KR20000016054A - Process for preparing 1,3-alkanediols - Google Patents

Abstract

PURPOSE: A selective manufacturing method for 1,3-alkaneediol including PDO from 3-hydroxyalkaneal including HPA by using a fixed layered hydrogenation catalyst is provided. CONSTITUTION: A process for preparing 1,3-alkaneediols via the hydrogenation of 3-hydroxyalkaneals wherein the process comprises passing an aqueous 3-hydroxyalkaneal solution to a hydrogenation zone and in contact with a fixed-bed hydrogenation catalyst under hydrogenation conditions to form an aqueous 1,3-alkaneediol solution, characterized in that the aqueous 3-hydroxyalkaneal solution has a 3 hydroxyalkaneal concentration within the range of 0.2 to 5 wt.%.

Description

Method for preparing 1,3-alkanediol

1,3-propanediol (PDO) is an intermediate in the production of polyester for fibers and films. It is known to produce PDO by a process involving the hydrogenation of 3-hydroxypropanal (HPA) (1). HPA can be prepared by hydroformylation of ethylene oxide (synthesis gas, reaction with H ₂ / CO). HPA can also be prepared, for example, from glycerin and acrolein.

Given the economics of the process, it is important to make the HPA hydrogenation step highly selective to the PDO. However, selectivity is complicated by the high reactivity of HPA, which can react with species in the hydrogenation reaction mixture to form byproducts that lower product yield and complicate product recovery. It is known to improve selectivity by using slurry catalysts at relatively low temperatures of 60 to 90 ° C. However, slurry catalyst systems are very expensive to operate.

Valerius et al. (Chemical Engineering and Processing 35 (1996) 11-19) have already shown how to hydrogenate a 10 wt% aqueous solution of HPA simultaneously with hydrogen through a trickle bed. However, an unattractive result is obtained when repeating these examples and other examples at slightly higher concentrations.

Therefore, it would be desirable to prepare PDO from HPA with high selectivity and activity in a relatively inexpensive fixed bed catalyst system.

The present invention relates to a process for the preparation of 1,3-alkanediols. In a specific aspect, the present invention relates to the preparation of 1,3-propanediol from ethylene oxide via hydrogenation of 3-hydroxypropanal.

It is therefore an object of the present invention to provide a process for the selective preparation of 1,3-alkanediols comprising PDO from 3-hydroxyalkanals comprising HPA using a fixed bed hydrogenation catalyst.

According to the present invention, 1,3-alkanediols, including 1,3-propanediol, send 3-hydroxyalkanal aqueous solution to a hydrogenation zone and contact with a fixed bed hydrogenation catalyst under hydrogenation conditions to form an aqueous 1,3-alkanediole solution Prepared through the hydrogenation of 3-hydroxyalkanal including the step, 3-hydroxyalkanal aqueous solution is characterized in that the 3-hydroxyalkanal concentration is in the range of 0.2 to 5% by weight.

According to a preferred embodiment of the invention, 1,3-propanediol is

(a) at temperatures in the range of 50-100 ° C. and pressures in the range of 500-35000 MPa (500-5000 psig), ethylene oxide is essentially an effective amount of non-phosphine-ligated in a non-water-miscible solvent. Contacting carbon monoxide and hydrogen under reaction conditions effective to produce an intermediate mixture comprising up to 15% by weight of 3-hydroxypropanal in the presence of a cobalt or rhodium catalyst and an effective amount of catalyst promoter;

(b) adding an aqueous solution to the intermediate mixture and providing an aqueous phase comprising 3-hydroxypropanal at a concentration of at least 20% by weight, and an organic phase comprising a cobalt or rhodium catalyst or a cobalt- or rhodium-containing derivative thereof. Most 3-hydroxypropanal was extracted into the aqueous solution at a temperature of 100 ° C. or lower so that;

(c) separating the aqueous phase from the organic phase;

(d) diluting the aqueous phase with an aqueous liquid to form a 3-hydroxypropanal solution having a 3-hydroxypropanal concentration in the range of 0.2 to 5% by weight;

(e) sending an aqueous 3-hydroxypropanal aqueous solution to a hydrogenation zone and contacting with a fixed bed hydrogenation catalyst under hydrogenation conditions to form an aqueous 1,3-propanediol;

(f) preparing 1,3-propanediol.

