GB1565979A - Enhancing the promoting of the catalytic process for making polyhydric alcohols - Google Patents

Enhancing the promoting of the catalytic process for making polyhydric alcohols Download PDF

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GB1565979A
GB1565979A GB40356/76A GB4035676A GB1565979A GB 1565979 A GB1565979 A GB 1565979A GB 40356/76 A GB40356/76 A GB 40356/76A GB 4035676 A GB4035676 A GB 4035676A GB 1565979 A GB1565979 A GB 1565979A
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promoter
amine
sulfolane
alkane
catalyst
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Union Carbide Corp
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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    • B01J31/0239—Quaternary ammonium compounds
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
    • B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1512—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1512—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions
    • C07C29/1514—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions the solvents being characteristic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/648—Fischer-Tropsch-type reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Description

(54) ENHANCING THE PROMOTING OF THE CATALYTIC PROCESS FOR MAKING POLYHYDRIC ALCOHOLS (71) We UNION CARBIDE CORPORATION, a corporation organized and existing under the laws of the State of New York, United States of America, of 270 Park Avenue, New York, State of New York 10017, United States of America, (assignee of LEONARD KAPLAN), do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention is concerned with the manufacture of polyhydric alcohols.
It is known that monofunctional compounds such as methanol can be obtained by reaction between carbon monoxide and hydrogen at elevated pressures, e.g., up to about 1000 atmospheres, and temperatures ranging from 250"C to 500"C, using mixtures of copper, chromium and zinc oxides as the catalyst therefor. It is disclosed in U.S. Patent No.
2,451,333 that polyhydroxyl compounds are produced by reaction of formaldehyde, carbon monoxide, and hydrogen in the presence of hydrogenation catalysts. It has also been reported that formaldehyde can be produced by reaction between carbon monoxide and hydrogen at elevated pressures but repeated attempts to carry out this synthesis of formaldehyde have invariably failed to yield any substantial quantity of the desired product.
It is generally recognized that the previously disclosed processes for the synthesis of formaldehyde from carbon monoxide and hydrogen at high pressures are either completely inoperative or else give rise to insignificantly small quantities of formaldehyde.
In U.K. Specification 655,237, published July 11, 1951, there is disclosed the reaction between carbon monoxide and hydrogen at elevated pressures and temperatures, e.g., above 1500 atmospheres at temperatures up to 400"C., using certain hydrogenation catalysts as exemplified by cobalt-containing compounds. U.S. Patents No. 2,523,018; 2,570,792, and 2,636,046 are substantially similar in disclosure to the above said British patent. The only catalysts employed in the numbered examples of said U.S. Patent 2,636,046 are those which contain cobalt.
It is also well-known that nickel is predominantly a catalyst for synthesis and for reforming methane according to the reaction CO + 3H2 CH4 + H2O whose equilibrium favors the right hand side of the equation at temperatures below about 500"C. and the left hand side of the equation at higher temperatures; see Kirk-Othmer, Encyclopedia of Chemical Technology, Second Edition, Volume 4, pages 452-453, John Wiley and Sons, New York (1964).
Polyhydric alcohols are presently being produced synthetically by the oxidation of petroleum derived materials. Owing to the limited availability of petroleum sources, the cost of these petroleum derived materials has been steadily increasing. Many have raised the dire prediction of a significant oil shortage in the future. The consequence of this has been recognition of the need for a new low cost source of chemicals which can be converted into such polyhydric alcohols.
This invention is oriented to the process of making alkane diols and triols, containing 2, 3 or 4 carbon atoms. A key product of the process of this invention are ethylene glycol.
Byproducts of this invention are the lesser valuable, but valuable nevertheless, monohydric alkanols such as methanol ethanol and propanols, and their ether and ester derivatives. The products of the process of this invention contain carbon, hydrogen and oxygen.
There is described in U.K. Patent Specifications 1424007 and 1424008 a process for reacting hydrogen and oxides of carbon in the presence of rhodium carbonyl complex catalysts. The conditions, broadly speaking, employed in that process involves reacting a mixture of an oxide of carbon and hydrogen with a catalytic amount of rhodium in complex combination with carbon monoxide, at a temperature of between about 100"C. to about 375"C. and a pressure of between about 500 p.s.i.a. to about 50,000 p.s.i.a. The patents discuss the use of catalyst complexes which have "ligands" as a component thereof.
Illustrations of such ligands are oxygen and/or nitrogen organic compounds. A similar description can be found in U.K. Patent Specification No. 1477391. These patents speak about the use of such "ligands" as well as a number of amines which can be used in the catalytic process.
It has been found that such "ligands" and amines enhance the glycol producing capacity of the rhodium carbonyl complex catalyst. In that sense, the "ligands" and amines can be considered to promote the activity of the catalyst. Since the filing of the the applications which resulted in U.K. Patent Specification 1424007 and 1424008, the mechanism of action of such ligands and amines with the rhodium carbonyl complex has not been clearly defined.
They may be functioning as ligands and/or forming counter-ions under the reaction conditions of the present process or they may be functioning just merely as Lewis bases and neutralizing or typing up a molecular species which if allowed to remain "free" or in its non-base-bound state would adversely affect the productivity of the present invention.
Because of this, it is more favorable to look at their presence in this process in terms of the results they achieve; hence, for the purposes of this invention they are defined as catalyst promoters or rhodium carbonyl complex catalyst promoters.
Even though such promoters were recognized to be beneficial in such a process for making alkane polyols as the important product of manufacture, there was a lack of appreciation that if employed in certain concentrations the productivity of such polyols would be materially and unexpctedly enhanced. In copending Application No. 40343/76, it is established that there is a specific concentration for each such promoter which will provide the optimium yield of alkane polyol that is obtainable under each selected condition of reaction and catalyst concentration. It follows from this that there now exists a recognition of a specific concentration of such promoter which creates that most favorable balance between the promoting and inhibiting effects of such promoters.
