CN108424359A - Catalyzed by ruthenium complexes CO in a kind of water phase2The method that hydrogenating reduction prepares formates/formic acid - Google Patents
Catalyzed by ruthenium complexes CO in a kind of water phase2The method that hydrogenating reduction prepares formates/formic acid Download PDFInfo
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- CN108424359A CN108424359A CN201810255395.8A CN201810255395A CN108424359A CN 108424359 A CN108424359 A CN 108424359A CN 201810255395 A CN201810255395 A CN 201810255395A CN 108424359 A CN108424359 A CN 108424359A
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- 0 CC*C(CC1=C=CC=C2C1CCC2)C(C)N Chemical compound CC*C(CC1=C=CC=C2C1CCC2)C(C)N 0.000 description 1
- KSPUUJZWUWVUCG-UHFFFAOYSA-N C[N+](CC1CC1)(N)=C1CC1 Chemical compound C[N+](CC1CC1)(N)=C1CC1 KSPUUJZWUWVUCG-UHFFFAOYSA-N 0.000 description 1
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—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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- 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
- B01J2531/02—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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- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides catalyzed by ruthenium complexes CO in a kind of water phase2The method that hydrogenating reduction prepares formates/formic acid belongs to the energy and homogeneous catalysis technical field.The present invention has synthesized a series of catalyzed by ruthenium complexes agent, and is applied to catalysis water phase CO2Hydrogenation formates/formic acid reaction.It is an advantage of the invention that：The preparation method of the series catalyzed by ruthenium complexes agent is relatively easy, and cost is relatively low；The catalyst series in aqueous solution, in the case where adding alkali, can efficient catalytic CO2Hydrogenation is for formates；Reaction temperature and pressure it is relatively low, be not added with alkali under conditions of, can effectively be catalyzed CO2Hydrogenating reduction directly prepares formic acid.
Description
Technical field
The invention belongs to the energy and homogeneous catalysis technical field, are related to homogeneous catalysis CO2Hydrogenating reduction is related specifically to
Catalyzed by ruthenium complexes CO in a kind of water phase2The method that hydrogenating reduction prepares formates/formic acid.
Background technology
Since the industrial revolution, a large amount of uses of the fossil fuels such as coal, oil, natural gas lead to a large amount of CO2The row of gas
It puts, greenhouse effects getting worse.Realize CO2Recycling, especially to the conversion of carbon based energy source, for slowing down temperature
Room effect and exploitation regenerative resource have strategic meaning.CO2With very high thermodynamic stability, activation or conversion
It is difficult to carry out, generally requires to consume a large amount of energy.Formic acid can pass through CO2Prepared by hydrogenating reduction, be a kind of relatively easy system
The product obtained.Formic acid is important industrial chemicals, can be used as fuel and is directly used in aminic acid fuel battery, in addition formic acid or one kind
Good hydrogen storage material, therefore develop CO2The catalyst system and catalyzing for being converted into formic acid has important practical significance.
Currently, catalysis CO2The heterogeneous catalytic system of Hydrogenation formic acid there are catalytic efficiencies low, poor selectivity and reaction condition
Harsh problem.Although reported homogeneous catalysis system selectivity good, high catalytic efficiency, generally require higher temperature and
Pressure condition, majority catalysis reaction carry out in organic solvent.In addition, needing that alkali is added mostly in catalyst system and catalyzing.Therefore add hydrogen
The product of reduction is formates, needs further can just obtain target product formic acid with acid neutralization.Processing procedure is cumbersome, also increases
Reaction cost.In recent years, it with the development of Green Chemistry, makees solvent using cheap, nontoxic, environmental-friendly water and carries out CO2
The research of hydrogenating reduction is concerned.Therefore, efficient metal complex catalysts are developed, are realized (lower under temperate condition
Temperature and pressure), CO is catalyzed in water phase2Hydrogenating reduction directly prepares formic acid, avoids using basic additive, meets Green Chemistry
Idea of development, for developing efficient, inexpensive, environmental-friendly CO2Catalyzed conversion system is significant.
Invention content
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, catalyzed by ruthenium complexes is provided
Greenhouse gases CO2The method of water phase hydrogenating reduction.The preparation method of this kind of catalyzed by ruthenium complexes agent is simple, and cost is relatively low, is adding
Under conditions of adding weak base, CO is catalyzed in water phase2Hydrogenating reduction prepares formates, in catalysis CO2It is shown in hydrogenation process good
Catalytic activity, TON is up to 3380；Under conditions of being not added with alkali, CO is catalyzed in water phase2Hydrogenating reduction directly prepares first
Acid, TON reach 920.
