CN1680034A - Rare earth silicon aluminium phosphate molecular sieve and synthesis thereof - Google Patents
Rare earth silicon aluminium phosphate molecular sieve and synthesis thereof Download PDFInfo
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- CN1680034A CN1680034A CN 200410030801 CN200410030801A CN1680034A CN 1680034 A CN1680034 A CN 1680034A CN 200410030801 CN200410030801 CN 200410030801 CN 200410030801 A CN200410030801 A CN 200410030801A CN 1680034 A CN1680034 A CN 1680034A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 63
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 21
- 239000010703 silicon Substances 0.000 title claims abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 31
- 150000002910 rare earth metals Chemical class 0.000 title claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims description 17
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims description 8
- 229940001007 aluminium phosphate Drugs 0.000 title description 5
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 239000004411 aluminium Substances 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 239000003292 glue Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- 238000010189 synthetic method Methods 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 5
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- 238000009415 formwork Methods 0.000 claims description 4
- -1 silicon ester Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 238000005216 hydrothermal crystallization Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000634 powder X-ray diffraction Methods 0.000 description 11
- 239000000084 colloidal system Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 239000003643 water by type Substances 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VMDFZGPHEWEXQX-UHFFFAOYSA-N ethene;prop-1-ene Chemical compound C=C.C=C.CC=C VMDFZGPHEWEXQX-UHFFFAOYSA-N 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical class [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
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- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A RE-silicon aluminium phophate molecular sieve used as the active component of the catalyst for the conversion reaction of hydrocarbons or oxygen-contained organic compound has the anhydrous chemical formula in the form of oxide: Al2O3:yP2O5:zSiO2:mRE2O3, where y=0.1-1.5, z=0.1-3 and m=0.001-1. Its preparing process includes such steps as mixing Al source, P source, Si source, RE source, water and triethylamin at 35-80 deg.C, and dynamic hydrothermal crystallizing at 120-250 deg.C for 4-500 hr.
Description
Technical field
The invention relates to a kind of rare earth silicoaluminophosphamolecular molecular sieves and synthetic method thereof.
Background technology
Aluminium phosphate molecular sieve is after al silicate molecular sieve, U.S. UCC company is at the molecular sieve of new generation (USP4310440) of the invention early 1980s, the characteristics of this molecular sieve analog are that its skeleton alternately is formed by connecting by phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron, because framework of molecular sieve is electric neutrality, therefore there are not cation exchange property and catalytic perfomance.Aluminium phosphate molecular sieve is a series of molecular sieves, have unique XRD feature spectrogram and data respectively, wherein existing and existing al silicate molecular sieve has the molecular sieve of same crystal structure, and the molecular sieve of the novel texture that does not have in the existing al silicate molecular sieve is also arranged.
In the aluminium phosphate molecular sieve skeleton, introduce silicon, then become silicoaluminophosphamolecular molecular sieves, it is SAPO series molecular sieve (U.S. UCC company, USP4440871), its framework of molecular sieve is made of phosphorus oxygen tetrahedron, aluminum-oxygen tetrahedron and silicon-oxy tetrahedron, because skeleton is electronegative, skeleton has balance cation to exist outward, therefore has cation exchange property, when the skeleton outer cationic is H
+The time, molecular sieve has acid sites, therefore has the acidic catalyst reactivity worth.Silicoaluminophosphamolecular molecular sieves has been widely used in oil refining and the field of petrochemical industry as the activity of such catalysts constituent element, as the conversion of catalytic cracking, hydrocracking, isomerization, alkylating aromatic hydrocarbon, oxygenatedchemicals etc.
Aluminium phosphate molecular sieve and silicoaluminophosphamolecular molecular sieves since its widely purposes and potential Application Areas obtained development fast, the molecular sieve and the synthetic method of novel texture constantly invent.
In " J.CHEM.SOC.FARADAY TRANS.; nineteen ninety; the 86th 2 phases of volume; 425-429 page or leaf ", having reported the result with triethylamine and the synthetic SAPO-34 molecular sieve of hydrofluoric acid, in the presence of hydrofluoric acid, is that template can synthesize the SAPO-34 molecular sieve with triethylamine, when no hydrofluoric acid, obtain the defective molecular sieve of crystallization.
Chinese patent CN1088483A has reported with triethylamine or based on the result of the synthetic SAPO-34 silicoaluminophosphamolecular molecular sieves of the organic compounds containing nitrogen of triethylamine.The X-ray diffraction spectral data of its synthetic product sees Table 1, and the X-ray diffraction spectral data of reporting among its feature and the U.S. Pat P4440871 with tetraethyl ammonium hydroxide synthetic SAPO-34 molecular sieve is basic identical.
Table 1
| ????2θ(°) | ????d() | Relative intensity |
| ????9.5 | ????9.25 | ????100 |
| ????12.85 | ????6.84 | ????17 |
| ????14.0 | ????6.28 | ????8 |
| ????16.0 | ????5.50 | ????49 |
| ????17.9 | ????4.92 | ????11 |
| ????19.0 | ????4.64 | ????9 |
| ????20.6 | ????4.28 | ????75 |
| ????23.1 | ????3.82 | ????10 |
| ????25.1 | ????3.52 | ????14 |
| ????25.9 | ????3.42 | ????21 |
| ????27.7 | ????3.20 | ????7 |
| ????28.28 | ????3.13 | ????7 |
| ????29.6 | ????3.00 | ????9 |
| ????30.6 | ????2.90 | ????25 |
| ????31.1 | ????2.86 | ????26 |
| ????32.4 | ????2.74 | ????9 |
| ????34.5 | ????2.58 | ????6 |
| ????36.2 | ????2.58 | ????5 |
| ????43.2 | ????2.08 | ????5 |
| ????47.7 | ????1.89 | ????4 |
| ????49.0 | ????1.85 | ????10 |
Summary of the invention
The inventor finds, when adopting triethylamine to be the template synthesized silicon-aluminum phosphate molecular sieve, control different reaction conditionss, particularly become glue temperature and crystallization condition, it is the silicoaluminophosphamolecular molecular sieves (SAPO-34) that template obtains with triethylamine that institute's synthetic molecular sieve is different from same in the prior art, what obtain is the molecular sieve with novel crystalline structure, when being embodied on its X-ray diffraction spectral data, has the position and the intensity at special different diffraction peak.
