CN112812140A - Complexes, process for their preparation and catalysts comprising them - Google Patents

Complexes, process for their preparation and catalysts comprising them Download PDF

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CN112812140A
CN112812140A CN202110103927.8A CN202110103927A CN112812140A CN 112812140 A CN112812140 A CN 112812140A CN 202110103927 A CN202110103927 A CN 202110103927A CN 112812140 A CN112812140 A CN 112812140A
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reaction
complex
carbon dioxide
catalyst
ligand
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CN112812140B (en
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董振鹏
朱建民
刘兆滨
张洪林
李明燃
王刚
石大川
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Liaoning Oxiranchem Co ltd
Jiangsu Oxiran Chemical Co ltd
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Jiangsu Oxiran Chemical Co ltd
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • 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
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • 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

Abstract

One embodiment of the present invention provides a complex, a preparation method thereof and a catalyst comprising the complex, wherein the complex has a chemical formula: (ZnX) · [ Fe (CN)4·mL]·(ZnX2)n(ii) a Wherein m is 1 or 1/2, n is selected from 1-40, and X represents F, Cl, Br or I. The complex of one embodiment of the invention is used as a catalyst for preparing cyclic carbonate and has higher selectivity.

Description

Complexes, process for their preparation and catalysts comprising them
Technical Field
The invention relates to a complex, in particular to a high-activity bimetallic complex which can be used as a catalyst.
Background
At present, there are many patents reported at home and abroad about the preparation of cyclic carbonates by coupling carbon dioxide and alkylene oxide. As in US 4314945, McMullen uses a tetraalkyl quaternary ammonium salt to catalyze the reaction of alkylene oxides with carbon dioxide to synthesize cyclic carbonates; in US4786741 and US4841072, Sachs and Harvey respectively use quaternary phosphonium salt catalyst to realize cycloaddition reaction of carbon dioxide and ethylene oxide under the pressure of 2.5-20 MPa, and prepare corresponding cyclic carbonate; in US4931571, Weinstein adopts quaternary arsine halide salt as a catalyst to catalyze the reaction of carbon dioxide and ethylene oxide at 90-200 ℃ to synthesize ethylene carbonate.
Some experts in China make certain breakthroughs in the field, for example, in CN1343668, Duntong adopts a binary catalytic system formed by ionic liquid and alkali metal halide or tetrabutylammonium bromide, and epoxy compounds are successfully converted into corresponding cyclic carbonates at 100-140 ℃ and the initial pressure of carbon dioxide of 1.5-4.5 MPa; in high hly active and selective binding system for the coupling reaction of CO2In the article of the and hydro-epoxides, a binary catalytic system which adopts a zinc-cobalt Double Metal Cyanide Catalyst (DMCC) and hexadecyl trimethyl ammonium bromide as cocatalysts is adopted by Zhang hong, propylene carbonate is selectively synthesized at the temperature of 120 ℃, the pressure of 5.0MPa and the moisture of 260ppm, and the highest catalytic efficiency can reach 9900mol of cyclic carbonate/mol of catalyst. DMCC has been accepted as a very efficient epoxy-activated ring-opening catalyst, but has the problems of poor catalyst stability, uneven distribution of active sites, and the like.
Disclosure of Invention
It is a primary object of the present invention to provide a complex of the formula:
(ZnX)·[Fe(CN)4·mL]·(ZnX2)n
wherein m is 1 or 1/2, n is selected from 1-40, and X represents F, Cl, Br or I;
l is selected from the following compounds:
Figure BDA0002917104750000021
an embodiment of the present invention further provides a preparation method of the complex, including the following steps:
(1) reacting trivalent ferric salt, ligand and potassium cyanide to prepare a tetracyanoferrate intermediate; and
(2) reacting the intermediate of the tetracyanoferrate with zinc chloride to prepare the complex;
wherein the ligand is selected from one or more of the following compounds:
Figure BDA0002917104750000022
Figure BDA0002917104750000031
an embodiment of the present invention further provides a catalyst comprising the complex, or the complex prepared by the method.
The complex of one embodiment of the invention is used as a catalyst for preparing cyclic carbonate and has higher selectivity.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below. It is to be understood that the invention is capable of other and different embodiments and its several details are capable of modification without departing from the scope of the invention, and that the description herein is intended to be taken in an illustrative rather than a limiting sense.
