CN113145176B - Cobalt-manganese-based catalyst for cyclohexene hydroformylation reaction, and preparation and application thereof - Google Patents

Cobalt-manganese-based catalyst for cyclohexene hydroformylation reaction, and preparation and application thereof Download PDF

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CN113145176B
CN113145176B CN202110494632.8A CN202110494632A CN113145176B CN 113145176 B CN113145176 B CN 113145176B CN 202110494632 A CN202110494632 A CN 202110494632A CN 113145176 B CN113145176 B CN 113145176B
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cobalt
manganese
raw material
cyclohexene
based catalyst
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CN113145176A (en
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黄唯平
张建国
范新川
王满
董建勋
朱宝林
谭凯元
徐蓓蕾
冯晓燕
张晓鹏
牛乐朋
李吉芳
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Nankai University
China Pingmei Shenma Energy and Chemical Group Co Ltd
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China Pingmei Shenma Energy and Chemical Group Co Ltd
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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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • B01J31/20—Carbonyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
    • 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
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • 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
    • B01J2531/845—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02P20/584—Recycling of catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a cobalt-manganese-based catalyst for cyclohexene hydroformylation reaction, and preparation and application thereof. Wherein the preparation method comprises the following steps: and (3) heating the dispersion liquid of the nanoscale cobalt-based raw material and cyclopentadiene manganese tricarbonyl and/or derivatives thereof to react under a protective atmosphere, and obtaining a solid-liquid mixture which is the cobalt-manganese-based catalyst. The preparation method provided by the invention has the advantages of simple process, stable reaction performance, high yield, high catalytic activity of the obtained catalyst, low preparation cost and high cyclic utilization rate.

