CN113145166A - Composite catalyst for preparing glycol by hydrating alkylene oxide - Google Patents

Composite catalyst for preparing glycol by hydrating alkylene oxide Download PDF

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CN113145166A
CN113145166A CN202010073750.7A CN202010073750A CN113145166A CN 113145166 A CN113145166 A CN 113145166A CN 202010073750 A CN202010073750 A CN 202010073750A CN 113145166 A CN113145166 A CN 113145166A
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catalyst
salicylidene
cyclohexanediamine
ethylenediamine
phenylenediamine
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CN113145166B (en
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陶桂菊
尚大伟
何文军
戈军伟
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a composite catalyst for preparing glycol by hydrating alkylene oxide, a preparation method and application thereof. The catalyst is a catalyst compounded by carbon nano materials and polymers, and the carbon nano materials are selected from at least one of modified or unmodified carbon nanotubes, carbon nanowires, graphene and fullerene; the polymer has the expression P [ M (Salen) X]M (Salen) X is a polymer basic structural unit, M is a metal ion selected from the group consisting of Co3+，Rh3+，Ga3+，Cr3+Salen is a Shiff base derivative, X is an axial anion, and PF is6 ‑Or BF4 ‑Or SbF6 ‑And a halogen.

Description

Composite catalyst for preparing glycol by hydrating alkylene oxide
Technical Field
The invention relates to a composite catalyst for preparing glycol by hydrating alkylene oxide, a preparation method and application thereof.
Background
Ethylene glycol is an important organic chemical raw material and an intermediate, has wide application, is mainly used for producing polyester fibers, engineering plastics, bottle resin, films, antifreeze and coolant, and is also commonly used as a production raw material of various chemical products such as a plasticizer, a drying agent, a lubricant and the like (Guangdong chemical industry, 2011, 38: 242). In 2017, the global capacity of the ethylene glycol is as high as 3925 ten thousand tons per year, and the consumption is nearly 3000 ten thousand tons; and the self-sufficient rate of the glycol in China does not exceed 41 percent for a long time (http:// www.chemsino.com/dailynews/newsview. aspxid 499321& cataid 62). Currently, ethylene glycol is produced industrially mainly by the direct ethylene oxide hydration process, and in order to reduce the production of by-products such as diethylene glycol and triethylene glycol, this technique requires that the reaction be carried out at a water to ethylene oxide feed molar ratio (simply referred to as water ratio) of 20 to 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., 2.4 tons of steam are consumed for the production of 1 ton of ethylene glycol when the water ratio is 20: 1), ultimately resulting in long flow, complex equipment, high energy consumption and, therefore, high production costs for the overall 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 imperative, and the core of the technology is the development of the catalyst.
Heretofore, various acid and base catalysts have been developed, such as anion/cation exchange resins (CN 102372815B; CN100413579C), supported metal oxides (CN104437607B) and the like. However, the activity of these catalysts is to be further increased and a high water ratio (. gtoreq.8: 1) is still required for good catalytic performance. A recent breakthrough development was the development of pseudo-homogeneous nanocage catalysts FDU-12- [ Co (Salen) X for the macronexides](X＝OAc-/OTs-) (CN201110070058.X), which obtains the yield of the glycol of more than 98 percent under the condition that the water ratio is 2: 1. However, FDU-12- [ Co (Salen) X](X＝OAc-/OTs-) The stability is poor, and on one hand, the method needing activation and regeneration has better cyclic usability; on the other hand, the existing encapsulation technology still has certain defects, so that the prepared nanocage catalyst generates active centers Co (Salen) X (X ═ OAc) in the using process-/OTs-) The condition of loss to the reaction system not only affects the recycling performance of the catalyst, but also causes the product to need further purification; thereby severely restricting the industrial application thereof. Therefore, there is a strong need in the art to develop a catalyst having high activity and stability for the hydration of alkylene oxides to glycols at low water ratios.
Disclosure of Invention
The invention aims to provide a composite catalyst which has high activity and stability for preparing glycol by hydrating alkylene oxide under high and low water ratios and a preparation method thereof, so as to solve the problems of high water ratio and poor stability of the catalyst for preparing glycol by hydrating alkylene oxide in the prior art.
