CA1091697A - Enhancing the promoting of the catalytic process for making polyhydric alcohols - Google Patents
Enhancing the promoting of the catalytic process for making polyhydric alcoholsInfo
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- CA1091697A CA1091697A CA262,263A CA262263A CA1091697A CA 1091697 A CA1091697 A CA 1091697A CA 262263 A CA262263 A CA 262263A CA 1091697 A CA1091697 A CA 1091697A
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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
- B01J31/1815—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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- B01J31/02—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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- B01J31/00—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
- B01J31/0239—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
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- 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
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- 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
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- 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
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- 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
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- 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
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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
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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
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- 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
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- 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
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- 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
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Abstract
ENHANCING THE PROMOTING OF A CATALYTIC PROCESS
FOR MAKING POLYHYDRIC ALCOHOLS
ABSTRACT OF THE DISCLOSURE
This invention relates to the manufacture of such valuable chemicals as polyhydric alcohols, their ether and ester derivatives, oligomers of such alcohols and monohydric alcohols and their ether and ester deriv-atives by reacting hydrogen and oxides of carbon in the presence of a rhodium carbonyl complex in combination with amine promoters which provide catalyst stability while maintaining high productivity and ease of process control.
1.
FOR MAKING POLYHYDRIC ALCOHOLS
ABSTRACT OF THE DISCLOSURE
This invention relates to the manufacture of such valuable chemicals as polyhydric alcohols, their ether and ester derivatives, oligomers of such alcohols and monohydric alcohols and their ether and ester deriv-atives by reacting hydrogen and oxides of carbon in the presence of a rhodium carbonyl complex in combination with amine promoters which provide catalyst stability while maintaining high productivity and ease of process control.
1.
Description
~ 10,555 This in~-cntion is concerned with the manu-facture of polyhydric alcohols, their ether and ester derlvatives, and oligomers of such alcohols. This invention also produces monohydric alcohols such as methanol, and their ether and ester derivatives.
It is know that monofunct~onal 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 250C to 500C, using mixtures of copper, chromium and zinc oxides as the catalyst therefor. It is dis-closed in U.S. Patent No. 2,451,333 that polyhydroxyl compounds are produced by reaction of formaldehyde, car-bon monoxide, and hydrogen in the presence of hydrogen-ation catalysts. It has also been reported that formal-dehyde can be produced by reaction between carbon mon-oxide and hydrogen at elevated pressures but repeated attempts to carry out this synthesis of formaldehyde have invariably failed to yield any substantial quantity of -Z0 the desired product. It is generally recognized that ~he previously disclosed processes for the synthesis of ormaLdehyde from carbon monoxide and hydrogen at high pressures are either completely inoperative or else give r~se to insignificantly small quanti~ies of formaldehyde.
In British 655,237, published July 11, 1951, there is disclosed the reaction between carbon monoxide and hydrogen at elevated pressures and temperatures,
It is know that monofunct~onal 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 250C to 500C, using mixtures of copper, chromium and zinc oxides as the catalyst therefor. It is dis-closed in U.S. Patent No. 2,451,333 that polyhydroxyl compounds are produced by reaction of formaldehyde, car-bon monoxide, and hydrogen in the presence of hydrogen-ation catalysts. It has also been reported that formal-dehyde can be produced by reaction between carbon mon-oxide and hydrogen at elevated pressures but repeated attempts to carry out this synthesis of formaldehyde have invariably failed to yield any substantial quantity of -Z0 the desired product. It is generally recognized that ~he previously disclosed processes for the synthesis of ormaLdehyde from carbon monoxide and hydrogen at high pressures are either completely inoperative or else give r~se to insignificantly small quanti~ies of formaldehyde.
In British 655,237, published July 11, 1951, there is disclosed the reaction between carbon monoxide and hydrogen at elevated pressures and temperatures,
- 2. g,, above 1500 atmospheres at temperatures up to .
2 ~ ~
10,555 ,S~
400C, 3 using certain hydrogenation catalysts as exempli-fied 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 abbve 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 predomin-àntly a catalyst for synthesis and for reforming methane according to the reaction CO ~ 3H2~ CH4 + H20 whose equilibrium favors the right hand side of the equation at temperatures below about 500C. and the left hand side o~ 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 saised the dire prediction of a significant oil shortage in the future. The consequence of thls 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 ~f making alkane diols and triols, containing 2, 3 or 4 carbon atoms, and derivatives such as their esters. Key products of the process o~ this invention are ethylene O 3.
7 10,555 glycol and lts ester derlvatives. Byproducts of this invention are the lesser valuable, but valuable neverthe-less, 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.S. Patent 3,833,634, issued September 3, 1974, 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 involve reacting a mixture of an oxide of carbon and hydrogen with a catalytic amount of rhodium in complex combination with carbon mon-oxide, at a temperature of between about 100C. to about 375C. and a pressure of between about 500 p.s.i.a. to about 50,000 p.s.i.a. The patent discusses 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.S. Patent 3,957,857, issued May 18, 1976, which is commonly assigned. Both 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 'lligands" and amines can be considered to promote the activity of the catalyst. Since the filing of 4.
10,555
2 ~ ~
10,555 ,S~
400C, 3 using certain hydrogenation catalysts as exempli-fied 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 abbve 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 predomin-àntly a catalyst for synthesis and for reforming methane according to the reaction CO ~ 3H2~ CH4 + H20 whose equilibrium favors the right hand side of the equation at temperatures below about 500C. and the left hand side o~ 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 saised the dire prediction of a significant oil shortage in the future. The consequence of thls 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 ~f making alkane diols and triols, containing 2, 3 or 4 carbon atoms, and derivatives such as their esters. Key products of the process o~ this invention are ethylene O 3.
