CN1108868C - MeAPSO-18 molecular sieve and its synthesizing method - Google Patents

MeAPSO-18 molecular sieve and its synthesizing method Download PDF

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CN1108868C
CN1108868C CN99127143A CN99127143A CN1108868C CN 1108868 C CN1108868 C CN 1108868C CN 99127143 A CN99127143 A CN 99127143A CN 99127143 A CN99127143 A CN 99127143A CN 1108868 C CN1108868 C CN 1108868C
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meapso
molecular sieve
molecular sieves
synthetic method
silicoaluminophosphamolecular molecular
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CN1301594A (en
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黄韬
刘中民
许磊
孙承林
田鹏
李宏愿
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a MeAPSO-18 molecular sieve whose anhydrous chemical composition is mR. nMe. (SixAlyPzO2), wherein R represents a template agent which exists in micropores of the molecular sieve; m represents the mole number of R in SixAlyPzO2 per mole, and m is from 0.001 to 0.3. x, y and z respectively represent mole fractions of Si, Al and P, wherein x is from 0.001 to 0.98, y is from 0.01 to 0.60, z is from 0.01 to 0.60, and the sum of x, y and z is 1; Me represents metal atoms; n represents the mole number of Me in SixAlyPzO2 per mole, and n is from 0.01 to 0.25. The molecular sieve has ion-exchange property and adsorbability and has higher catalytic activity to the reaction for preparing low-carbon olefin by the conversion of methanol, etc.

Description

MeAPSO-18 molecular sieve and synthetic method thereof
The present invention relates to a kind of novel aperture silicoaluminophosphamolecular molecular sieves MeAPSO-18 and synthetic method thereof.
1984, U.S. Pat P 4,440,871 disclose the synthetic method of several silicoaluminophosphamolecular molecular sieves, its technical characterstic is to adopt silicon source, aluminium source, phosphorus source and different template agent to synthesize a series of SAPO molecular sieves, the molecular sieve of some of them small structure such as SAPO ¨ C4 etc. have been successfully applied to methanol-to-olefins reaction processes such as (MTO), demonstrate good catalytic performance.This molecular sieve analog has been formed the class chabazite structure by phosphorus, silicon, aluminium and oxygen, and its construction unit is by PO2, AlO 2And SiO 2Tetrahedron is formed.Its anhydrous chemical constitution formula can be expressed as: mR (SixAlyPz) O 2, wherein R is the template agent that is present in the microporous molecular sieve, m is every mole of (SixAlyPz) O 2The molal quantity of middle R, x, y, z are respectively the molar fraction of Si, Al, P, and satisfy x+y+z=1.But above-mentioned patent does not relate to the synthetic of SAPO-18 molecular sieve.After this, along with the continuous concern of people to SAPO Series Molecules sieve, some different SAPO Series Molecules sieves are synthesized out in succession.But the report of relevant hetero atom MeAPO-18 molecular sieve is less.
The object of the present invention is to provide a kind of novel aperture hetero atom phosphoric acid Si-Al molecular sieve MeAPSO-18 and synthetic method thereof.By in the SAPO-18 framework of molecular sieve, introducing metal heteroatom, make its catalytic property and adsorption property be improved significantly.
A kind of novel aperture silicoaluminophosphamolecular molecular sieves MeAPSO-18 provided by the invention is characterized in that the anhydrous chemical composition of molecular sieve can be expressed as: mRnMe (SixAlyPz) O 2, wherein R is a kind of template agent that is present in the microporous molecular sieve, m is every mole of (SixAlyPz) O 2The molal quantity of middle R, and m=0.001~0.3; X, y, z are respectively the molar fraction of Si, Al, P, and its scope is x=0.001~0.98, y=0.01~0.60, and z=0.01~0.60, and satisfy x+y+z=1, and Me is a metallic atom, n is every mole of (SixAlyPz) O 2The molal quantity of middle Me, n=0.01~0.25.
In the molecular sieve MeAPSO-18 of the invention described above, its metallic atom Me is one or more in the metals such as zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and zinc.
