CN110227537A - A kind of preparation method of core-shell structure loaded catalyst - Google Patents
A kind of preparation method of core-shell structure loaded catalyst Download PDFInfo
- Publication number
- CN110227537A CN110227537A CN201910561499.6A CN201910561499A CN110227537A CN 110227537 A CN110227537 A CN 110227537A CN 201910561499 A CN201910561499 A CN 201910561499A CN 110227537 A CN110227537 A CN 110227537A
- Authority
- CN
- China
- Prior art keywords
- parts
- core
- shell structure
- preparation
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 239000011258 core-shell material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002808 molecular sieve Substances 0.000 claims abstract description 53
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 230000000694 effects Effects 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910002482 Cu–Ni Inorganic materials 0.000 claims abstract description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 19
- 238000011049 filling Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 17
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 239000002077 nanosphere Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 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 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000009416 shuttering Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000004927 clay Substances 0.000 claims 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 claims 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 230000008602 contraction Effects 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 9
- 230000002779 inactivation Effects 0.000 abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 7
- 210000003850 cellular structure Anatomy 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 241000790917 Dioxys <bee> Species 0.000 description 4
- 229910003978 SiClx Inorganic materials 0.000 description 4
- 238000005411 Van der Waals force Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000001934 delay Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- IGHXQFUXKMLEAW-UHFFFAOYSA-N iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Fe+2].[O-2] IGHXQFUXKMLEAW-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J29/42—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 containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/393—
-
- B01J35/397—
-
- B01J35/61—
-
- B01J35/647—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of preparation method of core-shell structure loaded catalyst, and the preparation method of the core-shell structure loaded catalyst includes the following steps: the first step, the preparation of iron oxide hollow sphere;Second step, Cu-Ni/Fe2O3The preparation of active component core-shell structure;Third step, hydro-thermal method synthesize ZSM-5 molecular sieve;4th step, the preparation of core-shell structure loaded catalyst.In the present invention when core-shell structure is attached to molecular sieve surface, since the lattice defect inside molecular sieve is along with the effect of stirring, guidance core-shell structure is embedded into molecular sieve inner frame, again by obtaining uniform gel after the hydrolytic precipitation of sodium bicarbonate, and the purpose roasted under 500-600 DEG C of high temperature is due in the event of high temperatures, intramolecular binding force is gradually increased, frame inside ZSM-5 molecular sieve has certain contraction, under this contraction state, prepared catalyst is more stable, not easy in inactivation during the reaction, it is supplied to the better catalytic activity of reaction.
Description
Technical field
The present invention relates to catalysis technical fields, and in particular to a kind of preparation method of core-shell structure loaded catalyst.
Background technique
Energy and environment are the two large problems that the world today faces.Into after 21 century, economy depends on the energy unduly
Environmental problem is caused to highlight, the development and utilization of new energy, which has become, to be alleviated world energy sources disparities between supply and demand, realizes energy multiplicity
Change, keep the Major Strategic Demand of economic environment sustainable development.
Hydrogen Energy does not generate any disposal of pollutants when utilizing, and is the ideal chose of the following clear energy sources carrier, and substitution
Petroleum solves the problems, such as an important channel of transportation fuel.From the nineties in last century, the U.S., Europe and Japan it is major
Car manufacturer and oil company, it is seen that the huge market potential of fuel cell car puts into huge fund one after another, forms alliance,
Correlative study, test and the production for carrying out fuel cell car have been developed hundreds fuel cell sample car till now, and have been added
Tightly formulate relevant industry index.However, hydrogen energy system is a huge and complicated energy resource system, in Hydrogen Energy and fuel cell
It needs to solve there are also many problems on the road of application.Other than economic and policy factor, Hydrogen Energy preparation, transport, conversion and
Using still had in link many technical problems have it is to be overcome.Therefore, various countries will all weigh while being demonstrated in succession at present
Point turns back to applied basic research, it is desirable to by research Hydrogen Energy and the various basic problems of fuel cell, find realization hydrogen
It can be with the basic method of fuel cell industrialization.
No matter from technology maturation degree or from existing infrastructure using from the point of view of degree, with fossil fuel (packet
Including methanol, gasoline, diesel oil, natural gas etc.) hydrogen manufacturing is the important channel for solving small-scale distributing hydrogen source at this stage.Permitted in the world
Mostly famous colleges and universities, research institute and National Laboratory all attach great importance to Hydrogen Energy in terms of research and development, have been devoted to exploitation be suitable for move
The catalyst of dynamic or live hydrogen production process, research emphasis are the work of catalyst under the conditions of raising hydrogen production process non-steady state operation
Property, selectivity and stability, develop the effective catalyst of heat shock resistance, redox condition impact and vibratory impulse.
Current hydrogen production process undergoes two processes of reformation and purification mostly, according to different fuel battery in reformation tail gas
The requirement of CO content is different, selected purification process different from, but in general, selects mostly using water-gas shift and CO
Property oxidation method realize reduce CO purpose, wherein water-gas shift be divided into again superheated vapor transformation with low temperature water-gas shift, after
Continuous complex disposal process and cumbersome.Therefore, how CO content is reduced in reforming process, improve catalyst CO2Selectively it is
One of bottleneck during reformation hydrogen production at present.
In view of the above problems, the present invention, using hydrogen production from methanol-steam reforming system as goal in research, exploitation has height emphatically
Activity, the copper-based catalysts of low CO selectivity and high stability.Currently, commercialized CuO/ZnO/Al2O3There are low temperature for catalyst
Activity is lower, reforms CO content higher (2%-3%) and the poor defect of stability in tail gas.To solve these problems, people
Research Cu base Molecular level is focused on, and is attempted different with addition by the preparation method for improving copper-based catalysts
Auxiliary agent to improve its catalytic performance, but currently, the CO selectivity and stability problem of catalyst for preparing hydrogen by reforming methanol and water vapour still
It is not well solved, the related data of CO selectivity and stability is also seldom.