The process of the present invention and the invention of copending application No.
(Serial No. 1565978) 40343/76 involve the production of alkane polyols where the primary product of the process is ethylene glycol mainly in terms of commercial value and secondly in terms of product efficiency. These processes involve providing carbon monoxide, and hydrogen in a homogeneous liquid phase reaction mixture containing a rhodium carbonyl complex and a nitrogen Lewis base promoter. The catalyst concentration, the temperature and the pressure during the reaction are correlated so as to result in the production of alkane polyol. In copending application (Serial No. 1565978) No. 40343/76 the promoter provided to the mixture is present in an amount to achieve the optimum rate of formation of said alkane poloyol at the correlated catalyst concentration, temperature and pressure of such reaction mixture. The present invention, however, provides for the selection of a promoter in terms of its basicity and the ability of its conjugate acid to ion pair with the rhodium carbonyl complex catalyst whereby to minimize inhibition of alkane polyol production by the presence of an excess of promoter.
The following (defined in terms of an amine as representative of a nitrogen Lewis base) postulate possible mechanisms which would result in the observed behavior discussed above: a.) the inhibitor function of the amine is of higher kinetic order in amine than is the promoter function; b.) the promoter function of the amine has a stoichiometric limit after which only the inhibitor function of the amine remains.
The term "inhibitor function" means that function of the amine which results in a decrease in alkane polyol yield as amine concentration increases.
The above postulates can be illustrated by the following reaction scheme:
An-mJamane Rh miomire) =RhirJmine)m=Rhimineln olkone polyol Promoter Function I Inhibitor Function *the looped arrow employed herein denotes several undefined process steps.
[NOTE: In the above reaction scheme the charge of the rhodium carbonyl complex is not shown; n and m represent integers; Rh denotes a species with a fixed number of rhodiums with the option of a changing number of CO's and H's; the rate and equilibrium constants implicity contain any appropriate CO and 112 concentrations.] In the above scheme, the amine aids production of glycol by forming a more active catalyst and hinders it by inactivating the active catalyst through a mass law effect. Both of these functions of the amine involve it as a ligand on rhodium. A consequence of this reaction scheme is that, if the rate of glycol formation passes through a maximum as a function of the concentration of the amine, the amine concentration which corresponds to the maximum increases as K increases. [Note: K is the equilibrium constant for dissociation of an amine ligand from rhodium to yield the active catalyst.] Since K would be expected to be larger for weaker bases, this scheme is consistent with the aforementioned observed results If the role of the amine as inhibitor involves it as a ligand on rhodium the rate of fall-off in the yield of alkane polyol (inhibitory ability of promoter) should increase as K decreases which would result from use of a more basic and less sterically hindered amine.
A second reaction scheme is characterized as follows:
Rhromlne lRh omlneH±---tRh+ omlneH+] olkone polyol [Note: Rh is defined as above in the note to equation (I)j In equation (II) the amine acts as a promoter because it helps to produce the active catalyst and as an inhibitor because its conjugate acid has an adverse mass law effect on the equilibrium concentration of a direct precursor of the active catalyst.
In terms of reaction scheme (II), with the use of a less basic amine, more amine would be necessary to ensure that the first step of the equation is quantitative. After enough of such an amine is provided, any further amine additions can have only negative effects in regard alkane polyol production because there is a consequent production of more amine H+, which serves to decrease Rh concentration. A consequence of the reaction scheme (II) is that the rate passes through a maximum as a function of amine concentration and that as basicity of the amine increases the optimum concentration of amine decreases to a limiting value corresponding to stoichiometric conversion of Rh.
A consequence of reaction scheme (II) is that the rate at which the rate decreases from the maximum with increasing amine concentration depends upon the magnitude of K' and the basicity of the amine: As K' increases, as a consequence, for example, of the use of an amine with a more weakly ion-pairing conjugate acid, the rate is attenuated less effectively up to the maximum and falls off more slowly thereafter; as amine basicity increases, the fraction of added amine converted to amine H+, presumably via the hydroxyl pool, increases to a limiting value of 1.
Thus, the invention of copending application 40343/76 (Serial No. 1565978) contemplates the recognition that there is an appropriate concentration for nitrogen Lewis base promoters to achieve optimum rate of formation of alkane polyol production and that amounts in excess of that concentration, in the typical case, will act to inhibit alkane polyol production. It is the contemplation of the present invention that the concentration of the promoter should be in excess of said concentration for the purpose of enhancing catalyst stability in the reaction. Catalyst stability relates to the desirable feature of keeping the catalyst in solution. A consequent fall-out from these features of this invention is the fact that allowing for some excess of the promoter over the concentration to produce optimum rate of promoters of alkane polyol will reduce the criticallity which would otherwise be imposed by having to operate the process under strict control of promoter concentration.
The process of the present invention is an improvement on the process described in U.S.
Patent No. 3,833,634 in that there is provided in the aforemention homogeneous liquid phase mixture a concentration of the nitrogen Lewis base promoter exceeding the concentration thereof which under the selected reaction conditions will produce the optimum rate of formation of alkane polyol obtainable with such promoter and the rate of formation of alkane polyol is not decreased from the optimum by more than 50%.
According to the present invention there is provided a process for producing alkane olyols having from 2 to 4 carbon atoms which comprises reacting carbon monoxide and hydrogen in a homogeneous liquid phase mixture containing a rhodium carbonyl complex catalyst and a nitrogen Lewis base promoter; the catalyst concentration, the temperature and the pressure being correlated so as to produce such alkane polyol; the promoter being provided in combination with the catalyst in an amount to achieve not less than 50% of the optimum rate of formation of the alkane polyol at said correlated catalyst concentration, temperatures and pressure of said mixture, and in which the amount of the promoter is greater than the amount which is sufficient to produce such optimum rate of formation.