7 10,555 glycol and lts ester derlvatives. Byproducts of this invention are the lesser valuable, but valuable neverthe-less, 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.S. Patent 3,833,634, issued September 3, 1974, 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 involve reacting a mixture of an oxide of carbon and hydrogen with a catalytic amount of rhodium in complex combination with carbon mon-oxide, at a temperature of between about 100C. to about 375C. and a pressure of between about 500 p.s.i.a. to about 50,000 p.s.i.a. The patent discusses 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.S. Patent 3,957,857, issued May 18, 1976, which is commonly assigned. Both 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 'lligands" and amines can be considered to promote the activity of the catalyst. Since the filing of 4.
10,555
3 ~
the applications which issued to U.S. 3,833,634, 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 tying 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 tQrms of the results they achieve; hence, for the purpose 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 con-centrations the productivity of such polyols would be materially and unexpectedly enhanced. In copending Canadian application Serial No. 262,265, filed September 29, 1976, it is established that there is a specific concentration for each such promoter which will provide the optimum 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 the most favorable balance between the promoting and inhibiti.ng effects of such promoters.
;- 5.
. ~
~391~9~ lo, 555 The process o~ this invention and t~e invention o aforementioned copending Canadian application Serial No. 262,265 involves the production of alkane polyols of two to four carbon atoms 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 oxides of carbon, particularly carbon monoxide, and hydrogen in a homogeneous liquid phase reaction mixture containing a rhodium carbonyl complex in combination with a nitrogen Lewis base promoter. The ca~alyst concentration, the temperature and the pressure during the reaction are correlated so as to result in the production of alkane polyol. In the aforementioned copending Canadian application Serial No. 262,265, the promoter provided to the mixture is present in an amount determined from the promoter's basici~y to achieve the optimum rate of formation of said alkane polyol at the correlated catalyst concentration, temperature and pressure of such reaction mixture.
This 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:
.~ 6.
, .
. 10,555 a.) the inhibitor function of the amine is of higher ~inetic order in amine than is the promoter function;
b.) the promoter function of the amine has a stoichi~metric 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 ab~ve postulates can be illustrated by the following reaction scheme: .
~n-m)amine (I) Rh ~ m(amine)~ Rh(amine)m~ ~ - Rh(amine~
alkane polinl Pr~moter Function ' 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 wlth the option of a chan~ing number of CO's and H's;
the rate and equilibri~m constants implicity contain any appr~priate CO and ~ concentrations.]
-. .
~ 10,555 In the above scheme, the amine aids productiono~ glycol by forming a more activ~ 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 re-action scheme is that, if the rate of glycol formation passes through a maximum as a function of the concentra-tion of the amine, the amine concentration which corres-ponds 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 obs~rved 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:
(II) Rh + amine ~ ~Rh amineH+ <~ aRh + amineH+]
alkane polyol ~Note: Rh is defined as above in the note to equation (I)~
In equation (II~ the amine acts as a promoter because it helps to produce the active catalyst and as an inhibitor because its conju~ate acid has an adverse ~ 6 ~ ~ 10,555 mass law effect on ~he equili~rium 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 insure 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 as regards alkane polyol production because there is a consequent production of more amineH+, 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 ~o 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 ~he 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~ , presumably via the hydroxyl pool, increases to a limiting value of 1.
Thus, the invention of a~orementioned copending Canadian application Serial No. 262~265 contemplates the recognition that there is an appropriate optimum ~' 9.
10,555 concentration for nitrogen Lewis base promoters to achieve maximum alkane polyol production and that amounts in excess of that optimum concentration, in the typical case, will act to inhibit alkane polyol production. It is the contemplation of this invention that the concentra-tion of the promoter should be in excess of said optimum concentration for the purpose of enhancing catalys~
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 optimum concentration will reduce the criticallity which would otherwise be imposed by having to operate the process under strict control of promoter concentrati~n.
The process o~ this 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 maximum yield of alkane polyol obtainable with such promoter and the yield of alkane polyol is not decreased ~r~m the maximum by more than 50%.
As pointed out previously, there are two ~ac-tors which govern the inhibitory ability of the promoter and, hence, the concentration o~ the promoter which can be used according to this invention. They are 10 .
~`~9:~9~7 lo, 555 the basicity of the promoter and the ion pairing qualities of the protonated version of the promoter [l/K' of reaction scheme (II?]. 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 minimum amount predicated on the amines basicity for producing the maximum amount of alkane polyols, particularly ethylene glycol, obtainable using that promoter. In aforementioned copending Canadian application Serial No. 262,265, the invention involves the selection of an amount of the promoter, based on its basicity, 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 .~ ~
...^ -, 10,555 ~1~9~6.q..~
inorgznic compounds. With respect to the organic c~mpounds, the carbon atoms can be part of an acyclic ~nd/or cyclic radical such as aliphatic, cycloaliphatic, ar~matic (including fused and bridged) carbon radicals, and the like. Preferably, the organic Lewis bases contain frcm 2 to 60, most preferably 2 to 40 carbon atDms. The nitrogen at~ms can be in the f~rm of ~mino (-N~), amino (-N-), nitrilo (N~), e~c. Desirably, the Lewis base nitrogen atoms are in the form of ~mino nitrogen and/or amino nitrogen. The oxygen atoms can be in the form of groups such as hydroxyl (aliphatic or .. ~.
phenolic), carboxyl (-COH), carbonyloxy (-CO-~, oxy (-O-), ., carbonyl (-C-), etc., all of said groups containing Lewis base oxygen at~ms. In this respect, it is the o "hydroxyl" oxygen in the -COH group and the "oxy"
o oxygen in the DCO- group that are acting as Lewis base atoms. The organic Lewis bases may also contain o~her 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 alkanolæmines, such as, e~hanolamine, - diethanol~mine, isopropanolamine, di-n-propanolamine, and the like; N,N-dLmethylglycine, N,N-diethylglycine;
~minodiacetic acid, N-methyliminodiacetic acid;
N-methyldiethanolamine; 2-hydroxypyridine, 2,4 dihydroxy-pyridine, 2-methoxypyridine, 2,6-dimethoxypyridine, 2-ethoxypyridine; lower alkyl substituted hydroxypyridines, 12.
