CN103534026B - The synthesis of M41S family molecular sieves and application - Google Patents
The synthesis of M41S family molecular sieves and application Download PDFInfo
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- CN103534026B CN103534026B CN201280023291.5A CN201280023291A CN103534026B CN 103534026 B CN103534026 B CN 103534026B CN 201280023291 A CN201280023291 A CN 201280023291A CN 103534026 B CN103534026 B CN 103534026B
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- 239000002808 molecular sieve Substances 0.000 title abstract description 25
- 102220420497 SKOR2 M41T Human genes 0.000 title abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title description 17
- 230000002194 synthesizing Effects 0.000 title description 17
- 238000003786 synthesis reaction Methods 0.000 title description 16
- 239000000203 mixture Substances 0.000 claims abstract description 107
- 239000000463 material Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Chemical group 0.000 claims description 7
- 239000011574 phosphorus Chemical group 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 3
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011363 dried mixture Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 210000000695 Crystalline Lens Anatomy 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 125000004429 atoms Chemical group 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 239000010970 precious metal Substances 0.000 claims 1
- 230000002829 reduced Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 16
- 230000005712 crystallization Effects 0.000 description 15
- 239000002351 wastewater Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000010413 mother solution Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910052904 quartz Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910001884 aluminium oxide Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- -1 Even more preferably Chemical compound 0.000 description 2
- IYJYQHRNMMNLRH-UHFFFAOYSA-N Sodium aluminate Chemical compound [Na+].O=[Al-]=O IYJYQHRNMMNLRH-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 210000003165 Abomasum Anatomy 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N Aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O Ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- MMHLLFDZWRPABJ-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)[P](C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)[P](C)(C)C MMHLLFDZWRPABJ-UHFFFAOYSA-N 0.000 description 1
- SVEKHHKMDXIVRF-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)[P](C)(C)C Chemical compound C(CCCCCCCCCCCCCCCCC)[P](C)(C)C SVEKHHKMDXIVRF-UHFFFAOYSA-N 0.000 description 1
- 229960004830 Cetylpyridinium Drugs 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N Potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- RKMJXTWHATWGNX-UHFFFAOYSA-N decyltrimethylammonium ion Chemical compound CCCCCCCCCC[N+](C)(C)C RKMJXTWHATWGNX-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003203 everyday Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005842 heteroatoms Chemical group 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting Effects 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000002269 spontaneous Effects 0.000 description 1
- 230000003068 static Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
Abstract
Describe the method preparing M41S family molecular sieves.The method includes preparing the synthetic mixture that can form described molecular sieve in the reactor, and this reactor is mounted with the blender with the Froude number of at least 1, and described synthetic mixture has the solids content of at least 20wt%.In described reactor, heat described synthetic mixture stir described mixture to form the product mixtures of the crystal comprising water and described molecular screen material with described blender simultaneously.Afterwards, in the described product mixtures from described reactor, at least some of water is removed so that the water content of the product mixtures of described inside reactor is reduced at least 5wt%.
Description
Prioity claim
This application claims on April 15th, 2011 submit to U.S. Provisional Patent Application Serial No. 61/475,687 and in
The interests of the European application number 11171341.8 that on June 24th, 2011 submits to and priority.
Invention field
Present disclosure relates to the synthetic method of M41S family molecular sieves and the molecular sieve of gained as catalyst, such as, makees
The application of the catalyst in arranging for lube oil hydrogenation.
Background of invention
Have been found that porous, inorganic solid has great use as catalyst and the separating medium of commercial Application.They
The opening of micro structure allows molecule to pass in and out the large surface area of these materials so that improving their catalysis and adsorption activity.At present
The porous material used uses their micro structure can be categorized into three major types as basis of classification.These classifications are amorphous materials
Material and paracrystalline materials, crystalline molecular sieve and modified stratified material.These materials detailed difference itself in terms of micro structure
For the significant differences in terms of the catalysis and absorption property of described material, and for characterizing their various observable performance
The difference of aspect, such as, the variability of their surface area, pore-size and those sizes, presence or absence X-ray are spread out
Penetrate the details in pattern and these patterns and when studying theirs by transmission electron microscopy and electron diffraction
The outward appearance of described material during micro structure.
