CN111099982B - Method for synthesizing 3-hydroxy-propionaldehyde - Google Patents

Method for synthesizing 3-hydroxy-propionaldehyde Download PDF

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CN111099982B
CN111099982B CN201811248608.0A CN201811248608A CN111099982B CN 111099982 B CN111099982 B CN 111099982B CN 201811248608 A CN201811248608 A CN 201811248608A CN 111099982 B CN111099982 B CN 111099982B
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ethylene oxide
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cobalt catalyst
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CN111099982A (en
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刘波
吕建刚
金照生
周海春
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size

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Abstract

The invention relates to a method for synthesizing 3-hydroxypropionaldehyde, which mainly solves the problem that a catalyst of a homogeneous system in the prior art is difficult to separate, and adopts the method for synthesizing the 3-hydroxypropionaldehyde, and comprises the following steps: adding an i-cobalt catalyst and a cocatalyst into a solvent, and heating for pretreatment under the atmosphere of synthesis gas; ii the technical proposal that the catalyst is cooled and decompressed after being pretreated, and ethylene oxide and synthesis gas are added to react to obtain the 3-hydroxypropionaldehyde, better solves the technical problem, and can be used in the industrial production of the 3-hydroxypropionaldehyde.

Description

Method for synthesizing 3-hydroxy-propionaldehyde
Technical Field
The invention relates to a method for synthesizing 3-hydroxypropionaldehyde.
Background
1, 3-propanediol is an important organic fine chemical, can be used as a raw material for producing antifreeze, plasticizer, preservative and emulsifier, and can be widely applied to the industries of food, cosmetics, pharmacy and the like, the most important application of the 1, 3-propanediol is to synthesize polytrimethylene terephthalate polyester fiber PTT as a monomer, compared with the common polyethylene terephthalate fiber PET, the PTT fiber has the advantages of light resistance, less water absorption, good stability and the like, good rebound resilience, easy biodegradation, small environmental pollution and the like, has wide application prospect, and is the focus of current research and development.
1, 3-propanediol can be synthesized by ethylene oxide carbonylation, and the carbonylation process is divided into a two-step method (formula 1) and a one-step method (formula 2): the two-step process involves the hydroformylation of ethylene oxide to produce 3-hydroxypropanal and a small amount of 1, 3-propanediol, with the 3-hydroxypropanal being catalytically hydrogenated to produce 1, 3-propanediol. The one-step process integrates hydroformylation reaction and catalytic hydrogenation reaction, and 1, 3-propylene glycol is synthesized by one step from ethylene oxide. Compared with the one-step process, the two-step process has the remarkable advantages of low catalyst cost and good product quality, and has wide application prospect.
Figure BDA0001841124360000011
The current major advances in ethylene oxide carbonylation are as follows:
patent CN95195314.1 discloses that the mass fraction of the product 3-hydroxypropionaldehyde in liquid materials can reach 4.3% -4.7% by taking prefabricated or in-situ prepared cobalt carbonyl as a catalyst and an organic phosphine compound as a ligand and adding benzoquinone and pyridine lipophilic additives.
Patent CN02811272.5 discloses a one-step process for synthesizing 1, 3-propylene glycol by taking Co-Ru binary metal as a catalyst and phosphine-containing heterocyclic pentyl alkyl alkane as a ligand; when cobalt octanoate and Ru are used 3 (CO) 12 As catalyst, 1, 2-bis [ (2R, 5R) -2, 5-dimethylphosphocyclopentyl]Ethane (BDMPE (R, R)) is used as a ligand, and when an auxiliary agent NaOAc is added, the yield of 1, 3-propanediol reaches 71 percent.
Patent CN02811696.8 discloses the one-step production of 1, 3-propanediol from ethylene oxide and synthesis gas using a Co-Fe catalyst, wherein the ligand is selected from N-heterocyclic compounds or organic phosphine compounds, and the sum of the selectivities of 1, 3-propanediol and 3-hydroxypropanal is 60%.
