CN1088483A - A kind of is the synthesized silicon phosphor aluminum molecular sieve and the preparation thereof of template with the triethylamine - Google Patents
A kind of is the synthesized silicon phosphor aluminum molecular sieve and the preparation thereof of template with the triethylamine Download PDFInfo
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Abstract
A kind of synthesized silicon phosphor aluminum molecular sieve SAPO-34 is to adopt triethylamine or is template and synthetic based on the organic compounds containing nitrogen group of triethylamine.This template and raw material are inexpensive, and preparation process is easy, can be suitable for adopting in the large-scale industrial production.This molecule sieve after being treated can be used as methyl alcohol or dimethyl ether conversion is the low-carbon alkene catalyst for reaction, its catalytic activity height, and catalyst stability is good, and reactant yield of light olefins height (can near 100%), C
2～C
4The selectivity of low-carbon alkene＞85%.
Description
The present invention relates to a kind of molecular sieve and synthetic method thereof, specifically providing a kind of is the silicon phosphorus aluminium SAPO-34 molecular sieve and preparation method thereof of lamina membranacea agent with the triethylamine, and providing again simultaneously and having utilized this molecular sieve is that feedstock conversion is the catalyzed reaction of low-carbon alkene as catalyzer by methyl alcohol or dme.
Synthesis silicon phosphorus aluminium SAPO-34 molecular sieve is a kind of molecular sieve of being made up of silicon, aluminium, phosphorus, oxygen with class chabazite structure.Its structural unit is by PO
+
2, AoO
-
2And SiO
2Tetrahedron constitutes.Anhydrous chemical constitution can be expressed as: mR(SixAlyPz) O
2, R is the template that is present in the molecular sieve crystal micropore in the following formula, and m is the mole number of R, and x, y, z are respectively the molar fraction of Si, Al, P, and satisfy x+y+g=1.Europe patent EP0103117 discloses a kind of hydrothermal synthesis method of SAPO-34 molecular sieve.One of its technical characterstic is to have used tetraethyl ammonium hydroxide in the building-up process, Isopropylamine or be template with the mixture of tetraethyl ammonium hydroxide and di-n-propylamine.On this basis, U.S. Pat 4440871 has been reported relevant SAPO-34 molecular sieve synthetic again and has been improved one's methods, and it also adopts identical template.The difficulty but these stencil-type cost an arm and a leg and originate is difficult in the industrial production and adopts.
The purpose of this invention is to provide that a kind of to adopt cheap triethylamine be SAPO-34 molecular sieve of template and preparation method thereof.It can reduce the cost of synthetic SAPO-34 molecular sieve significantly, is suitable for adopting in suitability for industrialized production.The present invention uses this molecular sieve again as catalyzer in addition, and setting up a kind of is the building-up reactions of low-carbon alkene by methyl alcohol or dimethyl ether conversion.
Provided by the invention is the SAPO-34 molecular sieve of template with the triethylamine, the still available mR(SixAlyPz of its structural formula) O
2Expression.Wherein x, y, z are the mole number of Si, Al, P, and satisfy x+y+z=1, R is a template, m is the mole number of template, the m value is 0.03～0.5, the template R that it is characterized in that being used for synthesis of molecular sieve is a triethylamine or based on the organic compounds containing nitrogen group of triethylamine, other organic compound can be: TPAOH tripropyl ammonium, TBAH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, diethanolamine, isopropylamine, di-n-propylamine, Kui quinoline etc.And the amount of triethylamine accounts for template (weight) and answers＞50%.In addition, molar fraction also should satisfy in the said structure formula: X=0.01～0.98; Y=0.01～0.60; G=0.01～0.60.