Description

Cobalt-manganese-based catalyst for cyclohexene hydroformylation reaction, and preparation and application thereof
Technical Field
The invention relates to the technical field of catalysts for hydroformylation reactions.
Background
Conversion of cyclohexene to cyclohexylformaldehyde by hydroformylation is the most economical and efficient process for preparing cyclohexylformaldehyde. However, the cost and performance of cyclohexene hydroformylation catalysts of the prior art have limited their further broad and efficient use. The existing cyclohexene hydroformylation catalyst is mainly Rh-based, co-cobalt-based, co-Ru and other catalysts. The activity of the Rh-based catalyst is high, the reaction condition is mild, but the expensive Rh restricts the economy of the Rh-based catalyst in the application of cyclohexene hydroformylation; although the cobalt-based catalyst has the price advantage, the cobalt-based catalyst has harsh catalytic reaction conditions for the hydroformylation of cyclohexene, does not accord with the current development trend of energy conservation and emission reduction, and also affects the wide use of the cobalt-based catalyst; although the Co-Ru catalyst can catalyze the hydroformylation of cyclohexene, the catalyst is complex to prepare and has no obvious advantage compared with a Co-based catalyst.
In addition, in order to overcome the defect of high price of Rh-based catalysts in the prior art, in order to efficiently utilize Rh, a mode of using a homogeneous Rh-based catalyst is adopted, but after cyclohexene hydroformylation, products and the catalyst are separated mainly through a reduced pressure distillation process, and due to the boiling point (161-163 ℃) of cyclohexyl formaldehyde, the homogeneous Rh catalyst is easy to decompose and generate precipitation during reduced pressure distillation, so that the catalyst is deactivated, lost and difficult to recycle.
Disclosure of Invention
The invention aims to provide a preparation method of a high-efficiency catalyst for cyclohexene hydroformylation reaction, which is a cobalt-manganese-based catalyst, has the characteristics of low cost, simple preparation process, convenient use and high catalytic activity and stability in cyclohexene hydroformylation reaction, and is a solid-liquid system, convenient to separate and easy to recycle.
The invention also aims to provide the cobalt-manganese-based catalyst prepared by the preparation method and an application method thereof.
The invention firstly discloses the following technical scheme:
a method for preparing a cobalt-manganese based catalyst for cyclohexene hydroformylation reaction, comprising:
(1) Obtaining powder of a nanoscale cobalt-based raw material;
(2) Dispersing the powder of the cobalt-based raw material in an organic solvent to obtain cobalt dispersion;
(3) Adding a manganese-based raw material into the cobalt dispersion liquid, heating and reacting at 100-120 ℃ under a protective atmosphere, and cooling to obtain a solid-liquid mixture which is the cobalt-manganese-based catalyst;
wherein the cobalt-based raw material is selected from cobalt simple substance and/or cobalt element-containing compound, and the manganese-based raw material is selected from cyclopentadiene manganese tricarbonyl and/or methylcyclopentadiene manganese tricarbonyl.
According to some preferred embodiments of the invention, the cobalt element-containing compound is selected from amorphous cobalt boride or cobalt aluminum alloys.
According to some preferred embodiments of the invention, the organic solvent is selected from toluene.
According to some preferred embodiments of the invention, the ratio of the amount of the cobalt-based raw material to the amount of the manganese-based raw material is 1:1 to 20:1.
According to some preferred embodiments of the invention, the content of dispersed cobalt-based raw material in the cobalt dispersion is 0.005-0.10g/ml.
The invention further provides the cobalt-manganese-based catalyst prepared by the preparation method.
The catalyst is a solid-liquid system, wherein the solid is a carbonyl compound containing cobalt-manganese, the liquid is a solution of the carbonyl compound dissolved with cobalt-manganese, and the infrared spectrograms of the solid-liquid system show bridge carbonyl absorption peaks.
The invention further provides application of the cobalt-manganese-based catalyst prepared by the preparation method in cyclohexene hydroformylation reaction.
According to some preferred embodiments of the invention, the application comprises: after the cobalt-manganese-based catalyst is added and synthesis gas is filled, cyclohexene is subjected to airtight reaction at the temperature of 100-150 ℃, and the synthesis gas is carbon monoxide and hydrogen.
According to some preferred embodiments of the present invention, in the above closed reaction, the cobalt-manganese based catalyst is used in an amount in which the cobalt element content is 6.0 to 10.0g/L.
The cobalt-manganese-based catalyst is a solid-liquid system, wherein the boiling point of a liquid part is 232-233 ℃, the boiling point of the cobalt-manganese-based catalyst is obviously distinguished relative to the boiling point of a cyclohexene hydroformylation product cyclohexyl formaldehyde of 161-163 ℃, the cobalt-manganese-based catalyst can be filtered and distilled under reduced pressure when the product and the catalyst are separated, and then the bottom of a reaction kettle is the catalyst liquid, so that the next hydroformylation reaction can be directly carried out.
The catalyst obtained by the invention has low cost, simple preparation process, convenient use, high catalytic activity and stability, and excellent cyclohexene conversion rate and aldehyde selectivity when being applied to cyclohexene hydroformylation reaction.
Detailed Description
The present invention will be described in detail with reference to the following examples, but it should be understood that the examples are only illustrative of the present invention and are not intended to limit the scope of the present invention in any way. All reasonable variations and combinations that are included within the scope of the inventive concept fall within the scope of the present invention.
According to the technical scheme of the invention, some specific embodiments for preparing the catalyst comprise the following steps:
(1) Preparing cobalt simple substance and/or compound powder with the particle size of nanometer scale, such as amorphous cobalt boride (CoB) powder, cobalt metal powder and the like;
(2) Dispersing cobalt simple substance and/or compound powder in an organic solvent such as toluene to obtain cobalt dispersion liquid;
(3) Adding cyclopentadiene manganese tricarbonyl and/or methyl cyclopentadiene manganese tricarbonyl into the cobalt dispersion liquid, stirring and refluxing under the reaction protective atmosphere to react to obtain a mixture;
(4) And cooling the reflux mixture in the given atmosphere, wherein the cooled mixture is the cobalt-manganese catalyst.
In the process, the organic solvent in the cooled mixture is not required to be removed, the catalyst can be directly used for catalyzing the hydroformylation of cyclohexene, and simultaneously, the solid and liquid parts of the catalyst prepared by the process have bridge carbonyl absorption peaks through infrared spectrogram analysis.
