CN108424359B - Ruthenium complex in water phase for catalyzing CO2Method for preparing formate/formic acid by hydrogenation reduction - Google Patents
Ruthenium complex in water phase for catalyzing CO2Method for preparing formate/formic acid by hydrogenation reduction Download PDFInfo
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- CN108424359B CN108424359B CN201810255395.8A CN201810255395A CN108424359B CN 108424359 B CN108424359 B CN 108424359B CN 201810255395 A CN201810255395 A CN 201810255395A CN 108424359 B CN108424359 B CN 108424359B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
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- 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
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
- B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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Abstract
The invention provides a ruthenium complex in a water phase for catalyzing CO2A method for preparing formate/formic acid by hydrogenation reduction belongs to the technical field of energy and homogeneous catalysis. The invention synthesizes a series of ruthenium complex catalysts and applies the ruthenium complex catalysts to catalyzing water-phase CO2And (4) hydrogenation to prepare formate/formic acid. The invention has the advantages that: the preparation method of the series of ruthenium complex catalysts is relatively simple and has low cost; the series of catalysts can efficiently catalyze CO in aqueous solution under the condition of adding alkali2Preparing formate by hydrogenation; can effectively catalyze CO under the conditions of low reaction temperature and pressure and no addition of alkali2Hydrogenation reduction is carried out to directly prepare formic acid.
Description
Technical Field
The invention belongs to the technical field of energy and homogeneous catalysis, and relates to homogeneous catalysis of CO2Hydrogenation reduction, in particular to CO catalyzed by ruthenium complex in water phase2A process for preparing formate/formic acid by hydrogenation reduction.
Background
Since the industrial revolution, the use of fossil fuels such as coal, oil, and natural gas in large quantities has resulted in large quantities of CO2The greenhouse effect is increasingly serious due to the emission of gas. Realization of CO2The resource utilization, especially the conversion to carbon-based energy materials, has strategic significance for slowing down the greenhouse effect and developing renewable energy sources. CO 22Has very high thermodynamic stability, is difficult to activate or convert, and often consumes a large amount of energy. Formic acid can pass through CO2Hydrogenation reduction preparation, which is a relatively easy product to prepare. Formic acid is an important chemical raw material, can be directly used in a formic acid fuel cell as a fuel, and is also a good hydrogen storage material, so CO is developed2The catalytic system for converting into formic acid has important practical significance.
At present, CO is catalyzed2The heterogeneous catalytic system for preparing the formic acid by hydrogenation has the problems of low catalytic efficiency, poor selectivity and harsh reaction conditions. The reported homogeneous catalysis system has good selectivity and high catalysis efficiency, but often needs higher temperature and pressure conditions, and most catalytic reactions are carried out in organic solvents. In addition, the addition of a base is often required in the catalytic system. Therefore, the product of hydrogenation reduction is formate, and further neutralization with acid is needed to obtain the target product formic acid. The treatment process is complicated and the reaction cost is also increased. In recent years, with the development of green chemistry, CO is carried out by using cheap, nontoxic and environment-friendly water as a solvent2Research on hydrogenation reduction is of great interest. Therefore, the efficient metal complex catalyst is developed, and the CO is catalyzed in the water phase under mild conditions (lower temperature and pressure)2The formic acid is directly prepared by hydrogenation reduction, alkaline additives are not used, the development concept of green chemistry is met, and the method is efficient, low in cost and environment-friendly to develop CO2The catalytic conversion system has great significance.
Disclosure of Invention
The invention is toAiming at overcoming the defects of the prior art, the technical problem is to provide the ruthenium complex for catalyzing greenhouse gas CO2A method for aqueous phase hydrogenation reduction. The ruthenium complex catalyst is simple in preparation method and low in cost, and can be used for catalyzing CO in a water phase under the condition of adding weak base2Preparation of formate by hydrogenation reduction in the presence of CO catalyst2The catalyst shows good catalytic activity in the hydrogenation process, and the TON is up to 3380; catalysis of CO in aqueous phase without addition of base2The formic acid is directly prepared by hydrogenation reduction, and TON reaches 920.