The purpose of this invention is to provide a kind of above-mentioned rare earth silicoaluminophosphamolecular molecular sieves and its synthetic method is provided with novel crystal structure.
The rare earth silicoaluminophosphamolecular molecular sieves that contains provided by the invention is characterized in that the XRD data before the roasting removed template method contain the diffraction peak shown in the table 2 at least; XRD data behind the roasting removed template method contain the diffraction peak shown in the table 3 at least, and mole is Al when forming with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2: mRE
2O
3, wherein the value of y is 0.1～1.5, and is preferred 0.2～1.4, more preferably 0.3～1.2; The value of z is 0.1～3, and is preferred 0.15～2, more preferably 0.2～1; The value of m is 0.001～1, and is preferred 0.002～0.5, more preferably 0.003～0.1.In table 2 and table 3, VS, S, M and W represent the relative intensity of diffraction peak, and W is 0～20%, and M is 20～60%, and S is 60～80%, and VS is 80～100%.
Mole before the molecular sieve provided by the present invention, its roasting removed template method is xR: Al when forming with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2: mRE
2O
3Wherein R is the organic formwork agent that is present in the molecular sieve crystal duct, and the value of x is 0.01～5.0, and is preferred 0.03～4.0, and the value of y and z as defined above.
Table 2
| ????2θ(°) | ????d() | Relative intensity |
| ????9.42-9.62 | ????9.39-9.19 | ????VS |
| ????12.80-12.95 | ????6.91-6.83 | ????W |
| ????13.88-14.13 | ????6.38-6.26 | ????W |
| ????15.90-16.10 | ????5.57-5.50 | ????M |
| ????16.75-17.15 | ????5.29-5.17 | ????W |
| ????18.88-19.13 | ????4.70-4.63 | ????W |
| ????19.55-19.95 | ????4.54-4.44 | ????W |
| ????20.50-20.70 | ????4.33-4.29 | ????W |
| ????21.00-21.40 | ????4.23-4.15 | ????M |
| ????21.88-22.13 | ????4.06-4.01 | ????W |
| ????22.95-23.15 | ????3.88-3.84 | ????W |
| ????23.85-24.45 | ????3.73-3.64 | ????W |
| ????25.70-25.95 | ????3.465-3.433 | ????W |
| ????27.50-27.75 | ????3.243-3.214 | ????W |
| ????28.00-28.30 | ????3.186-3.153 | ????W |
| ????29.35-29.65 | ????3.042-3.012 | ????W |
| ????30.30-30.70 | ????2.949-2.911 | ????W |
| ????30.90-31.30 | ????2.893-2.857 | ????W |
| ????31.50-31.75 | ????2.839-2.818 | ????W |
| ????32.15-32.45 | ????2.783-2.758 | ????W |
| ????48.80-49.20 | ????1.866-1.851 | ????W |
Table 3
| ????2θ(°) | ????d() | Relative intensity |
| ????9.47-9.67 | ????9.34-9.14 | ????VS |
| ????12.90-13.12 | ????6.86-6.74 | ????W-M |
| ????13.40-13.62 | ????6.61-6.50 | ????W |
| ????13.90-14.20 | ????6.37-6.24 | ????W |
| ????16.10-16.30 | ????5.50-5.43 | ????W |
| ????16.85-17.25 | ????5.26-5.14 | ????W |
| ????17.80-18.10 | ????4.98-4.90 | ????W |
| ????19.05-19.30 | ????4.66-4.60 | ????W |
| ????19.85-20.25 | ????4.47-4.38 | ????W |
| ????20.70-20.90 | ????4.29-4.25 | ????W-M |
| ????21.25-21.65 | ????4.18-4.10 | ????W |
| ????23.15-23.45 | ????3.84-3.79 | ????W |
| ????24.00-24.40 | ????3.71-3.64 | ????W |
| ????25.10-25.50 | ????3.547-3.492 | ????W |
| ????26.00-26.30 | ????3.426-3.388 | ????W |
| ????27.75-28.05 | ????3.214-3.180 | ????W |
| ????28.15-28.45 | ????3.169-3.136 | ????W |
| ????29.70-30.00 | ????3.007-2.978 | ????W |
| ????30.50-30.90 | ????2.930-2.893 | ????W |
| ????31.10-31.40 | ????2.875-2.848 | ????W |
| ????49.00-49.60 | ????1.851-1.837 | ????W |
Rare earth silicoaluminophosphamolecular molecular sieves provided by the invention, the XRD spectra data of its table 2 are compared with the data in the prior art table 1, can find, in 2 θ values is that 17.9 °, the 25.1 ° diffraction peaks of locating become very weak or are tending towards disappearance, is 16.95 ± 0.2 °, 19.75 ± 0.2 °, 21.2 ± 0.2 °, 24.15 ± 0.3 ° diffraction peaks of locating to occur new broadening in 2 θ values simultaneously; Sample behind the roasting removed template method, its XRD spectra data sheet 3 can be found, the obvious diffraction peak occurs at 13.5 ± 0.1 °.
