CN101353171A - Method for synthesis of beta-zeolite - Google Patents
Method for synthesis of beta-zeolite Download PDFInfo
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- CN101353171A CN101353171A CNA2007101195539A CN200710119553A CN101353171A CN 101353171 A CN101353171 A CN 101353171A CN A2007101195539 A CNA2007101195539 A CN A2007101195539A CN 200710119553 A CN200710119553 A CN 200710119553A CN 101353171 A CN101353171 A CN 101353171A
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Abstract
A synthetic method of beta zeolite comprises the steps as follows: an aluminium sources selected from one or a plurality of pseudoboehmite, hydrated alumina, aluminum hydroxide, aluminium chloride hydrate and SB aluminium hydroxide is acidified by acid and mixed with silica gel, the silica gel is fully mixed with the aluminum source by ultrasonic waves, dried, ground, and mixed with a tetraethylammonium ion template agent, fluoride and water, and crystallized at the temperature of 100-190 DEG C for 1-4 days. The mol ratio of TEA<+> and SiO2 in the mixture is 0.05-0.5, the mol ratio of the TEA<+> and F<-> is 1-2, and the mol ratio of H2O and the SiO2 is 2-10. The method can be used for synthesizing nano beta zeolite with the ratio of silicon to aluminium being not less than 300.
Description
Technical field
The present invention relates to a kind of synthetic method of β zeolite.
Background technology
The β zeolite is a kind of supersiliceous zeolite with intersection 12-membered ring pore canal system, its silica alumina ratio can tens to the total silicon scope modulation, have good thermostability, hydrothermal stability, acidity and excellent hydrophobic property, after its modification, be used for catalysis hydro carbons reaction table and reveal the characteristics that are difficult for coking and long service life, have excellent catalytic performance at aspects such as hydrocracking, hydrofining, Hydrodewaxing, diesel oil pour point depression, catalytic cracking, isomerization, alkylation and transalkylation reactions.
1967, U.S.'s Mobile (Mobil) company adopted the synthetic β zeolite of classical hydrothermal crystallization method (Wadlinger R.L, Kerr G.T, Rosinski E.J., USP 3,308,069) first.The synthetic method that US 3308069 announces comprises: will contain Na
2O, Al
2O
3, TEAOH, SiO
2Make slurries with the mixture of water, in 75～200 ℃ of crystallizations 3～60 days, its molar ratio was: SiO in autoclave
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 the employing aforesaid method obtains is generally 20～250, is difficult to prepare SiO
2/ Al
2O
3〉=300 nanometer high silica alumina ratio β zeolite.
Improve the silica alumina ratio of β zeolite in EP95304, EP488867, EP94827, US4554065, US5200168, CN 1105646A, CN 1035429C, these patents of CN 1113810C by the following method:
1. ammonium is taken off in high-temperature roasting: at 500～600 ℃ of following roasting some hrs, to remove the organic amine template in the raw material β zeolite;
2. acid treatment dealuminzation: with certain density mineral acid or organic acid, with the effect of raw material β zeolite, remove the part aluminium in the zeolite framework at a certain temperature, improve its silica alumina ratio.
With the synthetic β zeolite of aforesaid method, yield is low, cost is high, and institute's synthetic zeolite silica alumina ratio is no more than 300 usually, and defective is more, thermostability is relatively poor, solid acid amount height, anti-nitrogen poor performance, the β zeolite is used in high nitrogen medium be restricted.
Announced SiO among CN 1048697C and the CN 1051055C
2/ Al
2O
3It is 20～600 method for synthesis of beta-zeolite, be with any aperture, 20-300 purpose silica gel is the silicon source, mix or add again a kind of crystal seed glue with it with by the working solution that aluminium source, sodium source, tetraethylammonium cation source, water are formed, make silica gel particle surface wetting by this working solution, then in two steps or multistep carry out crystallization and obtain product.。
US5164169 announced utilize the sequestrant synthesizing Si-Al than be 20～1000, grain-size is the synthetic method of 0.1～3.0 micron big crystal grain Beta zeolite.This method is the silicon source with precipitation silica gel, the high silicon seed of high purity.
