CN110773232B - Catalyst for preparing glycol by hydrating alkylene oxide, preparation method and application - Google Patents
Catalyst for preparing glycol by hydrating alkylene oxide, preparation method and application Download PDFInfo
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 125000002947 alkylene group Chemical group 0.000 title claims abstract description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000000887 hydrating effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 8
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002091 nanocage Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- WCSLPBBQHFXWBW-QZTJIDSGSA-N 2-[[(1R,2R)-2-[(2-hydroxyphenyl)methylideneamino]cyclohexyl]iminomethyl]phenol Chemical group OC1=CC=CC=C1C=N[C@H]1[C@H](N=CC=2C(=CC=CC=2)O)CCCC1 WCSLPBBQHFXWBW-QZTJIDSGSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000036571 hydration Effects 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 16
- 229940093476 ethylene glycol Drugs 0.000 description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 13
- 230000004913 activation Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000004064 recycling Methods 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- VZHHNBNSMNNUAD-UHFFFAOYSA-N cobalt 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound [Co].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VZHHNBNSMNNUAD-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYNXDGNCEBQLGC-LOYHVIPDSA-N 2,4-ditert-butyl-6-[[(1R,2R)-2-[(3,5-ditert-butyl-2-hydroxyphenyl)methylideneamino]cyclohexyl]iminomethyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C=N[C@H]2[C@@H](CCCC2)N=CC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O FYNXDGNCEBQLGC-LOYHVIPDSA-N 0.000 description 1
- HRDGACHRSXGBGL-DNQXCXABSA-N 4-tert-butyl-2-[[(1R,2R)-2-[(5-tert-butyl-2-hydroxyphenyl)methylideneamino]cyclohexyl]iminomethyl]phenol Chemical compound C(C)(C)(C)C1=CC=C(C(C=N[C@H]2[C@@H](CCCC2)N=CC=2C(O)=CC=C(C=2)C(C)(C)C)=C1)O HRDGACHRSXGBGL-DNQXCXABSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- -1 hexafluorophosphate Chemical compound 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/48—Ring-opening reactions
- B01J2231/482—Ring-opening reactions asymmetric reactions, e.g. kinetic resolution of racemates
- B01J2231/485—Ring-opening reactions asymmetric reactions, e.g. kinetic resolution of racemates kinetic resolution of epoxide racemates
- B01J2231/487—Ring-opening reactions asymmetric reactions, e.g. kinetic resolution of racemates kinetic resolution of epoxide racemates by hydrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a high-performance catalyst for preparing glycol by hydrating alkylene oxide, a preparation method and application thereof. The catalyst is a nano cage-limited catalyst, and the expression is as follows: NC- [ M (salen) X]NC is a material with a nano cage structure; m (salen) X active center, M being a metal ion, particularly Co3+，Fe3+，Ga3+，Al3+，Cr3+Salen is a Shiff base derivative, X is an axial anion, and is specifically PF6 ‑，BF4 ‑。
Description
Technical Field
The invention relates to a catalyst for preparing glycol by hydrating high-performance alkylene oxide, a preparation method and application thereof.