A catalyst for preparing glycol by hydrating alkylene oxide, which is a catalyst compounded by carbon nano-materials and polymers, wherein the carbon nano-materials comprise at least one of carbon nano-tubes, carbon nano-wires, graphene and fullerene; the polymer has the expression P [ M (Salen) X]M (Salen) X is a polymer basic structural unit, M is a metal ion selected from the group consisting of Co3+，Rh3+，Ga3+，Cr3+Salen is a Shiff base derivative, X is an axial anion, and X is PF6 -Or/and BF4 -Or SbF6 -And a halogen anion.
In the above technical solution, the Shiff base derivative is selected from at least one of N-salicylidene-N '- (5-phenylsalicylidene) -1, 2-cyclohexanediamine, N-salicylidene-N' - (5-phenylsalicylidene) -1, 2-phenylenediamine, N-salicylidene-N '- (5-phenylsalicylidene) ethylenediamine, and substituted N-salicylidene-N' - (5-phenylsalicylidene) -1, 2-cyclohexanediamine, N-salicylidene-N '- (5-phenylsalicylidene) -1, 2-phenylenediamine, N-salicylidene-N' - (5-phenylsalicylidene) ethylenediamine; or at least one of N, N '-bis (5-ethenylsalicylidene) -1, 2-cyclohexanediamine, N, N' -bis (5-ethenylsalicylidene) -1, 2-phenylenediamine, N, N '-bis (5-ethenylsalicylidene) -ethylenediamine, and substituted N, N' -bis (5-ethenylsalicylidene) -1, 2-cyclohexanediamine, N, N '-bis (5-ethenylsalicylidene) -1, 2-phenylenediamine, N, N' -bis (5-ethenylsalicylidene) -ethylenediamine.
In the above technical solution, the carbon nanotube includes at least one of a single-walled carbon nanotube, a multi-walled carbon nanotube, and a double-walled carbon nanotube; the graphene includes at least one of single-layer graphene and multi-layer graphene.
In the above technical solution, the carbon nanomaterial includes at least one of a modified or unmodified carbon nanotube, a carbon nanowire, graphene, and fullerene.
In the technical scheme, the mass ratio of the carbon nano material to the polymer in the composite catalyst is 0.05-3. Preferably 0.8-1.2.
In the above technical solution, the halogen anion includes Cl-，Br-，I-。
The invention also provides a preparation method of the catalyst for preparing glycol by hydrating alkylene oxide, which comprises the following steps:
1) dispersing a carbon nano material into a solvent, adding a double-bond substituent-containing Shiff base derivative monomer, or a diamine and at least one monomer selected from 1,3, 5-tri (3-formyl-4-hydroxyphenyl) benzene or substituted 1,3, 5-tri (3-formyl-4-hydroxyphenyl) benzene, or an initiator, and polymerizing to obtain a composite material of the carbon nano material and the Shiff base derivative polymer;
2) dispersing the composite material in the step 1 in a solvent, and adding M' Y3And/or Co (OAc)2The solution of (3) is reacted;
3) dispersing the product obtained in the step 2 in a solvent, and adding a solvent containing hexafluorophosphate ions and/or tetrafluoroborate ions or SbF6 -Reacting to obtain the carbon nano material and polymer P [ M (Salen) X]Composite catalyst. For example, stoichiometric amounts of silver hexafluorophosphate and/or silver tetrafluoroborate (and optionally ferrocene hexafluorophosphate and/or ferrocene tetrafluoroborate if M is Co) or substoichiometric amounts of silver hexafluoroantimonate (and optionally Co) may be washed with a solution containing stoichiometric amounts of p-toluenesulfonic acid and then with a saturated NaX solution)
In the above technical solution, in step 1, the diamine is an alkyl diamine or an aryl diamine, and preferably includes at least one of cyclohexanediamine, phenylenediamine, ethylenediamine or substituted cyclohexanediamine, phenylenediamine, and ethylenediamine.