Technical scheme of the present invention：
Catalyzed by ruthenium complexes CO in a kind of water phase2The method that hydrogenating reduction prepares formates/formic acid, the ruthenium complex
Structural formula such as following formula：
In formula：R1Group is H, OH or OCH3, R group Ph,tBu oriPr；
The preparation method of formates is as follows：
Under nitrogen protection, the KHCO of a concentration of 1~2mol/L of deoxygenation is added into reaction kettle3Aqueous solution and 0.01
The catalyzed by ruthenium complexes agent of~0.1 μm of ol；Then with the CO of 1~4MPa2/H2Mixed gas replaces nitrogen, CO2With H2Volume
Than being 1:5~5:1；It under 90~130 DEG C of temperature conditions, is stirred to react for 24 hours, the formates that highest obtains 14.5mmol/L is molten
Liquid, TON are up to 3380.
The preparation method of formic acid is as follows：
By the KHCO in formic acid salt production process3Aqueous solution replaces with deaerated water, other reaction conditions keep identical, can be with
The formic acid solution of 3.3mmol/L is obtained, TON is up to 920.
Reaction condition is：0.01~0.1 μm of ol catalyzed by ruthenium complexes agent；1~4MP of reaction pressure；CO2/H2In mixed gas
CO2/H2Volume ratio is 1:5~5:1；90~130 DEG C of reaction temperature；The reaction solution for preparing formates is the KHCO of deoxygenation3Aqueous solution
10mL, a concentration of 1~2mol/L；The reaction solution for preparing formic acid is 10mL deaerated water.
The preparation method of the ruthenium complex, steps are as follows：
(1) it is 1 according to molar ratio:1 by PNN- tridentate ligands and catalyst precarsor RuCl2(PPh3)3It is dissolved in dry toluene
In, inert gas N2Under protection, it is stirred to react 12h at room temperature.After reaction, filtering reacting liquid is collected filter cake, is washed with ether
Filter cake is washed, is dried in vacuo, obtains catalyzed by ruthenium complexes agent I.
(2) it is 1 according to molar ratio:1 by PNN- tridentate ligands and catalyst precarsor RuCl2(PPh3)3It is dissolved in anhydrous THF,
Inert gas N2Under protection, 12h is stirred to react at 40 DEG C.After being cooled to room temperature, solvent is removed under reduced pressure, washed with ether remaining solid
Body three times, by residual solid recrystallize with dichloromethane, obtains catalyzed by ruthenium complexes agent II.
Beneficial effects of the present invention：
1, catalyzed by ruthenium complexes agent preparation method produced by the present invention is simple, and cost is relatively low, can be in relatively mild condition
Lower catalysis CO2Hydrogen is added to obtain formates；KHCO of the catalyst in 2mol/L3It is reacted in solution, TON is up to 3380, has excellent
Good catalytic activity.
2, catalysis reaction carries out in aqueous solution, avoids the pollution brought using organic solvent.
3, catalysis reaction can be catalyzed CO under conditions of not adding alkali2Hydrogenation reduction directly prepares formic acid, TON high
Up to 920.
Description of the drawings
Fig. 1 is catalyst trans-RuCl2(PPh3)[OH-PyCH2NH(CH2)2PPh2] (Cat.1)1HNMR spectrograms.
Fig. 2 is catalyst trans-RuCl2(PPh3)[PyCH2NH(CH2)2PPh2] (Cat.2)1H NMR spectras.
Fig. 3 is catalyst trans-RuCl2(PPh3)[CH3O-PyCH2NH(CH2)2PPh2] (Cat.3)1HNMR spectrograms.
Fig. 4 is the catalytic activity comparison diagram of three kinds of catalyst (Cat.1-3) under the same reaction conditions.
Fig. 5 is catalyst trans-RuCl2(PPh3)[OH-PyCH2NH(CH2)2PPh2] (Cat.1) catalysis CO2Add hydrogen
React TON time history plots, 120 DEG C of reaction condition, 4MPa (CO2/H2=1:1), the KHCO of 30mL 2mol/L3It is molten
Liquid, 0.15 μm of ol of catalyst amount.
Specific implementation mode
Below in conjunction with attached drawing and technical solution, the specific implementation mode that further illustrates the present invention.
