CN111871447A - 一种Au/Ti-S催化剂及其制备方法与应用 - Google Patents
一种Au/Ti-S催化剂及其制备方法与应用 Download PDFInfo
- Publication number
- CN111871447A CN111871447A CN202010834766.5A CN202010834766A CN111871447A CN 111871447 A CN111871447 A CN 111871447A CN 202010834766 A CN202010834766 A CN 202010834766A CN 111871447 A CN111871447 A CN 111871447A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- titanium
- composite material
- based composite
- reaction
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 229910004338 Ti-S Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 25
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 7
- 229910004042 HAuCl4 Inorganic materials 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- -1 aminoalkyl siloxane Chemical class 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 150000003608 titanium Chemical class 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 229910000104 sodium hydride Inorganic materials 0.000 claims 1
- 239000012312 sodium hydride Substances 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 52
- 229910052737 gold Inorganic materials 0.000 description 28
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002444 silanisation Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QMGLMRPHOITLSN-UHFFFAOYSA-N 2,4-dimethyloxolane Chemical compound CC1COC(C)C1 QMGLMRPHOITLSN-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 238000001889 high-resolution electron micrograph Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种Au/Ti‑S催化剂及其制备方法与应用,所述催化剂以金属Au为活性中心,以钛基复合材料为载体,化学通式可表述为Au/Ti‑S,其中,Ti‑S代表钛基复合材料,S为硅材料载体,所述催化剂组成中Au的重量比为0.1%~4%,余量为钛基复合材料载体,所述钛基复合材料为将钛以钛氧四面体嵌入氧化硅骨架得到的多孔材料,其中孔径范围为0.5~100nm。所述催化剂制备过程为:首先制备钛基复合材料Ti‑S,然后合成氨基修饰的钛基复合材料Ti‑S‑Amino,最后将Ti‑S‑Amino、水和HAuCl4混合搅拌均匀后加入硼氢化钠溶液进行反应,制备出Au/Ti‑S催化剂。本发明所提供的催化剂运用于催化丙烯环氧化反应,具有贵金属负载量小,成本低,反应条件温和,转化率高及选择性好等优点。
Description
技术领域
本发明属于催化技术领域,具体涉及一种Au/Ti-S催化剂及其制备方法与应用。
背景技术