In the above technical scheme, in step 1, the double bond substituent-containing Shiff base derivative monomer includes at least one of N, N '-bis (5-ethenylsalicylidene) -1, 2-cyclohexanediamine, N' -bis (5-ethenylsalicylidene) -1, 2-phenylenediamine, N '-bis (5-ethenylsalicylidene) -ethylenediamine, and substituted N, N' -bis (5-ethenylsalicylidene) -1, 2-cyclohexanediamine, N '-bis (5-ethenylsalicylidene) -1, 2-phenylenediamine, and N, N' -bis (5-ethenylsalicylidene) -ethylenediamine.
In the above technical solution, in step 2, the M' Y3Is a metal salt, M' is selected from the group consisting of Rh3+，Ga3+，Cr3+Y is selected from the group consisting of Cl-，Br-，I-At least one of (1).
In the above technical solution, in step 3, M is selected from the group consisting of Co3+，Rh3+，Ga3+，Cr3+X is PF6 -Or/and BF4 -Or SbF6 -And a halogen anion.
In the above technical scheme, in step 3, the SbF is contained6 -In solution of (1), SbF6 -Is less than the molar content of halide ions in the product of step 2.
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.
In the technical scheme, in the step 1, the polymerization condition is that the reflux is carried out for 30 min-24 h from room temperature to the boiling point of the solvent. .
In the technical scheme, in the step 2, the reaction condition is that the reaction is carried out for 30 min-24 h at room temperature. .
In the technical scheme, in the step 3, the reaction condition is that the reaction is carried out for 30 min-24 h at room temperature. .
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 1:1, 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 94%, 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 94%, the yield of ethylene glycol or propylene glycol obtained by directly recycling ethylene glycol or propylene glycol for 2 times without activation regeneration is more than or equal to 93%, the yield of ethylene glycol or propylene glycol obtained by directly recycling ethylene glycol or propylene glycol for 3 times without activation regeneration is more than or equal to 92%, and the yield of ethylene glycol or propylene glycol obtained by directly recycling ethylene oxide or propylene oxide for 4 times without activation regeneration is more than or equal to 92%.
The catalyst of the invention is a composite catalyst of carbon nano material and polymer, has high activity and stability for preparing glycol by hydrating alkylene oxide under high and low water ratios, and has excellent recycling performance without activation, thereby solving the problems of high water ratio and poor stability of the catalyst for preparing glycol by hydrating alkylene oxide in the prior art and obtaining unexpected technical effects. The method provided by the invention is simple and feasible, and can provide reference for synthesis of catalysts compounded by other carbon nano materials and polymers.
Drawings
FIG. 1 is an SEM photograph of the catalyst prepared in example 1.
Detailed Description
[ example 1 ]
Dispersing 5.4g of graphene oxide in CH2Cl2Weighing 6mmol of 1,3, 5-tri (3-formyl-4-hydroxyphenyl) benzene, dissolving in the solution, dripping a methanol solution containing 9mmol of ethylenediamine, refluxing at 60 ℃ for 1h, separating, washing with methanol thoroughly, and drying; redispersing the obtained graphene-polymer composite material to CH2Cl2In, N2Under stirring in the atmosphere, 9mmol Co (OAc) was added2After 10h of reaction, CH is separated2Cl2And methanol solution are fully washed and dried; dispersing the obtained product in CH2Cl2In the reaction solution, CH containing 9mmol of ferrocene hexafluorophosphate was added dropwise with stirring2Cl2And (5) stirring the solution for 10 hours in an open manner, separating, fully washing and drying to obtain the catalyst A.
[ example 2 ]
5.4g of carbon oxide nanotubes were dispersed in CH2Cl2Weighing 6mmol of 1,3, 5-tri (3-formyl-4-hydroxy-5-tert-butylphenyl) benzene, dissolving the benzene in the solution, dripping an ethanol solution containing 9mmol of cyclohexanediamine, refluxing at 80 ℃ for 1h, separating, fully washing with ethanol, and drying; redispersing the resulting carbon nanotube-polymer composite to CH2Cl2In, 9mmol of Rh (Cl) are added3Is subjected to a reaction for 10 hours and then separated, CH2Cl2And water/ethanol washing and drying thoroughly; dispersing the obtained product in CH2Cl2While stirring, add dropwise CH containing 9mmol of silver tetrafluoroborate2Cl2And (3) separating the solution after reacting for 10 hours, fully washing and drying to obtain the catalyst B.