Embodiment 1
trans-RuCl2(PPh3)[OH-PyCH2NH(CH2)2PPh2] preparation and its catalysis CO2Hydrogenation formates
Method：
(1) under nitrogen protection, by RuCl2(PPh3)3(0.1106g, 0.1153mmol) be added to ligand (0.0388g,
In dry toluene (5mL) solution 0.1153mmol), it is stirred to react 12h at room temperature.After reaction, filtering reacting liquid is collected
Filter cake washs filter cake three times with cold ether, collects filter cake, and vacuum drying obtains yellow solid trans-RuCl2(PPh3)[OH-
PyCH2NH(CH2)2PPh2]。
(2) KHCO of 2mol/L is prepared3Solution, and under nitrogen protection, deoxidation treatment is carried out to it, steps are as follows：It will
The KHCO of 2mol/L3Aqueous solution be placed in 100mL single port bottles, vacuum nitrogen gas operation it is continuous 3 times；Under nitrogen protection,
Solid is refrigerated in liquid nitrogen, then slowly heating under vacuum-pumping conditions, removes the oxygen dissolved in aqueous solution.Wait for that solid melts
Afterwards, nitrogen is poured.Repeat the freezing deoxygenation step 3 times；Then the aqueous solution after deoxidation is placed under nitrogen protection store it is spare.
(3) under nitrogen protection, by 1.00mg catalyst trans-RuCl2(PPh3)[OH-PyCH2NH-(CH2)2PPh2]
It is dissolved in 13mL and newly steams anhydrous THF, be configured to the catalyst solution of a concentration of 100 μm of ol/L.
(4) in nitrogen atmosphere glove box, the KHCO of 10mL 2mol/L is added into reaction kettle3With 100 μm of ol/L of 1mL
Catalyst solution, seal reaction kettle.Use CO2/H2Gaseous mixture (CO2/H2=1:1) after displacement three times, it is pressurized to 4MPa.It will be anti-
It answers kettle to be placed in 120 DEG C of oil bath pan, is stirred to react for 24 hours, HPLC detects the concentration of formates；According to catalyst amount and formic acid
The TON that the concentration of salt calculates catalysis reaction is 3380.
Embodiment 2：
trans-RuCl2(PPh3)[PyCH2NH(CH2)2PPh2] preparation and its catalysis CO2The side of Hydrogenation formates
Method：
(1) under nitrogen protection, by RuCl2(PPh3)3(0.1676g, 0.1747mmol) be added to ligand (0.0560g,
In toluene (5mL) solution 0.1747mmol), it is stirred to react 12h at room temperature.After reaction, filtering reacting liquid collects filter cake,
Filter cake is washed with cold ether three times, is dried in vacuo, is obtained yellow solid trans-RuCl2(PPh3)[PyCH2NH(CH2)2PPh2]。
(2)KHCO3The deoxidation treatment of solution is the same as 1 step of embodiment (2).
(3) under nitrogen protection, by 1.00mg catalyst trans-RuCl2(PPh3)[PyCH2NH-(CH2)2PPh2] be dissolved in
Anhydrous THF 13.3mL are newly steamed, the solution of a concentration of 100 μm of ol/L is made into.
(4) in nitrogen atmosphere glove box, the KHCO of 10mL 2mol/L is added into reaction kettle3100 μ of solution and 1mL
The catalyst solution of mol/L seals reaction kettle.Use CO2/H2Gaseous mixture (CO2/H2=1:1) after displacement three times, it is pressurized to 4MPa,
Reaction kettle is placed in 120 DEG C of oil bath pan, is stirred to react for 24 hours, HPLC detects concentration of formate greater, according to catalyst amount and first
The TON that hydrochlorate concentration calculates catalysis reaction is 2900.
Embodiment 3：
trans-RuCl2(PPh3)[CH3O-PyCH2NH(CH2)2PPh2] preparation and its catalysis CO2Hydrogenation formates
Method：
(1) under nitrogen protection, by RuCl2(PPh3)3(0.1628g, 0.1698mmol) be added to ligand (0.0595g,
In dry toluene (5mL) solution 0.1698mmol), it is stirred to react 12h at room temperature.After reaction, filtering reacting liquid is collected
Filter cake washs filter cake three times with cold ether, and vacuum drying obtains yellow solid product.
(2)KHCO3The deoxidation treatment of solution is the same as 1 step of embodiment (2).
(3) by 1.00mg catalyst trans-RuCl2(PPh3)[PyCH2NH(CH2)2PPh2] be dissolved in and newly steam anhydrous THF
12.7mL is made into the solution of a concentration of 100 μm of ol/L in glove box.