The present invention also provides the synthetic method of above-mentioned novel rare-earth silicoaluminophosphamolecular molecular sieves, and this method comprises: press feed ratio aR: Al under 35～80 ℃, preferred 40～70 ℃ of temperature
2O
3: bP
2O
5: cSiO
2: dRE
2O
3: eH
2O is mixed into glue with aluminium source, phosphorus source, silicon source, rare earth source, water and triethylamine, hydrothermal crystallizing 4～500 hours, preferred 10～100 hours under 120～250 ℃, preferred 150～220 ℃ temperature; Wherein R is an organic formwork agent, and the value of a is 0.3～5, and is preferred 0.4～4, more preferably 0.5～3; The value of b is 0.3～1.5, and is preferred 0.4～1.4, more preferably 0.5～1.2; The value of c is 0.05～5, and is preferred 0.1～4, more preferably 0.2～3; D's is 0.001～1, preferred 0.002～0.5, more preferably 0.003～0.1; The value of e is 10～150, and is preferred 20～120, more preferably 25～100.
In the synthetic method provided by the invention, said aluminium source is selected from aluminium hydroxide, hydrated aluminum oxide, aluminum isopropylate or aluminum phosphate, wherein preferred hydrated aluminum oxide or aluminum isopropylate; Said silicon source is selected from solid oxidation silicon, silicon sol or silicon ester; Said phosphorus source is selected from phosphoric acid or aluminum phosphate, wherein preferably phosphoric acid; Said rare earth source is single salt of planting rare earth or mishmetal, wherein preferably nitrate or muriate, and said rare earth source also can be the oxide compound that contains rare earth, and wherein preferred REY, REHY, REUSY etc. contain the FAU structure molecular screen of rare earth.
For the mole of the feed ratio that calculates mishmetal and synthetic gained molecular sieve is formed, the aqueous solution of the mixed chlorinated rare earth that adopt with routine in said mishmetal source in the inventive method, amount to into RE
2O
3Molecular-weight average 328.9 calculate for benchmark.
In synthetic method provided by the invention, its characteristic that is different from prior art is to adopt high temperature to become glue and dynamic crystallization operation.Said crystallization process preferably dynamically carries out under the closed system autogenous pressure, as synthesis reactor is being rotated under certain rotating speed around transverse axis, or heats up and thermostatic crystallization under agitation condition.This agitation condition removes the homogeneity of increase system in the general sense, comprise increase conduct heat and the efficient of mass transfer outside, to suppress things such as AEL, AFI, AFO and CHA mutually and other stray crystal thing phase tangible advantage is all arranged.Said agitation condition is generally 20～200 rev/mins, preferred 50～150 rev/mins.
At preferred feed ratio with preferably become under the glue temperature condition, to the requirement that becomes the glue order not necessarily, but select certain time ordered pair that feeds intake to improve the crystallization velocity of molecular sieve, thus the shortening crystallization time, the degree of crystallinity of raising product all has significant advantage.Preferably feed intake order at first phosphorus source, rare earth source and aluminium source being mixed with deionized water (or distilled water), after stirring, add template, add the silicon source after stirring again; The preferred order that feeds intake adds the solution of phosphoric acid and suitable quantity of water then for the aluminium source is mixed with suitable quantity of water, after stirring, adds rare earth source, template and silicon source more successively.
In the synthetic method provided by the invention, in the said crystallization condition, general crystallization temperature is 120～250 ℃, and preferred crystallization temperature is 150～220 ℃.
Molecular sieve provided by the present invention can be used for the conversion reaction of hydro carbons, acidic components as catalyzer such as catalytic cracking, hydrocracking, isomerization, catalytic dewaxings, also can be used for the conversion reaction of oxygen-containing organic compound, as the conversion reaction of methyl alcohol, ethanol, dme etc.Can be prepared into dual-function catalyst behind this molecular sieve carried transition metal such as VA, VIA, VIIA, VIIIA, IB and the IIB family metal, can behind loaded metal, use by the hydrogen conversion catalyst that faces as hydro carbons.For molecular sieve being prepared into metallic dual-function catalyst, can be with molecular sieve elder generation roasting removed template method, impregnating metal again; Perhaps earlier with roasting removed template method again behind the molecular sieve impregnating metal.
Embodiment
The following examples will be further described the present invention.
The X-ray powder diffraction of molecular sieve is measured used instrument and is produced Bruker D5005 for Germany in each embodiment and the Comparative Examples, adopts the CuK alpha-ray; Molecular sieve composition x-ray fluorescence spectrometry.
Raw materials used except that specifying among the embodiment, be chemically pure reagent.