[ example 3 ]
Dispersing 3g of carbon oxide nanotubes and 2.4g of graphene oxide in CH2Cl2Weighing 2mmol of 1,3, 5-tri (3-formyl-4-hydroxyphenyl) benzene and 4mmol of 1,3, 5-tri (3-formyl-4-hydroxy-5-tert-butylphenyl) benzene, dissolving the 1,3, 5-tri (3-formyl-4-hydroxy-5-tert-butylphenyl) benzene in the solution, dripping an ethanol solution containing 2mmol of ethylenediamine, 3mmol of cyclohexanediamine and 4mmol of phenylenediamine into the solution, refluxing the solution at 80 ℃ for 1 hour, separating the solution, and fully washing and drying the solution by using ethanol; the obtained carbon nano tube-graphene-polymer composite material is redispersed in CH2Cl2In, N2Under stirring in the atmosphere, 7mmol Co (OAc) was added2And 2mmol of Rh (Cl)3After 10h of reaction, CH is separated2Cl2And methanol and dried; dispersing the obtained product in CH2Cl2While stirring, CH containing 5mmol of silver hexafluorophosphate and 4mmol of silver tetrafluoroborate was added dropwise2Cl2And (3) reacting the solution for 10 hours, separating, fully washing and drying to obtain the catalyst C.
[ example 4 ]
Dispersing 5.4g of graphene oxide in CH2Cl2In the preparation, 6mmol of 1,3, 5-tri (3-formyl-4-hydroxy) is weighedPhenyl) benzene is dissolved in the mixture, then methanol solution containing 9mmol of ethylenediamine is dropped in the mixture, the mixture is separated after refluxing for 1 hour at the temperature of 60 ℃, and the methanol is fully washed and dried; redispersing the resulting carbon-polymer composite in the form of millimetre particles to CH2Cl2In, N2Under stirring in the atmosphere, 9mmol Co (OAc) was added2After 10h of reaction, CH is separated2Cl2And methanol solution are fully washed and dried; dispersing the obtained product in CH2Cl2While stirring, 9mmol of p-toluenesulfonic acid in CH was added dropwise2Cl2The solution is separated after being stirred for 10 hours in an open way, and is fully washed and dried; dispersing the obtained product in CH2Cl2In the reaction solution, the mixture was extracted three times with a saturated NaCl solution, the organic phase was sufficiently washed, and CH containing 4.5mmol of silver hexafluoroantimonate was dropped while stirring2Cl2And (3) reacting the solution for 10 hours, separating, fully washing and drying to obtain the catalyst D.
[ example 5 ]
Dispersing 2.4g of graphene oxide into 1-methyl-2-pyrrolidone, weighing 4mmol of N, N '-bis (5-vinyl salicylidene) -1, 2-cyclohexanediamine, dissolving the N, N' -bis (5-vinyl salicylidene) -1, 2-cyclohexanediamine in the graphene oxide, adding 0.6mmol of azobisisobutyronitrile, reacting for 24 hours at 100 ℃, separating, washing and drying; redispersing the obtained graphene-polymer composite material to CH2Cl2In, N2Under stirring in the atmosphere, 4mmol Co (OAc) was added2After 10h of reaction, CH is separated2Cl2And methanol and dried; dispersing the obtained product in CH2Cl2In the preparation, CH containing 4mmol of ferrocene tetrafluoroborate is added dropwise under stirring2Cl2And (5) stirring the solution for 10 hours in an open manner, separating, fully washing and drying to obtain the catalyst E.
Comparative example 1
Dispersing 5.4g of graphene oxide in CH2Cl2In the method, 6mmol of 1,3, 5-tri (3-formyl-4-hydroxyphenyl) benzene is weighed and dissolved in CH2Cl2Dripping methanol solution containing 9mmol of ethylenediamine into the mixture, refluxing at 80 ℃ for 1h, separating, fully washing with methanol and drying; redispersion of the graphene-polymer composite obtainedTo CH2Cl2In, N2Under stirring in the atmosphere, 9mmol Co (OAc) was added2After 10h of reaction, CH is separated2Cl2And methanol solution are fully washed and dried; dispersing the obtained product in CH2Cl2And dropwise adding a dichloromethane solution containing 9mmol of p-toluenesulfonic acid while stirring, stirring for 10 hours in an open manner, separating, fully washing, and drying to obtain the catalyst F.