Summary of the invention
In order to overcome above-mentioned technical problem, the purpose of the present invention is to provide a kind of core-shell structure loaded catalysts
Preparation method, prepared core-shell structure loaded catalyst are applied in methanol steam reforming reaction, and catalyst has height
Activity, high stability and lower CO selectivity.
Prepared its grain diameter size of iron oxide hollow sphere is in nanoscale in the present invention, and particle dispersion compared with
It is good;The purpose that hydrofluoric acid aqueous solution is added is can to form oxygen in this way to dissolve the silica nanosphere inside iron oxide
Change iron hollow sphere;And hydrofluoric acid with the hollow ball surface of slight erosion iron oxide and can form groove, and it is living to facilitate catalyst
Property component enter groove and form one layer of shell-like structure in the hollow ball surface of iron oxide, solve that shell-like structure is unstable to ask
Topic.
Surfactant is a kind of surface tension that can be reduced between different component in the present invention, and can guide work
Property component in the hollow ball surface of nano iron oxide carry out orderly self assembly, after the completion of to be assembled, surface can form one layer of reinforcing again
Film maintains the internal stability of core-shell structure.
Prepared ZSM-5 molecular sieve has the cellular structure of special rules in the present invention, in catalysis, absorption and separation
Equal fields are widely used, and internal special cellular structure provides strong supporting point for the insertion of catalytic active component, and
By hydrothermal synthesis method, increase the binding force inside ZSM-5 molecular sieve, so that ZSM-5 molecular sieve inner frame is at high temperature not
It easily collapses, provides foundation for the high activity of catalyst.
In the present invention when core-shell structure is attached to molecular sieve surface, is added and stirred due to the lattice defect inside molecular sieve
The effect mixed, guidance core-shell structure are embedded into molecular sieve inner frame, since polyethylene glycol has viscosity well, Ke Yixiu
Lattice defect inside compound molecule sieve stablizes overall structure, then obtains uniform gel after the hydrolytic precipitation for passing through sodium bicarbonate,
Restored under an atmosphere of hydrogen so that catalyst is active, and the purpose roasted under 500-600 DEG C of high temperature be due to
In the case where high temperature, intramolecular binding force is gradually increased, and the frame inside ZSM-5 molecular sieve has certain contraction,
Under this contraction state, prepared catalyst is more stable, during the reaction not easy in inactivation, is supplied to reaction and preferably urges
Change activity, solve catalyst easy in inactivation during the reaction, to be supplied to the better catalytic activity of reaction.
Synthesized composite mould plate agent is a kind of organic matter widely used in nano-composite mate-rial in the present invention, it
Purport is by power the effects of ionic bond, hydrogen bond and Van der Waals force, under the conditions of existing for the solution, to inorganic under free state
Or organic precursor guides, to generate the material with micro-nanometer ordered structure, solves ZSM-5 molecular sieve preparation process
Middle internal gutter structure problem of non-uniform.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of core-shell structure loaded catalyst, the preparation method packet of the core-shell structure loaded catalyst
Include following steps:
The first step, the preparation of iron oxide hollow sphere:
Ethyl orthosilicate is added in the beaker for filling dehydrated alcohol and is stirred, ammonium hydroxide is slowly added dropwise, after being added dropwise to complete,
Continue after stirring 2-3h, after being centrifuged, filtered, being washed, is put into 60-80 DEG C of sufficiently dry 10-15h in baking oven, is transferred to horse
Not 400-500 DEG C of roasting 2-3h in furnace, is cooled to room temperature, clays into power, obtain silica nanosphere;By silica nanometer
Ball is added in the beaker for filling dehydrated alcohol, forms silica suspension after being ultrasonically treated 2-3h;In silica suspension
Middle addition ferric nitrate stirs evenly, and ammonium hydroxide is slowly added dropwise, and after being added dropwise to complete, continues to stir 2-3h, adds 0.5mol/L hydrogen fluorine
Aqueous acid is centrifuged mixed solution, is filtered, is washed after stirring 0.5-1h, is put into 60-80 DEG C of sufficiently drying in baking oven
10-15h, 400-500 DEG C of roasting 2-3h in Muffle furnace, is cooled to room temperature, clays into power, obtain iron oxide hollow sphere;The present invention
In prepared its grain diameter size of iron oxide hollow sphere in nanoscale, and particle dispersion is preferable;Hydrofluoric acid is added
The purpose of aqueous solution is can to form iron oxide hollow sphere in this way to dissolve the silica nanosphere inside iron oxide;And
And hydrofluoric acid with the hollow ball surface of slight erosion iron oxide and can form groove, facilitate catalyst activity component and enter groove
And one layer of shell-like structure is formed in the hollow ball surface of iron oxide, the shell-like structure formed in this way is stronger.