Embodiment 1
With 184.5 gram phosphoric acid (85% phosphoric acid, chemically pure reagent, down with) and 334.1 gram deionized waters join the colloid generating kettle that places 50 ℃ of water-baths and mix and stir, stir after 30 minutes to wherein adding 19.6 and restrain the REUSY molecular sieves and (contain 20.2%Al
2O
3, 54.8%SiO
2, 10.0%RE
2O
3, 3.2%Na
2O, the Chang Ling catalyst plant is produced, down together) mixed 1 hour.After stirring, 334.1 gram deionized waters and 141.6 gram hydrated aluminum oxides (are contained 72%Al
2O
3, the Chang Ling catalyst plant is produced, down together) join in the glue reactor, mixed 2 hours.Then, 243 gram triethylamines (chemically pure reagent, down with) are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 230.8 gram silicon sol and (contain 26%SiO
2, Changhong chemical plant, Beijing produces, down together), fully stirred 2 hours, make reaction mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, under 190 ℃ and autogenous pressure and 120 rev/mins of rotating speeds, stirred crystallization 80 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is as shown in table 4.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result data is as shown in table 5.The mole of sample consists of after the roasting: Al
2O
3: 0.75P
2O
5: 0.52SiO
2: 0.0034RE
2O
3
Table 4
| ????2θ(°) | ????d() | Relative intensity |
| ????9.50 | ????9.31 | ????100 |
| ????10.50 | ????8.42 | ????1.5 |
| ????12.81 | ????6.91 | ????11.1 |
| ????13.98 | ????6.33 | ????2.8 |
| ????15.98 | ????5.54 | ????35.9 |
| ????16.93 | ????5.24 | ????5.4 |
| ????17.98 | ????4.93 | ????3.2 |
| ????18.99 | ????4.67 | ????3.4 |
| ????19.75 | ????4.49 | ????4.1 |
| ????20.50 | ????4.33 | ????40.5 |
| ????21.21 | ????4.19 | ????6.8 |
| ????22.00 | ????4.04 | ????1.4 |
| ????23.02 | ????3.86 | ????3.6 |
| ????23.98 | ????3.71 | ????3.3 |
| ????25.20 | ????3.533 | ????4.7 |
| ????25.78 | ????3.455 | ????10.8 |
| ????26.36 | ????3.380 | ????2.7 |
| ????27.61 | ????3.230 | ????2.7 |
| ????28.22 | ????3.161 | ????2.0 |
| ????29.50 | ????3.027 | ????3.6 |
| ????30.53 | ????2.927 | ????8.9 |
| ????31.09 | ????2.876 | ????9.9 |
| ????31.69 | ????2.822 | ????3.8 |
| ????32.35 | ????2.767 | ????3.2 |
| ????34.44 | ????2.603 | ????1.1 |
| ????36.20 | ????2.481 | ????0.8 |
| ????38.86 | ????2.317 | ????0.7 |
| ????39.32 | ????2.291 | ????0.7 |
| ????43.25 | ????2.091 | ????1.6 |
| ????47.64 | ????1.908 | ????0.7 |
| ????49.02 | ????1.858 | ????4.2 |
Table 5
| ????2θ(°) | ????d() | Relative intensity |
| ????9.57 | ????9.24 | ????100 |
| ????11.00 | ????8.04 | ????1.4 |
| ????13.00 | ????6.81 | ????18.1 |
| ????13.51 | ????6.55 | ????3.0 |
| ????14.04 | ????6.31 | ????0.9 |
| ????16.16 | ????5.48 | ????13.3 |
| ????17.03 | ????5.21 | ????4.2 |
| ????17.90 | ????4.95 | ????2.3 |
| ????19.20 | ????4.62 | ????4.1 |
| ????19.98 | ????4.44 | ????2.1 |
| ????20.79 | ????4.27 | ????18.1 |
| ????21.43 | ????4.15 | ????5.0 |
| ????22.15 | ????4.01 | ????1.4 |
| ????23.27 | ????3.82 | ????5.5 |
| ????24.25 | ????3.67 | ????3.5 |
| ????25.10 | ????3.547 | ????4.0 |
| ????26.14 | ????3.408 | ????8.0 |
| ????26.71 | ????3.337 | ????2.8 |
| ????27.88 | ????3.199 | ????3.0 |
| ????28.33 | ????3.149 | ????3.0 |
| ????29.79 | ????2.998 | ????3.4 |
| ????30.64 | ????2.17 | ????6.2 |
| ????31.26 | ????2.861 | ????10.1 |
| ????31.94 | ????2.801 | ????3.2 |
| ????32.59 | ????2.747 | ????2.7 |
| ????49.47 | ????1.842 | ????1.1 |
Embodiment 2
184.5 gram phosphoric acid and 779 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths mix and stir, stirs after 30 minutes, mixed 1 hour to wherein adding 27.6 gram lanthanum nitrates (analytical reagent, down together).After stirring, 141.6 gram hydrated aluminum oxides are joined in the glue reactor, mixed 2 hours.Then, 253 gram triethylamines are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 230.8 gram silicon sol, fully stirred 2 hours, make reaction mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, under 190 ℃ and 150 rev/mins of rotating speeds of autogenous pressure, stirred crystallization 80 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is as shown in table 6.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result data is as shown in table 7.The mole of the sample after the roasting consists of: Al