The synthetic method of molecular sieve provided by the invention, selecting above-mentioned triethylamine or triethylamine for use except that its template is master's the organic amine mixture, it is characterized in that other raw material, and ortho-phosphoric acid can be adopted in the phosphorus source, silicon source available silicon colloidal sol, active silica or positive silicon ester; The aluminium source can be activated alumina, pseudobochmite or aluminum alkoxide etc.Its feature of molecular sieve synthetic method provided by the invention is that also proportion of raw materials such as template, silicon source, aluminium source, phosphorus source and water meet following formula:
0.04-6R∶（Si0.01-0.30;Al0.01-0.60;P0.01-0.50）∶2-500H
2O。
Concrete molecular sieve preparation method is pressed step:
1, in the ratio of Si, Al, P and R in the said structure formula, takes by weighing a certain amount of template, silicon source, aluminium source, phosphorus source and water.
2,, and fully stir the formation gel with above-mentioned each mixing of materials;
3, with gel in 100～225 ℃ of crystallization, the reaction times should be no less than 0.5 hour, crystallization after-filtration or centrifugation gained solid, again through the washing, drying get final product the SAPO-34 molecular screen primary powder.Its drying can be seasoning or carries out under 80～150 ℃.
By the method that prepare the SAPO-34 molecular sieve provided by the invention, also can be used for synthesizing and have big crystal grain (＞10M) SAPO-34 molecular sieve.
What utilize that the present invention prepares is that the SAPO-34 molecular sieve of template can be used as methyl alcohol or dme is the catalyzer of raw material reaction for preparing light olefins with the triethylamine.This SAPO-34 molecule sieve after being treated has the yield of ethene height as this process catalyzer, the characteristics that temperature of reaction is low.The treating processes of its SAPO-34 molecular screen primary powder is pressed following step:
What 1, will utilize the inventive method preparation is that the SAPO-34 molecular screen primary powder of template carries out roasting and removes template and can prepare and be used for catalyst for reaction with the triethylamine under 300～700 ℃ in air;
2, the molecular sieve after roasting can change into H type molecular sieve catalyst with ion exchange technique again.
The SAPO-34 molecular sieve catalyst of utilization after above-mentioned 1 or 2 processing is converted into the low-carbon alkene reaction in oxygenates such as methyl alcohol or dme, its temperature of reaction is 280～550 ℃, preferable temperature of reaction is 400～450 ℃, material benzenemethanol or dme air speed WHSV=1～2hr
-1Under the condition, conversion of raw material can be near 100%(＞95%), C
2～C
4Selectivity of light olefin is higher than 85%(wt).Below by example technology of the present invention is given to illustrate further.
Example 1SAPO-34 molecular sieve preparation 1
Get 141 the gram aluminum isopropoxides [Al(0-i-Pr)
3] mixes with 150 gram deionized waters, add 63.75 gram 85wt% ortho-phosphoric acid then, add 39.3 successively after being stirred to evenly to restrain methyl silicate [Si(OCH
3)
4], 52.5 gram triethylamines, 137.1 gram deionizations also fully stir.
Above-mentioned gel dress is enclosed in the pressure vessel of inner liner polytetrafluoroethylene, in 170 ℃ of thermostatic crystallizations 120 hours.Filtration product gained solid is through washing, and 110 ℃ of dryings are carried out X-ray powder diffraction mensuration after 3 hours, must table 1 column data.This result shows that the gained synthetic product is pure SAPO-34 molecular sieve.Above-mentioned SAPO-34 molecular sieve is 4.4 μ through its median size of electron microscope observation.X-ray diffraction is measured, and adopts D-9C type x-ray diffractometer of science, and source of radiation is the copper target.Operational condition is 30～50 kilovolts, and 30～50 milliamperes, sweep velocity (20) is 8 °/minute.