环氧丙烷PO是最重要的基础化工原料之一,广泛用于合成聚醚多元醇、丙二醇、丙二醇醚、聚氨酯、表面活性剂、破乳剂、乳化剂、湿润剂、润滑剂、增塑剂、阻燃剂等下游产品,应用领域广泛分布于化工、轻工业、食品、纺织、医药、化妆品、汽车等行业。目前,PO的工业生产方法包括氯醇法、共氧化法和直接氧化法。其中,氯醇法和共氧化法是全球主要生产工艺,约占总产能90%。氯醇法后期处理成本较高,反应过程中生成的次氯酸对装置具有一定的腐蚀作用,此工艺正在被削减;共氧化法生产PO存在产物难以分离和提纯等缺点。以O2作为氧化剂直接氧化丙烯生产PO是非常具有吸引力的途径,但目前的催化剂体系仍存在因为深度氧化反应显著导致选择性低下的缺点。在氧化反应体系中引入适量的氢气已被发现能够大大提高PO选择性至90%以上,因此氢氧共存体系下的丙烯环氧化被认为具有良好的工业前景。
氢氧共存体系丙烯环氧化的催化剂体系主要是负载型贵金属催化剂,包括有Au、Pd-Pt和Ag基催化剂。其中,Au催化剂效率最佳,是最有应用前景的一类。制备相关Au催化剂的传统方法是沉积-沉淀法,即在引入金源氯金酸后使用NaOH等碱性物质调节pH值至一定值,使金化合物以微小纳米颗粒沉积至载体表面。使用沉积-沉淀法制备Au催化剂,金的利用效率非常低,以氯金酸形式加入体系中的金仅有不足5%能够沉积到载体上,余下的金需要进行回收再利用;此外,这种方法制备的催化剂对于制备条件要求非常苛刻,微小的变化都会带来催化性能的巨大波动,制备的重现性很擦,这一点非常不利于工业催化剂的生产。以上这些不利因素严重阻碍了工业化应用的开展,迫切需要开发出能够可靠地制备高性能、稳定性优异的金基催化剂的方法。
发明内容
本发明的目的在于提供一种Au/Ti-S催化剂及其制备方法与应用,本发明的解决方案是:
一种Au/Ti-S催化剂,所述催化剂以金属Au为活性中心,以钛基复合材料为载体,化学通式可表述为Au/Ti-S,其中,Ti-S代表钛基复合材料,载体S为MCF、SBA-15、TS-1或3D-SiO2中的一种,所述催化剂组成中Au的重量比为0.1%~4%,余量为钛基复合材料载体。
优选地,所述催化剂中钛基复合材料为囊泡状大尺寸多孔材料,其孔径为20~100nm。
Au/Ti-S催化剂的制备方法,具体步骤如下:
1)往四乙基氢氧化铵水溶液中加入丙三醇剧烈搅拌均匀后加入钛酸丁酯,所得混合物继续搅拌制得含钛混合溶液;
2)往步骤1)中制得的含钛混合溶液中加入干燥的载体S剧烈搅拌反应后进行高温静置,然后往所得混合物加水,离心分离收集所得固体,将所得固体干燥后进行焙烧制得钛基复合材料Ti-S;
3)将步骤2)中制得的钛基复合材料Ti-S与无水乙醇混合后加入氨烷基硅氧烷进行搅拌加热回流反应,然后往所得混合物中加乙醇,离心分离收集所得固体;将所得固体干燥后制得氨基修饰的钛基复合材料Ti-S-amino;
4)将步骤3)中制得的氨基修饰的钛基复合材料Ti-S-amino、水和HAuCl4混合搅拌均匀后搅拌下加入硼氢化钠溶液进行反应,然后离心分离收集所得固体,将所得固体干燥后即可制得所述Au/Ti-S催化剂。
优选地,步骤2)中所述的剧烈搅拌反应时间为12h;所述的高温静置条件为100~170℃,静置18~72h;所述的焙烧温度为500~770℃,焙烧时间为4~10h。
优选地,步骤3)中所述的钛基复合材料Ti-S与氨烷基硅氧烷的质量比为1:2.5。
优选地,步骤3)中所述的加热回流反应温度为90℃,加热回流反应时间为24h;所述的干燥温度为70℃,所述干燥时间为24h。
优选地,步骤4)中所述的Ti-S-amino、HAuCl4和硼氢化钠质量比为500:1:20~500:40:100。
优选地,步骤4)中所述的干燥温度为100℃,所述干燥时间为12h。
Au/Ti-S催化剂在催化丙烯环氧化中的应用,具体步骤如下:以丙烯、氢气和氧气为原料,氮气为稀释气体,Au/Ti-S为催化剂,反应温度为80~240℃,反应压力为1atm,反应空速为2000~15000mL h-1gcat -1。
本发明的原理是:本发明首先通过水热合成法制备一系列比表面积和孔径分布不同的大尺寸多孔氧化硅材料,所制备的氧化硅材料属于具有蜂窝状结构、超大孔径、高孔隙率的多孔材料;使用它们作为催化剂载体对反应底物和产物分子的扩散及传质具有优异的促进性能。其次,本发明还采用接枝法让载体与钛酸丁酯反应,往载体中高分散植入Ti元素,成功合成出具有3D结构的囊泡状新型钛硅复合材料Ti-MCF。在所合成的钛硅复合材料中金属Ti主要以四配位形式存在,几乎没有发现六配位钛和TiO2物相,而四配位的Ti有利于在催化丙烯环氧化反应中产物PO的生成。最后,通过将载体表面氨基官能团化-还原沉淀沉积法(包含硅烷化试剂修饰改性载体表面和NaBH4还原沉积金纳米粒子两个步骤),制备出高性能的丙烯环氧化Au/Ti-MCF催化剂。所制备的催化剂所具有独特的3D囊泡状大尺寸孔道结构、微弱的表面酸性、硅烷化试剂修饰后增强的表面憎水性都在不同程度上促进了环氧丙烷产物的快速脱附和内扩散,有效避免了难挥发沉积物的生成和活性位的覆盖,从而提升了催化剂的活性及稳定性。
