CN1131845C - Synthesis of silicon-aluminium phosphate molecular sieve with double or multiple template agent - Google Patents
Synthesis of silicon-aluminium phosphate molecular sieve with double or multiple template agent Download PDFInfo
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- CN1131845C CN1131845C CN 99126308 CN99126308A CN1131845C CN 1131845 C CN1131845 C CN 1131845C CN 99126308 CN99126308 CN 99126308 CN 99126308 A CN99126308 A CN 99126308A CN 1131845 C CN1131845 C CN 1131845C
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Abstract
The present invention relates to a method for a synthesizing silicon aluminium phosphate molecular sieve by a double template agent or a multiple template agent. The molecular sieve has the moisture-free basis chemical constitutions: (m1R1+m2R2+......... +mnRn): (SixAlyPz) O2, and the template agent is a mixture comprising two or more substances. The molecular sieve synthesized by the method, in this way, crystallizing time is shortened, and the use level of the template agent is saved; the crystal size of the synthesizing molecular sieve can be adjusted by changing the molar ratio of the template agent.
Description
The present invention relates to a kind of method of chemosynthesis molecular sieve, specifically provided a kind of method with the multi-template agent synthesized silicon-aluminum phosphate molecular sieve.
European patent EP 0103117 discloses a kind of synthetic method of silicoaluminophosphamolecular molecular sieves, and one of its technical characterstic is to have used the tetraethyl-oxyammonia in the building-up process, Isopropylamine or be template with the mixture of tetraethyl-oxyammonia and di-n-propylamine.It is a kind of molecular sieve of being made up of phosphorus, silicon, aluminium and oxygen with class chabazite structure, and its structural unit is by PO
2 +, AlO
2 -And SiO
2Tetrahedron is formed.Anhydrous chemical constitution formula can be expressed as: mR:(SixAlyPz) O
2, wherein R is the template that is present in the microporous molecular sieve, m is every mole of (SixAlyPz) O
2The mole number of middle R, x, y, z are respectively the molar fraction of Si, Al, P, and satisfy x+y+z=1.After this, reported the silicoaluminophosphamolecular molecular sieves synthetic again at U.S. Pat P 4,440,871 in 1984 and improved one's methods, but still used identical template.Because these template cost an arm and a leg, the source difficulty, thereby be difficult in industrial application.Present inventors, two kinds of technology (CN 92112230.6 and CN 93112015.2) that are suitable for the synthetic SAPO-34 molecular sieve of suitability for industrialized production employing had once been proposed in advance, promptly adopting triethylamine or diethylamine is the template synthesized silicon-aluminum phosphate molecular sieve, but it is adopt the above-mentioned technology synthetic SAPO-34 of institute zeolite crystal bigger, and also restive to the size of crystal grain.After this, once proposed a kind of double template method (CN94110059.6) of adjustable change molecular sieve grain size again, promptly tetraethyl-oxyammonia and triethylamine are the synthetic SAPO-34 molecular sieve of template, but have certain limitation.
The object of the present invention is to provide the method for a kind of mixture that adopts two or more materials as the synthetic multiple silicoaluminophosphamolecular molecular sieves of template, and the grain size that the composition proportioning by the change template can modulation institute synthesis of molecular sieve.
The silicoaluminophosphamolecular molecular sieves that method provided by the invention synthesized, its moisture-free basis chemical constitution can be expressed as: (m
1R
1+ m
2R+...+m
nR
2): (SixAlyPz) O
2, R wherein
1, R
2R
nFor being present in the template in the microporous molecular sieve, m
1, m
2+ ... m
nBe every mole of (SixAlyPz) O
2Corresponding R
1, R
2R
nMole number, m
1=0.01-5, m
2=0.01-5 ... m
n=0.01-5, and m
1+ m
2+ ... + m
n=0.03～8.00, n is≤2,3,4 or 5; X, y, z are respectively the molar fraction of Si, Al, P, and satisfy x+y+z=1, simultaneously, and x=0.00～0.98, y=0.01～0.60, z=0.01～0.60.In above-mentioned expression formula, the template kind is the most frequently used to be 2 kinds or 3 kinds, and promptly n is 2 or 3.