The X-ray diffraction result of table 1 embodiment 1 sample
2θ d(A°) 100×I/I
°
9.5 9.25 100
12.85 6.84 17
14.0 6.28 8
16.0 5.50 49
17.9 4.92 11
19.0 4.64 9(4)
20.6 4.28 75
23.1 3.82 10
25.1 3.52 14
25.9 3.42 21
27.7 3.20 7
28.28 3.13 7
29.6 3.00 9
30.6 2.90 25
31.1 2.86 26
32.4 2.74 9
34.5 2.58 6
36.2 2.46 5
43.2 2.08 5
47.7 1.89 4
49.0 1.85 10
Example 2 SAPO-34 molecular sieves preparation 2
Get 156.5 gram 85wt% H
3PO
4Be diluted in the 200 gram deionized waters and form A.The pseudobochmite of the moisture 36.5wt% of 109 grams and 250 gram deionized waters are mixed well and are formed B.Then A, B are mixed, add 68.6 gram triethylamines while stirring successively after evenly, 80.9 grams contain SiO
2The silicon sol of 40.32wt% and 135 gram deionized waters.Above-mentioned gel dress is enclosed in the stainless steel autoclave, after one day, be heated to 150 ℃ of constant temperature one day, be warmed up to 200 ℃ of crystallization 3 days again in aged at room temperature.Product obtains solid product after the centrifugation washing.Liquid is crossed in product seasoning in air, carried out the X-ray powder diffraction then and measure, the gained result is substantially the same manner as Example 1, is pure SAPO-34.
Gained SAPO-34 turns out to be big crystal grain crystal through electron microscope observation, mensuration, and grain size is＞10 μ.
Example 3 SAPO-34 molecular sieves preparation 3
With 122.2 gram 85wt% H
3PO
4Behind the mixing, add the moisture SiO of 67.3 grams again in the solution adding 200 gram deionized waters
2The silicon sol of 26.45wt%.Other get 48.13 the gram aluminium isopropoxides [Al(0-i-Pr)
3] mix with 50 gram deionized waters, add ortho-phosphoric acid and silicon solution that 78 grams are prepared previously again, 14.4 gram triethylamines and 8.4 gram deionized waters.Above-mentioned each step all carries out under well-beaten condition.The inclosure of gained gel is had in the stainless steel autoclave of teflon lined, be heated to 200 ℃, crystallization 50 hours, then reaction product is filtered, washed, 100 ℃ of dryings are 3 hours in the air, make the X-ray powder diffraction with drying products and measure, result and example 1 basically identical are pure SAPO-34 molecular sieve.
Embodiment 4 SAPO-34 molecular sieves preparation 4
To 66.3 gram 85wt%, H
3PO
4Be dissolved in the solution of 150 gram deionized waters and add 127.2 gram Al(OCH(CH
3)
2]
3With the mixture of 50 gram deionized waters, add again after being stirred to evenly and contain 26.45wt% SiO
2Silicon sol 32.7 gram and 80 gram deionized waters, add 46.6 gram triethylamines and 59.4 gram deionized waters and abundant stirring at last and can get gel.With having in the pressure vessel of polytetrafluoroethylene bushing in the inclosure of gel dress, 100 ℃ of reactions 50 hours, be warmed up to 150 ℃ of constant temperature 40 hours more earlier, be heated to 200 ℃ of constant temperature at last 20 hours.With the crystallization product centrifugation, washing back was 10 ℃ of dryings 5 hours.The X-ray diffraction result turns out to be pure SAPO-34 molecular sieve.
Embodiment 5 SAPO-34 molecular sieves preparation 5
The solution that consists of 86.4 gram ortho-phosphoric acid and 165.2 gram water successively with the pseudobochmite of the moisture 31.79wt% of 109.8 grams, 100 gram water, 333.5 grams contain SiO
2The silicon sol of 26.45wt% and 58.8 gram NaOH mix.In said mixture, add 66.9 gram triethylamines, 77.7 gram Diisopropylamine (1-Pr
2NH) and 21.1 gram deionized waters, stirred 3 hours, in the stainless steel autoclave of packing into then, at room temperature wore out 48 hours, again 200 ℃ of following crystallization 50 hours.Product after filtration, washing, drying.The X-ray powder diffraction turns out to be purified SAPO-34 molecular sieve.