Patent CN02811785.9 discloses a one-step production of 1, 3-propanediol from ethylene oxide and synthesis gas using a catalyst coordinated by an N-heterocyclic ligand, the catalyst used being Co 2 (CO) 8 -Ru 3 (CO) 12 The ligand of the double-component metal catalyst is mainly pyridine ligand, and when 2,2' -bipyrimidine is used as the ligand, the selectivity of 1, 3-propylene glycol reaches 60 percent.
Patent CN200410037658.6 discloses that preformed or in-situ prepared cobalt carbonyl is used as a catalyst, furan compounds are used as a solvent, ethylene oxide and synthesis gas are used as raw materials to synthesize 3-hydroxypropionaldehyde, and the selectivity of a target product is about 70%.
Disclosure of Invention
The invention provides a method for synthesizing 3-hydroxypropionaldehyde, which has the advantages of easy separation of a catalyst system from a reaction system, mild catalytic reaction conditions, high activity and the like.
The technical scheme of the invention is as follows: the synthesis method of 3-hydroxypropionaldehyde comprises the following steps:
i. adding a cobalt catalyst and a cocatalyst into a solvent, and heating for pretreatment under the atmosphere of synthesis gas;
ii. After the pretreatment of the catalyst is finished, adding ethylene oxide and synthesis gas, and reacting to obtain the 3-hydroxypropionaldehyde.
In the technical scheme, the pretreatment conditions comprise synthesis gas pressure of 6-10 MPa, temperature of 60-100 ℃ and time of 3-5 hours. Preferably, the pressure is 8MPa, the temperature is 80 ℃ and the time is 4 hours.
In the above technical solution, the solvent is preferably a C4-C8 ether compound or a C6-C8 aromatic hydrocarbon, and includes, but is not limited to, at least one of methyl tert-butyl ether, tetrahydrofuran, 1, 4-dioxane, 1, 3-dioxolane, and toluene.
The cobalt catalyst is a simple substance cobalt catalyst, preferably nanometer cobalt, and more preferably, the particle size of the nanometer cobalt is 10-20 nm.
In the technical scheme, the mol ratio of the nano cobalt catalyst to the cocatalyst is preferably (1-10): 1.
In the above technical scheme, the cocatalyst comprises an organic phosphine compound or an azacyclic compound, and the organic phosphine compound comprises R 3 P or R 2 P(CH 2 ) n PR 2 Wherein n is an integer of 1-3, R is C1-C6 straight-chain alkyl, phenyl, C5-C6 naphthenic base, and C6-C8 substituted phenyl; the nitrogen heterocyclic compound comprises pyridine and derivatives thereof, imidazole and derivatives thereof, and quinoline and derivatives thereof. Examples include, but are not limited to, triphenylphosphine, tricyclohexylphosphine, tributylphosphine, 1,3- (diphenylphosphino) propane, 1,3- (dicyclohexylphosphino) propane, 1,2- (dicyclohexylphosphino) ethane, pyridine, imidazole, quinoline, hydroxyquinoline, hydroxypyridine.
In the technical scheme, after the pretreatment of the catalyst is finished, the catalyst is cooled and then decompressed, and ethylene oxide and synthesis gas are added.
In the above technical solution, the molar ratio of ethylene oxide to cobalt catalyst is preferably (5-50): 1.
In the above technical scheme, the reaction pressure is preferably 6 to 15MPa.
In the technical scheme, the volume ratio of hydrogen to carbon monoxide in the synthesis gas is (1-3) to 1. Preferably, the composition of the synthesis gas used has a volume ratio of hydrogen to carbon monoxide of 1.
In the above technical scheme, the reaction temperature is preferably 80-120 ℃.
In the above technical scheme, the reaction time is preferably 3 to 10 hours.