~ 5 3 ,~L4~r~3 ;~ ~
such as 4-me~hyl-2-hydroxypyridine, 4-methyl-2,6~di-hydroxypyridine, and the like; morpholine, substituted morpholines, such as 4-me~hylmorpholine, 4-phenyl-morpholine; picolinic acid, methyl-substituted picolinic acid; nitrilotriacetic acid, 2,5-dicarboxypiperazine, N-(2-hydroxyethyl) iminodiacetic acid, ethylene-diaminetetraaceti~ acid; 2,6-dicarboxypyridine;
8-hydroxyquinoline, 2-carboxyquinoline, cyclo-hexane-1,2-di~mine-N,N,N',N'-tetraacetic acid, the tetramethyl ester of ethylenediamine-tetraacetic acid, and the like.
Other Lewis base nitrogen containing compounds include organic and inorganic amines.
Illustrative of such inorganic amines are~
e.g., ammonia, hydroxylamine, and hydrazine. Primary, secondary, or tert~ary organic amine are promoters. This.
includes the mono- and polyamines (such as di-, ~ri-, tetra~mines, etc.) and those compounds in which the Lewis base nitrogen forms part of a ring structure as in pyridine, quinoline, pyr~midine, morpholine, hexamethylene tetraamine, and the like. In addition any compound capable of yielding an amino ni~rogen under the reaction conditions of the present invention are pr~moters, as in ~he 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-propylæmine, isopropylamine, octylamine, dodecylamine, dimethyl~mine, diethylamineg diisoæmylamineg methylethylamine, diisobutylamine, trimethylamine, me~hyldiethylamine, triisobutylamine, ~ridecylæmine, and the -13.
n 10,555 ~ .~7 like; aliph~tic and aromat~c di- and polyamincs such as 1,2-e~hanediæmine, 1,3-propanediamine, N,N,N',N'-tetramethylenediamine, N,N,Nf,N~-tetraethylethylene-diamîne, N,N,N',N'-tetra-n-propylethylenediamine 7 N,N,Nr~N'-tetrabu~ylethylenediamine, o-phenylene-diamlne, m-phenylenediamine, ~-phenylenediamine, ~-tolylenediamine, o-tolidene, N,N,N',N'-tetra-methyl-p-phenylenediamine, N,N,N',N'-tetraethyl-
the applications which issued to U.S. 3,833,634, 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 tying 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 tQrms of the results they achieve; hence, for the purpose 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 con-centrations the productivity of such polyols would be materially and unexpectedly enhanced. In copending Canadian application Serial No. 262,265, filed September 29, 1976, it is established that there is a specific concentration for each such promoter which will provide the optimum 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 the most favorable balance between the promoting and inhibiti.ng effects of such promoters.
;- 5.
. ~
~391~9~ lo, 555 The process o~ this invention and t~e invention o aforementioned copending Canadian application Serial No. 262,265 involves the production of alkane polyols of two to four carbon atoms 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 oxides of carbon, particularly carbon monoxide, and hydrogen in a homogeneous liquid phase reaction mixture containing a rhodium carbonyl complex in combination with a nitrogen Lewis base promoter. The ca~alyst concentration, the temperature and the pressure during the reaction are correlated so as to result in the production of alkane polyol. In the aforementioned copending Canadian application Serial No. 262,265, the promoter provided to the mixture is present in an amount determined from the promoter's basici~y to achieve the optimum rate of formation of said alkane polyol at the correlated catalyst concentration, temperature and pressure of such reaction mixture.
This 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:
.~ 6.
, .
. 10,555 a.) the inhibitor function of the amine is of higher ~inetic order in amine than is the promoter function;
b.) the promoter function of the amine has a stoichi~metric 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 ab~ve postulates can be illustrated by the following reaction scheme: .
~n-m)amine (I) Rh ~ m(amine)~ Rh(amine)m~ ~ - Rh(amine~
alkane polinl Pr~moter Function ' 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 wlth the option of a chan~ing number of CO's and H's;
the rate and equilibri~m constants implicity contain any appr~priate CO and ~ concentrations.]
-. .
~ 10,555 In the above scheme, the amine aids productiono~ glycol by forming a more activ~ 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 re-action scheme is that, if the rate of glycol formation passes through a maximum as a function of the concentra-tion of the amine, the amine concentration which corres-ponds 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 obs~rved 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:
(II) Rh + amine ~ ~Rh amineH+ <~ aRh + amineH+]
alkane polyol ~Note: Rh is defined as above in the note to equation (I)~
In equation (II~ the amine acts as a promoter because it helps to produce the active catalyst and as an inhibitor because its conju~ate acid has an adverse ~ 6 ~ ~ 10,555 mass law effect on ~he equili~rium 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 insure 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 as regards alkane polyol production because there is a consequent production of more amineH+, 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 ~o 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 ~he 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~ , presumably via the hydroxyl pool, increases to a limiting value of 1.
Thus, the invention of a~orementioned copending Canadian application Serial No. 262~265 contemplates the recognition that there is an appropriate optimum ~' 9.
10,555 concentration for nitrogen Lewis base promoters to achieve maximum alkane polyol production and that amounts in excess of that optimum concentration, in the typical case, will act to inhibit alkane polyol production. It is the contemplation of this invention that the concentra-tion of the promoter should be in excess of said optimum concentration for the purpose of enhancing catalys~
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 optimum concentration will reduce the criticallity which would otherwise be imposed by having to operate the process under strict control of promoter concentrati~n.
The process o~ this 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 maximum yield of alkane polyol obtainable with such promoter and the yield of alkane polyol is not decreased ~r~m the maximum by more than 50%.
As pointed out previously, there are two ~ac-tors which govern the inhibitory ability of the promoter and, hence, the concentration o~ the promoter which can be used according to this invention. They are 10 .