Background
Ethylene glycol is an important organic chemical raw material and intermediate, is mainly used for producing polyester fibers, bottle resin, films, engineering plastics, antifreeze and coolant, is also used as a raw material for producing various chemical products such as plasticizers, drying agents, lubricants and the like in large quantity, and has very wide application (Guangdong chemical industry, 2011, 38: 242). By 2015, the global annual demand for ethylene glycol is as high as 2800 million tons (http:// www.shell.com/business-customers/chemicals/products-factories-and-aromatics/products-mono-ethylene-glycol. html), and especially the self-sufficiency of ethylene glycol in our country is no more than 40.2% for a long time (http:// www.chemsino.com/dailynews/news. aspred ═ 499321& catalyst ═ 62). At present, ethylene glycol is mainly produced industrially by a direct ethylene oxide hydration method, and the technology is monopolized by three companies, namely Shell, SD and DOW. In order to reduce the content of by-products such as diethylene glycol and triethylene glycol, the technique requires that the reaction is carried out at 190-200 ℃, at a temperature of more than 1.9MPa and at a feed molar ratio of water to ethylene oxide (simply referred to as water ratio) of 22-25:1, which results in a water content in the product of up to 85 wt.% or more. Removal of such large amounts of water requires the use of multiple effect evaporation systems and consumes large amounts of steam (e.g., 5.5 tons of steam are consumed for 1 ton of ethylene glycol when the water ratio is 20: 1), ultimately resulting in large energy consumption, complex equipment, long flow, and high production costs for the entire production process of ethylene glycol (industrial catalysis, 2002, 10: 3; petrochemical, 2010, 39: 562; chemical intermediates, 2009: 59). Therefore, the development of ethylene oxide catalytic hydration technology with low water ratio is expected to realize energy conservation and consumption reduction, and the core is the development of the catalyst.
Heretofore, various catalysts have been developed, such as anion/cation exchange resins (CN 102372815B; Journal of Applied Polymer Science, 2010, 115: 2946; RSC Advances, 2015, 5: 2550), supported metal oxides (CN 100413579C; Journal of Catalysis, 2006, 241:173), Sn zeolites (CN 104437607B; ACS Catalysis, 2016, 6: 2955), and the like. However, these catalysts still require a high water ratio (. gtoreq.8: 1) or a long reaction time (. gtoreq.24 h) for good catalytic performance. A recent breakthrough development, nanocage catalyst FDU-12- [ Co (Salen) X developed for the enlargement](X＝OAc-/OTs-) (cn201110070058. x; angewandte Chemie International Edition, 2012, 51: 11517; journal of Catalysis, 2016, 338: 184) the yield of the ethylene glycol can be more than 98 percent under the condition that the water ratio is 2: 1. However, FDU-12- [ Co (Salen) X](X＝OAc-/OTs-) Poor stability, need for activation, and good recyclability, which severely limits its industrial application. Therefore, there is an urgent need in the art to develop a catalyst having high activity for the hydration of alkylene oxide to glycol at a low water ratio and a short reaction time and having good recyclability without activation.
Disclosure of Invention
The invention aims to provide a catalyst which has high activity and good recycling performance without activation for preparing glycol by hydrating alkylene oxide under high and low water ratios and short reaction time and a preparation method thereof, so as to solve the problems that the catalyst for preparing glycol by hydrating alkylene oxide in the prior art has high water ratio and good recycling performance for an activated part. The catalyst provided by the invention has high activity for preparing glycol by hydrating alkylene oxide under high and low water ratios and short reaction time, has good recycling property without activation, and is obviously superior to the existing catalyst; the preparation method provided by the invention is simple and feasible, and can provide reference for synthesis of other nano cage-limited catalysts.
The invention provides a catalyst for preparing glycol by hydrating alkylene oxide, which is a nano cage-limited catalyst and has the expression as follows: NC- [ M (salen) X]NC is a material with a nano cage structure; m (salen) X active center, M is a metal ion, M includes Co3+，Fe3+，Ga3+，Al3+，Cr3+Salen is a Shiff base derivative, X is an axial anion, and X is PF6 -，BF4 -。
In the above technical solution, preferably, the Shiff base derivative is (1R,2R) -N, N '-disalicylidene-1, 2-cyclohexanediamine or substituted (1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine.
In the above technical solution, preferably, the NC is a mesoporous silica nanoparticle having a nanocage structure or an organic hybrid mesoporous silica nanoparticle having a nanocage structure. Preferably, the NC includes SBA-6, SBA-16, FDU-1, FDU-12, KIT-5, AMS-8, and the like.
The invention also provides a preparation method of the catalyst for preparing glycol by hydrating alkylene oxide, which comprises the following steps: dispersing active center M (Salen) X and nanocage material NC into a solvent, and stirring; removing the solvent; and adding an encapsulating reagent for encapsulating to obtain the nano cage-limited catalyst.
