CN1301598A - MeAPSO-56 molecular sieve and its synthesizing method - Google Patents
MeAPSO-56 molecular sieve and its synthesizing method Download PDFInfo
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Abstract
An anhydrous chemical composition of the molecular sieve MeAPSO-56 is expressed by mR.nMe(SizAlyPz)O2, where R is a template agent existing in micro pores of molecular sieve, m as the molar number of R in each mole of (SixAlyPz)O2 is 0.05-0.3; x,y and z are mole fractions of Si, Al and P atoms separately, x+y+z=1 and x=0.01-0.98, y=0.01-0.60 and z=0.01-0.52; Me is metal atom entering the molecular sieve skeleton, and n as the molar number of Me in each mole of (SixAlyPz)O2 is 0.01-0.20. The said molecular sieve has excellent ion exchange performance and adsorbing performance and may be used in various hydrocarbon reactions.
Description
The invention provides a kind of novel microporous metal-silicon aluminium phosphate molecular sieve MeAPSO-56 and synthetic method thereof.
1984, U.S. Pat P 4,440,871 disclose the synthetic of multiple silicoaluminophosphamolecular molecular sieves with different structure, and these molecular sieves are respectively SAPO-5, SAPO-11, SAPO-16, SAPO-17, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-40, SAPO-41, SAPO-42 and SAPO-44.The molecular sieve of some of them small structure such as SAPO-34 etc. have been successfully applied to processes such as MTG, MTO, and demonstrate good catalytic performance.After this, there is the silicoaluminophosphamolecular molecular sieves of some different structures to be synthesized out in succession again.SAPO-56 is people such as Stephen T.Wilson synthesized a kind of new structure in 1994 a silicoaluminophosphamolecular molecular sieves (USP5,370,851).
The metallic molecule sieve is that metal is incorporated on the skeleton of molecular sieve, thereby makes it have the characteristic that some are different from the original molecule sieve.U.S. Pat P4,554,143,4,752,651,4,853,179 grades have successively been reported the synthetic method of several metal aluminophosphates, but do not see the report that the MeAPSO-56 molecular sieve is studied as yet.
The metal-silicon aluminium phosphate molecular sieve MeAPSO-56 that the present invention synthesizes is characterized in that the anhydrous chemical composition of institute's synthesis of molecular sieve can be expressed as: mRnMe (SixAlyPz) O
2, wherein R is the template agent that is present in the microporous molecular sieve, m represents every mole of (SixAlyPz) O
2The molal quantity of corresponding templates agent, m=0.05～0.3; Me is the metallic atom that enters framework of molecular sieve, and n is every mole of (SixAlyPz) O
2The molal quantity of corresponding Me, n=0.001～0.20.X, y, z represent the molar fraction of Si, Al, P respectively, and its scope is respectively x=0.01～0.98, y=0.01～0.60, z=0.01～0.52, and x+y+z=1;
At above-mentioned metal-silicon aluminium phosphate molecular sieve MeAPSO-56, metallic atom Me is a kind of or several arbitrarily in vanadium, copper, molybdenum, zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and the zinc, and has part at least with MeO
2Tetrahedroid becomes framework of molecular sieve to be present in the molecular sieve.
The metal-silicon aluminium phosphate molecular sieve that the present invention synthesizes can be used as ion-exchanger and adsorbent, can be applicable in the multiple hydrocarbon reaction with its catalyst of making, as catalytic cracking, reformation, polymerization, alkylation, dealkylation, transalkylation, isomerization, hydrogenation cyclisation, dehydrogenation and hydrogenation etc.
The MeAPSO-56 molecular sieve that the present invention synthesizes is characterized in that 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, be no less than 1 hour 100～250 ℃ of crystallization, the best is 2～100 hours;
(3) solid crystallized product is separated with mother liquor, wash to neutrality, behind 80-130 ℃ of air drying, obtain the metal-silicon aluminium phosphate molecular screen primary powder with deionized water;
(4) molecular screen primary powder roasting in 300～700 ℃ of air is no less than 3 hours, promptly gets metal-silicon aluminium phosphate molecular sieve active catalyst.