M41S race mesoporous molecular sieve at J.Amer.Chem.Soc, J.S.Beck etc., 1992, volume 114, Issue27,
10834-10843 page is described.The member of M41S family molecular sieves includes MCM-41, MCM-48 and MCM-50.This kind of one-tenth
Member is that it prepares the MCM-41 being described in U.S. Patent number 5,098,684.MCM-41 is characterized by six sides
Crystal structure, this hexagonal crystallographic texture has the hole with the structure cell diameter more than about 13 angstroms of one dimensional arrangement.MCM-48 has
There is cubic symmetry and be such as described in U.S. Patent number 5,198,203.MCM-50 have layer paving or layer structure also
U.S. Patent number 5,246,689 is described.
M41S race mesoporous molecular sieve is generally by the aqueous reaction mixture (synthetic mixture) comprising suitable oxide source
Preparation.Generally can also be by organic additive, such as surfactant is included in this synthetic mixture to affect and having institute
Need the generation of the M41S race mesoporous molecular sieve of structure and channel dimensions.Suitably the component of synthetic mixture is being mixed with each other
After, allow this synthetic mixture experience suitable crystallization condition in autoclave and process.These conditions generally include and synthesis are mixed
Thing is heated to the temperature raised, and stirs the most simultaneously.After crystallization completes, reclaim crystallization from the remainder of synthetic mixture
Product, generally by filtering described crystal, then washes described crystal with water to remove mother solution and other residual synthetic mixture
Component.The most generally it is dried this crystal and it is carried out high-temperature calcination, such as, at 540 DEG C, otherwise may make point especially to remove
Any organic additive of the pore closure of son sieve.
The method of synthesis M41S race mesoporous molecular sieve uses expensive organic surface active agent.Additionally, dispose in crystallization, mistake
The cost of the waste water containing surfactant produced in filter and washing is high.Therefore, it is still necessary to manufacture M41S family molecular sieves more
Effectively and the method for cost effective, the method reduces the amount of the waste water of used water and generation simultaneously.Present disclosure provides
The reactor with high intensity mixer is used to be formed, by highly filled, the method that mixture manufactures M41S family molecular sieves.Should
Method does not require filter reactant mixture after crystallisation or wash molecular sieve product before being calcined.Therefore, this method is combined into
The advantage of the wastewater minimization that this reduction, shorter crystallization time and more high yield produce during manufacturing with molecular sieve.
U.S. Patent Application No. 60/899,785 relate to the method synthesizing medium-pore molecular screen composition, wherein reactant mixture
In solvent or solvent mixture comprise at least partially to come comfortable before the processing of mesoporous molecular sieve for preparing in synthesis batch
Waste water, such as mother solution, cleaning mixture, cleanout fluid and their any combination.
U.S. Patent Application Publication No. 2010/0280290 is directed to use with having highly filled synthetic mixture manufacture
M41S material also reduces the waste water containing surfactant formed in synthesis, such as mother solution, and minimized or eliminate synthesis
Filter and/or the method for washing step.
WO2009/055215 discloses and is formed mixture (20%-50wt%) manufacture M41S material, this mixture by high solid
Can reclaim in the case of there is no purification step (filter and/or wash).Can be under static state or stirring condition (0083 section)
Crystallize, but be not proposed for M41S crystallization and use disclosure or the suggestion of high intensity mixer.
The U.S.6,664,352 of Fredriksen discloses by by the catalyst in mechanical fluidisation state and porous particle
Shape carrier and catalyst material are mixed with metalloscene catalyst.The method uses has horizontal axis reversion interlocking hybrid blade
Blender, wherein at the different but blade in the most parallel rotary shaft through public mixed zone.This blender can
To have the Froude number of 1.05-2.2.For using this blender not advise in the crystallization of molecular sieve or open
Content.
The U.S.6 of Yamashita etc., 521,585 disclose the preparation of crystalline alkali metal silicate granules, and this is particle stabilized
It is formulated in detersive.The mixer of temperature-controllable is carried out crystalline alkali metal silicate and detersive at the Fu Lao of 1-12
The particle size distribution controlling granule is mixed under moral number.Blender includes that the cylinder of level is blended container, and it has at shaft
On agitator arm.
The various blenders that can be used for mixed slurry, thickener and plastic body are described in " Principles
OfCeramicsProcessing " second edition, JamesS.Reed, john wiley & sons, Inc., 347-354 page of 1995
In.