In certain embodiments of this process, a relatively concentrated 3-hydroxypropanal solution is sent from downstream hydrogenation to a 3-hydroxypropanal solution and diluted with an aqueous 1,3-propanediol solution. This dilution of the 3-hydroxypropanal aqueous solution prior to hydrogenation allows the use of relatively inexpensive fixed bed hydrogenation catalysts without sacrificing hydrogenation selectivity. The use of an aqueous 1,3-propanediol solution for dilution of the 3-hydroxypropanal solution further enhances the selectivity and yield of 1,3-propanediol, extends catalyst life and reduces equipment and cooling costs.

The present invention provides an aspect of the process of the invention for the preparation of 1,3-propanediol by hydroformylating ethylene oxide with 3-hydroxypropanal and then hydrogenating 3-hydroxypropanal with 1,3-propanediol. It may be conveniently described with reference to the accompanying drawings.

In the illustrated embodiment, a hydroformylation vessel, which may be a pressure reaction vessel, such as a bubble column or a stirred tank, in which a separate or combined stream of ethylene oxide (1), carbon monoxide and hydrogen (2) is operated batchwise or continuously ( Fill in 3). The feed stream is contacted in the presence of a hydroformylation catalyst, generally metal carbonyl selected from rhodium and cobalt carbonyl. The hydroformylation catalyst is generally present in the reaction mixture in an amount in the range of 0.01 to 1% by weight, preferably 0.05 to 0.3% by weight, based on the weight of the hydroformylation reaction mixture. Hydrogen and carbon monoxide are generally introduced into the reaction vessel in a molar ratio within the range of 1: 2 to 8: 1, preferably 1: 1 to 6: 1.

Most 3-hydroxypropanal and small amounts of acetaldehyde and 1,3-propanediol, while maintaining the level of 3-hydroxypropanal in the reaction mixture up to 15% by weight, preferably in the range of 5 to 10% by weight. The hydroformylation reaction is carried out under conditions effective to produce a hydroformylation reaction product mixture containing. (To provide solvents with different densities, the desired concentration of 3-hydroxypropanal in the reaction mixture can be expressed in molar concentrations, ie 1.5 M or less, preferably in the range from 0.5 to 1 M). Generally, the cobalt-catalyzed hydroformylation reaction is at or below 100 ° C., preferably 60 to 90 ° C., most preferably 75 to 85 ° C., and the rhodium-catalyzed hydroformylation is about 10 ° C. higher. Carried out at temperature. The hydroformylation reaction is generally carried out at a pressure in the range of 0.7 to 34.5 MPa (100 to 5000 psig), preferably in the range of 6.9 to 24.1 (1000 to 3500 psig) (for economical aspects of the process), for higher selectivity Higher pressures are preferred. The concentration of 3-hydroxypropanal in the intermediate mixture can be controlled by adjusting process conditions such as ethylene oxide concentration, catalyst concentration, reaction temperature and residence time. In general, relatively low reaction temperatures (up to 90 ° C.) and relatively short residence times (20 minutes to 1 hour) are preferred.

The hydroformylation reaction is carried out in a liquid solvent that is inert to the reactants. The term "inert" means that the solvent is not consumed during the reaction. In general, the ideal solvent for the hydroformylation process is to solubilize carbon monoxide and be essentially non-water-miscible, exhibiting low to moderate polarity, so that the 3-hydroxypropanal intermediate is subjected to hydroformylation conditions. Under solubilization to a desired concentration of at least 5% by weight, while a significant amount of solvent will remain in the separate phase when extracted with water. The term “essentially non-water-miscible” means that the solvent has a solubility in water of 25 ° C. at 25 ° C. to form a separated hydrocarbon-rich phase when the 3-hydroxypropanal is extracted with water from the hydroformylation reaction mixture. It means less than or equal to weight percent. Preferably, this solubility is at most 10% by weight, most preferably at most 5% by weight. The solubilization of carbon monoxide in the selective solvent will be expressed in terms of Ostwald constant, and will generally be 0.15 v / v (1 atm, 25 ° C.), preferably 0.25 v / v or higher.