In the method for synthesized silicon-aluminum phosphate molecular sieve of the present invention, used silicon source is one or more the mixture in silicon sol, water glass, active silica or the positive silicon ester; The aluminium source is a kind of or any several mixture in aluminium salt, aluminate, activated alumina, aluminum alkoxide, false boehmite or the pseudo-boehmite; The phosphorus source is a kind of or any several mixture in ortho-phosphoric acid, phosphoric acid salt, Organophosphorous compounds or the phosphorous oxides; Template is triethylamine, diethylamine, Tri N-Propyl Amine, Isopropylamine, di-n-propylamine, Diisopropylamine, tripropyl amine, n-Butyl Amine 99, isobutylamine, thanomin, diethanolamine, trolamine, six methynes time amine, hexanediamine, N, N, N ', the mixture of two or more in organic amine such as N '-4-methyl hexamethylene diamine, tetramethyl-oxyammonia, tetraethyl-oxyammonia, tetrapropyl oxyammonia or tetrabutylammonium hydroxide amine and the alcohols
The method of synthesized silicon-aluminum phosphate molecular sieve provided by the invention is characterized in that preparation process is as follows:
(1) in proportion silicon source material, aluminium source material, phosphorus source material, template and water are under agitation mixed, get initial gel mixture;
Proportioning between each raw material (by the oxide molecule ratio) is:
SiO
2/Al
2O
3＝0～10；
P
2O
5/Al
2O
3＝0.5～15；
H
2O/Al
2O
3＝10～100；
R/Al
2O
3=1～10; R=(R
1+ R
2+ ... R
n) be the mixture of two or more template;
(2) with sealing in the initial gel mixture material immigration stainless steel synthesis reactor, be no less than 0.1 hour 80～250 ℃ of crystallization;
(3) solid crystallized product is separated with mother liquor, wash to neutrality, behind 0～120 ℃ of air drying, obtain the former powder of silicoaluminophosphamolecular molecular sieves with deionized water;
Below by embodiment in detail the present invention is described in detail.
Embodiment 1～6 (SAPO-34)
According to formula (kTEA+1DEA): 0.2SiO
2: Al
2O
3: P
2O
5: 50H
2O takes by weighing raw material.K, 1 value are as shown in table 1.
The 7.06g activated alumina (is contained Al
2O
372.2wt%) be dissolved in the 19ml deionized water, stirring down, adding 2.40g silicon sol (contains SiO
225wt%), slowly add 11.53g ortho-phosphoric acid again and (contain H
3PO
485wt%), add water 10ml, continue to stir and to be no less than 30 minutes, add triethylamine then and diethylamine mixes, make gel.Will the said mixture material move in the stainless steel synthesis reactor and seal, crystallization is 72 hours under 200 ℃ and autogenous pressure, and solid product, is made SEM and measured and XRD analysis to neutral with the deionized water washing behind 100 ℃ of air dryings, and the results are shown in Table 1.
Table 1
TEA: DEA size of microcrystal embodiment production code member (mol ratio) XRD result (μ m)
1 SAPO1 1.0∶0.01 SAPO-34 7.6
2 SAPO2 0.8∶0.2 SAPO-34 6.8
3 SAPO3 0.6∶0.4 SAPO-34 5.2
4 SAPO4 0.4∶0.6 SAPO-34 3.8
5 SAPO5 0.2∶0.8 SAPO-34 2.6
6 SAPO6 0.01∶1.0 SAPO-34 1.2
Embodiment 7 (SAPO-34)
The 7.06g activated alumina (is contained Al
2O
372.2wt%) be dissolved in the 19ml deionized water, stirring down, adding 2.40g silicon sol (contains SiO
225wt%), slowly add 11.53g ortho-phosphoric acid again and (contain H
3PO
485wt%), add water 10ml, continue stirring and be no less than 30 minutes, add (7.58g triethylamine+4.58g thanomin) then and mix, make gel.Will the said mixture material move in the stainless steel synthesis reactor and seal, crystallization is 100 hours under 200 ℃ and autogenous pressure, and to neutral, it is as shown in table 2 to make XRD analysis behind 100 ℃ of air dryings with the deionized water washing for solid product.