The invention uses cobalt particles as the catalyst, can be recovered by simple and convenient filtration after reaction, effectively solves the problem of difficult separation of the homogeneous catalyst used in the prior art, and has the remarkable advantages of mild catalytic reaction conditions and high activity. Examples 14 and 15 show that the catalyst recovered by simple filtration can be reused, and the catalytic activity and selectivity can be maintained, which shows that the invention has important application value in the industrial synthesis of 3-hydroxypropionaldehyde.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Detailed Description
Example 1
Preparation of nano cobalt catalyst
The solvent is degassed beforehand. Sodium borohydride 3027mg (80 mmol) was dissolved in 50mL of deionized water. To a 250mL three-necked flask, 4657mg (16 mmol) of cobalt nitrate hexahydrate and 16mL of water were added and dissolved with stirring, and then 3mL of polyethylene glycol 600 was added and stirred uniformly. Under the protection of nitrogen, a constant-pressure dropping funnel is utilized to slowly drop the sodium borohydride aqueous solution into the rapidly-stirred cobalt nitrate solution. After the addition, the reaction was continued for 2 hours. After the reaction is finished, carrying out suction filtration, washing a filter cake by using distilled water, 0.1mol/L hydrochloric acid, distilled water and absolute ethyl alcohol in sequence, and carrying out vacuum drying to obtain black powder, namely the nano cobalt catalyst, wherein the yield is as follows: 905mg (96% yield). The grain diameter is 10-20 nm.
Example 2
Adding 354mg (6 mmol) of nano cobalt catalyst, 262mg (1 mmol) of triphenylphosphine and 30mL of methyl tert-butyl ether into a 100mL reaction kettle, and addingPurging the reaction kettle with pure nitrogen for three times, and adding synthesis gas (V) H2 :V CO = 1/1)), the system pressure was adjusted to 8MPa, and stirring was performed at 80 ℃ for 3 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly relieving pressure to normal pressure, injecting 2200mg (50 mmol) of ethylene oxide into a metering pump, and adding synthesis gas (V) H2 :V CO = 1/1)), the reaction was carried out at 90 ℃ for 6 hours while the system pressure was 10 MPa. The kettle body is fully cooled to-5 ℃, the pressure is slowly released to normal pressure, the reaction kettle is purged by nitrogen for three times, and sampling analysis shows that: the conversion of ethylene oxide was 37.2% and the selectivity to 3-hydroxypropanal was 75.5%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
Example 3
Adding 354mg (6 mmol) of nano cobalt catalyst, 336mg (1.2 mmol) of tricyclohexylphosphine and 30mL of tetrahydrofuran into a 100mL reaction kettle, purging the reaction kettle with high-purity nitrogen for three times, and adding synthesis gas (V) H2 :V CO = 1/1)), the system pressure was adjusted to 8MPa, and stirring was performed at 80 ℃ for 3 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly relieving pressure to normal pressure, injecting 2200mg (50 mmol) of ethylene oxide into a metering pump, and adding synthesis gas (V) H2 :V CO = 2/1), the reaction was carried out at 90 ℃ for 6 hours while the system pressure was 12 MPa. The kettle body is fully cooled to-5 ℃, the pressure is slowly released to normal pressure, the reaction kettle is purged by nitrogen for three times, and sampling analysis shows that: the conversion of ethylene oxide was 40.6% and the selectivity to 3-hydroxypropanal was 70.3%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
Example 4
Adding 118mg (2 mmol) of nano cobalt catalyst, 202mg (1 mmol) of tri-n-butylphosphine and 30mL of methyl tert-butyl ether into a 100mL reaction kettle, purging the reaction kettle with high-purity nitrogen for three times, and adding synthesis gas (V) H2 :V CO = 1/1)), the system pressure was adjusted to 8MPa, and stirring was performed at 80 ℃ for 3 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly releasing pressure to normal pressure, metering and pumpingEthylene oxide 2200mg (50 mmol) was added and synthesis gas (V) was added H2 :V CO = 1/1), the reaction is carried out at 90 ℃ for 5 hours while the system pressure is 8 MPa. The kettle body is fully cooled to-5 ℃, slowly decompressed to normal pressure, the reaction kettle is purged with nitrogen for three times, and sampling analysis shows that: the conversion of ethylene oxide was 25.1% and the selectivity to 3-hydroxypropanal was 66.4%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