CN1915817A has announced a kind of method of synthesizing beta zeolite in small crystal grain, by adopting high-content SiO
2Silicon sol be the silicon source, aluminate or Tai-Ace S 150 are the aluminium source, are template with the mixture of tetraethylammonium cation and fluorochemical, are that 1～8 day method of 80～160 ℃ of following hydrothermal crystallizings prepares the β zeolite in temperature.
The existing method for preparing nanometer β zeolite is difficult to obtain silica alumina ratio and is not less than 300 nanometer β zeolite.
Summary of the invention
The technical problem to be solved in the present invention provides the method that a kind of synthetic grain size is no more than the β zeolite of 100nm.
The invention provides a kind of synthetic method of β zeolite, may further comprise the steps:
(1) will be selected from one or more aluminium source in pseudo-boehmite, hydrated aluminum oxide, aluminium hydroxide, Wickenol CPS 325, the SB aluminium hydroxide, use acidifying, mix with silica gel afterwards, make the abundant dispersing and mixing of silica gel and aluminium source, obtain silica-alumina gel with ultrasonic wave;
(2), grind and obtain the alumino silica gel particle with the silica-alumina gel drying of step (1) gained;
(3) the alumino silica gel particle with step (2) mixed with tetraethylammonium cation template, fluorochemical and water, in 100～190 ℃ of crystallization 1～4 day; TEA in the mixture wherein
+/ SiO
2Mol ratio is 0.05～0.5, TEA
+/ F
-Mol ratio is 1～2, H
2O/SiO
2Mol ratio is 2～10.
The synthetic method of β zeolite provided by the invention, can be used for the nanometer β zeolite that synthetic grain size is no more than 100nm, the synthetic β of institute zeolite silica alumina ratio can reach more than 300, and the crystallization process water consumption is few, the relative crystallinity height of zeolite, Stability Analysis of Structures, defective is few, hydrothermal stability is high, the strength of acid height, and anti-nitrogen performance is good, especially for the vacuum distillate hydrocracking process, present intermediate oil selectivity and lytic activity preferably.
Embodiment
According to method provided by the present invention, the described acid of step (1) is selected from one or more in hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, citric acid, the oxalic acid, one or more in preferred hydrochloric acid, nitric acid, formic acid, the acetic acid.
According to method provided by the present invention, one or more in the preferred pseudo-boehmite in step (1) described aluminium source, hydrated aluminum oxide, the aluminium hydroxide.
According to method provided by the present invention, the described acidifying of step (1), the consumption of acid is enough to make aluminium source peptization, is beneficial to mix with silica gel, and preferred acid and aluminium source are (with Al
2O
3Meter) molar ratio (acid/Al
2O
3) be 0.25～0.55.
According to method provided by the present invention, the described silica gel of step (1) can prepare by existing method also can be commercially available.The granularity of preferred silica gel is 20～300 orders.
According to method provided by the present invention, the consumption in described silica gel of step (1) and aluminium source makes the mol ratio in silica gel and aluminium source with SiO
2/ Al
2O
3Count 300～2000, be preferably 300～1600.
According to method provided by the present invention, nH in the described mixture of step (1)
2O/ (nSiO
2+ nAl
2O
3) be 10～20 (mol ratios).
According to method provided by the present invention, the described exsiccant temperature of step (2) is 20～220 ℃, and described grinding makes and grinds resulting alumino silica gel particle is 20～300 orders, more preferably 40～300 orders.