Table 2
No. 2θ d() 100×I/I
0
1 9.430 9.3711 100
2 12.770 6.9266 13
3 13.970 6.3342 10
4 15.930 5.5589 29
5 17.840 4.9679 27
6 20.500 4.3289 69
7 22.030 4.0315 8
8 22.990 3.8653 8
9 25.030 3.5547 47
10 25.800 3.4503 14
11 28.230 3.1586 7
12 30.490 2.9294 27
13 31.090 2.8743 22
14 34.370 2.6071 6
15 36.150 2.4827 6
16 48.890 1.8614 5
17 50.790 1.7961 5
Embodiment 8 (SAPO-34)
In embodiment 7, only (7.58g triethylamine+4.58g thanomin) changed into (7.58g triethylamine+5.51g n-Butyl Amine 99), all the other components and crystallization condition are constant, and product is the SAPO-34 molecular sieve through XRD analysis, and is as shown in table 3.
Table 3
No. 2θ d() 100×I/I
0
1 9.340 9.4612 100
2 12.700 6.9646 15
3 13.950 6.3355 4
4 15.840 5.5903 29
5 17.620 5.0294 22
6 20.420 4.3456 81
7 21.830 4.0680 12
8 22.860 3.8870 13
9 24.770 3.5914 47
10 25.700 3.4635 17
11 27.990 3.1852 7
12 30.400 2.9379 36
13 30.890 2.8924 23
14 34.270 2.6145 9
15 35.830 2.5041 6
16 48.620 1.8711 7
17 50.500 1.8058 6
Embodiment 9 (SAPO-34)
In embodiment 7, only (7.58g triethylamine+4.58g thanomin) changed into (5.40g diethylamine+4.58g thanomin), all the other components and crystallization condition are constant, and product is the SAPO-34 molecular sieve through XRD analysis, and is as shown in table 4.
Table 4
No. 2θ d() 100×I/I
0
1 9.390 9.4109 100
2 12.750 6.9374 15
3 13.900 6.3659 6
4 15.900 5.5694 26
5 17.740 4.9956 26
6 20.470 4.3351 68
7 21.950 4.0461 10
8 22.940 3.8736 11
9 24.900 3.5730 43
10 25.760 3.4556 15
11 28.110 3.1718 6
12 30.450 2.9332 26
13 31.010 2.8815 26
14 34.330 2.6100 7
15 35.980 2.4940 6
16 48.730 1.8671 6
17 50.630 1.8014 6
Embodiment 10 (SAPO-35)
The 7.06g activated alumina (is contained Al
2O
372.2wt%) be dissolved in the 29ml deionized water, stirring down, adding 3.60g silicon sol (contains SiO
225wt%), slowly add 11.53g ortho-phosphoric acid again and (contain H
3PO
485wt%), add water 20ml, continue stirring and be no less than 30 minutes, add 7.50g six methynes time amine then and mix.Will the said mixture material move in the stainless steel synthesis reactor and seal, crystallization is 24 hours under 200 ℃ and autogenous pressure, and solid product to neutral, obtains SAPO-35 molecular sieve at 100 ℃ of air dryings with the deionized water washing, and its XRD analysis is as shown in table 4.
