WO2020024923A1 - 纳米笼限域催化剂、制备方法及应用 - Google Patents
纳米笼限域催化剂、制备方法及应用 Download PDFInfo
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- WO2020024923A1 WO2020024923A1 PCT/CN2019/098304 CN2019098304W WO2020024923A1 WO 2020024923 A1 WO2020024923 A1 WO 2020024923A1 CN 2019098304 W CN2019098304 W CN 2019098304W WO 2020024923 A1 WO2020024923 A1 WO 2020024923A1
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- catalyst
- salen1
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- nanocage
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/32—Gallium
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Definitions
- the invention relates to a nanocage limited-area catalyst, a preparation method and an application thereof.
- Ethylene glycol is an important organic chemical raw material and intermediate. It is mainly used in the production of polyester fibers, bottle resins, films, engineering plastics, antifreeze and coolants. It is also widely used in the production of plasticizers, desiccants, Raw materials such as lubricants have a wide range of uses (Guangdong Chemical Industry, 2011, 38: 242). As of 2015, the global annual demand for ethylene glycol reached more than 28 million tons (http://www.shell.com/business-customers/chemicals/factsheets-speeches-and-articles/factsheets/mono-ethylene-glycol. html). At present, ethylene glycol is mainly produced by direct hydration of ethylene oxide in the industry.
- the technology requires a reaction at 190-200 ° C, greater than 1.9 MPa, and a molar ratio of water to ethylene oxide (water ratio for short) of 22-25: 1. Under the conditions, this makes the water content in the product as high as 85 wt.% Or more.
- the invention aims to provide a catalyst with high activity, low water ratio and short reaction time, which has high activity for alkane oxide hydration to produce diol and does not require activation, and has good recycling performance, and a preparation method thereof to solve the existing problems.
- the catalyst for the hydration of alkylene oxide to diol has the problems of high water ratio required and good circulation of the activated side.
- the catalyst provided by the present invention has high activity for diols produced by hydration of alkylene oxide under high and low water ratios and short reaction times, and has good recyclability without activation; the preparation method provided by the present invention is simple It is feasible, which can provide reference for the synthesis of other nanocage confined catalysts.
- the present invention provides a nanocage confined catalyst, and the catalyst expression is:
- NC is a material with a nanocage structure
- M (Salen1) X of the subexpression (I-1) and M '(Salen2) of the subexpression (I-2) are the active centers, respectively; each occurrence of M is independent Ground is selected from Co ions, Fe ions, Ga ions, Al ions, Cr ions and mixtures thereof; each occurrence of M ′ is independently selected from Cu ions, Ni ions and mixtures thereof; m is 0-100; n is 0- 100, provided that at least one of m and n is not 0; each occurrence of Salen1 and Salen2 is a Shiff base derivative independently; X is an axial anion selected from substituted or unsubstituted acetate, substituted or unsubstituted the tosylate, a substituted or unsubstituted benzoate, halogen anion (e.g. F -, Cl -, Br - , I -), SbF 6 -, PF
- each occurrence of M is independently selected from Fe3 + , Ga3 + , Al3 + , Cr3 +, and mixtures thereof.
- each occurrence of M ' is independently selected from Cu2 + , Ni2 +, and mixtures thereof.
- m and n are integers used to represent the number of active center species in the sub-expressions (I-1) and (I-2) of the catalyst.
- the catalyst may be NC-2 [M (Salen1) X] -1 [M '(Salen2)], which means that the catalyst consists of 2 different formulas (I-1)
- the active center is combined with one active center in formula (I-2), for example, NC-1 [Fe (Salen1) OAc] -1 [Ga (Salen1) OTs] -1 [Cu (Salen2)], which represents [ Fe (Salen1) OAc], [Ga (Salen1) OTs], and [Cu (Salen2)] are used together in three active centers.
- the catalyst may be NC-1 [Ga (Salen1) SbF 6 ] -1 [Al (Salen1) Cl] -0 [Cu (Salen2)], which means [Ga (Salen1) SbF 6 ] is used with [Al (Salen1) Cl]; correspondingly, the catalyst can be uniformly expressed as NC- [Ga (Salen1) SbF 6 ]-[Al (Salen1) Cl].
- the proportion of the amount of use between the active sites of the neutron expressions (I-1) and (I-2) in the catalyst of formula (I) is not particularly limited.