A kind of novel aperture hetero atom phosphoric acid Si-Al molecular sieve MeAPSO-18 provided by the invention, its preparation process is as follows:
(1) in proportion silicon source material, aluminium source material, phosphorus source material, slaine, template agent and water are under agitation mixed, get initial gel mixture;
(2) with sealing in the initial gel mixture material immigration stainless steel synthesis reactor, place baking oven, be no less than 0.5 hour 100~250 ℃ of following crystallization;
(3) solid crystallized product is separated with mother liquor, to neutral, behind 80-130 ℃ of lower air drying, obtain the former powder of metal silicon aluminum phosphate molecular sieve with the deionized water washing;
(4) molecular screen primary powder is no less than 3 hours 300~700 ℃ of following bubbling air roastings, promptly gets metal-silicon aluminium phosphate molecular sieve MeAPSO-18 adsorbent or catalyst.
In above-mentioned preparation process, used silicon source is one or more the mixture in Ludox, waterglass, active silica or the positive esters of silicon acis; The aluminium source is one or more the mixture in aluminium salt, aluminate, activated alumina, aluminum alkoxide, false boehmite, boehmite or the organo-aluminium; The phosphorus source is one or more the mixture in orthophosphoric acid, phosphate, organic phosphorus compound or the phosphorous oxides; Metallic compound is oxide, the hydroxide of nitrate, acetate, sulfate or the hydrochloride of metals such as zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and zinc and these metals or the organic matter that contains these metals; The template agent can be N, N-diisopropylethylamine, N, N-diisopropyl propylamine or tetraethyl oxyammonia or the mixture between them etc.
In addition, in the above-mentioned preparation process, proportioning between each raw material (by the oxide molecule ratio) is:
Me/Al 2O 3=0.01~1.0;
SiO 2/Al 2O 3=0.001~10;
P 2O 5/Al 2O 3=0.5~10;
H 2O/Al 2O 3=10~100;
R/Al 2O 3=0.1~10; R is a kind of template.
The metal-silicon aluminium phosphate molecular sieve that synthesizes with the present invention can be used as ion-exchanger or adsorbent, and having unique catalytic perfomance, the catalyst made from this molecular sieve all has advantages of high catalytic activity for methanol-to-olefins reaction (MTO), hydrocarbon conversion reactions, alkylated reaction, isomerization reaction, catalytic cracking reaction and selective oxidation reaction etc.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1 ZrAPSO-18
The 7.06g activated alumina (is contained Al 2O 372.2wt%) be dissolved in the 39.64ml deionized water, stir the lower 10.95g of adding orthophosphoric acid and (contain H 3PO 485wt%), slowly add again the 2.35g Ludox and (contain SiO 225.5wt%), add then 2.15g zirconium nitrate [Zr (NO 3) 45H 2O], continue stirring and be no less than 30 minutes, add at last 10.34gN, the N-diisopropylethylamine.Continue to stir until become homogeneous phase.To seal in the said mixture material immigration stainless steel synthesis reactor, crystallization is 12 hours under 170 ℃ and self-generated pressure, solid product with the deionized water washing to neutral, 100 ℃ of following air dryings 12 hours, product is the ZrAPSO-18 molecular sieve, and the result is as shown in table 1 for its XRD analysis.XRD standard spectrogram with the SAPO-18 molecular sieve is compared, and part diffraction maximum position and intensity change, and illustrates that the Zr atom enters to cause that cell parameter etc. changes institute extremely behind the framework of molecular sieve.