Table 5
No. 2θ d() 100×I/I
0
1 8.590 10.2855 21
2 10.930 8.0881 50
3 13.300 6.6517 45
4 15.870 5.9290 8
5 17.270 5.1305 77
6 17.740 4.9956 10
7 21.020 4.2229 33
8 21.880 4.0588 100
9 23.180 3.8341 21
10 24.970 3.5631 10
11 26.830 3.3202 25
12 28.540 301250 24
13 29.050 3.0713 12
14 32.090 2.7869 48
15 34.490 2.5983 8
Embodiment 11 (SAPO-35)
In embodiment 10, only change 7.50g six methynes time amine into 4.95g six methynes time amine and 2.90g hexanediamine, all the other components and crystallization condition are constant, and product is the SAPO-35 molecular sieve, and its XRD analysis is as shown in table 6.
Table 6
No. 2θ d() 100×I/I
0
1 8.540 10.3456 26
2 10.880 8.1252 48
3 13.260 6.6717 39
4 15.820 5.9790 8
5 17.230 5.1423 67
6 17.700 5.0068 11
7 20.970 4.2329 41
8 21.820 4.0699 100
9 23.140 3.8406 20
10 23.450 3.7905 12
11 24.930 3.5687 12
12 26.770 3.3275 22
13 280530 3.1261 36
14 29.020 3.0744 13
15 32.040 2.7912 53
16 34.440 2.6020 10
Embodiment 12 (SAPO-56)
The 5.24g activated alumina (is contained Al
2O
372.2wt%) be dissolved in the 37ml deionized water, stirring down, adding 6.10g silicon sol (contains SiO
225wt%), slowly add 14.41g ortho-phosphoric acid again and (contain H
3PO
485wt%), continue stirring and be no less than 30 minutes, add 21.94g N then, N, N ', N '-4-methyl hexamethylene diamine mixes.Will the said mixture material move in the 100ml stainless steel synthesis reactor and seal, crystallization is 30 hours under 200 ℃ and autogenous pressure, and solid product to neutral, obtains SAPO-56 molecular sieve at 100 ℃ of air dryings with the deionized water washing, and its XRD analysis is as shown in table 7.
Table 7
No. 2θ d() 100×I/I
0
1 7.340 12.0341 17
2 8.559 10.3215 58
3 11.480 7.7018 63
4 12.800 6.9104 32
5 15.440 5.7342 37
6 17.260 5.1335 43
7 17.690 5.0096 70
8 20.150 4.4032 80
9 21.590 4.1127 100
10 23.430 3.7937 44
11 25.850 3.4438 37
12 27.780 3.2088 85
13 30.290 2.9483 37
14 31.290 2.8563 34
15 33.440 2.6774 32
16 34.450 2.6012 17
Embodiment 13 (SAPO-56)
In embodiment 12, only with 21.94g N, N, N ', N '-4-methyl hexamethylene diamine changes 19.50g N into, N, N ', N '-4-methyl hexamethylene diamine and 4.50g triethylamine, all the other components and crystallization condition are constant, and product is the SAPO-56 molecular sieve, and its XRD analysis is as shown in table 8.
Table 8
No. 2θ d() 100×I/I
0
1 7.430 11.8885 16
2 8.650 10.2143 50
3 11.560 7.6487 67
4 12.880 6.8677 30
5 15.530 5.7012 32
6 17.360 5.1041 42
7 17.790 4.9845 100
8 20.230 4.3860 66
9 21.670 4.0977 88
10 23.510 3.7810 48
11 25.930 3.4333 34
12 27.850 3.2008 94
13 30.370 2.9407 34
14 31.370 2.8492 30
15 33.510 2.6720 30
Embodiment 14 (SAPO-34)
In embodiment 7, only (7.58g triethylamine+4.58g thanomin) changed into (7.35g tetraethyl ammonium hydroxide+5.05g triethylamine+3.65g n-Butyl Amine 99), all the other components and crystallization condition are constant, and product is the SAPO-34 molecular sieve through XRD analysis.Recording its saturated water adsorptive value after 550 ℃ of roastings is 28.5%.