Second step, Cu-Ni/Fe2O3The preparation of active component core-shell structure:
Copper nitrate and nickel nitrate are added in the beaker for filling deionized water and dissolved completely, under 60-80 DEG C of water bath condition
The ammonium bicarbonate aqueous solution of 1.5mol/L is stirred and be slowly added dropwise, until gel occurs in solution, continues to stir 1-2h, obtains catalyst
Active component precursor;Iron oxide hollow sphere is added in catalyst activity component precursor, to abundant after stirring 0.5-1h
It is uniformly mixed, adds surfactant dodecyltrimethylammonium, continue after stirring 1-2h, obtained solution is poured into instead
It answers in kettle and is taken out after 160-180 DEG C of crystallization 1-2d, is cooled to room temperature, filter, washed with dehydrated alcohol, filter cake is put into baking oven
80-100 DEG C of sufficiently dry 10-15h, is transferred to 400-500 DEG C of roasting 3-4h in Muffle furnace, after being cooled to room temperature, grinds
End obtains Cu-Ni/Fe2O3Active component core-shell structure;In the present invention surfactant be one kind can reduce different component it
Between surface tension, and active component can be guided to carry out orderly self assembly in the hollow ball surface of nano iron oxide, it is to be assembled
After the completion, surface can form one layer of reinforcing film again, maintain the internal stability of core-shell structure;
Third step, hydro-thermal method synthesize ZSM-5 molecular sieve:
Aluminum sulfate and sodium metasilicate are added in the beaker for filling deionized water, to being completely dissolved after stirring 0.5-1h, obtained
Mixed solution;Composite mould plate agent is slowly added dropwise into mixed solution, after being added dropwise to complete, continues to stir 2-3h, obtains precursor
Solution;Precursor solution is poured into reaction kettle and is taken out after 160-180 DEG C of crystallization 1-2d, after being cooled to room temperature, filter, spend from
Sub- water washing, obtains filter cake;By filter cake after 80-100 DEG C of sufficiently dry 15-20h, it is put into 400-500 DEG C of roasting 3- of Muffle furnace
It after 4h, is cooled to room temperature, clays into power, obtain ZSM-5 molecular sieve;Prepared ZSM-5 molecular sieve has special in the present invention
The cellular structure of rule, is widely used in fields such as catalysis, absorption and separation, and internal special cellular structure is that catalysis is lived
Property component insertion strong supporting point is provided, and by hydrothermal synthesis method, increase the binding force inside ZSM-5 molecular sieve,
So that ZSM-5 molecular sieve inner frame is not easy to collapse at high temperature, foundation is provided for the high activity of catalyst;
4th step, the preparation of core-shell structure loaded catalyst:
Prepared core-shell structure and ZSM-5 molecular sieve are added in the beaker for filling deionized water, at 60-80 DEG C
It is uniform to being sufficiently mixed that 0.5-1h is stirred under water bath condition;Polyethylene glycol solid is added to dissolving completely, bicarbonate is slowly added dropwise
Sodium solution continues to stir 2-3h, after placing 15-20h at room temperature, filter after being washed with dehydrated alcohol to after forming gel;
After filter cake in an oven 80-100 DEG C of sufficiently dry 10-15h, 500-600 DEG C of roasting under atmosphere of hydrogen is transferred in tube furnace
2-3h, 10 DEG C/min of heating rate, obtains core-shell structure loaded catalyst;When core-shell structure is attached to molecular sieve in the present invention
When surface, since the lattice defect inside molecular sieve is along with the effect of stirring, guidance core-shell structure is embedded into inside molecular sieve
In frame, since polyethylene glycol has viscosity well, the lattice defect inside molecular sieve can be repaired, overall structure is stablized,
Again by obtaining uniform gel after the hydrolytic precipitation of sodium bicarbonate, restored under an atmosphere of hydrogen so that catalyst has work
Property, and the purpose roasted under 500-600 DEG C of high temperature is since in the event of high temperatures, intramolecular binding force gradually increases
Greatly, the frame inside ZSM-5 molecular sieve has certain contraction, and under this contraction state, prepared catalyst is more steady
Fixed, not easy in inactivation, is supplied to the better catalytic activity of reaction during the reaction.
Further, each raw material composition and its parts by weight in iron oxide hollow sphere preparation process: 30-40 parts of positive silicic acid second
Ester, 40-50 part dehydrated alcohol, 20-30 parts of ammonium hydroxide, 30-40 parts of ferric nitrates, 10-20 parts of 0.5mol/L hydrofluoric acid.
Further, Cu-Ni/Fe2O3Each raw material composition and its parts by weight in active component core-shell structure preparation process:
10-20 parts of copper nitrates, 10-20 parts of nickel nitrates, 30-40 parts of iron oxide, 5-10 parts of dodecyl trimethyl ammonium bromide, 40-50 parts
Deionized water.
Further, each raw material composition and its parts by weight in ZSM-5 molecular sieve preparation process: 15-30 parts of aluminum sulfate,
20-40 parts of sodium metasilicate, 30-40 parts of composite mould plate agents, 40-50 parts of deionized waters.
Further, each raw material composition and its parts by weight in core-shell structure loaded catalyst preparation process: 20-30 parts
Core-shell structure material, 40-50 part ZSM-5 molecular sieve, 10-20 parts of polyethylene glycol, 50-70 parts of deionized waters.
A kind of composite mould plate agent the preparation method is as follows:
Paraxylene and N- bromo-succinimide are added in dichloromethane solvent, it is to be mixed uniformly after, be added even
Nitrogen bis-isobutyronitrile initiator heats 4-5h under 60-80 DEG C of water bath, is filtered to remove unreacted N- bromo-succinimide,
Vacuum distillation removes solvent, obtains mixture;Mixture and triethylamine are dissolved in petroleum ether solvent, potassium carbonate, 70-80 is added
It DEG C is heated to reflux 2-3h, is filtered after cooling, obtained mother liquor is concentrated under reduced pressure, white solid is precipitated in removal, obtains composite shuttering
Agent;Synthesized composite mould plate agent is a kind of organic matter widely used in nano-composite mate-rial, its purport in the present invention
It is under the conditions of existing for the solution, to inorganic under free state or to have by power the effects of ionic bond, hydrogen bond and Van der Waals force
Machine precursor guides, so that generating has micro-nanometer ordered structure.
Further, each raw material composition and its parts by weight in composite mould plate agent preparation process: 10-20 parts of paraxylene,
15-20 parts of N- bromo-succinimides, 40-50 parts of methylene chloride, 5-10 parts of azodiisobutyronitriles, 30-40 parts of triethylamines, 20-
30 parts of petroleum ethers, 10-20 parts of potassium carbonate.