Summary of the invention
In an aspect, the present invention relates to the preparation method of molecular screen material, this molecular screen material has more than big
The position of about 18 angstrom unit's d spacing has the X-ray diffraction pattern at the peak that at least one relative intensity is 100, and in 50 torr
Having the benzene adsorption capacity more than about 15 grams of benzene/100 gram anhydrous crystallines at 25 DEG C, described method includes step:
A () as follows preparation can form synthetic mixture of described molecular screen material: be mounted with the Fu Lao with at least 1
By at least water in the reactor of the blender of moral number, selected from bivalent element W, trivalent element X, quadrivalent element Y and pentad Z
The source of at least one oxide, alkali metal or the source of alkaline-earth metal M, and there is formula R1R2R3R4Q+Organic directing agents (R) combine,
Wherein Q is nitrogen or phosphorus and wherein R1、R2、R3And R4In at least one selected from the aryl, big containing 6-containing about 36 carbon atoms of 6-
The alkyl of about 36 carbon atoms and combinations thereof, R1、R2、R3And R4In remainder selected from hydrogen, containing 1-5 carbon atom
Alkyl and combinations thereof；Described synthetic mixture has the solids content of at least 20wt%；
B () is heated described synthetic mixture in described reactor and is stirred described mixture with shape with described blender simultaneously
Become the product mixtures of the crystal comprising water and described molecular screen material；Then
C () described product mixtures from described reactor removes at least some of water so that by described reactor
The water content of the product mixtures in portion reduces at least 5wt%.
Aptly, described synthetic mixture has the solids content of about 20wt%-about 50wt%.
In one embodiment, described synthetic mixture has a composition according to mol ratio in the range of following:
In another embodiment, described synthetic mixture has a composition according to mol ratio in the range of following:
Aptly, by product mixtures apply heat and/or reduce the pressure on product mixtures in step (c) from
Product mixtures removes water.
Aptly, with described blender at removing step (c) period stirring product mixtures.
Aptly, described method further comprises the steps of:
(d) by partially dried mixture and extra granular materials in described reactor or in independent blender
Mixing, to prepare extrudable mixture.
Aptly, described extra granular materials is catalyst formulation ingredients, such as binding agent or matrix material.
Aptly, described method further comprises the steps of:
E described product mixtures of extruding is extruded into the caltalyst of shaping by ().
Aptly, described method further comprises the steps of:
F () is calcined the caltalyst of described shaping；With
G () makes the caltalyst experience ion exchange of described calcination to reduce the alkali metal in described caltalyst or alkaline earth
The content of metal M.
Aptly, allow formed body contact with the medium containing noble metal, be calcined the most in atmosphere and soaked by noble metal to provide
The catalyst of profit, such as, described noble metal is selected from platinum, palladium, iridium and their mixture.Preferably, described noble metal includes platinum,
Even more preferably, platinum and the combination of palladium.
In one embodiment, reactor has at least 5 liters, for example, at least 20 liters, such as, and the capacity of at least 200 liters.
In one embodiment, described blender includes at least one blade being positioned on axle, this axle can round with
Horizontal line is rotated by the axis of no more than 10 ° orientations.
In one aspect of the method, the method that the present invention relates to arrange lubricant base hydrogenation, exist including making described base material
Contact with the catalyst comprising the molecular screen material prepared by method described herein under hydrogenation finishing condition.
Accompanying drawing is sketched
Fig. 1 and 2 shows the 5 gallons of industry examinations with top assembling feed openings used in the synthetic method of embodiment
Test scale level plough shear mixer/exsiccator/reactor.
Fig. 3 is derived from X-ray diffraction (XRD) figure of just (as-calcined) MCM-41 material of calcination of embodiment 1
Case.
Fig. 4 is the PtMCM-41 catalyst using synthesis in embodiment 2 and the equivalent catalyst being prepared by a conventional method
Dewaxed lubricating oil base stock hydrogenation arrange in total aromatic content diagram to the operating time.
The detailed description of embodiment
Present disclosure provides the novel method of synthesis M41S race mesoporous molecular sieve.These materials are described in
J.Amer.Chem.Soc., J.S.Beck et al., volume 1992,114, Issue27, in the 10834-10843 page and feature
It is that having the X-ray having the peak that at least one relative intensity is 100 more than the position of about 18 angstrom unit's d spacing spreads out
Penetrate pattern, and more than the benzene adsorption capacity of about 15 grams of benzene/100 gram anhydrous crystallines at 50 torr and 25 DEG C.M41S family molecular sieves
Member include MCM-41, MCM-48 and MCM-50.
