Patent Publication Number: US-5256827-A

Title: Process for making 3-hydroxypropanal and 1,3-propanediol

Description:
FIELD OF THE INVENTION 
     This invention relates to a process for making 3-hydroxypropanal and 1,3-propanediol by hydroformylating ethylene oxide using tertiary phosphine ligand-complexed cobalt carbonyl catalysts wherein phosphine ligand has been partially oxidized. 
     BACKGROUND OF THE INVENTION 
     3-Hydroxypropanal is a useful chemical intermediate. It can be readily converted to 1,3-propanediol which finds use as an intermediate in the production of polyester fibers and films. 
     U.S. Pat. Nos. 3,463,819 and 3,456,017 teach a process for the hydroformylation of ethylene oxide to produce 1,3-propanediol and 3-hydroxypropanal using a tertiary phosphine-modified cobalt carbonyl catalysts. 
     It is an object of this invention to use an improved cobalt-tertiary phosphine ligand catalyst to hydroformylate ethylene oxide to 3-hydroxy-propanal and 1,3-propanediol in high yield, which 3-hydroxypropanal can then be hydrogenated with hydrogen to 1,3-propanediol in substantially quantitative yield using conventional hydrogenation catalysts. Special oxidation treatment of the tertiary phosphine ligand provides for a more active catalyst. 
     SUMMARY OF THE INVENTION 
     This invention relates to a process for making 3-hydroxypropanal and 1,3-propanediol which comprises intimately contacting 
     (a) ethylene oxide, 
     (b) tertiary phosphine-complexed cobalt carbonyl catalyst, wherein said phosphine, prior to being complexed with said cobalt carbonyl catalyst, is partially oxidized to provide an oxygen to phosphorus ratio no greater than about 0.5, 
     (c) carbon monoxide, and 
     (d) hydrogen, the molar ratio of carbon monoxide to hydrogen being from about 4:1 to about 1:6, 
     in liquid-phase solution in an inert reaction solvent, at a temperature of from about 30° C. to about 150° C. and a pressure of from about 50 psi to about 10,000 psi. 
     Preferably the tertiary phosphine ligand is a polydentate, preferably a bidentate phosphorus ligand. 
     Optionally, the product comprising 3-hydroxypropanal and 1,3-propanediol is hydrogenated with hydrogen in the presence of a hydrogenation catalyst to convert the aldehyde and aldehyde oligomers to 1,3-propanediol. 
     The preoxidation of the ligand increases the activity of the catalyst. Optional acid and alkali metal salt catalyst promoters can be utilized. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Ethylene oxide is hydroformylated by reaction with carbon monoxide and hydrogen in the presence of a phosphine-modified cobalt carbonyl catalyst. The reaction products comprise primarily 3-hydroxypropanal (and oligomers thereof) and 1,3-propanediol. The ratio of the two products can be adjusted by adjusting the amount of catalyst present in the reaction mixture, the reaction temperature or the amount of hydrogen present in the reaction mixture. When the term &#34;3-hydroxypropanal&#34; is used herein is understood to mean the monomer as well as dimers, such as 2-(2-hydroxyethyl)-4-hydroxy-1,3-dioxane, as well as trimers and higher oligomers of 3-hydroxypropanal. In a preferred embodiment, lower amounts of catalyst are used to produce primarily the aldehyde and its oligomers which are then hydrogenated to the 1,3-propanediol in a separate hydrogenation step using a conventional hydrogenation catalyst and hydrogen. The use of partially oxidized tertiary phosphines as complexing ligands for the cobalt catalyst results in catalysts with increased activity, which results in more ethylene oxide being converted to product aldehyde and diol. 
     The process is conducted, in one modification, by charging the epoxide reactant, catalyst, optional catalyst promoter(s) and reaction solvent to an autoclave or similar pressure reactor and introducing the hydrogen and carbon monoxide while the reaction mixture is maintained at reaction temperature. Alternatively, the process is conducted in a continuous manner as by contacting the reactants, catalyst and optional catalyst promoter(s) during passage through a reactor which is typically tubular in form. For best results the process is conducted under conditions of elevated temperature and pressure. Reaction temperatures range from about 30° C. to about 150° C., preferably from about 50° C. to about 125° C., and most preferably from about 70° C. to about 110° C. The reaction pressure is desirably in the range of from about 50 p.s.i. to about 10,000 p.s.i., preferably from about 500 p.s.i. to about 3000 p.s.i. In one modification of the process, inert gaseous diluent is present, e.g., inert gaseous diluents such as argon, helium, methane, nitrogen and the like, in which case the reaction pressure is properly considered to be the sum of the partial pressures of the materials other than the diluent. In the preferred modification of the process, however, the reaction is conducted in the substantial absence of added diluent. 
