6～9;
(3), and reclaim crystallization product with the mixture of step (2) crystallization 7 hours under 190 ℃ of temperature, closed container self-generated pressure.
Analytic sample, its XRD spectra (Fig. 1) have the feature of the XRD spectra (Fig. 2) of standard industry β 30 zeolites, do not contain other stray crystal, degree of crystallinity 120%.The silica alumina ratio of icp analysis sample is 15.5, and Fig. 3 is the TEM figure of sample, and TEM and Scherrer formula record crystallite dimension and be 21.5nm.
(1) silester is mixed with ammonium fluoride, water,, obtain silica gel in 80 ℃ of one-tenth glue, aging dry;
(2) silica gel that step (1) is obtained and boehmite, formic acid mix and obtain sial and mix glue, mix with tetraethyl ammonium fluoride and water after aging 15 hours at 80 ℃, obtain mole and consist of: SiO
2/ Al
2O
3=16, Na
2O/SiO
2=0, H
2O/SiO
2=2.5, TEA
+/ SiO
2=0.3, F
-/ SiO
2=0.3 mixture, and control pH is 6.5;
(3), and reclaim crystallization product with the mixture of step (2) crystallization 5 hours under 140 ℃ of temperature, closed container self-generated pressure.
Analytic sample, the feature that it has the XRD spectra of standard industry β 30 zeolites does not contain other stray crystals, degree of crystallinity 95%.The silica alumina ratio of icp analysis sample is 19.2, and it is 20.2nm that the Scherrer formula records crystallite dimension.
Embodiment 3
(1) methyl silicate and ammoniacal liquor are mixed, 60 ℃ become glue, aging dry, obtain silica gel;
(2) silica gel that step (1) is obtained and boehmite, mixed in hydrochloric acid evenly obtain sial and mix glue, mix with tetraethyl ammonium hydroxide, hydrofluoric acid and water after aging 20 hours at 30 ℃, obtain mole and consist of: SiO
2/ Al
2O
3=14, Na
2O/SiO
2=0, H
2O/SiO
2=4.0, TEA
+/ SiO
2=0.55, F
-/ SiO
2=0.50 mixture, and control pH is 8.5;
(3), and reclaim crystallization product with the mixture of step (2) crystallization 7 hours under 170 ℃ of temperature, closed container self-generated pressure
Analytic sample, the feature that it has the XRD spectra of standard industry β 30 zeolites does not contain other stray crystals, degree of crystallinity 100%.The silica alumina ratio of icp analysis sample is 18.5, and it is 19.6nm that the Scherrer formula records crystallite dimension.
Embodiment 4
(1) silester is mixed 40 ℃ with tartaric acid, water and become glue, aging dry, obtain silica gel;
(2) silica gel that step (1) is obtained and boehmite, nitric acid mix and obtain sial and mix glue, mix with tetraethylammonium bromide, ammonium fluoride and water after aging at least 15 hours at 120 ℃, obtain mole and consist of: SiO
2/ Al
2O
3=12, Na
2O/SiO
2=0.005, H
2O/SiO
2=8.0, TEA
+/ SiO
2=0.60, F
-/ SiO
2=0.50 mixture, and control pH is 6.8;
(3), and reclaim crystallization product with the mixture of step (2) crystallization 7 hours under 160 ℃ of temperature, closed container self-generated pressure.
Analytic sample, the feature that it has the XRD spectra of standard industry β 30 zeolites does not contain other stray crystals, degree of crystallinity 112%.The silica alumina ratio of icp analysis sample is 18.2, and it is 28.5nm that the Scherrer formula records crystallite dimension.
(1) silester, hydrofluoric acid and water are mixed 20 ℃ and become glue, 130 ℃ of aging dryings obtain silica gel;
(2) silica gel that step (1) is obtained and boehmite, nitric acid mix and obtain sial and mix glue, mix with tetraethyl ammonium hydroxide, hydrofluoric acid and water after aging 12 hours at 180 ℃, obtain mole and consist of: SiO
2/ Al
2O
3=6, Na
2O/SiO
2=0, H
2O/SiO
2=7.5, TEA
+/ SiO
2=0.70, F
-/ SiO
2=0.68 mixture, and control pH is 7.8;
(3), and reclaim crystallization product with the mixture of step (2) crystallization 11 hours under 135 ℃ of temperature, closed container self-generated pressure.