Example 5
295mg (5 mmol) of nano cobalt catalyst, 609mg (2 mmol) of tri (o-toluene) phosphine and 30mL of 1, 4-dioxane are added into a 100mL reaction kettle, the reaction kettle is purged with high-purity nitrogen for three times, and synthesis gas (V) is added H2 :V CO = 1/1)), the system pressure was adjusted to 8MPa, and stirring was performed at 80 ℃ for 3 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly relieving pressure to normal pressure, injecting 2200mg (50 mmol) of ethylene oxide into a metering pump, and adding synthesis gas (V) H2 :V CO = 2/1), the reaction was carried out at 100 ℃ for 6 hours while the system pressure was 13 MPa. The kettle body is fully cooled to-5 ℃, the pressure is slowly released to normal pressure, the reaction kettle is purged by nitrogen for three times, and sampling analysis shows that: the conversion of ethylene oxide was 39.1% and the selectivity to 3-hydroxypropanal was 78.3%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
Example 6
Adding 354mg (6 mmol) of nano cobalt catalyst, 158mg (2 mmol) of pyridine and 30mL of tetrahydrofuran into a 100mL reaction kettle, purging the reaction kettle with high-purity nitrogen for three times, and adding synthesis gas (V) H2 :V CO = 1/1), the system pressure was adjusted to 8MPa, and the mixture was stirred at 80 ℃ for 3 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly relieving pressure to normal pressure, injecting 2200mg (50 mmol) of ethylene oxide into a metering pump, and adding synthesis gas (V) H2 :V CO = 3/1), the reaction is carried out at 110 ℃ for 3 hours under a system pressure of 15MPa. The kettle body is fully cooled to-5 ℃, slowly decompressed to normal pressure, the reaction kettle is purged with nitrogen for three times, and sampling analysis shows that: epoxy resinThe conversion of ethane was 30.0% and the selectivity of 3-hydroxypropanal was 81.0%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
Example 7
Adding 472mg (8 mmol) of nano cobalt catalyst, 102mg (1.5 mmol) of imidazole and 30mL of tetrahydrofuran into a 100mL reaction kettle, purging the reaction kettle with high-purity nitrogen for three times, and adding synthesis gas (V) H2 :V CO = 1/1)), the system pressure was adjusted to 8MPa, and stirring was performed at 80 ℃ for 3 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly relieving pressure to normal pressure, injecting 2200mg (50 mmol) of ethylene oxide into a metering pump, and adding synthesis gas (V) H2 :V CO = 2/1), the reaction was carried out at 100 ℃ for 8 hours while the system pressure was 12 MPa. The kettle body is fully cooled to-5 ℃, slowly decompressed to normal pressure, the reaction kettle is purged with nitrogen for three times, and sampling analysis shows that: the conversion of ethylene oxide was 28.5% and the selectivity to 3-hydroxypropanal was 83.3%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1
Example 8
Adding 354mg (6 mmol) of nano cobalt catalyst, 190mg (2 mmol) of 3-hydroxypyridine and 30mL of toluene into a 100mL reaction kettle, purging the reaction kettle with high-purity nitrogen for three times, and adding synthesis gas (V) H2 :V CO = 1/1), the system pressure was adjusted to 8MPa, and the mixture was stirred at 80 ℃ for 3 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly relieving pressure to normal pressure, injecting 2200mg (50 mmol) of ethylene oxide into a metering pump, and adding synthesis gas (V) H2 :V CO = 2/1), the reaction was carried out at 100 ℃ for 5 hours while the system pressure was 13 MPa. The kettle body is fully cooled to-5 ℃, slowly decompressed to normal pressure, the reaction kettle is purged with nitrogen for three times, and sampling analysis shows that: the conversion of ethylene oxide was 50.3% and the selectivity to 3-hydroxypropanal was 82.0%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
Example 9