One embodiment of the present invention provides a complex, which has a chemical formula:
(ZnX)·[Fe(CN)4·mL]·(ZnX2)n
wherein m is 1 or 1/2, n is selected from 1-40, and X represents F, Cl, Br or I; l is a diamine ligand coordinated to the metal Fe and is selected from the following compounds:
Figure BDA0002917104750000032
Figure BDA0002917104750000041
the connection of the partial structure or group (or referred to as an iron-centered structural unit) of the complex according to an embodiment of the present invention is as follows:
Figure BDA0002917104750000042
in the above formula, the ligand L acts on iron through two N atoms (diamine bridge group) contained therein, wherein the ligand L acts on cyanide ion (CN)-) Each zinc ion of (2) is common to cyanide ions in a plurality of the above-mentioned structural units, Zn2+、X-(ZnX2) Free from the above structure, the corresponding chemical formula reflects the simplest ratio between atoms or groups of atoms.
In one embodiment, because of the presence of two sets of diamine bridging groups in the following compounds, which when acting as ligands, act simultaneously on both of the above structural units, the corresponding complex has the formula: (ZnX) · [ Fe (CN)4·1/2L]·(ZnX2)n。
Figure BDA0002917104750000043
The bimetallic complex contains a bimetallic cyano active group fixed by a diamine bridging group, and the metal active center is connected by the diamine bridging group, so that the spatial distribution of the bimetallic active center can be adjusted, the distribution of active sites is more uniform, and the complex has higher uniformity and stability when used as a catalyst.
In one embodiment, n is selected from 1 to 40, and further from 1 to 10. For example, n can be 2, 4, 5, 7, 8, 10, 12, 15, 18, 20, 22, 25, 30, 35, 40, and the like.
In one embodiment, n is selected from 1 to 2, 4 to 5, 7 to 8, or 9 to 10.
An embodiment of the present invention provides a preparation method of the complex, including the following steps:
(1) reacting trivalent ferric salt, ligand and inorganic salt containing cyanide ions to prepare a diamine-coordinated tetracyanoferrate intermediate; and
(2) reacting the intermediate of the tetracyanoferrate with zinc halide to prepare a complex;
wherein the ligand is selected from one or more of the following compounds:
Figure BDA0002917104750000051
in one embodiment, the reaction temperature in step (1) may be 50-80 ℃, such as 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 78 ℃ and the like; the reaction time can be 2-10 h, such as 3h, 5h, 6h, 8h, and the like.
In one embodiment, the ferric salt of step (1) can be a ferric halide (e.g., ferric chloride), ferric sulfate, or the like.
In one embodiment, the inorganic salt containing cyanide ions of step (1) comprises potassium cyanide and/or sodium cyanide.
In one embodiment, the molar ratio of the trivalent iron salt to the ligand in step (1) may be 1 (0.9 to 1.1), and the molar ratio of the inorganic salt containing cyanide ions to the trivalent iron salt may be 3.9 to 4.1: 1, for example, 4: 1.
In one embodiment, the reaction solvent of step (1) is a polar solvent, and further may be an organic polar solvent, such as one or more of methanol, ethanol, and acetonitrile.
In one embodiment, the reaction temperature in step (2) may be 30-60 ℃, such as 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ and the like; the reaction time can be 2-10 h, such as 3h, 4h, 6h, 8h, and the like.
In one embodiment, the zinc halide of step (2) comprises one or more of zinc fluoride, zinc chloride, zinc bromide, and zinc iodide.
In one embodiment, the molar ratio of the intermediate tetracyanoferrate of step (2) to the zinc halide may be 1 (2-41), for example, 1:5, 1:8, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, and the like.
In one embodiment, the method of preparing the complex comprises:
(1) adding ferric chloride and a ligand into an organic polar solvent, adding inorganic salt containing cyanide ions into the organic polar solvent, refluxing for 2-10 h at 50-80 ℃, and reacting to form a tetracyanoferrate intermediate;
(2) filtering the reaction solution containing the intermediate of the tetracyano, adding zinc chloride into the filtrate containing the intermediate of the tetracyano, and reacting for 2-10 h at 30-60 ℃ to obtain the complex.