Beneficial effects of the present invention:
1, its grain diameter size of iron oxide hollow sphere prepared in the present invention is in nanoscale, and particle dispersion
Preferably;The purpose that hydrofluoric acid aqueous solution is added can be formed in this way to dissolve the silica nanosphere inside iron oxide
Iron oxide hollow sphere;And hydrofluoric acid with the hollow ball surface of slight erosion iron oxide and can form groove, facilitate catalyst
Active component enters groove and forms one layer of shell-like structure in the hollow ball surface of iron oxide, and the shell-like structure formed in this way is more firm
Gu.
2, surfactant is a kind of surface tension that can be reduced between different component in the present invention, and can be guided
Active component carries out orderly self assembly in the hollow ball surface of nano iron oxide, and after the completion of to be assembled, surface can form one layer again and add
Gu film maintains the internal stability of core-shell structure;
3, ZSM-5 molecular sieve prepared in the present invention has the cellular structure of special rules, in catalysis, absorption and divides
It being widely used from equal fields, internal special cellular structure provides strong supporting point for the insertion of catalytic active component, and
And by hydrothermal synthesis method, increase the binding force inside ZSM-5 molecular sieve, so that ZSM-5 molecular sieve inner frame is at high temperature
It is not easy to collapse, provides foundation for the high activity of catalyst;
4, in the present invention when core-shell structure is attached to molecular sieve surface, since the lattice defect inside molecular sieve is added
The effect of stirring, guidance core-shell structure are embedded into molecular sieve inner frame, can be with since polyethylene glycol has viscosity well
The lattice defect inside molecular sieve is repaired, overall structure is stablized, then is uniformly coagulated after the hydrolytic precipitation for passing through sodium bicarbonate
Glue is restored under an atmosphere of hydrogen so that catalyst is active, and the purpose roasted under 500-600 DEG C of high temperature be due to
In the event of high temperatures, intramolecular binding force is gradually increased, and the frame inside ZSM-5 molecular sieve has certain contraction,
Under this contraction state, prepared catalyst is more stable, during the reaction not easy in inactivation, and it is better to be supplied to reaction
Catalytic activity.
5, composite mould plate agent synthesized in the present invention is a kind of organic matter widely used in nano-composite mate-rial, it
Purport be by power the effects of ionic bond, hydrogen bond and Van der Waals force, under the conditions of existing for the solution, to the nothing under free state
Machine or organic precursor guide, to generate the material with micro-nanometer ordered structure.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, all other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
The preparation method of core-shell structure loaded catalyst includes the following steps:
The first step, the preparation of iron oxide hollow sphere:
30g ethyl orthosilicate is added in the beaker for filling 20g dehydrated alcohol and is stirred, 10g ammonium hydroxide is slowly added dropwise, is dripped
After the completion of adding, continue after stirring 2-3h, after being centrifuged, filtered, being washed, be put into 60-80 DEG C of sufficiently dry 10-15h in baking oven,
It is transferred to 400-500 DEG C of roasting 2-3h in Muffle furnace, is cooled to room temperature, clays into power, obtain silica nanosphere;By dioxy
SiClx nanosphere is added in the beaker for filling 20g dehydrated alcohol, forms silica suspension after being ultrasonically treated 2-3h;In dioxy
30g ferric nitrate is added in SiClx suspension to stir evenly, 10g ammonium hydroxide is slowly added dropwise, after being added dropwise to complete, continues to stir 2-3h, then
10g0.5mol/L hydrofluoric acid aqueous solution is added, after stirring 0.5-1h, mixed solution is centrifuged, filter, is washed, baking is put into
10-15h is sufficiently dried for 60-80 DEG C in case, and 400-500 DEG C of roasting 2-3h in Muffle furnace is cooled to room temperature, clays into power, obtain
Iron oxide hollow sphere;
Second step, Cu-Ni/Fe2O3The preparation of active component core-shell structure:
10g copper nitrate and 10g nickel nitrate are added in the beaker for filling 40g deionized water and dissolved completely, in 60-80 DEG C of water
The ammonium bicarbonate aqueous solution of 1.5mol/L is stirred and be slowly added dropwise under the conditions of bath, until gel occurs in solution, is continued to stir 1-2h, be obtained
To catalyst activity component precursor;30g iron oxide hollow sphere is added in catalyst activity component precursor, 0.5- is stirred
To being sufficiently mixed uniformly after 1h, 5g surfactant dodecyltrimethylammonium is added, continues after stirring 1-2h, will obtain
Solution pour into reaction kettle and taken out after 160-180 DEG C of crystallization 1-2d, be cooled to room temperature, filter, washed, will be filtered with dehydrated alcohol
Cake is put into 80-100 DEG C of sufficiently dry 10-15h in baking oven, is transferred to 400-500 DEG C of roasting 3-4h in Muffle furnace, is cooled to room
Wen Hou clays into power, and obtains Cu-Ni/Fe2O3Active component core-shell structure;
Third step, hydro-thermal method synthesize ZSM-5 molecular sieve:
15g aluminum sulfate and 20g sodium metasilicate are added in the beaker for filling 40g deionized water, to complete after stirring 0.5-1h
Dissolution, obtains mixed solution;30g composite mould plate agent is slowly added dropwise into mixed solution, after being added dropwise to complete, continues to stir 2-
3h obtains precursor solution;Precursor solution is poured into reaction kettle and is taken out after 160-180 DEG C of crystallization 1-2d, is cooled to room temperature
Afterwards, it filters, is washed with deionized, obtains filter cake;By filter cake after 80-100 DEG C of sufficiently dry 15-20h, it is put into Muffle furnace
After 400-500 DEG C of roasting 3-4h, it is cooled to room temperature, clays into power, obtain ZSM-5 molecular sieve;
4th step, the preparation of core-shell structure loaded catalyst:
Prepared 20g core-shell structure and 40gZSM-5 molecular sieve are added in the beaker for filling 50g deionized water,
It is uniform to being sufficiently mixed that 0.5-1h is stirred under 60-80 DEG C of water bath condition;10g polyethylene glycol solid is added to dissolving completely, delays
The slow sodium bicarbonate solution that is added dropwise continues to stir 2-3h, after placing 15-20h at room temperature, be carried out with dehydrated alcohol to after forming gel
It is filtered after washing;After filter cake in an oven 80-100 DEG C of sufficiently dry 10-15h, it is transferred in tube furnace under atmosphere of hydrogen
500-600 DEG C of roasting 2-3h, 10 DEG C/min of heating rate obtain core-shell structure loaded catalyst.