Preferably the reaction mixture contains a solvent e.g. tetraglyme (i.e. the dimethyl ether of tetraethylene glycol) or sulfolane.
The reaction mixture preferably includes a salt.
The reaction is preferably carried out at a temperature of from 100 to 375"C.
The preferred pressure of reaction is from 800 psia to 50,000 psia As pointed out previously, there are two factors which govern the inhibitory ability of the promoter and, hence, the concentration of the promoter which can be used according to this invention. They are the basicity of the promoter and the ion pairing qualities of the protonated version of the promoter [lK' of reaction scheme (Il)]. In some promoters the basicity is low enough so that none of the conjugate acid would be produced and hence there would be no ion pairing. This is desirable in the terms of this invention. On the other hand, the conjugate acid of the promoter may be so poor at forming an ion pair that, even if the promoter is highly basic with a resultant high concentration of conjugate acid, the large concentrations of such a promoter would not be excessively harmful and could be well within the standards set forth above for this invention.
For the purposes of this invention, the ultimate promoter selected is one which is the least basic and forms the weakest ion pair with the rhodium catalyst. One should employ such a promoter in the homogeneous liquid phase reaction mixture in an amount which is greater than the amount predicated on the amines basicity for producing the optimum rate of formation of alkane polyols, particularly ethylene glycol, obtainable using that promoter.
In copending application No. 40343/76 (Serial No. 1565978) the invention involves the selection of an amount of the promoter which achieves the maximum amount of alkane polyol.
Nitrogen Lewis bases used as promoters generally contain hydrogen and nitrogen atoms.
They may also contain carbon and/or oxygen atoms. They may be organic or inorganic compounds With respect to the organic compounds, the carbon atoms can be part of an acyclic and/or cyclic radical such as aliphatic, cycloaliphatic aromatic (including fused and bridged) carbon radicals, and the like. Preferably, the organic Lewis bases contain from 2 to 60, most preferably 2 to 40 carbon atoms. The nitrogen atoms can be in the form of imino (-N=), amino (-N-), nitrilo (No), etc. Desirably, the Lewis base nitrogen atoms are in the form of imino nitrogen and/or amino nitrogen. The oxygen atoms can be in the form of groups such as hydroxyl (aliphatic or phenolic),
0 0 0 II carboxyl (-COH), carbonyloxy (-CO-), oxy (-0-), carbonyl (-C-), etc., all of said groups containing Lewis base oxygen atoms. In this respect, it is the
o 0 "hydroxyl" oxygen in - the - COH group and the "oxy" oxygen in the CO group tnat are acting as Lewis base atoms. lahe organic Lewis bases may also contain other atoms and/or groups as substituents of the aforementioned radicals, such as alkyl, cycloalkyl, aryl, chloro, trialkylsilyl substituents.
Illustrative of organic aza-oxa Lewis bases are, for example, the alkanolamines, such as, ethanolamine, diethanolamine, isopropanolamine and di-n-propanolamine; N,Ndimethylglycine, N,N-diethylglycine; iminodiacetic acid, N-methyliminodiacetic acid; N-methyldiethanolamine; 2-hydroxypyridine. 2,4-dihydroxypyridine, 2-methoxypyridine, 2,6-dimethoxypyridine, 2-ethoxypyridine; lower alkyl substituted hydroxypyridines, such as 4-methyl-2-hydroxypyridine and 4-methyl-2, 6-dihydroxypyridine; morpholine, substituted morpholines, such as 4-methylmorpholine, 4-phenyl-morpholine; picolinic acid, methylsubstituted picolonic acid; nitrilotriacetic acid, 2,5-dicarboxypiperazine, N-(2hydroxyethyl) iminodiacetic acid, ethylene-diaminetetraacetic acid; 2,6-dicarboxypyridine; 8-hydroxyquinoline, 2-carboxyquinoline, cyclohexane-1 ,2-diamine-N,N,N' ,N'-tetraacetic acid, the tetraacetic acid, the teramethyl ester of ethylenediamine-tetraacetic acid.
Other Lewis base nitrogen containing compounds include organic and inorganic gamines.
Illustrative of such inorganic amines are, e.g., ammonia, hydroxylamine, and hydrazine.
Primary, secondary, or tertiary organic amine are promoters. This includes the mono- and polyamines (such as di-, tri-, tetraamines, etc.) and those compounds in which the Lewis base nitrogen forms part of a ring structure as in pyridine, quinoline, pyrimidine, morpholine, hexamethylene tetraamine, and the like. In addition any compound capable of yielding an amino nitrogen under the reaction conditions of the present invention are promoters, as in the case of an amide, such as formamide, cyanamide, and urea, or an oxime. Further illustrative of these Lewis base nitrogen compounds are aliphatic amines such as methylamine, ethylamine, n-propylamine, isopropylamine, octylamine, dodecylamine, dimethylamine, diethylamine, diisoamylamine, methylethylamine, diisobutylamine, trimethylamine, methyldiethylamine, triisobutylamine and tridecylamine; aliphatic and aromatic di- and polyamines such as 1,2-ethanediamine, 1,3-propanediamine, N,N,N',N'- tetramethylenediamine, N,N,N' ,N'-tetraethylethylenediamine, N,N,N' ,N'-tetra-n- propylethylenediamine, N,N,N',N'-tetrabutylethylenediamine, o-phenylenediamine, mphenylenediamine, pphenylenediamine, p-tolylenediamine, o-tolidene, N,N,N',N'- tetramethyl-p-phenylenediamine and N,N,N' ,N'-tetraethyl4,4' -biphenyldiamine; aromatic amines such as aniline, 1-naphthylamine, 2-naphthylamine, p-toluidine, o-3-xylidine, p-2-xylidine, benzylamine, diphenylamine, dimethylaniline, diethylaniline, N-phenyl-1napthylamine and bis-(1 ,8)-dimethylaminonaphthalene; alicyclic amines such as cyclohexylamine and dicyclohexylamine, heterocyclic amines such as piperidine; substituted piperidines such as 2-methylpiperidine, 3-methylpiperidine, 4-ethylpiperidine, and 3phenylpiperidine; pyridine; substituted pyridines such as 2-methylpyridine, 2phenylpyridine, 2-methyl-4-ethylpyridine, 2,4 ,6,-trimethylpyridine, 2-dodecylpyridine, 2chloropyridine, and 2-(dimethylamino)pyridine; quinoline; substituted quinolines, such as 2-(dimethylamino)-6-methoxyquinoline; 4,5-phenanthroiine; 1 ,8-phenanthroline; 1,5phenanthroline; piperazine; substituted piperazines such as N-methylpiperazine, Nethylpiperazine, 2-methyl-N-methylpiperazine; 2,2'-dipyridyl, methyl-substituted 2,2'dipyridyl; ethyl-substituted 2,2' -dipyridyl; 4-triethylsilyl-2,2' -dipyridyl; 1 ,4-diazabicyclo [2.2.2] octane, methyl substituted 1,4-diazabicyclo [2.2.2] octane and purine.