~`~9:~9~7 lo, 555 the basicity of the promoter and the ion pairing qualities of the protonated version of the promoter [l/K' of reaction scheme (II?]. 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 minimum amount predicated on the amines basicity for producing the maximum amount of alkane polyols, particularly ethylene glycol, obtainable using that promoter. In aforementioned copending Canadian application Serial No. 262,265, the invention involves the selection of an amount of the promoter, based on its basicity, 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 .~ ~
...^ -, 10,555 ~1~9~6.q..~
inorgznic compounds. With respect to the organic c~mpounds, the carbon atoms can be part of an acyclic ~nd/or cyclic radical such as aliphatic, cycloaliphatic, ar~matic (including fused and bridged) carbon radicals, and the like. Preferably, the organic Lewis bases contain frcm 2 to 60, most preferably 2 to 40 carbon atDms. The nitrogen at~ms can be in the f~rm of ~mino (-N~), amino (-N-), nitrilo (N~), e~c. Desirably, the Lewis base nitrogen atoms are in the form of ~mino nitrogen and/or amino nitrogen. The oxygen atoms can be in the form of groups such as hydroxyl (aliphatic or .. ~.
phenolic), carboxyl (-COH), carbonyloxy (-CO-~, oxy (-O-), ., carbonyl (-C-), etc., all of said groups containing Lewis base oxygen at~ms. In this respect, it is the o "hydroxyl" oxygen in the -COH group and the "oxy"
o oxygen in the DCO- group that are acting as Lewis base atoms. The organic Lewis bases may also contain o~her 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 alkanolæmines, such as, e~hanolamine, - diethanol~mine, isopropanolamine, di-n-propanolamine, and the like; N,N-dLmethylglycine, N,N-diethylglycine;
~minodiacetic acid, N-methyliminodiacetic acid;
N-methyldiethanolamine; 2-hydroxypyridine, 2,4 dihydroxy-pyridine, 2-methoxypyridine, 2,6-dimethoxypyridine, 2-ethoxypyridine; lower alkyl substituted hydroxypyridines, 12.
~ 5 3 ,~L4~r~3 ;~ ~
such as 4-me~hyl-2-hydroxypyridine, 4-methyl-2,6~di-hydroxypyridine, and the like; morpholine, substituted morpholines, such as 4-me~hylmorpholine, 4-phenyl-morpholine; picolinic acid, methyl-substituted picolinic acid; nitrilotriacetic acid, 2,5-dicarboxypiperazine, N-(2-hydroxyethyl) iminodiacetic acid, ethylene-diaminetetraaceti~ acid; 2,6-dicarboxypyridine;
8-hydroxyquinoline, 2-carboxyquinoline, cyclo-hexane-1,2-di~mine-N,N,N',N'-tetraacetic acid, the tetramethyl ester of ethylenediamine-tetraacetic acid, and the like.
Other Lewis base nitrogen containing compounds include organic and inorganic amines.
Illustrative of such inorganic amines are~
e.g., ammonia, hydroxylamine, and hydrazine. Primary, secondary, or tert~ary organic amine are promoters. This.
includes the mono- and polyamines (such as di-, ~ri-, tetra~mines, etc.) and those compounds in which the Lewis base nitrogen forms part of a ring structure as in pyridine, quinoline, pyr~midine, morpholine, hexamethylene tetraamine, and the like. In addition any compound capable of yielding an amino ni~rogen under the reaction conditions of the present invention are pr~moters, as in ~he 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-propylæmine, isopropylamine, octylamine, dodecylamine, dimethyl~mine, diethylamineg diisoæmylamineg methylethylamine, diisobutylamine, trimethylamine, me~hyldiethylamine, triisobutylamine, ~ridecylæmine, and the -13.
n 10,555 ~ .~7 like; aliph~tic and aromat~c di- and polyamincs such as 1,2-e~hanediæmine, 1,3-propanediamine, N,N,N',N'-tetramethylenediamine, N,N,Nf,N~-tetraethylethylene-diamîne, N,N,N',N'-tetra-n-propylethylenediamine 7 N,N,Nr~N'-tetrabu~ylethylenediamine, o-phenylene-diamlne, m-phenylenediamine, ~-phenylenediamine, ~-tolylenediamine, o-tolidene, N,N,N',N'-tetra-methyl-p-phenylenediamine, N,N,N',N'-tetraethyl-
4,4'-biphenyldiamine, and the like; aromatic amines .
such as aniline, l-naphthylamine, 2-naphthylamine, ~-toluidine, o-3-xylidine, p-2-xylidine, benzylamine, 'diphenylamine, dimethylaniline, diethylaniline, N-phenyl-l-naphthylamine, bis (l,8)-dimethylamino-naphthalene, and the like; alicyclic amines such as cyclohexylamine, dicyclohexylamine, and the like;
heterocyclic amines such-as-piperidine-; substituted . piperidines such as 2-methylpiperidine, 3-methyl-piperidine, 4-ethylpiperidine, and 3-phenylpiperidine, pyridine; substituted pyridines such as 2-methyl-pyridine, 2-phenylpyridine, 2-methyl-4-ethylpyridine, 2,4,6j-trimethylpyridine, 2-dodecylpyridine, 2-chloropyridine, and 2-(dimethylamino)pyridine;
quinoline; substituted quinolines, such as 2-(dimethyl-~mino~-6-methoxyquinoline; 4,5-phenanthroline;
1,8-phenanthroline; 1,5-phenanthroline; piperazine;
substituted piperazines such as N-methylpiperazine, N-ethylpiperazine, 2-methyl-N-methylpiperazine;
2,2'-dipyridyl, methyl-substituted 2,2l-dipyridyl;
ethyl-substituted 2,2~-dipyridyl; 4-triethyl-14.
.
, _ __ __ '' ' 10 555 9'~ 6 silyl-2,2'-dipyridyl; 1,4-dlazabicyclo[2.2.2~octane, methyl substituted l,4-diazabicyclo~2.2.2~octane, purine ànd ~he like.
