CN109513457A - To be modified magnesium aluminate spinel as molecular sieve catalyst of carrier and preparation method thereof - Google Patents
To be modified magnesium aluminate spinel as molecular sieve catalyst of carrier and preparation method thereof Download PDFInfo
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- CN109513457A CN109513457A CN201811399040.2A CN201811399040A CN109513457A CN 109513457 A CN109513457 A CN 109513457A CN 201811399040 A CN201811399040 A CN 201811399040A CN 109513457 A CN109513457 A CN 109513457A
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- China
- Prior art keywords
- molecular sieve
- magnesium
- aluminate spinel
- preparation
- magnesium aluminate
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- -1 modified magnesium aluminate Chemical class 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000011029 spinel Substances 0.000 title claims abstract description 52
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 52
- 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 44
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011777 magnesium Substances 0.000 claims abstract description 26
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001051 Magnalium Inorganic materials 0.000 claims abstract description 22
- 150000004645 aluminates Chemical class 0.000 claims abstract description 21
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003483 aging Methods 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004411 aluminium Substances 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 230000001376 precipitating effect Effects 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 7
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 7
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910000632 Alusil Inorganic materials 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 2
- 229940082004 sodium laurate Drugs 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 34
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 229910002796 Si–Al Inorganic materials 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 241000269350 Anura Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 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
- 230000009467 reduction Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004575 stone Substances 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
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/162—Magnesium aluminates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of to be modified magnesium aluminate spinel as molecular sieve catalyst of carrier and preparation method thereof.This method comprises: S1, preparing nanoscale richness magnalium aluminate: aluminium salt, magnesium salts, surfactant is soluble in water, precipitating reagent is added, carries out ageing hydrothermal crystallizing after stirring, then filters, is dry, roasting nanoscale richness magnalium aluminate is made；S2, magnesium aluminate spinel are modified: nanoscale richness magnalium aluminate is impregnated sulfuric acid solution, it is dry, then it is mixed, is aged later, crystallization, washing, roasting with the silicon source of synthesis of molecular sieve, template, crystal seed and distilled water, obtain modified magnesium aluminate spinel；S3, catalyst is prepared using the raw material for including modified magnesium aluminate spinel, molecular sieve active component and binder.The present invention is using modified magnesium aluminate spinel as carrier, using Si-Al molecular sieve or phosphate aluminium molecular sieve as active component, widens the application range of spinel carrier and the carrier range of choice of methanol conversion catalyst.
Description
Technical field
The invention belongs to catalyst fields, and in particular to a kind of to be modified molecular sieve catalyst of the magnesium aluminate spinel as carrier
And preparation method thereof.
Background technique
Ethylene and propylene are the biggish basic organic chemical industry raw materials of demand in petro chemical industry.Due to petroleum resources by
Gradually short, all the time, many industrially developed country concentrate strength on developing the new technology path that non-petroleum feedstocks produces light olefin.
To the country of such a petroleum resources relative shortage in China, coal resources relative abundance, coal or natural gas are developed via methanol
Preparing low-carbon olefins process (MTO) technology has great importance, wherein the performance of methanol conversion catalyst is most important.
The catalyst used in the process of methanol-to-olefins generallys use SAPO molecular sieve and ZSM-5 molecular sieve as activity at present
Component, with kaolin support, using binder it is spray-dried be made methanol conversion catalyst (such as USP5248647,
USP6153552,USP6787501)；CN102029181B, CN102029182B, CN102294262A etc. disclose SAPO phosphoric acid
The preparation method of silicoaluminophosphate molecular sieve-type methanol-to-olefin catalyst.CN1341584A etc. is disclosed with SAPO-34, inorganic oxide
The atomizing preparing technique of adhesive and clay class matrix fill.
The reactivity worth and wear-resistant strength of mist projection granulating catalyst are two key indexes of catalyst, at present patent and text
Offer it is more to active component study on the modification in catalyst, it is less to the Study on Wear-resistance of catalyst.Patent CN01132533A is logical
Cross molecular sieve content in reduction catalyst, the wear-resistant index of Lai Tigao methanol conversion catalyst.CN102284302A is by slurry
Particle refinement is carried out after mixing, improves attrition resistance energy；CN104162448A then passes through improvement Binder Properties, i.e., using acid and
The method of phosphoric acid modification boehmite, to solve the defects of molecular sieve content is low, not wear-resisting, catalytic performance is unstable.And it urges
The reaction effect and wear-resisting property of agent and the selection of catalyst carrier are also closely related.