In order to determine that an excess of the promoter is being employed, it is necessary to appreciate how to select a concentration of promoter which achieves maximum yield of alkane polyol. The promoter is provided in the homogeneous reaction mixture in an amount which may be determined from its basicity, to achieve the optimum rate of formation. For the purposes of discussion of the above provision of the promoter in the reaction, the promoter shall be characterized initially in terms of basicity as either a strong or weak base. However, it is important to bear in mind that this determination of promoter concentration predicated on basicity is not intended to mean that of necessity the promoter is or becomes a cation in the homogeneous mixture as noted in the previous discussion relative to the so-called "ligands" and amines, and their function in the catalytic reaction.
It has been found that the optimum concentration of a strongly basic nitrogen Lewis base promoter in the process of this invention is a minimum concentration. This means that a relatively small amount of such promoter achieves the optimum rate of formation with that promoter. On the other hand, it has been found that as the base becomes progressively weaker, a greater and greater amount of the base is needed to achieve the maximum yield of the alkane polyol.
The effects of concentration of the nitrogen Lewis base promoter in the homogeneous liquid phase mixture of the process of this invention has been found to be dependent upon the temperature and, to some degree, the pressure of the reaction and the rhodium concentration or the solvent employed. Of these factors, temperature and solvent selection will have the more significant impact upon the effects of promoter concentration. Pressure and rhodium concentration provide a lesser effect.
The terms strong or weak base are relative, and in view of the preceding discussion, such relative values are considered appropriate in defining this invention when needed.
However, for convenience and to provide a numerical base from which it may be considered desirable to discuss this invention, one may characterize a strong base as having a pK greater than about 5 and a weak base as having a pK less than 5, with the assumption that each is definitive in the region of a pK of 5. Of course one may give values more limiting in regards to such pK characterizations by stating that a strong base has a pK of 5 to about 15 and a weak base has a pK of 0 to about 5. By pK, it is meant the acid dissociation constant of the conjugate acid of the nitrogen Lewis base in water at 25"C.
The optimum concentration of an untried promoter may be determined on a relative scale by comparing the pK of that promoter to those set forth in Table I below and selecting a concentration according to the pK relationships and trends indicated. Overall, the optimum concentration of promoter one can employ will be within about 0.001 to about 10 molar. Obviously this range is definitive of the potential scatter of concentrations predicated on the varieties of promoter basicity available.
TABLE I Optimum* Other moles promoter amine/ Amine pKt Solvent Temp. present mole Rh 1,8-bis(dimethyl- 12.3 Sulfolane 240 - -0.1 amino)naphthalene " " 0.2-0.3 Sparteine 12.0 " " 260 - 0.2-0.3 Dibutylamine 11.3 " 240 - 0.3-0.5.
Piperidine 11.1 " 220 - 0.3-0.5 Triethylamine 10.7 " 240 - 0.3 N-methyl piperidine 10.4 " " - 0.3-0.5 Piperazine 9.7 " 240 - 0.3-0.5 4-dimethylaminopyridine 9.6 " 220 - 0.2 Ammonia 9.3 " 240 - 0.3 Amberlite IRA-93 9.0≈" D ~ 0.3-0.5 1,4-diazabicyclo [2.2.2] octane 8.8 " 220 - 0.1 " " " " 240 - 0.2-0.3 2,4,6-trimethylpyridine 7.4 " 240 - 0.2-0.3 N-,methylmorpholin 7.4 " " - 0.3-0.4 Trimethylenedi- morpholine 7.3 " 260 - 0.5 Pyridine 5.2 " 220 - 0.2-0.3 " " " 240 - ~ 0.1 " " " " (Ph3P)2NO Ac ~0.1 tetraglyme 220 " 0.2-0.6 " " " " HCO2Cs 0.2-0.4 " " " 230 PhCO2Cs 0.3-0.6 1,10-phenanthroline 4.8 Sulfolane 240 - 1.6 Aniline 4.6 " " - 2.3 2-hydroxypyridine 0.8 tetraglyme 220 Cs2-pyridinolate 1 pK of benzyldimethylamine; IRA-93 is an arylmethyl dimethyl amine ion exchange resin sold by Rohm & Haas Co., Phila., Pa.
* The smallest which maximizes the yield of glycol.
# H2O, 25 .
The ion pairing abilities of the conjugate acids of the nitrogen Lewis base promoters are determined by standard procedures. The pK's for the dissociation of ion pairs formed by the conjugate acids of a number of amines are recited in Tables II and III below. The values there depicted demonstrate a consistent relative ion pairing ability.
