CN1096496A - With the diethylamine is the template synthesized silicon-aluminum phosphate molecular sieve - Google Patents
With the diethylamine is the template synthesized silicon-aluminum phosphate molecular sieve Download PDFInfo
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Abstract
A kind of silicon phosphorus aluminium SAPO-34 molecular sieve, its structural formula can be used mR (Si
xAl
yP
z) O
2, wherein x, y, z are respectively the molar fraction of Si, Al, P, and satisfy x+y+z=1; R is a template, and m is the mole number of template, and m=0.03～0.6, it is characterized in that: template R is a diethylamine or based on the organic compounds containing nitrogen group of diethylamine, the molar fraction of diethylamine is greater than 0.5, simultaneously, x=0.01～0.98, y=0.01～0.60, z=0.01～0.60.Cost of the present invention is low, is fit to suitability for industrialized production, and can be as methyl alcohol or/and dimethyl ether conversion is the low-carbon alkene catalyst for reaction.
Description
The present invention relates to the SAPO-34 molecular sieve, specifically just having provided a kind of is template synthetic silicon aluminium phosphate SAPO-34 molecular sieve with diethylamine, and by methyl alcohol or/and dimethyl ether conversion is the catalytic applications aspect the reaction of low-carbon alkene.
Synthesized silicon-aluminum phosphate SAPO-34 molecular sieve is a kind ofly to be made up of phosphorus, silicon, aluminium and oxygen, has the molecular sieve of class chabazite structure.Its structural unit is by PO
+ 2, Al
- 2And SiO
2Tetrahedron constitutes.Anhydrous chemical constitution can be expressed as: mR(Si
xAl
yP
z) O
2, wherein R is the template that is present in brilliant this micropore of molecular sieve, 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+z=1.European patent EP 0103117 discloses a kind of hydrothermal synthesis method of SAPO-34 molecular sieve, and 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.After this, U.S. Pat 4440871 has reported that again relevant SAPO-34 molecular sieve synthetic improves one's methods, but adopts identical template.Because these template cost an arm and a leg, the source difficulty is difficult in the industrial production and adopts.Chinese patent application number is in 921122306 the patent application of awaiting the reply, and once having described the triethylamine that is significantly less than tetraethyl ammonium hydroxide with market value is the method for template synthesized silicon-aluminum phosphate SAPO-34 molecular sieve.
The object of the present invention is to provide a kind of silicon aluminium phosphate SAPO-34 molecular sieve, its cost is lower, is more suitable for suitability for industrialized production.
The invention provides a kind of silicon phosphorus aluminium SAPO-34 molecular sieve, its structural formula can be used mR(Si
xAl
yP
z) O
2, wherein x, y, z are respectively the molar fraction of Si, Al, P, and satisfy x+y+z=1; R is a template, and m is the mole number of template, and m=0.03～0.6, it is characterized in that: template R is a diethylamine or based on the organic compounds containing nitrogen group of diethylamine, the molar fraction of diethylamine is greater than 0.5, simultaneously, x=0.01～0.98, y=0.01～0.60, z=0.01～0.60.Described template also can contain other organic compound as tetraethyl ammonium hydroxide, triethylamine, TPAOH, tripropyl amine, TBAH, Tetramethylammonium hydroxide, Trimethylamine 99, n-Butyl Amine 99, isopropylamine, di-n-propylamine, diethanolamine, pyrroles, pyrroles, Kui quinoline etc.
Above-mentioned molecular sieve synthetic method is characterised in that: the silicon source can be silicon sol, active silica or positive silicon ester, and the aluminium source can be aluminum alkoxide, pseudobochmite or activated alumina, and the phosphorus source can be that ortho-phosphoric acid, aluminum phosphate synthetic primary process are as follows:
(1) according to above-mentioned catalyst structure formula mR(Si
xAl
yP
z) O
2: 2～500H
2The amount of O takes by weighing a certain amount of template, silicon source, aluminium source, phosphorus source and water;
(2), fully stir again and make gel with above-mentioned each mixing of materials;
(3) with gel in 100～250 ℃ of crystallization, the crystallization time is not shorter than 0.5 hour;
(4) complete after-filtration of crystallization or centrifugation, washing, drying again, drying can be carried out under the condition of air and 0～120 ℃.With the big crystal-size SAPO-34 zeolite of the synthetic easily particle diameter of synthetic method provided by the invention greater than 15 microns.