In the above technical solution, preferably, M is Co3+，Fe3+，Ga3+，Al3+，Cr3+。
In the technical scheme, the mass ratio of the nano cage material NC to the active center M (Salen) X is preferably 5: 1-100: 1.
In the above technical solution, preferably, the solvent removal is specifically to volatilize the solvent under open stirring.
In the above technical solution, preferably, the solvent includes at least one of dichloromethane, ethanol and methanol.
In the above technical solution, preferably, the temperature of the stirring and solvent removal is-96 ℃ to 61 ℃. The stirring time is more than or equal to 30 min.
In the above technical solution, preferably, the encapsulation of the active center is achieved by using prehydrolyzed methyl orthosilicate, prehydrolyzed ethyl orthosilicate or silane coupling agent.
The invention also provides an application of the catalyst or the catalyst prepared by the preparation method in the reaction of preparing glycol by hydrating alkylene oxide.
The application conditions are that the water ratio is more than or equal to 2:1, the reaction time is 10 min-24 h, the yield of ethylene glycol or propylene glycol obtained by catalyzing hydration reaction of ethylene oxide or propylene oxide for the first time is more than or equal to 93%, the yield of ethylene glycol or propylene glycol obtained by directly recycling ethylene oxide or propylene oxide for 1 time without activation regeneration is more than or equal to 90%, and the yield of ethylene glycol or propylene glycol obtained by directly recycling ethylene oxide or propylene oxide for 2 times without activation regeneration is more than or equal to 83%.
The catalyst comprises a base material containing a nano cage structure and an active center M (Salen) X confined in the nano cage, wherein M is Co3+，Fe3+，Ga3+，Al3+，Cr3+And X is PF6 -，BF4 -. The catalyst has high activity for preparing glycol by hydrating alkylene oxide under high and low water ratios and short reaction time, and has good recycling property without activation, thereby solving the problems of high water ratio, long reaction time and good recycling property of the catalyst for preparing glycol by hydrating alkylene oxide in the prior art, and achieving unexpected technical effects. The method provided by the invention is simple and feasible, and provides reference for synthesis of other nano cage-limited catalysts.
Drawings
Fig. 1 is a TEM photograph of the catalyst prepared in example 1.
Detailed Description
[ example 1 ]
Weighing 0.50g of F127, 0.6g of mesitylene and 2.5g of KCl, dissolving in 30mL of 2M HCl aqueous solution at 16 ℃, and stirring for 2 h; 2.08g TEOS was added, stirred at 16 ℃ for 24h and then hydrothermal treated in an oven at 100 ℃ for 24 h. Taking out, washing, drying, and calcining at 550 ℃ for 6h to obtain the nano cage matrix material FDU-12. Weighing 0.331g of ferrocene hexafluorophosphate and 0.492g of Co ((1R,2R) -N, N '-disalicylidene-1, 2-cyclohexanediamine), dissolving in a mixed solution of 15mL of dichloromethane and 15mL of acetonitrile, stirring for 12h at room temperature in an open manner, removing the solvent by spinning, fully washing with N-hexane and drying to obtain the active center Co ((1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine) PF6. 1.0g of FDU-12 was weighed out and placed in 6mL of PF containing 100mg of Co ((1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine)6Then the mixture is stirred for 2 hours at the temperature of 20 ℃ in a sealed way, and then the mixture is stirred in an open way at the temperature of 20 ℃ until the solvent is volatilized to be dry. Adding prehydrolyzed methyl orthosilicate, stirring for 40min, adding ethanol, centrifugally separating, fully washing, and drying to obtain catalyst A.
[ example 2 ]
1.0g of SBA-6 was weighed out and placed in 6mL of PF containing 100mg of Fe ((1R,2R) -N, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine)6Then the mixture is stirred for 2 hours at the temperature of 20 ℃ in a sealed way, and then the mixture is stirred in an open way at the temperature of 20 ℃ until the solvent is volatilized to be dry. Adding prehydrolyzed methyl orthosilicate, stirring for 40min, adding ethanol, centrifugally separating, fully washing, and drying to obtain catalyst B.
