CN1310864C - Process for preparing 3-hydroxy propionic aldehyde and 1,3-propylene glycol - Google Patents
Process for preparing 3-hydroxy propionic aldehyde and 1,3-propylene glycol Download PDFInfo
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- CN1310864C CN1310864C CNB2004100376586A CN200410037658A CN1310864C CN 1310864 C CN1310864 C CN 1310864C CN B2004100376586 A CNB2004100376586 A CN B2004100376586A CN 200410037658 A CN200410037658 A CN 200410037658A CN 1310864 C CN1310864 C CN 1310864C
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Abstract
The present invention discloses a method for preparing 3-hydroxy propionic aldehyde and 1, 3-propylene glycol, and the method comprises the following steps: carrying out hydroformylation on ethylene oxide and synthetic gas in an organic solvent with the following structural formula (disclosed in the specification) in the existence of carbonyl cobalt catalyst, leading in air or oxygen to cause the cobalt carbonyl catalyst to generate cobalt precipitate by oxidation, centrifugally separating and filtering the cobalt precipitate and the solution, circulating and returning the cobalt precipitate to a reaction kettle for the next reaction, adding deionized water to filter liquor, carrying out vacuum distillation on the solution after water is added to obtain a water solution containing 3-hydroxy propionic aldehyde, and generating 1, 3-propylene glycol after carrying out hydrogenization reaction finally. Additionally, the method does not use cocatalyst of organic phosphine ligand and has no need of adding various reaction promoters for hydroformylation, and the method with low cost is an effective method for preparing propylene glycol.
Description
Technical field
The present invention relates to a kind of oxyethane and carry out hydroformylation reaction preparation 1, and ammediol (1,3-PDO) and intermediate---the method for 3-hydroxy propanal (HPA).Specifically, the present invention relates to a kind ofly in the presence of cobalt catalyst, the oxyethane hydroformylation prepares 3-hydroxy propanal and 1, ammediol, and recycle the method for cobalt catalyst.
Background technology
1, ammediol (PDO) is the monomer of production Poly(Trimethylene Terephthalate) (PTT), and the PTT of excellent performance has a market application foreground widely in that fashionable dress, carpet etc. are industrial.
Known available two-step approach prepares PDO, and described method comprises 1) oxyethane is carried out the catalytic hydroformylation reaction generation of cobalt intermediate 3-hydroxy propanal and 2) 3-hydroxy propanal shortening is prepared PDO.The first step can be carried out being higher than under 100 ℃ and the high synthetic gas pressure, and to reach practical speed of reaction, still, the selectivity of reaction is very poor.
A kind of improvement synthetic method of having developed is with cobalt catalyst and the ligand united use of phosphine, so as can be under low relatively temperature and pressure the preparation HPA of highly selective.As the CN1299803A disclosed method, this method is to be raw material with oxyethane and synthetic gas, in the catalyzer of forming by cobalt salt and organophosphorus ligand, and step input reactant, straight line program heats up, reaction production purpose product under 110-150 ℃ and 11-13MPa.But be to use the phosphine part to increase the cost of catalyzer and increased the complicacy of catalyst recirculation.
It is raw material with oxyethane that CN1158603A and CN1158604A disclose a kind of; at one or more cobalt hydroformylation catalysts; this catalyzer contains the catalyzer and the organic solvent existence of the phosphine-modified of 50mol% (based on metal) at the most to be descended, and carries out the method for hydroformylation reaction.This method is reacted under 50-100 ℃ and 3.5-34.6MPa, selects to make solvent with the immiscible ether of water basically, as methyl tertiary butyl ether, is catalyzer with Co and adds oil loving quaternary amine and prepare HPA as hydroformylation reaction promotor; The HPA that obtains uses liquid, aqueous extracting and separating under carbon monoxide atmosphere.CN1161685A discloses a kind of oxyethane hydroformylation preparation 1 in the presence of cobalt catalyst and promotor, the method of ammediol, described promotor is the quaternary salt of oil loving V group element, as acetate benzyl three (normal-butyl) ammonium, methyl alcohol benzyltrimethylammon.um etc.; This class lipophilicity quaternary salt with liquid, aqueous extraction after, tend to stay in the organic phase.Though the rate of recovery of aforesaid method cobalt catalyst is very high, in hydroformylation reaction mixture and product HPA water extraction separation process, exist the promotor quaternary amine easily to be extracted and the shortcoming that runs off by water.