Preferred solvent systems are alcohols and ethers that can be represented by formula (1).

R ₂ -OR ₁

In the above formula,

R ₁ is hydrogen or C _1-20 straight, branched, cyclic or aromatic hydrocarbyl or mono- or polyalkylene oxide,

R ₂ is C _1-20 straight, branched, cyclic or aromatic hydrocarbyl, alkoxy or mono- or polyalkylene oxide.

Most preferred hydroformylation solvents may be represented by formula (2).

In the above formula,

R ₁ is hydrogen or C _1-8 hydrocarbyl,

R ₃ , R ₄ and R ₅ are independently selected from C _1-8 hydrocarbyl, alkoxy and alkylene oxides.

Such ethers include, for example, methyl-t-butyl ether, ethyl-t-butyl ether, diethyl ether, phenylisobutyl ether, ethoxyethyl ether, diphenyl ether and diisopropyl ether. Blends of solvents such as tetrahydrofuran / toluene, tetrahydrofuran / heptane and t-butylalcohol / hexane can also be used to achieve the desired solvent properties. Currently preferred solvents are methyl-t-butyl ether in that the yield of 3-hydroxypropanal which can be achieved under moderate reaction conditions is high.

In order to further improve the yield under moderate reaction conditions, the hydroformylation reaction mixture preferably comprises a catalyst promoter for accelerating the reaction rate. Suitable promoters include monovalent and polyvalent metal cation sources of weak bases such as alkali, alkaline earth and rare earth metal salts of carboxylic acids. Also suitable are lipophilic promoters, such as lipophilic phosphonium salts, lipophilic amines and lipophilic ruthenium catalyst promoters, which accelerate the hydroformylation rate without imparting hydrophilicity (water solubility) to the active catalyst. As used herein, the term "lipophilic" means that the promoter tends to remain in the organic phase after 3-hydroxypropanal is extracted with water. The promoter will generally be present in an amount in the range of 0.001 to 1.0 mole per mole of cobalt or rhodium. Suitable metal salts include sodium, potassium and cesium acetate, propionate and octoate; Calcium carbonate and lanthanum acetate. A preferred ruthenium source is triruthenium dodecacarbonyl (available from Aldrich Chemical Company), which is used in an amount in the range of 0.001 to 0.5 moles, preferably 0.008 to 0.1 moles / mole per mole of cobalt. Presently preferred lipophilic promoters are tetrabutylphosphonium acetate and dimethyldodecyl amine. Other promoters include substituted and unsubstituted porphyrins of the formula:

Chemical formula

In the above formula,

M is a transition metal, preferably manganese, cobalt or rhodium,

R and R 'are each independently selected from hydrogen, halides, alkoxy, aryloxy, and substituted or unsubstituted hydrocarbyls including alkyl and aryl groups.

Preferred porphyrins are 5,10,15,20-tetraphenyl-21H, 23H-porphyrin cobalt (II), CAS # [14172-90-8] and 5,10, for commercially available and proven efficacy. 15,20-tetraphenyl-21H, 23H-porphyrin manganese (III) chloride. The transition metal will generally be present in the promoter in an amount ranging from about 0.001 to about 0.5 moles, preferably from about 0.008 to about 0.1 moles per mole of cobalt or rhodium metal in the hydroformylation catalyst. A higher amount of porphyrin promoter may be used but is not necessary for the promoting effect.

It is generally desirable to control the concentration of water in the hydroformylation reaction mixture because excess water can reduce (HPA + PDO) selectivity below the acceptable level and lead to the formation of a second liquid phase. At low concentrations, water can help to promote the formation of the desired cobalt carbonyl catalytic species. The acceptable level of water depends on the solvent used, and the more polar the solvent, the more generally it will withstand higher water concentrations. For example, it is assumed that the optimum water level for hydroformylation in methyl-t-butyl ether solvent is in the range of 1 to 2.5% by weight.