2O
3: 0.70P
2O
5: 0.49SiO
2: 0.064La
2O
3
Table 6
| ????2θ(°) | ????d() | Relative intensity |
| ????9.53 | ????9.28 | ????100 |
| ????10.50 | ????8.42 | ????1.4 |
| ????12.87 | ????6.88 | ????8.5 |
| ????14.00 | ????6.32 | ????3.9 |
| ????14.42 | ????6.14 | ????3.7 |
| ????16.04 | ????5.52 | ????26.4 |
| ????16.94 | ????5.23 | ????5.1 |
| ????17.94 | ????4.94 | ????1.8 |
| ????19.05 | ????4.66 | ????4.1 |
| ????19.80 | ????4.48 | ????6.1 |
| ????20.58 | ????4.31 | ????30.4 |
| ????21.24 | ????4.18 | ????7.1 |
| ????22.02 | ????4.04 | ????1.4 |
| ????23.10 | ????3.85 | ????3.0 |
| ????24.00 | ????3.71 | ????3.7 |
| ????25.10 | ????3.547 | ????4.9 |
| ????25.87 | ????3.443 | ????8.5 |
| ????26.49 | ????3.364 | ????2.8 |
| ????27.64 | ????3.226 | ????2.8 |
| ????28.19 | ????3.165 | ????3.0 |
| ????29.01 | ????3.077 | ????5.1 |
| ????29.50 | ????3.027 | ????4.5 |
| ????30.45 | ????2.935 | ????7.1 |
| ????31.07 | ????2.878 | ????13.2 |
| ????31.69 | ????2.823 | ????4.1 |
| ????32.35 | ????2.767 | ????2.6 |
| ????49.03 | ????1.857 | ????3.2 |
Table 7
| ????d() | Relative intensity | |
| ????9.55 | ????9.26 | ????100 |
| ????10.67 | ????8.29 | ????1.5 |
| ????12.98 | ????6.82 | ????19.1 |
| ????13.49 | ????6.56 | ????5.2 |
| ????14.00 | ????6.32 | ????2.7 |
| ????14.35 | ????6.17 | ????3.3 |
| ????16.16 | ????5.48 | ????10.6 |
| ????17.01 | ????5.21 | ????4.8 |
| ????18.03 | ????4.92 | ????0.6 |
| ????19.14 | ????4.64 | ????6.1 |
| ????19.89 | ????4.46 | ????7.6 |
| ????20.80 | ????4.27 | ????17.3 |
| ????21.40 | ????4.15 | ????6.1 |
| ????22.30 | ????3.99 | ????0.5 |
| ????23.27 | ????3.82 | ????6.4 |
| ????24.01 | ????3.71 | ????5.8 |
| ????25.10 | ????3.547 | ????6.4 |
| ????26.13 | ????3.409 | ????10.6 |
| ????26.70 | ????3.338 | ????4.5 |
| ????27.89 | ????3.198 | ????6.1 |
| ????28.34 | ????3.148 | ????6.6 |
| ????29.75 | ????3.002 | ????6.1 |
| ????30.62 | ????2.919 | ????11.2 |
| ????31.24 | ????2.862 | ????24.2 |
| ????31.92 | ????2.803 | ????6.0 |
| ????32.55 | ????2.750 | ????3.3 |
| ????49.43 | ????1.843 | ????2.1 |
Embodiment 3
184.5 gram phosphoric acid and 468.3 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths mix and stir, stirs after 30 minutes to wherein adding 37.6 and restrain the REY molecular sieves and (contain 18.3%Al
2O
3, 51.8%SiO
2, 14.7%RE
2O
3, Na
2O3.6%, the Chang Ling catalyst plant is produced, down together), mixed 1 hour.After stirring, 234.1 gram deionized waters are joined in the glue reactor with 141.6 gram hydrated aluminum oxides, mixed 2 hours.Then, 243 gram triethylamines are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 184.6 gram silicon sol, fully stirred 2 hours, make reaction mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, under 190 ℃ and 100 rev/mins of rotating speeds of autogenous pressure, stirred crystallization 80 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is as shown in table 8.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result data is as shown in table 9.The mole of the sample after the roasting consists of: Al
2O
3: 0.79P
2O
5: 0.50SiO
2: 0.0098RE
2O
3
Table 8
| ????2θ(°) | ????d() | Relative intensity |
| ????9.53 | ????9.28 | ????100.0 |
| ????10.52 | ????8.41 | ????5.7 |
| ????12.90 | ????6.86 | ????15.1 |
| ????14.10 | ????6.28 | ????5.4 |
| ????16.06 | ????5.52 | ????39.8 |
| ????17.07 | ????5.19 | ????7.9 |
| ????18.09 | ????4.90 | ????5.7 |
| ????19.10 | ????4.65 | ????5.7 |
| ????19.93 | ????4.45 | ????7.5 |
| ????20.60 | ????4.31 | ????44.4 |
| ????21.40 | ????4.15 | ????8.4 |
| ????22.10 | ????4.02 | ????4.0 |
| ????23.13 | ????3.85 | ????6.2 |
| ????24.17 | ????3.682 | ????6.1 |
| ????25.28 | ????3.523 | ????6.5 |
| ????25.90 | ????3.440 | ????12.8 |
| ????26.62 | ????3.349 | ????4.6 |
| ????27.72 | ????3.218 | ????4.4 |
| ????28.37 | ????3.146 | ????4.0 |
| ????29.62 | ????3.016 | ????5.0 |
| ????30.62 | ????2.920 | ????10.8 |
| ????31.19 | ????2.868 | ????11.5 |
| ????31.85 | ????2.810 | ????5.0 |
| ????32.48 | ????2.757 | ????4.3 |
