CN102452670B - Modified silicoaluminophosphate molecular sieve - Google Patents
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Abstract
The invention relates to a modified silicoaluminophosphate molecular sieve, which is characterized by being prepared by modifying Me1 and Me2, wherein the X-ray diffraction spectrogram data of the molecular sieve after a template is removed by roasting at least comprises a diffraction peak shown as a table 1; the structural expression of the molecular sieve is xMe1:yMe2:(Al2O3:0.1-1.7P2O5:0.01-3SiO2); Me1 is one of group IIA and VB elements or boron or gallium in the periodic table of elements; x represents the molar percent of the Me1 in the molecular sieve (based on oxide) and is 0.15 to 25; Me2 is one of group IVB elements or aluminum in the periodic table of elements; y represents the molar percent of the Me2 in the molecular sieve (based on oxide) and is 0.05 to 10; and the ratio of x to y is 0.05 to 10.
Description
Technical field
The present invention relates to a kind of modified silicon aluminum phosphoric acid molecular sieve, particularly relate to one kind of multiple element modified silicoaluminophosphamolecular molecular sieves.
Background technology
Light olefin (being defined as: ethene, propylene and butylene) is as the raw material of a lot of chemicals, and traditional method for making is petroleum cracking.Because the cost that reducing gradually of the growing and petroleum resources of demand makes petroleum cracking prepare light olefin is soaring steadily.
By contacting with various dissimilar catalyst, to change into alkene be a feasible way preparing light olefin to oxygenatedchemicals (for example methyl alcohol, dimethyl ether, ethanol), and said catalyst comprises zeolite and non-zeolite molecular sieve catalyst.
SAPO molecular sieve is the SAPO series SAPO molecular sieve (US4440871) of U.S. combinating carbide company (UCC) exploitation.This molecular sieve is a class crystalline silico-alumino-phosphate, and its three-dimensional framework structure is by PO
2 +, AlO
2 -, SiO
2form.SAPO-34 is a kind of crystalline silico-alumino-phosphate molecular sieve with chabasie (CHA) structure.It shows good activity and selectivity at methyl alcohol to conversion of olefines, but SAPO-34 easily forms coke in catalysis cage, causes inactivation.SAPO-18 is a kind of crystalline silico-alumino-phosphate molecular sieve of the AEI of having structure type.The chemical composition of SAPO-18 and SAPO-34 molecular sieve is close, and the catalytic performance in MTO reaction is more or less the same.But because SAPO-18 has lower slightly acid strength and has the longer life-span compared with low surperficial strong acid center density than SAPO-34.
AEI/CHA intergrowth phase molecule sieve is exactly " a " and " b " layer stacking that comprises CHA structure type and AEI structure type.The periodic structure unit of AEI and CHA is two hexa-atomic circular layers.It has two kinds of layers " a " and " b ", and " b " is the mirror image (in the plane Rotate 180 ° or perpendicular to standard flat mirror image operation) of " a ".When stacking layer is while being identical, aaa or bbb, just produce CHA structure type.When stacking layer is a and b while alternately forming, abab, just produces AEI structure type.
US6334994B1 discloses a kind of metal aluminophosphate molecular sieve---RUW-19, there is AEI/CHA and mix phase structure, this proportion that mixes phase molecule sieve AEI/CHA is very large, but the molecular sieve of not all mixing phase all has advantages of that life-span length-coking amount is little.
CN 101208149A discloses the method for preparing the silicoaluminophosphamolecular molecular sieve of at least one coexisting phase that comprises the molecular sieve with AEI and CHA framework types, wherein this coexisting phase has the AEI/CHA mass ratio of about 7/93-38/62, and this ratio is determined by the DIFFaX analysis of powder x-ray diffraction (XRD) figure of the calcining sample of the described silicoaluminophosphamolecular molecular sieve of use.
CN101450806A discloses a kind of AEI/CHA eutectic molecular sieve and synthetic method thereof that contains triethylamine.Described molecular sieve, wherein, x-ray diffraction pattern is at least one characteristic diffraction peak in the scope of 16.7 ° to 17.1 ° or 21.0 ° to 21.4 ° (2 θ).In described molecular sieve, can also contain metallic compound.Wherein, a kind of in the oxide that the metallic compound using is titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, magnesium, calcium, strontium, barium and lanthanum, oxychlorination thing or inorganic, acylate or arbitrarily several mixtures.