In the preparation process of the invention described above MeAPSO-56 molecular sieve, used silicon source is one or more the mixture in Ludox, silicon gel, 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 or the boehmite; The phosphorus source is one or both the mixture in orthophosphoric acid, phosphate, organic phosphorus compound or the phosphorous oxides; Metal is a kind of in oxide, inorganic salts or the organic salt of vanadium, copper, molybdenum, zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and zinc etc. or several mixture arbitrarily; The template agent is N ', N ', N, N-tetramethyl-1, the mixture of one or more in 6-hexamethylene diamine, tripropyl amine (TPA) or the n-propylamine.
Proportioning between each raw material (by the oxide molecule ratio) is:
Me/Al
2O
3=0.01～0.7；
SiO
2/Al
2O
3=0.1～10；
P
2O
5/Al
2O
3=0.5～15；
H
2O/Al
2O
3=10～100；
R/Al
2O
3=0.7～6; R is the mixture of one or more template agent;
In addition, in above-mentioned preparation method, synthetic crystallization pressure is self-generated pressure or nitrogen, air or the inert gas etc. that charge into 0.01～1Mpa.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1 SAPO-56
The 12.75g activated alumina (is contained Al
2O
373.0wt%) be dissolved in the 75ml deionized water, order adds the 10.40g Ludox and (contains SiO under stirring
240wt%) (contain H with 26.28g orthophosphoric acid
3PO
485wt%).Add 40g N ' at last, N ', N, N-tetramethyl-1, the 6-hexamethylene diamine after mixing, will seal in this mixed material immigration stainless steel synthesis reactor.Crystallization is 24 hours under 200 ℃ and self-generated pressure, and to neutral, roasting promptly obtained the SAPO-56 molecular sieve in 5 hours to solid product in 100 ℃ of air dryings, 550 ℃ of air with the deionized water washing, and its XRD analysis is as shown in table 1.
Table 1
| ??No. | ????2θ | ????d() | ????100×I/I 0 |
| ????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 ????13 ????14 ????15 ????16 ????17 ????18 | ????7.380 ????8.610 ????11.530 ????12.840 ????15.490 ????17.310 ????17.720 ????20.180 ????21.610 ????21.960 ????23.440 ????25.870 ????27.780 ????29.900 ????30.320 ????31.310 ????33.430 ????34.470 | ????11.9689 ????10.2616 ????7.6686 ????6.8890 ????5.7158 ????5.1188 ????5.0012 ????4.3968 ????4.1089 ????4.0442 ????3.7921 ????3.4412 ????3.2088 ????2.9859 ????2.9455 ????2.8546 ????2.6782 ????2.5998 | ????18 ????58 ????56 ????35 ????36 ????44 ????65 ????78 ????100 ????24 ????36 ????36 ????67 ????24 ????38 ????33 ????27 ????19 |
Embodiment 2 TiAPSO-56
The 12.10g activated alumina (is contained Al
2O
373.0wt%) be dissolved in the 70ml deionized water, order adds the 10.40g Ludox and (contains SiO under stirring
240wt%) (contain H with 26.28g orthophosphoric acid
3PO
485wt%), make solution A.2.85g titanium sulfate (96%) and 5ml deionized water are mixed, get solution B.Under the strong agitation solution B is joined among the A, stirring is no less than 30 minutes.Add 40g N ' at last, N ', N, N-tetramethyl-1, the 6-hexamethylene diamine after mixing, will seal in this mixed material immigration stainless steel synthesis reactor.Crystallization is 24 hours under 200 ℃ and self-generated pressure, and to neutral, roasting promptly obtained the TiAPSO-56 molecular sieve in 5 hours to solid product in 100 ℃ of air dryings, 550 ℃ of air with the deionized water washing, and its XRD analysis is as shown in table 2.Table 2,1 is compared, can see that the relative intensity of each diffraction maximum changes in the table 2, illustrate that titanium atom enters framework of molecular sieve aperture, interplanar distance etc. are changed.
