CN101410363A - Method of treating an aldehyde mixture, use of the treated aldehyde, and an alcohol - Google Patents

Abstract

A method of treating an aldehyde mixture comprising a carboxylic acid and a metal cation, which method comprises: contacting the aldehyde mixture with a basic separating medium, and subsequently or simultaneously contacting with an acidic separating medium; use of the treated aldehyde mixture to prepare an alcohol; and the alcohol.

Description

The purposes and the alcohol of the method for processing aldehyde mixture, the aldehyde of handling

Technical field

The present invention relates to handle the method for aldehyde mixture, pure purposes and the alcohol of handling of aldehyde preparation.

Background technology

Usually prepare aldehyde and be hydrogenated to corresponding alcohol.The difficulty relevant with this method is formoxy-formation carboxylic acid byproduct.The existence of carboxylic acid particularly if neutralization ground does not keep, can have a negative impact to the performance of most of heterogeneous hydrogenation catalysts.In addition, carboxylic acid can react with the alcohol that forms in hydrogenation process, thereby causes additional loss of yield and additional separation costs.Carboxylic acid can cause the processing unit corrosion, particularly when existing in the process-stream that heats more than envrionment temperature.Typically, before hydrogenation, the part in and carboxylic acid.For example U.S.2004/0087819 disclosed before hydrogenation, in and the 3-hydroxy propanal aqueous solution.Yet it is problematic carrying out the part neutralization by interpolation alkali (typically being alkali metal base), and this is owing to cause aldehyde to have the possibility of degraded because of undercompounding.In the presence of the excess base that comes from the insufficient mixing generation, aldehyde can be in conjunction with the by product that forms such as acetal and/or aldol, and these by products can experience further condensation, obtain the polymeric heavy ends.Formed number acid is known to be alcohol acid, and the negative impact to hydrogenation catalyst may not be eliminated in wherein independent neutralization fully.In addition, the gained an alkali metal salt that forms in the part N-process produces ash component, the marketable value of the final common property thing of the obvious reduction of described ash component meeting heavy and the equipment that formed an alkali metal salt can make the downstream is the reboiler and the fouling of heat exchangers of downstream distillation tower for example.

1, ammediol is industrial important chemical.1, ammediol is as form the monomeric unit that gathers (terephthalic acid Sanya methyl esters) that polymkeric substance for example uses in producing carpet and textiles.1, ammediol also can be used as engine coolant, particularly in the cooling system that requires the low and refrigerant that corrodibility is low of specific conductivity.

Can in two-step approach, prepare 1, ammediol, wherein at metal catalyst for example in the presence of cobalt-carbonyl or the rhodium, in organic solution, oxyethane forms the 3-hydroxy propanal at first by hydroformylation.Under pressure, water extracts 3-hydroxy propanal intermediate from organic phase, and in the hydroformylation reaction of recycle metal catalyzer in the organic phase.In step subsequently, the aqueous 3-hydroxy propanal of hydrogenation becomes 1, ammediol.

It is desirable to, moisture 3-hydroxy propanal extract can directly direct in the hydrogenation reactor.Yet as mentioned above, the carboxylic acid that forms as by product in hydroformylation process can have a negative impact to the performance of most of heterogeneous hydrogenation catalysts.In addition, typically in extracting 3-hydroxy propanal process, be leached into also may most of heterogeneous hydrogenation catalysts be had a negative impact in the water from a small amount of metal in the hydroformylation catalysts.

U.S.2004/0087819 discloses by using Zeo-karb, removes hydroformylation catalysts from the 3-hydroxy propanal aqueous solution.As previously mentioned, during this reference also discloses and the 3-hydroxy propanal aqueous solution.With after Zeo-karb contacts and before hydrogenation, neutralize.

Undoubtedly, highly desirable is to improve the method that is prepared alcohol by aldehyde.

Summary of the invention

The invention provides the method for handling the aldehyde mixture that contains carboxylic acid and metallic cation, this method comprises:

-aldehyde mixture is contacted with alkaline separating medium and

-contact with acid separating medium subsequently or simultaneously.In one embodiment of the invention, aldehyde comprises the 3-hydroxy propanal, and carboxylic acid comprises the 3-hydroxy-propionic acid, and metallic cation comprises the group VIII metallic cation, comprise in addition that with this method the pH value of controlling mixture mostly is 6 most, this is by measuring under service temperature.

The present invention also provides preparation 1, the method for ammediol, and this method comprises the aldehyde mixture that hydrogen treatment is crossed, described mixture obtains by treatment process of the present invention.

The present invention also provides 1, the ammediol product.

Description of drawings

The synoptic diagram of Fig. 1 has been described by hydroformylation oxyethane, carbon monoxide and hydrogen, forms the 3-hydroxy propanal, becomes 1 by hydrogenation 3-hydroxy propanal subsequently, and ammediol prepares 1, the method for ammediol, and described method is introduced treatment process of the present invention.

Embodiment

According to the present invention, can contact with alkaline separating medium by making aldehyde mixture, further contact then, thereby improve the method for producing alcohol by aldehyde with acid separating medium.Especially, aldehyde mixture is contacted with alkaline separating medium will remove in this mixture, exist to the small part carboxylic acid, so that as previously mentioned, it can reclaim with by-product form, the ash component that elimination is supervened with in the fouling relevant with carboxylic acid, and reduce the reaction of carboxylic acid and pure product subsequently.In addition, with before acid separating medium contacts, aldehyde mixture is contacted to improve removing of the metallic cation that in mixture, exists with alkaline separating medium.

Aldehyde mixture can be any mixture that contains aldehyde.Aldehyde can be any aldehyde, and can be alkyl or aryl aldehyde, hydroxy aldehyde, keto-aldehyde, halogenated aldehyde or other replacement aldehyde.Preferably, aldehyde comprises maximum 12 carbon atoms, more preferably maximum 8 carbon atoms and most preferably maximum 4 carbon atoms.It is that 2-10 is individual, more preferably scope is 2-4 a carbon atom that aldehyde preferably includes scope.Preferred aldehydes comprises that 3 carbon atoms, particularly aldehyde can comprise the 3-hydroxy propanal.

Preferably, can obtain aldehyde mixture by the aqueous extract of hydroformylation products mixture.Term as used herein " hydroformylation products mixture " is the mixture that contains aldehyde, hydroformylation catalysts and carboxylic acid.The hydroformylation products mixture can comprise reaction diluent or " solvent ", the residual reactants that comprises carbon monoxide, hydrogen and oxirane and a spot of other by product in addition.