Following the hydroformylation reaction, the hydroformylation reaction product mixture (4) containing 3-hydroxypropanal, reaction solvent, 1,3-propanediol, catalyst and small amount of reaction by-products is cooled to extract the extraction vessel (5). Wherein an aqueous liquid, generally water and any mixed solvent, are added via (6) for extraction and concentration of 3-hydroxypropanal for subsequent hydrogenation steps. Liquid extraction can be carried out by any suitable means, such as a mixer-settler, a packed or trayed extraction column, or a rotating disk contactor. The extraction process can be performed in multiple stages as needed. The amount of water added to the hydroformylation reaction product mixture will generally be such that it provides a water: mixture ratio in the range of 1: 1 to 1: 20, preferably 1: 5 to 1: 15. Water extraction is preferably carried out at a temperature in the range from 25 to 55 ° C., with lower temperatures being preferred. Water extraction at 25-55 ° C. under 0.3-1.4 MPa (50-200 psig) carbon monoxide maximizes catalyst recovery in the organic phase.

The organic phase containing the reaction solvent and most of the catalyst can be recycled via (7) to the hydroformylation reaction in the extraction vessel, under any purge of the heavy end. The aqueous extract 8 is passed through an acid ion exchange resin layer, reextraction with a non-water-miscible solvent, complete or partial oxidation of the catalyst metal followed by precipitation and filtration, deposition on a solid, or removal of residual catalyst. It may optionally be added to further operations, such as extraction with a non-water-miscible solvent. The aqueous extract 8 is sent to a hydrogenation zone 11 and reacted with hydrogen 12 in the presence of a hydrogenation catalyst to produce a hydrogenation product mixture 13 containing 1,3-propanediol.

According to the process of the invention, the input stream 10 to the hydrogenation vessel 11 is 3-hydroxy at a concentration within the range of 0.2 to 5% by weight, preferably 0.3 to 4.8% by weight, based on the weight of the aqueous liquid. It is an aqueous solution containing propanal. In the illustrated embodiment, the effluent stream 8 from the aqueous extraction of the hydroformylation product contains 3-hydroxypropanal at a concentration (typically 20 to 40% by weight) higher than desired for selective hydrogenation. Dilution is performed by adding an aqueous solution to the relatively concentrated 3-hydroxypropanal solution.

Although aqueous solutions, including water, which will not interfere with the hydrogenation of 3-hydroxypropanal, can be used to dilute the 3-hydroxypropanal solution to the desired concentration, 1,3- such as hydrogenation outlet stream 9 Preference is given to using propanediol-containing aqueous solutions. The dilution with this PDO-containing solution serves to concentrate the PDO in the system water, thus avoiding the high recovery of dilute PDO from the water that would be generated by using only water as the diluent. Preferred dilution streams will contain 1,3-propanediol and 3-hydroxypropanal in an amount in the range of 20 to 40% by weight, which itself can be conveniently procedured from the initial stage of hydrogenation. The dilution stream 9 is preferably cooled prior to mixing with the hydroformylation outlet stream to bring the temperature of the merged stream to the desired temperature for introducing the initial stage of hydrogenation.

In the described embodiment, the aqueous 1,3-propanediol stream (9) is used to dilute the aqueous 3-hydroxypropanal stream (8). Other batches of hydrogenation input and recycle streams can be used within the concept of using 1,3-propanediol-containing streams for dilution of 3-hydroxypropanal. For example, stream 8 can be split into a first hydrogenation catalyst bed and a second hydrogenation catalyst bed located downstream therefrom for input. The aqueous product stream passing from the first catalyst bed to the downstream second layer serves to dilute the 3-hydroxypropanal feed into this second catalyst bed.

The hydrogenation of aqueous 3-hydroxypropanal to 1,3-propanediol is carried out over a fixed bed supported hydrogenation catalyst. The catalyst may be a Group VIII metal such as nickel, cobalt, ruthenium, platinum or palladium, and copper, zinc, chromium, and mixtures and alloys thereof. Preferred catalysts are granular nickel-based compositions on water-stable (eg ceramic) supports, which themselves are Calsicat E-475SR (nickel on ceramic supports, 8 x 14 mesh spheres) and R-3142 (WR Grace) It is marketed by. The particle size for the catalyst will be of a size consistent with fixed bed operation, generally from 10 microns to 3 mm, with larger particles at the expense of activity resulting in lower pressure drops.