Table 2
| ??No. | ????2θ | ????d() | ??100×I/I 0 |
| ??1 ??2 ??3 ??4 ??5 ??6 ??7 ??8 ??9 ??10 ??11 ??12 ??13 ??14 ??15 ??16 ??17 | ????7.340 ????8.559 ????11.480 ????12.790 ????15.440 ????17.260 ????17.680 ????19.650 ????20.140 ????21.570 ????23.410 ????25.840 ????27.760 ????30.280 ????31.270 ????33.410 ????34.440 | ????12.0341 ????10.3215 ????7.7018 ????6.9158 ????5.7342 ????5.1335 ????5.0125 ????4.5141 ????4.4054 ????4.1165 ????3.7969 ????3.4451 ????3.2110 ????2.9493 ????2.8581 ????2.6798 ????2.6020 | ????20 ????64 ????61 ????35 ????35 ????42 ????47 ????18 ????79 ????100 ????32 ????36 ????60 ????36 ????30 ????26 ????15 |
Comparative Examples 1
With the N among the embodiment 2, N, N ', N '-tetramethyl-1,6-hexamethylene diamine consumption becomes 10g.At this moment, template agent and Al in the reactant mixture material
2O
3Ratio be 0.62.All the other each amounts of components, addition sequence and crystallization condition are constant, and product is the TiAPSO-11 molecular sieve, and its XRD analysis is as shown in table 3.
Table 3
| ??No. | ????2θ | ????d() | ??100×I/I 0 |
| ??1 ??2 ??3 ??4 ??5 ??6 ??7 ??8 ??9 ??10 ??11 ??12 | ????8.070 ????9.450 ????13.200 ????15.700 ????20.510 ????21.050 ????22.760 ????23.240 ????24.780 ????26.700 ????28.740 ????33.020 | ????10.9470 ????9.3513 ????6.7019 ????5.6399 ????4.3268 ????4.2170 ????3.9039 ????3.8243 ????3.5900 ????3.3360 ????3.1037 ????2.7105 | ????20 ????56 ????24 ????47 ????77 ????93 ????91 ????100 ????29 ????30 ????33 ????25 |
Embodiment 3 FAPSO-56
The 15.90g activated alumina (is contained Al
2O
373.0wt%) be dissolved in the 70ml deionized water, order adds the 12.80g Ludox and (contains SiO under stirring
240wt%) (contain H with 19.50g orthophosphoric acid
3PO
485wt%), make solution A.Simultaneously 3.27g ferric sulfate (96%) and 5ml deionized water are mixed, get solution B.Under the strong agitation solution B is joined among the A, stirring is no less than 30 minutes.Add 40g N ' at last, N ', N, N-tetramethyl-1, the 6-hexamethylene diamine after mixing, will seal in this mixed material immigration stainless steel synthesis reactor.Crystallization is 24 hours under 200 ℃ and self-generated pressure, and to neutral, roasting promptly obtained the FAPSO-56 molecular sieve in 5 hours to solid product in 100 ℃ of air dryings, 550 ℃ of air with the deionized water washing, and its XRD analysis is as shown in table 4.Table 4,1 is compared, can see that the relative intensity of each diffraction maximum changes in the table 4, illustrate that iron atom enters framework of molecular sieve aperture, interplanar distance etc. are changed.
Table 4
| ??No. | ????2θ | ????d() | ????100×I/I 0 |
| ????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 ????13 ????14 ????15 ????16 ????17 ????18 | ????7.360 ????8.559 ????11.480 ????12.810 ????15.450 ????17.270 ????17.700 ????19.660 ????20.150 ????21.580 ????23.420 ????25.840 ????27.770 ????29.870 ????30.280 ????31.280 ????33.420 ????34.460 | ????12.0041 ????10.3215 ????7.7018 ????6.9050 ????5.7306 ????5.1305 ????5.0068 ????4.5119 ????4.4032 ????4.1146 ????3.7953 ????3.4451 ????3.2099 ????2.9888 ????2.9493 ????2.8572 ????2.6790 ????2.6005 | ????14 ????49 ????60 ????28 ????28 ????40 ????100 ????15 ????65 ????76 ????45 ????35 ????98 ????21 ????31 ????26 ????27 ?????17 |
Embodiment 4 (ZrAPSO-56)
Solution B among the embodiment 2 is become 3.71g zirconium oxychloride (ZrOCl
28H
2O 99%) mix with the 5ml deionized water, the template agent adopts the 36g tripropyl amine (TPA) to replace N ', N ', N, N-tetramethyl-1, the 6-hexamethylene diamine, all the other each amounts of components, addition sequence and crystallization condition are constant, and product is the ZrAPSO-56 molecular sieve, and its XRD analysis is as shown in table 5.Table 5,1 is compared, can see that the relative intensity of each diffraction maximum changes in the table 5, illustrate that zirconium atom enters framework of molecular sieve aperture, interplanar distance etc. are changed.