The carrier of methanol conversion catalyst is mainly the clays such as kaolin at present, and selection is single, and wear resistence can not be significantly
It improves.Magnesium aluminate spinel has acid and alkaline two kinds of activated centres simultaneously, and mechanical strength is good, and property is stablized, not easy-sintering,
Using very extensively in catalysis reaction, catalyst both can be used as, can also be used as catalyst carrier use.But due to the acid of spinelle
Property with L acid based on, it is unfavorable to the generation of methanol conversion process alkene, at present seldom the field use.Therefore, it is necessary to magnalium
Spinelle, which carries out modification appropriate, just can be used as methanol conversion catalyst carrier.
Summary of the invention
Based on background above technology, the present invention provide it is a kind of using be modified magnesium aluminate spinel as the molecular sieve catalyst of carrier and
Preparation method.Method of the invention is using the modified magnesium aluminate spinel of in situ synthesis as carrier, with Si-Al molecular sieve or phosphorus
Aluminum molecular screen is active component, widens the application range of spinel carrier and the carrier range of choice of methanol conversion catalyst.
In order to achieve the goal above, the invention adopts the following technical scheme:
One aspect of the present invention provide it is a kind of to be modified magnesium aluminate spinel as the preparation method of the molecular sieve catalyst of carrier, should
Method the following steps are included:
S1, nanoscale richness magnalium aluminate is prepared:
Aluminium salt, magnesium salts, surfactant is soluble in water, precipitating reagent is added, carries out ageing hydrothermal crystallizing after stirring, then
It filters, is dry, roasting obtained nanoscale richness magnalium aluminate；
S2, magnesium aluminate spinel are modified:
Nanoscale richness magnalium aluminate is impregnated into sulfuric acid solution, it is dry, then with the silicon source of synthesis of molecular sieve, template
Agent, crystal seed and distilled water are mixed, and are aged later, crystallization, washing, roasting, and modified magnesium aluminate spinel is obtained；
S3, molecule is prepared using the raw material for including modified magnesium aluminate spinel, molecular sieve active component and binder
Sieve catalyst.
It is illustrated below for each each step:
S1, nanoscale richness magnalium aluminate is prepared:
Aluminium salt, magnesium salts, surfactant is soluble in water, precipitating reagent is added, carries out ageing hydrothermal crystallizing after stirring, then
It filters, is dry, roasting obtained nanoscale richness magnalium aluminate.
Preferably, the aluminium salt and magnesium salts are soluble；Precipitating reagent is soluble alkali precipitating reagent.
Preferably, the aluminium salt is one or more of sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminium chloride and aluminium acetate
Combination.
Preferably, the magnesium salts is the combination of one or more of magnesium nitrate, magnesium chloride, magnesium sulfate and magnesium carbonate.
Preferably, the surfactant is cetyl trimethylammonium bromide, dodecyl trimethyl ammonium bromide, 12
Alkyl dimethyl ammonium bromide, in neopelex, lauryl sodium sulfate, sodium laurate and sodium citrate
One or more of combinations.
Preferably, the precipitating reagent is urea.
Preferably, described in S1 " ageing hydrothermal crystallizing is carried out after stirring, then filters, is dry, roasting obtained nanoscale richness
After the step of magnalium aluminate " includes: 5-20 DEG C of stirring 1-10h, it is fitted into crystallizing kettle, the static ageing 2- at 25-60 DEG C
Then 48h, the hydrothermal crystallizing 5-80h at 80-200 DEG C are filtered, 100-200 DEG C of dry 1-10h, 400-700 DEG C of roasting 1-10h
Nanoscale richness magnalium aluminate is made.
Preferably, the molar ratio of magnesium and aluminium is 1:(2-200 in solution in S1)；Dosage of surfactant is the total of magnesium and aluminium
0.01-2 times of molal quantity；The dosage of precipitating reagent is 0.05-9 times of the total mole number of magnesium and aluminium, and water is the molal quantity of magnesium
1-100 times.
S2, magnesium aluminate spinel are modified:
Nanoscale richness magnalium aluminate is impregnated into sulfuric acid solution, it is dry, then with the silicon source of synthesis of molecular sieve, template
Agent, crystal seed and distilled water are mixed, and are aged later, crystallization, washing, roasting, and modified magnesium aluminate spinel is obtained.
Preferably, the concentration of the sulfuric acid solution is 0.01-5mol/L.
Preferably, the molar ratio (0.01-20) of sulfuric acid and magnesium aluminate spinel: 1.
Preferably, the condition of the drying is 10-200 DEG C of dry 2-20h.