The hydrogenation process of the invention can be carried out in one step or in two or more sequential temperature steps. In a preferred embodiment, the hydrogenation is carried out as described above at a temperature in the range from 50 to 130 ° C., followed by a second step at a temperature higher than that of the first step and at a temperature in the range from 70 to 155 ° C., followed by heavy A third step is performed at a temperature of at least 120 ° C. to return the end to 1,3-propanediol. In this process, the illustrated hydrogenation zone 11 optionally comprises a series of two or more hydrogenation steps carried out in two or more separate reaction vessels. Dilution stream 9 is preferably withdrawn from the first hydrogenation step. Preferred catalysts for the second stage hydrogenation include nickel-based catalysts such as those described above for the first stage, and copper chromite or copper zinc catalysts.

Residual solvent and extract water may be recovered in column 14 by distillation and recycled via 15 to a water extraction process via additional distillation (not shown) for separation and purging of the light end. The 1,3-propanediol-containing product stream 16 can be sent to distillation column 17 for recovery of 1,3-propanediol from heavy end 19.

Example 1

A series of hydrogenation experiments are performed in a 0.5 liter autoclave reactor under agitation provided by a draft-tube gas dispersion impeller to enhance the rate of transport of hydrogen gas into the liquid phase. Approximately 28 g of commercially available 8/14 mesh spherical supported nickel catalyst (50 wt% nickel on silica / alumina, 0.43 ml / g pore volume) is held in a cyclic catalyst basket for inspection of fixed bed catalyst performance. . The same catalyst is ground in an inert atmosphere to yield particles of 1 to 20 microns in size for inspection of slurry catalyst performance. For slurry studies, the ground catalyst is added directly to the reactor in the absence of a catalyst basket. The reactor is charged with 300-350 ml of an aqueous hydroformylation product rich in 3-hydroxypropanal (HPA) intermediate. The reactor is operated at 1000 to 1700 rpm agitation and at 6.9 MPa (1000 psi) hydrogen, supplementing as hydrogen is depleted during the reaction. The reaction progress is monitored by sampling the reactor with a filtered dip tube. Samples are analyzed using temperature-programmed capillary gas chromatography to determine the residual HPA and 1,3-propanediol (PDO) formed.

Apparent selectivity is calculated as the number of moles of PDO formed per mole of converted HPA. Apparent selectivity above 100% indicates heavy end (formed during ethylene oxide hydroformylation) → PDO reversion.

Runs 1 to 3 examine slurry catalyst performance. Hydrogenation activity (defined as pseudo-first rate constant for HPA consumption, assuming primary dependence on catalyst concentration) ranges from 96 to 233 1 / h / wt.cat, with selectivity 22 wt% Exceeded 100% at HPA concentration up to.

Runs 4 to 7 examine particulate (8 × 14 mesh) catalysts at HPA concentrations of 18 to 23 weight percent. For this run, the hydrogenation activity was reduced by at least 10 times compared to slurry catalyst hydrogenation. The selectivity for the initial hydrogenation run was only 85%. The selectivity and activity observed decreased during catalyst recycle, suggesting degradation of catalyst performance.

Runs 8 to 11 examine the performance of the particulate catalysts over the initial HPA concentration range. For this run, the HPA solution is diluted with deionized water. (Separate execution results obtained equivalent results for water alone dilution by dilution with PDO / water solution. Water dilution however gave more accurate product analysis than PDO / water dilution) Dilution with unused particulate catalyst (2.9-3.3) % By weight) For the initial run at HPA concentration (Run 8) and the first recycle of the catalyst (Run 9), the hydrogenation activity remained essentially constant upon recycling, while the selectivity remained essentially 100%. As the initial HPA concentration increased to 10.8% by weight, the hydrogenation activity decreased drastically. As the initial HPA concentration increased to 21% by weight in the fourth cycle, a further decrease in activity and a decrease in selectivity to 85% were observed (run 11).