The inventive method is the synthesis debottleneckling of M41S material, the waste water that following minimizing is synthetically produced: in high intensity
Blender/reactor is prepared and made the reaction of highly filled crystal preparation and allows at the most partially dried rear of crystallized product
M41S crystallized product and inorganic oxide binder, such as aluminium oxide, extrusion.This new high solid crystallization procedure provides and is better than
Conventional low (solids content is less than 5wt%) in (solids content is less than about 15wt%) solids crystallization method some excellent
Point.These advantages include being synthesized by minimizing in produce mother solution amount and by minimized or eliminate filtration and/or purge step
Suddenly (this reduces the amount of the waste water produced in synthesis further) is significantly simplified synthetic method and significantly decreases containing surface activity
The generation of the waste water of agent.By using the high solid crystal preparation of present disclosure, the amount of the waste water produced in synthesis can reduce
At least 50%.
In the methods of the invention, generation has the highly filled aqueous synthetic mixture of at least 20wt% and is being equipped with
Having in the same reactor of high intensity mixer and be under agitation allowed to crystallize, this high intensity mixer can be at least 1, such as 1-
12, such as operate under the Froude number of 2-10.In this approach, the Froude number of the impeller of super mixer is worn as impeller
Cross the measuring of resistance of fluid media (medium).At this on the one hand, there is the impeller of diameter (d) (rice) and with the N revolutions per second of blender rotated
Froude number (Fr) limited by below equation:
Fr=N2d/g
Wherein g is acceleration of gravity (9.81m/s2).Aptly, the reactor used in the inventive method is configured satisfied
The impeller of high intensity mixer be assemblied in can round with horizontal line by no more than 10 ° orientation axis rotate axle on.Generally,
Reactor has more than 0.75, is greater than 1, be greater than 1.5 draw ratio and at least 5 liters, for example, at least 20 liters, the most extremely
The capacity of few 200 liters.
In the inventive method use synthetic mixture by add in reactor at least following components and prepare: water,
Selected from the source of at least one oxide of bivalent element W, trivalent element X, quadrivalent element Y and pentad Z, alkali metal or alkaline earth
The source of metal M, and there is formula R1R2R3R4Q+Organic directing agents (R), wherein Q is nitrogen or phosphorus and wherein R1、R2、R3And R4In
At least one is selected from the aryl containing about 36 carbon atoms of 6-, the alkyl containing about 36 carbon atoms of 6-and combinations thereof, R1、
R2、R3And R4In remainder selected from hydrogen, alkyl containing 1-5 carbon atom and combinations thereof.Then high intensity mixing is used
The content of device mixing reactor is until preparation has the homogeneous slurry of desired solids content.Generally, about 20 DEG C-about 50
Carry out mixing the time of about 30 minutes to about 2 hours at a temperature of DEG C.
It is said that in general, synthetic mixture has at least 20wt%, the most about 20wt%-about 50wt%, preferably at least
25wt%, the most about 25wt%-about 45wt%, the solid of most preferably at least 30wt%, the most about 30wt%-about 40wt% contains
Amount.Term as used herein " solids content " is defined as tetravalence and the trivalent element oxide gross weight to synthetic mixture
The weight percent of (getting rid of any seed) is the most calculated as below:
Generally, reactant mixture has at least 105MPa sec, the most about 106-about 109MPa sec's is apparent viscous
Degree.
The example of the oxide being suitable for of the bivalent element W can being included in synthetic mixture includes that bivalence first is drained through
Cross the oxide of metal such as manganese, cobalt, ferrum and/or magnesium.
The example of oxide being suitable for of the trivalent element X can being included in synthetic mixture include aluminum, boron, ferrum and/
Or the oxide of gallium, particularly aluminum.The alumina source being suitable for includes hydrated alumina, and such as boehmite, zirlite and vacation are vigorous
Nurse stone, sodium aluminate and oxygen containing aluminium salt, such as aluminum nitrate.
The example of the oxide being suitable for of the quadrivalent element Y can being included in synthetic mixture includes silicon, germanium and stannum
The oxide of oxide, preferably silicon.The source being suitable for of silicon oxide includes cabosil, precipitated silica, potassium silicate, sodium silicate
And fumed silica.Preferably silica source includes containing those of at least about 30wt% solid oxidation silicon, such as by
Silicon oxide (the silicon oxide Han about 90wt% that EvonikDegussa sells with trade name Aerosil, Ultrasil or Sipernat
Precipitation, be spray-dried silicon oxide) and can obtain from Grace Davison with trade name Ludox() silicon oxide sold, or
The HiSil(precipitation hydration SiO containing about 87wt% silicon oxide2, can obtain from PPGIndustries).