Summary of the invention
The purpose of this invention is to provide a kind of in the presence of VIII family cobalt metal Co carbonylating catalyst and a kind of organic solvent, with oxyethane, CO and H
2The method for preparing HPA and PDO for raw material through hydroformylation reaction.
The inventor finds by long term studies, carries out hydroformylation reaction in the presence of the solvent that the present invention uses, and can effectively improve speed of reaction, thus highly-selective preparation HPA.
Particularly, the present invention prepares 3-hydroxy propanal and 1, and the method for ammediol comprises the steps:
(1) with oxyethane and synthetic gas in structural formula organic solvent as follows, at the cobalt-carbonyl (Co of significant quantity
2(CO)
8) catalyzer exists down, under the reaction conditions that can effectively generate 3-hydroxy propanal midbody product mixture, contact,
Wherein, R
1, R
2, R
3And R
1Can be identical or different, be selected from hydrogen, straight chain C
1～C
10Alkyl and side chain C
1～C
10Alkyl; Preferred R
1, R
2, R
3And R
4Identical, represent hydrogen or methyl;
More preferably used solvent is tetrahydrofuran (THF) (THF);
(2) in the midbody product mixture that step (1) obtains, under the condition that can make cobalt carbonyl catalyst generation oxidizing reaction, bubbling air or oxygen make cobalt carbonyl catalyst generate the cobalt throw out;
(3) the cobalt throw out that step (2) is obtained separates, filters with solution centrifugal; The cobalt throw out returns in the reactor, carries out the reaction of step (1) next time;
(4) add deionized water in the filtrate that step (3) obtains, the solution that will add behind the water carries out vacuum distilling, and described organic solvent is removed, and obtains containing the aqueous solution of 3-hydroxy propanal;
(5) aqueous solution that will contain the 3-hydroxy propanal is contacting under hydrogenation conditions in the presence of the hydrogenation catalyst with hydrogen, generates to contain 1, the hydrogenation product mixtures of ammediol.
The described hydroformylation reaction of preferred steps (1) is 60-120 ℃ in temperature of reaction, and reaction pressure is to carry out under the 2-25MPa, and synthetic gas consists of CO: H
2=2: 1-1: 8.Described CATALYST Co
2(CO)
8Cobalt volumetric molar concentration in solvent for use is 0.005-1.0M, and the volumetric molar concentration of oxyethane in solvent for use is 0.5-3M.
More preferably the described hydroformylation reaction of step (1) is 70-90 ℃ in temperature of reaction, and reaction pressure is to carry out under the 8-15MPa, and synthetic gas consists of CO: H
2=1: 1-1: 5, described CATALYST Co
2(CO)
8Cobalt volumetric molar concentration in solvent for use is 0.02-0.2M.
The described hydroformylation reaction of preferred steps (1) 30～60 minutes, stopped reaction, cooling, pressure release, sampling analysis.
In described step (2), the midbody product mixture solution is poured out reactor, preferably under 5～40 ℃ and normal pressure, carry out oxidizing reaction, the residence time looks the precipitation degree of cobalt salt and determines, preferably in 1O～60 minute.If oxidation intermediates product mixtures solution can adopt oxygen and solution to enter the method for counter current contact respectively from the lower end and the upper end of reactor continuously.
In described step (4), preferably the filtrate that step (3) is obtained at first by storng-acid cation exchange resin, as styrene type cation exchange resin, further removes incomplete as yet sedimentary cobalt carbonyl catalyst, and then adds deionized water.
In described step (4), preferably by organic solvent: the volume ratio of water is 5: 1-1: 5, and more preferably organic solvent: the volume ratio of water is 2: 1-1: 2, add deionized water in the reaction soln after taking off cobalt.