| ????34.68 | ????2.587 | ????2.8 |
| ????36.30 | ????2.475 | ????2.8 |
| ????38.90 | ????2.315 | ????2.7 |
| ????39.35 | ????2.290 | ????2.8 |
| ????43.32 | ????2.089 | ????3.1 |
| ????47.74 | ????1.905 | ????2.5 |
| ????49.05 | ????1.857 | ????5.4 |
Table 9
| ????2θ(°) | ????d() | Relative intensity |
| ????9.63 | ????9.18 | ????100.0 |
| ????10.70 | ????8.27 | ????7.6 |
| ????13.05 | ????6.78 | ????24.2 |
| ????13.62 | ????6.50 | ????7.0 |
| ????14.34 | ????6.18 | ????5.8 |
| ????16.26 | ????5.45 | ????18.1 |
| ????17.25 | ????5.14 | ????8.2 |
| ????18.10 | ????4.90 | ????7.1 |
| ????19.30 | ????4.60 | ????8.0 |
| ????20.25 | ????4.39 | ????7.3 |
| ????20.86 | ????4.26 | ????21.7 |
| ????21.56 | ????4.12 | ????9.4 |
| ????22.40 | ????3.97 | ????6.2 |
| ????23.42 | ????3.80 | ????9.4 |
| ????24.40 | ????3.648 | ????8.0 |
| ????25.32 | ????3.517 | ????8.3 |
| ????26.24 | ????3.396 | ????13.0 |
| ????26.84 | ????3.322 | ????6.8 |
| ????27.99 | ????3.188 | ????7.4 |
| ????28.45 | ????3.137 | ????6.7 |
| ????30.00 | ????2.979 | ????7.0 |
| ????30.90 | ????2.894 | ????11.2 |
| ????31.21 | ????2.866 | ????12.5 |
| ????31.94 | ????2.802 | ????12.9 |
| ????32.78 | ????2.732 | ????6.6 |
| ????49.56 | ????1.839 | ????3.8 |
Embodiment 4
184.5 gram phosphoric acid and 560 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths mix and stir, stirs after 30 minutes and restrain the REUSY molecular sieves, mixed 1 hour to wherein adding 123.2.After stirring, 279 gram deionized waters are joined in the glue reactor with 141.6 gram hydrated aluminum oxides, mixed 2 hours.Then, 243 gram triethylamines are joined in the above-mentioned colloid generating kettle, fully stirred 2 hours, make reaction mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, under 190 ℃ and 120 rev/mins of rotating speeds of autogenous pressure, stirred crystallization 80 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is as shown in table 10.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result data is as shown in table 11.The mole of the sample after the roasting consists of: Al
2O
3: 0.64P
2O
5: 0.95SiO
2: 0.041RE
2O
3
Table 10
| ????2θ(°) | ????d() | Relative intensity |
| ????9.53 | ????9.28 | ????100.0 |
| ????10.55 | ????8.39 | ????11.3 |
| ????12.89 | ????6.87 | ????20.3 |
| ????14.13 | ????6.27 | ????11.5 |
| ????16.04 | ????5.53 | ????45.4 |
| ????17.02 | ????5.21 | ????13.8 |
| ????17.96 | ????4.94 | ????10.6 |
| ????19.13 | ????4.64 | ????10.3 |
| ????19.95 | ????4.45 | ????14.4 |
| ????20.60 | ????4.31 | ????42.2 |
| ????21.31 | ????4.17 | ????15.1 |
| ????22.13 | ????4.02 | ????9.2 |
| ????23.15 | ????3.84 | ????11.4 |
| ????24.18 | ????3.681 | ????12.2 |
| ????25.27 | ????3.524 | ????12.4 |
| ????25.90 | ????3.440 | ????18.6 |
| ????26.49 | ????3.365 | ????10.7 |
| ????27.70 | ????3.220 | ????10.5 |
| ????28.40 | ????3.143 | ????9.8 |
| ????29.42 | ????3.036 | ????10.9 |
| ????29.61 | ????3.017 | ????11.3 |
| ????30.90 | ????2.894 | ????15.5 |
| ????31.75 | ????2.818 | ????19.2 |
| ????32.53 | ????2.752 | ????7.6 |
| ????34.80 | ????2.578 | ????4.9 |
| ????36.26 | ????2.477 | ????5.2 |
| ????39.03 | ????2.308 | ????5.3 |
| ????39.70 | ????2.270 | ????5.2 |
| ????43.34 | ????2.088 | ????5.5 |
| ????47.73 | ????1.905 | ????5.4 |
| ????49.05 | ????1.857 | ????8.6 |
Table 11
| ????2θ(°) | ????d() | Relative intensity |
| ????9.60 | ????9.21 | ????100.0 |
| ????10.60 | ????8.35 | ????13.0 |
| ????13.04 | ????6.79 | ????25.8 |
| ????13.57 | ????6.53 | ????13.2 |
| ????14.49 | ????6.11 | ????12.7 |
| ????16.22 | ????5.46 | ????21.4 |
| ????17.07 | ????5.19 | ????13.8 |
| ????18.08 | ????4.91 | ????10.9 |
| ????19.23 | ????4.62 | ????15.2 |
| ????20.25 | ????4.39 | ????14.4 |
| ????20.83 | ????4.26 | ????24.5 |
| ????21.50 | ????4.13 | ????14.9 |
| ????22.40 | ????3.97 | ????12.0 |
| ????23.37 | ????3.81 | ????14.2 |
| ????24.33 | ????3.658 | ????13.9 |
| ????25.08 | ????3.551 | ????14.5 |
| ????26.27 | ????3.392 | ????16.6 |
| ????26.84 | ????3.322 | ????12.3 |
| ????28.04 | ????3.182 | ????12.5 |
| ????28.15 | ????3.170 | ????12.9 |
| ????29.89 | ????2.989 | ????13.5 |
| ????30.89 | ????2.895 | ????16.6 |