[ example 3 ]
1.0g of SBA-16 was weighed out and placed in 6mL of PF containing 100mg of Ga ((1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine)6Then the mixture is stirred for 2 hours at the temperature of 20 ℃ in a sealed way, and then the mixture is stirred in an open way at the temperature of 20 ℃ until the solvent is volatilized to be dry. Adding prehydrolyzed methyl orthosilicate, stirring for 40min, adding ethanol, centrifugally separating, fully washing, and drying to obtain catalyst C.
[ example 4 ]
1.0g of FDU-1 was weighed into 6mL of a solution containing 100mg of Al ((1R,2R) -N, N' -bis (b) ((1R, 2R))3-tert-butylsalicylidene) -1, 2-cyclohexanediamine) PF6Then the mixture is stirred for 2 hours at the temperature of 20 ℃ in a sealed way, and then the mixture is stirred in an open way at the temperature of 20 ℃ until the solvent is volatilized to be dry. Adding prehydrolyzed methyl orthosilicate, stirring for 40min, adding ethanol, centrifugally separating, fully washing, and drying to obtain catalyst D.
[ example 5 ]
1.0g of KIT-5 was weighed out and placed in 6mL of PF containing 100mg of Cr ((1R,2R) -N, N' -bis (5-t-butylsalicylidene) -1, 2-cyclohexanediamine)6Then the mixture is stirred for 2 hours at the temperature of 20 ℃ in a sealed way, and then the mixture is stirred in an open way at the temperature of 20 ℃ until the solvent is volatilized to be dry. Adding prehydrolyzed methyl orthosilicate, stirring for 40min, adding ethanol, centrifugally separating, fully washing, and drying to obtain catalyst E.
[ example 6 ]
1.0g of SBA-16 was weighed out and placed in 6mL of BF containing 100mg of Co ((1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine)4Then the mixture is stirred for 2 hours at the temperature of 20 ℃ in a sealed way, and then the mixture is stirred in an open way at the temperature of 20 ℃ until the solvent is volatilized to be dry. Adding prehydrolyzed methyl orthosilicate, stirring for 40min, adding ethanol, centrifugally separating, fully washing, and drying to obtain catalyst F.
Comparative example 1
1.0g of SBA-16 was weighed into 6mL of a dichloromethane solution containing 100mg of Co ((1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine) OTs, sealed and stirred at 20 ℃ for 2h, and then stirred open at 20 ℃ until the solvent was evaporated. Adding prehydrolyzed methyl orthosilicate, stirring for 40min, adding ethanol, centrifugally separating, fully washing, and drying to obtain catalyst G.
[ examples 7 to 15 ]
1.32g of ethylene oxide was weighed out, and the performance of the catalyst A, B, C was examined under the conditions of a temperature of 20 ℃, a pressure of 1.0MPa, a water ratio of 2:1, a quantitative ratio of the catalyst to the ethylene oxide of 1:1000, and a reaction time of 7 hours. The used catalyst A, B, C was recovered by centrifugation and used under the same conditions for the next catalytic reaction without activation regeneration (so doing twice), and the results are shown in Table 1.
TABLE 1 Recycling of catalyst A, B, C
[ examples 16 to 24 ]
1.32g of ethylene oxide was weighed out, and the performance of the catalyst D, E, F was examined under the conditions of a temperature of 40 ℃, a pressure of 1.0MPa, a water ratio of 6:1, a quantitative ratio of the catalyst to the ethylene oxide of 1:500, and a reaction time of 4 hours. The used catalyst D, E, F was recovered by centrifugation and used under the same conditions directly without activation regeneration (so circulated twice) for the next catalytic reaction, and the results are shown in Table 2.