In one embodiment, the method of preparing the complex comprises:
(1) adding a certain amount of ethanol as a solvent into a reaction vessel, and dissolving FeCl with a molar ratio of 1:13And ligand L, and slowly dripping KCN ethanol solution (KCN and FeCl)3The molar ratio of (1) to (4) is added into a reaction vessel, the mixture is refluxed and stirred for 8 hours at 78 ℃, and a diamine-coordinated tetracyanoferrate intermediate is formed after the reaction;
(2) cooling and filtering the reaction liquid, transferring the filtrate containing the intermediate into a reaction kettle, and slowly adding a certain amount of ZnCl2Stirring for 4h at 50 ℃, cooling and filtering after the reaction is finished, and drying the obtained solid in vacuum to obtain the target product.
An embodiment of the present invention provides a catalyst comprising the complex described above.
The catalyst of one embodiment of the invention can be used for catalyzing the reaction of synthesizing the cyclic carbonate by coupling carbon dioxide and alkylene oxide.
In one embodiment, the alkylene oxide may be, for example, ethylene oxide and/or propylene oxide.
One embodiment of the present invention provides a method for preparing cyclic carbonate, using the above complex as a catalyst, and carbon dioxide and alkylene oxide as reactants.
In one embodiment, the mass ratio of the alkylene oxide to the complex catalyst may be 50:1 to 50000:1, such as 100:1, 200:1, 500:1, 1000:1, 2000:1, 5000:1, 10000:1, 20000:1, and the like.
In one embodiment, the reaction temperature for preparing the cyclic carbonate may be 25 to 180 ℃, for example, 30 ℃, 50 ℃, 80 ℃, 100 ℃, 110 ℃, 120 ℃, 150 ℃, etc.; the reaction pressure may be 0.2 to 5.0MPa, for example, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 3MPa, etc.; the reaction time can be 0.5-8 h, 1h, 1.5h, 2h, 3h, 5h and the like.
The complex catalyst provided by the embodiment of the invention can catalyze the reaction of synthesizing the cyclic carbonate by coupling carbon dioxide and alkylene oxide with high activity and high selectivity.
In the method for preparing a cyclic carbonate according to an embodiment of the present invention, the above complex is used as a catalyst, and a cyclic loop gas-liquid contact process is used, so that the cyclic carbonate can be prepared under a relatively low carbon dioxide pressure (for example, 0.2 MPa).
In one embodiment, the cyclic loop gas-liquid contacting process includes cyclic spraying and cyclic spraying. The specific reaction process can be as follows:
adding cyclic carbonate containing a catalyst into a circulating loop reactor, heating the initial material to a reaction temperature through a heat exchanger, and introducing carbon dioxide until the pressure of a reaction system is a reaction pressure; introducing alkylene oxide and carbon dioxide into the circulating loop reactor, and maintaining the reaction pressure; and after the feeding is finished, continuously reacting until the alkylene oxide is completely consumed, transferring the reaction material in the circulating loop reactor into a flash tank, discharging carbon dioxide, carrying out reduced pressure distillation to obtain cyclic carbonate, and recycling the residual liquid containing the catalyst as the initial material of the next reaction.
Hereinafter, the complex catalyst and the application thereof according to an embodiment of the present invention will be further described with reference to specific examples. The raw materials used in the examples were commercially available.
Example 1
Preparation of the Complex
Adding 800mL of ethanol as a solvent into a 2L reaction kettle, and dissolving 6.48g of FeCl3(0.04mol) and 4.64g of ligand
Figure BDA0002917104750000071
(0.04mol), a mixed solution of 10.4g KCN (0.16mol) and 500mL ethanol was slowly added dropwise to the reaction vessel, and after the addition was completed, the mixture was stirred under reflux at 78 ℃ for 6 hours. Cooling and filtering after the reaction is finished, transferring the filtrate into a stirring reaction kettle, and slowly adding 49g of ZnCl2(0.36mol), stirring for 4h at 50 ℃, cooling and filtering after the reaction is finished, and drying the obtained solid in vacuum to obtain 52g of a target product. The resulting product has the formula (ZnCl) [ Fe (CN)4·L]·(ZnCl2)7～8(n is calculated on the basis of the molar mass) and L is
Figure BDA0002917104750000081
The following percentages were determined by elemental analysis: zn 39.3% and Fe 3.9%, consistent with theory.