Synthetic is that the silicon aluminium phosphate SAPO-34 molecular sieve of template can be used as methyl alcohol or/and dimethyl ether conversion is the catalyzer of low-carbon alkene with the diethylamine according to the present invention.Its catalytic performance has following advantage: the transformation efficiency height of reaction, and the selectivity height of low-carbon alkene in the product, temperature of reaction is low.Particularly, the pure SAPO-34 molecular sieve with synthetic gained carries out following processing:
1. the roasting in air and 300～750 ℃ of temperature ranges of exsiccant SAPO-34 molecular sieve is become active catalyst to remove template;
2. calcination process is crossed, the SAPO-34 molecular sieve with catalytic activity changes into H type molecular sieve catalyst with ion exchange technique.
SAPO-34 molecular sieve catalyst after will handling through above-mentioned 1 or 1 and 2 be used for catalysis methanol or/and dimethyl ether conversion when being the reaction of low-carbon alkene, and temperature of reaction is 300～550 ℃, and preferable temperature of reaction is 400～500 ℃.Methyl alcohol is or/and the weight space velocity WHSV=1～2h of dme
-1The time, conversion of raw material is higher than 95%, even can reach 100%, C
2～C
4Selectivity of light olefin is higher than 85%(wt).
Following illustrative example is described further technology of the present invention.
Table 1 table 2
2θ d(
) 100×I/I
02θ d(
) 100×I/I
0
9.45 9.36 77 *8.3 10.65 4
12.86 6.88 17 9.5 9.31 98
14.05 6.30 5 12.95 6.84 22
16.0 5.54 32 14.05 6.30 5
17.8 4.98 18 *14.3 6.19 2
19.05 4.66 4 16.05 5.52 34
20.55 4.32 100 17.8 4.98 22
22.05 4.03 11 19.1 4.65 6
22.35 3.98 3 20.6 4.31 100
23.05 3.86 15 22.1 4.02 15
24.95 3.57 35 22.4 3.97 5
25.85 3.45 20 23.1 3.85 16
27.55 3.24 7 24.95 3.57 52
28.25 3.16 5 25.95 3.43 20
29.55 3.02 5 27.7 3.22 9
30.55 2.93 41 28.2 3.16 7
31.05 2.88 28 29.6 3.02 5
31.6 2.83 4 *30.05 2.97 2
32.35 2.77 3 30.6 2.92 40
33.55 2.67 3 31.1 2.87 28
34.4 2.61 10 31.6 2.83 4
34.9 2.57 3 32.5 2.75 3
36.05 2.49 5 33.5 2.67 5
39.7 2.27 4 34.55 2.60 22
42.9 2.11 4 34.95 2.57 2
43.45 2.08 4 36.1 2.49 9
47.6 1.91 5 *38.7 2.33 3
48.8 1.87 6 39.7 2.27 5
49.2 1.85 5 42.8 2.11 6
50.65 1.80 9 43.4 2.08 6
52.9 1.73 1 47.6 1.91 5
53.1 1.72 6 48.8 1.87 8
54.35 1.68 5 49.2 1.85 5
55.1 1.67 4 50.7 1.80 10
55.9 1.644 5 52.9 1.73 1
59.4 1.555 4 53.1 1.72 7
54.4 1.69 4
55.1 1.66 4
55.9 1.64 5
59.4 1.55 4
Embodiment 1 SAPO-34 molecular sieve synthetic 1
Take by weighing 71.0 gram aluminium isopropoxides (Al(O-i-Pr)
3), levigate back mixes with 80 gram deionized waters, adds 38.0 gram 85wt% ortho-phosphoric acid again, stirs.Then, add 36.2 gram tetraethoxy (Si(OC successively
2H
5)
4), 12.7 gram diethylamine (HN(C
2H
5)
2) and 85.0 gram deionized waters, fully stir and make amine with fixed attention.
The gel that makes dress is enclosed the stainless steel autoclave of inner liner polytetrafluoroethylene, and reaction is 45 hours under 200 ℃ and autogenous pressure.Then, solid product is filtered out, spend ion-cleaning again after, promptly got the exsiccant zeolite product in 4 hours 100 ℃ of bakings.Get portioned product and make x-ray powder diffraction mensuration, obtain table 1 column data.These data show that synthetic product is purified SAPO-34 molecular sieve.