The gross weight content range that aldehyde mixture can contain with respect to aldehyde mixture is 1-99wt%, and preferable range is 10-80wt%, and more preferably scope is that 15-60wt% and most preferred range are the aldehyde of 20-40wt%.

Carboxylic acid can be any carboxylic acid, preferably contains maximum 12 carbon atoms, the carboxylic acid of more preferably maximum 8 carbon atoms and most preferably maximum 4 carbon atoms.It is 1-10 that carboxylic acid preferably comprises scope, and more preferably scope is a 1-4 carbon atom.Carboxylic acid can comprise one or more carboxylic acids.Preferably, carboxylic acid comprises the oxidised form of aldehyde, more preferably carboxylic acid comprise hydroxycarboxylic acid and most preferably carboxylic acid comprise the 3-hydroxy-propionic acid.Carboxylic acid can comprise the acetate and the formic acid that may exist with the 3-hydroxy-propionic acid.The gross weight content range that aldehyde mixture can contain with respect to aldehyde mixture is 0.1-5wt%, and typically scope is 0.03-3.5wt%, more typically scope be 0.06-1.5wt% and the most typically scope be one or more carboxylic acids of 0.1-0.8wt%.

Metallic cation can be any metallic cation, the preferable alloy positively charged ion comprise one or more IB to the group VIII metallic cation (as " CRC Handbook of Chemistryand Physics ", 69 ^ThEd. define in the periodic table of elements in (CRC Press Inc.1988)), more preferably one or more group VIII metallic cations, in preferred cobalt, ruthenium, rhodium, palladium, platinum, osmium and the iridium one or more, most preferably rhodium, cobalt, iridium and ruthenium and particularly cobalt and/or rhodium positively charged ion.Metallic cation can be included in one or more metallic compounds, title complex or the species.It is maximum 0.03 that aldehyde mixture can contain content, typically maximum 0.02, more typically maximum 0.01, the most maximum 0.002, particularly maximum 0.001 molar equivalent metallic cations/rise metallic cation of aldehyde mixture.Aldehyde mixture can contain content and be at least 0.000001, or at least 0.00001, or at least 0.0001 molar equivalent metallic cation/the rise metallic cation of aldehyde mixture.

In one embodiment, aldehyde mixture may be dissolved in one or more liquid diluents for example in water, alcohol, glycol, ketone, ester and the glycol ether.Especially, thinner comprises the water that forms the aqueous solution.Moisture aldehyde mixture can be any aqueous solution that contains an amount of dissolved aldehyde, carboxylic acid and metallic cation.Preferably, with respect to the gross weight of moisture aldehyde mixture, moisture aldehyde mixture can contain 4-60wt% aldehyde, more typically 20-40wt% aldehyde.Preferably, moisture aldehyde mixture can contain an amount of foregoing carboxylic acid and metallic cation.

Aldehyde mixture is contacted with alkaline separating medium, and this will be to small part separation carboxylic acid from aldehyde mixture.Coming from the aldehyde mixture that contacts with alkaline separating medium can be described as first and contains the aldehyde effluent.The alkalescence separating medium can be any physical form, for example liquid, or preferred solid.

In one embodiment, alkaline separating medium can comprise basic anion exchange resin.The ion exchange resin that can use in the method for the invention can have any physical structure.Preferably, employed in the method for the invention ion exchange resin can have gel type (micropore) or macroreticular type (macropore) structure.The main chemical composition of resin can be based on polyphenol, polystyrene, polyacrylic acid or polyvinylpyridine, and typically with divinyl benzene crosslinked.But the Encyclopedia of Chemical Technology of reference example such as Kirk-Othmer, 4 ^ThEd., Vol.14,1995, the 737-783 pages or leaves.

Basic anion exchange resin can comprise weak base anion-exchange resin.Especially, the pKa of weak base anion-exchange resin can be less than 13, or pKb is greater than 1.Weak base anion-exchange resin is normally defined and can not be dissociated into for example those of NaCl (sodium-chlor) of neutral salt, and these are different with the strongly basic anion exchange resin that can be dissociated into neutral salt.Preferably, weak base anion-exchange resin can be an amine anionite-exchange resin, wherein amine be primary, the second month in a season or tertiary amine and more preferably tertiary amine anion exchange and most preferably dimethylamino SDVB anionite-exchange resin.The commercially available tertiary amine SDVB anionite-exchange resin that can be used for the inventive method comprises available from Rohm; Haas Company, 5000Richmond Street, Philadelphia, Pennsylvania 19137, the AMBERLYST of USA ^TMA21 tertiary amine SDVB anionite-exchange resin; With available from DowChemical Company, Liquid Separations Group, P.O.Box 1206, Midland, Michigan 48641, the DOWEX of USA ^TMM-43 tertiary amine SDVB anionite-exchange resin.

Basic anion exchange resin can comprise strongly basic anion exchange resin.Strongly basic anion exchange resin can be a buffered, preferred buffered quaternary ammonium anion resin, more preferably use list or dibasic phosphate or carbonate buffered quaternary ammonium anion resin and most preferably use dibasic phosphate buffered quaternary ammonium anion resin.Basic anion exchange resin also can be incorporated into for example Rohm ﹠amp of hybrid resin bed; The STRATABED of Haas ^TMIn (mixture of weak base anion-exchange resin and strongly basic anion exchange resin), or, be incorporated into MONOBED not so in the embodiment preferred ^TMIn (strongly basic anion exchange resin and storng-acid cation exchange resin).

In an alternative embodiment, alkaline separating medium can comprise metal oxide.Preferably, metal oxide can be one or more activated aluminas, titanium oxide, zirconium white, chromic oxide and their mixture and more preferably metal oxide comprise activated alumina.Under situation about being not wishing to be bound by theory, it is believed that metal oxide has basic site, when particularly contacting with aqueous mixture, but described aqueous mixture ion-exchange acidic species when contacting with metal oxide.The commercially available metal oxide of Shi Yonging comprises AlcoaF200 or LDS aluminum oxide in the method for the invention.