Preparation of cyclic carbonates
2.0Kg of propylene carbonate containing 40g of a bimetallic complex catalyst, which was (ZnCl) [ Fe (CN) ] prepared as described above, was placed in a 10L effective volume recycle loop reactor4·L]·(ZnCl2)7～8L is
Figure BDA0002917104750000082
Starting the reaction device, heating the initial material to 25 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 0.2 MPa. 4.6Kg of propylene oxide and 3.5Kg of carbon dioxide (equimolar amounts) were added continuously over 3 hoursThe consistent feeding amount of the alkylene oxide and the carbon dioxide is required to be kept, and the system pressure is maintained at 0.2 MPa. After the addition was complete, the reaction was continued for 60 minutes. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8Kg of propylene carbonate was obtained by distillation under reduced pressure (selectivity by gas chromatography)>99.5%) and the catalyst-containing residual liquid was recycled as the starting material.
Example 2
Preparation of the Complex
Adding 800mL of ethanol as a solvent into a 2L reaction kettle under the protection of nitrogen, and dissolving 6.48g of FeCl3(0.04mol) and 6.24g of ligand
Figure BDA0002917104750000083
(0.04mol), a mixed solution of 10.4g KCN (0.16mol) and 500mL ethanol was slowly added dropwise to the reaction vessel, and after the addition was completed, the mixture was stirred under reflux at 78 ℃ for 6 hours. Cooling and filtering after the reaction is finished, transferring the filtrate into a stirring reaction kettle, and slowly adding 32.6g of ZnCl2(0.24mol), stirring for 4h at 50 ℃, cooling and filtering after the reaction is finished, and drying the obtained solid in vacuum to obtain 39g of a target product. The resulting product has the formula (ZnCl) [ Fe (CN)4·L]·(ZnCl2)4～5L is
Figure BDA0002917104750000091
The following percentages were determined by elemental analysis: zn 34.8% and Fe 5.4%, consistent with theory.
Preparation of cyclic carbonates
2.0Kg of propylene carbonate containing 4.5g of a bimetallic complex catalyst, which was the (ZnCl) [ Fe (CN) ], was charged into a circulation loop reactor having an effective volume of 10L4·L]·(ZnCl2)4～5L is
Figure BDA0002917104750000092
Starting the reaction device, heating the starting material to 110 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 2.0 MPa. 4.6Kg of propylene oxide and 3.5Kg of carbon dioxide (equimolar amounts) are added continuously over 1 hour, addingIn the feeding process, the feeding amount of the alkylene oxide and the carbon dioxide is required to be kept consistent, and the system pressure is maintained at 2.0 MPa. After the addition was complete, the reaction was continued for 10 minutes. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8Kg of propylene carbonate (selectivity) was obtained by distillation under reduced pressure>99.5%) and the catalyst-containing residual liquid was recycled as the starting material.
Example 2-1
Preparation of cyclic carbonates
2.0Kg of propylene carbonate containing 4.5g of a bimetallic complex catalyst, which was (ZnCl) [ Fe (CN) ] obtained in example 2 after drying and standing at ambient temperature for 15 days, was charged into a 10L-volume recycle loop reactor4·L]·(ZnCl2)4～5L is
Figure BDA0002917104750000093
Starting the reaction device, heating the starting material to 110 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 2.0 MPa. 4.6Kg of propylene oxide and 3.5Kg of carbon dioxide (equimolar amount) were continuously added over 1 hour, and the feeding amounts of alkylene oxide and carbon dioxide were kept constant during the addition, and the system pressure was maintained at 2.0 MPa. After the addition was complete, the reaction was continued for 10 minutes. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8Kg of propylene carbonate (selectivity) was obtained by distillation under reduced pressure>99.5%) and the catalyst-containing residual liquid was recycled as the starting material.
Examples 2 to 2
Preparation of cyclic carbonates
2.0Kg of propylene carbonate containing 4.5g of a bimetallic complex catalyst, which was (ZnCl) [ Fe (CN) ] obtained in example 2, was charged into a 10L effective volume recycle loop reactor4·L]·(ZnCl2)4～5L is
Figure BDA0002917104750000101
Starting the reaction device, heating the initial material to 180 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 0.8 MPa. Within 1 hour4.6Kg of propylene oxide and 3.5Kg of carbon dioxide (equimolar amounts) were continuously added while keeping the feeding amounts of alkylene oxide and carbon dioxide uniform and the system pressure at 0.8 MPa. After the addition was complete, the reaction was continued for 10 minutes. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8Kg of propylene carbonate (selectivity) was obtained by distillation under reduced pressure>99%) and the catalyst-containing residual liquid was recycled as the starting material.