Table 1No. 2 θ d () 100 * I/I 01 9.450 9.3513 1002 10.540 8.3865 173 12.870 6.6730 104 14.740 6.0050 145 15.920 5.5624 326 16.910 5.2389 687 19.530 4.5416 228 20.020 4.4315 279 20.510 4.3268 3610 21.280 4.1719 2711 23.830 3.7309 2812 26.250 3.3922 2713 27.800 3.2065 2214 30.300 2.9474 1715 30.980 2.8842 2616 32.150 2.7819 20
Embodiment 2 CoAPSO-18
In embodiment 1, the 7.06g activated alumina (is contained Al 2O 372.2wt%) change the 6.00g boehmite into and (contain Al 2O 385.0wt%), the 2.15g zirconium nitrate changes the 1.46g cobalt nitrate into and [contains Co (NO 3) 26H 2O 99%], all the other components and crystallization condition are constant, and product is the CoAPSO-18 molecular sieve, and the result is as shown in table 2 for its XRD analysis.XRD standard spectrogram with the SAPO-18 molecular sieve is compared, and the part diffraction maximum disappears, and peak shape changes, illustrate the Co atom enter cause behind the framework of molecular sieve cell parameter etc. change extremely.
Table 2No. 2 θ d () 1000 * I/I 01 9.460 9.3414 1002 10.500 8.4184 123 12.800 6.9104 104 13.950 6.3432 95 14.750 6.0009 86 15.920 5.5624 377 16.920 5.2359 508 19.570 4.5324 179 20.490 4.3309 3710 21.210 4.1855 2411 23.890 3.7217 1912 25.730 3.4596 1413 26.210 3.3973 2114 27.750 3.2122 1315 30.320 2.9455 1716 30.920 2.8897 24
Embodiment 3 TiAPSO-18
In embodiment 1, change the 2.35g Ludox into the 1.50g active silica and (contain SiO 240%), the 2.15g zirconium nitrate changes 0.63g titanium sulfate [Ti (SO into 4) 296%], all the other components and crystallization condition are constant, and product is the TiAPSO-18 molecular sieve, and the result is as shown in table 3 for its XRD analysis.XRD standard spectrogram with the SAPO-18 molecular sieve is compared, and the part diffraction maximum disappears, and peak shape changes, illustrate the Ti atom enter cause behind the framework of molecular sieve cell parameter etc. change extremely.
Table 3No. 2 θ d () 100 * I/I 01 9.490 9.3119 1002 10.430 8.4747 143 10.860 8.1401 124 12.950 6.8307 95 14.760 5.9969 116 15.520 5.7049 307 15.910 5.5659 178 16.880 5.2482 739 17.680 5.0125 2110 19.500 4.5485 1511 20.020 4.4315 3112 20.810 4.2651 3513 21.740 4.0847 1514 23.820 3.7325 1615 26.170 3.4024 2316 26.720 3.3336 1417 27.930 3.1919 2218 30.090 2.9675 1819 30.720 2.9080 1820 32.330 2.7668 20
Comparative Examples 1 TiAPSO
In embodiment 1, change the 2.15g zirconium nitrate into 13.75g titanium sulfate [Ti (SO 4) 296%], all the other components and crystallization condition are constant, and product is mixed crystal, and by the mixture that TiAPSO-18 and TiAPSO-5 form, the result is as shown in table 4 for its XRD analysis.Illustrate that the amount that the Ti atom enters framework of molecular sieve exists certain quantitative limitation.
Table 4No. 2 θ D () 100 * I/I 01 7.390 11.9527 722 9.450 9.3513 173 12.840 6.8890 124 14.860 5.9567 265 15.940 5.5555 126 16.880 5.2482 137 19.710 4.5005 608 20.880 4.2509 1009 22.330 3.9781 7610 23.830 3.7309 1011 25.910 3.4359 3812 28.930 3.0838 1613 30.020 2.9742 2114 34.550 2.5939 1715 37.530 2.3945 12
Embodiment 4 MnAPSO-18
In embodiment 1, change the 2.15g zirconium nitrate into 1.23g manganese acetate [Mn (CH 3COO) 24H 2O], all the other components and crystallization condition are constant, and product is the MnAPSO-18 molecular sieve, and the result is as shown in table 4 for its XRD analysis.XRD standard spectrogram with the SAPO-18 molecular sieve is compared, and the part diffraction maximum disappears, and peak shape changes, illustrate the Mn atom enter cause behind the framework of molecular sieve cell parameter etc. change extremely.