The example of the oxide being suitable for of the pentad Z can being included in synthetic mixture includes the oxide of phosphorus.
The alkali metal being suitable for or the example of alkaline-earth metal M include sodium, potassium and calcium, and sodium is preferred.Metal M is generally as hydrogen
Oxide is present in synthetic mixture.
The directing agent R being suitable for includes cetyltrimethyl ammonium, cetyl trimethyl phosphorus, octadecyl trimethyl
Ammonium, octadecyl trimethyl phosphorus, benzyltrimethylammon.um, cetyl pyridinium, decyl trimethyl ammonium, dimethyl double 12
Alkyl ammonium compound and comprise the combination of at least one in above-mentioned substance.Preferably, described quaternary ammonium or phosphorusIon is derived from phase
Hydroxide, halogenide or the silicate answered.
Additional Organic substance can also be with above-mentioned quaternary ammonium or phosphorusDirecting agent R is present in synthetic mixture together.One
In individual embodiment, additional Organic substance can be quaternary ammonium or the phosphorus with above-mentioned directing agent formulaIon, wherein R1、R2、
R3And R4It is each independently selected from hydrogen and the alkyl containing 1-5 carbon atom.
Generally, the synthetic mixture used in the inventive method has a composition according to mol ratio in the range of following:
Wherein e and f is the quantivalence of M and R respectively.
It is said that in general, the M41S material being prepared by the method for the present invention is silicate or aluminosilicate, in this case,
Synthetic mixture has a composition according to mol ratio in the range of following:
| Mol ratio | Wide | Preferably |
| Al2O3/SiO2 | 0-0.5 | 0.001-0.05 |
| H2O/SiO2 | 2-10 | 4-8 |
| OH-/SiO2 | 0-10 | 0.05-5 |
| M2/eO/(SiO2+Al2O3) | 0-10 | 0.05-5 |
| R2O/(SiO2+Al2O3) | 0.01-2.0 | 0.03-1.0 |
Wherein e is the quantivalence of metal M.
When the formation of synthetic mixture completes, the temperature of this mixture in reactor is risen to required crystallization temperature,
General about 25 DEG C-about 200 DEG C, the most about 100 DEG C-about 160 DEG C, and maintain about 0-at these temperatures about
200 hours, the most about 4-about 48 hours.In crystallization process, stir this synthesis mixing continuously by high intensity mixer
Thing.It addition, generally seal this reactor in crystallization process so that in this process reactor existing spontaneous pressure and rising.
The product of crystallization process is the aqueous slurry containing required mesoporous molecular sieve, such as MCM-41.Generally, will be from reactor
Take out this product mixtures, and after filtering to remove mother solution, molecular sieve crystal is washed and is dried.But, side of the present invention
In method, when crystallization completes, reactor opened and from product mixtures, removes at least some of water, then taking from reactor
Go out mixture.This can be reached by the pressure applied in heat and/or reduction reactor to mixture, and continuation the most simultaneously is high
Intensity mixer stirs this mixture.General continuation removes water until the water content of mixture has already decreased to few 5wt%, the most extremely
Few 10%, such as, about 10-about 20wt%.By removing excessive water, the molecular sieve crystalline substance can being dried from reactor recovery section
Body, then carries out calcining to remove organic directing agents, and does not has inceptive filtering or washing step.Generally, partially dried molecule
Sieve crystal contains about 15-about 25wt% water and about 40-45% surfactant.
Or, when having crystallized and during mixture in the most partially dried reactor, it is also possible to it is desirable that to
Reactor adds extra granular materials, then use high intensity mixer by this extra granular materials with after drying process
The crystalline molecular sieve retained and mother solution blend.Such as, extra granular materials can be catalyst formulation ingredients, such as binding agent
Or matrix material, can extrude after adding extra granular materials from the product mixtures that reactor reclaims in this case
The caltalyst shaped.After calcining is to remove organic directing agents, formed body can be directly used as in organic transformation reaction
Catalyst.
As another alternative, crystallization and partially dried after, can from reactor take out product mixtures and with
Extra granular materials, such as binding agent or matrix material mix in independent blender, are then extruded into the catalysis of shaping
Agent body also is calcined to remove organic directing agents.
In either case, after calcining is to remove organic directing agents, caltalyst experience ion exchange can be allowed with fall
Alkali metal or the content of alkaline-earth metal M present in low catalyst.It is said that in general, ion exchange is to exchange with ammonium cation ion
And followed by calcine from ammonium form, molecular sieve is changed into hydrogen form.