| ????31.39 | ????2.850 | ????20.5 |
| ????32.01 | ????2.796 | ????12.7 |
| ????32.80 | ????2.730 | ????10.0 |
| ????49.41 | ????1.844 | ????6.4 |
Embodiment 5
184.5 gram phosphoric acid and 779 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths mix and stir, stirs that (the Chang Ling catalyst plant, the rare earth composition is distributed as La to wherein adding 103 milliliters of mixed chlorinated rare earth solution after 30 minutes
2O
353.2%, CeO
213.0%, Pr
6O
1113.0%, Nd
2O
320.8%, RE
2O
3Content be 160 grams per liters, molecular-weight average is 328.9), mixed 1 hour.After stirring, 141.6 gram hydrated aluminum oxides are joined in the glue reactor, mixed 2 hours.Then, 253 gram triethylamines are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 230.8 gram silicon sol, fully stirred 2 hours, make reaction mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, under 190 ℃ and 120 rev/mins of rotating speeds of autogenous pressure, stirred crystallization 80 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is as shown in table 12.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result data is as shown in table 13.The mole of the sample after the roasting consists of: Al
2O
3: 0.69P
2O
5: 0.51SiO
2: 0.085RE
2O
3
Table 12
| ????2θ(°) | ????d() | Relative intensity |
| ????9.50 | ????9.31 | ????100 |
| ????10.52 | ????8.41 | ????1.7 |
| ????12.85 | ????6.89 | ????10.5 |
| ????14.08 | ????6.29 | ????3.2 |
| ????14.45 | ????6.13 | ????3.9 |
| ????16.10 | ????5.50 | ????23.5 |
| ????16.99 | ????5.22 | ????5.1 |
| ????17.98 | ????4.93 | ????1.8 |
| ????19.15 | ????4.63 | ????4.1 |
| ????19.91 | ????4.46 | ????6.1 |
| ????20.55 | ????4.32 | ????27.4 |
| ????21.32 | ????4.17 | ????7.5 |
| ????22.13 | ????4.02 | ????1.5 |
| ????23.08 | ????3.85 | ????3.2 |
| ????24.05 | ????3.70 | ????3.2 |
| ????25.17 | ????3.538 | ????4.9 |
| ????25.88 | ????3.443 | ????8.7 |
| ????26.42 | ????3.373 | ????2.9 |
| ????27.68 | ????3.223 | ????2.8 |
| ????28.29 | ????3.155 | ????3.1 |
| ????29.05 | ????3.074 | ????5.1 |
| ????29.57 | ????3.021 | ????4.5 |
| ????30.47 | ????2.934 | ????9.1 |
| ????31.11 | ????2.875 | ????13.2 |
| ????31.71 | ????2.822 | ????4.1 |
| ????32.39 | ????2.764 | ????2.6 |
| ????49.09 | ????1.856 | ????4.2 |
Table 13
| ????2θ(°) | ????d() | Relative intensity |
| ????9.56 | ????9.25 | ????100 |
| ????10.69 | ????8.28 | ????3.5 |
| ????13.02 | ????6.80 | ????19.1 |
| ????13.52 | ????6.55 | ????5.2 |
| ????14.02 | ????6.32 | ????2.7 |
| ????14.40 | ????6.15 | ????3.3 |
| ????16.19 | ????5.47 | ????15.6 |
| ????17.05 | ????5.20 | ????4.8 |
| ????18.02 | ????4.92 | ????0.6 |
| ????19.18 | ????4.63 | ????6.1 |
| ????19.95 | ????4.45 | ????4.6 |
| ????20.85 | ????4.26 | ????17.3 |
| ????21.45 | ????4.14 | ????6.1 |
| ????22.28 | ????3.99 | ????0.5 |
| ????23.30 | ????3.82 | ????6.4 |
| ????24.08 | ????3.70 | ????5.8 |
| ????25.14 | ????3.542 | ????6.4 |
| ????26.18 | ????3.404 | ????10.6 |
| ????26.75 | ????3.333 | ????4.5 |
| ????27.92 | ????3.196 | ????6.1 |
| ????28.28 | ????3.156 | ????6.6 |
| ????29.85 | ????2.993 | ????9.7 |
| ????30.71 | ????2.911 | ????11.2 |
| ????31.35 | ????2.853 | ????14.2 |
| ????31.95 | ????2.801 | ????4.3 |
| ????32.62 | ????2.745 | ????6.0 |
| ????49.50 | ????1.841 | ????4.3 |
Embodiment 6
Rare earth silicoaluminophosphamolecular molecular sieves after the roasting in the various embodiments described above is got a part of compressing tablet, fragmentation, sieve out 20～40 purpose particles, on the pulse micro-inverse device, carry out the Dehydration of methanol evaluation as catalyzer.
Test parameter is: 0.10 mol of packing in silica glass pipe reactor sieve; Reactant is a methyl alcohol, and the reactant pulses amount is 0.5 microlitre; Carrier gas is a helium, and carrier gas flux is 30 ml/min.Reaction product is analyzed by on-line gas chromatography.Catalyzer carries out earlier reaction evaluating after treatment again.Treatment condition are: with 5 ℃/minute speed temperature programmings to 500 ℃, and constant temperature 2 hours.Temperature of reaction is 450 ℃.Its evaluation result is as shown in table 14.