In order to determine that n excess of the promoter is being employed, it is necessary to appreciate how to select a concentratio~ of promoter which achieves maximum yield of alkane polyol. The pr~moter is provided in the homogeneous reaction mixture in an amount determined from its basicity to achieve the maximum yield. 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 predicate~ on basicity is not intended to mean that o~ necessity the promoter is or -' becomes a cation in the homogeneous mixture as no~ed in the previous discussion relative ~o the so-called "ligands" and amines, and their function in the catalytic 2 û reaction .
It has been found ,that the opt~mum 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 achie~es the optimum yield obtainable wi~h that promo~er.
On the other hand, it has been found that as the base bec~mes progressi~ely weaker, a greater and greater amount o~ the base is needed to achieve the maximum yield o the alkane polyol.
15.
.. ..
10,555 9'~
The e~feo~s of cDncentration of the nitrogen Lewis base promoter ln the homogéneous liquid phase mixture of the process of ~his invention has been fDund to he dependent upon the tempera~ure and, tD some degree, the pressure of the reaction and the rhodium c~ncentration 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 tc 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 a to about
such as aniline, l-naphthylamine, 2-naphthylamine, ~-toluidine, o-3-xylidine, p-2-xylidine, benzylamine, 'diphenylamine, dimethylaniline, diethylaniline, N-phenyl-l-naphthylamine, bis (l,8)-dimethylamino-naphthalene, and the like; alicyclic amines such as cyclohexylamine, dicyclohexylamine, and the like;
heterocyclic amines such-as-piperidine-; substituted . piperidines such as 2-methylpiperidine, 3-methyl-piperidine, 4-ethylpiperidine, and 3-phenylpiperidine, pyridine; substituted pyridines such as 2-methyl-pyridine, 2-phenylpyridine, 2-methyl-4-ethylpyridine, 2,4,6j-trimethylpyridine, 2-dodecylpyridine, 2-chloropyridine, and 2-(dimethylamino)pyridine;
quinoline; substituted quinolines, such as 2-(dimethyl-~mino~-6-methoxyquinoline; 4,5-phenanthroline;
1,8-phenanthroline; 1,5-phenanthroline; piperazine;
substituted piperazines such as N-methylpiperazine, N-ethylpiperazine, 2-methyl-N-methylpiperazine;
2,2'-dipyridyl, methyl-substituted 2,2l-dipyridyl;
ethyl-substituted 2,2~-dipyridyl; 4-triethyl-14.
.
, _ __ __ '' ' 10 555 9'~ 6 silyl-2,2'-dipyridyl; 1,4-dlazabicyclo[2.2.2~octane, methyl substituted l,4-diazabicyclo~2.2.2~octane, purine ànd ~he like.
In order to determine that n excess of the promoter is being employed, it is necessary to appreciate how to select a concentratio~ of promoter which achieves maximum yield of alkane polyol. The pr~moter is provided in the homogeneous reaction mixture in an amount determined from its basicity to achieve the maximum yield. 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 predicate~ on basicity is not intended to mean that o~ necessity the promoter is or -' becomes a cation in the homogeneous mixture as no~ed in the previous discussion relative ~o the so-called "ligands" and amines, and their function in the catalytic 2 û reaction .
It has been found ,that the opt~mum 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 achie~es the optimum yield obtainable wi~h that promo~er.
On the other hand, it has been found that as the base bec~mes progressi~ely weaker, a greater and greater amount o~ the base is needed to achieve the maximum yield o the alkane polyol.
15.
.. ..
10,555 9'~
The e~feo~s of cDncentration of the nitrogen Lewis base promoter ln the homogéneous liquid phase mixture of the process of ~his invention has been fDund to he dependent upon the tempera~ure and, tD some degree, the pressure of the reaction and the rhodium c~ncentration 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 tc 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 a to about
5. By pK, it is meant the acid dissociation constant of the conjugate acid of the nitrogen Lewis base ~n water at 25C.
The optimum concentrati~n of an untried pr~moter is determinable on a relative scale by cDmparing the pK
of that promot~r to those set forth in Table I below 16.
10~555 and ~clecting a concentra~ion acc~rding to the pIC
relationships and trends ~ndicated. Overall, the optimu~ concentration of promoter one can e~ploy 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 pr~moter .
basicity available.
~ 7.
~ 7 10,555 TA~LE I
Optimun*
Other Moles Promoter Amine/
Amine pK~ Solvent Temp. Present Mole Rh 1,8-bis(dimethyl- 12.3 Sulfolane 2400 _ ~ 0.1 amino)-- naphthalene Sparteine 12.0 " " - 0.2-0.3 " " " 260 - 0.4-0.7 Dibutylamine 11.3 " 240 - 0.3-0.5 Piperidine 11.1 " 220 - 0.3-0.5 Triethylamine10.7 " 240 - 0.3 N-methyl piperidine10.4 " " - 0.3-0.5 Piperazine 9.7 " 240 - 0.3~0.5 4-dimethylamino-pyridine 9.6 " 220 - ~J 0.2 Ammonia TM 9.3 " 240 - O.3 Amberlite-IRA-93 9.0 " " - 0.3-0.5 1,4-diazabicyclo [2.2.2] octane 8.8 " 220 - 0.1 " " " " 240 - 0.2-0.3 2,4,6-trimethyl-pyridine 7.4 " 240 - 0.2-0.3 N-methylmorpholine 7.4 " " - 0.3_0.4 Trimethylenedi-morpholine7.3 " 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 " " " "HC02CS 0.2-0.4 ~' " " 230PhC02CS 0.3-0.6 l.10-phenanthro-line 4.8Sulfolane 240 - 1.6 Aniline 4.6 " " - 2-3 2-hydroxypyridine 0.8tetraglyme 220Cs2-pyri- ~1 dinolate -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.
t H20, 25~
10,555 The ion pairing a~ilities 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 pair-ing ability.
19 .
10, 555 JJ
oo U~ U~ ~ ~ ~ o ~
~l ~ ~ ~ ~ o ~J . , N , ~4 .
o ~ ' ~
U~ O ~
~ ~ C~,., C , C~
a~ ~:1 N ~
. ~ ~ ~
U) C ,~0, ~ '~- Z
N~
" ~1 O 1~
~_ ¢ ~d h ~~ ~ u l o 1:
., ~ P: .