Table 5
| ??No. | ????2θ | ????d() | ??100×I/I 0 |
| ????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 ????13 ????14 ????15 ????16 ????17 | ????7.360 ????8.580 ????11.510 ????12.820 ????15.480 ????17.280 ????17.700 ????20.180 ????21.610 ????23.430 ????25.890 ????27.750 ????30.330 ????31.340 ????33.420 ????34.500 ????50.650 | ????11.9851 ????10.2855 ????7.6855 ????6.8997 ????5.7269 ????5.1246 ????5.0125 ????4.3968 ????4.1089 ????3.7937 ????3.4386 ????3.2122 ????2.9445 ????2.8519 ????2.6790 ????2.5976 ????1.8008 | ????21 ????61 ????63 ????40 ????35 ????46 ????67 ????77 ????100 ????39 ????44 ????78 ????37 ????36 ????29 ????22 ????18 |
Embodiment 5 MnAPSO-56
Solution B among the embodiment 2 is become 2.82g manganese acetate (MnAc24H2O 99%) mixes with the 5ml deionized water, 10gN ' is adopted in the template agent, N ', N, N-tetramethyl-1, the mixing of 6-hexylamine and 25g n-propylamine and, all the other each amounts of components, addition sequence and crystallization condition are constant, product is the MnAPSO-56 molecular sieve, and its XRD analysis is as shown in table 6.Table 6,1 is compared, can see that the relative intensity of each diffraction maximum changes in the table 6, illustrate that manganese atom enters framework of molecular sieve aperture, interplanar distance etc. are changed.
Table 6
| ????No. | ????2θ | ????d() | ??100×I/I 0 |
| ????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 ????13 ????14 ????15 ????16 ????17 ????18 ????19 ????20 | ????7.380 ????8.600 ????11.520 ????12.830 ????14.810 ????15.490 ????17.290 ????17.710 ????19.660 ????20.170 ????21.600 ????21.940 ????23.450 ????25.860 ????27.790 ????29.900 ????30.280 ????31.300 ????33.440 ????34.470 | ????11.9689 ????10.2735 ????7.6752 ????6.8943 ????5.9767 ????5.7158 ????5.1246 ????5.0040 ????4.5119 ????4.3989 ????4.1108 ????4.0479 ????3.7905 ????3.4425 ????3.2076 ????2.9859 ????2.9493 ????2.8554 ????2.6774 ????2.5998 | ????19 ????56 ????58 ????38 ????12 ????37 ????44 ????68 ????19 ????81 ????100 ????22 ????37 ????37 ????71 ????25 ????39 ????33 ????29 ????20 |
Embodiment 6 CoAPSO-56
Solution B among the embodiment 2 is become 2.05g cobalt acetate (CoAc24H2O 99.5%) mixes with the 5ml deionized water.All the other each amounts of components, addition sequence and crystallization condition are constant, and product is the CoAPSO-56 molecular sieve.
Embodiment 7 NiAPSO-56
Solution B among the embodiment 2 is become 2.45g nickel nitrate (Ni (NO3) 26H2O 98%) mixes with the 5ml deionized water.All the other each amounts of components, addition sequence and crystallization condition are constant, and product is the NiAPSO-56 molecular sieve.
Comparative Examples 2
2.45g nickel nitrate among the embodiment 7 (Ni (NO3) 26H2O 98%) is become 19.6g to be mixed with the 15ml deionized water.At this moment, metal and Al
2O
3The ratio of molal quantity be 0.75.All the other each amounts of components, addition sequence and crystallization condition are constant, and product is unknown crystal, and its XRD analysis is as shown in table 7.
Table 7
| ??No. | ????2θ | ????d() | ????100×I/I 0 |
| ????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 | ??13.840 ??19.670 ??22.000 ??24.160 ??27.990 ??31.390 ??34.450 ??40.020 ??42.580 ??47.360 ??51.740 ??55.980 | ????6.3934 ????4.5096 ????4.0370 ????3.6807 ????3.1856 ????2.8475 ????2.6012 ????2.2511 ????2.1215 ????1.9175 ????1.7654 ????1.6413 | ????43 ????43 ????6 ????100 ????15 ????14 ????18 ????7 ????8 ????6 ????11 ????4 |
Embodiment 8 CuAPSO-56
Solution B among the embodiment 2 is become 3.05g copper sulphate (Cu (SO4) 26H2O 98%) mixes with the 5ml deionized water.All the other each amounts of components, addition sequence and crystallization condition are constant, and product is the CuAPSO-56 molecular sieve.