Example 1
0.50 g of CoB powder was placed in a three-necked flask with CO atmosphere and a stirring and refluxing apparatus, 70ml of toluene and 2ml of methylcyclopentadienyl manganese tricarbonyl were further added, heated and refluxed for 1 hour, cooled, the mixture was transferred to a 250ml autoclave, 10ml of cyclohexene was added, the autoclave was closed, the air in the autoclave was replaced, and then a synthesis gas (nCO/nH was used 2 =1) the autoclave was pressurized to 4.0Mpa, the heating and stirring of the reaction kettle were started, and the reaction was carried out at 120 ℃ for 2 hours. Cooling the reaction kettle, decompressing, sampling, and carrying out qualitative and quantitative analysis by using Agilent GC-2014.
Example 2
Putting 0.50 g Co powder newly prepared from cobalt aluminum alloy into a three-necked flask with CO atmosphere and a stirring and refluxing device, adding 70ml toluene and 2ml methylcyclopentadienyl manganese tricarbonyl, heating and refluxing for 1 hour, cooling, transferring the mixture into a 250ml autoclave, adding 10ml cyclohexene, sealing the autoclave, replacing air in the autoclave, and using synthesis gas (nCO/nH) 2 =1) the autoclave was pressurized to 4.0Mpa, the heating and stirring of the reaction kettle were started, and the reaction was carried out at 120 ℃ for 2 hours. Cooling the reaction kettle, decompressing, sampling, and carrying out qualitative and quantitative analysis by using Agilent GC-2014.
Example 3
A three-necked flask with a CO atmosphere and a stirring and refluxing apparatus was charged with 0.50 g of Co powder freshly prepared from a cobalt-aluminum alloy, followed by 70ml of toluene and 2ml of methylcyclopentadieneManganese enetricarbonyl, heating and refluxing for 1 hr, cooling, transferring the mixture into 250ml autoclave, adding 10ml cyclohexene, sealing the autoclave, replacing air in the autoclave, and using synthesis gas (nCO/nH) 2 =1) the autoclave was pressurized to 6.0Mpa, the heating and stirring of the reaction kettle were started, and the reaction was carried out at 120 ℃ for 2 hours. Cooling the reaction kettle, decompressing, sampling, and carrying out qualitative and quantitative analysis by using Agilent GC-2014.
Example 4
Putting 0.50 g Co powder newly prepared from cobalt-aluminum alloy into a three-necked flask with CO atmosphere and a stirring and refluxing device, adding 70ml toluene and 2 g cyclopentadiene manganese tricarbonyl, heating and refluxing for 1 hour, cooling, transferring the mixture into a 250ml autoclave, adding 10ml cyclohexene, sealing the autoclave, replacing air in the autoclave, and using synthesis gas (nCO/nH) 2 =1) the autoclave was pressurized to 4.0Mpa, the heating and stirring of the reaction kettle were started, and the reaction was carried out at 120 ℃ for 2 hours. Cooling the reaction kettle, decompressing, sampling, and carrying out qualitative and quantitative analysis by using Agilent GC-2014.
Example 5
The cobalt-aluminum alloy freshly prepared 0.50 g Co powder, 50ml toluene and 2ml methylcyclopentadienyl manganese tricarbonyl were placed in a 250ml autoclave, the autoclave was closed, the air in the autoclave was replaced, and then a synthesis gas (nCO/nH was used 2 =1) the autoclave was pressurized to 4.0Mpa, the reaction vessel was heated and stirred, stirred at 120 ℃ for 10 minutes, and then 20ml of toluene+10 ml of cyclohexene mixed solution was poured into the autoclave, and the reaction was further carried out for 1.5 hours after half an hour. Cooling the reaction kettle, decompressing, sampling, and carrying out qualitative and quantitative analysis by using Agilent GC-2014.
Example 6
The cobalt-aluminum alloy was freshly prepared from 0.50 g of Co powder, 50ml of toluene and 2 g of cyclopentadienyl manganese tricarbonyl were placed in a 250ml autoclave, the autoclave was closed, the air in the autoclave was replaced, and synthesis gas (nCO/nH was used 2 =1) the autoclave was pressurized to 4.0Mpa, the reaction vessel was heated and stirred, stirred at 120 ℃ for 10 minutes, and then 20ml of a mixture of toluene and 10ml of cyclohexene was poured into the autoclave, and the reaction was continued for 1.5 hours after half an hour. Cooling the reaction kettle, decompressing, sampling, and using AgilentGC-2014 was analyzed qualitatively and quantitatively.
Example 7
The cobalt-aluminum alloy freshly prepared 0.50 g Co powder, 50ml toluene and 2ml methylcyclopentadienyl manganese tricarbonyl were placed in a 250ml autoclave, the autoclave was closed, the air in the autoclave was replaced, and then a synthesis gas (nCO/nH was used 2 =1) the autoclave was pressurized to 6.0Mpa, the reaction vessel was heated and stirred, stirred at 120 ℃ for 10 minutes, and then 20ml of a mixture of toluene and 10ml of cyclohexene was poured into the autoclave, and the reaction was continued for 1.5 hours after half an hour. Cooling the reaction kettle, decompressing, sampling, and carrying out qualitative and quantitative analysis by using Agilent GC-2014.
Example 8
The reaction product of example 7 was distilled off under nitrogen, the reaction product was distilled off under reduced pressure, after cooling the residue, 50ml of toluene was added, the whole residue was transferred to a 250ml autoclave, the autoclave was closed, the air in the autoclave was replaced, and then a synthesis gas (nCO/nH was used 2 =1) the autoclave was pressurized to 6.0Mpa, the reaction vessel was heated and stirred, stirred at 120 ℃ for 10 minutes, and then 20ml of a mixture of toluene and 10ml of cyclohexene was poured into the autoclave, and the reaction was continued for 1.5 hours after half an hour. Cooling the reaction kettle, decompressing, sampling, and carrying out qualitative and quantitative analysis by using Agilent GC-2014.
The catalysts of examples 1-8 were tested for catalytic performance, wherein the chromatographic conditions were: nitrogen is carrier gas, hydrogen flame detector, detector temperature 265 ℃, SE-30 capillary column, length 20m; the temperature programming conditions are as follows: the retention at 45℃was 3',5℃per minute was raised to 60℃and the retention at 1min was raised to 260℃per minute and the retention at 20℃per minute was carried out for 5min, the results of which are shown in Table 1 below:
TABLE 1 catalytic Properties of catalysts of different examples in cyclohexene hydroformylation
Figure BDA0003053860790000051
Figure BDA0003053860790000061
* Cyclohexyl formaldehyde, cyclohexyl methanol and aldol condensates.
As shown by the results of the table, the preparation method of the Co-Mn catalyst for cyclohexene hydroformylation reaction is simple, the reaction process and the device are simple, the reaction can be carried out in a conventional autoclave reactor, the reaction performance is stable, the yield is high, the catalyst recycling result is good, the problems of severe noble metal usage and reaction conditions, catalyst recycling and the like in the prior art are effectively solved, and the method has a wide industrial application prospect.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.