PC1 ~
p o ~d .U~ . ~ P
a +~+
) V~ $
20 .
.. . . .. .
10~ ss5 ~L~3 3 ~; r3~7 c.) . ~
O ~1 /
h ~/ ~
g .a~
o ~4 ,. a ~:: U
td ~ O
C.7 ~ O
~ '~
E~ C~
o Ll~
_~ 01 ~ U) U~
O O
o^l~ a~
O c~ ~ a E~ O N
., ~ tl~ ' .. ,~ _ J~
o--~
: ~_, ~ X U~
V' ,.
, 10,555 3~
~ LE III
Ion Pairin~ Ability of Ammonium Ions in Nitrobenzene Cation pKdissocn (M, 25 ? of Ion ~air wlth Picrate NH4 3.8b PrNH3~ 3 gc 3 3 8b'C
Et2NH2~ 3.7C
BU2NH2~ 3 8b Me NH~ 3.8 Et3N~ 3.7 Bu3NH+ . 3 7b,e Piperidinium 3.8 PhNH3~ 4.7b PhNHMe ~ 3.9a,f, 4.4b PyH~ . 4.3 aActivity-based. bC. R. Witschonke and C. A. Kraus, J.~Am.
. Chem. Soc., 69, 2472 (1947). cJ. Macau and L. Lamberts, ~.
Chim. Phys., 67, 633 (1970). dE. G. Taylor and C. A. Kraus, J. hm. Chem. Soc., 69, 1731 (1947). eJ. B. Ezell and W. R.
Gilkerson, J. Phys. Chem., 72, 144 (1968). fH. W. Aitken and W. R. Gilkerson, J. Am. Chem. Soc., 95, 8551 (1973).
, 10,555 Acetonitrile and nitrobenzene are similar to sul~olane in that they are dipolar aprotic solvents and their dielectric constants are similar to sulf~lane (-43). The dielectric constant for acetonitrile is 36 and nitr~benzene is 35.
Thus from a consideration of the ion pairing ability data recited in Tables II and III above, plus consideration of ~he factors affecting "F-strain" (See H. C. Brown, Boranes in Organic Chemistry, Cornell University Press, 1972, starting at page 102), to which is added general concepts of electrostatic~,permits the prediction of ion pairing ability to the rhodium catalyst _ which with the aforemention discussion of basicity allows for the ready selection of an appropriate amine promoter in ~he aforemention homogeneous liquid phase reaction .... . . . .
For the purpose of aiding the characterization of this invention re~erence is made to Table IV and the drawings to graphically depict the yield of ethylene glycol to the concentration of certain amine promoters.
20 Table IV.lists a variety amines tested as promoters under the conditions characteri~ed in footnot~
.. , .. .. . . .. ~ . . .. . .. . .
a. The process procedure employed is recited in the examples below. The results are depicted in the enumerated Figures of Table IV.
The drawings, showing F~gures I through VI, graphically depict the effect that certain amine promoters have on the glycol yield. In particular, it is important l~J ~ir l~i~ 10,555 to note the effect of the amount of the amine on the glycol yield. The concentration of amine which gives the highest glycol yield is considered ~rom the standpoint of applicant's aforemen~ioned copending Canadian application Serial No. 262,265, to be the optimum concentration. However, from the standpoint of this invention, the utilization of an amount of amine in excess of the optimum concentration provides for the benefits described herein. For example, in regard to Figure II there is shown the effect that N-methylmorpholine has on the glycol yield when used in excess of an amount which is the minimum amount that achieves the optimum result. This particular effect on productivity is more readily appreciated from comparing the result of Figure II with Figure V.
A particularly desirable amine promoter is characterized in Figure VI. Ammonia is shown in Figure V to be a most desirable promoter. The data supporting the drawings can be found in the examples.
24.
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.
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e~ 10, 555 The observed (Figs. 3 5) relative inhibitory abilities of those amines in Table IV for which data are available in Table II or III are N~3 CEt3Nr~ 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 counteriGm than are aryl carboxylates, small differences in pKdissocn are of greater significance for picrate, the conjugate acids ion pairing ability is ordered as NH4+ Et3NH~ ~ BU2NH2+ <pyH~
This ranking must be considered along with the relative basicities of the amines (see above). Based on 1) basicity date (Table V below) in water and in the two solvents in which the ion pairing abilities were deter-mined and 2) the Ho function in sulfolane ~See R.W. Alder et alO, Chemical Communications, p. 405 (1966)], the pK's in sulfolane are ordered as Et3NH ~ Bu2NH2 ~ NH4 ~ PY
Thus, the observed inhibitory abilities of the amines may be explained in terms of 1) the conjugate acids of Et3N
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 Et3Nand Bu2NH but ammonia being less basic. Note that the effective ion pairing ability in sulfolane may, in the 26.
10~ 555 2 12 ~ RNH3, and especially NH ~ be decreased by H-bonding to each of the sulEone oxygens .
O' ~L~ ;7 10 ~ 5 5 S
T~BLE V
Acidity of Ammonium Ions, PKa (25) ....
H20 Acetonitrilea'b NitrobenzeneC
NH4~ 9.3 16.5 EtNH3 10.6 18.4 7 1 BuNH~+ 10.6 18.3 Et2NH2+11.0 18.8 7.1 ~l~2NH2+11.3 7.1d Et3NH+ 10.7 18.5 7.3 Bu3NH+ 11.0 18.1 7.3d pyH+ 5.2 12.3 2.1 a J.F. Coetzee and GoRo Padmanabhan, J. Am. Chem. Soc., 87, 5005 (1965).
bI.M. Kolthoff, M.K. Chantooni, Jr., and S. Bhowmik, ibid. 90, 23 (1968).
c D. Feakins, W.A. Last and R.A. Shaw, J. Chem. Soc., 2387 (1964).
dBased on 1) results for EtNH3+ vs. BuNH3+ in H20 and MeCN, Et2NH2 vs. Bu2NH2 in water, and Et3NH~ vs. Bu3NH+ in H20 and MeCN and 2) the constancy of t~e effects of solvent on pK, we estimate pK (Et2NH2+)~ pK ~Bu2NH2+) in MeCN and PhN02 and pK(Et3NH~) ~ pK(Bu3NH+) in PhN02.