- the molar ratio between the active centers of the sub-expressions (I-1) and (I-2) is 0.001-1000, such as 0.01-100, or 0.1-10, or 0.5-5.
- m is 0-20, preferably 0-10, and also preferably 0-5, such as 0-2.
- n is 0-10, preferably 0-5, and still more preferably 0-3, such as 0-1.
- m is 0-2 and n is 0-1. In a preferred embodiment, m is 2, n is 0-1, and each M (Salen1) X is the same or different. In a preferred embodiment, m is 2, n is 0, and each M (Salen1) X is the same or different.
- M (Salen1) X in each (I-1) is independently the same or different.
- M ′ (Salen2) in each (I-2) is independently the same or different.
- m is 1 and n is 0, M is not of Co, X is not halogen; and m is 2, wherein the at least one X is SbF 6 -, and preferably, the other X is F - , Cl -, Br - or I -.
- the NC is a mesoporous silica nanoparticle having a nanocage structure or an organic hybrid mesoporous silica nanoparticle having a nanocage structure.
- the NC includes SBA-6, SBA-16, FDU-1, FDU-12, KIT-5, AMS-8, and the like.
- the Shiff base derivative is N, N′-disalicylidene-1,2-cyclohexanediamine or substituted N, N′-disalicylidene- 1,2-cyclohexanediamine, such as (1R, 2R) -N, N'-disalicylidene-1,2-cyclohexanediamine or substituted (1R, 2R) -N, N'- Disalicylidene-1,2-cyclohexanediamine.
- the catalyst may have the following expression (I-3) or (I-4):
- M (Salen1) X and M '(Salen2) are active centers, respectively, and M and M' are metal ions.
- M includes Fe 3+ , Ga 3+ , Al 3+ , Cr 3+ , and M 'includes Cu 2+ , Ni 2+ , and X are axial anions, and Salen1 and Salen2 have the same definition as Salen1 and Salen2 described in the first aspect, that is, Shiff base derivatives.
- X includes acetate, benzenesulfonate, benzoate, substituted acetate, substituted benzenesulfonate, and substituted benzoate.
- the catalyst may have the following expression (II-2):
- M (Salen1) SbF 6 --M (Salen1) X is the active center, M is a metal ion, Salen1 is a Shiff base derivative, X is an axial anion, and X is a halogen anion.
- M includes Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , and Cr 3+ .
- halogen anion is F -, Cl -, Br - , I -.
- the catalyst may have the following expression (III):
- M (Salen1) X is the active center
- M is a metal ion
- M includes Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , Cr 3+
- Salen is a Shiff base derivative
- X is an axial anion
- X is PF 6 -, BF 4 -.
- Salen1 has the same definition as Salen1 or Salen2 described in the first aspect.
- the catalyst may have the following expression (II-3):
- M is a metal ion
- NC and Salen1 each independently have the same definition as in the aforementioned first aspect and one embodiment of the first to third exemplary variants
- X is a halogen anion
- M includes Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , and Cr 3+ .
- halogen anion is F -, Cl -, Br - , I -.
- the catalyst may have the following expression (II-4):
- M is a metal ion
- NC and Salen1 each independently have the same definition as in the aforementioned first aspect and one embodiment of the first to fourth exemplary variants
- X is a halogen anion
- M includes Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , and Cr 3+ .
- halogen anion is F -, Cl -, Br - , I -.
- the nanocage confined catalyst according to the present invention may have formula (III-1) or (III-2):
- NC and Salen1 each independently have the same definition as in the aforementioned first aspect and one embodiment of each exemplified variation.
- the active centers NC, M, Salen1, Salen2, X, m, and n, etc. have The definition of the first aspect has the same meaning.
- the second aspect of the present invention also provides a method for preparing a nanocage-limited catalyst, including the following steps:
- the active center M (Salen1) X or M '(Salen2) and the nanocage material NC are added to a solvent and stirred; the solvent is removed; and the nanocage confined catalyst is obtained by encapsulation.
- M, M ', Salen1, or Salen2, X, and NC each independently have the same definition as in the aforementioned first aspect and one embodiment of each exemplified variation.
- the preparation method according to the second aspect of the present invention can be used to prepare the nanocage confined catalyst of the first aspect of the present invention and its exemplary variants.
- the solvent includes at least one of dichloromethane, ethanol, and methanol.