In described step (4), add solution behind the water through vacuum distilling, unreacted oxyethane, by product acetaldehyde, the organic solvent of boiling point less than water steamed, solvent can return reactor and react next time; In the vacuum distillation process, should keep alap vacuum tightness, the vacuum tightness of preferred vacuum distilling is 0.1mmHg～10
-6MmHg, temperature aggregates into heavy fraction less than 60 ℃ to avoid HPA.
The used cobalt carbonyl catalyst of method of the present invention can directly add reactor with cobalt-carbonyl, also can synthesize in reactor, and concrete grammar is as follows: will be selected from Co (OH)
2, CoCl
2, CoAc
2, Co
2O
3, at least a cobalt compound among the CoO and synthetic gas are in solvent, at a small amount of Co
2(CO)
8Seed exists down, at 100-140 ℃, under the 8-10MPa, reacts 1～5 hour, obtains the cobalt carbonyl catalyst of significant quantity.Then temperature of reaction kettle is reduced to the temperature of hydroformylation reaction, adds oxyethane, under the reaction conditions that can effectively generate 3-hydroxy propanal midbody product mixture, react.
In described step (5), the aqueous solution that will contain the 3-hydroxy propanal goes out 1 through hydrogenation preparing, 3-PDO, and preferred used hydrogenation catalyst is load-type nickel series catalysts or Raney nickel by powder catalyzer; The hydrogenation process of preferred step of the present invention (5) is divided into secondary hydrogenation, and first section 40～80 ℃ of temperature, carries out under the above condition of pressure 5MPa, and second section at temperature 70-150 ℃, carries out under the above pressure of 5MPa.
Beneficial effect of the present invention is as follows:
1, method of the present invention uses tetrahydrofuran (THF) or its derivative to make solvent, only uses cobalt-carbonyl Co
2(CO)
8Be catalyzer, need do not add any hydroformylation reaction promotor or organophosphorus ligand promotor, therefore, the catalyst system of present method is simple, has saved the inconvenience of the subsequent disposal that the adding of various auxiliary agents brings, and greatly reduces the running cost of catalyzer.
2, method of the present invention uses tetrahydrofuran (THF) or its derivative to make solvent; improved speed of response; shortened the residence time of HPA in reactor; the dimerization that has suppressed HPA greatly; improved the selectivity of hydroformylation reaction; can high yield and highly-selective preparation HPA and PDO, the oxyethane transformation efficiency reaches as high as 99%, and the HPA selectivity is greater than 74%.
3, the cobalt catalyst that method of the present invention can reclaim effectively and recirculation is all basically, the cobalt rate of recovery can be applicable to suitability for industrialized production fully more than 95%.
Therefore, method of the present invention is a kind of effective ways of low-cost preparation propylene glycol.
Embodiment
Illustrate content of the present invention below, but protection scope of the present invention is not limited to following examples.
The preparation of embodiment 1 cobalt carbonyl catalyst
With 0.04g Co (OH)
2, 0.10g Co
2(CO)
8(making seed), 1.80g deionized water and 200mlTHF put into the 300ml autoclave.At 120 ℃, react 3hr under the 10MPa synthetic gas condition.The still liquid that takes a morsel utilizes iodine oxidation Co
2(CO)
8The CO volume number that discharges is determined Co
2(CO)
8Growing amount.Analytical results shows, Co (OH) behind the reaction 3hr
2Be converted into Co fully
2(CO)
8Co
2(CO)
8Concentration is 0.025M.
The preparation of embodiment 2 HPA
Press embodiment 1 and prepared Co
2(CO)
8Behind the catalyzer, temperature of reaction kettle is reduced to 80 ℃, add 10g oxyethane, at 12MPa, CO/H
2Reaction is 60 minutes under=1: 1 condition, cooling back sampling analysis.The oxyethane transformation efficiency is 64%, and the HPA selectivity is 76%.Main by product is acetaldehyde and propenal.