Can be according to being enough to cause that carboxylic acid in the aldehyde mixture contacts any way that preferably minimizes any degraded of aldehyde simultaneously aldehyde mixture is contacted with alkaline separating medium with alkaline separating medium.Can be by making the fixed bed of mixture flow through alkaline separating medium, perhaps make mixture through containing the chromatographic column of alkaline separating medium, such as auger tank, HIGGINS LOOP ^TM, the rotating disc type device, alternately in the container of hybrid devices and so on aldehyde mixture is contacted with alkaline separating medium.Preferably, aldehyde mixture and alkaline separating medium can be at HIGGINS LOOP ^TMOr other moving-bed device, rotating disc type device, alternately contact in hybrid devices or other fixed bed device.Can be for example with reference to Chemical Engineers ' Handbook of Perry, 6 ^ThEd., 1984, the 19-40 are to the 19-45 page or leaf.HIGGINS LOOP ^TMBe the example of continuous countercurrent exchange column loop system, and comprise have ion-exchange/adsorption zone, the airtight loop of rinsing district, breeding blanket and pulse area.The rotating disc type device can be included on the rotating disk arranges a plurality of pillars that contain separating medium, perhaps uses valve feed switched in a predetermined manner between a plurality of fixed legs.When alkaline separating medium comprises metal oxide, preferred rotating disc type device.

Can when aldehyde contacts with alkaline separating medium, minimize under the temperature of aldehyde degraded, preferably under 5-45 ℃ temperature, and aldehyde mixture contacted with alkaline separating medium.

Preferably, aldehyde mixture is contacted with alkaline separating medium, the pH that controls aldehyde mixture simultaneously mostly is most 6, and more preferably maximum 5.5 and most preferably maximum 5.By the pH of control aldehyde mixture, can minimize any degraded of aldehyde mixture.Preferably, only the initial carboxylic acid of 90-98% is removed by alkaline separating medium, thereby the starting acid that stays 2-10% is to keep in the described in front scope of pH.The concentration that depends on starting acid, this can be about 1 * 10 corresponding to the concentration of unneutralized acid ^-6To 2 * 10 ^-3Molar equivalent carboxylic acid/rise aldehyde mixture.Can easily realize the aequum of residual carboxylic acid by based on the hierarchy of control of directly monitoring pH.

Except as otherwise noted, think that the pH value uses the standard pH probe that immerses the routine in the aldehyde mixture directly to measure under service temperature.

Carboxylic acid amount of removing from aldehyde mixture and gained pH value can be depending on several factors.Especially, the separating power that acid amount of removing and pH can be depending on alkaline separating medium, the aldehyde mixture amount that contacts with alkaline separating medium with respect to being used for of existing is in the amount of the employed alkaline separating medium of separating step, the carboxylic acid amount that in aldehyde mixture, exists, implement duration of contact of contacting employed device between aldehyde mixture and alkaline separating medium and being used for technological process.Can regulate the time length of these factors, particularly contact procedure, to control the pH with aldehyde mixture of removing of acid.

For the method for batch type, in the medium-weight with respect to aldehyde mixture weight, the alkaline separating medium of capacity can be 0.1-25wt% and preferred 1-10wt% with respect to the weight of aldehyde mixture.For continuation method, can make aldehyde mixture with 0.1-40h ^-1, preferred 0.5-20h ^-1And more preferably 1-10h ^-1Volumctric hourly space velocity (with respect to the alkaline separating medium of every volume per hour, the volume of aldehyde mixture charging) the alkaline separating medium of flowing through.

Preferably, avoid making and remove carboxylic acid and contact with unneutralized alkaline separating medium to the aldehyde mixture of the above pH value.This can preferably by the ion-exchange of additional use successive, particularly have the short bed of high dispersive mixing force by regulating foregoing factor, and the back-mixing section that perhaps has frequent regeneration realizes.The ion-exchange of preferred employing successive is wherein by using the described bed of discrete container (rotating disc type) or recurrent pulses to pass through ion-exchange area (HIGGINS ^TMLOOP), total ion exchange bed volume is divided into a series of " N " individual equivalence section.For single section, volumctric hourly space velocity therefore than single bigger bed big " N " doubly.Owing to mix in the longitudinal diffusion, the higher volumes space-time speed section of causing, the result has avoided removing the zone that disacidify causes high pH in bed fully because of the part.As a result, minimize the degraded of aldehyde, operate comparing under the more constant and best outlet pH with bigger bed with this method.

First contains the aldehyde effluent can contain at least 70% aldehyde that is present in the aldehyde mixture, and more preferably at least 80% and most preferably at least 90%.

First contains the aldehyde effluent can contain the carboxylic acid and preferred first littler than aldehyde mixture amount and contain the aldehyde effluent and can contain maximum 20% carboxylic acid that is present in the aldehyde mixture, more preferably maximum 10% and most preferably maximum 5%.First contains the aldehyde effluent can contain at least 1% carboxylic acid that is present in the aldehyde mixture, and more preferably at least 1.5% and most preferably at least 2%.First pH that contains the aldehyde effluent can be maximum 6, preferred maximum 5.5 and more preferably maximum 5.

Can be identical at first content that contains metallic cation in the aldehyde effluent with the metallic cation content in the aldehyde mixture, this is because metallic cation may not can be removed with any tangible amount by alkaline separating medium.

After separating power descends, can carry out alkaline purification to alkaline separating medium, with the alkaline performance of regeneration separating medium.Preferably, if alkaline separating medium is a solid, then alkaline purification can be alkali cleaning.Before alkali cleaning, can wash alkaline separating medium.The alkalescence separating medium can contact the competent time with alkaline wash under competent concentration, with the alkaline performance of regeneration separating medium.Having of alkaline wash is higher than alkaline separating medium pK _bPH so that this medium of fullest ground regeneration.The preferred pH of alkaline wash is that more preferably pH is more than or equal to 10 more than or equal to 8.Alkaline wash is potassium hydroxide solution preferably, more preferably the potassium hydroxide solution of 4wt%.Yet other alkali can be used as alkaline wash, comprising but be not limited to sodium hydroxide, ammonium hydroxide or other metal hydroxides.The alkalescence separating medium can contact under 5-45 ℃ temperature with alkaline wash.

First contains the aldehyde effluent can subsequently or contact the aldehyde mixture that obtains handling simultaneously with acid separating medium.The aldehyde mixture that comes from the processing that contacts with acid separating medium can be described as second and contains the aldehyde effluent.First contains the aldehyde effluent contacts with acid separating medium to small part and contains separating metal positively charged ion the aldehyde effluent from first.