The technical scheme of the invention is as follows:
ruthenium complex in water phase for catalyzing CO2A method for preparing formate/formic acid by hydrogenation reduction, wherein the structural formula of the ruthenium complex is as follows:
in the formula: r1The radical being H, OH or OCH3R is Ph,tBu oriPr；
The preparation method of the formate is as follows:
under the protection of nitrogen, adding 1-2 mol/L KHCO with deoxygenation concentration into a reaction kettle3An aqueous solution and 0.01-0.1 mu mol of ruthenium complex catalyst; then using 1-4 MPa of CO2/H2Replacement of Nitrogen and CO by Mixed gas2And H2The volume ratio of (A) to (B) is 1: 5-5: 1; stirring and reacting for 24 hours at the temperature of 90-130 ℃, and obtaining a formate solution with the highest concentration of 14.5mmol/L and the TON as high as 3380.
The preparation method of formic acid comprises the following steps:
KHCO from formate preparation method3The aqueous solution is replaced by deoxygenated water, other reaction conditions are kept the same, 3.3mmol/L formic acid solution can be obtained, and TON is up to 920.
The reaction conditions are as follows: 0.01-0.1 mu mol of ruthenium complex catalyst; the reaction pressure is 1-4 MP; CO 22/H2CO in mixed gas2/H2The volume ratio is 1: 5-5: 1; reaction ofThe temperature is 90-130 ℃; the reaction liquid for preparing the formate is the deoxidized KHCO310mL of aqueous solution with the concentration of 1-2 mol/L; the reaction solution for preparing formic acid was 10mL of deoxygenated water.
The preparation method of the ruthenium complex comprises the following steps:
(1) PNN-tridentate ligand and catalyst precursor RuCl in a molar ratio of 1:12(PPh3)3Dissolving in anhydrous toluene, and adding inert gas N2The reaction was stirred at room temperature for 12h under protection. And after the reaction is finished, filtering the reaction solution, collecting a filter cake, washing the filter cake with diethyl ether, and drying in vacuum to obtain the ruthenium complex catalyst I.
(2) PNN-tridentate ligand and catalyst precursor RuCl in a molar ratio of 1:12(PPh3)3Dissolved in anhydrous THF, inert gas N2The reaction is stirred for 12 hours at 40 ℃ under protection. After cooling to room temperature, the solvent was evaporated under reduced pressure, the residual solid was washed with diethyl ether three times, and the residual solid was recrystallized from dichloromethane to obtain ruthenium complex catalyst ii.
The invention has the beneficial effects that:
1. the ruthenium complex catalyst prepared by the invention has the advantages of simple preparation method and low cost, and can catalyze CO under relatively mild conditions2Hydrogenation is carried out to obtain formate; KHCO of catalyst at 2mol/L3The highest TON of the catalyst can reach 3380 after reaction in the solution, and the catalyst has excellent catalytic activity.
2. The catalytic reaction is carried out in aqueous solution, and pollution caused by using an organic solvent is avoided.
3. The catalytic reaction can catalyze CO without adding alkali2The formic acid is directly prepared by hydrogenation reduction reaction, and TON is up to 920.
Drawings
FIG. 1 shows the catalyst trans-RuCl2(PPh3)[OH-PyCH2NH(CH2)2PPh2](Cat.1) of1H NMR spectrum.
FIG. 2 shows the trans-RuCl catalyst2(PPh3)[PyCH2NH(CH2)2PPh2](Cat.2) of1H NMR Spectra.
FIG. 3 is catalyst trans-RuCl2(PPh3)[CH3O-PyCH2NH(CH2)2PPh2](Cat.3) of1H NMR spectrum.
FIG. 4 is a graph comparing the catalytic activity of three catalysts (Cat.1-3) under the same reaction conditions.