Example 3
Preparation of the Complex
Adding 800mL of ethanol as a solvent into a 2L reaction kettle, and dissolving 8g of Fe2(SO4)3(0.02mol) and 4.64g of ligand
Figure BDA0002917104750000102
(0.04mol), a mixed solution of 10.4g of KCN (0.16mol) and 500mL of acetonitrile was slowly added dropwise to the reaction vessel, and after completion of the addition, the mixture was stirred at 80 ℃ under reflux for 8 hours. Cooling and filtering after the reaction is finished, transferring the filtrate into a stirring reaction kettle, and slowly adding 38.3g of ZnI2(0.12mol), stirring for 4h at 50 ℃, cooling and filtering after the reaction is finished, and drying the obtained solid in vacuum to obtain 38g of a target product. The resulting product has the formula (ZnI) [ Fe (CN)4·L]·(ZnI2)1～2(n is calculated on the basis of the molar mass) and L is
Figure BDA0002917104750000103
The following percentages were determined by elemental analysis: zn 17.3% and Fe 5.9%, consistent with theory.
Preparation of cyclic carbonates
2.0Kg of propylene carbonate containing 4g of a bimetallic complex catalyst, which was (ZnI) [ Fe (CN) obtained as described above, was placed in a 10L effective volume recycle loop reactor4·L]·(ZnI2)1～2L is
Figure BDA0002917104750000104
Starting the reaction device, heating the initial material to 25 ℃ through a heat exchanger, and introducing carbon dioxide into the reaction systemThe pressure was 0.8 MPa. 4.6Kg of propylene oxide and 3.5Kg of carbon dioxide (equimolar amount) were continuously added over 3 hours while keeping the feeding amounts of alkylene oxide and carbon dioxide constant and the system pressure at 0.8 MPa. After the addition was complete, the reaction was continued for 60 minutes. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8Kg of propylene carbonate was obtained by distillation under reduced pressure (selectivity by gas chromatography)>99.5%) and the catalyst-containing residual liquid was recycled as the starting material.
Example 4
Preparation of the Complex
Adding 800mL of ethanol as a solvent into a 2L reaction kettle, and dissolving 6.48g of FeCl3(0.04mol) and 10.2g of ligand
Figure BDA0002917104750000111
(0.04mol), a mixed solution of 7.84g of NaCN (0.16mol) and 500mL of acetonitrile was slowly added dropwise to the reaction vessel, and after completion of the addition, the mixture was stirred at 80 ℃ under reflux for 8 hours. After the reaction is finished, cooling and suction filtration are carried out, the filtrate is transferred to a stirring reaction kettle, and 369g of ZnBr is slowly added2(1.64mol), stirring for 4h at 50 ℃, cooling and filtering after the reaction is finished, and drying the obtained solid in vacuum to obtain 378g of a target product. The resulting product has the formula (ZnBr) [ Fe (CN)4·L]·(ZnBr2)39～40(n is calculated on the basis of the molar mass) and L is
Figure BDA0002917104750000112
The following percentages were determined by elemental analysis: zn 27.8% and Fe 0.6%, consistent with theory.
Preparation of cyclic carbonates
2.0Kg of propylene carbonate containing 90g of a bimetallic complex catalyst, which was (ZnBr) [ Fe (CN).)4·L]·(ZnBr2)39～40L is
Figure BDA0002917104750000113
Starting the reaction apparatus and heating the starting material toAnd introducing carbon dioxide at 180 ℃ until the pressure of the reaction system is 5 MPa. 4.6Kg of propylene oxide and 3.5Kg of carbon dioxide (equimolar amounts) were continuously added over 4 hours, while keeping the feeding amounts of alkylene oxide and carbon dioxide constant and the system pressure at 5 MPa. After the addition was complete, the reaction was continued for 60 minutes. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8Kg of propylene carbonate was obtained by distillation under reduced pressure (selectivity by gas chromatography)>98%) and the catalyst-containing residual liquid was recycled as the starting material.
Example 5
Preparation of the Complex
Adding 800mL of ethanol as a solvent into a 2L reaction kettle, and dissolving 6.48g of FeCl3(0.04mol) and 4.64g of ligand
Figure BDA0002917104750000121
(0.04mol), a mixed solution of 10.4g KCN (0.16mol) and 500mL ethanol was slowly added dropwise to the reaction vessel, and after the addition was completed, the mixture was stirred under reflux at 78 ℃ for 6 hours. Cooling and filtering after the reaction is finished, transferring the filtrate into a stirring reaction kettle, and slowly adding 86.5g of ZnF2(0.84mol), stirring for 4h at 50 ℃, cooling and filtering after the reaction is finished, and drying the obtained solid in vacuum to obtain 95g of a target product. The resulting product has the formula (ZnF) [ Fe (CN)4·L]·(ZnF2)19～20(n is calculated on the basis of the molar mass) and L is
Figure BDA0002917104750000122
The following percentages were determined by elemental analysis: zn 55.7% and Fe 2.3%, consistent with theory.