Preferably, first contains the aldehyde effluent can separate from alkaline separating medium, contacts with acid separating medium subsequently.With before acid separating medium contacts, first contains the aldehyde effluent can experience or not experience further modification, thereby changes each component concentrations in the effluent.The modification of effluent can comprise any method, for example dilution or concentrated.Preferably, this method does not have obviously to change the chemical structure of aldehyde.Obvious variation is understood to mean the aldehyde that exists in effluent molar weight typically exists and is not more than 25% decline.Acid separating medium can be any physical form, for example liquid or preferred solid.

Acid separating medium can comprise Lewatit, i.e. weakly acidic cation-exchange resin.Preferably, the Lewatit can be the vinylformic acid Zeo-karb.The Lewatit that can use in the method for the invention can have any physical structure, preferred gel type (micropore) or macroreticular type (macropore) structure.Commercially available vinylformic acid Zeo-karb comprises the Company available from Dow Chemical, LiquidSeparations, and P.O.Box 1206, Midland, Michigan 48642, the DOW MAC-3 vinylformic acid Zeo-karb of USA; Available from Rohm ﹠amp; Haas Company, IonExchange Resins, 100 Independence Mall West, Philadelphia, Pennsylvania 19106, the IRC76 vinylformic acid Zeo-karb of USA; With available from Purolite Company, 150 Monument Road, Bala Cynwyd, Pennsylvania19004, the C140E vinylformic acid Zeo-karb of USA.

First contains the aldehyde effluent can contain any way that the metallic cation in the aldehyde effluent contacts with acid separating medium according to sufficient to guarantee first and contact with acid separating medium.For example, perhaps make mixture flow through containing the chromatographic column of acid separating medium by making the fixed bed of mixture flow through separating medium, make first contain aldehyde effluent and acid separating medium can be such as auger tank, HIGGINS LOOP ^TM, rotating disc type device, alternately contact in the container of hybrid devices and so on.

For the method for batch type, the scope of ratio that the medium-weight of the acid separating medium of capacity and first contains the weight of aldehyde effluent can be 1: 5-1: 25 and preferable range be 1: 10-1: 15.Can change to a few hours, for example 1-50 hour duration of contact from 30 minutes.For continuous processing, first contains the aldehyde effluent can be at 0.1-100h ^-1, preferred 2-30h ^-1Volumctric hourly space velocity (with respect to the acid separating medium of every volume per hour, first contains the volume of aldehyde effluent charging) under the acid separating medium of flowing through.

First contains the aldehyde effluent can contact with acid separating medium under any temperature that minimizes the degraded of separating medium or aldehyde.Preferably, first contains aldehyde effluent and acid separating medium can be at 5-45 ℃, and more preferably contacts under 15-25 ℃ the temperature.

Second contains the aldehyde effluent can contain at least 70% aldehyde that is present in the aldehyde mixture, and more preferably at least 80% and most preferably at least 90%.

Second contains the aldehyde effluent can contain at least 70% and be present in first aldehyde that contains in the aldehyde effluent, and more preferably at least 80% and most preferably at least 90%.Second contains the aldehyde effluent can contain than aldehyde mixture and first and contain the medium and small metallic cation amount of aldehyde effluent, preferably, second contains the aldehyde effluent and can contain maximum 50%, more preferably maximum 25% and most preferably maximum 10% and be present in aldehyde mixture and first and contain metallic cation in the aldehyde effluent.Preferably, second contains the aldehyde effluent and can contain and amount to maximum 0.001, more preferably maximum 0.0001 and the metallic cation of most preferably maximum 0.00001 molar equivalents/liter second contain the aldehyde effluent.

Before hydrogenation, second contains the aldehyde effluent can experience or not experience further modification, thereby changes each component concentrations in the effluent.The modification of effluent can comprise any method, for example dilution or concentrated.

After separating power descends, can carry out acid treatment to acid separating medium, with the acid performance of regeneration separating medium.Preferably, if acid separating medium is a solid, then acid treatment can be pickling.Can be 70-100 ℃, most preferably make acid separating medium contact the competent time with pickle solution under 85-95 ℃ the temperature, at least 45 ℃, preferable range with the acid performance of regenerated acidic separating medium.Pickle solution should have and is lower than acid separating medium pK _aPH so that fullest ground regeneration separating medium.Except as otherwise noted, pK _aValue is regarded as measuring under 25 ℃ temperature.The pH of pickle solution preferably is less than or equal to 2, and more preferably pH is less than or equal to 1.Pickle solution is sulphuric acid soln preferably, more preferably 10% sulphuric acid soln.Yet other acid can be used as pickle solution, comprising but be not limited to hydrochloric acid, phosphoric acid or other mineral acid.

Refer now to Fig. 1, the synoptic diagram of Fig. 1 has been described by hydroformylation oxyethane, carbon monoxide and hydrogen and has been formed the 3-hydroxy propanal, and then hydrogenation 3-hydroxy propanal becomes 1; ammediol; preparation 1, the method for ammediol, this method is introduced treatment process of the present invention.

Fig. 1 has described 1, embodiment of the present invention in the ammediol method.Logistics independent or bonded oxyethane (1), carbon monoxide and hydrogen (2) is introduced in the hydroformylation container (3), and reacts the product mixtures that produces hydroformylation in the presence of hydroformylation catalysts.

After hydroformylation reaction; can cool off the hydroformylation products mixture that contains the 3-hydroxy propanal also flow in the extraction vessel (5) by pipeline (4); wherein liquid, aqueous; normally water and optional miscible thinner add in order to extract and concentrated 3-hydroxy propanal is used for subsequently step of hydrogenation by pipeline (6).With heavy end product purge randomly, can circulate from extraction vessel by pipeline (7) comes from organic phase that liquid-liquid extracts in hydroformylation reaction.Can the aqueous solution of the 3-hydroxy propanal that generates from liquid-liquid extracts be flowed in degasifier-stripper-oxidizer container (9) in order to remove carbon monoxide and hydrogen and to be used for any residual catalyst with oxidation carbonyl form by pipeline (8).Can be easily by introduce oxygen containing gas for example air in 3-hydroxy propanal water solution extract, carry out oxidation.Preferred oxidation technology comprises when the pending 3-hydroxy propanal aqueous solution flows by container (9) in a downward direction, passes through degasifier-stripper-oxidizer container (9) from inlet (11) injection air in the upward direction.Stripping gas can be used as oxidizing gas through identical inlet (11), and perhaps independent inlet (not shown) that the 3-hydroxy propanal aqueous solution arranges sprays by degasifier-stripper-oxidizer container (9) by allow when container (9) stripping gas to flow through when solution stream.