Embodiment 9
With the roasting 4 hours in 550 ℃ of following bubbling airs of the sample of gained among the embodiment 2.Take by weighing the sample after the 2g roasting, join in the copper chloride solution of 100 milliliters of 1M.50 ℃ of down exchanges 12 hours, exchange repeatedly 4 times, resulting sample after filtration, the deionized water washing and in 100 ℃ dry down, promptly get the sample Cu-TiAPSO-56 after the Copper Ion Exchange.
Embodiment 10
Resulting sample among the embodiment 2 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 the variation of sample front and back quality, obtain the suction numerical value of sample.Experiment shows that the TiAPSO-56 molecular sieve has adsorptivity, and the adsorptive value to water under its room temperature is 29.6%.
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 70%, it is to C
2 =And C
3 =Initial selectivity be more than 60%.Illustrate that reaction has very high activity to the TiAPSO-56 molecular sieve for MTO.
Result by the foregoing description can see that the present invention adopts N ', N ', and N, N-tetramethyl-1,6-hexamethylene diamine, tripropyl amine (TPA) or n-propylamine are template agent and the use level of controlling the template agent, utilize different metal salt can synthesize the MeAPSO-56 molecular sieve.This building-up process is easy, and easily-controlled reaction conditions is suitable for industrialization and adopts.In addition, the present invention synthesizes the MeAPSO-56 molecular sieve and can be used as the ion friendship from agent and adsorbent after roasting, and can be used as multiple nytron catalyst for reaction, react especially for methanol-to-olefins reaction, has very high catalytic activity and to product selectivity, for condition has been created in the industrialization of this course of reaction.
Claims (12)
1. a metal-silicon aluminium phosphate molecular sieve MeAPSO-56 is characterized in that the anhydrous state chemical composition is expressed as mRnMe (SixAlyPz) O
2Wherein R is the template agent that is present in the microporous molecular sieve, and m represents every mole of (SixAlyPz) O
2The molal quantity of middle template agent, m=0.05～0.3; Me is the metallic atom that enters framework of molecular sieve, and n is every mole of (SixAlyPz) O
2The molal quantity of middle Me, n=0.001～0.20.X, y, z represent the molar fraction of Si, Al, P respectively, and its scope is respectively x=0.01～0.98, y=0.01～0.60, z=0.01～0.52, and x+y+z=1.
2. according to the described metal-silicon aluminium phosphate molecular sieve of claim 1 MeAPSO-56, it is characterized in that metallic atom Me is a kind of or several arbitrarily in vanadium, copper, molybdenum, zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and the zinc, and have part at least with MeO
2Tetrahedroid becomes framework of molecular sieve to be present in the molecular sieve.
3. the method for a synthetic metal-silicon aluminium phosphate molecular sieve MeAPSO-56 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, be no less than 1 hour 100～250 ℃ of crystallization;
(3) solid crystallized product is separated with mother liquor, wash to neutrality, behind 80-130 ℃ of air drying, obtain the metal-silicon aluminium phosphate molecular screen primary powder with deionized water;
(4) molecular screen primary powder roasting in 300～700 ℃ of air is no less than 3 hours, promptly gets metal-silicon aluminium phosphate molecular sieve active catalyst.
4. according to the described synthetic metal-silicon aluminium phosphate molecular sieve MeAPSO-56 of claim 3, it is characterized in that each used raw material proportioning (by the oxide molecule ratio) is:
Me/Al
2O
3=0.01～0.7；
SiO
2/Al
2O
3=0.1～10；
P
2O
5/Al
2O
3=0.5～15；
H
2O/Al
2O
3=10～100；
R/Al
2O
3=0.7～6; R is the mixture of one or more template agent;
5. according to the method for the described synthetic metal-silicon aluminium phosphate molecular sieve MeAPSO-56 of claim 3, it is characterized in that used silicon source is one or more the mixture in Ludox, silicon gel, waterglass, active silica or the positive esters of silicon acis.