Embodiment 15 (SAPO-34)
In embodiment 7, only (7.58g triethylamine+4.58g thanomin) changed into (7.35g tetraethyl ammonium hydroxide+5.05g triethylamine+4.55g four basic ammonium hydroxide), all the other components and crystallization condition are constant, and product is the SAPO-34 molecular sieve through XRD analysis.Recording its saturated water adsorptive value after 550 ℃ of roastings is 29.8%.
Embodiment 16 catalyzed reactions tests (SAPO-34)
Embodiment 1～6 synthetic SAPO-34 molecular screen primary powder is made molecular sieve catalyst (numbering identical with table 1) after 550 ℃ of roastings, carry out methanol to olefins reaction on atmospheric fixed bed reaction unit, it the results are shown in table 2.Reaction conditions is: methyl alcohol air speed WHSV=2h-1, pressure are normal pressure, methanol conversion 100%.
Table 2 numbering temperature products distribution (wt%) C
2 =～C
3 =
(℃) CH
4 C
2H
4 C
2H
6?C
3H
6 C
3H
8 (wt％)SAPO1 451 0.58 45.25 4.83 33.14 0.30 78.39SAPO2 451 0.88 48.45 0.27 40.30 0.56 88.75SAPO3 450 0.95 47.24 0.32 40.26 0.36 87.50SAPO4 450 1.04 53.49 0.30 36.92 0.44 90.41SAPO5 453 1.46 53.34 0.36 36.58 0.51 89.92SAPO6 450 0.64 45.71 3.22 35.66 0.32 81.37
Can see the grain size that the composition proportioning of the present invention by changing template can modulation institute synthesis of molecular sieve by the foregoing description.And institute's synthetic molecular sieve is that low-carbon alkene has advantages of high catalytic activity and selectivity of product for methanol conversion.
Claims (7)
1. the method for a multi-template agent synthesized silicon-aluminum phosphate molecular sieve is characterized in that institute's synthetic molecular sieve moisture-free basis chemical constitution can be expressed as: (m
1R
1+ m
2R
2+ ...+m
nR
n): (SixAlyPz) O
2, R wherein
1, R
2... R
nFor being present in the template in the microporous molecular sieve, m
1, m
2... m
nBe every mole of (SixAlyPz) O
2In corresponding R
1, R
2... R
nMole number, m
1=0.01-5, m
2=0.01-5...m
n=0.01-5, and m
1+ m
2+ ...+m
n=0.03～8.00, n is 3,4 or 5; X, y, z are respectively the molar fraction of Si, Al, P, and satisfy x+y+z=1, simultaneously, and x=0.00～0.98, y=0.01～0.60, z=0.01～0.60; The template of using is the mixture of two or more materials in synthetic above-mentioned molecular sieve.
2. according to the method for the described synthesized silicon-aluminum phosphate molecular sieve of claim 1, it is characterized in that preparation process is as follows:
(1) takes by weighing a certain amount of several template and corresponding silicon source, aluminium source, phosphorus source and water in proportion;
(2) above-mentioned each material is mixed according to a definite sequence, fully stir into gel again;
(3) with gel 80～250 ℃ of following crystallization, crystallization time is no less than 0.1 hour;
(4) solid product after filtration or centrifugation, 0～120 ℃ of air drying, the former powder of silicoaluminophosphamolecular molecular sieves.
3. according to the method for the described synthesized silicon-aluminum phosphate molecular sieve of claim 2, it is characterized in that taking by weighing proportioning between each raw material of silicon source, aluminium source, phosphorus source, template and water (by oxide molecule than) be:
SiO
2/Al
2O
3＝0～10；
P
2O
5/Al
2O
3＝0.5～15；
H
2O/Al
2O
3＝10～100；
R/Al
2O
3=1～10; R=(R
1+ R
2+ ...+R
n) be the mixture of several template.