US2007/0100188A1 discloses a kind of metal aluminophosphate molecular sieve, has the AEI/CHA ratio of about 0/100-40/60, and this ratio is determined with the DIFFaX analysis of the x-ray diffractogram of powder of the calcining sample of described aluminophosphate molecular sieve.In described molecular sieve, can also contain metallic compound, and in sieve synthesis procedure, add slaine to obtain.Wherein, the metal species of using is a kind of of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, magnesium, calcium, strontium, barium and lanthanum or any several mixture.
Can find, modification to silicoaluminophosphamolecular molecular sieves in prior art, its target is mainly in methanol-to-olefins reaction process, to improve the yield of target product ethene and propylene, and less to the yield concern of accessory substance alkane and coke, and the process of separating by-products can increase the production cost of methanol-to-olefins reaction undoubtedly from object product ethene and propylene.
Summary of the invention
Inventor finds by a large amount of experiment accident ground, when adopting specific two kinds of elements to carry out modification to silicoaluminophosphamolecular molecular sieves, the ratio of these two kinds of element-specific of modulation, make this ratio when a suitable scope, at methanol oxidation, transform in the process of producing light olefins, can keep the high yield of target product ethene and propylene, simultaneously, the yield of accessory substance alkane and coke can also be reduced, and the longer life-span can be maintained.
Therefore, the object of the invention is to for the deficiencies in the prior art, a kind of modified silicon aluminum phosphoric acid molecular sieve is provided, this molecular sieve, for the reaction of methanol-to-olefins reaction, has better product selectivity and less accessory substance.
Modified silicon aluminum phosphoric acid molecular sieve provided by the invention, a kind of modified silicon aluminum phosphoric acid molecular sieve, it is characterized in that this molecular sieve is obtained by Me1 and Me2 modification, its X-ray diffraction spectral data at least contains the diffraction maximum shown in table 1, and the structure expression of this molecular sieve is xMe1: yMe2: (Al
2o
3: 0.1～1.7P
2o
5: 0.01～3SiO
2), Me1 is selected from periodic table of elements ZhongIIA family, a kind of element in VB family or boron or gallium, x represents that Me1 accounts for the mole percent of this molecular sieve in oxide, x=0.15～25, Me2 is selected from a kind of element or the aluminium in periodic table of elements ZhongIVB family, y represents that Me2 accounts for the mole percent of this molecular sieve in oxide, y=0.05～10, the ratio of x and y is 0.05～10, in table, VS, M and W represent the relative intensity of diffraction maximum, W is > 0～20%, M is > 20～60%, VS is > 80～100%,
Table 1
In modified silicon aluminum phosphoric acid molecular sieve provided by the invention, said Me1 is selected from a kind of element in boron in periodic table of elements ZhongIIAZu, VBZu, IIIA family or gallium, a kind of in preferably magnesium, vanadium, copper and boron wherein, x represents that Me1 accounts for the mole percent of this molecular sieve in oxide, x=0.15～25, preferably x=0.5～20.Said Me2 is selected from a kind of element or the aluminium in periodic table of elements ZhongIVB family, preferred a kind of in aluminium, titanium and zirconium wherein, and y represents that Me2 accounts for the mole percent of this molecular sieve in oxide, y=0.05～10, preferred y=0.1～8, more preferably 0.5～5.
The mole percent in silicoaluminophosphamolecular molecular sieves as modulation modifying element Me1 and Me2, particularly the ratio of x and y is when a suitable scope, silicoaluminophosphamolecular molecular sieves acidity through modification is moderate, when making to keep in methanol-to-olefins reaction process the high yield of target product ethene and propylene, the yield of accessory substance alkane and coke reduces, and can maintain the longer life-span, therefore, in modified silicon aluminum phosphoric acid molecular sieve provided by the invention, the ratio of x and y is 0.05～10, the ratio of preferred x and y is 0.1～5, the ratio of preferred x and y is 0.5～4.
In most preferred embodiment of the present invention, the combination of the element of two kinds of modifications is such as being magnesium and aluminium, magnesium and zirconium, magnesium and copper etc.