- the temperature for stirring and removing the solvent is -96 ° C to 61 ° C. More preferably, it is 20-50 ° C. In an exemplary embodiment, the stirring time is ⁇ 30 min. In an exemplary embodiment, removing the solvent is specifically volatile the solvent with open stirring.
- the packaging is performed by adding a packaging reagent.
- the encapsulation of the active center is achieved by using a pre-hydrolyzed ortho-silicate or a pre-hydrolyzed ortho-silicate or a silane coupling agent.
- the application conditions are water ratio ⁇ 2: 1, reaction time is 10min ⁇ 24h, the yield of ethylene glycol or propylene glycol obtained by first catalyzing the hydration reaction of ethylene oxide or propylene oxide is ⁇ 91%, preferably ⁇ 93%; Yield of ethylene glycol or propylene glycol obtained by direct recycling once after activation regeneration is ⁇ 75%, preferably ⁇ 90%; yield of ethylene glycol or propylene glycol obtained by direct recycling without activation regeneration is ⁇ 64%. It is preferably ⁇ 83%, and more preferably ⁇ 84%.
- the catalyst of the present invention comprises a matrix material containing a nanocage structure and an active center M (Salen1) X or M '(Salen2) confined in the nanocage, wherein M is Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , Cr 3+ , M 'is Cu 2+ , Ni 2+ , Salen1 and Salen2 are Shiff base derivatives, X is an axial anion, and the catalyst has high and low water ratios and short reactions. Under the time, they have high activity to diols produced by hydration of alkylene oxides, and do not need to be activated to have good recyclability, good stability, and achieved unexpected technical effects.
- the method provided by the present invention is simple and feasible, and can provide reference for the synthesis of other nanocage confined catalysts.
- FIG. 1 is a TEM photograph of the catalyst prepared in Example I-1.
- FIG. 2 is a TEM photograph of the catalyst prepared in Example II-1.
- FIG. 3 is a TEM photograph of the catalyst prepared in Example III-1.
- range is given in the form of lower and upper limits, such as one or more lower limits and one or more upper limits.
- a given range can be defined by selecting a lower limit and an upper limit, and the selected lower and upper limits define the boundaries of the given range. All ranges defined in this way are inclusive and combinable, that is, any lower limit can be combined with any upper limit to form a range.
- the ranges of 60-110 and 80-120 are listed for specific parameters, and it is understood that the ranges of 60-120 and 80-110 are also expected.
- the lower limits listed are 1 and 2 and the upper limits listed are 3, 4, and 5, the following ranges are all predictable: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.
- the numerical range "a-b” represents a shortened representation of any combination of real numbers between a and b, where a and b are both real numbers.
- the value range "0-5" indicates that all real numbers between "0-5" have been listed in this document, and "0-5" is only an abbreviated representation of the combination of these values.
- the method includes steps (a) and (b), meaning that the method may include steps (a) and (b) performed sequentially, and may also include steps (b) and (a) performed sequentially.
- the method can also include step (c), meaning that step (c) can be added to the method in any order, for example, the method can include steps (a), (b), and (c), also It can include steps (a), (c), and (b), and it can also include steps (c), (a), and (b).
- reaction temperature is 10-100 ° C
- specific reaction temperature described in the examples is 20 ° C. It can be considered that the range of 10-20 ° C has been specifically disclosed herein, or 20 -100 ° C range, and this range can be combined with other features of other parts of the description to form a new technical solution.
- a nanocage confined catalyst characterized in that the catalyst expression is: NC- [M (Salen) X] or NC- [M '(Salen)], and NC is a material having a nanocage structure; M (Salen) X and M '(Salen) are active centers, M and M' are metal ions, M includes Fe 3+ , Ga 3+ , Al 3+ , Cr 3+ , and M 'includes Cu 2+ and Ni 2 + , Salen is a Shiff base derivative, and X is an axial anion.
- NC is a mesoporous silica nanoparticle having a nanocage structure or an organic hybrid mesoporous silica nanoparticle having a nanocage structure.
- a method for preparing a nanocage confined catalyst comprising the following steps:
- the active center M (Salen) X or M '(Salen) and the nanocage material NC are added to a solvent, stirred; the solvent is removed; and the nanocage confined catalyst is obtained by encapsulation.
- the preparation method according to the exemplary embodiment 1.6 wherein the M includes Fe 3+ , Ga 3+ , Al 3+ , Cr 3+ , and M ′ includes Cu 2+ and Ni 2+ ; Salen is Shiff base derivatives, X is an axial anion, and X includes acetate, benzenesulfonate, benzoate, substituted acetate, substituted benzenesulfonate, and substituted benzoate.