     The course of the reaction is easily followed as by observing the pressure decrease within the reactor, by in situ infrared absorption techniques or by periodic withdrawal and analysis of samples from the reaction system. At the conclusion of reaction, the product mixture is separated by conventional methods such as selective extraction, fractional distillation, decantation, selective crystallization and the like. The unreacted starting material as well as the catalyst and reaction solvent are suitably recycled for further reaction. 
     The catalysts employed in the process of the invention are tertiary phosphine-modified cobalt carbonyl complexes. As is discussed in greater detail hereinbelow, the tertiary phosphine complexing ligand portion of the catalyst complex comprises a tertiary phosphine wherein each phosphorus is completely substituted with organic substituents attached to the phosphorus by carbon-phosphorus bonds and which ligand has been partially oxidized prior to complexing with the cobalt catalyst. 
     In one modification of the process of the invention, the tertiary phosphine stabilizing ligand is a monodentate ligand, that is, the stabilizing ligand is a tertiary phosphine of a single phosphorus atom as the sole complexing site in the tertiary phosphine ligand. This class of tertiary phosphines, herein termed monophosphines, is generically classified as tertiary monophosphine of from 3 to about 60 carbon atoms wherein each phosphorus substituent is a hydrocarbon substituent, i.e., contains only atoms of carbon and hydrogen. A preferred class of tertiary monophosphines is represented by the formula 
     
         RRRP                                                       (I) 
    
     wherein R independently is monovalent hydrocarbon (i.e., &#34;hydrocarbyl&#34;) of up to 30 carbon atoms, preferably up to 20, more preferably up to 12, with the proviso that two R may together form a divalent hydrocarbon moiety of up to 60 carbon atoms. The group R, when monovalent, is therefore alkyl, cycloalkyl or aryl of up to 30 carbon atoms, preferably of up to 12 carbon atoms, and is illustrated by alkyl R groups such as methyl, ethyl, butyl, isobutyl, 2-ethylhexyl, octyl, benzyl, β-phenylethyl and dodecyl; by cycloalkyl R groups such as cyclopentyl, cyclohexyl, cyclooctyl, 2,3-diethylcyclooctyl, 4-butylcyclohexyl, 2,4,5-trimethylcyclohexyl and 3-butylcyclooctyl; and by aryl R groups such as phenyl, tolyl, xylyl, o-phenylphenyl, p-tert-butylphenyl, 2,4-diethylphenyl and m-cyclohexylphenyl. 
     An additional class of tertiary monophosphines comprises the class wherein two R groups together form a divalent hydrocarbon moiety. Such cyclophosphines are illustrated by 1-ethylphospholidine, 1-phenylphospholidine, 1-phenylphosphorinane, 1-butylphosphorinane, 4,4-dimethyl-1-phenylphosphorinane, 1-phenylphosphepane, 1-ethylphosphepane,3,6-dimethyl-1-phenylphosphepane, 9-phenyl-9-phosphabicyclo[3.3.1]nonane and 9-butyl-9-phosphabicyclo[4.2.1[nonane. 
     In an alternate modification of the phosphine-modified cobalt complexes of the invention, the tertiary phosphine employed is a bidentate ligand, i.e., the phosphine ligand is a tertiary di-phosphine. A suitable class of tertiary di-phosphine ligands are represented by the formula 
     
         RRP--Q--PRR                                                (II) 
    
     wherein R has the previously stated significance, and Q is hydrocarbylene of up to 30 carbon atoms, preferably of from 2 to 30 carbon atoms; more preferably from 2 to 20 carbons, even more preferably from 2 to 10. In a preferred embodiment Q is ethylene, propylene or butylene, more preferably ethylene. The group R, when monovalent, may be alkyl, cycloalkyl, bicycloalkyl or aryl of up to about 30 carbon atoms, preferably up to about 20 carbon atoms, more preferably of up to 12 carbon atoms, and is illustrated by alkyl R groups such as methyl, ethyl, butyl, isobutyl, 2-ethylhexyl, octyl, benzyl, β-phenylethyl and dodecyl; by cycloalkyl R groups such as cyclopentyl, cyclohexyl, cyclooctyl, 2,3-diethylcyclopentyl, 4-butylcyclohexyl, 2,4,5-tri-methylcyclohexyl and 3-butylcyclooctyl; and by aryl R groups such as phenyl, tolyl, xylyl, o-phenylphenyl, p-tert-butylphenyl, 2,4-diethylphenyl and m-cyclohexylphenyl. When two Rs on one phosphorus together form a divalent moiety, such moiety (with the phosphorus) may include 9-phosphabicyclo-[4.2.1]nonyl- and 9-phosphabicyclo[3.3.1 ]nonyl-. Illustrative di-phosphines of this class include 1,2-bis(diphenylphosphino)ethane, 1,2-bis(dibutylphosphino)ethane, 1,3-bis(dimethylphosphino)propane, 1,2-bis(dihexylphosphino)propane, 1,2-bis(ditolylphosphino)ethane, 1,3-bis(phenylpropylphosphino)propane, 1-(dibutylphosphino)-3-(diphenylphosphino)propane and 1-(dioctylphosphino)-2-(dibutylphosphino)propane. 