TABLE II Ion pairing ability of ammonium ions in acetonitrile pKdissocn (M, activity-based) of ion pair, 25 Salicylatea Benzoatea 3-Bromobenzoatea (PhCH2)3NH + Piperidinium 0.5 4.1 4.0 BuNH3+ Bu2NH2 + Et2NH2+ 2.9 3.4 1.8 Bu3NH+ Et3NH+ 1.9 5.6 3.9 2,6-Dimethyl -pyridinium PhNH3+ PyH+ 13.7 10.5 11.5 4-Nitrobenzoatea 3,5-Dinitrobenzoate Picrate 1.8d 1.6 1.3a 2.5" 2.5e 4.6 1.4a 2.3e 5.7 2.7a, 4.9b 2.3a, 2.4 2,4C 3.00, d 11.6 10.4a 3.4, 2.5" aA.P. Kreshkov, V.I. Plastun, aND E. Kalinina, Zh. Fiz. Khim., 48, 459 (1974). bI.M.
Kolthoff and M.K. Chantooni, Jr., J. Am. Chem. Soc., 85, 426 (1963). CM.K. Chantooni, Jr., and I.M. Kolthoff, J. Am. Chem. Soc., 90, 3005 (1968). dC.M. French and D. F.
Muggleton, J. Chem. Soc., 2131(1957). eJ. F. Coetzee and G. P. Cunningham, J. Am.
Chem. Soc., 87, 2534 (1965).
"Py", "Ph", "Bu" and "Et", respectively, as used herein mean pyridine, phenyl, butyl and ethyl.
TABLE III Ion pairing ability of ammonium ions in nitrobenzene Cation pKdissocn (M, 25 ) of Ion Pair with Picrate NH4+ 3 8b PrNH3+ 3,9c BuNH3+ 3 8b,c Et2NH2+ 3,7C Bu2NH2+ 3.8b Me3NH+ 3.8d Et3NH+ 3,7c Bu3NH+ 3,7be Piperidinium 3,8b PhNH3+ 4,7b PhNHMe2+ 3,9a,f, 4.4b PyH+ 4.3b aActivity-based. bC. R. Witschonke and C.A. Kraus, J. Am. Chem. Soc., 69, 2472 (1947).
cJ. Macau and L. Lamberts, J. Chim. Phys., 67, 633 (1970). dE. G. Taylor and C. A. Kraus, J. Am. Chem. Soc., 69, 1731 (1947). eJ. B. Ezell and W. R. Gilkerson, J. Phys. Chem., 72, 144 (1968). H. W. Aitken and W.R. Gilkerson, J. Am. Chem. Soc., 95, 8551 (1973).
Acetonitrile and nitrobenzene are similar to sulfolane in that they are dipolar aprotic solvents and their dielectric constants are similar to sulfolane (=43). The dielectric constant for acetonitrile is 36 and nitrobenzene is 35.
Thus from a consideration of the ion pairing ability data recited in Tables II and III above, plus consideration of the factors affecting "F-strain" (See H. C. Brown, Boranes in Organic Chemistry, Cornell University Press. 1972, starting at page 102), to which is added goiicral concepts of electrostatics, permits the prediction of ion p
TABLE IV Amine pK(H2O, 250) Figure 220 a pyridine 5.2 1 1 ,4-diazabicyclo[2.2.2]octane 8.8 1 quinuclidine 11.2 1 240"a pyridine 5.2 3 2,4,6-trimethylPyridine 7.4 3,5 N-methylmorpholine 7.4 2,5 1 ,4-diazabicyclo[2. 2. 2ioctane 8.8 4 N,N'-dimethylpiperazme 9.orb 2 ammonia 9.3 5 piperazine 9.7 4 N-methylpiperidine 10.4 2,4 triethylamine 10.7 3,4 dibutylamine 11.3 4 bis- (1,8)dimethylaminonaphthalene 12.3 6 aConditions other than temperature: 75 ml sulfolane, 1/1 H2/CO, 8000 psig, 4 hr., 3 mmoles Rh(CO)2 acetylacetonate, and the amine concentrations recited in the drawings.
bEstimated from the pK's of piperazine (9.7), piperidine (11.1), and N-methylpiperidine (10.4).
The observed (Figures 3-5) relative inhibitory abilities of those amines in Table IV for which data are available in Table II or III are NH3 < Et3N - Bu2NH < py Based on the data in Tables II and III and noting that, since the more highly charge-delocalized picrate is a more levelling counterion than are aryl carboxylates, small differences in pKdissocn are of greater significance for picrate, the conjugate acids' ion pairing ability is ordered as NH4+ ~ Et3H+ ~ Bu2NH2+ < pyH+ This ranking must be considered along with the relative basicities of the amines (see above).
Based on 1) basicity data (Table V below) in water and in the two solvents in which the ion pairing abilities were determined and 2) the Ho function in sulfolane [See R. W. Alder et al., Chemical Communications, p. 405 (1966)], the pK's in sulfolane are ordered as Et3NH+ ~ Bu2NH2+ > NH4+ > pyH+ Thus, the observed inhibitory abilities of the amines may be explained in terms of 1) the conjugate acids of Et3N and Bu2NH having the same ion pairing abilities and the amines having the same basicity, 2) the conjugate acid of pyridine being an extremely strong ion pairer, and 3) the conjugate acid of NH3 having the same ion pairing ability as those of Et3N and Bu2NH but ammonia being less basic. Note that the effective ion pairing ability in sulfolane may, in the cases of R2NH2, RNH3+, and especially NH4+, be decreased by H-bonding to each of the sulfone oxygens.