Modified silicon aluminum phosphoric acid molecular sieve provided by the invention, can obtain according to following preparation process:
1) first the silicoaluminophosphamolecular molecular sieves for modification is added to the mixing salt solution of two kinds of soluble elements, concentration of salt solution is respectively 0.0001～0.3 mol/L, and exchange temperature is room temperature, and be 0.5～5 hour swap time;
2) by step 1) silicoaluminophosphamolecular molecular sieves after exchange carries out drying and roasting, and baking temperature is 80～140 ℃, and be 2～12 hours drying time, and sintering temperature is 400～700 ℃, roasting time is 1～8 hour, obtains described modified silicon aluminum phosphoric acid molecular sieve.
The silicoaluminophosphamolecular molecular sieves of modification provided by the invention, can also obtain according to following preparation process:
1) first the silicoaluminophosphamolecular molecular sieves for modification is added to the soluble-salt solution of soluble a kind of element, concentration of salt solution is 0.0001～0.3 mol/L, and exchange temperature is room temperature, and be 0.5～5 hour swap time;
2) silicoaluminophosphamolecular molecular sieves after step 1 exchange is carried out to drying and roasting, baking temperature is 80～140 ℃, and be 2～12 hours drying time, and sintering temperature is 400～700 ℃, and roasting time is 1～8 hour;
3) by step 2) silicoaluminophosphamolecular molecular sieves after roasting puts in the soluble-salt solution of another kind of element again, and solution concentration is 0.0001～0.3 mol/L, and exchange temperature is room temperature, and be 0.5～5 hour swap time;
4) by step 3) silicoaluminophosphamolecular molecular sieves after exchange carries out drying and roasting, and baking temperature is 80～140 ℃, and be 2～12 hours drying time, and sintering temperature is 400～700 ℃, roasting time is 1～8 hour, obtains described modified silicon aluminum phosphoric acid molecular sieve.
In above-mentioned preparation process, the said silicoaluminophosphamolecular molecular sieves for modification, open by CN1680035A, take triethylamine as template synthetic, before roasting removed template method triethylamine, in its X-ray diffraction spectrogram, 2 θ values are 16.95 ± 0.2 °, 19.75 ± 0.2 °, 21.2 ± 0.2 °, 24.15 ± 0.3 ° diffraction maximums of locating to occur broadening; Sample after roasting removed template method triethylamine, is 13.5 ± 0.1 ° in 2 θ values and occurs obvious diffraction maximum.
In above-mentioned preparation process, the soluble-salt of said element can be selected from magnesium nitrate hexahydrate, nine water aluminum nitrates, nitrate trihydrate copper, eight water zirconium oxychlorides etc.
Modified silicon aluminum phosphoric acid molecular sieve provided by the invention, for silicoaluminophosphamolecular molecular sieves in prior art, acidity is too strong on the one hand, the easy carbon distribution of molecular sieve causes inactivation, and on the other hand acidity too a little less than, the double-barreled question that can cause again the activity decline of molecular sieve, the element modified silicoaluminophosphamolecular molecular sieves that a kind of acidity is moderate is provided, make in methanol-to-olefins reaction process when improving the yield of target product ethene and propylene, the yield of accessory substance alkane and coke reduces, and can maintain the longer life-span.
Accompanying drawing explanation
Accompanying drawing is the X-ray diffraction spectrogram of molecular sieve.
Silicoaluminophosphamolecular molecular sieves after the modification that wherein prepared by the respectively corresponding embodiment 1～6 of curve 1～6, the silicoaluminophosphamolecular molecular sieves after the modifications of curve 7 and the 8 corresponding comparative examples 1 of difference and 2 preparations, curve A is the silicoaluminophosphamolecular molecular sieves before modification.
The specific embodiment
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
Embodiment and comparative example, the X-ray powder diffraction spectrogram of molecular sieve, by Philips X ' pert Instrument measuring, adopts CuK alpha ray, tube voltage 40KV, tube current 40mA, sweep limits 4-35 °; The composition x-ray fluorescence spectrometry of molecular sieve.
Embodiment 1
The present embodiment illustrates the preparation process of magnesium provided by the invention and aluminium modified silicon aluminum phosphoric acid molecular sieve.
1.28 grams of magnesium nitrate hexahydrates are dissolved in 100 grams of deionized waters, stir, then add again wherein 3.75 gram of nine water aluminum nitrate, stir, and then add 10 grams of A molecular sieves (synthetic according to the patent of CN1680035A, X-ray powder diffraction spectrogram after roasting removed template method is shown in the A curve in accompanying drawing, lower same), at room temperature stir 1 hour, then suction filtration with deionized water washing, is dried a night at 100 ℃, the roasting 2 hours at 600 ℃ of dried molecular sieve, obtains the silicoaluminophosphamolecular molecular sieves of magnesium and aluminium modification.