It addition, when gained catalyst is ready to use in lube oil hydrogenation arrangement, it may be desirable that noble metal is introduced
In catalyst, it is selected from the noble metal of the mixture of platinum, palladium, iridium and above-mentioned metal, preferably at least platinum, more preferably platinum and palladium
Combination.This can be exchanged by infiltration or the ion of shaped body catalyst body with the compound containing noble metal, is typically followed by sky
Calcining in gas reaches.
Hydrogenation arranges and typically carries out the crude lube stock experiencing hydrodewaxing step in advance.Hydrogenation arrangement is that one is intended to make to take off
Any lube range alkene in wax product and residual aromatic compounds are saturated, and remove any remaining heteroatoms and color development
The mild hydrogenation processing form of body.Dewaxing back end hydrogenation arranges and generally carries out with dewaxing hydrodewaxing step cascade.It is said that in general, be hydrogenated with whole
Reason will be carried out at a temperature of preferably 180 DEG C-250 DEG C at about 150 DEG C-350 DEG C.Gross pressure is typically 2859-20786kPa
(about 400-3000psig), liquid hourly space velocity (LHSV) is typically 0.1-5hr-1, preferably 0.5-3hr-1, speed of regulating the flow of vital energy at hydrogen is 44.5-
1780m3/m3(250-10,000scf/B).
Now with reference to following non-limiting example and the accompanying drawing present invention more particularly described below.
In an embodiment, BrukerD4X ray powder diffractometer use copper K α radiation in 2 θ scopes of 2-40 degree
Record is by the XRD diffraction pattern of the material of former state during synthesis.
HITACHIS4800 Field Emission Scanning Electron microscope (SEM) obtains SEM image.
By MicromeriticsTriStar3000V6.05A(Micromeritics Corporation,
Norcross, GA) measure BET surface area, wherein sample pretreatment in atmosphere at 350 DEG C.
In embodiment use reactor be described in fig 1 and 2 and include can from Florence,
The Littleford of Kentucky, USA, 5 gallons of business exercise scale level plough shear mixer that Day, Inc. obtain/be dried
Device, M/DVT-22LabMixer.This reactor includes having about 10 inches of (25.4cm) length, and about 12 inches (30cm) is straight
Footpath and the horizontal cylinder of draw ratio of 0.83.This reactor has the charging aperture installed at top and the discharge port of bottom installation, it
Can seal during the operation of reactor.Be arranged in reactor is horizontally disposed rotatable shaft, and it is such as Fig. 2 institute
Show support four internal heat transfer plough blade.Each plough blade be V-arrangement so that, when rotated, reactant mixture is divided by it
Stream becomes independent stream and promotes on the two sides of this blade and the stream of this shunting of roll-in, even if causing full-bodied slurry
Effective mixing.This container is to add chuck and can seal and pressurize and heat with hot water or steam.This container can be installed
There is condenser to be removed and condensation by the tail gas produced in dry run of this container.
Embodiment 1
By 3203g tetraethylammonium hydroxide (TEAOH) 35% solution, 405g sodium aluminate 45% solution, 15g is by DowCorning62
The defoamer solution of dilution prepared by defoamer, 5651gARQUAD12/37 solution and 3677gSipernat silicon oxide preparation tool
There is the mixture of about 27wt% solid.The component of this mixture is directly fed into shown in Fig. 1 via top construction opening
Blender/exsiccator also mixes 20 minutes under 110rpm rotates with this blender.This mixture has a following mole of composition:
Seal this reactor and under 20rpm stirs, make mixture reaction 24 hours under 240 (116 DEG C).Then arrange
Put the high viscosity slurry product of one gallon of gained and be stored in 5-GPB container to use after a while.Then charging valve is opened
With allow water to escape to reduce the water content of slurry from reactor and generation have 33.2% the partially dried product of solids content
Thing.
What this was partially dried shows the typical pure phase of MCM-41 topological structure by the material of former state during synthesis, in figure 3
Be given.Show that this material is made up of the agglomerate of small crystals by the SEM of the material of former state during synthesis.Calcination, the product of washing show
Show about 950m2The surface area of/g.Based on these results, it will be observed that high-quality MCM-41 product can be by having about
The synthetic mixture of the higher solids content of 27wt% is prepared in this reactor under mild agitation.That do not wash, partially dried
Product estimation containing the oxygen soluble SiClx of about 10-15wt%.