In the method for the invention, the aqueous solution of 3-hydroxy propanal is that the aqueous mixture of 3-hydroxy propanal can flow to the container (10) from container (9), can be by aqueous mixture and the alkaline separating medium contact separation carboxylic acid that makes the 3-hydroxy propanal at this.The effluent that contains the 3-hydroxy propanal from first of container (10) can flow to container (22) then, can contact the separating metal positively charged ion with acid separating medium by making first effluent that contains the 3-hydroxy propanal at this.

Coming from effluent that second of container (22) contains the 3-hydroxy propanal can flow in the hydrogenation zone (13) then and produce with hydrogen (14) reaction in the presence of hydrogenation catalyst and contain 1, the hydrogenation product mixtures of ammediol (15).In this method, shown hydrogenation zone (13) comprises placed in-line two or more independent reaction vessels.

Can reclaim residual thinner and extraction agent water by distillation hydrogenation product mixtures (15) in tower (16), and be recycled in the water extraction process for further distilling (not shown) and separating and purge light ends.Contain 1, the product stream (18) of ammediol can flow in the distillation tower (19) for reclaiming 1, ammediol (20) and heavy ends (21).

The hydroformylation container can be a pressure reacting container, for example the bubble tower or the stirring tank of intermittence or operation in a continuous manner.Can in the presence of hydroformylation catalysts, make the feed stream contact.Hydroformylation catalysts can comprise one or more foregoing metallic cations.Hydroformylation catalysts can further comprise carbonyl, particularly water-insoluble cobalt-carbonyl and/or rhodium, for example Co ₄(CO) ₁₂(ten dicarbapentaborane, four cobalts), Co ₂(CO) ₈(cobalt octacarbonyl) and Rh ₆(CO) ₁₆(16 carbonyls, six cobalts).With respect to the gross weight of hydroformylation reaction mixture, hydroformylation catalysts typically is that the content of 0.01-1wt%, preferred 0.05-0.3wt% is present in the reaction mixture with the scope.Hydrogen and carbon monoxide are that 1: 2 to 8: 1, preferred 1: 1 to 6: 1 mol ratio are incorporated in the reaction vessel with scope usually.

Can contain the 3-hydroxy propanal of major portion and the acetaldehyde and 1 of less important part producing effectively, under the condition of the hydroformylation products mixture of ammediol, carry out hydroformylation reaction.With respect to the gross weight of hydroformylation reaction mixture, the content of 3-hydroxy propanal is preferably less than 15wt% in the reaction mixture, and more preferably scope is 5-10wt%.For the thinner with different densities is provided, the desired concn of 3-hydroxy propanal can be expressed with volumetric molar concentration in the reaction mixture, promptly less than 1.5M, preferably in the 0.5-1M scope.Usually, can be less than 100 ℃, preferred 60-90 ℃ and most preferably carry out the catalytic hydroformylation reaction of cobalt under 75-85 ℃ the temperature, and the catalytic hydroformylation reaction of rhodium is carried out under the about 10 ℃ magnitude of height.Usually can under being the pressure of 1-35MPa, preferred (for the economy of technology) 7-25MPa, scope carry out hydroformylation reaction, and for obtaining bigger selectivity, preferred higher pressure.Can carry out hydroformylation reaction in the inert liquid diluent in that reactant is.'inertia' is meant that thinner is not consumed in reaction process.Usually; the desirable thinner that is used for hydroformylation technology is with the solubilising carbon monoxide; basically with the water unmixing, and under the hydroformylation condition dissolving 3-hydroxy propanal to the desired concn of 5wt% at least, simultaneously most of thinners when water extraction as independent reservation mutually." basically with the water unmixing " is meant that thinner solubleness in water under 25 ℃ forms independent organic phase less than 25wt% during water extraction 3-hydroxy propanal with box lunch from the hydroformylation products mixture.Preferably, the hydroformylation reaction thinner can be pure and mild ether.More preferably, the hydroformylation reaction thinner can be an ether, for example methyl tertiary butyl ether, Ethyl Tertisry Butyl Ether, diethyl ether, phenyl isobutyl ether, ethoxyethyl group ether, phenyl ether and Di Iso Propyl Ether.Also can use the blend of thinner, for example tetrahydrofuran (THF)/toluene, tetrahydrofuran (THF)/heptane, and the trimethyl carbinol/hexane.Most preferably the hydroformylation reaction thinner can be a methyl tertiary butyl ether, and this is because can realize the high yield of 3-hydroxy propanal under moderate reaction conditions.

In order further to improve productive rate under moderate reaction conditions, the hydroformylation reaction mixture preferably includes catalyst promoting agent with fast reaction speed.Preferred lipophilic promotor comprises lipophilic De phosphonium salt and lipophilic amine, and they will be accelerated hydroformylation speed and not give active catalyst wetting ability (water-soluble).Preferably, lipophilic promotor can be 4-butyl-phosphonium and dimethyl lauryl amine." lipophilic " as used herein is meant that promotor tending to is retained in the organic phase after with water extraction 3-hydroxy propanal.Usually, the promotor amount is the metal component (for example cobalt and/or rhodium) in the 0.01-1mol/mol catalyzer.

Under lower concentration, water serves as the promotor that forms required carbonylic catalyst species.With respect to the gross weight of hydroformylation reaction mixture, the optimum water scope that is used for hydroformylation in the methyl tertiary butyl ether thinner is 1-2.5wt%.Yet excessive water will reduce the selectivity of 3-hydroxy propanal and can impel formation second liquid phase.

Can be by any suitable device, for example mixing tank-settling vessel, filler or column plate extraction column or rotary-disk contactor carry out liquid-liquid and extract the 3-hydroxy propanal in water.By volume, the water yield scope that joins in the hydroformylation products mixture is generally 1: 1 to 1: 20, preferred 1: 5 to 1: 15.Preferably under being 25-55 ℃ temperature, scope carries out water extraction, wherein preferred lesser temps.Under 25-55 ℃, be the reservation that water extraction will maximize the organic phase inner catalyst under the 0.5-5MPa in the dividing potential drop of carbon monoxide.

Typically, come from the organic phase that liquid-liquid extracts and contain the hydroformylation reaction thinner of major portion and the catalyzer of major portion.Available optional heavy ends purge, the circulation organic phase is in hydroformylation reaction from extraction vessel.

Preferably, with respect to the gross weight of moisture 3-hydroxy propanal mixture, can contain the 3-hydroxy propanal of 4-60wt%, more preferably the 3-hydroxy propanal of 20-40wt% by the moisture 3-hydroxy propanal mixture that generates in liquid-liquid water extraction.