(4) in nitrogen atmosphere glove box, the KHCO of 10mL 2mol/L is added into reaction kettle3100 μ of solution and 1mL
The catalyst solution of mol/L seals reaction kettle.Replace gaseous mixture (CO2/H2=1:1) it three times, is pressurized to 4MPa, reaction kettle is set
In 120 DEG C of oil bath pan, it is stirred to react for 24 hours.HPLC detects concentration of formate greater, according to catalyst amount and concentration of formate greater meter
The TON for calculating catalysis reaction is 1450.
Embodiment 4：
trans-RuCl2(PPh3)[OH-PyCH2NH(CH2)2PPh2] under the conditions of alkali-free it is catalyzed CO2Hydrogenation formic acid
Method：
(1) deoxidation treatment is carried out to deionized water, freezing deoxidation operation is the same as 1 step of embodiment (2).
(2) under nitrogen protection, by 1.00mg catalyst trans-RuCl2(PPh3)[OH-PyCH2NH-(CH2)2PPh2]
It is dissolved in 13mL and newly steams anhydrous THF, be configured to the catalyst solution of a concentration of 100 μm of ol/L.
(3) in nitrogen atmosphere glove box, the catalyst of 100 μm of ol/L of 10mL deoxygenated waters and 1mL is added into reaction kettle
Solution seals reaction kettle.Use CO2/H2Gaseous mixture (CO2/H2=1:1) after displacement three times, it is pressurized to 4MPa.Reaction kettle is placed in
In 120 DEG C of oil bath pan, it is stirred to react for 24 hours.HPLC detects the concentration of formic acid, is calculated according to the concentration of catalyst amount and formic acid
The TON of catalysis reaction is 920.
Claims (2)
1. catalyzed by ruthenium complexes CO in a kind of water phase2The method that hydrogenating reduction prepares formates/formic acid, which is characterized in that described
The structural formula of ruthenium complex such as following formula：
In formula：R1Group is H, OH or OCH3, R group Ph,tBu oriPr；
The preparation method of formates is as follows：
Under nitrogen protection, the KHCO of a concentration of 1~2mol/L of deoxygenation is added into reaction kettle3Aqueous solution and 0.01~0.1
The catalyzed by ruthenium complexes agent of μm ol；Then with the CO of 1~4MPa2/H2Mixed gas replaces nitrogen, CO2With H2Volume ratio be 1:
5~5:1；It under 90~130 DEG C of temperature conditions, is stirred to react for 24 hours, highest obtains the formate solution of 14.5mmol/L, and TON reaches
3380；
The preparation method of formic acid is as follows：
By the KHCO in formic acid salt production process3Aqueous solution replaces with deaerated water, other reaction conditions with prepare reacting for formates
Condition is identical, obtains the formic acid solution of 3.3mmol/L, and TON is up to 920.
2. catalyzed by ruthenium complexes CO in water phase according to claim 12The method that hydrogenating reduction prepares formates/formic acid,
It is characterized in that, the preparation method of the ruthenium complex, steps are as follows：
(1) it is 1 according to molar ratio:1 by PNN- tridentate ligands and catalyst precarsor RuCl2(PPh3)3It is dissolved in dry toluene, it is lazy
Property gas N2Under protection, it is stirred to react 12h at room temperature；After reaction, filtering reacting liquid collects filter cake, filter is washed with ether
Cake, vacuum drying, obtains catalyzed by ruthenium complexes agent I；
(2) it is 1 according to molar ratio:1 by PNN- tridentate ligands and catalyst precarsor RuCl2(PPh3)3It is dissolved in anhydrous THF, inertia
Gas N2Under protection, 12h is stirred to react at 40 DEG C；After being cooled to room temperature, solvent is removed under reduced pressure, residual solid three is washed with ether
It is secondary, by residual solid recrystallize with dichloromethane, obtain catalyzed by ruthenium complexes agent II.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116082143A (en) * | 2023-02-14 | 2023-05-09 | 大连理工大学 | MOF encapsulated metal Ir complex catalyzed CO 2 Method for preparing formate/formic acid by hydrogenation reduction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116082143A (en) * | 2023-02-14 | 2023-05-09 | 大连理工大学 | MOF encapsulated metal Ir complex catalyzed CO 2 Method for preparing formate/formic acid by hydrogenation reduction |
| CN116082143B (en) * | 2023-02-14 | 2024-03-22 | 大连理工大学 | MOF encapsulated metal Ir complex catalyzed CO 2 Method for preparing formate/formic acid by hydrogenation reduction |
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