     In an alternate modification of the phosphine-modified cobalt complexes of the invention, the tertiary phosphine employed is a polydentate ligand, i.e., the phosphine ligand is a tertiary polyphosphine represented by the formula ##STR1## wherein Z is independently selected from R and --QP(R 2 )wherein R and Q are as previously defined and n is a whole number ranging from 0 to about 10 with the proviso that at least two phosphorus atoms are present. 
     A particularly preferred ditertiary phosphine complexing ligand comprises a hydrocarbylene-bis(monophosphabicycloalkane) in which each phosphorus atom is joined to hydrocarbylene and is a member of a bridge linkage without being a bridgehead atom and which hydrocarbylene-bis(monophosphabicycloalkane) has 11 to about 300, preferably 11 to about 200, more preferably 11 to about 100 and most preferably 18 to about 80 carbon atoms; 5 to 12, preferably 6 to 12, more preferably 7 to 12 and most preferably 8, carbon atoms thereof together with a phosphorus atom being members of each of the two bicyclic skeletal structures. Particularly preferred ditertiary phosphines are chosen from α, ω-hydrocarbylene-P,P&#39;-bis(monophosphabicyclononanes) in which ring systems (a) each phosphorus atom is a member of a bridge linkage, (b) each phosphorus atom is not in a bridgehead position, and (c) each phosphorus atom is not a member of the bicyclic system of the other, and (d) the smallest phosphorus-containing rings contain at least five atoms. The hydrocarbylene is preferably selected from ethylene, propylene and butylene. Most preferably the hydrocarbylene is ethylene and each of the monophosphabicyclononane moieties of the ditertiary phosphine is independently selected from 9-phosphabicyclo[4.2.1]-nonane and 9-phosphabicyclo[3.3.1]nonane. As used herein the term &#34;9-phosphabicyclononyl&#34; or &#34;9-phosphabicyclononane&#34; will refer to 9-phosphabicyclo[4.2.1]nonane and 9-phosphabicyclo[3.3.1]nonane moieties and mixtures thereof. 
     In general terms the preferred ditertiary phosphine ligands used to form the cobalt-carbonyl-phosphine complexes comprise bicyclic heterocyclic ditertiary phosphines. They are hydrocarbylene-connected monophosphabicycloalkanes in which the smallest phosphorus-containing rings contain at least four, preferably at least five atoms, and the phosphorus atom therein is a member of a bridge linkage but is not a bridgehead atom. In addition to the hydrocarbylene substitution on the phosphorus atoms, the ring carbons may also be substituted. One class of such compounds has from 11 to about 300, preferably 11 to about 200, more preferably 11 to about 100 and most preferably 18 to about 80 carbon atoms, and is represented by the formula ##STR2## where Q represents hydrocarbylene; R independently represents hydrogen and hydrocarbyl of 1 to about 30 carbon atoms; y and z represent zero or positive integers whose sum is from 0 to 7; y&#39; and z&#39;, independent of the values of y and z, represent zero or positive integers whose sum is from 0 to 7; preferably y and z represent positive integers whose sum is from 1 to 7, more preferably from 2 to 7 and most preferably 3 with each of which having a minimum value of 1; y&#39; and z&#39;, independent of the values of y and z, represent positive integers whose sum is from 1 to 7, more preferably from 2 to 7 and most preferably 3 with each of which having a minimum value of 1. 
     Hence, a preferred group of bicyclic heterocyclic ditertiary phosphines includes those represented by Formula IV where Q represents hydrocarbylene of 2 to 30 carbons and especially of 2 to 20; y and z represent positive integers whose sum is 3 and each of which has a minimum value of 1; y&#39; and z&#39;, independent of the values of y and z, represent positive integers whose sum is 3 and each of which has a minimum value of 1; and R represents hydrogen and optionally hydrocarbyl of from 1 to 20 carbons. 