Embodiment two SAPO-34 molecular sieve Synthetic 2s
With 99.2 gram aluminium isopropoxides (AlO-i-Pr)
3) wear into fine powder after, with 100 the gram deionized waters mix, add again 56 the gram 85wt% ortho-phosphoric acid and 100 the gram deionized waters solution.After stirring, add 22.0 gram 40wt%SiO again
2Silicon sol and 20 gram diethylamine, stir, make gel, dress is enclosed in the stainless steel autoclave of inner liner polytetrafluoroethylene, is heated to 160 ℃, crystallization is 170 hours under autogenous pressure.Then, centrifugation goes out reaction product, after washing, obtains zeolite product in 5 hours 100 ℃ of dryings.Product is measured through the x-ray powder diffraction, proves purified SAPO-34 molecular sieve.
Embodiment Three S's APO-34 molecular sieve synthetic 3
In 250 gram deionized waters, add 72.3 gram tetraethoxy (Si(OC
2H
5)
4), after stirring, add 49 grams and contain 72.18wt%Al
2O
3The pseudobochmite powder, and stir.Add 80 grams again and contain H
3PO
4The phosphoric acid solution of 85wt% stirs.Then, add 25.0 gram diethylamine and 80.0 gram deionized waters again, fully stir and make gel, and adorn and enclose in the stainless steel autoclave, be heated to 200 ℃, crystallization is 65 hours under autogenous pressure.Reaction product is carried out the x-ray powder diffraction and is measured after centrifugation, washing, drying, and the gained result is consistent with the result of embodiment one, is the SAPO-34 molecular sieve.
Embodiment four SAPO-34 molecular sieves synthetic 4
In 250 gram deionized waters, add 105.6 grams and contain H
3PO
4The ortho-phosphoric acid solution of 85wt% and 58.8 grams contain Al
2O
3The pseudobochmite powder of 72.18wt%, be stirred well to evenly after, add 49.2 grams successively and contain SiO
2The silicon sol of 40wt%, 118 gram deionized waters and 72 gram diethylamine.Make gel after stirring hour, dress is enclosed to be had in the teflon-lined stainless steel autoclave, 100 ℃ aging 24 hours, again 200 ℃ of reactions 72 hours.Filter out solid product then, make the x-ray powder diffraction and measure after washing, drying, result and table 1 data consistent prove that sintetics is pure SAPO-34 molecular sieve.Sample thief is made determination of electron microscopy in addition, and the particle diameter that draws zeolite single crystal can reach more than 15 microns.
Get the part zeolite product 550 ℃ of roastings after 4 hours, record its chemical constitution with chemical analysis and be: P
2O
542.98wt%, Al
2O
337.17wt%, SiO
29.75wt%, other volatile component 10.10wt%, the relative mol ratio of silicon phosphorus aluminium is P
2O
5: SiO
2: Al
203=0.831: 1,000: 0.445.
Embodiment five SAPO-34 molecular sieves synthetic 5
Active silica fine powder and 73.5 grams of the moisture 5wt% of 33 grams are contained Al
2O
3The pseudobochmite powder of 72.18wt% mixes, and after the grinding evenly, adding 400 gram deionized water and stirring are even, add 108 grams again and contain H
3PO
4The phosphoric acid solution of 85wt% and 95 gram deionized waters, and stir.Add 60 gram diethylamine again, continue to stir after 1 hour and make gel, and be encapsulated in the stainless steel autoclave of inner liner polytetrafluoroethylene, crystallization is 150 hours under 180 ℃ and autogenous pressure, promptly gets solid product.Product after centrifugation, washing, drying, is made the x-ray powder diffraction and measured, obtain table 2 column data.What " * " mark was arranged in the table 2 is the stray crystal signal.Table 2 explanation product contains micro-stray crystal, mainly is the SAPO-34 molecular sieve.
Embodiment six SAPO-34 molecular sieves synthetic 6
Going to add in dried up 86.4 at 100 grams restrains and contains H
3PO
4The phosphoric acid solution wiring solution-forming A of 85wt% adds 44.1 grams and contains Al in 170 gram deionized waters
2O
3The pseudobochmite powder of 72.18wt%, and stir.When stirring, add above-mentioned 186.4 gram solution A successively, 23.4 grams contain SiO
2The silicon sol of 40wt%, 36 gram diethylamine, 30 grams contain [N(C
2H
5)
4] the tetraethyl ammonium hydroxide aqueous solution of OH25wt%.Fully stir and make gel, dress is enclosed in the stainless steel autoclave, is heated to 200 ℃, and crystallization is 60 hours under autogenous pressure.With product filtration, washing, drying, obtain solid phase prod.Sample thief is done the test of x-ray powder diffraction.The gained result is consistent with the result of embodiment one, illustrates that the crystallization product is pure SAPO-34 molecular sieve.