TABLE V Acidity of ammonium ions, pKa (250) H2o Acetonitrile ah Nitrobenzenec NH4+ 9.3 16.5 EtNH3+ 10.6 18.4 7.1 BuNH3+ 10.6 18.3 Et2NH2 11.0 18.8 7.1 Bu2NH+2 11.3 7 Id Et3NH 10.7 18.5 7.3 Bu3NH 042 11.0 18.1 7.3d pyH+ 5.2 12.3 2.1 aJ. F. Coetzee and G. R. Padmanabhan, J. Am. Chem. Soc., 87, 5005 (1965).
bI. M. Kolthoff, M. K. Chantooni, Jr., and S. Bhowmik, ibid. 90, 23 (1968).
CD. Feakins, W. A. Last, and R. A. Shaw, J. Chem. Soc., 2387 (1964).
dBased on 1) results for Et3NH+ vs. BuNH3+ in H2O and MeCN, Et2NH2+ vs. Bu NH2+ in water, and Et3NH+ vs. Bu3NH+ in H2O and MeCN and 21 the constancy of the effects of solvent on pK, we estimate pK (Et2NH2+) ~ pK (Bu2NH2 ) in MeCN and PhNO2 and pK (Et3NH+) ~ pK (Bu3NH+) in PhNO2.
Relationships apparent from the data referred to in Table IV are explained in Table VI.
In order to minimize inhibition by the amine and obtain thereby, without suffering a significant decrease in rate to glycol, the higher recoveries of rhodium which usually accompany higher than rate-optimum concentrations of amine, a weakly basic amine whose conjugate acid has poor ion pairing ability should be used. An amine whose conjugate acid's positive charge is not substantially localized on only one atom is particularly good.
TABLE VI Observed Inhibitory Effect of Figure py > dabcoC 1 py > 2,4,6-trimethylpy 3 N-methylpiperidine~Et3N 4 dabco~Et3N 4 piperazine-N-methyIpiperidine 4 Bu2NH~Et3N 4 quinuclidine > Et3N 4a 2,4,6-trimethylpy > N-methylmorpholine 5 NH3 5 bis-(1,8)dimethylaminonaphthalene 6 pyH+ stronger ion-pairer than dabconium; basicity difference overcome pyH+ stronger ion-pairer than 2,4,6-trimethylpyridinium; basicity difference overcome basicities of amines and ion pairing abilities of conjugate acids similar dabconium stronger ion-pairer than EtSNH+, but dabco less basic than Et3N basicities of amines and ion pairing abilities of conjugate acids similar basicities of amines and ion pairing abilities of conjugate acids similar quinuclidinium stronger ion-pairer than Et3NH+, basicities of amines similar 2,4,6-trimethylpyridium stronger ion-pairer than N-methylmorpholinium; basicities of amines similar anomalously weak; NH4+ anomalously weak ion-pairer because of 4-point solvation by two-sulfolanes basicity overcome by extremely weak ion pairing ability of conjugate acid (two onium nitrogensb) aAssuming quinuclidine > dabco at 240 as well as at 220 (Figure 1).
bF. Hibbert, J. C. S. Perkin II, 1862 (1974) C1,4-diazabicyclo[2.2.2]octane.
The present invention will now be further illustrated by way of the following examples which are merely illustrative and are not presented as a definition of the limits of the invention.
Procedure employed in examples: A 150 ml. capacity stainless steel reactor capable of withstanding pressures up to 7,000 atmospheres was charged with a premix of 75 cubic centimeters (cc) of solvent, 3.0 millimoles (mmol), 0.77 grams, of rhodium dicarbonylacetylacetonate, and promoter(s).
The reactor was sealed and charged with a gaseous mixture, containing equal molar amounts of carbon monoxide and hydrogen, to a pressure of 8,000 pounds per square inch (psig). Heat was applied to the reactor and its contents; when the temperature of the mixture inside the reactor reached 1900C as measured by a suitably placed thermocouple, an additional adjustment of carbon monoxide and hydrogen (H2:CO=1:1 mole ratio) was made to bring the pressure back to 80000 psig. The temperature (in "C.) was maintained at the desired value for 4 hours. During this period of time additional carbon monoxide and hydrogen was added whenever the pressure inside the reactor dropped below about 7500 psig. With these added repressurizations the pressure inside the reactor was maintained at 8000 psig + 400 psig over the entire 4 hour period.
After the 4 hour period, the vessel and its contents were cooled to room temperature, the excess gas vented and the reaction product mixture was removed. Analysis of the reaction product mixture was made by gas chromatographic analysis using a Hewlett Packard FM model 810 Research Chromatograph.
Rhodium recovery was determined by atomic absorption analysis of the contents of the reactor after the venting of the unreacted gases at the end of the reaction. A further analysis was run on a "wash" of the reactor. The wash of the reactor consisted of charging to the reactor 100 cc of the solvent used for that experiment, and bringing the reactor and its contents to a temperature of 1600C. and a pressure of 14,000 to 15,000 psig and maintaining these conditions for a period of 30 minutes. The reactor was then cooled and the unreacted gases vented and an atomic absorption analysis for rhodium was run on the reactor's contents. The rhodium recovery values recited below are the percent rhodium based on the total rhodium charged to the reactor that is soluble or suspended in the reaction mixture plus the wash after the specified reaction time.
The same equipment and procedure were used in all the examples in Tables A-S except for the reactants and conditions specified. The product weights in the Tables are reported in grams.