Preferably, the silicon source is one or two kinds of mixing in silica solution, ethyl orthosilicate, silicon tetrachloride and sodium metasilicate
Object.
Preferably, the template be triethylamine, n-butylamine, ethylenediamine, di-n-propylamine, diisopropylamine, 1,6- hexamethylene diamine,
One or both of tetraethyl ammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium hydroxide and 4-propyl bromide mixture.
Preferably, the crystal seed is ZSM-5 or ZSM-11 molecular sieve.
Preferably, the time of the mixing is 1-40 hours；The step of ageing, crystallization, washing, roasting, wraps
It includes: being put into crystallizing kettle, 1-80h, 110-200 DEG C of crystallization 10-150h are aged at 10-200 DEG C, wash, 500 DEG C of roasting 2-
10h obtains modified magnesium aluminate spinel, as molecular sieve primary structure units.
Preferably, the molar ratio of silica and magnesium aluminate spinel is (0.01-500): 1, wherein template and titanium dioxide
The molar ratio of silicon is (0.01-20): 1, the molar ratio of water and silica is (10-500): and 1, the quality of crystal seed and silica
Than for (0.01-50): 1；The silicon source of addition finally exists in the form of silica, therefore here with the mole of silica
It calculates, the mole of silica converts to obtain by the mole of silicon source.
S3, molecule is prepared using the raw material for including modified magnesium aluminate spinel, molecular sieve active component and binder
Sieve catalyst.
Preferably, the molecular sieve active component be one of Y, ZSM-5, ZSM-11, SAPO-34 and SAPO-18 or
Several combinations.
Preferably, the mass content that the molecular sieve catalyst respectively forms are as follows: molecular sieve active component 20-70%, it is modified
Magnesium aluminate spinel 10-70%, binder 5-30%.
Preferably, the binder is the combination of one or more of silica solution, Aluminum sol, Alusil and phosphorus aluminium glue.
Crystallizing kettle used in the embodiment of the present invention is preferably polytetrafluoro crystallizing kettle.
Another aspect of the present invention provides the molecule to be modified magnesium aluminate spinel as carrier that method made above is prepared
Sieve catalyst.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Comparative example
This comparative example prepares a kind of using no magnesium aluminate spinel modified as the molecular sieve catalyst of carrier
The preparation of nanoscale richness magnalium aluminate:
By the magnesium nitrate of 4g, the ANN aluminium nitrate nonahydrate of 20.2g, the urea of 10g, the cetyl trimethylammonium bromide of 5g,
It is dissolved in 20g water, then 10 DEG C of stirring 4h are loaded into polytetrafluoro crystallizing kettle, in 40 DEG C of static ageing 10h, are warming up to 180
DEG C crystallization is for 24 hours.Distilled water washing filters, and magnesium aluminate spinel is made in 100 DEG C of dry 3h, 500 DEG C of roasting 5h.
The preparation of catalyst: taking ZSM-5 molecular sieve 2.4g, magnesium aluminate spinel 4g, and catalyst is made in silica sol binder 4g.
Embodiment 1
The present embodiment prepares a kind of molecular sieve catalyst to be modified magnesium aluminate spinel as carrier
The preparation of nanoscale richness magnalium aluminate: by the magnesium nitrate of 4g, the ANN aluminium nitrate nonahydrate of 20.2g, the urine of 10g
Element, the cetyl trimethylammonium bromide of 5g are dissolved in 20g water, then 10 DEG C of stirring 4h are loaded into polytetrafluoro crystallizing kettle
In, in 40 DEG C of static ageing 10h, it is warming up to 180 DEG C of crystallization for 24 hours.Distilled water washing filters, in 100 DEG C of dry 3h, 500 DEG C of roastings
It burns 5h and magnesium aluminate spinel is made.
The modification of magnesium aluminate spinel: weighing the spinelle of 4g, weighs the sulfuric acid solution that 28mL concentration is 0.5mol/L, carries out
Dipping, in 100 DEG C of dry 8h；By the spinelle and 25g silica solution, 20g n-butylamine, 2g ZSM-5 crystal seed and 30g water after drying
It is mixed.10h is aged at 50 DEG C, for 24 hours, washing, 500 DEG C of roasting 8h obtain molecular sieve primary structure units to 200 DEG C of crystallization
Modified magnesium aluminate spinel.
The preparation of catalyst: taking ZSM-5 molecular sieve 2.4g, the modified magnesium aluminate spinel 4g of in situ synthesis, and silica solution glues
Catalyst is made in knot agent 4g.