4. according to the method for claim 2 or 3 described synthesized silicon-aluminum phosphate molecular sieves, it is characterized in that employed template is by triethylamine, diethylamine, Tri N-Propyl Amine, Isopropylamine, di-n-propylamine, Diisopropylamine, tripropyl amine, n-Butyl Amine 99, isobutylamine, thanomin, diethanolamine, trolamine, six methynes time amine, hexanediamine, N, N, N ', selected several mixture in N '-4-methyl hexamethylene diamine, tetramethyl-oxyammonia, tetraethyl-oxyammonia, tetrapropyl oxyammonia or the tetrabutylammonium hydroxide amine.
5. according to the method for claim 2 or 3 described synthesized silicon-aluminum phosphate molecular sieves, it is characterized in that used silicon source is one or more the mixture in silicon sol, water glass, active silica or the positive silicon ester;
6. according to the method for claim 2 or 3 described synthesized silicon-aluminum phosphate molecular sieves, it is characterized in that used aluminium source is one or more the mixture in aluminium salt, aluminate, activated alumina, aluminum alkoxide, false boehmite or the pseudo-boehmite;
7. according to the method for claim 2 or 3 described synthesized silicon-aluminum phosphate molecular sieves, it is characterized in that used phosphorus source is one or more the mixture in ortho-phosphoric acid, phosphoric acid salt, Organophosphorous compounds or the phosphorous oxides.
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Cited By (1)
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|---|---|---|---|---|
| WO2014047801A1 (en) | 2012-09-26 | 2014-04-03 | 中国科学院大连化学物理研究所 | Sapo-34 molecular sieve and synthesis method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6696032B2 (en) * | 2001-11-29 | 2004-02-24 | Exxonmobil Chemical Patents Inc. | Process for manufacturing a silicoaluminophosphate molecular sieve |
| US6927187B2 (en) | 2003-07-11 | 2005-08-09 | Exxonmobil Chemical Patents Inc. | Synthesis of silicoaluminophosphates |
| US6835363B1 (en) | 2003-08-06 | 2004-12-28 | Exxonmobil Chemical Patents Inc. | Synthesis of molecular sieves of CHA framework type |
| CN101417811B (en) * | 2007-10-25 | 2010-12-22 | 中国石油化工股份有限公司 | Method for synthesizing SAPO-35 molecular sieve by using bi-template |
| CN101633508B (en) * | 2008-07-24 | 2012-05-23 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve and synthesis method thereof |
| CN101492169B (en) * | 2009-03-05 | 2011-05-18 | 上海兖矿能源科技研发有限公司 | Production method of composite mould plate agent synthesized silicon-aluminum phosphate molecular sieve |
| CN103058208B (en) * | 2011-10-24 | 2015-01-07 | 中国石油化工股份有限公司 | Preparation method of SAPO-56 molecular sieve |
| CN103663483B (en) * | 2012-09-26 | 2015-12-02 | 中国科学院大连化学物理研究所 | A kind of synthetic method of SAPO-34 molecular sieve and catalyzer prepared therefrom |
| WO2014047802A1 (en) | 2012-09-26 | 2014-04-03 | 中国科学院大连化学物理研究所 | Sapo-34 molecular sieves and synthesis method thereof |
| WO2014047800A1 (en) * | 2012-09-26 | 2014-04-03 | 中国科学院大连化学物理研究所 | Method for synthesizing sapo-34 molecular sieve and catalyst prepared thereby |
| 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 |
| CN103274426A (en) * | 2013-05-08 | 2013-09-04 | 天津众智科技有限公司 | High-temperature hydro-thermal synthesis method for preparing SAPO-34 molecular sieve by using double templates |
| CN106542547B (en) * | 2016-08-03 | 2018-12-14 | 刘希尧 | A kind of preparation method of the SAPO-34 molecular sieve of high activity low silicon content |
| CN108862315B (en) * | 2018-07-03 | 2020-05-01 | 天津大学 | Preparation method of SAPO-56/SAPO-34 composite molecular sieve |
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1999
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014047801A1 (en) | 2012-09-26 | 2014-04-03 | 中国科学院大连化学物理研究所 | Sapo-34 molecular sieve and synthesis method thereof |
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