For runs 12-14, the initial HPA concentration is maintained at 4.5 wt% or less. The observed hydrogenation activity remained high (at least equivalent to 50 L / h / wt.cat corrected to 70 ° C.), although somewhat reduced with catalyst recycle, and selectivity remained above 100% for all runs.

Execution Reaction temperature, ℃ Initial HPA, Weight% Gram catalyst Catalyst type cycle k (T) k (70 ° C) Apparent PDO Selectivity One 60 17.32 5 Crushing sphere unused 68.79 116.26 111 2 60 22.55 5 Crushing sphere unused 137.87 233.00 102 3 80 3.04 7 Crushing sphere unused 162.95 96.42 105 4 70 19.49 28 rectangle unused 21.3 21.30 85 5 70 18.48 28 rectangle REC-1 ⁽¹⁾ 7.77 7.77 66 6 70 23.35 28 rectangle REC-2 5.66 5.66 43 7 70 21.90 28 rectangle REC-3 3.3 3.30 53 8 70 3.31 28 rectangle unused 36.24 36.24 99 9 70 2.93 28 rectangle REC-1 38.54 38.64 104 10 50 10.80 28 rectangle REC-2 6.69 19.11 106 11 50 21.16 28 rectangle REC-3 2.3 6.57 85 12 60 4.19 23 rectangle unused 90.8 153.45 132 13 60 3.85 23 rectangle REC-1 40.44 66.34 122 14 60 3.51 23 rectangle REC-2 29.34 49.58 142 ⁽¹⁾ REC = recycle

Example 2

This experiment is performed to determine whether an aqueous PDO solution can be used to dilute the hydrogenation input stream without adversely affecting the hydrogenation activity.

Two batch hydrogenation reactions are performed at 70 ° C., 6.9 MPa using a Calsicat E-475SR hydrogenation catalyst. In Run A, the 28 wt% HPA concentrate produced by ethylene oxide hydroformylation and water extraction was diluted with deionized water to obtain an aqueous solution of 4.8 wt% HPA (0.2 wt% PDO residue). In run B, the HPA concentrate is diluted with purified PDO and water to give an aqueous solution of 3.9 wt% HPA and 24.4 wt% PDO. The observed hydrogenation activity is equivalent within the experimental error range. Gas chromatographic analysis of the product showed no difference in the byproduct nature from the two hydrogenation reactions.

Example 3

A series of experiments were performed in an autoclave reactor containing 500 g of the hydrogenation catalyst used in Example 2 and 300-325 g of HPA containing aqueous feed. The aqueous feed is diluted with water to provide an aqueous solution containing 3.8 to 4.8 wt% HPA. After the pressure uptake (70 ° C., 6.9 MPa H ₂ ) is complete, the liquid is withdrawn from the reactor and replaced with unused feed to perform a recycle test of catalyst performance. The activity and selectivity for 9 recycles performed in this manner using a dilute HPA solution is compared with those performed under the same conditions using high (19.5 to 21.9 wt%) HPA concentrations.

The use of a dilute HPA solution resulted in high intrinsic catalytic activity stabilized at higher values as compared to the recycle reaction using a more concentrated HPA solution. The selectivity to PDO formation was drastically reduced with the use of undiluted feed and decreased over time. Excellent selectivity that did not decrease over time was observed with the use of dilute HPA solution.

Example 4

This example illustrates hydroformylation of ethylene oxide using a cobalt porphyrin-promoted cobalt catalyst, a manganese porphyrin-promoted cobalt catalyst and a ruthenium-promoted cobalt catalyst. 5,10,15,20-tetraphenyl-21H, 23H-porphyrin manganese (III) (manganese TPP), 5,10,15,20-tetraphenyl-21H, 23H-porphyrin cobalt (II) (cobalt TPP), Triruthenium dodecarbonyl (Ru ₃ (CO) ₁₂ ) and dicobalt octacarbonyl (Co ₂ (CO) ₈ ) are used as metal sources. The amount of each catalyst component is listed as mmol of metal atoms to allow quantitative comparison on an atomic basis.