EXAMPLES Table A. 1,8-Bis (dimethylamino) naphthalene as Promoter Weight of Conditions mmoles Product and Other of Amine Reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 2402 0.20 2.4 0.8 34 + 5 " 0.31 2.9 6.0 78 + 3 " 0.63 2.7 5.1 67 + 4 " 0.94 2.8 5.0 66 + 3 1.25 3.7 5.5 69 + 5 " 2.5 2.7 4.6 72 + 4 " 5.0 3.7 4.3 85 + 2 " 7.0 4.4 4.8 83 + 7 Table B. Sparteine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 240 0.31 2.9 0.3 65 + 6 " 0.63 3.3 5.7 79 + 8 " 1.25 3.9 4.8 80 + 8 " 5.0 0.9 0.6 94 + 6 Sulfolane, 260 0.6 4.9 5.0 66 + 4 1.25 5.1 6.3 84 + 5 2.0 6.4 6.9 71 + 5 3.0 5.4 4.8 83 + 5 Table C. Dibutylamine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 240 0.65 2.7 5.4 77 + 5 1.25 3.5 6.2 77 + 6 2.5 4.3 4.9 86 + 5 " 5.0 4.7 4.0 77 + 6 Table D. Piperidine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 220 0 0.4 0.0 11 + 21 " 0.63 1.2 1.5 74 + 7 1.25 2.7 2.5 89 + 8 2.5 3.4 2.2 94 + 6 Table E. Triethylamine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 240 0.65 3.3 2.2 71 + 7 " 0.8 2.8 5.5 80 + 7 1.25 3.5 5.1 79 + 5 2.5 5.0 4.0 81 + 8 " 7.0 4.0 2.2 80 + 8 Table F. N-Methylpiperidine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 240 0.63 3.0 3.0 66 + 3 0.94 2.6 5.0 # # 65 1.25 3.5 4.9 69 + 7 2.5 4.5 3.8 86 + 7 Table G. Piperazine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 240 0.65 2.5 4.6 60 + 14 1.25 3.8 6.1 71 + 6 2.5 4.6 5.1 83 + 4 Table I. Ammonia as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 240 0.50 2.7 4.3 65 + 15 " 0.65 2.2 4.7 79 + 5 0.80 2.3, 2.4 4.9, 5.2 81 + 6, 86 + 5 1.0 3.2, 3.6, 2.8 6.6, 5.3, 5.2 84 + 6, 77 + 9, 83 + 7 1.25 2.7, 3.3, 3.1 5.2, 5.0, 5.1 69 + 4, 80 + 4, 84 + 5 1.5 3.6 4.8 81 + 5 " 2.0 4.6 4.6 83 + 8 " 2.5 4.6 4.8 78 + 5 " 10. 2.3 1.6 84 + 5 Table K. 1,4-Diazabicyclo [2.2.2] octane as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 220 0 0.4 0.0 11 + 21 " 0.31 1.4 0.9 71 + 3 " 0.63 1.2 3.5 81 + 7 1.25 2.9 2.6 87 + 6 " 2.50 2.8 1.5 90 + 3 Sulfolane, 240 0.31 2.8 0.5 41 + 11 " 0.63 3.1 6.5 75 + 6 " 1.25 4.4 6.1 76 + 4 " 2.5 4.3 4.5 74 + 6 " 5.0 4.4 3.7 75 + 7 Table L. 2,4,6-Trimethylpyridine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 240 0.31 2.6 1.0 60 + 3 " 0.63 2.5 5.0 77 + 6 " 1.25 3.6 4.3 71 + 4 " 2.5 4.5 3.3 77 + 4 " 5.0 4.9 2.5 76 + 3 Table M. N-Methylmorpholine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 240 0.63 3.2 4.2 66 + 5 1.25 3.2 5.8 64 + 4 2.5 4.5 5.4 74 + 4 5.0 3.6 5.3 80 + 4 " 7.0 4.1 5.4 82 + 2 Sulfolane, 250 C 7.0 3.6 6.4 64 + 3 " 11.0 4.6 6.0 67 + 7 " 20. 5.4 5.4 69 + 6 Table N. Trimethylenedimorpholine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 260 0.65 3.3 3.2 49 + 4 1.25 4.0 5.6 67 + 6 " 7.0 4.9 6.1 78 + 6 " 12.0 5.1 6.0 77 + 5 Table 0. Pyridine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 220 0 0.4 0.0 11 + 21 n 0.31 1.9 0.5 66 + 6 " 0.63 2.2 3.8 91 + 8 " 1.25 3.3 2.1 87 + 7 " 2.50 3.4 1.2 97 + 7 Sulfolane, 240 0.31 2.4, 2.6 2.1, 5.7 74 + 4, 82 + 2 " 0.63 2.7 5.7 76 + 4 " 0.94 3.0 5.2 73 + 6 " 1.25 3.4 4.7 76 + 3 " 2.5 3.5 3.4 79 + 2 " 5.0 2.6 2.0 87 + 3 Table P. 1, 10-Ph en an thro line as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 240 0.50 3.4 1.7 61 + 6 " 1.0 3.3 2.4 76 + 6 2.0 3.6 4.0 76 + 6 3.0 3.4 4.4 73 + 4 5.0 3.4 5.3 77 + 5 " 7.0 1.7, 2.6, 2.6 3.0, 3.9, 3.9 56 + 3, 69 + 4, 74 + 4 10.0 3.0, 2.7 4.7, 4.8 77 + 3, 77 + 4 15. 3.2 4.9 74 + 5 20. 2.5 4.3 77 + 5 Table S. Quinuclidine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 220 0 0.4 0.0 11 + 21 " 0.63 2.5 3.5 76 + 7 1.25 4.1 1.7 90 + 9 WHAT WE CLAIM IS: 1. A process for producing alkane polyols having from 2 to 4 carbon atoms which comprises reacting carbon monoxide and hydrogen in a homogeneous liquid phase mixture containing a rhodium carbonyl complex catalyst and a nitrogen Lewis base promoter; the catalyst concentration, the temperature and the pressure being correlated so as to produce such alkane polyol; the promoter being provided in combination with the catalyst in an amount to achieve not less than 50% of the optimum rate of formation of the alkane polyol at said correlated catalyst concentration temperatures and pressure of said mixture, and in which the amount of the promoter is greater than the amount which is sufficient to produce such optimum rate of formation.