The composite mould plate agent the preparation method is as follows:
10g paraxylene and 15gN- bromo-succinimide are added in 40g dichloromethane solvent, it is to be mixed uniform
Afterwards, 5g azodiisobutyronitrile initiator is added, heats 4-5h under 60-80 DEG C of water bath, is filtered to remove unreacted N- bromo
Succimide, vacuum distillation remove solvent, obtain mixture;Mixture and 30g triethylamine are dissolved in 20g petroleum ether solvent
In, 10g potassium carbonate is added, 70-80 DEG C is heated to reflux 2-3h, filters after cooling, obtained mother liquor is concentrated under reduced pressure, removal is precipitated
White solid obtains composite mould plate agent.
Embodiment 2
The preparation method of core-shell structure loaded catalyst includes the following steps:
The first step, the preparation of iron oxide hollow sphere:
40g ethyl orthosilicate is added in the beaker for filling 25g dehydrated alcohol and is stirred, 15g ammonium hydroxide is slowly added dropwise, is dripped
After the completion of adding, continue after stirring 2-3h, after being centrifuged, filtered, being washed, be put into 60-80 DEG C of sufficiently dry 10-15h in baking oven,
It is transferred to 400-500 DEG C of roasting 2-3h in Muffle furnace, is cooled to room temperature, clays into power, obtain silica nanosphere;By dioxy
SiClx nanosphere is added in the beaker for filling 25g dehydrated alcohol, forms silica suspension after being ultrasonically treated 2-3h;In dioxy
40g ferric nitrate is added in SiClx suspension to stir evenly, 15g ammonium hydroxide is slowly added dropwise, after being added dropwise to complete, continues to stir 2-3h, then
20g0.5mol/L hydrofluoric acid aqueous solution is added, after stirring 0.5-1h, mixed solution is centrifuged, filter, is washed, baking is put into
10-15h is sufficiently dried for 60-80 DEG C in case, and 400-500 DEG C of roasting 2-3h in Muffle furnace is cooled to room temperature, clays into power, obtain
Iron oxide hollow sphere;
Second step, Cu-Ni/Fe2O3The preparation of active component core-shell structure:
20g copper nitrate and 20g nickel nitrate are added in the beaker for filling 50g deionized water and dissolved completely, in 60-80 DEG C of water
The ammonium bicarbonate aqueous solution of 1.5mol/L is stirred and be slowly added dropwise under the conditions of bath, until gel occurs in solution, is continued to stir 1-2h, be obtained
To catalyst activity component precursor;40g iron oxide hollow sphere is added in catalyst activity component precursor, 0.5- is stirred
To being sufficiently mixed uniformly after 1h, 10g surfactant dodecyltrimethylammonium is added, is continued after stirring 1-2h, will
To solution pour into reaction kettle and taken out after 160-180 DEG C of crystallization 1-2d, be cooled to room temperature, filter, washed with dehydrated alcohol, will
Filter cake is put into 80-100 DEG C of sufficiently dry 10-15h in baking oven, is transferred to 400-500 DEG C of roasting 3-4h in Muffle furnace, is cooled to
It after room temperature, clays into power, obtains Cu-Ni/Fe2O3Active component core-shell structure;
Third step, hydro-thermal method synthesize ZSM-5 molecular sieve:
30g aluminum sulfate and 40g sodium metasilicate are added in the beaker for filling 50g deionized water, to complete after stirring 0.5-1h
Dissolution, obtains mixed solution;40g composite mould plate agent is slowly added dropwise into mixed solution, after being added dropwise to complete, continues to stir 2-
3h obtains precursor solution;Precursor solution is poured into reaction kettle and is taken out after 160-180 DEG C of crystallization 1-2d, is cooled to room temperature
Afterwards, it filters, is washed with deionized, obtains filter cake;By filter cake after 80-100 DEG C of sufficiently dry 15-20h, it is put into Muffle furnace
After 400-500 DEG C of roasting 3-4h, it is cooled to room temperature, clays into power, obtain ZSM-5 molecular sieve;
4th step, the preparation of core-shell structure loaded catalyst:
Prepared 30g core-shell structure and 50gZSM-5 molecular sieve are added in the beaker for filling 70g deionized water,
It is uniform to being sufficiently mixed that 0.5-1h is stirred under 60-80 DEG C of water bath condition;20g polyethylene glycol solid is added to dissolving completely, delays
The slow sodium bicarbonate solution that is added dropwise continues to stir 2-3h, after placing 15-20h at room temperature, be carried out with dehydrated alcohol to after forming gel
It is filtered after washing;After filter cake in an oven 80-100 DEG C of sufficiently dry 10-15h, it is transferred in tube furnace under atmosphere of hydrogen
500-600 DEG C of roasting 2-3h, 10 DEG C/min of heating rate obtain core-shell structure loaded catalyst.