The pH scope of moisture 3-hydroxy propanal mixture can be 2-4, typically 2.5-3.5 and more typically 2.9-3.3.

With respect to the gross weight of moisture 3-hydroxy propanal mixture, moisture 3-hydroxy propanal mixture can contain content range be 0.03-3wt%, typically scope be 0.06-1wt% and more typically scope be the carboxylic acid of 0.1-0.6wt%.

Typically, with respect to the gross weight of the carboxylic acid that exists in moisture 3-hydroxy propanal mixture, carboxylic acid comprises that content is 50wt%, more typically 60wt%, 75wt%, particularly the 3-hydroxy-propionic acid of 90wt% at least the most at least at least at least.

It is maximum 0.03, typically maximum 0.02, more typically maximum 0.01, the most typically cobalt and/or rhodium positively charged ion maximum 0.002, particularly maximum 0.001 molar equivalent cobalts and/or rhodium positively charged ion/liter moisture 3-hydroxy propanal mixture that moisture 3-hydroxy propanal mixture can contain total amount.Moisture 3-hydroxy propanal mixture can contain cobalt and/or the rhodium positively charged ion of total amount at least 0.000001 or at least 0.00001 or at least 0.0001 molar equivalent cobalt and/or rhodium positively charged ion/liter moisture 3-hydroxy propanal mixture.Typically, moisture 3-hydroxy propanal mixture can contain cobalt and/or the rhodium positively charged ion that total weight range is 0.001-0.003 molar equivalent cobalt and/or rhodium positively charged ion/liter moisture 3-hydroxy propanal mixture.Cobalt and/or rhodium cations comprise from cobalt and/or rhodium positively charged ion in water-soluble and water-insoluble title complex, compound or the species.

The oxidable 3-hydroxy propanal aqueous solution that produces from liquid-liquid water extraction.Preferably, can for example water-insoluble cobalt and/or rhodium species become water soluble metallic compound for example under aqueous cobalt and/or the cationic solutions of weak acidity of rhodium moisture 3-hydroxy propanal mixture to be contacted with oxygen at the insoluble metallic compound of oxidation effectively.The oxidation of insoluble metallic compound will help to remove metallic compound in ion-exchange step subsequently.

Typically, helping forming under the condition of 3-hydroxy propanal, generation is being suitable for the solutions of weak acidity of oxidation as the carboxylic acid amount of oxyethane hydroformylation by product generation.If the acid of capacity exists with the byproduct of reaction form, can be 3-6, the preferably organic or inorganic acid of the amount of the solution of 3-4 then by adding the living pH of effective real estate, make the 3-hydroxy propanal aqueous solution become acidity.Suitable acid comprises C _1-4Organic acid.

Can be 50-200kPa, preferably carry out oxidation under the pressure of about 101.3kPa (normal atmosphere) under 5-45 ℃ the temperature and in scope.Residence time scope typically can be 1-15 minute.

In degasifier-stripper-oxidizer, stripping gas for example nitrogen or carbonic acid gas also can be sprayed by the 3-hydroxy propanal aqueous solution, to prevent to form fuel mixture and auxiliaryly to remove carbon monoxide and hydrogen from the 3-hydroxy propanal aqueous solution.Even a spot of carbon monoxide residual in solution is removed in expectation, this is because carbon monoxide can disturb the performance of hydrogenation catalyst.

After the degasifier-stripper of flowing through-oxidizer, the moisture 3-hydroxy propanal of gained mixture can contain 3-hydroxy propanal and by product, and comprising one or more water miscible metallic cation and carboxylic acid, main ingredient is the 3-hydroxy-propionic acid.

The moisture 3-hydroxy propanal mixture that is obtained by degasifier-stripper-oxidizer can contact with alkaline separating medium, thereby obtains first effluent that contains the 3-hydroxy propanal.As previously mentioned, alkaline separating medium can contact with moisture 3-hydroxy propanal mixture, and the pH that controls mixture simultaneously is maximum 6, preferred maximum 5.5 and more preferably maximum 5 times, so that minimize the degraded of 3-hydroxy propanal.At pH is more than 5, and 3-hydroxy propanal degraded can increase and be more than 6 in the pH value, but obvious degradation.

Be used to make that the condition of moisture 3-hydroxy propanal mixture and the contact of alkaline separating medium and container can be used for aldehyde mixture described the same with the front.

First effluent that contains the 3-hydroxy propanal can contain at least 70% aldehyde that is present in the moisture 3-hydroxy propanal mixture, and more preferably at least 80% and most preferably at least 90%.

First effluent that contains the 3-hydroxy propanal can contain than the lower carboxylic acid content of moisture 3-hydroxy propanal mixture, can contain maximum 20% carboxylic acid that is present in the moisture 3-hydroxy propanal mixture with preferred first effluent that contains the 3-hydroxy propanal, more preferably maximum 10% and most preferably maximum 5%.First effluent that contains the 3-hydroxy propanal can contain at least 1% carboxylic acid that is present in the moisture 3-hydroxy propanal mixture, and more preferably at least 1.5% and most preferably at least 2%.First pH that contains the effluent of 3-hydroxy propanal can be maximum 6, preferred maximum 5.5 and more preferably maximum 5.

Can be identical at the first metallic cation content that contains in the effluent of 3-hydroxy propanal with the metallic cation content in moisture 3-hydroxy propanal mixture, this is because metallic cation is not removed with any tangible amount by alkaline separating medium.

First effluent that contains the 3-hydroxy propanal is contacted with acid separating medium, thereby obtain second effluent that contains the 3-hydroxy propanal.Being used to make the condition of first effluent that contains the 3-hydroxy propanal and acid separating medium contact and container to be used for first with the front, to contain the aldehyde effluent described the same.

Second effluent that contains the 3-hydroxy propanal can contain at least 70% aldehyde that is present in the moisture 3-hydroxy propanal mixture, and more preferably at least 80% and most preferably at least 90%.

Second effluent that contains the 3-hydroxy propanal can contain at least 70% and be present in first aldehyde that contains in the effluent of 3-hydroxy propanal, and more preferably at least 80% and most preferably at least 90%.