     The term &#34;hydrocarbylene&#34; is used in its accepted meaning as representing a di-radical formed by removal of two hydrogen atoms from a carbon atom or preferably one hydrogen atom from each of two different carbons of a hydrocarbon. The hydrocarbylene groups represented by Q in the formula above may be any nonacetylenic acyclic or cyclic organic radical composed solely of carbon and hydrogen. Wide variation is possible in that the (nonacetylenic) acyclic or cyclic hydrocarbylene group may be arene, alkylene, alkenylene, aralkylene, cycloalkylene, straight chain, branched chain, large or small. Representative hydrocarbylene groups include methylene, ethylene, trimethylene, tetramethylene, butylene, pentamethylene, pentylene, methylpentylene, hexamethylene, hexenylene, ethylhexylene, dimethylhexylene, octamethylene, octenylene, cyclooctylene, methylcyclooctylene, dimethylcyclooctylene, isooctylene, dodecamethylene, hexadecenylene, octadecamethylene, eicosamethylene, hexacosamethylene, triacontamethylene, phenylenediethylene, and the like. A particularly useful class of tertiary phosphines is that containing only carbon, hydrogen, and phosphorus atoms. Substituted hydrocarbylene groups are also contemplated and may contain a functional group such as the carbonyl, carboxyl, nitro, amino, hydroxy (e.g. hydroxyethyl), cyano, sulfonyl, and sulfoxyl groups. A particularly useful group of tertiary polyphosphines consists of those in which Q is hydrocarbylene of up to 30 carbon atoms, preferably from 2 to 30 carbon atoms; more preferably from 2 to 20 carbons, even more preferably from 2 to 10. In a preferred embodiment Q is ethylene, propylene or butylene, more preferably ethylene. 
     The term &#34;hydrocarbyl&#34; is used in its accepted meaning as representing a radical formed by removal of one hydrogen atom from a carbon atom of a hydrocarbon. The hydrocarbyl groups represented by R in the formula above may be any nonacetylenic acyclic or cyclic organic radical composed solely of carbon and hydrogen. Wide variation is possible in that the (nonacetylenic) acyclic or cyclic hydrocarbylene group may be arene, alkylene, alkenylene, aralkylene, cycloalkylene, straight chain, branched chain, large or small. Representative hydrocarbyl groups include methyl, ethyl, butyl, pentyl, methylpentyl, hexenyl, ethylhexyl, dimethylhexyl, octamethylene, octenylene, cyclooctylene, methylcyclooctylene, dimethylcyclooctyl, isooctyl, dodecyl, hexadecenyl, octyl, eicosyl, hexacosyl, triacontyl, phenylethyl, and the like. Substitute hydrocarbyl groups are also contemplated and may contain a functional group such as the carbonyl, carboxyl, nitro, amino, hydroxy (e.g. hydroxyethyl), cyano, sulfonyl, and sulfoxyl groups. Preferably R is hydrogen or hydrocarbyl, preferably alkyl, having 1 to about 30, preferably 1 to about 20 and most preferably from 8 to 20 carbon atoms. 
     Generically, the tertiary phosphine-modified cobalt complexes are characterized as dicobalt hexacarbonyl complexes of additionally present tertiary phosphine ligand sufficient to provide one non-oxidized phosphorus complexing atom for each atom of cobalt present within the complexed molecule. 
     Ditertiary phosphine ligands are known in the art and their method of preparation are described in detail in U.S. Pat. Nos. 3,401,204 and 3,527,818, which are both incorporated by reference herein. Other tertiary phosphine ligands are disclosed in the art, particularly the art of hydroformylation of olefins (e.g., see U.S. Pat. No. 3,448,157), and are useful in the instant process upon being suitably oxidized in part. 
     A key aspect of the instant invention is to partially oxidize the tertiary phosphine ligands to convert the phosphine(s) in part to phosphine oxide. The oxidation is carried out with an oxidant under mild oxidizing conditions such that an oxygen will bond to a phosphorus, but phosphorus-carbon, carbon-carbon and carbon-hydrogen bonds will not be disrupted. By suitable selection of temperatures, oxidants and oxidant concentrations such mild oxidation can occur. The oxidation of the phosphine ligands is carried out prior to the forming of the catalyst complex. 
     Suitable oxidizing agents include peroxy-compounds, persulfates, permanganates, perchromates and gaseous oxygen. Preferred compounds, for ease of control, are the peroxy-compounds. Peroxy-compounds are those which contain the peroxy (--O--O--) group. Suitable peroxy-compounds may be inorganic or organic. Suitable inorganic compounds include hydrogen peroxide as well as inorganic compounds with in contact with water liberate hydrogen peroxide, such compounds include the mono-valent, di-valent and trivalent metal peroxides as well as hydrogen peroxide addition compounds. Also suitable are the organic peroxy-compounds, including hydroperoxides; α-oxy- and α-peroxy-hydroperoxides and peroxides; peroxides; peroxyacids; diacyl peroxides; and peroxyesters. Suitable peroxyorgano-compounds include t-butyl hydroperoxide, cumene hydroperoxide, dibenzoyl peroxide and peroxyacetic acid. Peroxy-compounds suitable for carrying out the oxidation process are known in the art, and suitable examples can be found in The Encyclopedia of Chemical Technology, Vol. 17, pp. 1-89, Third Edition (John Wiley &amp; Sons, 1982), incorporated by reference herein. 