Table 14
| Molecular sieve | Olefins yield (heavy %) | Methanol conversion % | ||
| Ethene | Propylene | Ethene+propylene | ||
| Embodiment 1 | ????26.91 | ????47.23 | ????74.13 | ????100 |
| Embodiment 2 | ????30.02 | ????44.20 | ????74.22 | ????100 |
| Embodiment 3 | ????25.50 | ????48.24 | ????73.75 | ????100 |
| Embodiment 4 | ????25.94 | ????47.48 | ????73.42 | ????100 |
| Embodiment 5 | ????28.10 | ????45.18 | ????73.28 | ????100 |
Claims (29)
1, a kind of rare earth silicoaluminophosphamolecular molecular sieves is characterized in that the X-ray diffraction data before the roasting removed template method contain the diffraction peak shown in the table 2 at least; X-ray diffraction data behind the roasting removed template method contain the diffraction peak shown in the table 3 at least, and the anhydrous chemical formulation that mole is formed with oxide form is Al
2O
3: yP
2O
5: zSiO
2: mRE
2O
3, wherein the value of y is 0.1～1.5, and the value of z is 0.1～3, and the value of m is 0.001～1.
2, according to the molecular sieve of claim 1, wherein the value of y is 0.2～1.4, and the value of z is 0.15～2.
3, according to the molecular sieve of claim 2, wherein the value of y is 0.3～1.2, and the value of z is 0.2～1.
4, according to the molecular sieve of claim 1, the value of m is 0.002～0.5.
5, according to the molecular sieve of claim 4, the value of m is 0.003～0.1.
6, according to the molecular sieve of claim 1, said molecular sieve is before the roasting removed template method, and its anhydrous chemical formulation of forming with oxide form is xR:Al
2O
3: yP
2O
5: zSiO
2: mRE
2O
3, wherein, R is the organic formwork agent that is present in the molecular sieve crystal duct; X, y, z, m are respectively R, P
2O
5, SiO
2, RE
2O
3Mole number, the value of x is 0.01～5.0, the value of y, z and m such as claim 1 definition.
7, according to the molecular sieve of claim 6, the value of x is 0.03～4.0.
8, according to the process of claim 1 wherein that the condition of said roasting removed template method is 300～700 ℃ of following constant temperature 2～10 hours.
9, the synthetic method of the described rare earth silicoaluminophosphamolecular molecular sieves of claim 1 is characterized in that under 35～80 ℃ by feed ratio aR:Al
2O
3: bP
2O
5: cSiO
2: dRE
2O
3: eH
2O, aluminium source, phosphorus source, silicon source, rare earth source, water and organic formwork agent are mixed into glue, dynamic hydrothermal crystallizing is 4～500 hours under 120～250 ℃, wherein R is a triethylamine, the value of a is 0.3～5, and the value of b is 0.3～1.5, and the value of c is 0.05～5, the value of d is 0.001～1, and the value of e is 10～150.
10, according to the method for claim 9, wherein said aluminium source is selected from aluminium hydroxide, hydrated aluminum oxide, aluminum isopropylate or aluminum phosphate, said silicon source is selected from solid oxidation silicon, silicon sol or silicon ester, said phosphorus source is selected from phosphoric acid or aluminum phosphate, and said rare earth source is single oxide compound of planting the salt of rare earth or mishmetal or containing rare earth.
11, according to the method for claim 10, wherein said aluminium source is hydrated aluminum oxide or aluminum isopropylate, and said phosphorus source is a phosphoric acid, and said rare-earth salts is the nitrate or the muriate of rare earth, and the said oxide compound that contains rare earth is the molecular sieve that contains the FAU structure of rare earth.
12, according to the method for claim 9, the temperature during wherein said one-tenth glue is 40～70 ℃.
13, according to the method for claim 9, wherein said crystallization temperature is 150～220 ℃.
14, according to the method for claim 9, wherein said crystallization time is 10～100 hours.
15, according to the method for claim 9, wherein the value of a is 0.4～4.
16, according to the method for claim 15, wherein the value of a is 0.5～3.
17, according to the method for claim 9, wherein the value of b is 0.4～1.4.
18, according to the method for claim 17, wherein the value of b is 0.5～1.2.
19, according to the method for claim 9, wherein the value of c is 0.1～4.
20, according to the method for claim 19, wherein the value of c is 0.2～3.
21, according to the method for claim 9, wherein the value of d is 0.002～0.5.
22, according to the method for claim 21, wherein the value of d is 0.003～0.1.
23, according to the method for claim 9, wherein the value of e is 20～120.
24, according to the method for claim 23, wherein the value of e is 25～100.
25, according to the method for claim 9, wherein the order that feeds intake of said raw material is at first phosphorus source, rare earth source and aluminium source to be mixed with water, after stirring, adds template, adds the silicon source after stirring again.
26, according to the method for claim 9, wherein the order that feeds intake of said raw material adds the solution of phosphoric acid and water then for the aluminium source is mixed with water, after stirring, adds rare earth source, template, silicon source more successively.
27, according to the method for claim 9, wherein said hydrothermal crystallization process is dynamically to carry out under the autogenous pressure.
28, the molecular sieve of claim 1 in hydro carbons or oxygen-containing organic compound conversion reaction catalyst as the application of active ingredient.
29, according to the application of claim 28, said oxygen-containing organic compound is alcohols or ethers.
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| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| US4666875A (en) * | 1984-11-27 | 1987-05-19 | Union Carbide Corporation | Catalytic cracking catalysts using silicoaluminophosphate molecular sieves |
| CN1037334C (en) * | 1992-12-19 | 1998-02-11 | 中国科学院大连化学物理研究所 | Synthesis silicon phosphorus aluminium molecular sieve and equipment using triethylamine as mould agent |
| CN1194890A (en) * | 1997-04-01 | 1998-10-07 | 樊海峰 | Method for regenerating aluminium sulfate and wood pulp from waste aluminium foil paper |
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