The composite mould plate agent the preparation method is as follows:
20g paraxylene and 20gN- bromo-succinimide are added in 50g dichloromethane solvent, it is to be mixed uniform
Afterwards, 10g azodiisobutyronitrile initiator is added, heats 4-5h under 60-80 DEG C of water bath, is filtered to remove unreacted N- bromo
Succimide, vacuum distillation remove solvent, obtain mixture;Mixture and 40g triethylamine are dissolved in 30g petroleum ether solvent
In, 20g potassium carbonate is added, 70-80 DEG C is heated to reflux 2-3h, filters after cooling, obtained mother liquor is concentrated under reduced pressure, removal is precipitated
White solid obtains composite mould plate agent.
Embodiment 3
Change composite mould plate agent in embodiment 2 into triethylamine single template.
Embodiment 4
Change iron oxide hollow sphere in embodiment 2 into conventional oxidation iron.
Embodiment 5
Surfactant dodecyltrimethylammonium in embodiment 2 is removed.
Embodiment 6
The specific surface area and average pore size of catalyst in 1 embodiment 1-5 of table
Catalyst | Specific surface area (m2/g) | Average pore size (nm) |
Embodiment 1 | 365 | 6.3 |
Embodiment 2 | 358 | 6.5 |
Embodiment 3 | 315 | 8.3 |
Embodiment 4 | 306 | 9.5 |
Embodiment 5 | 285 | 12.6 |
From table 1 we: prepared specific surface area of catalyst is larger, shows can to adsorb in unit volume more
Active component, play the role of to the raising of catalytic activity critically important, and its average pore size is between 2-50nm, has and is situated between
Pore structure, mesoporous material not only possess adjustable aperture, while pore wall thickness also shows outstanding, has stronger stability,
Can be used as nanoscale reacting environment, in the present invention synthesized composite mould plate agent be one kind in nano-composite mate-rial using wide
General organic matter, its purport be by power the effects of ionic bond, hydrogen bond and Van der Waals force, it is right under the conditions of existing for the solution
Inorganic or organic precursor under free state guides, to generate the material with micro-nanometer ordered structure, template agent method
There is certain facilitation to the increasing of material specific surface area and mesoporous formation.
Embodiment 7
At T=260 DEG C, water and methanol molar ratio=1.3, mass space velocity WHSV=3.2h-1Reaction condition under, methanol-water
The catalytic activity investigation of vapour reforming hydrogen producing reaction is shown in Table 2.
The catalytic activity of 2 embodiment 1-5 of table is investigated
We are it follows that core-shell structure loaded catalyst prepared in the present invention is shown from table 2
Superior catalytic activity out, and carbon monoxide content is few in product, has the effect of being pushed further into the application of fuel cell.
Higher catalytic activity be mainly due to: prepared ZSM-5 molecular sieve has the hole of special rules in the present invention
Road structure is widely used in fields such as catalysis, absorption and separation, and internal special cellular structure is catalytic active component
Insertion provides strong supporting point, and by hydrothermal synthesis method, increases the binding force inside ZSM-5 molecular sieve, so that ZSM-5
Molecular sieve inner frame is not easy to collapse at high temperature, provides foundation for the high activity of catalyst;The purpose of hydrofluoric acid treatment be for
So that the hollow ball surface of iron oxide is formed groove, and remove silica, facilitates catalyst activity component and enter groove simultaneously
One layer of shell-like structure is formed in hollow ball surface, the shell-like structure formed in this way is stronger;Surfactant is that one kind can be with
The surface tension between different component is reduced, and it is orderly that active component can be guided to carry out in the hollow ball surface of nano iron oxide
Self assembly, after the completion of to be assembled, surface can form one layer of reinforcing film again, maintain the internal stability of core-shell structure;Work as nucleocapsid
When structure is attached to molecular sieve surface, since the lattice defect inside molecular sieve is along with the effect of stirring, core-shell structure is guided
It is embedded into molecular sieve inner frame, since polyethylene glycol has viscosity well, the lattice inside molecular sieve can be repaired and lacked
It falls into, stablizes overall structure, then obtain uniform gel after the hydrolytic precipitation for passing through sodium bicarbonate, restored under an atmosphere of hydrogen
So that catalyst is active, and the purpose roasted under 500-600 DEG C of high temperature is the intramolecule due in the event of high temperatures
Binding force be gradually increased, the frame inside ZSM-5 molecular sieve has certain contraction, prepared under this contraction state
Catalyst it is more stable, not easy in inactivation, is supplied to the better catalytic activity of reaction during the reaction.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
Above content is only citing made for the present invention and explanation, affiliated those skilled in the art are to being retouched
The specific embodiment stated does various modifications or additions or is substituted in a similar manner, and without departing from invention or surpasses
More range defined in the claims, is within the scope of protection of the invention.