According to method provided by the present invention, described tetraethylammonium cation (TEA
+) template is derived from one or more among tetraethyl ammonium fluoride TEAF, tetraethyl ammonium hydroxide TEAOH, etamon chloride TEACl and the tetraethylammonium bromide TEABr.Described fluorochemical is selected from HF, NH
4F, (NH
4)
2SiF
6In one or more; When described template was TEAF, TEAF also was considered as described fluorochemical, can no longer introduce other fluorochemical.
According to method provided by the present invention, described crystallization can also can be the static crystallization process for the dynamic crystallization process, is preferably the dynamic crystallization process.
According to the method described in the present invention, also comprise to the qualified zeolite of crystallization wash, the exsiccant step, the washing and the exsiccant method be well known to those skilled in the art.
The inventive method can be used for preparing sial and is not less than 300 nanometer β zeolite.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
The mean grain size of embodiment mesolite is recorded by x-ray powder diffraction (XRD) and Scherrer Scherrer equation (seeing that " commercial catalysts analytical test sign " Liu Xiyao etc. writes, hydrocarbon processing press, nineteen ninety publication); The relative crystallinity of zeolite is recorded by xrd method, builds long catalyst Co. production piece β 30 as the external standard sample with the Sinopec Group Hunan.The silica alumina ratio of zeolite is measured by x ray fluorescence spectrometry (XRF) method.
Embodiment 1～4 explanation method for preparing the nanometer high-silicon beta zeolite provided by the invention.
Embodiment 1
(1) alumina trihydrate (is contained Al
2O
356.5 weight %, Shandong Aluminum Plant produces) mix with water, hydrochloric acid (analytical pure, concentration 37 weight %), carry out acidifying and form colloidal sol, HCl: Al
2O
3=0.25 (mol ratio); Add 80～120 purpose silochroms (Haiyang Chemical Plant, Qingdao's product) afterwards, then the pseudo-boehmite that makes silica gel and acidifying peptization with ultrasonic wave at room temperature thorough mixing obtain silica-alumina gel, nH in the said mixture wherein
2O/ (nSiO
2+ nAl
2O
3)=10.0 (mol ratio), the consumption of silica gel and alumina trihydrate makes the SiO of resulting silica-alumina gel
2/ Al
2O
3Mol ratio is 350;
(2) with silica-alumina gel dry 48h under 120 ℃ temperature of step (1) gained, grind to form 40～200 purpose alumino silica gel particles;
(3) with the alumino silica gel particle of step (2) gained (with SiO
2Meter), template tetraethyl ammonium fluoride TEAF (TEAF, Aldrich company, analytical pure) and water are according to SiO
2: TEAF: the mixed in molar ratio of water=1: 0.05: 2.0 is even, places rotary oven, and in 140 ℃ of crystallization 2 days, washing obtained the nanometer high-silicon beta zeolite in 12 hours 120 ℃ of dryings then.Preparation condition and product property see Table 1.
Embodiment 2
(1) pseudo-boehmite (is contained Al
2O
368.21 weight %, Shandong Aluminum Plant produces) mix with water, with acetate acidifying (Beijing chemical reagents corporation, analytical pure), form colloidal sol, acetate and Al
2O
3Mol ratio be 0.35; Add 80～120 purpose Kiselgel As (Haiyang Chemical Plant, Qingdao's product) then, the mol ratio of silica gel and pseudo-boehmite is (with SiO
2/ Al
2O
3Meter) be 650, then the pseudo-boehmite that makes silica gel and acidifying peptization with ultra-sonic dispersion at room temperature thorough mixing obtain silica-alumina gel, nH in the said mixture wherein
2O/ (nSiO
2+ nAl
2O
3)=12.0 (mol ratio);
(2) with the silica-alumina gel of step (1) gained temperature drying 48h, grind to form 40～200 purpose alumino silica gel particles at 120 ℃;
(3) with the alumino silica gel particle of step (2) gained raw material as the synthesis of nano high-silicon beta zeolite, with TEAOH (the emerging good fortune fine chemistry in Beijing institute, analytical pure, content 20 weight %), HF (chemical reagents corporation of traditional Chinese medicines group, top grade is pure, concentration is 40 weight %), water mixes, wherein the mol ratio of each raw material is as follows: TEA
+/ SiO
2=0.08, TEA
+/ F
-=1.5, H
2O/SiO
2=4.5, place rotary oven then, in 170 ℃ of dynamic crystallizations 2 days, washing, drying obtained the nanometer high-silicon beta zeolite.Preparation condition and product property see Table 1.