Sample after roasting is measured through X-ray powder diffraction, and its result data is as table 2, and spectrogram is shown in the curve 1 of Fig. 1.Mole consisting of of modified sample: 0.38MgO: 0.12Al
2o
3(100Al
2o
3: 81P
2o
5: 29SiO
2).
Table 2
Embodiment 2
The present embodiment illustrates the preparation process of magnesium provided by the invention and aluminium modified silicon aluminum phosphoric acid molecular sieve.
12.86 grams of magnesium nitrate hexahydrates are dissolved in 100 grams of deionized waters, stir, and then add 10 grams of A molecular sieves, at room temperature stir 1 hour, and then add 9.38 gram of nine water aluminum nitrate, at room temperature stir 1 hour, then suction filtration with deionized water washing, is dried a night at 100 ℃, the roasting 2 hours at 600 ℃ of dried molecular sieve, obtains the silicoaluminophosphamolecular molecular sieves of magnesium and aluminium modification.
Sample after roasting is measured through X-ray powder diffraction, and its result data is as table 3, and spectrogram is shown in the curve 2 of accompanying drawing.Mole consisting of of modified sample: 48MgO: 8Al
2o
3: (100Al
2o
3: 69P
2o
5: 27SiO
2).
Table 3
Embodiment 3
The present embodiment illustrates the preparation process of magnesium provided by the invention and aluminium modified silicon aluminum phosphoric acid molecular sieve.
3.75 gram of nine water aluminum nitrate is dissolved in 100 grams of deionized waters, stir, and then add 10 grams of A molecular sieves, and at room temperature stir 1 hour, then add again wherein 2.58 grams of magnesium nitrate hexahydrates, at room temperature stir 1 hour, then suction filtration with deionized water washing, is dried a night at 100 ℃, the roasting 2 hours at 600 ℃ of dried molecular sieve, obtains the silicoaluminophosphamolecular molecular sieves of magnesium and aluminium modification.
Sample after roasting is measured through X-ray powder diffraction, and its result data is as table 4, and spectrogram is shown in the curve 3 of accompanying drawing.Mole consisting of of modified sample: 16MgO: 3.5Al
2o
3: (100Al
2o
3: 76P
2o
5: 30SiO
2).
Table 4
The present embodiment illustrates the preparation process of magnesium provided by the invention and aluminium modified silicon aluminum phosphoric acid molecular sieve.
5.12 grams of magnesium nitrate hexahydrates are dissolved in 100 grams of deionized waters, stir, and then add 10 grams of A molecular sieves, at room temperature stir 1 hour, suction filtration, washs by deionized water.Wash at 100 ℃ a dry night, the roasting 2 hours at 600 ℃ of dried catalyst.18.78 gram of nine water aluminum nitrate is dissolved in 100 grams of deionized waters, stir, gained molecular sieve is added again, at room temperature stir 1 hour, then suction filtration with deionized water washing, is dried a night at 100 ℃, the roasting 2 hours at 600 ℃ of dried molecular sieve, obtains the silicoaluminophosphamolecular molecular sieves of magnesium and aluminium modification.
Sample after roasting is measured through X-ray powder diffraction, and its result data is as table 5, and spectrogram is shown in the curve 4 of accompanying drawing.Mole consisting of of modified sample: 14MgO: 4.5Al
2o
3: (100Al
2o
3: 78P
2o
5: 27SiO
2).
Table 5
The present embodiment illustrates the preparation process of magnesium provided by the invention and copper modified silicon aluminum phosphoric acid molecular sieve.
1.28 grams of magnesium nitrate hexahydrates are dissolved in 100 grams of deionized waters, stir, then add again wherein 1.23 grams of nitrate trihydrate copper (Beijing Yili Fine Chemicals Co., Ltd., AR), stir, and then add 10 grams of A molecular sieves, at room temperature stir 1 hour, then suction filtration, by deionized water, wash, at a dry night at 100 ℃, the roasting 2 hours at 600 ℃ of dried molecular sieve, obtains the silicoaluminophosphamolecular molecular sieves of magnesium and copper modification.
Sample after roasting is measured through X-ray powder diffraction, and its result data is as table 6, and spectrogram is shown in the curve 5 of accompanying drawing.Mole consisting of of modified sample: 11MgO: 15CuO: (100Al
2o
3: 76P
2o
5: 26SiO
2).