在丙烯环氧化的催化反应过程中,O2和H2分子首先在Au纳米粒子表面原位反应产生过氧化氢中间体,随后过氧化氢快速转移并吸附到邻近的四配位骨架Ti活性位点上形成Ti-OOH物种,该物种进而与丙烯分子反应最终生成PO产物。
相对于现有的催化丙烯环氧化催化剂,本发明的优点如下:
1)本发明所提供的Au/Ti-S催化剂中活性中心Au和四配位的Ti协同分工作用,提高了催化剂的活性及PO的选择性,降低了生产成本。
2)本发明所提供的制备Au/Ti-S催化剂的方法通过将载体表面氨基官能团化和还原沉淀沉积法引入到制备过程中,具体包含使用硅烷化试剂修饰改性载体表面和使用NaBH4还原沉积金纳米粒子两个步骤,大大提高了活性组分金在载体表面的锚定效率和分散效果,显著降低了活性组分贵金属的用量,这样可极大地降低催化剂的生产成本,有利于大规模商业化应用。此外,本发明所提供的催化剂的制备方法还具有重复性好、催化性能佳的优点。
3)本发明所提供的催化剂用于催化丙烯环氧化反应中,反应条件温和,操作简单,具有优异的稳定性。
附图说明
图1MCF材料的高分辨电镜图;
图2催化剂0.5%Au/Ti-MCF的HR-TEM电镜图;
图3载体Ti-MCF的固体紫外漫反射光谱图;
图4载体Ti-MCF的FT-IR光谱图;
图5载体Ti-MCF的Raman光谱图。
具体实施方式
下面进一步结合实施例以详细说明本发明。同样应理解,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,示例中具体的质量、反应时间和温度、工艺参数等也仅是合适范围中的一个示例,本领域的技术人员根据本发明的上述内容做出的一些非本质的改进和调整均属于本发明的保护范围。实施例中未注明具体技术或条件者,均为按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者,均为可以通过市场购买的常规产品。
在所有的实施例中,转化率和选择性的计算方法如下:
丙烯转化率(%)=(反应前丙烯的摩尔数-反应后丙烯的摩尔数)/反应前丙烯的摩尔数*100%
环氧丙烷(PO)选择性(%)=生成的环氧丙烷摩尔数/反应的丙烯摩尔数*100%
氢气效率定义成产物PO的生成量与氢气总消耗量之间的比值。
实施例1
载体MCF的制备步骤如下:往75ml 1.6mol/L盐酸中加入2.0g P123表面活性剂,完全溶解后加入4.0g均三甲苯(TMB),搅拌溶解,往所得溶液中滴加4.4g正硅酸乙酯(TEOS);然后将所得混合物在35℃下加热搅拌24h制得充分水解的硅溶胶,往所制备的硅溶胶中加入50mg的NH4F;转移至水热釜中,在100℃水热晶化48h。将水热产物离心分离,洗涤直至上层清液pH=7,收集所得固体。将所得固体在110℃干燥12h,在空气中以2℃/min的程升速率升高至550℃焙烧6h,后即可制得载体MCF。
Au/Ti-MCF催化剂的制备步骤如下:
(1)往12.5ml四乙基氢氧化铵(TEAOH)水溶液加入50ml丙三醇中,剧烈搅拌30min后,加入700uL钛酸丁酯(TBOT),继续搅拌2h制得含钛混合溶液;
(2)往步骤(1)中制得的含钛混合溶液中加入干燥的载体MCF剧烈搅拌反应12h后在100℃下静置72h,然后往所得混合物加去离子水,离心分离收集所得固体,将所得固体在110℃干燥12h,在空气中以1℃/min的程升速率升高至500℃焙烧4h制得钛基复合材料,记为Ti-MCF;
(3)将1g步骤(2)中制得的钛基复合材料Ti-MCF与50ml无水乙醇混合后加入2.52g3-氨丙基三乙氧基硅烷,所得反应混合物在90℃搅拌加热回流反应24h,然后往所得混合物中加乙醇,离心分离收集所得固体;将所得固体在70℃干燥24h后制得氨基修饰的钛基复合材料,记为Ti-MCF-amino;
(4)将0.50g步骤(3)制得到的Ti-MCF-amino和525L 4.783mg mL-1HAuCl4加入到50mL去离子水中;搅拌均匀后,超声10min后加入由50mg硼氢化钠和20mL去离子水组成的溶液,将所得混合物老化30min,在充分还原[AuCl4]-离子后以10000r/min的离心速率离心10min,重复多次,直至上层清液检测不到Cl-为止;将所得到的固体100℃下干燥后即可制得所述Au/Ti-MCF,记为0.5%Au/Ti-MCF。
催化剂表征结果:
图1为载体MCF的高倍透射电子显微镜(HR-TEM)图,从图中可以清晰地观察到所合成载体MCF(mesocellular foam silica)材料具有无序的蜂窝状介孔泡沫3D结构,孔道大而明显;仔细观察还可以看出MCF材料中的三维孔道结构的球形孔室是由小孔径窗口连通组成。
从图2a可以看出0.5%Au/Ti-MCF催化剂具有明显的泡沫状结构,纳米金粒子的尺寸较小且呈高度分散的状态;从图2b中可以看出采用传统沉淀沉积法制备的4%Au/Ti-MCF-DP催化剂(合成和表征见对比例2)中可见的Au纳米粒子数量明显少于0.5%Au/Ti-MCF。Au是丙烯环氧化反应的主要活性金属,金含量低导致有效活性位数量少反应活性差,这与两者的催化性能结果相吻合(见表1)。
图3所示为MCF基载体和Ti-MCF的固体紫外漫反射的谱图,Ti-MCF载体在210nm附近都出现了一个明显的吸收峰,可归属于四配位的骨架钛物种的吸收峰。260-270nm处肩峰归属于四配位的骨架钛经水合作用形成的六配位或八配位的钛物种,但本材料中并没有观察到该特征峰。
图4为载体Ti-MCF的FT-IR光谱图,FT-IR光谱能够有效表征钛是否进入氧化硅骨架中:图4中位于960cm-1处的特征吸收峰被认为是四配位骨架钛(Si-O-Ti-O-Si化学键)的伸缩振动吸收峰。
在图5载体Ti-MCF的Raman谱图中,808及917cm-1处的特征峰可归属于Si-O-Si的振动吸收峰;而495、532及1084cm-1处的特征峰一般认为是四配位骨架钛物种的特征吸收峰。
催化剂考评条件:催化剂活性评价在常压固定床装置上进行,催化剂置于内径为8mm的石英反应管,外部使用管式电炉加热,两路反应原料气通过质量流量计精准控制经在线混合后通过催化剂床层。反应气体组成为C3H6:H2:O2:N2=1:1:1:7(体积比),空速为10000mL·gcat·h-1,催化剂为0.5%Au/Ti-MCF。反应尾气由加热带110℃全程保温,流经两台气相色谱仪进行在线分析;其中Aglient 7890A气相氢焰色谱仪配置有30m长FFAP毛细柱,主要用于分析各种有机物质,如丙烯、环氧丙烷、乙醛、丙醛、丙酮、丙烯醛;GC2060气相热导色谱仪配置有双色谱柱检测器:5A色谱柱(3米)和Porapak-Q(3米),主要用来分析C3H6、N2、O2、H2和CO2,两台色谱通过丙烯进行关联分析。考评结果见表1。
实施例2
载体SBA-15的制备步骤如下:将12.0g P123溶解于去离子水,加入60mL的浓盐酸;向上述溶液中滴加27.6mL的TEOS;将所得混合溶液在38℃下加热搅拌24h后转移至水热釜中在100℃水热晶化48h。将水热产物离心分离,洗涤直至上层清液pH=7,收集所得固体。将所得固体在110℃干燥12h,在空气中以2℃/min的程升速率升高至550℃焙烧8h后即可制得载体SBA-15。
催化剂0.5%Au/Ti-SBA-15的制备与实施例1类似,不同之处在于将MCF换为SBA-15,其余条件相同。
催化剂考评条件参照实施例1,考评结果见表1。
实施例3
载体TS-1分子筛的制备步骤如下:将2g吐温20加入到35ml去离子水在30℃油浴搅拌10min后,加入12.7ml四丙基氢氧化铵(TPAOH),再以0.5滴/秒的速率滴加24.6ml的TEOS,水解反应1h。然后以0.25滴/秒的速率滴加由异丙醇20ml和TBOT 1.1ml组成的混合溶液,滴加完再加入4.6g TPAOH反应1h;所得混合物在170℃下水热晶化18h。将水热产物离心分离,收集所得固体。将所得固体在110℃干燥24h,然后在空气中以2℃/min的程升速率升高至550℃焙烧5h后即可制得载体TS-1分子筛。
催化剂0.5%Au/Ti-TS-1的制备与实施例1类似,不同之处在于将MCF换为TS-1,其余条件相同。
催化剂考评条件参照实施例1,考评结果见表1。
实施例4
载体3D-SiO2的制备步骤如下:将2.1g TBOT滴加到20.8g TEOS中搅拌混合后滴加29.8g三乙醇胺和19.8g去离子水,所得混合物进一步搅拌2h后再滴加14.7g TEAOH;将所得溶液在室温下静置24h后在100℃下烘干15-20h;将所得固体在空气氛下以1℃/min升温至700℃焙烧10h后即可制得载体。
催化剂0.5%Au/3D-Ti-SiO2的制备与实施例1类似,不同之处在于将MCF换为3D-SiO2,其余条件相同。
催化剂考评条件参照实施例1,考评结果见表1。
实施例5
将实施例1中步骤(4)中的525L 4.783mg mL-1HAuCl4换成105L 4.783mg mL-1,其余条件相同,即可制得本例催化剂,记为0.1%Au/Ti-MCF。
催化剂考评条件参照实施例1,考评结果见表1。
对比例1
载体TS-1分子筛的制备步骤参照实施例3。