Embodiment 3
(1) aluminium hydroxide (is contained Al
2O
356.8 weight %, Shandong Aluminum Plant produces) as the aluminium source, mix with water, carry out acidifying with formic acid (Beijing chemical reagents corporation, analytical pure, concentration 40.0 weight %), form colloidal sol, formic acid: Al
2O
3=0.55; Add 120～200 purpose mesopore silica gel (Haiyang Chemical Plant, Qingdao's product) afterwards, the mol ratio of silica gel and aluminium hydroxide is with SiO
2/ Al
2O
3Count 1050, use ultrasonic dispersing then, the pseudo-boehmite that makes silica gel and acidifying peptization at room temperature thorough mixing obtains silica-alumina gel, wherein nH in the said mixture
2O/ (nSiO
2+ nAl
2O
3)=16.0 (mol ratio).
(2) with the silica-alumina gel of step (1) gained in 80 ℃ of dry 24h, again in 120 ℃ of dry 24h, grind to form 40～200 purpose alumino silica gel particles then;
(3) with the alumino silica gel particle of step (2) gained raw material, with TEABr (the emerging good fortune fine chemistry in Beijing institute, analytical pure, content 90 weight %), NH as the synthesis of nano high-silicon beta zeolite
4F (Chengde milky way optics Materials Co., Ltd, analytical pure), water mix, and the mol ratio of each raw material is as follows in the system: TEA
+/ SiO
2=0.5, TEA
+/ F
-=1.0, H
2O/SiO
2=8.0, then at 120 ℃, dynamic crystallization is 4 days in rotary oven, and washing, drying obtain the nanometer high-silicon beta zeolite.Preparation condition and product property see Table 1.
Embodiment 4
(1) pseudo-boehmite (is contained Al
2O
368.21 weight %, Shandong Aluminum Plant produces) as the aluminium source, mix with water, carry out acidifying, wherein nitric acid: Al with nitric acid (Beijing chemical reagents corporation, analytical pure, concentration 97.2 weight %)
2O
3=0.45 (mol ratio) adds 40～80 purpose silochroms (Haiyang Chemical Plant, Qingdao's product) afterwards, and the mol ratio of silica gel and pseudo-boehmite is with SiO
2/ Al
2O
3Count 1600, use ultrasonic dispersing then, make silica gel and peptization pseudo-boehmite at room temperature thorough mixing obtain alumino silica gel, nH in the said mixture wherein
2O/ (nSiO
2+ nAl
2O
3)=20.0 (mol ratio);
(2) with the alumino silica gel of step (1) gained temperature drying 48h, grind to form 20～200 purpose alumino silica gel particles at 120 ℃;
(3) with the alumino silica gel particle of step (2) gained raw material, with TEAOH (the emerging good fortune fine chemistry in Beijing institute, analytical pure, content 20 weight %), (NH as the synthesis of nano high-silicon beta zeolite
4)
2SiF
6(Beijing Chemical Plant, analytical pure, content 90 weight %), water mix, and the mol ratio of each raw material is as follows in the system: TEA
+/ SiO
2=0.25, TEA
+/ F
-=2.0, H
2O/SiO
2=6.5, then in 135 ℃ of dynamic crystallizations 3 days, washing, drying obtain the nanometer high-silicon beta zeolite.Preparation condition and product property see Table 1.
Comparative Examples 1
According to CN1048697C disclosed method synthesizing high-silicon β zeolite.