Preparation of cyclic carbonates
2.0Kg of ethylene carbonate containing 30g of a bimetallic complex catalyst, which was (ZnF) [ Fe (CN) prepared as described above, was charged into a 10L effective volume recycle loop reactor4·L]·(ZnF2)19～20L is
Figure BDA0002917104750000123
Starting the reaction apparatus and changingThe starting material is heated to 150 ℃ by a heater, and carbon dioxide is introduced until the pressure of the reaction system is 3 MPa. 4Kg of ethylene oxide and 4Kg of carbon dioxide (in equimolar amounts) were continuously added over 4 hours while keeping the feed rates of alkylene oxide and carbon dioxide uniform and maintaining the system pressure at 3 MPa. After the addition was complete, the reaction was continued for 60 minutes. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8Kg of ethylene carbonate was obtained by distillation under reduced pressure (selectivity by gas chromatography)>98.5%) and the catalyst-containing residual liquid was recycled as the starting material.
Example 6
Preparation of the Complex
Adding 800mL of ethanol as a solvent into a 2L reaction kettle, and dissolving 6.48g of FeCl3(0.04mol) and 8.08g of ligand
Figure BDA0002917104750000131
(0.04mol), a mixed solution of 10.4g KCN (0.16mol) and 500mL ethanol was slowly added dropwise to the reaction vessel, and after the addition was completed, the mixture was stirred under reflux at 78 ℃ for 6 hours. Cooling and filtering after the reaction is finished, transferring the filtrate into a stirring reaction kettle, and slowly adding 59.8g of ZnCl2(0.44mol), stirring for 4h at 60 ℃, cooling and filtering after the reaction is finished, and drying the obtained solid in vacuum to obtain 70g of a target product. The resulting product has the formula (ZnCl) [ Fe (CN)4·L]·(ZnCl2)9～10(n is calculated on the basis of the molar mass) and L is
Figure BDA0002917104750000132
The following percentages were determined by elemental analysis: zn 38.9% and Fe 3.2%, in line with theory.
Preparation of cyclic carbonates
2.0Kg of ethylene carbonate containing 10g of a bimetallic complex catalyst, which was (ZnCl) [ Fe (CN) ] prepared as described above, was charged into a 10L effective volume recycle loop reactor4·L]·(ZnCl2)9～10L is
Figure BDA0002917104750000133
Starting the reaction device, heating the starting material to 110 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 0.8 MPa. 4Kg of ethylene oxide and 4Kg of carbon dioxide (equimolar amount) were continuously added over 3 hours while keeping the feeding amounts of alkylene oxide and carbon dioxide uniform and the system pressure at 0.8 MPa. After the addition was complete, the reaction was continued for 60 minutes. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8Kg of ethylene carbonate was obtained by distillation under reduced pressure (selectivity by gas chromatography)>99.5%) and the catalyst-containing residual liquid was recycled as the starting material.
Example 7
Preparation of the Complex
A2L reactor was charged with 800mL of methanol as a solvent to dissolve 6.48g of FeCl3(0.04mol) and 8.08g of ligand
Figure BDA0002917104750000141
(0.04mol), a mixed solution of 10.4g KCN (0.16mol) and 500mL ethanol was slowly added dropwise to the reaction vessel, and after the addition was completed, the mixture was stirred under reflux at 65 ℃ for 8 hours. Cooling and filtering after the reaction is finished, transferring the filtrate into a stirring reaction kettle, and slowly adding 49g of ZnCl2(0.36mol), stirring for 4h at 60 ℃, cooling and filtering after the reaction is finished, and drying the obtained solid in vacuum to obtain 69g of a target product. The resulting product has the formula (ZnCl) [ Fe (CN)4·L]·(ZnCl2)7～8(n is calculated on the basis of the molar mass) and L is
Figure BDA0002917104750000142
The following percentages were determined by elemental analysis: zn 31.9% and Fe 3.2%, consistent with theory.