Second effluent that contains the 3-hydroxy propanal can contain and contain the lower metallic cation content of the effluent of 3-hydroxy propanal and preferred second effluent that contains the 3-hydroxy propanal than moisture 3-hydroxy propanal mixture or first and can contain maximum 50%, more preferably maximum 25% and most preferably maximum 10% metallic cation that is present in the effluent that moisture 3-hydroxy propanal mixture or first contains the 3-hydroxy propanal.Preferably, second effluent that contains the 3-hydroxy propanal can contain and amounts to maximum 0.001, more preferably maximum 0.0001 and the metallic cation of most preferably maximum 0.0001 molar equivalents/liter second contain the effluent of 3-hydroxy propanal.

The second pH scope that contains the effluent of 3-hydroxy propanal can be 3-6, and preferable range is 3.5-5.5.

Hydrogenation catalyst can preferably fixed bed carried nickel catalyzator, for example is available commercially from W.R.Grace as CalsicatE-475SR and R-3142.

Can in single hop or two sections or more successive temperature sections, carry out hydrogenation process.In preferred embodiments, can be as mentioned above, be to carry out hydrogenation under 50-130 ℃ the temperature in scope, then by being higher than first section and be to carry out second section under 70-155 ℃ the temperature in scope, randomly carry out the 3rd section under greater than 120 ℃ temperature then and be inverted to 1 for heavy ends, ammediol.

Usually describing on the basis of the present invention, can be by obtaining further understanding with reference to following embodiment, these embodiment only provide with illustrative purposes, and are not used in the scope of the present invention described herein that limits.

Embodiment 1

The moisture 3-hydroxy propanal mixture that preparation is used in embodiment 2-4:

4: 1 hydrogen at 1350psi (9300kPa): under the carbon monoxide, at 35 ℃ of hydroformylation products mixtures of using water extraction oxyethane down, wherein moisture extract phase forms the aqueous solution.After being depressured to normal atmosphere, separating moisture extract phase and, cobalt carbonyl catalyst is changed into water-soluble cationic cobalt metal species with the air that dilutes/nitrogen mixture injection.By the moisture 3-hydroxy propanal of gas chromatographic analysis mixture, determine that the 3-hydroxy propanal concentration of moisture 3-hydroxy propanal mixture is 12.25wt%.Use based on thiocyanide deutero-colorimetric technical measurement and be 77ppmw to the concentration of cobalt.At the stoichiometric point place of pH=8 to 9, when when measuring down for 25 ℃, causing concentration with 0.1N KOH titrating solution titration acidity is carboxylic acid/g 3-hydroxy propanal mixture of 0.051meq.When measuring down for 25 ℃, the pH of moisture 3-hydroxy propanal mixture is 3.3.This moisture 3-hydroxy propanal mixture is divided into the many equal portions that use in embodiment 2-4.

Embodiment 2

The method according to this invention, measuring alkaline separating medium (particularly tertiary amine ion exchange resin) removes the effectiveness of carboxylic acid and acid separating medium (particularly Lewatit) and contains the effluent of 3-hydroxy propanal from first and remove the cationic effectiveness of cobalt from moisture 3-hydroxy propanal mixture.By vibration, in vial, under 24 ℃, make moisture 3-hydroxy propanal mixture and the 1 gram wet AMBERLYST of 10g from embodiment 1 ^TMA-21 (available from the dimethylamino macroreticular SDVB of Rohmand Haas Company) ion exchange resin contact 18 hours is to guarantee liquid-solid balance.By under 65 ℃, the independent sample of vacuum oven overnight dry resin, the dry solids content of 52wt% in the realization wet resin.Be 5 with liquid phase after resin contacts (i.e. first effluent that contains the 3-hydroxy propanal) analysis revealed pH, this measures down at 25 ℃, and the carboxylic acid concentration is 0.002meq/g, and cobalt concentration is that 76ppmw and 3-hydroxy propanal concentration are 11.9wt%.Consider the interior normal experimental error of gas chromatographic analysis of this reactive intermediate, any difference less than 3wt% between the initial sum ultimate density of 3-hydroxy propanal can be ignored.

This shows and can use alkaline separating medium to remove carboxylic acid that 96wt% exists in moisture 3-hydroxy propanal mixture and the degraded of 3-hydroxy propanal can be ignored.

By vibration, the DOWEX that residual liquid supernatant liquor of 4.55g (i.e. first effluent that contains the 3-hydroxy propanal) and 0.038g are wet ^TMMac-3 (available from the macroreticular vinylformic acid of DowChemical Company) ion exchange resin contact 18 hours.By under 65 ℃, the independent sample of vacuum oven overnight dry resin, the dry solids content of 53wt% in the realization wet resin.Be 4.4 with liquid phase after resin contacts (i.e. second effluent that contains the 3-hydroxy propanal) analysis revealed pH, cobalt concentration is that 18ppmw and 3-hydroxy propanal concentration are 11.5wt%.

With respect to moisture 3-hydroxy propanal mixture, contact with alkaline separating medium and the combination of acid separating medium remove 96wt% carboxylic acid and 77wt% cobalt and only the 3-hydroxy propanal of 7wt% degrade.The cobalt concentration on the resin (based on exsiccant gram number) be 741 at second ratio that contains cobalt concentration residual in the effluent of 3-hydroxy propanal.

Embodiment 3 (contrast)

By vibration, in vial, under 24 ℃, make 4.34g contain the effluent and the wet AMBERLYST of additional 0.56g of 3-hydroxy propanal from first of embodiment 2 ^TMA-21 (available from the dimethylamino macroreticular SDVB of Rohm and Haas Company) ion exchange resin contact 18 hours.With this resin Continuous Contact after, liquid phase analysis shows that carboxylic acid removes fully, pH is 7.07, cobalt concentration is that 76ppmw and 3-hydroxy propanal concentration are 3.17wt%.

This embodiment proves that the 3-hydroxy propanal was degraded after the pH that does not control moisture 3-hydroxy propanal mixture will cause removing carboxylic acid from moisture 3-hydroxy propanal mixture.

Embodiment 4 (contrast)

By vibration, in vial, under 24 ℃, make moisture 3-hydroxy propanal mixture and the 0.063g exsiccant DOWEX of 10g from embodiment 1 ^TMMac-3 (available from the macroreticular vinylformic acid of Dow ChemicalCompany) ion exchange resin contact 18 hours.Liquid phase analysis shows that pH is 3.3 after contacting with resin, and cobalt concentration is that 48ppmw and 3-hydroxy propanal concentration are 12.45wt%.Ratio at the cobalt concentration on the resin (based on exsiccant gram number) and cobalt concentration residual in the aqueous mixture of 3-hydroxy propanal is 96.