With 0.26g sodium hydroxide (chemical pure, the Beijing Chemical Plant) with 24.4ml tetraethyl ammonium hydroxide (2.633N, go in in a big way emerging good fortune fine chemistry industry institute) add in the 36.3g deionized water, heating for dissolving stirs, make working solution, with 20.0g silochrom (80～120 orders, igloss 3.7, Haiyang Chemical Plant, Qingdao, impure aluminium) mix with above-mentioned working solution, make silica gel surface wetting by working solution, in autoclave prior to 120 ℃ of crystallization 48h, then in 150 ℃ of crystallization 60h, isolate solid product after the reaction, washing, 110 ℃ of dryings, getting relative crystallinity is 98.9%, silica alumina ratio is 487.5, and grain size is the β zeolite of 0.1～1.0 μ m.Preparation condition and product property see Table 1.
Comparative Examples 2
According to US5164169 disclosed method synthesizing high-silicon β zeolite.
With chromatographic silica gel 11.5g (Haiyang Chemical Plant, Qingdao, the 80-100 order, igloss is less than 3.7 weight %), with 1.0g concentration be that 50 weight %NaOH, 20.3g concentration are TEAOH (the emerging good fortune fine chemistry in Beijing institute of 40 weight %, analytical pure), 17.3g triethylamine TEA is (as sequestrant, Beijing chemical reagents corporation, analytical pure, concentration 20 weight %), 49.2g H
2O mixes, and to wherein adding 1.18g β zeolite seed crystal (silica alumina ratio is 110, and synthetic method is with reference to patent US 3308069), then this raw mix has the mol ratio of following composition then:
The above-mentioned raw materials mixture in room temperature crystallization 5～8 hours, in 135 ℃ of following crystallization 10 days, obtains the β zeolite product again under 300rpm stirs, relative crystallinity is 95%, silica alumina ratio is 642, and the stray crystal of trace is arranged, and shows that by scanning electron microscope the product grains size is 0.3～0.8 micron.Preparation condition and product property see Table 1.
Comparative Examples 3
According to method synthesizing high-silicon β zeolite in the CN 1915817A patent.
(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.
(D), Sodium Fluoride, content 98 weight %, commercially available product.
Get 2.143 gram Sodium Fluorides and be dissolved in the 63.1 gram tetraethyl ammonium hydroxide solution, stir and add 0.593 gram sodium aluminate and 75 gram silicon sol down, after stirring, change over to and carry out crystallization in the stainless steel cauldron, 120 ℃ of crystallization 3 days.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.The original constitutive molar ratio that feeds intake is:
1?Al
2O
3·200SiO
2·30(TEA)
2O·20F
-·1.5Na
2O·1911H
2O
Preparation condition and product property see Table 1.
Table 1
Claims (9)
1, a kind of synthetic method of β zeolite may further comprise the steps:
(1) will be selected from one or more aluminium source in pseudo-boehmite, hydrated aluminum oxide, aluminium hydroxide, Wickenol CPS 325, the SB aluminium hydroxide, use acidifying, mix with silica gel afterwards, make the abundant dispersing and mixing of silica gel and aluminium source, obtain silica-alumina gel with ultrasonic wave;
(2), grind and obtain the alumino silica gel particle with the silica-alumina gel drying of step (1) gained;
(3) the alumino silica gel particle with step (2) mixed with tetraethylammonium cation template, fluorochemical and water, in 100～190 ℃ of crystallization 1～4 day; TEA in the mixture wherein
+/ SiO
2Mol ratio is 0.05～0.5, TEA
+/ F
-Mol ratio is 1～2, H
2O/SiO
2Mol ratio is 2～10.
2, in accordance with the method for claim 1, it is characterized in that the described aluminium of step (1) source is one or more in pseudo-boehmite, hydrated aluminum oxide, the aluminium hydroxide.
