CN1038125C - Aluminosilicophosphate molecular sieve synthesis using diethylamine as template agent - Google Patents
Aluminosilicophosphate molecular sieve synthesis using diethylamine as template agent Download PDFInfo
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- CN1038125C CN1038125C CN93112015A CN93112015A CN1038125C CN 1038125 C CN1038125 C CN 1038125C CN 93112015 A CN93112015 A CN 93112015A CN 93112015 A CN93112015 A CN 93112015A CN 1038125 C CN1038125 C CN 1038125C
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Abstract
The present invention relates to a silicon aluminum phosphorus SAPO-34 molecular sieve. The present invention has the structural formula: mR (Si<x> Al<y> P<z>)O2, wherein the x, the y and the z are respectively the molar fraction of the Si, the Al and the P, and x+y+z=1; the R is a mould plate agent, the m is a mole number of the mould plate agent, and m=0.03 to 0.6. The present invention is characterized in that the mould plate agent is diethylamine or an organic compound which comprises nitrogen and mainly contains the diethylamine, the molar fraction of the diethylamine is larger than 0.5, and x=0.01 to 0.98, y=0.01 to 0.60 and z=0.01 to 0.60. The present invention has low cost, is suitable for industrialization, and can be used as a catalyst for converting methyl alcohol or / and dimethyl ether into low-carbon alkene.
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
2 -And 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 the mole that x, y, z are respectively Si, Al, P divides effect, and satisfies 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 921 122306 the patent application of awaiting the reply, and once having described the triethylamine that is significantly less than tetraethyl ammonium hydroxide with cloth field price 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, x=0.01～0.98, and y=0.01～0.60, z=0.01～0.60, and satisfy x+y+z=1; R is a template, and m is that the mole of template is imitated, and m=0.5～0.6, it is characterized in that: template R is a diethylamine or based on the organic compounds containing nitrogen group of diethylamine.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.
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 molecular sieve 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.
Embodiment 1 SAPO-34 molecular sieve synthetic 1
Take by weighing 71.0 gram aluminium isopropoxide (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 diethyls are by (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 2 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.
Table 1 table 22 θ d (A) 100 * I/I
o2 θ d (A), 100 * I/I
o9.45 9.36 77 *8.3 10.65 412.86 6.88 17 9.5 9.31 9814.05 6.30 5 12.95 6.84 2216.0 5.54 32 14.05 6.30 517.8 4.98 18 *14.3 6.19 219.05 4.66 4 16.05 5.52 3420.55 4.32 100 17.8 4.98 2222.05 4.03 11 19.1 4.65 622.35 3.98 3 20.6 4.31 10023.05 3.86 15 22.1 4.02 1524.95 3.57 35 22.4 3.97 525.85 3.45 20 23.1 3.85 1627.55 3.24 7 24.95 3.57 5228.25 3.16 5 25.95 3.43 2029.55 3.02 5 27.7 3.22 930.55 2.93 41 28.2 3.16 731.05 2.88 28 29.6 3.02 531.6 2.83 4 *30.05 2.97 232.35 2.77 3 30.6 2.92 4033.55 2.67 3 31.1 2.87 2834.4 2.61 10 31.6 2.83 434.9 2.57 3 32.5 2.75 336.05 2.49 5 33.5 2.67 539.7 2.27 4 34.55 2.60 2242.9 2.11 4 34.95 2.57 243.45 2.08 4 36.1 2.49 947.6 1.91 5 *38.7 2.33 348.8 1.87 6 39.7 2.27 549.2 1.85 5 42.8 2.11 650.65 1.80 9 43.4 2.08 652.9 1.73 1 47.6 1.91 553.1 1.72 6 48.8 1.87 854.35 1.68 5 49.2 1.85 555.1 1.67 4 50.7 1.80 1055.9 1.644 5 52.9 1.73 159.4 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 3 SAPO-34 molecular sieves 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 4 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%, the relative mol ratio of other volatile component 10.10wt% silicon phosphorus aluminium is P
2O
5: SiO
2: Al
2O
3=0.831: 1.000: 0.445.