Embodiment 2
The present embodiment prepares a kind of molecular sieve catalyst to be modified magnesium aluminate spinel as carrier
The preparation of nanoscale richness magnalium aluminate: by the magnesium carbonate of 5g, the aluminium acetate of 30g, the urea of 10g, the ten of 5g
Dialkyl benzene sulfonic acids sodium is dissolved in 30g water, and then 15 DEG C of stirring 4h are loaded into polytetrafluoro crystallizing kettle, static old at 60 DEG C
Change 13h, is warming up to 170 DEG C of crystallization 30h.Distilled water washing filters, and in 110 DEG C of dry 4h, it is brilliant that magnalium point is made in 550 DEG C of roasting 6h
Stone.
The modification of magnesium aluminate spinel: weighing the spinelle of 5g, weighs the sulfuric acid solution that 40mL concentration is 0.1mol/L, carries out
Dipping, in 80 DEG C of dry 6h；By after drying spinelle and 50g waterglass (dioxide-containing silica 27%), 30g 1,6 oneself two
Amine, 3g ZSM-11 crystal seed and 40g water are mixed.It is aged 15h, 180 DEG C of crystallization 32h at 60 DEG C, washs, 500 DEG C of roastings
5h obtains the modified magnesium aluminate spinel of molecular sieve primary structure units.
The preparation of catalyst: taking ZSM-11 molecular sieve 3.2g, the modified magnesium aluminate spinel 4g of in situ synthesis, and silica solution glues
Catalyst is made in knot agent 2g.
Embodiment 3
The present embodiment prepares a kind of molecular sieve catalyst to be modified magnesium aluminate spinel as carrier
The preparation of nanoscale richness magnalium aluminate: by the magnesium chloride of 5g, the aluminium chloride of 23g, the urea of 10g, the ten of 8g
Dialkyl group trimethylammonium bromide is dissolved in 40g water, and then 15 DEG C of stirring 4h are loaded into polytetrafluoro crystallizing kettle, quiet at 40 DEG C
It is only aged 15h, is warming up to 160 DEG C of crystallization 40h.Distilled water washing filters, and magnesium is made in 120 DEG C of dry 3h, 500 DEG C of roasting 10h
Aluminate.
The modification of magnesium aluminate spinel: weighing the spinelle of 8g, weighs the sulfuric acid solution that 35mL concentration is 0.3mol/L, carries out
Dipping, in 70 DEG C of dry 8h；By the spinelle and 60g ethyl orthosilicate, 50g ethylenediamine, 4g ZSM-5 crystal seed and 50g after drying
Water is mixed.20h is aged at 50 DEG C, for 24 hours, washing, 500 DEG C of roasting 5h obtain molecular sieve primary structure list to 190 DEG C of crystallization
The modified magnesium aluminate spinel of member.
The preparation of catalyst: SAPO-34 molecular sieve 2.5g, the modified magnesium aluminate spinel 4g of in situ synthesis, Aluminum sol are taken
Catalyst is made in binder 2.7g.
Catalyst performance test
The catalyst of preparation is first at 700 DEG C, 100% vapor aging process 4 hours.Then in small fixed flowing bed
In reactor, methanol transformation experiment is carried out to catalyst sample.Loaded catalyst is 3g, synthesis under normal pressure, reaction temperature 450
DEG C, pure methanol feeding, inlet amount 0.16g/min.MTO fixed bed evaluation result is as shown in table 1.
1 MTO fixed bed evaluation result of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example | |
| Abrasion index | 2.1 | 1.8 | 2.0 | 3 |
| Conversion ratio/% | 100 | 100 | 100 | 98 |
| C2 = | 34 | 35 | 37 | 33 |
| C3 = | 41 | 43 | 42 | 36 |
| C4 = | 7.5 | 5 | 5 | 7 |
| C2 =+C3 = | 75 | 78 | 79 | 69 |
| C2-4 = | 83 | 83 | 84 | 76 |
In 1 data of table, the abrasion index of the catalyst of embodiment 1-3 is respectively less than the catalyst of comparative example, illustrates the present invention
What is prepared is excellent as the abrasion resistance properties of the molecular sieve catalyst of carrier to be modified magnesium aluminate spinel.1-3's of the embodiment of the present invention
Conversion ratio has reached 100%, compared with unmodified magnesium aluminate spinel is the catalyst of carrier, modified methanol conversion
Height, alkene dramatically increase.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of to be modified magnesium aluminate spinel as the preparation method of the molecular sieve catalyst of carrier, which is characterized in that this method packet
Include following steps:
S1, nanoscale richness magnalium aluminate is prepared:
Aluminium salt, magnesium salts, surfactant is soluble in water, precipitating reagent is added, carries out ageing hydrothermal crystallizing after stirring, then takes out
Nanoscale richness magnalium aluminate is made in filter, dry, roasting；
S2, magnesium aluminate spinel are modified:
Nanoscale richness magnalium aluminate is impregnated into sulfuric acid solution, it is dry, then with the silicon source of synthesis of molecular sieve, template, crystalline substance
Kind and distilled water are mixed, and are aged later, crystallization, washing, roasting, and modified magnesium aluminate spinel is obtained；
S3, it is urged using the molecular sieve that is prepared for the raw material for including modified magnesium aluminate spinel, molecular sieve active component and binder
Agent.