3, in accordance with the method for claim 1, it is characterized in that described rapid (1) described acid is selected from one or more in hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, citric acid, the oxalic acid.
4, in accordance with the method for claim 1, it is characterized in that described tetraethylammonium cation template is derived from one or more among TEAF, TEAOH, TEACl and the TEABr; Described fluorochemical is selected from HF, NH
4F, (NH
4)
2SiF
6In one or more.
5, in accordance with the method for claim 1, it is characterized in that the mol ratio in described silica gel and aluminium source is with SiO
2/ Al
2O
3Count 300～2000.
6, in accordance with the method for claim 5, it is characterized in that described SiO
2/ Al
2O
3Mol ratio be 300～1600.
7, in accordance with the method for claim 1, it is characterized in that it is 20～300 orders that the described grinding of step 2 makes the alumino silica gel particulate granularity that obtains.
8, in accordance with the method for claim 1, it is characterized in that in the described acidifying of step (1), acid is 0.25～0.55 with the mol ratio of aluminum oxide.
9, a kind of β zeolite is characterized in that, described zeolite is by each described method preparation of claim 1～8, and silica alumina ratio is 300～2000, and grain-size is no more than 100nm.
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|---|---|---|---|
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|---|---|---|---|
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| CN101353171B CN101353171B (en) | 2011-08-10 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ303890B6 (en) * | 2010-10-20 | 2013-06-12 | Výzkumný ústav anorganické chemie, a. s. | Process for preparing zeolite beta from dried half-finished product with porogen |
| CZ303889B6 (en) * | 2010-10-20 | 2013-06-12 | Výzkumný ústav anorganické chemie, a. s. | Process for preparing dried half-finished product for synthesis of zeolites |
| CN104229818A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Synthetic method of beta molecular sieve |
| CZ306725B6 (en) * | 2016-06-02 | 2017-05-24 | Unipetrol výzkumně vzdělávací centrum, a.s. | A method of production of zeolite Beta with secondary porosity |
| CN108217684A (en) * | 2018-02-11 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of method for promoting Beta Zeolite synthesis |
| CN110372003A (en) * | 2019-08-22 | 2019-10-25 | 正大能源材料(大连)有限公司 | A kind of preparation method of big partial size Beta molecular sieve |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5164169A (en) * | 1991-06-14 | 1992-11-17 | Mobil Oil Corporation | Zeolite Beta |
| CN1096417C (en) * | 2000-10-19 | 2002-12-18 | 北京嘉德凯化工科技发展有限公司 | Synthesis method for beta zeolite |
| CN1335258A (en) * | 2001-02-28 | 2002-02-13 | 刘希尧 | Synthesis of nanometer size beta-zeolite |
| 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 |
-
2007
- 2007-07-26 CN CN 200710119553 patent/CN101353171B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ303890B6 (en) * | 2010-10-20 | 2013-06-12 | Výzkumný ústav anorganické chemie, a. s. | Process for preparing zeolite beta from dried half-finished product with porogen |
| CZ303889B6 (en) * | 2010-10-20 | 2013-06-12 | Výzkumný ústav anorganické chemie, a. s. | Process for preparing dried half-finished product for synthesis of zeolites |
| CN104229818A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Synthetic method of beta molecular sieve |
| CN104229818B (en) * | 2013-06-18 | 2016-04-06 | 中国石油天然气股份有限公司 | A kind of synthetic method of beta-molecular sieve |
| CZ306725B6 (en) * | 2016-06-02 | 2017-05-24 | Unipetrol výzkumně vzdělávací centrum, a.s. | A method of production of zeolite Beta with secondary porosity |
| CN108217684A (en) * | 2018-02-11 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of method for promoting Beta Zeolite synthesis |
| CN110372003A (en) * | 2019-08-22 | 2019-10-25 | 正大能源材料(大连)有限公司 | A kind of preparation method of big partial size Beta molecular sieve |
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|---|---|
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