- a high-performance nanocage confined catalyst characterized in that the catalyst expression is: NC- [M (Salen) SbF 6 . M (Salen) X], NC is a material with a nanocage structure; M (Salen) SbF 6 . M (Salen) X is the active center, M is a metal ion, Salen is a Shiff base derivative, X is an axial anion, and X is a halogen anion.
- the NC is a mesoporous silica nanoparticle having a nanocage structure or an organic hybrid mesoporous silica nanoparticle having a nanocage structure
- the NC includes SBA-6, SBA-16, FDU-1, FDU-12, KIT-5, AMS-8.
- halogen anion is F -, Cl -, Br - , I -.
- a method for preparing a nanocage confined catalyst including the following steps:
- the active centers M (Salen) SbF 6 , M (Salen) X, and nanocage material NC are added to a solvent, stirred; the solvent is removed; and the nanocage confined catalyst is obtained by encapsulation.
- a catalyst for the production of diols from the hydration of alkylene oxides characterized in that the catalyst is a nanocage confined catalyst with the expression: NC- [M (Salen) X], M (Salen) X confined
- NC is a material with a nanocage structure
- M (Salen) X active center M is a metal ion
- M includes Co 3+ , Fe 3+ , Ga 3+ , Al 3+ , Cr 3+
- Salen is Shiff bases derivative
- X is PF 6 -, BF 4 -.
- NC is a mesoporous silica nanoparticle having a nanocage structure or an organic hybrid mesoporous silica nanoparticle having a nanocage structure.
- a method for preparing an alkylene oxide hydration catalyst for diol comprising the following steps:
- the active center M (Salen) X and the nanocage material NC are dispersed in a solvent and stirred; the solvent is removed; and a packaging reagent is added for encapsulation to obtain a nanocage confined catalyst.
- Example I-7 The catalyst that was used once in Example I-7 was recovered without regeneration. The catalytic performance was examined under the same catalytic conditions as in Example I-7. The results are shown in Table I-1.
- Example I-8 The catalyst used in Example I-8 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-7 and I-8. The results are shown in Table I-1.
- Example I-10 The catalyst once used in Example I-10 was recovered without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Example I-10. The results are shown in Table I-1.
- Example I-11 The catalyst used in Example I-11 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-10 and 11. The results are shown in Table I-1.
- Example I-13 The catalyst used in Example I-13 was recovered without regeneration. The catalytic performance was examined under the same catalytic conditions as in Example I-13. The results are shown in Table I-1.
- Example I-14 The catalyst used in Example I-14 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-13 and 14. The results are shown in Table I-1.
- Example I-16 The catalyst once used in Example I-16 was recovered without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Example I-16. The results are shown in Table I-2.
- Example I-17 The catalyst used in Example I-17 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-16 and 17. The results are shown in Table I-2.
- Example I-19 The catalyst used in Example I-19 was recovered and regenerated without activation. The catalytic performance was examined under the same catalytic conditions as in Example I-19. The results are shown in Table I-2.
- Example I-20 The catalyst used in Example I-20 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-19 and 20. The results are shown in Table I-2.
- Example I-22 The catalyst used in Example I-22 was recovered and regenerated without activation. The catalytic performance was examined under the same catalytic conditions as in Example I-22. The results are shown in Table I-2.
- Example I-23 The catalyst used in Example I-23 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-22 and 23. The results are shown in Table I-2.
- Example I-25 The catalyst once used in Example I-25 was recovered without regeneration. The catalytic performance was examined under the same catalytic conditions as in Example I-25. The results are shown in Table I-3.
- Example I-26 The catalyst used in Example I-26 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-25 and 26. The results are shown in Table I-3.
- Example I-28 The catalyst used in Example I-28 was recovered without regeneration and activation. The catalytic performance was examined under the same catalytic conditions as in Example I-28. The results are shown in Table I-3.
- Example I-29 The catalyst used in Example I-29 was recovered twice without regeneration. Under the same catalytic conditions as in Examples I-28 and 29, the catalytic performance was examined. The results are shown in Table I-3.
- Example I-31 The catalyst once used in Example I-31 was recovered and regenerated without activation. The catalytic performance was examined under the same catalytic conditions as in Example I-31. The results are shown in Table I-3.