TABLE 2 Recycling of catalyst D, E, F
| Catalyst and process for preparing same | First ethylene glycol yield (%) | Ethylene glycol yield (%) -1 cycle | Ethylene glycol yield (%) -2 cycles |
| D | ≥95 | ≥92 | ≥85 |
| E | ≥94 | ≥91 | ≥84 |
| F | ≥95 | ≥92 | ≥86 |
[ examples 25 to 33 ]
Weighing 1.74g of propylene oxide, and reacting at a temperature of 40 ℃, a pressure of 1.0MPa, a water ratio of 2:1, and a catalyst and propylene oxide substance in a weight ratio of 1: the performance of the catalyst D, E, F was examined at 1000 f and a reaction time of 7 h. The used catalyst D, E, F was recovered by centrifugation and used under the same conditions directly without activation regeneration (so circulated twice) for the next catalytic reaction, and the results are shown in Table 3.
TABLE 3 Recycling of catalyst D, E, F
| Catalyst and process for preparing same | First propylene glycol yield (%) | Recycle 1 propylene glycol yield (%) | Recycle 2 propylene glycol yield (%) |
| D | ≥94 | ≥91 | ≥83 |
| E | ≥93 | ≥90 | ≥83 |
| F | ≥94 | ≥90 | ≥84 |
[ examples 34 to 42 ]
Weighing 1.74g of propylene oxide, and reacting at a temperature of 60 ℃, a pressure of 1.0MPa, a water ratio of 8:1, and a catalyst and propylene oxide mass ratio of 1: the performance of the catalyst A, B, C was examined at 500 f and 4h reaction time. The used catalyst A, B, C was recovered by centrifugation and used under the same conditions for the next catalytic reaction without activation regeneration (so cycling twice), and the results are shown in Table 4.
TABLE 4 catalyst A, B, C Recycling
Comparative examples 2 to 3
Weighing 1.32g of ethylene oxide, and inspecting the active center Co ((1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine) PF under the conditions of temperature of 20 ℃, pressure of 1.0MPa, water ratio of 2:1, amount ratio of catalyst to ethylene oxide substance of 1:1000 and reaction time of 7h6And Co ((1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine) OTs as homogeneous catalysts, the results are given in Table 5.
TABLE 5 active center Co ((1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine) PF6And Co ((1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine) OTs as homogeneous catalysts
| Catalyst and process for preparing same | Ethylene glycol yield (%) |
| Co ((1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine) PF6 | ≥85 |
| Co ((1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine) OTs | ≥92 |
Comparative example 4
1.32G of ethylene oxide was weighed out, and the performance of catalyst G was examined under conditions of a temperature of 20 ℃, a pressure of 1.0MPa, a water ratio of 2:1, a quantitative ratio of catalyst to ethylene oxide of 1:1000 and a reaction time of 7 hours. The used catalyst G was recovered by centrifugation and used directly in the next catalytic reaction under the same conditions without activation regeneration, and the results are shown in Table 6.
TABLE 6 Cyclic utilization of catalyst G
| Catalyst and process for preparing same | First ethylene glycol yield (%) | Ethylene glycol yield (%) -1 cycle |
| G | ≥97 | ≥45 |
Claims (6)
1. The catalyst for preparing glycol by hydrating alkylene oxide is characterized in that the catalyst is a nano-caged catalyst and has the expression: NC- [ M (salen) X]M (Salen) X is confined in NC, which is a material with a nanocage structure; m (salen) X active center, M is a metal ion, M includes Co3+，Fe3+，Ga3+，Al3+，Cr3+Salen is a Shiff base derivative, X is an axial anion, and X is PF6 -，BF4 -One or two of them;
the NC is mesoporous silica nanoparticles with a nano cage structure or organic hybrid mesoporous silica nanoparticles with a nano cage structure;
the Shiff alkali derivative is (1R,2R) -N, N '-disalicylidene-1, 2-cyclohexanediamine or substituted (1R,2R) -N, N' -disalicylidene-1, 2-cyclohexanediamine.