Embodiment seven SAPO-34 molecular sieve catalysts preparation 1
With embodiment one synthetic SAPO-34 molecular screen primary powder through 350 ℃ 1 hour, 400 ℃ 1 hour, 450 ℃ 1 hour, 500 ℃ 0.5 hour, after 550 ℃ of roastings in 6 hours, be cooled to room temperature, with a part of compressing tablet, smash, the sieve particle that sieves out 20-40 order granularity is catalyzer a.
Embodiment eight catalyzed reactions test 1
Adopt atmospheric fixed bed reaction unit, reactor is a quartz glass tube, utilizes the catalyzer a of embodiment seven preparations.The 1.28 gram catalyzer a that pack in reactor are warmed up to 550 ℃ and constant temperature earlier and activated in 1 hour in flow velocity is the nitrogen gas stream of 60 ml/min, be cooled to 450 ℃ then, bring reaction raw materials methyl alcohol into reactor with nitrogen.The mole molecule rate of methyl alcohol is 35% in the unstripped gas, and the weight space velocity of methyl alcohol is WHSV=2h
-1, reaction pressure is 0.1～0.15MPa, the gas chromatographic analysis of the product when reaction proceeds to 30 minutes the results are shown in table 3.
Table 3
Methanol conversion hydrocarbon product distribution (wt%)
(wt%)
CH
4C
2H
4C
2H
6C
3H
6C
3H
8C
4H
8C
= 2-C
= 4
100 1.0 46.93 4.69 33.69 6.78 6.58 87.20
Embodiment nine SAPO-34 molecular sieve catalysts preparation 2
With baked another part SAPO-34 molecular sieve among the embodiment seven in 85 ℃ of waters bath with thermostatic control, with 4 times (the weight solid-to-liquid ratio is 1: 10) of the ammonium nitrate solution of 1.0 volumetric molar concentrations exchange.There is not NO with deionized water wash to liquid phase then
- 3Again the oven dry, then 350 ℃ 2 hours, 450 ℃ 2 hours, 550 ℃ of roastings in 4 hours.After being cooled to room temperature, with the sample compressing tablet, fragmentation, the particle that sieves out 20-40 order granularity is a catalyzer.
Embodiment ten catalyzed reactions test 2
Adopt reaction unit identical and reaction conditions to carry out methanol conversion and react, only use the catalyzer b that embodiment nine makes instead with embodiment eight.The gas chromatographic analysis of the product when reaction proceeds to 30 minutes the results are shown in table 4.
Table 4
Methanol conversion hydrocarbon product distribution (wt%)
(wt%)
CH
4C
2H
4C
2H
6C
3H
6C
3H
8C
4H
8C
4H
4C
= 2-C
= 4
98.9 1.80 50.20 2.27 33.09 3.33 5.03 4.28 88.32
Embodiment 11 catalyzed reactions test 3
Adopt reaction unit and the reaction conditions identical with embodiment eight, different is: employing catalyzer b, raw material is that dme and weight space velocity are WHSV=1.5h
-1The gas chromatographic analysis of the product when reaction proceeds to 30 minutes the results are shown in table 5.
Table 5
Methanol conversion hydrocarbon product distribution (wt%)
(wt%)
CH
4C
2H
4C
2H
6C
3H
6C
3H
8C
4H
8C
4H
10C
= 2-C
= 4
100 2.89 52.55 3.26 34.69 5.46 1.15 1.0 88.39
To sum up each embodiment as seen, the raw materials used source of the synthetic method of silicon aluminium phosphate SAPO-34 molecular sieve provided by the invention is abundant, and is cheap, helps industrial production.Synthetic SAPO-34 molecular sieve can be used for methyl alcohol or/and the dimethyl ether conversion catalyst for reaction through suitably handling.The transformation efficiency of conversion reaction is up to 100%, and the selectivity of low-carbon alkene has demonstrated fully the high reactivity and the highly selective of catalyzer up to more than 85% in the product.
Claims (6)
1, a kind of silicon phosphorus aluminium SAPO-34 molecular sieve, its structural formula can be used mR (Si
xAl
yP
z) O
2, wherein x, y, z are respectively the molar fraction of Si, Al, P, and satisfy x+y+z=1; R is a template, and m is the mole number of template, and m=0.03～0.6, it is characterized in that: template R is a diethylamine or based on the organic compounds containing nitrogen group of diethylamine, the molar fraction of diethylamine is greater than 0.5, simultaneously, x=0.01～0.98, y=0.01～0.60, z=0.01～0.60.