     Typically oxidation is carried out by adding to the ligand a measured amount of oxidizing agent, sufficient to carry out the degree of oxidation required. The ligand may be dissolved in a suitable solvent. The oxidizing agent is typically added slowly over a period of time to control the oxidizing conditions. The temperature is maintained to provide mild oxidizing conditions. When hydrogen peroxide is used as the oxidizing agent, the temperature is typically maintained at room temperature. 
     The oxidation of the ligand is carried out to provide no more than about 0.5 oxygen atoms per phosphorus atoms, on the average, in the oxidized ligand product. Preferably the ratio of oxygen atoms to phosphorus atoms in the oxidized ligand will range, on the average, from about 0.01:1 to about 0.5:1, and more preferably from about 0.05:1 to about 0.3:1. 
     The catalysts can be prepared by a diversity of methods. A convenient method is to combine a cobalt salt, organic or inorganic, with the desired oxidized phosphine ligand, for example, in liquid phase followed by reduction and carbonylation. Suitable cobalt salts comprise, for example, cobalt carboxylates such as acetates, octanoates, etc., which are preferred, as well as cobalt salts of mineral acids such as chlorides, fluorides, sulfates, sulfonates, etc. Operable also are mixtures of these cobalt salts. It is preferred, however, that when mixtures are used, at least one component of the mixture be cobalt alkanoate of 6 to 12 carbon atoms. The valence state of the cobalt may be reduced and the cobalt-containing complex formed by heating the solution in an atmosphere of hydrogen and carbon monoxide. The reduction may be performed prior to the use of the catalysts or it may be accomplished simultaneously with the hydroformylation process in the hydroformylation zone. Alternatively, the catalysts can be prepared from a carbon monoxide complex of cobalt. For example, it is possible to start with dicobalt octacarbonyl and, by heating this substance with a suitable phosphine ligand, the ligand replaces one or more, preferably at least two, of the carbon monoxide molecules, producing the desired catalyst. When this latter method is executed in a hydrocarbon solvent, the complex may be precipitated in crystalline form by cooling the hot hydrocarbon solution. This method is very convenient for regulating the number of carbon monoxide molecules and phosphine ligand molecules in the catalyst. Thus, by increasing the proportion of phosphine ligand added to the dicobalt octacarbonyl, more of the carbon monoxide molecules are replaced. 
     The optimum ratio of ethylene oxide feed to phosphine-modified cobalt carbonyl complex will in part depend upon the particular cobalt complex employed. However, molar ratios of ethylene oxide to cobalt complex from about 2:1 to about 10,000:1 are generally satisfactory, with molar ratios of from about 50:1 to about 500:1 being preferred. When batch processes are used, it is understood that the above ratios refer to the initial starting conditions. In one modification, the phosphine-modified cobalt carbonyl complex is employed as a preformed material, being prepared as by reaction of a cobalt salt with carbon monoxide and hydrogen in the presence of the phosphine ligand, then isolated and subsequently utilized in the present process. In an alternate modification, the phosphine-modified cobalt complex is prepared in situ as by addition to the reaction mixture of a cobalt salt or cobalt octacarbonyl together with the phosphine ligand whose introduction into the catalyst complex is desired. 
     In practice, it is preferable to employ the phosphine-modified cobalt complex in conjunction with a minor proportion of excess tertiary phosphine ligand (oxidized or unoxidized) which is the same as or is different from the phosphine ligand(s) of the cobalt complex. Although the role of the excess phosphine is not known with certainty, the presence thereof in the reaction system appears to promote or otherwise modify catalyst activity. 
     Phosphorus:cobalt atom ratios utilized in conjunction with the catalyst complex will range from about 1:1 to about 3:1, preferably from about 1.2:1 to about 2.5:1. A ratio of about 2:1 is particularly preferred. 