催化剂4%Au/TS-1-DP的制备步骤如下:
将8ml 4.783mg mL-1氯金酸溶液加入80ml去离子水中,加热至60℃;缓慢滴加0.1M NaOH溶液使溶液pH=7.0±0.1;然后往得到的溶液中加入1g TS-1载体,再次调节pH至7.0±0.1,在60℃下继续搅拌1.5h;将所得混合物抽滤,分别用去离子水和无水乙醇洗涤;将所得固体在100℃下干燥12h后转至马弗炉300℃焙烧4h,即可得到本例催化剂,记4%Au/TS-1-DP。
催化剂考评条件参照实施例1,考评结果见表1。
对比例2
载体Ti-MCF的制备步骤参照实施例1。
催化剂4%Au/Ti-MCF-DP的制备步骤与对比例1类似,不同之处在于将TS-1换成Ti-MCF,其余条件相同,即可得到本例催化剂,记为4%Au/Ti-MCF-DP。
催化剂考评条件参照实施例1,考评结果见表1。
对比例3
催化剂4%Au/TiO2-DP的制备步骤与对比例1类似,不同之处在于将TS-1换成TiO2,其余条件相同,即可得到本例催化剂,记为4%Au/TiO2-DP。
催化剂考评条件参照实施例1,考评结果见表1。
表1各种催化剂用于丙烯环氧化的催化活性
实施例 | 丙烯转化率(%) | PO选择性(%) | 氢气效率(%) |
1 | 3.15 | 95.5 | 24.5 |
2 | 1.13 | 88.5 | 19.3 |
3 | 2.38 | 91.7 | 19.2 |
4 | 0.89 | 69.5 | 14.5 |
5 | 2.08 | 92.5 | 19.4 |
对比例1 | 0.63 | 86.2 | 18.7 |
对比例2 | 0.86 | 83.2 | 16.5 |
对比例3 | 0.26 | 84.6 | 10.8 |
反应条件:催化剂填充量:0.15g,140℃,常压,V(C3H6)/V(H2)/V(O2)/V(N2)=1/1/1/7(vol%),空速=10000mL h-1gcat -1
从表1可以看出:除了实施例4中的3D-Ti-Si-O载体因骨架中钛物种分布不均匀的原因外,经由表面氨基官能团化-化学还原沉积法制备的三种金催化剂对丙烯环氧化都有着较好的催化活性,反应产物都以PO为主。其中孔径较大的催化剂Au/Ti-MCF有利于产物PO的脱附和提高外扩散速率,从而减少二次副反应发生的概率并提高PO选择性。由对比例1-3可以看出:采用传统沉积-沉淀法(DP)制备的催化剂,虽然PO选择性可达到80%,但转化率却很低,不到1%。
Claims (9)
1.一种Au/Ti-S催化剂,其特征在于:所述催化剂以金属Au为活性中心,以钛基复合材料为载体,化学通式可表述为Au/Ti-S,其中,Ti-S代表钛基复合材料,载体S为MCF、SBA-15、TS-1或3D-SiO2中的一种,所述催化剂组成中Au的重量比为0.1%~4%,余量为钛基复合材料载体。
2.如权利要求1所述的Au/Ti-S催化剂,其特征在于,所述催化剂中钛基复合材料为多孔材料,其孔径为0.5~100nm。
3.一种如权利要求1所述的Au/Ti-S催化剂的制备方法,其特征在于,具体步骤如下:
1)往四乙基氢氧化铵水溶液中加入丙三醇剧烈搅拌均匀后加入钛酸丁酯,所得混合物继续搅拌制得含钛混合溶液;
2)往步骤1)中制得的含钛混合溶液中加入干燥的载体S剧烈搅拌反应后进行高温静置,然后往所得混合物加水,离心分离收集所得固体,将所得固体干燥后进行焙烧制得钛基复合材料Ti-S;
3)将步骤2)中制得的钛基复合材料Ti-S与无水乙醇混合后加入氨烷基硅氧烷进行搅拌并加热回流反应,然后往所得混合物中加乙醇,离心分离收集所得固体;将所得固体干燥后制得氨基修饰的钛基复合材料Ti-S-amino;
4)将步骤3)中制得的氨基修饰的钛基复合材料Ti-S-amino、水和HAuCl4混合搅拌均匀后搅拌下加入硼氢化钠溶液进行反应,然后离心分离收集所得固体,将所得固体干燥后即可制得所述Au/Ti-S催化剂。
4.如权利要求3所述的Au/Ti-S催化剂的制备方法,其特征在于,步骤2)中所述的剧烈搅拌反应时间为12h;所述的高温静置条件为100~170℃,静置18~72h;所述的焙烧温度为500~770℃,焙烧时间为4~10h。
5.如权利要求3所述的Au/Ti-S催化剂的制备方法,其特征在于,步骤3)中所述的钛基复合材料Ti-S与氨烷基硅氧烷的质量比为1:2.5。
6.如权利要求3所述的Au/Ti-S催化剂的制备方法,其特征在于,步骤3)中所述的加热回流反应温度为90℃,加热回流反应时间为24h;所述的干燥温度为70℃,所述干燥时间为24h。