Embodiment 3
Changing temperature of reaction is 90 ℃, and all the other conditions are with embodiment 2.Analysis revealed oxyethane transformation efficiency 100%, HPA selectivity 68%.
Embodiment 4
Method according to embodiment 1 prepares catalyzer.Temperature of reaction kettle is reduced to 80 ℃, add 10g oxyethane, at 12MPa, CO/H
2Reaction is 45 minutes under=1: 2 conditions, cooling back sampling analysis.Oxyethane 96%, HPA selectivity are 74%.
Embodiment 5
Changing the reaction times is 60 minutes, and other condition is with embodiment 4.Analysis revealed, oxyethane transformation efficiency are 100%, and the HPA selectivity is 74%.
Embodiment 6
The change cobalt carbonyl catalyst is 0.0125M, and in 60 minutes reaction times, other condition is with embodiment 4.The oxyethane transformation efficiency is 70%, and the HPA selectivity is 73%.
Embodiment 7
React according to embodiment 4, react and be cooled in 45 minutes under 25 ℃ of the room temperatures.With the flow blowing air of 60ml/min 1 hour.Generation khaki color precipitation, centrifugation.Analyze with atomic absorption spectrophotometry that Co concentration is 24 mcg/ml among the THF, show that 98.3% cobalt is precipitated to come out.
Embodiment 8
Precipitation with embodiment 7 is made raw material, substitutes Co (OH)
2Condition by embodiment 4 is carried out hydroformylation reaction.Oxyethane transformation efficiency 96%, HPA selectivity 73%.Show that throw out can repeat hydroformylation reaction.
Embodiment 9
Filtrate with embodiment 8 is raw material, after styrene type cation exchange resin takes off cobalt, analyzes wherein Co content＜0.01ppm with atomic absorption spectrophotometry, shows that Co is all removed.
Embodiment 10 HPA hydrogenation preparing propylene glycol
Add isopyknic water in the THF solution of embodiment 9 after taking off Co.Use rotatory evaporator, with the oxyethane of boiling point less than water, by product and THF steam under less than the condition of 50 ℃ and 0.1mmHg, and the THF of collection returns reactor and reacts next time.Excess is the HPA aqueous solution, and at 50 ℃, hydrogenation reaction is 1 hour under the 10MPa with Raney Ni, and at 90 ℃, hydrogenation reaction gets PDO half an hour under the 10MPa, transformation efficiency 99%, PDO selectivity 99%.
Comparative Examples 1
With methyl tertiary butyl ether MTBE is solvent, substitutes THF.Carry out synthetic test according to the condition identical with embodiment 4.React after 45 minutes, the oxyethane transformation efficiency is 77%, HPA selectivity only 65%.This Comparative Examples explanation is made solvent with THF, and selectivity and the formation speed of HPA obviously improve.
Claims (10)
1, a kind of preparation 3-hydroxy propanal and 1, the method for ammediol is characterized in that this method may further comprise the steps:
(1) with oxyethane and synthetic gas in structural formula organic solvent as follows, in the presence of the cobalt carbonyl catalyst of significant quantity, under the reaction conditions that can effectively generate 3-hydroxy propanal midbody product mixture, contact,
Wherein, R
1, R
2, R
3And R
4Can be identical or different, be selected from hydrogen, straight chain C
1～C
10Alkyl and side chain C
1～C
10Alkyl; Described cobalt carbonyl catalyst is Co
2(CO)
8Catalyzer;
(2) in the midbody product mixture that step (1) obtains, under the condition that can make cobalt carbonyl catalyst generation oxidizing reaction, bubbling air or oxygen make cobalt carbonyl catalyst generate the cobalt throw out;
(3) the cobalt throw out that step (2) is obtained separates, filters with solution centrifugal; The cobalt throw out is transferred in the reaction of step (1);
(4) add deionized water in the filtrate that step (3) obtains, the solution that will add behind the water carries out vacuum distilling, and described organic solvent is removed, and obtains containing the aqueous solution of 3-hydroxy propanal;
(5) aqueous solution that will contain the 3-hydroxy propanal is contacting under hydrogenation conditions in the presence of the hydrogenation catalyst with hydrogen, generates to contain 1, the hydrogenation product mixtures of ammediol.