     The process of the invention is conducted in liquid-phase solution in an inert solvent. Although a variety of solvents which are inert to the reactants and catalyst and which are liquid at reaction temperature and pressure are in part operable. Illustrative of suitable solvent are hydrocarbons, particularly aromatic hydrocarbons of up to 16 carbon atoms such as benzene, toluene, xylene, ethylbenzene, and butylbenzene; alkanes such as hexanes, octanes, dodecanes, etc.; alkenes such as hexanes, octenes, dodecenes, etc.; alcohols such as t-butyl alcohol, hexanol, dodecanol, including alkoxylated alcohols; nitrites such acetonitrile, propionitrile, etc.; ketones, particularly wholly aliphatic ketones, i.e., alkanones, of up to about 16 carbon atoms such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl hexyl ketone and dibutyl ketone; esters of up to 16 carbon atoms, particularly lower alkyl esters of carboxylic acids which are aliphatic or aromatic carboxylic acids having one or more carboxyl groups, preferably from 1 to 2, such as ethyl acetate, methyl propionate, propyl butyrate, methyl benzoate, diethyl glutarate, diethyl phthalate and dimethyl terephthalate; and ethers of up to about 16 carbon atoms and up to 4  ether oxygen atoms, which ethers are cyclic or acyclic ethers and which are wholly aliphatic ethers, e.g., diethyl ether, diisopropyl ether, dibutyl ether, ethyl hexyl ether, methyl octyl ether, dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetraglyme, glycerol trimethyl ether, 1,2,6-trimethoxyhexane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, 1,3-dioxolane and 2,4-dimethyl-1,3-dioxane, or which are at least partially aromatic, e.g., diphenyl ether, phenylmethyl ether, 1-methylnaphthalene, phenylisopropyl ether, halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, fluorobenzene, methyl chloride, methylene dichloride. Mixtures of solvents can also be utilized. 
     The amount of solvent to be employed is not critical. Typical molar ratios of reaction solvent to ethylene oxide reactant vary from about 5:1 to about 150:1. 
     Suitable selection of solvents can enhance product recovery. By selecting solvents with suitable polarity, a two phase system will form upon cooling of the reaction mixture with selective distribution of the catalyst and ligand in one phase and product 3-hydroxypropanal and 1,3-propanediol in a second phase. This will allow for easier separation of catalyst and ligand and recycle thereof back to the reactor. When a two phase separation process is used, solvents that would not be desirable in the reaction mixture, such as water and acids, can be used to enhance distribution of product to one phase and catalyst/ligand to the other phase. 
     Illustrative solvents for use in a one phase system are diethylene glycol, tetraglyme, tetrahydrofuran, t-butyl alcohol, and dodecanol. Illustrative solvents for use to provide a two phase system upon cooling are toluene, 1-methylnaphthalene, xylenes, diphenyl ether and chlorobenzene. 
     The process of the invention comprises contacting the ethylene oxide reactant, catalyst and optional catalyst promoter and with carbon monoxide and molecular hydrogen. The molar ratio of carbon monoxide to hydrogen most suitably employed is from about 4:1 to about 1:6, with best results being obtained when ratios of from about 1:1 to about 1:4 are utilized. No special precautions need to be taken with regard to the carbon monoxide and hydrogen and commercial grades of these reactants are satisfactory. The carbon monoxide and hydrogen are suitable employed as separate materials although it is frequently advantageous to employ commercial mixtures of these materials, e.g., synthesis gas. 
     The addition of small amounts of acids and alkali metal salts to the hydroformylation reaction mixture can further enhance or promote the conversion of ethylene oxide by increasing the activity of the catalyst. Acids are defined herein to mean those compounds which can donate a proton under reaction conditions. 
     Suitable acids can include inorganic acids such HCl, HBr, HI, boric acid and organic acids in amounts ranging from trace amounts up to about two times the molar amount of catalyst utilized. Suitable organic acids include the organs-acids having carbon numbers of 1 to about 16, such as carboxylic acids, sulfonic acids, phosphonic acids, phosphinic acids as well as other organic compounds that will donate protons under reaction conditions such as imidazole, benzoimidazole, pyridinium salts, pyrazinium salts, pyrimidinium salts, particularly salts of the aforementioned acids. Non-limiting examples of organic acids include acetic acid, propionic acid, hexanoic acid, 2-ethylhexanoic acid, octanoic acid, 3-(phenylsulfonyl)propionic acid, para-toluenesulfonic acid, 2-carboxyethylphosphonic acid, ethylphosphonic acid, n-butylphosphonic acid, t-butylphosphonic acid, phenylphosphonic acid, phenylphosphenic acid, phenyl boric acid, pyridinium para-toluenesulfonate and pyridinium octoate. 
     Another suitable method for providing promoter acids is to use as a catalyst precursor a cobalt salt of an organic acid, which will convert to cobalt carbonyl and the organic acid under reaction conditions. Such precursor salts include cobalt acetate, cobalt 2-ethylhexanoate, cobalt benzoate, cobalt formate and cobalt oleate. The ratio of gram equivalents of acid promoter to gram atoms of cobalt in the catalyst present in the reaction mixture will generally range from about 0.001:1 to about 4:1, preferably from about 0.01:1 to about 2:1. 