Table 5No. 2 θ d () 100 * I/I 01 7.380 11.9686 72 9.480 9.3217 1003 10.540 8.3865 144 12.820 6.8997 105 14.750 6.0009 106 15.940 5.5555 337 16.960 5.2236 628 19.560 4.5347 209 20.030 4.4294 2210 20.510 4.3268 3411 21.290 4.1700 2812 23.860 3.7263 2213 25.820 3.4477 1514 26.250 3.3922 2115 27.910 3.1941 1716 30.250 2.9521 1717 31.010 2.8815 24
Embodiment 5 MgAPSO-18
In embodiment 1, change the 2.15g zirconium nitrate into 1.07g magnesium acetate [Mg (CH 3COO) 24H 2O], all the other components and crystallization condition are constant, and product is the MgAPSO-18 molecular sieve, and the result is as shown in table 5 for its XRD analysis.XRD standard spectrogram with the SAPO-18 molecular sieve is compared, and the part diffraction maximum disappears, and peak shape changes, illustrate the Mg atom enter cause behind the framework of molecular sieve cell parameter etc. change extremely.
Table 6No. 2 θ d () 100 * I/I 01 9.490 9.3119 1002 10.460 8.4505 173 10.910 8.1029 154 15.540 5.6976 325 16.910 5.2389 936 17.730 4.9984 247 19.530 4.5416 228 20.060 4.4228 399 20.870 4.2529 4510 21.960 4.0442 2011 22.360 3.9728 1612 23.880 3.7232 2013 24.320 3.6569 1614 26.220 3.3960 2715 27.970 3.1874 2316 30.110 2.9655 2217 31.070 2.8761 2218 32.350 2.7651 25
Embodiment 6 FASPO-18
In embodiment 1, change the 2.15g zirconium nitrate into 2.02g ferric nitrate [Fe (NO 3) 39H 2O], and use 10.61g N, N ,-diisopropyl propylamine replaces DIPEA, and all the other components and crystallization condition are constant, and product is the FAPSO-18 molecular sieve, and the result is as shown in table 6 for its XRD analysis.XRD standard spectrogram with the SAPO-18 molecular sieve is compared, and the part diffraction maximum disappears, and peak shape changes, illustrate the Fe atom enter cause behind the framework of molecular sieve cell parameter etc. change extremely.
Table 7No. 2 θ d () 100 * I/I 01 9.510 9.2924 1002 10.440 8.4666 143 10.860 8.1401 144 15.560 5.6903 285 16.950 5.2267 716 17.670 5.0153 187 19.540 4.5393 168 20.060 4.4228 329 20.820 4.2630 4010 21.780 4.0773 1811 23.990 3.7064 1412 24.320 3.6569 1613 26.210 3.3973 2514 30.120 2.9646 1715 31.090 2.8743 1916 32.340 2.7660 21
Embodiment 7 NiAPSO-18
In embodiment 1, change the 2.15g zirconium nitrate into 1.45g nickel nitrate [Ni (NO 3) 26H 2O], and replace DIPEA with 9.96g tetraethyl oxyammonia, all the other components and crystallization condition are constant, and product is the NiAPSO-18 molecular sieve, and the result is as shown in table 7 for its XRD analysis.XRD standard spectrogram with the SAPO-18 molecular sieve is compared, and the part diffraction maximum disappears, and peak shape changes, illustrate the Ni atom enter cause behind the framework of molecular sieve cell parameter etc. change extremely.
Table 8No. 2 θ d () 100 * I/I 01 9.450 9.3513 1002 10.550 8.3786 153 12.780 6.9212 124 14.740 6.0050 95 15.960 5.5486 486 16.880 5.2482 477 19.560 4.5347 218 20.510 4.3268 439 21.290 4.1700 3510 23.830 3.7309 3111 25.760 3.4556 1912 26.270 3.3897 2413 27.790 3.2076 2114 30.330 2.9445 1815 31.020 2.8806 28
Embodiment 8 ZnAPSO-18
In embodiment 1, change the 2.15g zirconium nitrate into 1.10g zinc acetate [Zn (CH 3COO) 22H 2O], all the other components and crystallization condition are constant, and product is the ZnAPSO-18 molecular sieve, and the result is as shown in table 8 for its XRD analysis.XRD standard spectrogram with the SAPO-18 molecular sieve is compared, and the part diffraction maximum disappears, and peak shape changes, illustrate the Zn atom enter cause behind the framework of molecular sieve cell parameter etc. change extremely.