7.如权利要求3所述的Au/Ti-S催化剂的制备方法,其特征在于,步骤4)中所述的Ti-S-Amino、HAuCl4和硼氢化钠质量比为500:1:20~500:40:100。
8.如权利要求3所述的Au/Ti-S催化剂的制备方法,其特征在于,步骤4)中所述的干燥温度为100℃,所述干燥时间为12h。
9.一种如权利要求1所述的Au/Ti-S催化剂在催化丙烯环氧化中的应用,其特征在于,具体步骤如下:以丙烯、氢气和氧气为原料,氮气为稀释气体,Au/Ti-S为催化剂,反应温度为80~240℃,反应压力为1atm,反应空速为2000~15000mL h-1gcat -1。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010834766.5A CN111871447A (zh) | 2020-08-19 | 2020-08-19 | 一种Au/Ti-S催化剂及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010834766.5A CN111871447A (zh) | 2020-08-19 | 2020-08-19 | 一种Au/Ti-S催化剂及其制备方法与应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111871447A true CN111871447A (zh) | 2020-11-03 |
Family
ID=73202944
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010834766.5A Pending CN111871447A (zh) | 2020-08-19 | 2020-08-19 | 一种Au/Ti-S催化剂及其制备方法与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111871447A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114713212A (zh) * | 2022-03-11 | 2022-07-08 | 华东理工大学 | 用于丙烯氢氧环氧化制备环氧丙烷的钛硅材料及制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1247575B1 (en) * | 1999-12-28 | 2007-06-20 | Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdeleniya Rossiiskoj Akademii Nauk | Silica-rich carrier, catalyst for heterogeneous reactions and method for the production thereof |
CN101367049A (zh) * | 2008-10-10 | 2009-02-18 | 厦门大学 | 一种丙烯气相环氧化制环氧丙烷的催化剂及其制备方法 |
EP2205578A1 (en) * | 2007-10-24 | 2010-07-14 | Lyondell Chemical Technology, L.P. | Direct epoxidation process using improved catalyst composition |
CN102895994B (zh) * | 2011-07-27 | 2014-12-31 | 中国石油化工股份有限公司 | Ti-SBA-15分子筛及改性Ti-SBA-15分子筛及其和环氧丙烷的制备方法 |
-
2020
- 2020-08-19 CN CN202010834766.5A patent/CN111871447A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1247575B1 (en) * | 1999-12-28 | 2007-06-20 | Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdeleniya Rossiiskoj Akademii Nauk | Silica-rich carrier, catalyst for heterogeneous reactions and method for the production thereof |
EP2205578A1 (en) * | 2007-10-24 | 2010-07-14 | Lyondell Chemical Technology, L.P. | Direct epoxidation process using improved catalyst composition |