Preparation of cyclic carbonates
2.0Kg of ethylene carbonate containing 10g of a bimetallic complex catalyst, which was (ZnCl) [ Fe (CN) ] prepared as described above, was charged into a 10L effective volume recycle loop reactor4·L]·(ZnCl2)7～8L is
Figure BDA0002917104750000143
Starting the reaction device, heating the starting material to 130 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 0.8 MPa. 4Kg of ethylene oxide and 4Kg of carbon dioxide (in equimolar amounts) were continuously added over 4 hours while keeping the feeding amounts of alkylene oxide and carbon dioxide uniform and the system pressure at 0.8 MPa. After the addition was complete, the reaction was continued for 60 minutes. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8Kg of ethylene carbonate was obtained by distillation under reduced pressure (selectivity by gas chromatography)>99%) and the catalyst-containing residual liquid was recycled as the starting material.
Example 8
Preparation of the Complex
Adding 800mL of ethanol as a solvent into a 2L reaction kettle, and dissolving 6.48g of FeCl3(0.04mol) and 9.6g of ligand
Figure BDA0002917104750000151
(0.02mol), a mixed solution of 10.4g KCN (0.16mol) and 500mL ethanol was slowly added dropwise to the reaction vessel, and after the addition was completed, the mixture was stirred under reflux at 78 ℃ for 6 hours. Cooling and filtering after the reaction is finished, transferring the filtrate into a stirring reaction kettle, and slowly adding 49g of ZnCl2(0.36mol), stirring for 4h at 60 ℃, cooling and filtering after the reaction is finished, and drying the obtained solid in vacuum to obtain 60g of a target product. The resulting product has the formula (ZnCl) [ Fe (CN)4·1/2L]·(ZnCl2)7～8(n is calculated on the basis of the molar mass) and L is
Figure BDA0002917104750000152
The following percentages were determined by elemental analysis: zn 36.3% and Fe 3.7%, consistent with theory.
Preparation of cyclic carbonates
2.0Kg of ethylene carbonate containing 10g of a bimetallic complex catalyst, which was (ZnCl) [ Fe (CN) ] prepared as described above, was charged into a 10L effective volume recycle loop reactor4·1/2L]·(ZnCl2)7～8L is
Figure BDA0002917104750000153
Starting the reaction device, heating the starting material to 110 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 0.8 MPa. 4Kg of ethylene oxide and 4Kg of carbon dioxide (in equimolar amounts) were continuously added over 5 hours while keeping the feeding amounts of alkylene oxide and carbon dioxide uniform and the system pressure at 0.8 MPa. After the addition was complete, the reaction was continued for 60 minutes. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8Kg of ethylene carbonate was obtained by distillation under reduced pressure (selectivity by gas chromatography)>99%) and the catalyst-containing residual liquid was recycled as the starting material.
Example 9
Preparation of the Complex
Adding 800mL of ethanol as a solvent into a 2L reaction kettle, and dissolving 6.48g of FeCl3(0.04mol) and 4.64g of ligand
Figure BDA0002917104750000161
(0.04mol), a mixed solution of 10.4g KCN (0.16mol) and 500mL ethanol was slowly added dropwise to the reaction vessel, and after the addition was completed, the mixture was stirred under reflux at 78 ℃ for 6 hours. Cooling and filtering after the reaction is finished, transferring the filtrate into a stirring reaction kettle, and slowly adding 49g of ZnCl2(0.36mol), stirring for 4h at 50 ℃, cooling and filtering after the reaction is finished, and drying the obtained solid in vacuum to obtain 52g of a target product. The resulting product has the formula (ZnCl) [ Fe (CN)4·L]·(ZnCl2)7～8(n is calculated on the basis of the molar mass) and L is
Figure BDA0002917104750000162
The following percentages were determined by elemental analysis: zn 39.3% and Fe 3.9%, consistent with theory.
Preparation of cyclic carbonates
2.0Kg of ethylene carbonate containing 0.8g of a bimetallic complex catalyst, which was (ZnCl) [ Fe (CN) ] prepared as described above, was charged into a 10L effective volume recycle loop reactor4·L]·(ZnCl2)7～8L is
Figure BDA0002917104750000163
Starting the reaction device, heating the initial material to 150 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 2 MPa. 4Kg of ethylene oxide and 4Kg of carbon dioxide (in equimolar amounts) were continuously added over 6 hours while keeping the feed rates of alkylene oxide and carbon dioxide uniform and maintaining the system pressure at 2 MPa. After the addition was complete, the reaction was continued for 60 minutes. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8Kg of ethylene carbonate was obtained by distillation under reduced pressure (selectivity by gas chromatography)>99.5%) and the catalyst-containing residual liquid was recycled as the starting material. The reaction activity is higher, and the catalytic efficiency can reach 1667g of product/g of catalyst per hour.