100mL reaction kettleAdding cobalt nanocatalyst 354mg (6 mmol), quinoline 194mg (1.5 mmol), tetrahydrofuran 15mL and toluene 15mL, purging the reaction kettle with high-purity nitrogen for three times, and adding synthesis gas (V) H2 :V CO = 1/1)), the system pressure was adjusted to 8MPa, and stirring was performed at 80 ℃ for 2 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly relieving pressure to normal pressure, injecting 2200mg (50 mmol) of ethylene oxide into a metering pump, and adding synthesis gas (V) H2 :V CO = 2/1), the reaction was carried out at 80 ℃ for 10 hours while the system pressure was 12 MPa. The kettle body is fully cooled to-5 ℃, slowly decompressed to normal pressure, the reaction kettle is purged with nitrogen for three times, and sampling analysis shows that: the conversion of ethylene oxide was 37.4% and the selectivity of 3-hydroxypropanal was 70.0%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
Example 10
Adding 354mg (6 mmol) of nano cobalt catalyst, 218mg (1.5 mmol) of 8-hydroxyquinoline and 30mL of tetrahydrofuran into a 100mL reaction kettle, purging the reaction kettle with high-purity nitrogen for three times, and adding synthesis gas (V) H2 :V CO = 1/1), the system pressure was adjusted to 8MPa, and the mixture was stirred at 80 ℃ for 3 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly relieving pressure to normal pressure, injecting 2200mg (50 mmol) of ethylene oxide into a metering pump, and adding synthesis gas (V) H2 :V CO = 2/1), the reaction was carried out at 120 ℃ for 3 hours while the system pressure was set to 14 MPa. The kettle body is fully cooled to-5 ℃, slowly decompressed to normal pressure, the reaction kettle is purged with nitrogen for three times, and sampling analysis shows that: the conversion of ethylene oxide was 38.2% and the selectivity to 3-hydroxypropanal was 85.8%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1
Example 11
Adding 354mg (6 mmol) of nano cobalt catalyst, 413mg (1 mmol) of 1, 3-bis (diphenylphosphino) propane and 30mL of tetrahydrofuran into a 100mL reaction kettle, purging the reaction kettle with high-purity nitrogen for three times, and adding synthesis gas (V) H2 :V CO = 1/1)), the system pressure was adjusted to 8MPa, and stirring was performed at 80 ℃ for 3 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly relieving pressure to normal pressure, injecting 2200mg (50 mmol) of ethylene oxide into a metering pump, and adding synthesis gas (V) H2 :V CO = 2/1), the reaction was carried out at 120 ℃ for 4 hours while the system pressure was 15MPa. The kettle body is fully cooled to-5 ℃, slowly decompressed to normal pressure, the reaction kettle is purged with nitrogen for three times, and sampling analysis shows that: the conversion of ethylene oxide was 47.5% and the selectivity to 3-hydroxypropanal was 82.0%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
Example 12
Adding 354mg (6 mmol) of nano cobalt catalyst, 437mg (1 mmol) of 1, 3-bis (dicyclohexylphosphino) propane and 30mL of tetrahydrofuran into a 100mL reaction kettle, purging the reaction kettle with high-purity nitrogen for three times, and adding synthesis gas (V) H2 :V CO = 1/1)), the system pressure was adjusted to 8MPa, and stirring was performed at 80 ℃ for 3 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly relieving pressure to normal pressure, injecting 2200mg (50 mmol) of ethylene oxide into a metering pump, and adding synthesis gas (V) H2 :V CO = 2/1), the reaction was carried out at 120 ℃ for 4 hours while the system pressure was 15MPa. The kettle body is fully cooled to-5 ℃, the pressure is slowly released to normal pressure, the reaction kettle is purged by nitrogen for three times, and sampling analysis shows that: the conversion of ethylene oxide was 53.6% and the selectivity to 3-hydroxypropanal was 85.0%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
Example 13
Adding 354mg (6 mmol) of nano cobalt catalyst, 423mg (1 mmol) of 1, 2-bis (dicyclohexylphosphino) ethane and 30mL of tetrahydrofuran into a 100mL reaction kettle, purging the reaction kettle with high-purity nitrogen for three times, and adding synthesis gas (V) H2 :V CO = 1/1), the system pressure was adjusted to 8MPa, and the mixture was stirred at 80 ℃ for 3 hours.