2. A process as claimed in claim 1 wherein the mixture contains a solvent.
3. A process as claimed in claim 2 wherein the solvent is tetraglyme.
4. A process as claimed in claim 2 wherein the solvent is sulfolane.
5. A process as claimed in any one of claims 1 to 4 wherein the mixture contains a salt therein.
6. A process as claimed in any one of claims 1 to 5 wherein the oxide of carbon is carbon monoxide.
7. A process as claimed in any one of claims 1 to 6 wherein the temperature is between 100 C to 375"C.
8. A process as claimed in any one of claims 1 to 7 wherein the pressure is between 800 psia to 50,000 psia.
9. A process as claimed in claim 1, for producing alkane polyols substantially as hereinbefore described and with reference to any one of the examples.
10. A process as claimed in claim 1, for producing alkane polyols substantially as hereinbefore described and with reference to the accompanying drawings.
11. An alkane polyol whenever produced by a process as claimed in any one of claims 1 to 9.
12. An alkane polyol whenever produced by a process as claimed in claim 10.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (12)

**WARNING** start of CLMS field may overlap end of DESC **. Table P. 1, 10-Ph en an thro line as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 240 0.50 3.4 1.7 61 + 6 " 1.0 3.3 2.4 76 + 6 2.0 3.6 4.0 76 + 6 3.0 3.4 4.4 73 + 4 5.0 3.4 5.3 77 + 5 " 7.0 1.7, 2.6, 2.6 3.0, 3.9, 3.9 56 + 3, 69 + 4, 74 + 4 10.0 3.0, 2.7 4.7, 4.8 77 + 3, 77 + 4 15. 3.2 4.9 74 + 5 20. 2.5 4.3 77 + 5 Table S. Quinuclidine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, % Sulfolane, 220 0 0.4 0.0 11 + 21 " 0.63 2.5 3.5 76 + 7 1.25 4.1 1.7 90 + 9 WHAT WE CLAIM IS:
1. A process for producing alkane polyols having from 2 to 4 carbon atoms which comprises reacting carbon monoxide and hydrogen in a homogeneous liquid phase mixture containing a rhodium carbonyl complex catalyst and a nitrogen Lewis base promoter; the catalyst concentration, the temperature and the pressure being correlated so as to produce such alkane polyol; the promoter being provided in combination with the catalyst in an amount to achieve not less than 50% of the optimum rate of formation of the alkane polyol at said correlated catalyst concentration temperatures and pressure of said mixture, and in which the amount of the promoter is greater than the amount which is sufficient to produce such optimum rate of formation.
2. A process as claimed in claim 1 wherein the mixture contains a solvent.
3. A process as claimed in claim 2 wherein the solvent is tetraglyme.
4. A process as claimed in claim 2 wherein the solvent is sulfolane.
5. A process as claimed in any one of claims 1 to 4 wherein the mixture contains a salt therein.
6. A process as claimed in any one of claims 1 to 5 wherein the oxide of carbon is carbon monoxide.
7. A process as claimed in any one of claims 1 to 6 wherein the temperature is between 100 C to 375"C.
8. A process as claimed in any one of claims 1 to 7 wherein the pressure is between 800 psia to 50,000 psia.
9. A process as claimed in claim 1, for producing alkane polyols substantially as hereinbefore described and with reference to any one of the examples.
10. A process as claimed in claim 1, for producing alkane polyols substantially as hereinbefore described and with reference to the accompanying drawings.
11. An alkane polyol whenever produced by a process as claimed in any one of claims 1 to 9.
12. An alkane polyol whenever produced by a process as claimed in claim 10.
GB40356/76A 1975-09-30 1976-09-29 Enhancing the promoting of the catalytic process for making polyhydric alcohols Expired GB1565979A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4421863A (en) * 1982-02-01 1983-12-20 Texaco Inc. Process for preparing low molecular weight oxygenated compounds from syngas using a novel catalyst system
US4724241A (en) * 1986-05-10 1988-02-09 Basf Aktiengesellschaft Preparation of ethylene glycol

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2326399A1 (en) * 1975-09-30 1977-04-29 Union Carbide Corp PROCESS FOR THE PRODUCTION OF AN ALKANE-POLYOL
US4111975A (en) * 1977-03-30 1978-09-05 Union Carbide Corporation Catalytic process for producing polyhydric alcohols and derivatives
CA1099296A (en) * 1977-05-26 1981-04-14 Leonard Kaplan Enhancing the promoting of a catalytic process for making polyhydric alcohols
US4115428A (en) * 1977-09-29 1978-09-19 Union Carbide Corporation Catalyst and process for producing polyhydric alcohols and derivatives

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Publication number Priority date Publication date Assignee Title
US3833634A (en) * 1971-12-21 1974-09-03 Union Carbide Corp Manufacture of polyfunctional compounds
CA1069540A (en) * 1975-01-02 1980-01-08 Union Carbide Corporation Catalytic process for polyhydric alcohols and derivatives
FR2326399A1 (en) * 1975-09-30 1977-04-29 Union Carbide Corp PROCESS FOR THE PRODUCTION OF AN ALKANE-POLYOL

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4421863A (en) * 1982-02-01 1983-12-20 Texaco Inc. Process for preparing low molecular weight oxygenated compounds from syngas using a novel catalyst system
US4724241A (en) * 1986-05-10 1988-02-09 Basf Aktiengesellschaft Preparation of ethylene glycol

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NL7610785A (en) 1977-04-01
FR2326398A1 (en) 1977-04-29
FR2326398B1 (en) 1980-10-24
CA1091697A (en) 1980-12-16
DE2643897C2 (en) 1982-02-11
BE846709A (en) 1977-03-29

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