6. according to the method for the described synthetic metal-silicon aluminium phosphate molecular sieve MeAPSO-56 of claim 3, 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 boehmite.
7. according to the method for the described synthetic metal-silicon aluminium phosphate molecular sieve MeAPSO-56 of claim 3, 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 method for the described synthetic metal-silicon aluminium phosphate molecular sieve MeAPSO-56 of claim 3, it is characterized in that used template agent is N ', N ', N, N-tetramethyl-1, the mixture of one or more in 6-hexamethylene diamine, tripropyl amine (TPA) or the n-propylamine.
9. according to the method for the described synthetic metal-silicon aluminium phosphate molecular sieve MeAPSO-56 of claim 3, it is characterized in that the source of the metal that uses is a kind of or any several mixture in oxide, inorganic salts or the organic salt of vanadium, copper, molybdenum, zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and zinc etc.
10. according to the method for the described synthetic metal-silicon aluminium phosphate molecular sieve MeAPSO-56 of claim 3, it is characterized in that the crystallization pressure that synthesizes is self-generated pressure or nitrogen, air or the inert gas etc. that charge into 0.01～1Mpa.
11. one kind according to the described metal-silicon aluminium phosphate molecular sieve of claim 1 MeAPSO-56, as ion-exchanger and adsorbent.
12. according to the described metal-silicon aluminium phosphate molecular sieve of claim 1 MeAPSO-56, as adsorbent.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835363B1 (en) | 2003-08-06 | 2004-12-28 | Exxonmobil Chemical Patents Inc. | Synthesis of molecular sieves of CHA framework type |
| US6927187B2 (en) | 2003-07-11 | 2005-08-09 | Exxonmobil Chemical Patents Inc. | Synthesis of silicoaluminophosphates |
| WO2013181833A1 (en) * | 2012-06-08 | 2013-12-12 | 中国科学院大连化学物理研究所 | Metal silicoaluminophosphate molecular sieve having rho skeleton structure and preparation process therefor |
| CN111099605A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Phosphate molecular sieve with AFX structure and preparation method thereof |
| CN112441595A (en) * | 2019-08-30 | 2021-03-05 | 大连海事大学 | Multi-metal doped silicon-phosphorus-aluminum molecular sieve and preparation method and application thereof |
-
1999
- 1999-12-29 CN CN 99127147 patent/CN1108870C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2013181833A1 (en) * | 2012-06-08 | 2013-12-12 | 中国科学院大连化学物理研究所 | Metal silicoaluminophosphate molecular sieve having rho skeleton structure and preparation process therefor |
| AU2012381962B2 (en) * | 2012-06-08 | 2015-08-27 | Dalian Institute Of Chemical Physics,Chinese Academy Of Sciences | Metal silicoaluminophosphate molecular sieve having RHO skeleton structure and preparation process therefor |
| JP2015525194A (en) * | 2012-06-08 | 2015-09-03 | ダーリエン インスティテュート オブ ケミカル フィジクス チャイニーズ アカデミー オブ サイエンシーズＤａｌｉａｎ Ｉｎｓｔｉｔｕｔｅｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ， Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Metal silicoaluminophosphate molecular sieve having RHO skeleton structure and method for producing the same |
| US9499409B2 (en) | 2012-06-08 | 2016-11-22 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Metal silicoaluminophosphate molecular sieve with RHO framework structure, and method for preparing the same |
| EA028185B1 (en) * | 2012-06-08 | 2017-10-31 | Чайниз Академи Оф Сайэнсиз | Metal silicoaluminophosphate molecular sieve with rho framework structure and method for preparing the same |
| CN111099605A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Phosphate molecular sieve with AFX structure and preparation method thereof |
| CN111099605B (en) * | 2018-10-25 | 2022-05-24 | 中国石油化工股份有限公司 | Phosphate molecular sieve with AFX structure and preparation method thereof |
| CN112441595A (en) * | 2019-08-30 | 2021-03-05 | 大连海事大学 | Multi-metal doped silicon-phosphorus-aluminum molecular sieve and preparation method and application thereof |
| CN112441595B (en) * | 2019-08-30 | 2022-07-19 | 大连海事大学 | Multi-metal doped silicon-phosphorus-aluminum molecular sieve and preparation method and application thereof |
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| CN1108870C (en) | 2003-05-21 |
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