2. preparation method according to claim 1, which is characterized in that the aluminium salt is sodium metaaluminate, aluminum nitrate, sulfuric acid
The combination of one or more of aluminium, aluminium chloride and aluminium acetate；
Preferably, the magnesium salts is the combination of one or more of magnesium nitrate, magnesium chloride, magnesium sulfate and magnesium carbonate；
Preferably, the surfactant is cetyl trimethylammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl
Ditallowdimethyl ammonium bromide, one of neopelex, lauryl sodium sulfate, sodium laurate and sodium citrate
Or several combination；
Preferably, the precipitating reagent is urea.
3. preparation method according to claim 1, which is characterized in that " carry out ageing hydrothermal crystallizing after stirring, then in S1
The step of suction filtration, dry, the obtained nanoscale richness magnalium aluminate of roasting " includes: loading crystallization after 5-20 DEG C of stirring 1-10h
In kettle, the static ageing 2-48h at 25-60 DEG C, the hydrothermal crystallizing 5-80h at 80-200 DEG C, then filter, 100-200 DEG C it is dry
Nanoscale richness magnalium aluminate is made in dry 1-10h, 400-700 DEG C of roasting 1-10h.
4. preparation method according to claim 1, which is characterized in that the molar ratio of magnesium and aluminium is 1:(2- in solution in S1
200)；Dosage of surfactant is 0.01-2 times of the total mole number of magnesium and aluminium；The dosage of precipitating reagent is the total moles of magnesium and aluminium
Several 0.05-9 times, water are 1-100 times of the molal quantity of magnesium.
5. preparation method according to claim 1, which is characterized in that the concentration of sulfuric acid solution described in S2 is 0.01-
5mol/L；
Preferably, in S2 sulfuric acid and magnesium aluminate spinel molar ratio (0.01-20): 1.
6. preparation method according to claim 1, which is characterized in that the silicon source is silica solution, ethyl orthosilicate, tetrachloro
One or two kinds of mixtures in SiClx and sodium metasilicate；
Preferably, the template is triethylamine, n-butylamine, ethylenediamine, di-n-propylamine, diisopropylamine, 1,6- hexamethylene diamine, tetrem
One or both of base ammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium hydroxide and 4-propyl bromide mixture；
Preferably, the crystal seed is ZSM-5 or ZSM-11 molecular sieve；
Preferably, the molecular sieve active component is one or more of Y, ZSM-5, ZSM-11, SAPO-34 and SAPO-18
Combination；
Preferably, the binder is the combination of one or more of silica solution, Aluminum sol, Alusil and phosphorus aluminium glue.
7. preparation method according to claim 1, which is characterized in that dry condition described in S2 is 10-200 DEG C of drying
2-20h；
Preferably, the time of mixing described in S2 is 1-40 hours；The step of ageing, crystallization, washing, roasting, wraps
It includes: being put into crystallizing kettle, 1-80h, 110-200 DEG C of crystallization 10-150h are aged at 10-200 DEG C, wash, 500 DEG C of roasting 2-
10h obtains modified magnesium aluminate spinel.
8. preparation method according to claim 1, which is characterized in that the molar ratio of silica and magnesium aluminate spinel in S2
For (0.01-500): 1, wherein the molar ratio of template and silica is (0.01-20): 1, the molar ratio of water and silica
For (10-500): 1, the mass ratio of crystal seed and silica is (0.01-50): 1；
Wherein, the mole of silica converts to obtain by the mole of silicon source.
9. preparation method according to claim 1, which is characterized in that the quality that molecular sieve catalyst described in S3 respectively forms
Content are as follows: molecular sieve active component 20-70%, modified magnesium aluminate spinel 10-70%, binder 5-30%.
10. point to be modified magnesium aluminate spinel as carrier that any one of -9 preparation methods are prepared according to claim 1
Sub- sieve catalyst.
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