2, by the described silicon phosphorus of claim 1 aluminium SAPO-34 molecular sieve, it is characterized in that described template also can contain other organic compound as tetraethyl ammonium hydroxide, triethylamine, TPAOH, tripropyl amine, TBAH, Tetramethylammonium hydroxide, Trimethylamine 99, n-Butyl Amine 99, isopropylamine, di-n-propylamine, diethanolamine, pyridine, pyrroles, Kui quinoline etc.
3, the synthetic method of the described molecular sieve of a kind of claim 1, it is characterized in that it being that the silicon source can be a silicon sol, active silica or positive silicon ester, the aluminium source can be aluminum alkoxide, pseudobochmite or activated alumina, the phosphorus source can be ortho-phosphoric acid, aluminum phosphate, and synthetic primary process is as follows:
(1) according to claim 1 described catalyzer mR(Si
xAl
yP
z) O
2: 2～500H
2The amount of O takes by weighing a certain amount of template, silicon source, aluminium source, phosphorus source and water;
(2), fully stir again and make gel with above-mentioned each mixing of materials;
(3) with gel in 100～250 ℃ of crystallization, the crystallization time is not shorter than 0.5 hour;
(4) complete after-filtration of crystallization or centrifugation, washing, drying again, drying can be carried out under the condition of air and 0～120 ℃.
4, or/and dimethyl ether conversion is the application in the low-carbon alkene reaction, reaction conditions is: 300～550 ℃ of temperature, methyl alcohol is or/and the weight space velocity WHSV=1～2h of dme at methyl alcohol for claim 1,2 described molecular sieves
-1, it is characterized in that, with described molecular sieve through following processing as methyl alcohol or/and dimethyl ether conversion is the catalyzer in the low-carbon alkene reaction: with exsiccant SAPO-34 molecular sieve in air, roastings in 300～750 ℃ of temperature ranges.
5, by the described application method of claim 4, it is characterized in that: molecular sieve changes into H type molecular sieve with ion exchange technique again after roasting.
6, by claim 4,5 described application methodes, it is characterized in that: temperature of reaction is preferably in 400～500 ℃.
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|---|---|---|---|
| CN93112015A CN1038125C (en) | 1993-06-18 | 1993-06-18 | Aluminosilicophosphate molecular sieve synthesis using diethylamine as template agent |
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|---|---|---|---|
| CN93112015A CN1038125C (en) | 1993-06-18 | 1993-06-18 | Aluminosilicophosphate molecular sieve synthesis using diethylamine as template agent |
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| CN1038125C CN1038125C (en) | 1998-04-22 |
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ID=4989760
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| CN1076219C (en) * | 1996-08-02 | 2001-12-19 | 中国科学院大连化学物理研究所 | Silicon phosphorus aluminium molecular sieve containing alkaline earth metal and its synthesis |
| WO2008022532A1 (en) * | 2006-08-08 | 2008-02-28 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A method for rapidly synthesizing a silicoaluminophosphate sapo-34 molecular sieve |
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| CN101195492B (en) * | 2006-12-04 | 2010-09-29 | 中国科学院大连化学物理研究所 | Method for synthesizing SAPO-11 and SAPO-34 molecular sieve with diethylamine as template agent |
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| US5208005A (en) * | 1988-02-12 | 1993-05-04 | Chevron Research And Technology Company | Synthesis of a crystalline silicoaluminophosphate |
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| 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 |
| 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 |
| CN105174279A (en) * | 2015-09-17 | 2015-12-23 | 中国石油大学(华东) | Preparation method of nanosize aluminum phosphate molecular sieve |
| CN105236445A (en) * | 2015-09-17 | 2016-01-13 | 中国石油大学(华东) | Microwave preparation method for nanometer-dimension aluminium phosphate molecular sieve |
| CN108557838A (en) * | 2018-06-25 | 2018-09-21 | 陕西延长石油（集团）有限责任公司 | A kind of preparation method of aluminium silicophosphate molecular sieve |
| CN108557838B (en) * | 2018-06-25 | 2021-05-07 | 陕西延长石油（集团）有限责任公司 | Preparation method of silicon-phosphorus-aluminum molecular sieve |
| CN110028259A (en) * | 2019-04-26 | 2019-07-19 | 湖南腾达岩土工程技术有限公司 | A kind of steel slag neutrality activation cementitious material and its preparation method and application |
| CN110028259B (en) * | 2019-04-26 | 2023-08-29 | 湖南腾达岩土工程技术有限公司 | Neutral steel slag activated cementing material and preparation method and application thereof |
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