28.
' 10,555 ~ '7 Relationships apparent rom the data referred to in Table IV are explained in Table VI. In order to minimiæe inhibition by the amine and obtain thereby, withDut 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 c~njugate acid's positive charge is not substantially localized on only one atom is particularly good.
29.
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The following examples are merely illustrative and are not presented as a definition of the limits of this invention.
Procedure employed in examples:
A 150 ml. capacity stainless steel reactor capable of withstanding pressures up ~o 7,000 atmo-spheres was charged with a premix of 75 cubic centi-meters (cc) o~ 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 190C, as measured by a suitably placed thermocouple, an additional adjust-ment of carbon monoxide and hydrogen (H2:C0=1:1 mole ratio) was made to bring the pressure back to 8000 psig.
The temperature (in C.) was maintained at the desired value for 4 hoursO 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 + 4G0 psig over the entire 4 hour period.
10,555 After the 4 hour period, the vessel and its contents were cooled ~o ro~m 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 TM 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 reac~or con-sisted of charging to the reactor 100 cc of the solvent used for that experLment, and bringing the reactor and it contents to a temperature of 160C.
and a pressure of 14,000 to 15,000 psig and main-taining these conditions for a period o~ 30 minutes.
The reactor was then cooled and the unreacted gases .
vented and an at~mic absorption analysis for rhodium was run Dn the reactor's contents. ~le rhodium recovery values recited beIow 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 t~me The same equipment and procedure were used i~ all the examples in Tables A-S except for the reactants and conditions specified The product weights in ~he Tables are reported in grams.
33' ._.. . . .
10,555 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 240~ 0.20 ~.4 0.8 34 + 5 " " 0.31 2.9 6.0 78 ~ 3 " " 0.63 2.7 5.1 67 +
" ll 0.94 2.8 5O0 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. SE~rteine as Promoter Weight of Conditions mmoles Product and other of Amine Reactants Promoter Methanol Glycol Rh Recover~%
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 34, . . lO,S55 Table. C. Dibutylamine as Promoter Conditions ~moles Weight of and other` of Amine Product reactants_ Promoter MetbanDl Glycoï 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, ~/O
~ .. ..... ~ .
Sulfolane, 220 0 0.4 0.0 11 + 21 " " ~.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 Tr_ethylamine as Promoter Conditions mmolesWeight o~
and other of AmineProduct -_ reactants Promoter Methanol Glycol Rh Recovery~ ~10 .
Sulfolane, . 240 0.65 3.3 2.2 71 + 7 " " 0.8 2.8 5.5 80 + 7 " " . 1.~5 3.5 . 5.1 79 + 5 " " 2.5 5.0 4.0 81 + 8 " " 7.0 4.0 2.2 80 + 8 35.
.
93 jL~ 7 10,555 Table F. N-Methylpiperidine as Promoter ConditionsmmolesWeight of and otherof AmineProduc~
ReactantsPromoterMethanol _lycol Rh Recovery, V/o Sulfolane 2400.63 3.0 3.0 66 ~ 3 " " 0O94 2.6 5.0 ~ 65 " " 1.25 3.5 4.~ 69 + 7 " " 2.5 4.5 3.8 86 ~ 7 Table G. Pieerazine as Promoter Conditionsmmoles~eight of and otherof AmineProduct ReactantsPromoterMethanol Glycol Rh Recovery, %
Sulfolane 2400,65 2.5 4.6 60 + 14 " " 1025 3.8 6.1 71 + 6 " " 2.5 4.6 5.1 83 ~ 4 Table I. Ammonia as Promoter ConditionsmmolesWeight of and otherof AmineProduct ReactantsPromoterMethanol ~ 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 6.6,5.3,52 84+6,77+9, 83 255 2.7,3.33361 5.4,58.0,5.1 691+4,50+4, 84 " " 2.0 4.6 4 6 83 + 8 " " 2.5 4.6 4.8 78 + 5 " " 10. 2.3 1.6 84 + 5 36.
10~ 555 31. i3~ ~ fi r3 ~
Tabl~ I~. 1 4-Diazabicy~lo ~2.2.2~ octanc as Pr~moter _._ __. _ . . __ ___ _~ ~_ _ _____~_ , . _ _ _ . _ _ Conditions mmoles Weight of and other of Amine Product reactan~s Pr~moter Methanol Glycol Rh Recovery, %
_ Sulf~lane, 220 .0 0,~ 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 ~.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 omoter Methanol Glycol 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 7;7 ~ 4 : " " 5.0 4.9 ~.5 . 76 + 3 . _ ., Table M. N-Methylmorpholine as Promo~er .` Conditions mmoles Weight of . and other of Amine Product _ reactants Promoter Methanol Glycol Rh Recovery7 7O
_ _ .
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 +
Sulfolane, 250C 7.0 3.6 6.4 64 ~ 3 11.0 4.6 6.0 67 + 7 " " ~0. 5.4 ~.4 ~9 + 6 .
.
10 ,555 Table N. Trimethylenedimorpholine as Promoter ConditionsmmolesWeight of and otherof AmineProduct reactarlts Promoter Methanol Glycol 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 " ll 12.0 5.1 6.0 77+5 Table 0. ridine as Promoter Conditions ~noles Weight of and otherof Amine Product _ reactantsPromoter Methanol Glycol Rh Recovery, %
Sulfolane, 220 0 0.4 0.0 11 + 21 " " 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, 0.312.4, 2.6 2.1, 5.7 74 ~ 4, 82 + 2 " " 0.63 2.7 5.7 76+4 " " 0.94 3.0 502 73 + 6 " " 1.25 3.4 4.7 76 + 3 " " 2.5 3.5 3.4 79 + 2 " " 5.0 206 2.0 87 ~ 3 Table P. l,10-Phenanthroline as Promoter Conditions mmoles Weight of and otherof Amine _ Product re ctantsPromoter Methanol Glycol Rh Recovery, ~/O
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 38.