Claims (9)

1. The preparation method of the cobalt-manganese-based catalyst for the hydroformylation of cyclohexene is characterized by comprising the following steps of: comprising the following steps:
(1) Obtaining powder of a nanoscale cobalt-based raw material;
(2) Dispersing the powder of the cobalt-based raw material in an organic solvent to obtain cobalt dispersion;
(3) Adding a manganese-based raw material into the cobalt dispersion liquid, heating the mixture to react at 100-120 ℃ in a protective atmosphere, and cooling the mixture to obtain a solid-liquid mixture, namely the cobalt-manganese-based catalyst;
wherein the cobalt-based raw material is selected from cobalt simple substances and/or cobalt element-containing compounds, and the manganese-based raw material is selected from cyclopentadiene manganese tricarbonyl and/or methylcyclopentadiene manganese tricarbonyl; the organic solvent is selected from toluene.
2. The method of manufacturing according to claim 1, characterized in that: the cobalt element-containing compound is selected from amorphous cobalt boride.
3. The method of manufacturing according to claim 1, characterized in that: the ratio of the amounts of the substances of the cobalt-based raw material to the manganese-based raw material is 1:1-20:1.
4. The method of manufacturing according to claim 1, characterized in that: the content of the dispersed cobalt-based raw material in the cobalt dispersion liquid is 0.005-0.10g/ml.
5. A cobalt-manganese based catalyst prepared by the preparation method of any one of claims 1 to 4.
6. Use of the cobalt-manganese-based catalyst prepared by the preparation method of any one of claims 1 to 4 in cyclohexene hydroformylation.
7. The use according to claim 6, characterized in that: comprising the following steps: after the cobalt-manganese-based catalyst is added and synthesis gas is filled, cyclohexene is subjected to airtight reaction at the temperature of 100-150 ℃, and the synthesis gas is carbon monoxide and hydrogen.
8. The use according to claim 7, characterized in that: the dosage of the cobalt-manganese based catalyst is 6.0-10.0g/L of cobalt element.
9. The use according to claim 7, characterized in that: comprising the following steps: after the completion of the closed reaction, the resultant reaction product was distilled off by distillation under reduced pressure, and the organic solvent was added to the remaining residue to be used again as a catalyst.
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钴基催化剂催化环己烯氢甲酰化研究.《有机化学》.2010,全文. *

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