     Promoting amounts of alkali metals salts can also added to the reaction mixture along with the promoting amounts of acid to provide an even further enhanced promoting effect. Any alkali metal salt that is at least partially soluble in the reaction mixture is suitable. Both inorganic salts and organic salts of alkali metals are suitable. Included in the inorganic salts are halides, chromates, sulfates, borates, carbonates, bicarbonates, chlorates, phosphates, etc. Particularly desirable organic salts are salts of carboxylic acids having carbon numbers ranging from 1 to about 20. Examples of alkali metal salts that have been found suitable as copromoters include sodium bromide, sodium iodide, potassium iodide, sodium acetate, sodium borate, lithium acetate, potassium acetate, cesium acetate. In general any alkali metal salt that does not react with ethylene oxide, the reaction solvent or the hydroformylation products are suitable as copromoters with acids. The ratio of gram equivalents of alkali metal of the salt promoter to gram atoms of cobalt in the catalyst present in the reaction mixture will generally range from about 0.001:1 to about 2:1, preferably from about 0.01:1 to about 1:1, and more preferably from about 0.1:1 to about 0.5:1. 
     In a preferred embodiment the product of the hydroformylation reaction is further hydrogenated to produce a product comprising substantially 1,3-propanediol. The hydroformylated product is preferably separated from the catalyst before being hydrogenated. Inert solvent may be added to the product prior to hydrogenation, or, if an inert (to hydrogenation) solvent was used in the hydroformylation reaction, it may be separated with the product and passed to the hydrogenation reactor. The hydrogenation catalyst can be any of the well known hydrogenation catalysts used in the art such as Raney nickel, palladium, platinum, ruthenium, rhodium, cobalt and the like. It is desirable to employ as the hydrogenation catalyst a metal or a compound of a metal which may be easily and economically prepared, which has a high degree of activity, and retains this activity for extended periods of time. The hydrogenation catalyst may be employed homogeneously, in a finely divided form and dispersed throughout the reaction mixture, or preferably it may be employed on a support or carrier material such as alumina, carbon or the like. Preferred catalysts are Raney nickel and supported platinum, particularly platinum on carbon. Hydrogenation conditions include pressures ranging from 50-10,000 psi and temperatures ranging from 30° C. to 175° C. The hydrogenating gas used is molecular hydrogen or a mixture of hydrogen and carbon monoxide such as that used for the hydroformylation reaction. 
     The ranges and limitations provided in the instant specification and claims are those which are believed to particularly point out and distinctly claim the instant invention. It is, however, understood that other ranges and limitations that perform substantially the same function in substantially the same way to obtain the same or substantially the same result are intended to be within the scope of the instant invention as defined by the instant specification and claims. 
    
    
     In the examples and tables the following definitions are used: 
     &#34;PDO&#34; is 1,3-propanediol. 
     &#34;PDO Precursors&#34; are those compounds which upon hydrogenation produce PDO and include primarily 3-hydroxypropanal with smaller amounts of dimers, trimers and other oligomers of 3-hydroxypropanal being present. Also included are small amounts of acrolein and propionaldehyde. Most of the acrolein is an artifact of the gas chromatographic (GC) measuring process as a result of decomposition of 3-hydroxypropanal during analysis. In situ infrared spectroscopic analyses after completion of the hydroformylation reactions showed no acrolein present in the products. Lowering the temperature and chemically passifying the injection port of the GC instrument dramatically lowered these artifact peak heights, indicating that it is at most only a minor product (1-2%). 
     ILLUSTRATIVE EMBODIMENT I 
     In this illustrative embodiment the oxidation of the complexing phosphine ligand is illustrated. 
     1.56 Grams of 1,2-bis-(9-phosphabicyclononyl)ethane was loaded into a 100 ml three neck round bottom flask, fitted with a rubber septum, thermometer and gas stopcock. A stir bar was added, and 25 ml. of ethanol was poured into the flask. The mixture was then degassed with argon. An argon filled balloon was attached to the gas inlet and the mixture was stirred for 15 minutes at room temperature. 0.36 Grams of (30% by vol.) aqueous hydrogen peroxide solution was weighed into a 10 ml two neck flask fitted with a rubber septum and gas stopcock. Five ml. of ethanol was added via a syringe through the septum and the mixture was then degassed with argon. A length of teflon tubing for a cannula was cut and each end was threaded through a 12 gauge needle. The rubber septum on the smaller flask was pierced with one needle and the needle was then pulled out, leaving the tubing in place above the liquid level. The argon flow was turned on to flush through the tubing. The septum on the larger flask was pierced with the other needle, then the needle was withdrawn, leaving the tubing in place approximately 0.5 inches above the liquid level. The tubing in the small flask was carefully inserted into the liquid as far as possible and using the argon flow, the flow of liquid from the peroxide mixture into the ligand mixture was regulated so that it was transferred drop by drop. The solution was stirred at room temperature for one hour. 