Manganese TPP and dicobalt octacarbonyl are introduced into a 100 ml Parr autoclave containing 34 ml of water-saturated (about 2 wt.%) Nitrogen-purged methyl-t-butyl ether (MTBE). The reactor is pressurized to 4.8 MPa (700 psig) 2: 1 H ₂ / CO. Subsequently, the reaction solution is heated under stirring, and 1.5 g (34 mmol) of ethylene oxide is charged to the reaction vessel after reaching the reaction temperature. The pressure is increased to about 11.4 MPa (1500 psig) using additional H ₂ / CO. Stirring continued for 1 hour and the reaction mixture was cooled to 5 ° C. Slowly discharge the gas to ambient pressure and add 20 ml of nitrogen-purged deionized water. The reaction mixture is stirred for 5 minutes and then the phases are separated. The aqueous phase containing the reaction product is removed and analyzed by gas chromatography (acetaldehyde, "AA";oligomers;HPA; in the presence of PDO and other compounds). The results are shown in Table 1.

In some cases, the reactor containing residual MTBE and catalyst is repressurized to 4.8 MPa with H ₂ / CO and heated to reaction temperature. After 30 minutes, 1.5 g of ethylene oxide is injected again and the pressure is increased to about 11.4 MPa with additional H ₂ / CO. After stirring for 1 hour under reaction conditions, the reaction mixture is cooled, discharged to ambient pressure, extracted with deionized water, and the phases separated under inert atmosphere. The aqueous and organic phases are analyzed for product content by gas chromatography. In some cases, the separated phases are also analyzed for metal content. Experiments using "recycle" catalysts are indicated by "R" in the table. The percentage of catalyst remaining in MTBE after the reaction in run 3R amounted to 96.8% cobalt and 89.0% manganese.

As can be seen from the results, ruthenium, manganese TPP and cobalt TPP have a promoting effect on the dicobalt octacarbonyl catalyst. Accelerators are effective even at very low concentrations.

Example 5

This example illustrates the hydroformylation of propylene oxide promoted by manganese porphyrin-promoted cobalt catalyst in accordance with the process of the present invention.

115 mg (0.34 mmol) of dicobaltoctacarbonyl, 25 mg (0.037 mmol) of manganese TPP, 34 ml of water-saturated (about 2 wt.%) Nitrogen-purge MTBE, and 1.98 g (34) propylene oxide in a 100 ml Parr autoclave mmol). The reaction mixture is heated at 80 ° C. and 10.7 MPa (1400 psig) H ₂ / CO (2: 1) under stirring for 1 hour and then cooled to 5 ° C. The gas is slowly withdrawn to ambient pressure and 25 ml of nitrogen-purged deionized water are introduced into the reactor. After stirring for 5 minutes and allowing phase separation, the aqueous phase is removed from the reactor and analyzed by gas chromatography. Selectivity to organic products was 10.1% acetone, 71.4% 3-hydroxybutyraldehyde, 7.4% 2-methylpropionaldehyde, 6.7% 1,3-butanediol and 4.4% oligomers. Propylene oxide conversion is 60%.

Similar results are achieved with cobalt TPP and triruthenium dodecacarbonyl.

Hydroformylation of Ethylene Oxide (EO) Execution Catalyst (mmol of metal) Temperature (℃) EO conversion rate (%) Selectivity, (mol%) AA HPA PDO Oligomer One Co ₂ (CO) ₈ (0.67) 70 29 6.2 93.8 - 2 Co ₂ (CO) ₈ 0.67 cobalt TPP (0.037) 70 58 8.1 91.9 - 2R 〃 70 52 12.9 87.1 - 3 Co ₂ (CO) ₈ (0.67) Manganese (III) TPP (0.037) 70 38 12.1 87.9 - 3R Co ₂ (CO) ₈ (0.67) Manganese (III) TPP (0.037) 70 33 11.7 88.3 - 4 Co ₂ (CO) ₈ (0.67) 80 67 5.7 94.3 - 5 Co ₂ (CO) ₈ (0.67) Manganese (III) TPP (0.037) 80 86 9.3 85.9 4.8 6 Co ₂ (CO) ₈ (0.67) Ru ₃ (CO) ₁₂ (0.15) 80 76 11.0 86.1 - 2.9