FIG. 5 shows the trans-RuCl catalyst2(PPh3)[OH-PyCH2NH(CH2)2PPh2](Cat.1) catalyzed CO2The TON of hydrogenation reaction varies with time under 120 deg.C and 4MPa (CO)2/H21:1), 30mL of 2mol/L KHCO3Solution, catalyst amount 0.15. mu. mol.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
trans-RuCl2(PPh3)[OH-PyCH2NH(CH2)2PPh2]Preparation of (1) and catalysis of CO therewith2The method for preparing the formate by hydrogenation comprises the following steps:
(1) under the protection of nitrogen, RuCl is added2(PPh3)3(0.1106g, 0.1153mmol) was added to a solution of ligand (0.0388g, 0.1153mmol) in dry toluene (5mL) and the reaction was stirred at room temperature for 12 h. After the reaction is finished, filtering the reaction liquid, collecting a filter cake, washing the filter cake with cold diethyl ether for three times, collecting the filter cake, and drying in vacuum to obtain a yellow solid trans-RuCl2(PPh3)[OH-PyCH2NH(CH2)2PPh2]。
(2) Preparing 2mol/L KHCO3And (3) deoxidizing the solution under the protection of nitrogen, wherein the deoxidizing treatment comprises the following steps: adding 2mol/L KHCO3The aqueous solution is put into a 100mL single-mouth bottle, and the operations of vacuumizing and filling nitrogen are continued for 3 times; freezing in liquid nitrogen under the protection of nitrogen until solid, and slowly heating under the condition of vacuum-pumping to remove oxygen dissolved in the water solution. After the solid melted, nitrogen was flushed. Repeating the freezing and deoxidizing step for 3 times; then the deoxidized water is addedThe solution was stored under nitrogen for future use.
(3) Under the protection of nitrogen, 1.00mg of catalyst trans-RuCl2(PPh3)[OH-PyCH2NH- (CH2)2PPh2]Dissolved in 13mL of freshly distilled anhydrous THF to prepare a catalyst solution having a concentration of 100. mu. mol/L.
(4) In a nitrogen atmosphere glove box, 10mL of 2mol/L KHCO was added to the reaction kettle3And 1mL of 100. mu. mol/L catalyst solution, and the reaction vessel was sealed. With CO2/H2Mixed gas (CO)2/H21:1) three times, and then pressurized to 4 MPa. Placing the reaction kettle in an oil bath kettle at 120 ℃, stirring for reaction for 24 hours, and detecting the concentration of formate by HPLC; the TON of the catalyzed reaction was calculated to be 3380 based on the amount of catalyst and the concentration of formate salt.
Example 2:
trans-RuCl2(PPh3)[PyCH2NH(CH2)2PPh2]preparation of (1) and catalysis of CO therewith2The method for preparing the formate by hydrogenation comprises the following steps:
(1) under the protection of nitrogen, RuCl is added2(PPh3)3(0.1676g, 0.1747mmol) was added to a solution of ligand (0.0560g, 0.1747mmol) in toluene (5mL) and the reaction stirred at room temperature for 12 h. After the reaction is finished, filtering reaction liquid, collecting filter cakes, washing the filter cakes three times by using cold diethyl ether, and drying in vacuum to obtain yellow solid trans-RuCl2(PPh3)[PyCH2NH(CH2)2PPh2]。
(2)KHCO3The deoxygenation treatment of the solution was performed in the same manner as in step (2) of example 1.
(3) Under the protection of nitrogen, 1.00mg of catalyst trans-RuCl2(PPh3)[PyCH2NH- (CH2)2PPh2]Dissolved in 13.3mL of freshly distilled anhydrous THF to prepare a solution having a concentration of 100. mu. mol/L.
(4) In a nitrogen atmosphere glove box, 10mL of 2mol/L KHCO was added to the reaction kettle3The solution and 1mL of 100. mu. mol/L catalyst solution were added, and the reaction vessel was sealed. With CO2/H2Mixed gas (CO)2/H21:1) and pressurizing to 4MPa after three times of replacement, placing the reaction kettle in an oil bath kettle at 120 ℃, stirring for 24 hours, detecting the concentration of formate by HPLC, and calculating the TON of the catalytic reaction to be 2900 according to the using amount of the catalyst and the concentration of the formate.