Embodiment 5 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 6 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 7 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 8 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 distributes (wt%) (wt%)
CH
4 C
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 9 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 L0 volumetric molar concentration exchange.There is not NO with deionized water wash to liquid phase then
3 -Again 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 catalyzer b.
Embodiment 10 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 distributes (wt%) (wt%)
CH
4 C
2H
4C
2H
6C
3H
6C
3H
6?C
4H
6C
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 distributes (wt%) (wt%)
C
2H
4C
2H
4C
2H
6C
3H
6C
3H
8?C
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 (4)
1. 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, x=0.01～0.98, and y=0.01～0.60, z=0.01～0.60, and satisfy x+y+z=1; R is a template, and m is the mole number of template, and m=0.5～0.6, it is characterized in that: template R is a diethylamine or based on the organic compounds containing nitrogen group of diethylamine.
2. connect 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 claim 1, it is characterized in that it being that the silicon source can be silicon sol, active silica or positive silicon ester, the aluminium source can be aluminum alkoxide, pseudobochmite or activated alumina, and the phosphorus source can be ortho-phosphoric acid, aluminum phosphate, and synthetic primary process is as follows:
(1) according to molecular sieve: 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. claim 1,2 described molecular sieves are applied to methyl alcohol as catalyzer or/and dimethyl ether conversion is the low-carbon alkene reaction.
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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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| CN1096496A CN1096496A (en) | 1994-12-21 |
| CN1038125C true CN1038125C (en) | 1998-04-22 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100898127B1 (en) | 2007-09-13 | 2009-05-18 | 한국화학연구원 | Synthesis method of silicoaluminophosphate molecular sieve?????-???as a catalyst with high performance and stability for the production of light olefins and production method of light olefins thereof |
| US10259757B2 (en) | 2006-08-23 | 2019-04-16 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for starting up a fluidized catalytic reaction apparatus used for producing lower olefins |
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| CN1067603C (en) * | 1996-06-07 | 2001-06-27 | 中国科学院大连化学物理研究所 | Metal modified small-porosity P-Si-Al molecular sieve catalyst, its preparing process and use thereof |
| 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 |
| CN100584758C (en) * | 2006-08-08 | 2010-01-27 | 中国科学院大连化学物理研究所 | Fast synthetic method for phosphorus-silicon-aluminum 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 |
| CN102134081A (en) * | 2010-01-25 | 2011-07-27 | 天津海赛纳米材料有限公司 | Method for synthesizing SAPO-34 molecular sieve in absence of template agent |
| 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 |
| CN103864097B (en) * | 2012-12-10 | 2015-09-23 | 中国科学院大连化学物理研究所 | A kind of take diglycolamine as SAPO-34 molecular sieve and the synthetic method thereof of template |
| WO2014089738A1 (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 n-methyldiethanolamine 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 |
| CN105236445B (en) * | 2015-09-17 | 2017-06-20 | 中国石油天然气集团公司 | The microwave preparation of nano-scale aluminium phosphate molecular sieve |
| CN105174279B (en) * | 2015-09-17 | 2017-06-20 | 中国石油天然气集团公司 | The preparation method of nano-scale aluminium phosphate 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 |
| 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10259757B2 (en) | 2006-08-23 | 2019-04-16 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for starting up a fluidized catalytic reaction apparatus used for producing lower olefins |
| KR100898127B1 (en) | 2007-09-13 | 2009-05-18 | 한국화학연구원 | Synthesis method of silicoaluminophosphate molecular sieve?????-???as a catalyst with high performance and stability for the production of light olefins and production method of light olefins thereof |
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| Publication number | Publication date |
|---|---|
| CN1096496A (en) | 1994-12-21 |
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