Claims (7)
1. a kind of preparation method of core-shell structure loaded catalyst, which is characterized in that the core-shell structure loaded catalyst
Preparation method includes the following steps:
The first step, the preparation of iron oxide hollow sphere:
Ethyl orthosilicate is added in the beaker for filling dehydrated alcohol and is stirred, ammonium hydroxide is slowly added dropwise, after being added dropwise to complete, is continued
After stirring 2-3h, after being centrifuged, filtered, being washed, it is put into 60-80 DEG C of sufficiently dry 10-15h in baking oven, is transferred to Muffle furnace
Middle 400-500 DEG C of roasting 2-3h, is cooled to room temperature, clays into power, obtain silica nanosphere;By silica nanosphere plus
Enter to fill in the beaker of dehydrated alcohol, forms silica suspension after being ultrasonically treated 2-3h;Add in silica suspension
Enter ferric nitrate to stir evenly, ammonium hydroxide is slowly added dropwise, after being added dropwise to complete, continues to stir 2-3h, add 0.5mol/L hydrofluoric acid water
Solution is centrifuged mixed solution, is filtered, is washed after stirring 0.5-1h, is put into 60-80 DEG C of sufficiently dry 10- in baking oven
15h, 400-500 DEG C of roasting 2-3h in Muffle furnace, is cooled to room temperature, clays into power, obtain iron oxide hollow sphere;
Second step, Cu-Ni/Fe2O3The preparation of active component core-shell structure:
Dissolution in the beaker for filling deionized water is added in copper nitrate and nickel nitrate completely, to stir under 60-80 DEG C of water bath condition
And the ammonium bicarbonate aqueous solution of 1.5mol/L is slowly added dropwise, until gel occurs in solution, continues to stir 1-2h, obtain catalyst activity
Component precursor;Iron oxide hollow sphere is added in catalyst activity component precursor, is stirred after 0.5-1h to being sufficiently mixed
Uniformly, surfactant dodecyltrimethylammonium is added, continues after stirring 1-2h, obtained solution is poured into reaction kettle
It takes out, is cooled to room temperature after middle 160-180 DEG C of crystallization 1-2d, filter, washed with dehydrated alcohol, filter cake is put into 80- in baking oven
100 DEG C of sufficiently dry 10-15h, are transferred to 400-500 DEG C of roasting 3-4h in Muffle furnace, after being cooled to room temperature, clay into power,
Obtain Cu-Ni/Fe2O3Active component core-shell structure;
Third step, hydro-thermal method synthesize ZSM-5 molecular sieve:
Aluminum sulfate and sodium metasilicate are added in the beaker for filling deionized water, to being completely dissolved after stirring 0.5-1h, mixed
Solution;Composite mould plate agent is slowly added dropwise into mixed solution, after being added dropwise to complete, continues to stir 2-3h, obtains precursor solution;
Precursor solution is poured into reaction kettle and is taken out after 160-180 DEG C of crystallization 1-2d, after being cooled to room temperature, filters, uses deionized water
Washing, obtains filter cake;By filter cake after 80-100 DEG C of sufficiently dry 15-20h, after being put into 400-500 DEG C of roasting 3-4h of Muffle furnace,
It is cooled to room temperature, clays into power, obtain ZSM-5 molecular sieve;
4th step, the preparation of core-shell structure loaded catalyst:
Prepared core-shell structure and ZSM-5 molecular sieve are added in the beaker for filling deionized water, in 60-80 DEG C of water-bath
Under the conditions of stirring 0.5-1h to be sufficiently mixed uniformly;Polyethylene glycol solid is added to dissolving completely, it is molten that sodium bicarbonate is slowly added dropwise
Liquid continues to stir 2-3h, after placing 15-20h at room temperature, filter after being washed with dehydrated alcohol to after forming gel;It will filter
Cake after 80-100 DEG C of sufficiently dry 10-15h, is transferred in tube furnace 500-600 DEG C of roasting 2-3h under atmosphere of hydrogen in an oven,
10 DEG C/min of heating rate, obtains core-shell structure loaded catalyst.
2. a kind of preparation method of core-shell structure loaded catalyst according to claim 1, which is characterized in that the oxygen
Change each raw material composition and its parts by weight in iron hollow sphere preparation process: 30-40 parts of ethyl orthosilicates, 40-50 parts of dehydrated alcohols,
20-30 parts of ammonium hydroxide, 30-40 parts of ferric nitrates, 10-20 parts of 0.5mol/L hydrofluoric acid.
3. a kind of preparation method of core-shell structure loaded catalyst according to claim 1, which is characterized in that described
Cu-Ni/Fe2O3Each raw material composition and its parts by weight in active component core-shell structure preparation process: 10-20 parts of copper nitrates, 10-
20 parts of nickel nitrates, 30-40 parts of iron oxide, 5-10 parts of dodecyl trimethyl ammonium bromide, 40-50 parts of deionized waters.
4. a kind of preparation method of core-shell structure loaded catalyst according to claim 1, which is characterized in that described
Each raw material composition and its parts by weight in ZSM-5 molecular sieve preparation process: 15-30 parts of aluminum sulfate, 20-40 parts of sodium metasilicate, 30-40
Part composite mould plate agent, 40-50 parts of deionized waters.
5. a kind of preparation method of core-shell structure loaded catalyst according to claim 1, which is characterized in that the core
Each raw material composition and its parts by weight in shell structure loaded catalyst preparation process: 20-30 parts of Core-shell structure materials, 40-50
Part ZSM-5 molecular sieve, 10-20 parts of polyethylene glycol, 50-70 parts of deionized waters.
6. a kind of preparation method of core-shell structure loaded catalyst according to claim 1, which is characterized in that described multiple
Shuttering agent the preparation method is as follows:
Paraxylene and N- bromo-succinimide are added in dichloromethane solvent, it is to be mixed uniformly after, be added azo two
Isobutyronitrile initiator heats 4-5h under 60-80 DEG C of water bath, is filtered to remove unreacted N- bromo-succinimide, depressurizes
Solvent is distilled off, obtains mixture;Mixture and triethylamine are dissolved in petroleum ether solvent, potassium carbonate is added, 70-80 DEG C adds
Heat reflux 2-3h, filters after cooling, obtained mother liquor is concentrated under reduced pressure, and white solid is precipitated in removal, obtains composite mould plate agent.