The preparation of embodiment 6 SAPO-34 molecular sieve catalysts
The former powder of the SAPO-34 that embodiment 2 obtains through 350 ℃ 2 hours, 450 ℃ 2 hours, after 550 ℃ of roastings in 5 hours, compressing tablet, sieve, choose 20-40 order granularity and partly be catalyzer a.
Embodiment 7 catalyzed reactions experiment 1
Adopt fixed-bed catalytic reactor, carrying out methanol conversion with catalyzer a among the embodiment 6 is the low-carbon alkene reaction.Catalyst-assembly is 1.28 grams.The reaction procatalyst is warming up to 550 ℃ of activation 1 hour in the nitrogen gas stream of 60 ml/min.Reaction raw materials methyl alcohol is carried by nitrogen and enters reactor, and the methyl alcohol molar content is 35% in the reactor feed gas, methyl alcohol weight space velocity WHSU=2h
-1, reaction pressure is～0.05MPa.The results are shown in table 2.
The methanol conversion reaction result of table 2 catalyzer a (400 ℃)
Methanol conversion hydrocarbon product distribution (wt%)
(wt%) CH
4C
2H
4C
2H
6C
3H
6C
3H
8C
4H
8C
2～C
4
99.1 2.86 40.77 2.19 39.42 8.86 5.91 86.10
The ※ reaction times is 1 hour.
Embodiment 8 SAPO4-34 molecular sieve catalysts preparation 2
The former powder of the SAPO-34 of embodiment 5 through 350 ℃ 2 hours, 450 ℃ 2 hours, after 550 ℃ of 5 hours burn off template, under 85 ℃ of water bath with thermostatic control conditions, with 1N ammonium nitrate solution exchange 4 times, solid-to-liquid ratio (weight) is 1: 10.There is not NO with deionized water wash to liquid phase then
-
3Above-mentioned sample after 110 ℃ of oven dry are spent the night, with 350 ℃ 2 hours, 450 ℃ of 2 hours and 550 ℃ of heating schedule roastings in 5 hours.Sample footpath compressing tablet sieves after the roasting, chooses 20-40 order granularity and partly is catalyzer b.
Embodiment 9 catalyzed reactions experiment 2
Adopting reaction unit identical with embodiment 7 and reaction conditions to carry out dimethyl ether conversion reacts.With embodiment 7 different persons is to adopt catalyzer b, and reaction raw materials is a dme, the weight space velocity WHSU=1.5h of dme
-1Reaction result is listed in table 3.
The dimethyl ether conversion result of table 3 catalyzer b
400 ℃ 450 ℃ of temperature of reaction
45 minutes 60 minutes reaction times
Transformation efficiency (wt%) 100 100
Hydrocarbon product distribution wt%
CH
41.01 2.83
C
2H
439.12 43.05
C
2H
61.34 1.34
C
3H
640.55 45.79
C
8H
87.26 5.09
C
4H
87.7 1.47
C
4H
100 0.40
C
2-C
4Selectivity (wt%) 87.70 90.31
By above-mentioned example triethylamine provided by the invention is the SAPO-34 molecular sieve of template, and other raw material sources of its template and synthesis of molecular sieve are abundant, and are cheap, and building-up reactions carries out easily, is suitable for suitability for industrialized production and adopts.In addition, this molecular sieve can be used as oxygenates such as methyl alcohol or dme through calcination process (or being exchanged into H type molecular sieve again) and is converted into the low-carbon alkene catalyst for reaction.Active high, the good stability of this catalyst, the yield height of reaction product low-carbon alkene (can near 100%), selectivity good (285%), and temperature of reaction is low.
Claims (6)
1, a kind of synthesized silicon phosphor aluminum molecular sieve possible constructions formula mR (Si
xAl
yP
z) O
2Expression, wherein x, y, z are the molar fraction of Si, Al, P, R is a template, m is the mole number of template R, it is characterized in that template R is a triethylamine or based on the organic compounds containing nitrogen group of triethylamine, other organic compound is TPAOH, tripropylamine, TBAH, tetraethyl ammonium hydroxide, tetramethyl-hydrogen ammonium hydroxide, diethanolamine, isopropylamine, di-n-propylamine, Kui quinoline etc., and the amount of triethylamine (weight) in template answers＞50%.