Table 6
Embodiment 6
The present embodiment illustrates the preparation process of magnesium provided by the invention and modified zirconia silicoaluminophosphamolecular molecular sieves.
1.28 grams of magnesium nitrate hexahydrates are dissolved in 100 grams of deionized waters, stir, then add again wherein 0.64 gram of eight water zirconium oxychloride (Beijing Chemical Plant, AR), stir, and then add 10 grams of A molecular sieves, at room temperature stir 1 hour, then suction filtration, by deionized water, wash, at a dry night at 100 ℃, the roasting 2 hours at 600 ℃ of dried molecular sieve, obtains the silicoaluminophosphamolecular molecular sieves of magnesium and modified zirconia.
Sample after roasting is measured through X-ray powder diffraction, and its result data is as table 7, and spectrogram is shown in the curve 6 of accompanying drawing.Mole consisting of of modified sample: 11MgO: 5.3ZrO
2: (100Al
2o
3: 78P
2o
5: 27SiO
2).
Table 7
Comparative example 1
0.3 gram of magnesium nitrate hexahydrate is dissolved in 100 grams of deionized waters, stir, then add again wherein 3 gram of nine water aluminum nitrate, stir, and then add 10 grams of A molecular sieves, at room temperature stir 1 hour, then suction filtration with deionized water washing, is dried a night at 100 ℃, the roasting 2 hours at 600 ℃ of dried molecular sieve, obtains the comparative sample of the silicoaluminophosphamolecular molecular sieves of magnesium and aluminium modification.
Sample after roasting is measured through X-ray powder diffraction, and its result data is as table 8, and spectrogram is shown in the curve 7 of accompanying drawing.Mole consisting of of comparative sample: 0.068MgO: 1.15Al
2o
3: (100Al
2o
3: 80P
2o
5: 28SiO
2).
Table 8
Comparative example 2
4.2 grams of magnesium nitrate hexahydrates are dissolved in 100 grams of deionized waters, stir, then add again wherein 0.6 gram of nine water aluminum nitrate, stir, and then add 10 grams of A molecular sieves, at room temperature stir 1 hour, then suction filtration with deionized water washing, is dried a night at 100 ℃, the roasting 2 hours at 600 ℃ of dried molecular sieve, obtains the silicoaluminophosphamolecular molecular sieves comparative sample of magnesium and aluminium modification.
Sample after roasting is measured through X-ray powder diffraction, and its result data is as table 9, and spectrogram is shown in the curve 8 of accompanying drawing.Mole consisting of of comparative sample: 12.5MgO: 1.6Al
2o
3: (100Al
2o
3: 82P
2o
5: 28SiO
2).
Table 9
Test case
The molecular sieve of above-described embodiment 1～6 preparation is got to a part of compressing tablet, fragmentation, sieve out 20-40 object particle, on the micro-anti-experimental provision of WFS-5C heavy oil, carry out the reaction evaluating of preparing olefin by conversion of methanol.
Experiment parameter is: in titanium pipe reactor, pack 1.0 gram molecule sieves into, reactant is methyl alcohol, and carrier gas is nitrogen, and carrier gas flux is 30 ml/min.Product is analyzed by gas chromatograph.Reaction temperature is 450 ℃.
Evaluation result is as shown in table 10.
Contrast test example
With the method for test case, the reaction evaluating that the molecular sieve of above-mentioned comparative example 1 and comparative example 2 preparations and the silicoaluminophosphamolecular molecular sieves A before modification are carried out to preparing olefin by conversion of methanol.
Evaluation result is as shown in table 10.