7. a kind of preparation method of core-shell structure loaded catalyst according to claim 6, which is characterized in that described multiple
Each raw material composition and its parts by weight in shuttering agent preparation process: 10-20 parts of paraxylene, 15-20 parts of N- bromo succinyl
Imines, 40-50 part methylene chloride, 5-10 parts of azodiisobutyronitriles, 30-40 parts of triethylamines, 20-30 parts of petroleum ethers, 10-20 parts of carbon
Sour potassium.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910561499.6A CN110227537A (en) | 2019-06-26 | 2019-06-26 | A kind of preparation method of core-shell structure loaded catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910561499.6A CN110227537A (en) | 2019-06-26 | 2019-06-26 | A kind of preparation method of core-shell structure loaded catalyst |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110227537A true CN110227537A (en) | 2019-09-13 |
Family
ID=67857381
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910561499.6A Withdrawn CN110227537A (en) | 2019-06-26 | 2019-06-26 | A kind of preparation method of core-shell structure loaded catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110227537A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111082008A (en) * | 2019-12-14 | 2020-04-28 | 浙江农林大学 | Preparation method of nanocellulose/zinc oxide compound for electrochemical energy storage |
CN114163317A (en) * | 2021-12-10 | 2022-03-11 | 江西永通科技股份有限公司 | Preparation method of p-hydroxyacetophenone |
CN114853584A (en) * | 2022-04-20 | 2022-08-05 | 江西永通科技股份有限公司 | Preparation method of 2-chloro-1- (1-chlorocyclopropyl) ethanone |
CN115159584A (en) * | 2022-07-07 | 2022-10-11 | 重庆邮电大学 | Preparation method of nickel-induced hollow walnut-shaped/spherical ferric oxide |
CN115228874A (en) * | 2022-05-25 | 2022-10-25 | 海南省智慧环境投资控股有限公司 | Dynamic circulation organic solid waste treatment process |
-
2019
- 2019-06-26 CN CN201910561499.6A patent/CN110227537A/en not_active Withdrawn
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111082008A (en) * | 2019-12-14 | 2020-04-28 | 浙江农林大学 | Preparation method of nanocellulose/zinc oxide compound for electrochemical energy storage |
CN114163317A (en) * | 2021-12-10 | 2022-03-11 | 江西永通科技股份有限公司 | Preparation method of p-hydroxyacetophenone |
CN114853584A (en) * | 2022-04-20 | 2022-08-05 | 江西永通科技股份有限公司 | Preparation method of 2-chloro-1- (1-chlorocyclopropyl) ethanone |
CN115228874A (en) * | 2022-05-25 | 2022-10-25 | 海南省智慧环境投资控股有限公司 | Dynamic circulation organic solid waste treatment process |
CN115228874B (en) * | 2022-05-25 | 2023-12-29 | 海南省智慧环境投资控股有限公司 | Dynamic circulation organic solid waste treatment process |
CN115159584A (en) * | 2022-07-07 | 2022-10-11 | 重庆邮电大学 | Preparation method of nickel-induced hollow walnut-shaped/spherical ferric oxide |
CN115159584B (en) * | 2022-07-07 | 2023-06-06 | 重庆邮电大学 | Preparation method of nickel-induced hollow walnut-shaped/spherical ferric oxide |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110227537A (en) | A kind of preparation method of core-shell structure loaded catalyst | |
Sun et al. | The state-of-the-art synthetic strategies for SAPO-34 zeolite catalysts in methanol-to-olefin conversion | |
CN103979570B (en) | The synthetic method of a kind of novel ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve | |
CN104030314B (en) | A kind of ZSM-5 Quito level porous molecular sieve material and preparation method thereof | |
CN108002402B (en) | A kind of middle micro-diplopore MFI type nano molecular sieve and its preparation method and application with multi-layer steamed bread shape pattern | |
CN107715843B (en) | Method for rapidly synthesizing mesoporous and microporous ZIF-8 material at normal temperature | |
CN104525245A (en) | Nanocrystalline accumulation meso-microporous ZSM-5 catalyst and preparation and application | |
CN103626202A (en) | Method for preparing catalyst used for methanol/dimethyl ether high selectivity propylene preparation | |
CN104043477A (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
CN103214006A (en) | Preparation method of composite zeolite with core/shell structure | |
CN110217804B (en) | ZSM-5 molecular sieve and preparation method thereof, hydrogen type ZSM-5 molecular sieve and application thereof, and methanol conversion method | |
CN110227456A (en) | MOFs derives two-dimensional multistage hole Cu/C composite material and preparation method | |
CN104944411B (en) | Method for preparing nano mesoporous carbon microspheres by adopting soft template | |
CN104326484B (en) | A kind of molecular sieve nanotube aeroge and preparation method thereof | |
CN105435848B (en) | A kind of zeolite catalyst | |
CN104229827A (en) | Mesoporous-microporous dual-porous ZSM-5 molecular sieve as well as preparation method and application thereof | |
CN110156038B (en) | Microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve and preparation method and application thereof | |
CN109399660A (en) | Multi-stage porous Beta molecular sieve, multi-stage porous Beta molecular sieve Ca-Ni type catalyst and preparation method | |
CN112250877B (en) | Hierarchical pore ZIF-67 material and synthetic method thereof | |
CN103285844B (en) | Method taking lignin as template to synthetize mesoporous TiO2 photocatalyst | |
CN106268928A (en) | A kind of synthetic method of ordered big hole-mesoporous-micropore multi-stage porous catalyst | |
CN102040470A (en) | Method for preparing low carbon alcohol by using synthesis gas | |
CN107051589A (en) | A kind of method of the short mesoporous molecular sieve catalytic biodiesel synthesis of DCNH Zr SBA 15 | |
Chen et al. | A green and efficient strategy for utilizing of coal fly ash to synthesize K-MER zeolite as catalyst for cyanoethylation and adsorbent of CO2 | |
CN110586198A (en) | Hierarchical porous macroporous-mesoporous gamma-Al2O3Catalyst carrier material and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190913 |
|
WW01 | Invention patent application withdrawn after publication |