2, method according to claim 1 is characterized in that described R
1, R
2, R
3And R
4Identical, represent hydrogen or methyl.
3, method according to claim 1 is characterized in that described solvent is a tetrahydrofuran (THF).
4, method according to claim 1 is characterized in that in described step (4), and the filtrate that step (3) obtains is passed through storng-acid cation exchange resin, removes incomplete as yet sedimentary cobalt carbonyl catalyst, and then adds deionized water.
5, method according to claim 1 is characterized in that in described step (4), and by organic solvent: the volume ratio of water is 5: 1-1: 5, in the filtrate that step (3) obtains, add deionized water.
6, method according to claim 5 is characterized in that in described step (4), and by organic solvent: the volume ratio of water is 2: 1-1: 2, in the filtrate that step (3) obtains, add deionized water.
7, method according to claim 1 is characterized in that in described step (4), the vacuum tightness of vacuum distilling is 0.1mmHg～10
-6MmHg, temperature is less than 60 ℃.
8, method according to claim 1 is characterized in that described cobalt carbonyl catalyst prepares in reactor, will be selected from Co (OH)
2, CoCl
2, CoAc
2, Co
2O
3, at least a cobalt compound among the CoO and synthetic gas are in solvent, at a small amount of Co
2(CO)
8Seed exists down, at 100-140 ℃, under the 8-10MPa, reacts 1～5 hour, obtains the cobalt carbonyl catalyst of significant quantity.
9, according to the described method of one of claim 1-8, it is characterized in that described hydroformylation reaction is 60-120 ℃ in temperature of reaction, reaction pressure is to carry out under the 2-25MPa, synthetic gas consists of CO: H
2=2: 1-1: 8, the volumetric molar concentration of described cobalt carbonyl catalyst in solvent for use is 0.005-1.0M, and the volumetric molar concentration of oxyethane in solvent for use is 0.5-3M.
10, method according to claim 9 is characterized in that described hydroformylation reaction is 70-90 ℃ in temperature of reaction, and reaction pressure is to carry out under the 8-15MPa, and synthetic gas consists of CO: H
2=1: 1-1: 5, the volumetric molar concentration of described cobalt carbonyl catalyst in solvent for use is 0.02-0.2M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100376586A CN1310864C (en) | 2004-04-29 | 2004-04-29 | Process for preparing 3-hydroxy propionic aldehyde and 1,3-propylene glycol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100376586A CN1310864C (en) | 2004-04-29 | 2004-04-29 | Process for preparing 3-hydroxy propionic aldehyde and 1,3-propylene glycol |
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|---|---|
| CN1690033A CN1690033A (en) | 2005-11-02 |
| CN1310864C true CN1310864C (en) | 2007-04-18 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831381A (en) * | 2015-12-03 | 2017-06-13 | 中国石油化工股份有限公司 | The preparation method of 3-HPA |
| CN106861759A (en) * | 2015-12-11 | 2017-06-20 | 上海华谊能源化工有限公司 | A kind of epoxyalkane hydroformylation prepares catalyst of terminal hydroxy group aldehyde and its preparation method and application |
| CN111018688B (en) * | 2018-10-09 | 2022-10-11 | 上海华谊能源化工有限公司 | Method for preparing 3-hydroxypropionaldehyde and method for preparing 1,3-propylene glycol |
| CN111170843B (en) * | 2019-12-30 | 2023-10-10 | 上海华谊能源化工有限公司 | Method for removing volatile substances in 3-hydroxy-propionaldehyde mixed aqueous solution |
| CN115701418A (en) * | 2021-08-02 | 2023-02-10 | 中国石油化工股份有限公司 | Aldehyde-alcohol composition, preparation method thereof, and method for continuously preparing aldehyde and alcohol |
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|---|---|---|---|---|
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