Comparative example 2
Dispersing 2.4g of graphene oxide into 1-methyl-2-pyrrolidone, weighing 4mmol of N, N' -bis (5-vinyl salicylidene) -1, 2-cyclohexanediamine, dissolving in the solution, adding 0.6mmol of azobisisobutyronitrile, reacting at 100 ℃ for 24 hours, separating, washing and drying; redispersing the obtained graphene-polymer composite material to CH2Cl2In, N2Under stirring in the atmosphere, 4mmol Co (OAc) was added2After 10h of reaction, CH is separated2Cl2And methanol and dried; dispersing the obtained product in CH2Cl2And dropwise adding a dichloromethane solution containing 4mmol of p-toluenesulfonic acid while stirring, stirring for 10 hours in an open atmosphere, separating, fully washing, and drying to obtain the catalyst G.
[ examples 6 to 25 ]
1.32g of ethylene oxide was weighed out, and the performance of the catalyst A, B, C, D 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. This used catalyst A, B, C, D was used under the same conditions directly without activation regeneration for the next catalytic reaction (so cycled four times), and the results are shown in table 1.
TABLE 1 Recycling of catalyst A, B, C, D
Figure BDA0002377946160000061
[ examples 26 to 30 ]
1.32g of ethylene oxide was weighed out, and the performance of catalyst E was examined under conditions of a temperature of 40 ℃, a pressure of 1.0MPa, a water ratio of 6:1, a quantitative ratio of catalyst to ethylene oxide of 1:500 and a reaction time of 4 hours. This used catalyst E was used again under the same conditions without regeneration by activation for the next catalytic reaction (so circulated four times), and the results are shown in Table 2.
TABLE 2 Recycling of catalyst E
Figure BDA0002377946160000062
[ examples 31 to 35 ]
Weighing 1.74g of propylene oxide, and reacting at 40 ℃, 1.0MPa of pressure, 1:1 of water ratio and 1: the performance of catalyst E was examined at 1000 f and a reaction time of 7 h. This used catalyst E was used again under the same conditions without regeneration by activation for the next catalytic reaction (so circulated four times), and the results are shown in Table 3.
TABLE 3 Recycling of catalyst E
Figure BDA0002377946160000063
[ examples 36 to 55 ]
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, D was examined at 500 f and 4h reaction time. This used catalyst A, B, C, D was used under the same conditions directly without activation regeneration for the next catalytic reaction (so cycled four times), and the results are shown in table 4.
TABLE 4 catalyst A, B, C, D Recycling
Figure BDA0002377946160000071
Comparative example 3
1.32g of ethylene oxide was weighed out, and the performance of catalyst F 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. This used catalyst F was used again in the next catalytic reaction under the same conditions without regeneration by activation, and the results are shown in Table 5.
TABLE 5 Cyclic usability of catalyst F
Catalyst and process for preparing same First ethylene glycol yield (%) Ethylene glycol yield (%) -1 cycle
F ≥97 ≥45
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 40 ℃, a pressure of 1.0MPa, a water ratio of 6:1, a quantitative ratio of catalyst to ethylene oxide of 1:500 and a reaction time of 4 hours. This used catalyst G was used in the next catalytic reaction under the same conditions without regeneration by activation, 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 ≥47

Claims (10)

1. The catalyst for preparing glycol by hydrating alkylene oxide is characterized in that the catalyst is a catalyst compounded by a carbon nano material and a polymer, and the carbon nano material comprises at least one of carbon nano tube, carbon nano wire, graphene and fullerene; the polymer has the expression P [ M (Salen) X]M (Salen) X is a polymer basic structural unit, M is a metal ion selected from the group consisting of Co3+，Rh3+，Ga3+，Cr3+Salen is a Shiff base derivative, X is an axial anion, and X is PF6 -Or/and BF4 -Or X is SbF6 -And a halogen anion.