Embodiment 2
The sample of that do not washed by three kinds, partially dried product and Versal300 aluminium oxide (can obtain from UOP) are respectively
Preparation has three kinds of MCM-41/ aluminium oxide catalysts of the ratio of 95/5,90/10 and 80/20, they is ground and is formed as ten
/ 6th inches of (1.6mm) cylindrical extrudates.Under 250 (121 DEG C), it is dried the extrudate of preparation, then uses.So
After under 1000 (538 DEG C), be calcined this extrudate four hours being dried in atmosphere.Final catalyst shows about 620m2/g
High surface and the Na content of about 1wt%.Then as follows this calcination extrudate is changed into hydrogen form: with ammonium nitrate solution
Ion exchange under room temperature and 140 (60 DEG C), is then dried under 250 (121 DEG C) and calcines under 1000 (538 DEG C)
Six hours.The treated extrudate of gained shows low-down Na content, for 95/5 sample (1.06wt% before exchange), for
0.18wt%；For 90/10 sample (1.02wt% before exchange), for 0.15wt%；For 80/20 sample (before exchange
0.914wt%), for 0.13wt%.
Then and do at 120 DEG C through the exchange extrudate sample of calcination by 0.3wt% platinum and 0.9wt% palladium total immersion profit these three
Dry.Catalyst then accepts aerial final calcining at 304 DEG C so that platinum and palladium compound decompose.The catalyst of gained
Benzene hydrogenation activity index measure as follows:
First at selected temperature (120-350 DEG C) in hydrogen by every kind of catalyst reduction one hour.By catalyst
It is cooled to reaction temperature and allows raw material (benzene and hydrogen) through this catalyst.Measure the benzene hydrogenation speed of 50,75,100 and 125 DEG C
Rate.Data are zeroth orders Arrhenius and are reported in the speed constant of 100 DEG C, and unit is the moles/mole metal/little of product
Time.
The performance of finished catalyst is summarized as follows:
| Describe | Pt,wt% | Pd,wt% | Surface area, m2/g | Benzene hydrogenation activity index |
| 95/5 | 0.253 | 0.68 | 754 | 73 |
| 90/10 | 0.26 | 0.78 | 648 | 110 |
| 80/20 | 0.26 | 0.73 | 686 | 97 |
Embodiment 3
Hydrotreating in advance arranges so that sulfur content to be reduced to the 600N dewaxed oil of about 200ppm for hydrogenation, evaluates
From 90/10 sample of embodiment 2.About 5cc catalyst is loaded and flows up micro--reactor, by the 80-120 mesh of about 3cc
Sand adds in this catalyst to guarantee uniform liquid stream.After the pressure test with nitrogen and hydrogen, 260 in nitrogen
At DEG C, dry catalyst about 3 hours, are cooled to room temperature, activate 8 hours and be cooled to 150 in hydrogen at about 260 DEG C
℃.Introduce raw material and operating condition be adjusted to 2.0LHSV, 6995kPa(1000psig) and about 450NM3/M3(2500scf/
B).Temperature of reactor is brought up to 275 DEG C, then keeps constant about 7-10 days.Hydrogen purity is 100% not use gas
Recirculation.
Every day monitors the product quality limited by aromatic compounds, sulfur, hydrogen and nitrogen content.For present disclosure 90/
10 samples, and (difference is that it is by the conventional method system causing bigger waste water to produce for the comparative catalyst containing MCM-41
Make), draw via UV absorptiometry aromatic compounds (mmole/kg) operating time relatively.Conventional method uses lower leading to
Amount, is dried completely, and washing/filtration step before extruding with aluminium oxide.As shown in Figure 4, by according in the disclosure
Hold the catalyst the prepared total aromatic compounds yield interior at about 40-170 hour to be substantially equal to by conventional method system
Total aromatic compounds yield of the comparative catalyst made.
Although by reference to specific embodiment, invention has been described and illustrates, but art technology
Personnel will be recognized by the change programme that the present invention is applicable to illustrate the most in this article.Therefore, then should be according only to institute
Attached claims determine the true scope of the present invention.