Comparative example
Preparation of the Complex
Adding 800mL of ethanol as a solvent into a 2L reaction kettle, and dissolving 6.48g of FeCl3(0.04mol) and 4.64g of ligand
Figure BDA0002917104750000171
(0.04mol), a mixed solution of 10.4g KCN (0.16mol) and 500mL ethanol was slowly added dropwise to the reaction vessel, and after the addition was completed, the mixture was stirred under reflux at 78 ℃ for 6 hours. Cooling and filtering after the reaction is finished, transferring the filtrate into a stirring reaction kettle, and slowly adding 48.5g of anhydrous CuCl2(0.36mol), stirring for 4h at 50 ℃, cooling and filtering after the reaction is finished, and drying the obtained solid in vacuum to obtain 55g of a target product. The resulting product has the formula (CuCl) [ Fe (CN)4·L]·(CuCl2)7～8(n is calculated on the basis of the molar mass) and L is
Figure BDA0002917104750000172
The following percentages were determined by elemental analysis: cu 39%, Fe 4%, in line with theory.
Preparation of cyclic carbonates
Adding 2.0Kg of propylene carbonate containing 90g of bimetallic complex catalyst into a circulating loop reactor with the effective volume of 10L, wherein the catalyst is prepared by the method(CuCl) [ Fe (CN)4·L]·(CuCl2)7～8L is
Figure BDA0002917104750000173
Starting the reaction device, heating the initial material to 150 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 4 MPa. Propylene oxide and equimolar carbon dioxide are continuously added, the feeding amount of alkylene oxide and carbon dioxide is kept consistent during the feeding process, and the system pressure is maintained at 4 MPa. Only 0.1Kg of epoxy, and CO, was added over 6h2The pressure can not be maintained to be stable at 4MPa, and the reaction is almost inactive.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.

Claims (10)

1. A complex of the formula:
(ZnX)·[Fe(CN)4·mL]·(ZnX2)n
wherein m is 1 or 1/2, n is selected from 1-40, and X represents F, Cl, Br or I;
l is selected from the following compounds:
Figure FDA0002917104740000011
2. the complex of claim 1, wherein n has a value selected from 1 to 10.
3. A method for preparing a complex comprising the steps of:
(1) reacting trivalent ferric salt, ligand and inorganic salt containing cyanide ions to prepare a tetracyanoferrate intermediate; and
(2) reacting the intermediate of the tetracyanoferrate with zinc halide to prepare the complex;
wherein the ligand is selected from one or more of the following compounds:
Figure FDA0002917104740000021
4. the method according to claim 3, wherein the reaction temperature in the step (1) is 50-80 ℃.
5. The method according to claim 3, wherein the reaction temperature of the step (2) is 30-60 ℃.
6. The method according to claim 3, wherein the molar ratio of the trivalent iron salt to the ligand is 1 (0.9-1.1), and the molar ratio of the inorganic salt containing cyanide ions to the trivalent iron salt is 3.9-4.1: 1.
7. The method of claim 3, wherein the molar ratio of the intermediate tetracyanoferrate to the zinc halide is 1 (2-41).
8. The method of claim 3, wherein the inorganic salt containing cyanide ions comprises potassium cyanide and/or sodium cyanide, the ferric salt comprises ferric chloride and/or ferric sulfate, and the zinc halide comprises one or more of zinc fluoride, zinc chloride, zinc bromide, and zinc iodide.
9. The method of claim 3, comprising:
(1) adding ferric chloride and the ligand into an organic polar solvent, adding the inorganic salt containing cyanide ions into the organic polar solvent, refluxing for 2-10 h at 50-80 ℃, and reacting to form the intermediate of the tetracyanoferrate;
(2) and filtering the reaction solution containing the intermediate of the ferricyanide, adding zinc chloride into the filtrate containing the intermediate of the ferricyanide, and reacting for 2-10 h at 30-60 ℃ to obtain the complex.
10. A catalyst comprising the complex of claim 1 or 2, or the complex made by the process of any one of claims 3 to 9.
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