Table 9No. 2 θ d () 100 * I/I 01 9.430 9.3711 1002 10.500 8.4184 123 12.790 6.9158 114 15.920 5.5624 455 16.880 5.2482 556 19.560 4.5347 207 20.460 4.3372 418 21.240 4.1797 309 23.810 3.7340 2610 25.720 3.4609 1611 26.270 3.3897 2212 27.780 3.2088 1513 30.310 2.9464 1714 30.980 2.8842 27
Comparative Examples 2
In embodiment 1, with 10.34gN, the N-diisopropylethylamine changes 5.82g N into, the N-diisopropylethylamine, and all the other components and crystallization condition are constant, and product is unknown phase, and the result is as shown in table 10 for its XRD analysis.
Table 10No. 2 θ d () 100 * I/I 01 7.500 11.7777 82 13.000 6.8045 23 14.930 5.9290 34 19.800 4.4803 65 20.530 4.3226 176 21.160 4.1953 67 21.890 4.0570 1008 22.480 3.9518 119 23.260 3.8211 710 25.970 3.4281 411 28.320 3.1488 812 30.050 2.9713 413 31.270 2.8581 914 35.920 2.4981 1215 42.400 2.1301 316 46.710 1.9431 517 48.310 1.8824 518 53.790 1.7028 319 56.700 1.6221 3
Embodiment 9
With resulting sample among the embodiment 1 in 550 ℃ of following bubbling air roastings 4 hours.Take by weighing the sample after the 2g roasting, join in the copper chloride solution of 100 milliliters of 1M.Exchange is 12 hours under 50 ℃, repeatedly exchanges 4 times, and resulting sample after filtration, deionized water washs and in 100 ℃ of lower dryings, namely get the sample Cu-ZrAPSO-18 molecular sieve after copper exchanges.
Embodiment 10
Resulting sample among the embodiment 1 is taken out a part be put in the monkey, in 550 ℃ of following bubbling air roastings 4 hours.Accurately the quality of weighing sample is placed in the drier that saturated aqueous common salt is housed.Placed 12 hours under the room temperature.By taking by weighing sample front and back qualitative change, obtain the suction numerical value of sample.Experiment shows that the ZrAPSO-18 molecular sieve has adsorptivity, and the adsorptive value to water under its room temperature is 23.7%.
Embodiment 11
With resulting sample among the embodiment 1 in 550 ℃ of following bubbling air roastings 4 hours.Then compressing tablet, be crushed to 20~40 orders.Take by weighing the 1.28g sample fixed bed reactors of packing into, carry out methanol-to-olefins reaction (MTO) reaction evaluating.Methyl alcohol is carried by nitrogen, and its weight space velocity WHSV is 2.0h -1, reaction temperature is 450 ℃, product is analyzed by online gas-chromatography.The result shows that conversion of methanol is 100%, to C 2 =And C 3 =Selectivity reach more than 85%, it is to C 2 =And C 3 =Initial selectivity be more than 75%.Illustrate that reaction has very high activity to the ZrAPSO-18 molecular sieve for MTO.
Can be seen by above-described embodiment, adopt DIPEA, N among the present invention, N-diisopropyl propylamine or tetraethyl oxyammonia are template, can synthesize MeAPSO-18 by adjusting each raw material proportioning.The aperture hetero atom MeAPSO-18 that is synthesized can make the catalyst of adsorbent and hydrocarbon conversion reaction, and particularly reaction has very high activity and selectivity to the methanol conversion low-carbon alkene.