Claims (15)
1. the preparation method of molecular screen material, this molecular screen material have more than the position of 18 angstrom unit's d spacing have to
A few relative intensity is the X-ray diffraction pattern at the peak of 100, and has more than 15 grams of benzene/100 gram nothings at 50 torr and 25 DEG C
The benzene adsorption capacity of crystalline lens, described method includes step:
A () preparation as follows can form the synthetic mixture of described molecular screen material: will in the reactor be equipped with blender
At least water, selected from the source of at least one oxide of bivalent element W, trivalent element X, quadrivalent element Y and pentad Z, alkali gold
Belong to or the source of alkaline-earth metal M, and there is formula R1R2R3R4Q+Organic directing agents (R) combine, wherein said blender has at least 1
Froude number；And wherein Q is nitrogen or phosphorus and wherein R1、R2、R3And R4In at least one selected from containing 6-36 carbon atom
Aryl, alkyl containing 6-36 carbon atom and combinations thereof, R1、R2、R3And R4In remainder selected from hydrogen, containing 1-5 carbon
The alkyl of atom and combinations thereof；Described synthetic mixture has the solids content of at least 20wt%；
B () is heated described synthetic mixture in described reactor and is stirred described mixture to form bag with described blender simultaneously
The product mixtures of the crystal of aqueous and described molecular screen material；Then (c) the described product mixtures from described reactor
At least some of water of middle removing is so that reducing at least 5wt% by the water content of the product mixtures of described inside reactor.
2. the process of claim 1 wherein that described synthetic mixture has a composition according to mol ratio in the range of following:
Wherein e and f is the quantivalence of M and R respectively.
3. the process of claim 1 wherein that described synthetic mixture has a composition according to mol ratio in the range of following:
Wherein e and f is the quantivalence of M and R respectively.
4. the process of claim 1 wherein that described reactor has the capacity of at least 5 liters.
5. the process of claim 1 wherein that described blender includes at least one blade being positioned on axle, this axle can round with
Horizontal line is rotated by the axis of no more than 10 ° orientations.
6. the process of claim 1 wherein and existed by the pressure applied in heat and/or reduction product mixtures to product mixtures
Step (c) removes water from product mixtures.
7. the process of claim 1 wherein with described blender at removing step (c) period stirring product mixtures.
8. the method for claim 1, further comprises the steps of:
D partially dried mixture is mixed in described reactor or in independent blender by () with extra granular materials
Close, to prepare extrudable mixture.
9. the method for claim 8, wherein said extra granular materials is catalyst formulation ingredients.
10. the method for claim 8, wherein said extra granular materials is binding agent or matrix material.
The method of 11. claim 8, further comprises the steps of:
E described extrudable mixture is extruded into the caltalyst of shaping by ().
The method of 12. claim 11, further comprises the steps of:
F () is calcined the caltalyst of described shaping；With
G () makes the caltalyst experience ion exchange of described calcination to reduce the alkali metal in described caltalyst or alkaline-earth metal
The content of M.
The method of 13. claim 11, further comprises the steps of:
F described caltalyst is combined by () with at least one precious metal chemical complex.
The method of 14. claim 13, wherein said noble metal is selected from platinum, palladium, iridium and their mixture.
15. methods arranged by lubricant base hydrogenation, and comprise by power including making described base material under hydrogenation finishing condition
Profit requires the catalyst contact of molecular screen material prepared by the method any one of 1-14.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161475687P | 2011-04-15 | 2011-04-15 | |
| US61/475,687 | 2011-04-15 | ||
| EP11171341.8 | 2011-06-24 | ||
| EP11171341 | 2011-06-24 | ||
| PCT/US2012/028819 WO2012141834A1 (en) | 2011-04-15 | 2012-03-12 | Synthesis and use of m41s family molecular sieves |
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| CN103534026A CN103534026A (en) | 2014-01-22 |
| CN103534026B true CN103534026B (en) | 2016-11-30 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205071A (en) * | 2007-12-18 | 2008-06-25 | 华东理工大学 | Method for preparing molecular sieve in reaction vessel |
| CN101873997A (en) * | 2007-10-26 | 2010-10-27 | 埃克森美孚化学专利公司 | The manufacture method of M41S family molecular sieve |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101873997A (en) * | 2007-10-26 | 2010-10-27 | 埃克森美孚化学专利公司 | The manufacture method of M41S family molecular sieve |
| CN101205071A (en) * | 2007-12-18 | 2008-06-25 | 华东理工大学 | Method for preparing molecular sieve in reaction vessel |
Non-Patent Citations (1)
| Title |
|---|
| 润滑油加氢催化剂的现状及进展;安军信 等;《润滑油》;20070831;第22卷(第4期);第1-7页 * |
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