CN101367049A (zh) * | 2008-10-10 | 2009-02-18 | 厦门大学 | 一种丙烯气相环氧化制环氧丙烷的催化剂及其制备方法 |
CN102895994B (zh) * | 2011-07-27 | 2014-12-31 | 中国石油化工股份有限公司 | Ti-SBA-15分子筛及改性Ti-SBA-15分子筛及其和环氧丙烷的制备方法 |
Non-Patent Citations (1)
Title |
---|
顾正强: "氢氧共存条件下Au/Ti-MCF催化剂用于丙烯气相环氧化的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114713212A (zh) * | 2022-03-11 | 2022-07-08 | 华东理工大学 | 用于丙烯氢氧环氧化制备环氧丙烷的钛硅材料及制备方法 |
CN114713212B (zh) * | 2022-03-11 | 2024-02-06 | 华东理工大学 | 用于丙烯氢氧环氧化制备环氧丙烷的钛硅材料及制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Chen et al. | Encapsulating uniform Pd nanoparticles in TS-1 zeolite as efficient catalyst for catalytic abatement of indoor formaldehyde at room temperature | |
CN100398448C (zh) | 花状结构的纳米氧化铈材料及其制备方法和用途 | |
CN106457229A (zh) | 在沸石和类沸石中引入金属纳米粒子的通用方法 | |
CN109926060B (zh) | 一种核-壳结构纳米铜铈复合氧化物催化剂、制备方法与应用 | |
CN107855123B (zh) | 一种Pd/SiO2@Al2O3纳米晶材料及其制备方法、应用 | |
CN107020147A (zh) | 一种封装金属氧化物或金属纳米颗粒的mfi结构片层状分子筛催化剂、其制备方法及用途 | |
CN107754826B (zh) | 一种直接合成过氧化氢用中空核壳结构Pd催化剂及其制备方法 | |
CN113385217B (zh) | 一种用于低浓度甲烷催化燃烧的钯基核壳结构催化剂及其制备方法 | |
CN105772027A (zh) | 一种负载型四氧化三钴催化剂及其制备方法和应用 | |
CN109078642B (zh) | 一种花型纳米金复合金属氧化物催化剂及其制备方法和应用 | |
CN105478019B (zh) | 一种复合金属氢气分离膜及其制备方法和应用 | |
CN113145163A (zh) | 一种全硅分子筛负载钯的甲烷氧化催化剂及其制备方法 | |
CN111871447A (zh) | 一种Au/Ti-S催化剂及其制备方法与应用 | |
CN102909034B (zh) | 一种担载型金镍合金纳米催化剂的制备 | |
EP1776187A1 (en) | Supported gold catalysts | |
CN111841623A (zh) | 分子筛催化剂及其制备方法及用途 | |
CN109174092B (zh) | 一种氧化锌/铂复合材料微球及其制备方法和应用 | |
CN112108145A (zh) | 一种氧化铝负载铱团簇催化剂及其制备与应用 | |
CN113083299A (zh) | Yolk-shell双功能催化剂及其制备方法和在葡萄糖氢解制备乙二醇中的应用 | |
CN110721685A (zh) | 一种复合光催化材料及其制备方法和应用 | |
CN102407153A (zh) | 一种增加催化剂酸性的纳米金催化剂的制备方法 | |
CN109482184A (zh) | 一种草酸二甲酯加氢合成乙二醇催化剂制备方法 | |
CN108579784A (zh) | 一种助催化剂高度分散于蜂巢状氮化碳空腔内的制备方法 | |
CN109433206B (zh) | 具有中心辐射状孔道介孔氧化硅负载铜催化剂制备方法 | |
CN110116018B (zh) | 一种包覆贵金属的硅分子筛催化材料及其制备方法 |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201103 |