     The solution was then transferred to a 250 ml. round bottom flask in a nitrogen atmosphere, using degassed ethanol to rinse out the solids. The ethanol was removed from the solution using a rotovapor, then the solid was dried under vacuum for several hours. The resulting oxidized phosphine ligand was analyzed by phosphorus-31 NMR to determine the oxygen:phosphorus ratio. 
     ILLUSTRATIVE EMBODIMENT II 
     In this illustrative embodiment catalysts complexed with the oxidized ligands are prepared and tested for hydroformylation of ethylene oxide. 
     In Situ Catalyst Preparation and Hydroformylation 
     In an inert atmosphere, a 100 ml air-stirred Parr autoclave was charged with 113 mg (0.33 mmole) of dicobalt octacarbonyl, 204 mg (0.66 mmole) of 1,2-bis(9-phosphabicyclononyl)ethane which had been oxidized as described above to provide an oxygen to phosphorus of 0.20 and 23 ml of dry, nitrogen-purged toluene-chlorobenzene solution (5:1 volume ratio). The autoclave was sealed and pressured to 1300 psig with a hydrogen-carbon monoxide gas mixture (1:1 molar ratio). The reaction was stirred and heated at 130° C. for 30 minutes at 1500 psig. The reactor was then cooled to an internal temperature of 5° C. and the gases were vented to leave the autoclave at ambient pressure. 
     Ethylene oxide (4.5 gm, 102 mmole) was added to the reactor and the reactor was then heated and stirred for 3 hours at 105° C. at a pressure of 1400-1500 psig of hydrogen-carbon monoxide gas (1:1 molar ratio). 
     After cooling to 5° C., the reactor was purged with nitrogen and the two-phase product mixture was collected to give about 29 grams of solvent phase and about 2 grams of an oil phase. The two phases were independently analyzed by gas chromatography. Results are shown in Table 1. 
     Example 1 was repeated except that differing amounts of ligand to cobalt octacarbonyl, differing reaction temperatures and differing amounts of oxidation of the phosphine ligand were used. The results are presented in Table 1 as Examples 2-13. 
     Example 1 was repeated using as a ligand 1,2-bis(diphenylphosphino)ethane in differing amounts with differing amounts of oxidation. The results are presented in Table 1 as Examples 14-18. 
     
                                           TABLE 1
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              Rxn EO   PDO
     O/P P/Co Temp.
                  Conv.
                       Precursor
                              PDO  CH.sub.3 CHO
Example
     Ratio
         Ratio
              °C.
                  Mole %
                       Mole % Mole %
                                   Mole %
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1    0   2.0  105 1.0  100    --   --
2    0   1.5  105 3.7  89.0   --   11.0
3    0   2.0  105 0.7  100    --   --
4    Trace
         2.0  105 3.4  100    --   --
     P = O
5    0.07
         1.9  105 8.7  94.7   --   5.3
6    0.07
         2.0  105 10.1 98.5   1.5  --
7    0.13
         2.0  110 17.7 86.3   1.9  4.9
8    0.20
         2.5  105 21.2 90.1   3.6  4.0
9    0.20
         2.0  105 33.9 86.9   3.2  7.2
10   0.20
         1.5  105 42.9 65.9   1.5  18.2
11   0.20
         2.0  100 20.9 90.3   4.0  4.0
12   0.30
         1.4  105 47.0 81.3   3.3  15.5
13   0.30
         1.4   90 30.3 90.0   4.2  3.8
14   0   1.5   90 3.0  100    0    0
15   0.06
         1.5   90 8.2  94.1   1.0  4.9
16   0.06
         1.0   90 30.9 84.6   3.9  10.7
17   0.36
         1.5   90 27.8 88.0   3.8  8.1
18   0.17
         1.5   90 15.4 91.5   2.4  6.1
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     ILLUSTRATIVE EMBODIMENT III 
     Hydrogenation of Hydroformylation Product 
     Example 19 
     Ten grams of the reaction product from an ethylene oxide hydroformylation reaction such as example 1 was charged to a 300 ml autoclave along with 40 grams of deionized water and 2 grams of Raney nickel catalyst. The autoclave was flushed with hydrogen, pressured with hydrogen to 1000 psig and heated to 110° C. for 5 hours. The autoclave was cooled to room temperature, vented of excess gas, and samples were removed for analysis by gas chromatography and mass spectroscopy. This analysis showed 1,3-propanediol as the major product in the water solution. The selectivity to 1,3-propanediol was estimated to be about 90% with greater than 80% of 3-hydroxypropanal converted to the diol. 
     Example 20 
     Example 19 was repeated except 18 grams of hydroformylation product, 42 grams of water and 1.5 grams of molybdenum-promoted Raney nickel catalyst were charged to the autoclave with a reaction pressure of 600 psi and a reaction temperature of 60° C. being used. Analysis of the hydrogenated product showed that 3-hydroxypropanal was converted to 1,3-propanediol as the major product.