Claims (10)

Sending the aqueous 3-hydroxyalkanal solution to the hydrogenation zone and contacting with a fixed bed hydrogenation catalyst under hydrogenation conditions to form an aqueous 1,3-alkanediol solution, wherein the 1,3-alkanediole is hydrogenated. In the process for the preparation, 3-hydroxyalkanal aqueous solution is characterized in that the 3-hydroxyalkanal concentration is in the range of 0.2 to 5% by weight. The process of claim 1 wherein the aqueous 1,3-hydroxypropanal aqueous solution is sent to a first hydrogenation reactor and then to a second hydrogenation reactor maintained at a higher temperature than the first hydrogenation reactor. The method of claim 2, wherein the first hydrogenation reactor is operated at a temperature in the range of 50 to 130 ° C., and the second hydrogenation reactor is operated at a higher temperature and a temperature in the range of 70 to 155 ° C. than the first hydrogenation reactor. The process of claim 1, wherein the hydrogenation catalyst comprises nickel. The method of claim 4 wherein the catalyst comprises nickel on a ceramic support. The aqueous solution of 3-hydroxyalkanal according to any one of claims 1 to 5, wherein (a) at a temperature in the range of 50 to 100 ° C. and a pressure in the range of 0.7 to 34.5 MPa, the alkylene oxide is essentially an effective amount of a non-phosphine-linked cobalt or rhodium catalyst and an effective amount of a non-water-miscible solvent Contacting with carbon monoxide and hydrogen under reaction conditions effective to produce an intermediate mixture comprising up to 15% by weight of 3-hydroxyalkanal in the presence of a catalyst promoter; (b) an aqueous phase comprising adding an aqueous solution to the intermediate mixture and containing at least 20% by weight of 3-hydroxyalkanal, and an organic phase comprising at least a portion of a cobalt or rhodium catalyst or a cobalt- or rhodium-containing derivative thereof Most 3-hydroxyalkanal was extracted into the aqueous solution at a temperature of 100 ° C. or lower to provide (c) separating the aqueous phase from the organic phase; (d) diluting the aqueous phase comprising 3-hydroxyalkanal with an aqueous solution to form a solution having a 3-hydroxypropanal concentration in the range of 0.2-5% by weight. . 7. The process of claim 6, wherein the dilution of step (d) is performed by adding an aqueous solution of 1,3-alkanediol. 7. The method of claim 6, wherein the promoter is a lipophilic ruthenium promoter, or transition metal porphyrin. The method of claim 1, wherein the 1,3-propanediol is prepared from 3-hydroxypropanal. (a) ethylene oxide comprising essentially 15% by weight or less of 3-hydroxypropanal in the presence of an effective amount of non-phosphine-linked cobalt catalyst and an effective amount of catalyst promoter in a non-water-miscible solvent Contacting with carbon monoxide and hydrogen under reaction conditions effective to produce an intermediate mixture; (b) an aqueous phase, wherein the aqueous solution is added to the intermediate mixture and 3-hydroxypropanal is present at a concentration greater than the concentration of 3-hydroxypropanal in the intermediate mixture, and at least the cobalt catalyst or cobalt-containing derivative thereof Most 3-hydroxypropanal was extracted into the aqueous liquid at a temperature of 100 ° C. or lower to provide a portion comprising an organic phase; (c) separating the aqueous phase from the organic phase; (d) adding an aqueous solution of 1,3-propanediol to the aqueous phase to form a 3-hydroxypropanal dilute aqueous solution having a 3-hydroxypropanal concentration in the range of 0.3 to 4.8 wt%; (e) sending a 3-hydroxypropanal dilution solution to a hydrogenation vessel containing a fixed bed nickel hydrogenation catalyst maintained under hydrogenation temperature and pressure conditions, where at least a portion of 3-hydroxypropanal is converted to 1,3-propanediol Then; (f) A method for producing 1,3-propanediol comprising recovering 1,3-propanediol.