- Example I-32 The catalyst used in Example I-32 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-31 and 32. The results are shown in Table I-3.
- Example I-34 The catalyst used in Example I-34 was recovered and regenerated without activation. The catalytic performance was examined under the same catalytic conditions as in Example I-34. The results are shown in Table I-4.
- Example I-35 The catalyst used in Example I-35 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-34 and 35. The results are shown in Table I-4.
- Example I-37 The catalyst once used in Example I-37 was recovered without regeneration and activation. The catalytic performance was examined under the same catalytic conditions as in Example I-37. The results are shown in Table I-4.
- Example I-38 The catalyst used in Example I-38 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-37 and 38. The results are shown in Table I-4.
- Example I-40 The catalyst once used in Example I-40 was recovered without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Example I-40. The results are shown in Table I-4.
- Example I-41 The catalyst used in Example I-41 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples I-40 and 41. The results are shown in Table I-4.
- Comparative Example I-2 The catalyst used in Comparative Example I-2 was recovered and regenerated without activation. The catalytic performance was examined under the same catalytic conditions as Comparative Example I-2. The results are shown in Table I-5.
- Example II-5 The catalyst used in Example II-5 was recovered without regeneration and activation. The catalytic performance was examined under the same catalytic conditions as in Example II-5. The results are shown in Table II-1.
- Example II-6 The catalyst used in Example II-6 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-5 and 6. The results are shown in Table II-1.
- Example II-8 The catalyst used in Example II-8 was recovered without regeneration. The catalytic performance was examined under the same catalytic conditions as in Example II-8. The results are shown in Table II-1.
- Example II-8 The catalyst used in Example II-8 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-8 and 9. The results are shown in Table II-1.
- Example II-11 The catalyst once used in Example II-11 was recovered and was regenerated without activation. The catalytic performance was examined under the same catalytic conditions as in Example II-11. The results are shown in Table II-2.
- Example II-12 The catalyst used in Example II-12 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-11 and 12. The results are shown in Table II-2.
- Example II-14 The catalyst that was used once in Example II-14 was recovered without regeneration. The catalytic performance was examined under the same catalytic conditions as in Example II-14. The results are shown in Table II-2.
- Example II-15 The catalyst used in Example II-15 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as those in Examples II-14 and 15. The results are shown in Table II-2.
- Example II-17 The catalyst once used in Example II-17 was recovered without regeneration and activation. The catalytic performance was examined under the same catalytic conditions as in Example II-17. The results are shown in Table II-3.
- Example II-18 The catalyst used in Example II-18 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-17 and 18. The results are shown in Table II-3.
- Example II-20 The catalyst once used in Example II-20 was recovered without regeneration and activation. The catalytic performance was examined under the same catalytic conditions as in Example II-20. The results are shown in Table II-3.
- Example II-21 The catalyst used in Example II-21 was recovered twice without regeneration. Under the same catalytic conditions as those in Examples II-21 and 22, the catalytic performance was examined. The results are shown in Table II-3.
- Example II-23 The catalyst once used in Example II-23 was recovered without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Example II-23. The results are shown in Table II-4.
- Example II-24 The catalyst used in Example II-24 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-23 and 24. The results are shown in Table II-4.
- Example II-26 The catalyst once used in Example II-26 was recovered without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Example II-26. The results are shown in Table II-4.
- Example II-27 The catalyst used in Example II-27 was recovered twice without regeneration, and its catalytic performance was examined under the same catalytic conditions as in Examples II-26 and 27. The results are shown in Table II-4.