Claims (10)

1. a silicoaluminophosphamolecular molecular sieves MeAPSO-18 is characterized in that anhydrous chemical composition can be expressed as: mRnMe (SixAlyPz) O 2, wherein R is a kind of template agent that is present in the microporous molecular sieve, m is every mole of (SixAlyPz) O 2The molal quantity of middle R, and m=0.001~0.3; X, y, z are respectively the molar fraction of Si, Al, P, and its scope is x=0.001~0.98, y=0.01~0.60, z=0.01~0.60, and satisfy x+y+z=1, Me is one or more in zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and the zinc metal, and n is every mole of (SixAlyPz) O 2The molal quantity of middle Me, n=0.01~0.25.
2. the synthetic method of the described silicoaluminophosphamolecular molecular sieves MeAPSO-18 of claim 1 is characterized in that being undertaken by following step:
(1) in proportion silicon source material, aluminium source material, phosphorus source material, slaine, template agent and water are under agitation mixed, get initial gel mixture;
(2) with sealing in the initial gel mixture material immigration stainless steel synthesis reactor, place baking oven, under 100~250 ℃, carry out crystallization;
(3) solid crystallized product is separated with mother liquor, to neutral, behind 80-130 ℃ of lower air drying, obtain metal silicon aluminum phosphate molecular sieve MeAPSO-18 with the deionized water washing.
3. according to the synthetic method of the described silicoaluminophosphamolecular molecular sieves MeAPSO-18 of claim 2, it is characterized in that each used raw material proportioning of synthetic this molecular sieve (by the oxide molecule ratio) is:
Me/Al 2O 3=0.01~1.0;
SiO 2/Al 2O 3=0.001~10;
P 2O 5/Al 2O 3=0.5~10;
H 2O/Al 2O 3=10~100;
R/Al 2O 3=0.1~10; R is a kind of template.
4. according to the synthetic method of the described silicoaluminophosphamolecular molecular sieves MeAPSO-18 of claim 3, it is characterized in that employed slaine is oxide, the hydroxide of nitrate, acetate, sulfate or the hydrochloride of metals such as zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and zinc and these metals or the organic matter that contains these metals.
5. according to the synthetic method of the described silicoaluminophosphamolecular molecular sieves MeAPSO-18 of claim 2, it is characterized in that used silicon source is one or more the mixture in Ludox, waterglass, active silica or the positive esters of silicon acis.
6. according to the synthetic method of the described silicoaluminophosphamolecular molecular sieves MeAPSO-18 of claim 2, it is characterized in that used aluminium source is one or more the mixture in aluminium salt, aluminate, activated alumina, aluminum alkoxide, false boehmite, boehmite or the organo-aluminium.
7. according to the synthetic method of the described silicoaluminophosphamolecular molecular sieves MeAPSO-18 of claim 2, it is characterized in that used phosphorus source is one or more the mixture in orthophosphoric acid, phosphate, organic phosphorus compound or the phosphorous oxides.
8. according to the synthetic method of the described silicoaluminophosphamolecular molecular sieves MeAPSO-18 of claim 2, it is characterized in that used organic amine template agent is N, N-diisopropylethylamine, N, in N-diisopropyl propylamine or the tetraethyl oxyammonia one or more.
9. one kind according to the purposes of the described silicoaluminophosphamolecular molecular sieves MeAPSO-18 of claim 1 as ion-exchanger or adsorbent.
10. one kind according to the purposes of the described silicoaluminophosphamolecular molecular sieves MeAPSO-18 of claim 1 as methanol-to-olefins reaction, hydrocarbon conversion reactions, alkylated reaction, isomerization reaction, catalytic cracking reaction and selective oxidation catalysts.
CN99127143A 1999-12-29 1999-12-29 MeAPSO-18 molecular sieve and its synthesizing method Expired - Lifetime CN1108868C (en)

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CN1172695A (en) * 1996-08-02 1998-02-11 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
CN1207722A (en) * 1995-12-13 1999-02-10 埃克森化学专利公司 Use of transition metal contg. small pore molecular sieve catalysts in oxygenate conversion

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US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
CN1207722A (en) * 1995-12-13 1999-02-10 埃克森化学专利公司 Use of transition metal contg. small pore molecular sieve catalysts in oxygenate conversion
CN1172695A (en) * 1996-08-02 1998-02-11 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

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