Example 3:
trans-RuCl2(PPh3)[CH3O-PyCH2NH(CH2)2PPh2]preparation of (1) and catalysis of CO therewith2The method for preparing the formate by hydrogenation comprises the following steps:
(1) under the protection of nitrogen, RuCl is added2(PPh3)3(0.1628g, 0.1698mmol) was added to a solution of ligand (0.0595g, 0.1698mmol) in dry toluene (5mL) and the reaction stirred at room temperature for 12 h. After the reaction is finished, filtering the reaction liquid, collecting a filter cake, washing the filter cake with cold diethyl ether for three times, and drying in vacuum to obtain a yellow solid product.
(2)KHCO3The deoxygenation treatment of the solution was performed in the same manner as in step (2) of example 1.
(3) 1.00mg of catalyst trans-RuCl2(PPh3)[PyCH2NH(CH2)2PPh2]Dissolved in 12.7mL of freshly distilled anhydrous THF, and made up into a solution with a concentration of 100. mu. mol/L in a glove box.
(4) In a nitrogen atmosphere glove box, 10mL of 2mol/L KHCO was added to the reaction kettle3The solution and 1mL of 100. mu. mol/L catalyst solution were added, and the reaction vessel was sealed. Replacement gas mixture (CO)2/H21:1) three times, pressurizing to 4MPa, placing the reaction kettle in an oil bath kettle at 120 ℃, and stirring for reaction for 24 hours. And detecting the concentration of formate by HPLC, and calculating the TON of the catalytic reaction to be 1450 according to the using amount of the catalyst and the concentration of formate.
Example 4:
trans-RuCl2(PPh3)[OH-PyCH2NH(CH2)2PPh2]catalysis of CO in the absence of base2The method for preparing the formic acid by hydrogenation comprises the following steps:
(1) the deionized water was subjected to deoxidation treatment, and the freeze deoxidation operation was the same as in step (2) of example 1.
(2) Under the protection of nitrogen, 1.00mg of catalyst trans-RuCl2(PPh3)[OH-PyCH2NH- (CH2)2PPh2]Dissolved in 13mL of freshly distilled anhydrous THF to prepare a catalyst solution having a concentration of 100. mu. mol/L.
(3) In a glove box under nitrogen atmosphere, 10mL of deoxygenated water and 1mL of 100. mu. mol/L catalyst solution were added to the reaction vessel, and the reaction vessel was sealed. With CO2/H2Mixed gas (CO)2/H21:1) three times, and then pressurized to 4 MPa. The reaction kettle is placed in an oil bath kettle at the temperature of 120 ℃, and is stirred to react for 24 hours. The concentration of formic acid was measured by HPLC, and the TON of the catalyzed reaction was calculated to be 920 based on the amount of catalyst and the concentration of formic acid.
Claims (2)
1. Ruthenium complex in water phase for catalyzing CO2The method for preparing formate/formic acid by hydrogenation reduction is characterized in that the structural formula of the ruthenium complex is as follows:
in the formula: r1The radical being H, OH or OCH3R is Ph,tBu oriPr；
The preparation method of the formate is as follows:
under the protection of nitrogen, adding 1-2 mol/L KHCO with deoxygenation concentration into a reaction kettle3An aqueous solution and 0.01-0.1 mu mol of ruthenium complex catalyst; then using 4MPa of CO2/H2Replacement of Nitrogen and CO by Mixed gas2And H2The volume ratio of (A) to (B) is 1: 1; stirring and reacting for 24 hours at the temperature of 120 ℃ to obtain a formate solution;
the preparation method of formic acid comprises the following steps:
KHCO from formate preparation method3The aqueous solution is replaced by deoxygenated water, and other reaction conditions are the same as the reaction conditions for preparing the formate, so that the formic acid solution is obtained.
2. Ruthenium complexes in aqueous phase according to claim 1 for the catalysis of CO2The method for preparing formate/formic acid by hydrogenation reduction is characterized in that the preparation method of the ruthenium complex comprises the following steps:
PNN-tridentate ligand and catalyst precursor RuCl in a molar ratio of 1:12(PPh3)3Dissolving in anhydrous toluene, and adding inert gas N2Stirring and reacting for 12 hours at room temperature under protection; and after the reaction is finished, filtering the reaction solution, collecting a filter cake, washing the filter cake with diethyl ether, and drying in vacuum to obtain the ruthenium complex catalyst I.
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