Table 10
| Embodiment numbering | Conversion ratio/% | Triolefin yield | C 2 ＝/C 3 ＝ | Coke | Alkane |
| A | 100 | 84.31 | 1.17 | 7.85 | 3.39 |
| Embodiment 1 | 100 | 83.44 | 1.14 | 7.40 | 3.16 |
| Embodiment 2 | 100 | 83.92 | 1.13 | 7.49 | 3.72 |
| Embodiment 3 | 100 | 84.89 | 1.15 | 7.63 | 2.75 |
| |
99.09 | 84.04 | 1.14 | 7.34 | 2.84 |
| |
100 | 83.66 | 1.20 | 7.67 | 3.24 |
| Embodiment 6 | 100 | 83.15 | 1.15 | 7.62 | 3.31 |
| Comparative example 1 | 100 | 80.22 | 1.18 | 8.74 | 5.85 |
| Comparative example 2 | 96.89 | 79.03 | 1.18 | 8.45 | 4.32 |
From table 10, comparative example 1 is compared with the silicoaluminophosphamolecular molecular sieves before modification with comparative example 2, obviously finds out that methanol conversion declines, and molecular sieve activity decreased be described, and meanwhile, the yield of triolefin declines obvious, and by-product coke and alkane yield obviously increase.Embodiment compares with the silicoaluminophosphamolecular molecular sieves before modification, and in the situation that before the molecular sieve after modification and modification, molecular sieve maintenance olefin yields is close, the yield of these two kinds of accessory substances of alkane and coke is lower, has reached modification object.
Claims (10)
1. a modified silicon aluminum phosphoric acid molecular sieve, it is characterized in that this molecular sieve is obtained by Me1 and Me2 modification, X-ray diffraction spectral data after its roasting removed template method at least contains the diffraction maximum shown in table, and the structure expression of this molecular sieve is xMe1:yMe2:(Al
2o
3: 0.1～1.7P
2o
5: 0.01～3SiO
2), Me1 is selected from periodic table of elements ZhongIIA family, a kind of element in VB family or boron or gallium, x represents that Me1 accounts for the mole percent of this molecular sieve in oxide, x=0.15～25, Me2 is selected from a kind of element or the aluminium in periodic table of elements ZhongIVB family, y represents that Me2 accounts for the mole percent of this molecular sieve in oxide, y=0.05～10, the ratio of x and y is 0.05～10, in table, VS, M and W represent the relative intensity of diffraction maximum, W is > 0～20%, M is > 20～60%, VS is > 80～100%,
Table
。
2. according to the molecular sieve of claim 1, wherein, said x=0.5～20.
3. according to the molecular sieve of claim 1, wherein, said y=0.1～8.
4. according to the molecular sieve of claim 3, wherein, said y=0.5～5.
5. according to the molecular sieve of claim 1, wherein, the ratio of x and y is 0.1～5.
6. according to the molecular sieve of claim 5, wherein, the ratio of x and y is 0.5～4.
7. according to the molecular sieve of one of claim 1～6, wherein, said Me1 is selected from a kind of in magnesium, vanadium and boron.
8. according to the molecular sieve of one of claim 1～6, wherein, said Me2 is selected from a kind of in aluminium, titanium and zirconium.
9. according to the molecular sieve of one of claim 1～6, said Me1 is magnesium, and said Me2 is aluminium.
10. according to the molecular sieve of one of claim 1～6, said Me1 is magnesium, and said Me2 is zirconium.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6334994B1 (en) * | 1996-10-09 | 2002-01-01 | Norsk Hydro Asa | Microporous crystalline silico-alumino-phosphate composition, catalytic material comprising said composition and use of these for production of olefins from methanol |
| CN1680035A (en) * | 2004-04-06 | 2005-10-12 | 中国石油化工股份有限公司 | Silicon aluminium phosphate molecular sieve and synthesis thereof |
| CN101031361A (en) * | 2004-10-01 | 2007-09-05 | 埃克森美孚化学专利公司 | Aluminophosphate molecular sieve, its synthesis and use |
-
2010
- 2010-10-27 CN CN201010521570.7A patent/CN102452670B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6334994B1 (en) * | 1996-10-09 | 2002-01-01 | Norsk Hydro Asa | Microporous crystalline silico-alumino-phosphate composition, catalytic material comprising said composition and use of these for production of olefins from methanol |
| CN1680035A (en) * | 2004-04-06 | 2005-10-12 | 中国石油化工股份有限公司 | Silicon aluminium phosphate molecular sieve and synthesis thereof |
| CN101031361A (en) * | 2004-10-01 | 2007-09-05 | 埃克森美孚化学专利公司 | Aluminophosphate molecular sieve, its synthesis and use |
Non-Patent Citations (2)
| Title |
|---|
| 新型磷酸硅铝分子筛的制备及其在甲醇转化制丙烯中的应用;朱杰 等;《石油化工》;20081231;第37卷;371-373 * |
| 朱杰 等.新型磷酸硅铝分子筛的制备及其在甲醇转化制丙烯中的应用.《石油化工》.2008,第37卷371-373. |
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