The relatively proof of embodiment 2 and embodiment 4 with before acid separating medium contact, will obviously be improved the cobalt amount of removing by acid separating medium with alkaline separating medium processing, minimize the degraded of 3-hydroxy propanal simultaneously.

Embodiment 5

Measure the method according to this invention metal oxide is removed carboxylic acid from moisture 3-hydroxy propanal mixture effectiveness.

Be similar to the moisture 3-hydroxy propanal mixture of embodiment 1 preparation, different is that moisture 3-hydroxy propanal mixture has the 3-hydroxy propanal concentration of 22wt% and the carboxylic acid concentration of 0.041meq/g solution.

Washing 2g LDS (available from the activated alumina of Coastal Chemical Corporation) removes the residual alkali line space air dry of going forward side by side.The LDS that washed is joined in the bottle that contains the moisture 3-hydroxy propanal mixture that 18g obtains from oxyethane hydroformylation products mixture.At room temperature bottle was rotated 68 hours on the top of the shelf.The LDS aluminum oxide is removed the acid of 79wt%, and this causes first pH that contains the effluent of 3-hydroxy propanal is 3.3, with after the LDS aluminum oxide contacts less than 4% 3-hydroxy propanal degraded.

The carboxylic acid that this proof can be used metal oxide to remove to exist in moisture 3-hydroxy propanal mixture and the degraded minimum of 3-hydroxy propanal.

Make first to contain the effluent of 3-hydroxy propanal and an amount of DOWEX then ^TMMac-3 (available from the macroreticular vinylformic acid of Dow Chemical Company) ion exchange resin contact obtains second effluent that contains the 3-hydroxy propanal.Second effluent that contains the 3-hydroxy propanal contains less than first and contains the cobalt amount that exists in the effluent of 3-hydroxy propanal.

Embodiment 6

Measure the method according to this invention effectiveness that metal oxide is removed carboxylic acid from moisture 3-hydroxy propanal mixture in continuous processing.

1300g LDS is alumina filled in the pillar of 2 inches (5cm) * 18 inch (46cm).With moisture 3-hydroxy propanal mixture with 0.4 to 0.6hr ^-1Weight hourly space velocity (WHSVhr ^-1) join in the pillar.Moisture 3-hydroxy propanal mixture contains carboxylic acid concentration that scope is a 0.021-0.038meq/g solution and the 3-hydroxy propanal content of 17-23wt%.With after aluminum oxide contacts, first effluent that contains the 3-hydroxy propanal demonstrates negligible 3-hydroxy propanal degraded, and still removes 92wt% and be present in acid in the moisture 3-hydroxy propanal mixture.After penetrating acid, use the potassium hydroxide solution of 4wt% to carry out the regeneration of aluminum oxide.

Make first effluent that contains the 3-hydroxy propanal and an amount of DOWEX then ^TMMac-3 (available from the macroreticular vinylformic acid of Dow Chemical Company) ion exchange resin contact obtains second effluent that contains the 3-hydroxy propanal.Second effluent that contains the 3-hydroxy propanal contains less than first and contains the cobalt amount that exists in the effluent of 3-hydroxy propanal.

Claims (18)

1. a processing contains the method for the aldehyde mixture of carboxylic acid and metallic cation, and this method comprises:

-aldehyde mixture is contacted with alkaline separating medium and

-contact with acid separating medium subsequently or simultaneously.

2. the process of claim 1 wherein that this method comprises that in addition the pH that controls aldehyde mixture is maximum 6 numerical value, this measures under service temperature.

3. claim 1 or 2 method, wherein the pH of aldehyde mixture maintains under maximum 5.5 the pH, and this measures under service temperature, particularly maximum 5 pH, this measures under service temperature.

4. each method of claim 1-3, its neutral and alkali separating medium comprises basic anion exchange resin.

5. the method for claim 4, wherein basic anion exchange resin comprises weak base anion-exchange resin.

6. each method of claim 1-3, its neutral and alkali separating medium comprises metal oxide.

7. the method for claim 6, wherein metal oxide comprises one or more in activated alumina, titanium oxide, zirconium white, chromic oxide and their mixture, particularly activated alumina.

8. each method of claim 1-7, wherein under 5-45 ℃ the temperature and 1-10 volume of liquid/volume alkalescence separating medium/hour air speed under, aldehyde mixture is contacted with alkaline separating medium.

9. each method of claim 1-8, wherein to comprise scope be 2-8, particularly 2-4 carbon atom to carboxylic acid.

10. each method of claim 1-9, wherein carboxylic acid comprises the 3-hydroxy-propionic acid.

11. each method of claim 1-10, aldehyde mixture is contacted with alkaline separating medium obtain first and contain the aldehyde effluent, described first contains the aldehyde effluent comprises at least 70% aldehyde that is present in the aldehyde mixture, particularly at least 80%, at least 90% aldehyde that is present in the aldehyde mixture more especially.

12. each method of claim 1-11, wherein aldehyde mixture comprises the 3-hydroxy propanal.

13. each method of claim 1-12, wherein metallic cation comprises group VIII metallic cation, particularly cobalt and/or rhodium positively charged ion.

14. each method of claim 1-13, wherein acid separating medium comprises the Lewatit.

15. each method of claim 1-14, wherein contact and obtain second and contain the aldehyde effluent with acid separating medium, described second contains the aldehyde effluent comprises and amounts to maximum 0.001 molar equivalent metallic cations/liter second and contain the aldehyde effluent, and particularly maximum 0.0001 molar equivalent metallic cations/liter second contains the aldehyde effluent.

16. each method of claim 12-15, wherein by under acidic conditions, under 5-45 ℃ temperature, oxidation comprises the moisture 3-hydroxy propanal mixture of 3-hydroxy-propionic acid and cobalt-carbonyl and/or rhodium compound, forms 3-hydroxy propanal mixture.

17. one kind prepares 1, the method for ammediol, and this method comprises:

-contact with alkaline separating medium by making 3-hydroxy propanal mixture, the pH that controls 3-hydroxy propanal mixture simultaneously is under maximum 6 numerical value, this is by measuring under service temperature, contact with acid separating medium subsequently or simultaneously, thereby handle contain carboxylic acid and cobalt and/or rhodium cationic 3-hydroxy propanal mixture and

The 3-hydroxy propanal mixture that-hydrogen treatment is crossed.

18. the method by claim 17 obtain 1, the ammediol product.

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