2,, it is characterized in that molar fraction X=0.01～0.98 of Si, Al, P according to the described molecular sieve of claim 1; Y=0.01～0.6; Z=0.01～0.6; And X+Y+z=1, the mole number of m are 0.03～0.5.
3, a kind of preparation method who is used for according to the described molecular sieve of claim 1 is characterized in that adopting following step:
(1) meets following formula by proportioning: 0.04～6R(Si0.01～0.30 Al0.01～0.60 P0.01～0.50): 2～500H
2The ratio of Si, Al, P, R and water takes by weighing an amount template among the O, and silicon source, aluminium source and phosphorus source and water with its each mixing of materials, stir and form gel;
(2) make the gel crystallization in 100～225 ℃, the reaction times should be no less than 0.5 hour, and gained solid after filtration after the crystallization can obtain molecular sieve through washing, drying again.
4, according to the preparation method of the described synthesis of molecular sieve of claim 3, ortho-phosphoric acid, silicon source available silicon colloidal sol can be adopted in the raw material phosphorus source that it is characterized in that synthesis of molecular sieve, active silica or positive silicon ester, activated alumina can be used in the aluminium source, pseudobochmite or aluminum alkoxide etc.
5, a kind of is the reaction process of low-carbon alkene by methyl alcohol or dimethyl ether conversion, it is characterized in that:
(1) it adopts according to claim 1 molecular sieve as catalyzer;
(2) temperature of reaction is carried out under 280～550 ℃.
6,, it is characterized in that used molecular sieve should carry out roasting before use in air under 300～700 ℃, or after roasting, make H type molecular sieve with ion exchange technique again according to the described reaction of claim 5.
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|---|---|---|---|
| CN92112230A CN1037334C (en) | 1992-12-19 | 1992-12-19 | Synthesis silicon phosphorus aluminium molecular sieve and equipment using triethylamine as mould agent |
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|---|---|---|---|
| CN92112230A CN1037334C (en) | 1992-12-19 | 1992-12-19 | Synthesis silicon phosphorus aluminium molecular sieve and equipment using triethylamine as mould agent |
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| CN103864095B (en) * | 2012-12-10 | 2016-01-13 | 中国科学院大连化学物理研究所 | A kind of take diisopropanolamine (DIPA) as SAPO-34 molecular sieve and the synthetic method thereof of template |
| WO2014089736A1 (en) * | 2012-12-10 | 2014-06-19 | 中国科学院大连化学物理研究所 | Sapo-34 zeolite having diisopropanolamine as templating agent and synthesis method for the zeolite |
| EA025394B1 (en) * | 2012-12-10 | 2016-12-30 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайэнс | Sapo-34 molecular sieve using diglycolamine as templating agent and method for preparation thereof |
| CN103864097A (en) * | 2012-12-10 | 2014-06-18 | 中国科学院大连化学物理研究所 | SAPO-34 molecular sieve adopting diglycol amine as template agent, and synthesis method thereof |
| US9611150B2 (en) | 2012-12-10 | 2017-04-04 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | SAPO-34 zeolite having diglycolamine as templating agent and synthesis method for the zeolite |
| CN104445245A (en) * | 2013-09-25 | 2015-03-25 | 天津神能科技有限公司 | Synthesis method of silicoaluminophosphate molecular sieve SAPO-34 |
| CN108545758A (en) * | 2018-04-09 | 2018-09-18 | 浙江大学 | The method of synthesizing P-Al molecular sieve or aluminium silicophosphate molecular sieve in strong basicity system |
| CN108545758B (en) * | 2018-04-09 | 2020-06-16 | 浙江大学 | Method for synthesizing phosphorus-aluminum molecular sieve or silicon-phosphorus-aluminum molecular sieve in strong alkaline system |
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