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Abstract
Description
催化剂 | 首次乙二醇产率(%) | 循环1次乙二醇产率(%) | 循环2次乙二醇产率(%) |
I-A | 94 | 79 | 69 |
I-B | 94 | 78 | 68 |
I-C | 92 | 76 | 66 |
催化剂 | 首次乙二醇产率(%) | 循环1次乙二醇产率(%) | 循环2次乙二醇产率(%) |
I-D | 94 | 79 | 68 |
I-E | 92 | 77 | 67 |
I-F | 93 | 78 | 68 |
催化剂 | 首次丙二醇产率(%) | 循环1次丙二醇产率(%) | 循环2次丙二醇产率(%) |
I-D | 93 | 78 | 67 |
I-E | 91 | 75 | 64 |
I-F | 92 | 77 | 66 |
催化剂 | 首次丙二醇产率(%) | 循环1次丙二醇产率(%) | 循环2次丙二醇产率(%) |
I-A | 93 | 77 | 68 |
I-B | 93 | 76 | 67 |
I-C | 92 | 76 | 66 |
催化剂I- | 首次乙二醇产率(%) | 循环1次乙二醇产率(%) |
G | 96 | 44 |
催化剂 | 首次乙二醇产率(%) | 循环1次乙二醇产率(%) | 循环2次乙二醇产率(%) |
II-A | 95 | 90 | 84 |
II-B | 93 | 88 | 81 |
催化剂 | 首次乙二醇产率(%) | 循环1次乙二醇产率(%) | 循环2次乙二醇产率(%) |
II-C | 94 | 89 | 83 |
II-D | 93 | 87 | 80 |
催化剂 | 首次丙二醇产率(%) | 循环1次丙二醇产率(%) | 循环2次丙二醇产率(%) |
II-C | 92 | 87 | 81 |
II-D | 91 | 85 | 79 |
催化剂 | 首次丙二醇产率(%) | 循环1次丙二醇产率(%) | 循环2次丙二醇产率(%) |
II-A | 94 | 89 | 83 |
II-B | 93 | 87 | 81 |
催化剂 | 首次乙二醇产率(%) |
II-E | 12 |
II-F | 63 |
催化剂 | 首次乙二醇产率(%) | 循环1次乙二醇产率(%) | 循环2次乙二醇产率(%) |
III-A | ≥97 | ≥94 | ≥89 |
III-B | ≥96 | ≥93 | ≥88 |
III-C | ≥96 | ≥93 | ≥87 |
催化剂 | 首次乙二醇产率(%) | 循环1次乙二醇产率(%) | 循环2次乙二醇产率(%) |
III-D | ≥95 | ≥92 | ≥85 |
III-E | ≥94 | ≥91 | ≥84 |
III-F | ≥95 | ≥92 | ≥86 |
催化剂 | 首次丙二醇产率(%) | 循环1次丙二醇产率(%) | 循环2次丙二醇产率(%) |
III-D | ≥94 | ≥91 | ≥83 |
III-E | ≥93 | ≥90 | ≥83 |
III-F | ≥94 | ≥90 | ≥84 |
催化剂 | 首次丙二醇产率(%) | 循环1次丙二醇产率(%) | 循环2次丙二醇产率(%) |
III-A | ≥96 | ≥93 | ≥88 |
III-B | ≥95 | ≥92 | ≥86 |
III-C | ≥95 | ≥93 | ≥87 |
催化剂 | 乙二醇产率(%) |
Co(N,N′-二亚水杨基-1,2-环己二胺)PF 6 | ≥85 |
Co(N,N′-二亚水杨基-1,2-环己二胺)OTs | ≥92 |
催化剂 | 首次乙二醇产率(%) | 循环1次乙二醇产率(%) |
III-G | ≥97 | ≥45 |
Claims (20)
- 一种纳米笼限域催化剂,其特征在于,所述催化剂具有式(I-1)和/或(I-2)的活性中心:M(Salen1)X (I-1)M'(Salen2) (I-2)从而使得该催化剂具有式(I):NC-m[M(Salen1)X]-n[M'(Salen2)] (I)其中:NC为具有纳米笼结构的材料,每次出现的M独立地选自Co离子,Fe离子,Ga离子,Al离子,Cr离子及其混合;每次出现的M'独立地选自Cu离子,Ni离子及其混合;m为0-100的整数,n为0-100的整数;条件是m和n中至少一个不为0;每次出现的Salen1和Salen2各自独立地为Shiff碱类衍生物;X为轴阴离子,每次出现的X独立地选自取代或未取代的醋酸根、取代或未取代的苯磺酸根、取代或未取代的苯甲酸根,F -,Cl -,Br -,I -,SbF 6 -,PF 6 -,BF 4 -及其混合;条件是:(1)X为取代或未取代的醋酸根、取代或未取代的苯磺酸根、或取代或未取代的苯甲酸根时,M不为Co离子,或者(2)X为F -,Cl -,Br -,或I -时,m不小于2,且至少一个式(I-1)中的X为SbF 6 -。