2. The catalyst of claim 1 wherein the Shiff base derivative is selected from the group consisting of N-salicylidene-N '- (5-phenylalicylidene) -1, 2-cyclohexanediamine, N-salicylidene-N' - (5-phenylalicylidene) -1, 2-phenylenediamine, N-salicylidene-N '- (5-phenylalicylidene) ethylenediamine, and substituted N-salicylidene-N' - (5-phenylalicylidene) -1, 2-cyclohexanediamine, N-salicylidene-N '- (5-phenylalicylidene) -1, 2-phenylenediamine, N-salicylidene-N' - (5-phenylalicylidene) ethylenediamine; or at least one of N, N '-bis (5-ethenylsalicylidene) -1, 2-cyclohexanediamine, N, N' -bis (5-ethenylsalicylidene) -1, 2-phenylenediamine, N, N '-bis (5-ethenylsalicylidene) -ethylenediamine and substituted N-salicylidene-N' - (5-phenylsalicylidene) -1, 2-cyclohexanediamine, N-salicylidene-N '- (5-phenylsalicylidene) -1, 2-phenylenediamine, N-salicylidene-N' - (5-phenylsalicylidene) ethylenediamine.
3. The catalyst of claim 1, wherein the carbon nanotubes comprise at least one of single-walled carbon nanotubes, multi-walled carbon nanotubes, double-walled carbon nanotubes; the graphene includes at least one of single-layer graphene and multi-layer graphene.
4. The catalyst according to claim 1, wherein the mass ratio of the carbon nanomaterial to the polymer in the composite catalyst is 0.05 to 3.
5. A preparation method of a catalyst for preparing glycol by hydrating alkylene oxide comprises the following steps:
1) dispersing a carbon nano material into a solvent, adding a double-bond substituent-containing Shiff base derivative monomer, or a diamine and at least one monomer selected from 1,3, 5-tri (3-formyl-4-hydroxyphenyl) benzene or substituted 1,3, 5-tri (3-formyl-4-hydroxyphenyl) benzene, or an initiator, and polymerizing to obtain a composite material of the carbon nano material and the Shiff base derivative polymer;
2) dispersing the composite material in the step 1 in a solvent, and adding M' Y3And/or Co (OAc)2The solution of (3) is reacted;
3) dispersing the product obtained in the step 2 in a solvent, and adding a solvent containing hexafluorophosphate ions and/or tetrafluoroborate ions or SbF6 -Solution, reacting to obtain carbon nano material and polymer P [ M (Salen) X]Composite catalyst.
6. The method according to claim 5, wherein in step 1, the diamine comprises at least one of cyclohexanediamine, phenylenediamine, ethylenediamine or substituted cyclohexanediamine, phenylenediamine, ethylenediamine.
7. The method according to claim 5, wherein the double bond substituent-containing Shiff base derivative monomer in step 1 comprises N, N ' -bis (5-ethenylsalicylidene) -1, 2-cyclohexanediamine, N, N ' -bis (5-ethenylsalicylidene) -1, 2-phenylenediamine, N, N ' -bis (5-ethenylsalicylidene) -ethylenediamine, and at least one of substituted N-salicylidene-N ' - (5-phenylsalicylidene) -1, 2-cyclohexanediamine, N-salicylidene-N ' - (5-phenylsalicylidene) -1, 2-phenylenediamine, and N-salicylidene-N ' - (5-phenylsalicylidene) ethylenediamine.
8. The method according to claim 5, wherein in step 2, M' Y is3Is a metal salt, M' is selected from the group consisting of Rh3+，Ga3+，Cr3+Y is selected from the group consisting of Cl-，Br-，I-At least one of (1).
9. The method according to claim 5, wherein in step 3, M is selected from the group consisting of Co3+，Rh3+，Ga3 +，Cr3+X is PF6 -Or/and BF4 -Or SbF6 -And a halogen anion.
10. Use of the catalyst according to any one of claims 1 to 4 or the catalyst obtained by the production process according to any one of claims 5 to 9 in a process for producing a glycol by hydration of an alkylene oxide.
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