Analytic sample, the feature that it has the XRD spectra of standard industry β 30 zeolites does not contain other stray crystals, degree of crystallinity 45%.The silica alumina ratio of icp analysis sample is 13.1, and it is 365nm that the Scherrer formula records crystallite dimension.
Claims (6)
1. the preparation method of a nano aluminum-rich beta-zeolite is characterized in that this method comprises the steps:
(1) the silicon source that will be soluble in alcohols is mixed in 15～150 ℃ with hydrolytic reagent and becomes glue, aging dry, obtain silica gel, wherein hydrolytic reagent is selected from ammoniacal liquor, ammonium fluoride, organic acid, inorganic acid or its mixture, said organic acid is formic acid or tartaric acid, and said inorganic acid is nitric acid or hydrochloric acid;
(2) silica gel that step (1) is obtained and hydrated alumina, acid mix and obtain sial and mix glue, 20～220 ℃ after aging at least 12 hours with the tetraethylammonium cation compound, contain F
-Ionic compound and water mix, and obtain mole and consist of: SiO
2/ Al
2O
3=5～20, Na
2O/SiO
2=0～0.01, H
2O/SiO
2=1.0～8.0, TEA
+/ SiO
2=0.1～1.0, F
-/ SiO
2=0.1～1.0 mixture, and control pH is 6～9, TEA wherein
+The expression tetraethylammonium cation, said acid is selected from one or more in formic acid, acetate, nitric acid and the hydrochloric acid;
(3), and reclaim crystallization product with mixture crystallization under 75～200 ℃ of temperature, closed container self-generated pressure of step (2).
2. according to the preparation method of claim 1, wherein the said silicon of step (1) source is selected from silester or methyl silicate.
3. according to the preparation method of claim 1, wherein the silicon source is mixed in 25～80 ℃ with hydrolytic reagent and becomes glue in the step (1), and gelation time is controlled at 0.3h～24h.
4. according to the preparation method of claim 1, wherein said hydrated alumina is a boehmite in the step (2), and ageing time is 12～48 hours.
5. according to the preparation method of claim 1, wherein said silica gel and hydrated alumina, acid mix under ultrasonic wave and obtain the mixed glue of sial in the step (2).
6. according to any one preparation method of claim 1～5, it is characterized in that preparing the nano aluminum-rich beta-zeolite that contains above-mentioned element with ion-exchange method with the compound that is selected from alkaline-earth metal, rare earth element, Pt, Pd, Re, Sn, Ni, W, Co again after the step (3).
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| CN102249258A (en) * | 2011-05-06 | 2011-11-23 | 大连理工大学 | Method for synthesizing heteroatom Sn-beta zeolite |
| CN103102240B (en) * | 2011-11-14 | 2015-02-25 | 中国石油化工股份有限公司 | Synthesis method of sec-butylbenzene |
| CN105621437B (en) * | 2014-10-30 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of method for preparing low silicon Beta zeolites |
| CN105540605B (en) * | 2014-10-30 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of method of synthesizing aluminum-enriched Beta zeolites |
| TWI831784B (en) | 2018-05-28 | 2024-02-11 | 大陸商中國石油化工科技開發有限公司 | NaY molecular sieve with aluminum-rich surface and preparation method thereof |
| CN110540214B (en) * | 2018-05-28 | 2021-02-09 | 中国石油化工股份有限公司 | NaY molecular sieve with aluminum-rich surface and preparation method thereof |
| CN110856819B (en) * | 2018-08-24 | 2022-07-26 | 国家能源投资集团有限责任公司 | Surface aluminum-rich molecular sieve, preparation method and application thereof, isomerization reaction catalyst and application thereof |
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