- 根据权利要求1所述的催化剂,其特征在于,每个式(I-1)中出现的M独立地选自Co 3+,Fe 3+,Ga 3+,Al 3+,Cr 3+及其混合,和/或每个式(I-2)中出现的M'独立地选自Cu 2+,Ni 2+及其混合。
- 根据权利要求1所述的催化剂,其特征在于,m为0-20,优选0-10,还优选0-5,例如0-2。
- 根据权利要求1所述的催化剂,其特征在于,n为0-10,优选0-5,还优选0-3,例如0-1。
- 根据权利要求1所述的催化剂,其特征在于,m为0-2,n为0-1。
- 根据权利要求1所述的催化剂,其特征在于,m为1,且n为0, X选自取代或未取代的醋酸根、取代或未取代的苯磺酸根、取代或未取代的苯甲酸根,SbF 6 -,PF 6 -和BF 4 -。
- 根据权利要求1所述的催化剂,其特征在于,m为2,n为0-1,每个式(I-1)的M(Salen1)X不同以形成式(II)的催化剂:NC-[M(Salen1)X]-[M(Salen1)X]-n[M'(Salen2)] (II);优选地,m为2,n为0,每个M(Salen1)X不同以形成式(II-1)的催化剂NC-[M(Salen1)X]-[M(Salen1)X] (II-1),式(II)或(II-1)中,每个M不同且独立地选自Co 3+,Fe 3+,Ga 3+,Al 3+,Cr 3+,每个Salen1相同或不同。
- 根据权利要求7所述的催化剂,其特征在于其中一个X为SbF 6 -,另一个X为F -,Cl -,Br -或I -。
- 根据权利要求1所述的催化剂,其特征在于,m为2或更大,每个式(I-1)的M(Salen1)X不同。
- 根据权利要求1所述的催化剂,其特征在于,n为2或更大,每个式(I-2)的M'(Salen2)不同。
- 根据权利要求1所述的催化剂,其特征在于,所述NC为具有纳米笼结构的介孔二氧化硅纳米颗粒或者具有纳米笼结构的有机杂化的介孔二氧化硅纳米颗粒。
- 根据权利要求1所述的催化剂,其特征在于,所述NC选自SBA-6,SBA-16,FDU-1,FDU-12,KIT-5和AMS-8。
- 根据权利要求1所述的催化剂,其特征在于,所述Shiff碱类衍生物为N,N′-二亚水杨基-1,2-环己二胺或取代的N,N′-二亚水杨基-1,2-环己二胺。
- 一种纳米笼限域催化剂,其特征在于,所述催化剂具有式(II-3):NC-[Co(Salen1)SbF 6-M(Salen1)X] (II-3),其中,NC、Salen1各自独立地如前述权利要求任一项中所定义;X选自F -,Cl -,Br -,和I -;且M选自Co 3+,Fe 3+,Ga 3+,Al 3+和Cr 3+。
- 一种纳米笼限域催化剂,其特征在于,所述催化剂具有式(II-4):NC-[M(Salen1)SbF 6-Co(Salen1)X] (II-4),其中,NC、Salen1各自独立地如前述权利要求任一项中所定义;X选自F -,Cl -,Br -,和I -;且M选自Co 3+,Fe 3+,Ga 3+,Al 3+和Cr 3+。
- 一种纳米笼限域催化剂,其特征在于,所述催化剂具有式(III-1)或(III-2):NC-[Co(Salen1)PF 6] (III-1),或NC-[Co(Salen1)BF 4] (III-2),其中,NC、Salen1各自独立地如前述权利要求任一项中所定义。
- 一种纳米笼限域催化剂的制备方法,包括以下步骤:将活性中心M(Salen1)X或M'(Salen2)、纳米笼材料NC加入溶剂中,搅拌;移除溶剂;封装,得纳米笼限域催化剂。
- 根据权利要求17所述的制备方法,其特征在于,所述M包括Fe 3+,Ga 3+,Al 3+,Cr 3+,M'包括Cu 2+,Ni 2+;Salen1和Salen2为Shiff碱类衍生物,X为轴阴离子,所述X包括醋酸根、苯磺酸根、苯甲酸根、取代的醋酸根、取代的苯磺酸根、取代的苯甲酸根,F -,Cl -,Br -,I -,SbF 6 -,PF 6 -,BF 4 -。
- 根据权利要求17所述的制备方法,其特征在于,所述的溶剂包括二氯甲烷、乙醇、和甲醇中的至少一种。
- 权利要求1-16任一所述催化剂或采用权利要求17-20任一所述制备方法制得的催化剂在环氧烷烃水合制二醇反应中的用途。
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