2. The catalyst of claim 1, wherein the NC comprises one or more of SBA-6, SBA-16, FDU-1, FDU-12, KIT-5, AMS-8.
3. A method for preparing the catalyst for the hydration of alkylene oxide to glycol according to claim 1, comprising the steps of:
dispersing active center M (Salen) X and nanocage material NC into a solvent, and stirring; removing the solvent; and adding an encapsulating reagent for encapsulation to obtain the nano cage-limited catalyst, wherein the solvent comprises at least one of dichloromethane, ethanol and methanol.
4. The production method according to claim 3, wherein the stirring and solvent removal temperature is-96 ℃ to 61 ℃.
5. The method according to claim 3, wherein the solvent is removed by stirring with an open air to volatilize the solvent.
6. Use of the catalyst according to any one of claims 1 to 2 or the catalyst obtained by the production method according to any one of claims 3 to 5 in a reaction for producing a glycol by hydrating an alkylene oxide.
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| CN201810854835.1A CN110773232B (en) | 2018-07-31 | 2018-07-31 | Catalyst for preparing glycol by hydrating alkylene oxide, preparation method and application |
| JP2021505279A JP7432580B2 (en) | 2018-07-31 | 2019-07-30 | Nanocage-enclosed catalyst, its preparation method and use |
| BR112021001734-8A BR112021001734A2 (en) | 2018-07-31 | 2019-07-30 | catalyst confined in nanocage, preparation process and their use |
| PCT/CN2019/098304 WO2020024923A1 (en) | 2018-07-31 | 2019-07-30 | Nanocaged catalyst, preparation method, and application |
| EP19844935.7A EP3831478A4 (en) | 2018-07-31 | 2019-07-30 | Nanocaged catalyst, preparation method, and application |
| KR1020217006072A KR20210038653A (en) | 2018-07-31 | 2019-07-30 | Nano cage-limited catalyst, preparation method and use thereof |
| SG11202101016QA SG11202101016QA (en) | 2018-07-31 | 2019-07-30 | Nanocage-confined catalyst, preparation process and use thereof |
| MX2021001265A MX2021001265A (en) | 2018-07-31 | 2019-07-30 | Nanocaged catalyst, preparation method, and application. |
| US17/265,178 US20210299644A1 (en) | 2018-07-31 | 2019-07-30 | Nanocage-confined catalyst, preparation process and use thereof |
| CA3107987A CA3107987A1 (en) | 2018-07-31 | 2019-07-30 | Nanocage-confined catalyst, preparation process and use thereof |
| TW108127116A TWI801638B (en) | 2018-07-31 | 2019-07-31 | Nanocage confined catalyst, preparation method and use |
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| CN102688776A (en) * | 2011-03-23 | 2012-09-26 | 中国科学院大连化学物理研究所 | Solid catalyst for hydration of epoxy compound to prepare diol and its application |
| CN102728407A (en) * | 2012-07-17 | 2012-10-17 | 岳阳亚王精细化工有限公司 | Synthetic method of (S,S)-salenCo(II) catalyst and application thereof in split of end epoxide compound |
| CN104437607A (en) * | 2014-11-06 | 2015-03-25 | 南开大学 | Tin-containing molecular sieve catalyst used for preparing ethylene glycol by hydrating ethylene oxide and application method |
| CN110773232A (en) * | 2018-07-31 | 2020-02-11 | 中国石油化工股份有限公司 | Catalyst for preparing glycol by hydrating alkylene oxide, preparation method and application |
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| CN102688776A (en) * | 2011-03-23 | 2012-09-26 | 中国科学院大连化学物理研究所 | Solid catalyst for hydration of epoxy compound to prepare diol and its application |
| CN102728407A (en) * | 2012-07-17 | 2012-10-17 | 岳阳亚王精细化工有限公司 | Synthetic method of (S,S)-salenCo(II) catalyst and application thereof in split of end epoxide compound |
| CN104437607A (en) * | 2014-11-06 | 2015-03-25 | 南开大学 | Tin-containing molecular sieve catalyst used for preparing ethylene glycol by hydrating ethylene oxide and application method |
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