Stopping heating, cooling the reaction kettle to room temperature, slowly relieving pressure to normal pressure, injecting 2200mg (50 mmol) of ethylene oxide into a metering pump, and adding synthesis gas (V) H2 :V CO = 2/1), the system pressure is 15MPa,the reaction was carried out at 120 ℃ for 4 hours. The kettle body is fully cooled to-5 ℃, slowly decompressed to normal pressure, the reaction kettle is purged with nitrogen for three times, and sampling analysis shows that: the conversion of ethylene oxide was 65.8% and the selectivity of 3-hydroxypropanal was 86.1%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
Example 14
The reaction mixture of example 13 was filtered, washed with tetrahydrofuran several times, and the recovered catalyst was reused in the hydroformylation of ethylene oxide according to the procedure of example 13. The analysis result shows that: the conversion of ethylene oxide was 64.3% and the selectivity of 3-hydroxypropanal was 85.0%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
Example 15
The reaction mixture of example 14 was filtered, washed with tetrahydrofuran several times, and the catalyst obtained was recovered and reused for the hydroformylation of ethylene oxide according to the procedure of example 13. The analysis result shows that: the conversion of ethylene oxide was 63.0% and the selectivity to 3-hydroxypropanal was 86.6%.
For comparison, the results of the 3-hydroxypropanal synthesis reaction are shown in Table 1.
TABLE 1
Figure BDA0001841124360000081
Figure BDA0001841124360000091

Claims (7)

1. A method for synthesizing 3-hydroxypropionaldehyde comprises the following steps:
i. adding a cobalt catalyst and a cocatalyst into a solvent, and heating for pretreatment under the atmosphere of synthesis gas;
ii. After the pretreatment of the catalyst is finished, adding ethylene oxide and synthesis gas, and reacting to obtain the 3-hydroxypropionaldehyde;
the cobalt catalyst is a simple substance cobalt catalyst;
the pretreatment conditions comprise synthetic gas pressure of 6 to 10MPa, temperature of 60 to 100 ℃ and time of 3 to 5 hours;
the cocatalyst is an organic phosphine compound or a nitrogen heterocyclic compound;
the organic phosphine compound comprises R 3 P、R 2 P(CH 2 ) n PR 2 Wherein n is an integer of 1 to 3, R is a C1-C6 linear alkyl group, a C5-C6 cycloalkyl group, a phenyl group, a C6-C8 substituted phenyl group; the nitrogen heterocyclic compound comprises pyridine and derivatives thereof, imidazole and derivatives thereof, and quinoline and derivatives thereof.
2. The synthesis method according to claim 1, wherein the solvent is a C4-C8 ether compound or a C6-C8 aromatic hydrocarbon.
3. A synthesis method according to claim 1, characterized in that the cobalt catalyst is nanocobalt.
4. The synthesis method according to claim 1, wherein the molar ratio of the cobalt catalyst to the cocatalyst is (1 to 10): 1.
5. The synthesis method according to claim 1, wherein the molar ratio of the ethylene oxide to the cobalt catalyst is (5 to 50): 1.
6. The synthesis method according to claim 1, wherein the volume ratio of hydrogen to carbon monoxide in the synthesis gas is (1 to 3) to 1.
7. The synthesis method according to claim 1, wherein the reaction pressure is 6-15 MPa, and the reaction temperature is 80-120 ℃; the reaction time is 3 to 10 hours.
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