10, 555 ... .
lfi~'~
Table S. Quln~lclidine as Promoter Conditions ~noles~Jeight of and other of Amine Produc t reac~cants omoter Methanol Glycol RecDvery~ %
Sulf olane, 220 0 0.4 0.0 11 + 21 " " 0.63 2,5 3.5 76 + 7 " " 1.25 4.1 1.7 90+9 , 39.
.. , " . . ._ .
The optimum concentrati~n of an untried pr~moter is determinable on a relative scale by cDmparing the pK
of that promot~r to those set forth in Table I below 16.
10~555 and ~clecting a concentra~ion acc~rding to the pIC
relationships and trends ~ndicated. Overall, the optimu~ concentration of promoter one can e~ploy 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 pr~moter .
basicity available.
~ 7.
~ 7 10,555 TA~LE I
Optimun*
Other Moles Promoter Amine/
Amine pK~ Solvent Temp. Present Mole Rh 1,8-bis(dimethyl- 12.3 Sulfolane 2400 _ ~ 0.1 amino)-- naphthalene Sparteine 12.0 " " - 0.2-0.3 " " " 260 - 0.4-0.7 Dibutylamine 11.3 " 240 - 0.3-0.5 Piperidine 11.1 " 220 - 0.3-0.5 Triethylamine10.7 " 240 - 0.3 N-methyl piperidine10.4 " " - 0.3-0.5 Piperazine 9.7 " 240 - 0.3~0.5 4-dimethylamino-pyridine 9.6 " 220 - ~J 0.2 Ammonia TM 9.3 " 240 - O.3 Amberlite-IRA-93 9.0 " " - 0.3-0.5 1,4-diazabicyclo [2.2.2] octane 8.8 " 220 - 0.1 " " " " 240 - 0.2-0.3 2,4,6-trimethyl-pyridine 7.4 " 240 - 0.2-0.3 N-methylmorpholine 7.4 " " - 0.3_0.4 Trimethylenedi-morpholine7.3 " 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 " " " "HC02CS 0.2-0.4 ~' " " 230PhC02CS 0.3-0.6 l.10-phenanthro-line 4.8Sulfolane 240 - 1.6 Aniline 4.6 " " - 2-3 2-hydroxypyridine 0.8tetraglyme 220Cs2-pyri- ~1 dinolate -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.
t H20, 25~
10,555 The ion pairing a~ilities 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 pair-ing ability.
19 .
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, 10,555 3~
~ LE III
Ion Pairin~ Ability of Ammonium Ions in Nitrobenzene Cation pKdissocn (M, 25 ? of Ion ~air wlth Picrate NH4 3.8b PrNH3~ 3 gc 3 3 8b'C
Et2NH2~ 3.7C
BU2NH2~ 3 8b Me NH~ 3.8 Et3N~ 3.7 Bu3NH+ . 3 7b,e Piperidinium 3.8 PhNH3~ 4.7b PhNHMe ~ 3.9a,f, 4.4b PyH~ . 4.3 aActivity-based. bC. R. Witschonke and C. A. Kraus, J.~Am.
. Chem. Soc., 69, 2472 (1947). cJ. Macau and L. Lamberts, ~.
Chim. Phys., 67, 633 (1970). dE. G. Taylor and C. A. Kraus, J. hm. Chem. Soc., 69, 1731 (1947). eJ. B. Ezell and W. R.
Gilkerson, J. Phys. Chem., 72, 144 (1968). fH. W. Aitken and W. R. Gilkerson, J. Am. Chem. Soc., 95, 8551 (1973).
, 10,555 Acetonitrile and nitrobenzene are similar to sul~olane in that they are dipolar aprotic solvents and their dielectric constants are similar to sulf~lane (-43). The dielectric constant for acetonitrile is 36 and nitr~benzene is 35.
Thus from a consideration of the ion pairing ability data recited in Tables II and III above, plus consideration of ~he factors affecting "F-strain" (See H. C. Brown, Boranes in Organic Chemistry, Cornell University Press, 1972, starting at page 102), to which is added general concepts of electrostatic~,permits the prediction of ion pairing ability to the rhodium catalyst _ which with the aforemention discussion of basicity allows for the ready selection of an appropriate amine promoter in ~he aforemention homogeneous liquid phase reaction .... . . . .
For the purpose of aiding the characterization of this invention re~erence is made to Table IV and the drawings to graphically depict the yield of ethylene glycol to the concentration of certain amine promoters.
20 Table IV.lists a variety amines tested as promoters under the conditions characteri~ed in footnot~
.. , .. .. . . .. ~ . . .. . .. . .
a. The process procedure employed is recited in the examples below. The results are depicted in the enumerated Figures of Table IV.
The drawings, showing F~gures I through VI, graphically depict the effect that certain amine promoters have on the glycol yield. In particular, it is important l~J ~ir l~i~ 10,555 to note the effect of the amount of the amine on the glycol yield. The concentration of amine which gives the highest glycol yield is considered ~rom the standpoint of applicant's aforemen~ioned copending Canadian application Serial No. 262,265, to be the optimum concentration. However, from the standpoint of this invention, the utilization of an amount of amine in excess of the optimum concentration provides for the benefits described herein. For example, in regard to Figure II there is shown the effect that N-methylmorpholine has on the glycol yield when used in excess of an amount which is the minimum amount that achieves the optimum result. This particular effect on productivity is more readily appreciated from comparing the result of Figure II with Figure V.
A particularly desirable amine promoter is characterized in Figure VI. Ammonia is shown in Figure V to be a most desirable promoter. The data supporting the drawings can be found in the examples.
24.
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e~ 10, 555 The observed (Figs. 3 5) relative inhibitory abilities of those amines in Table IV for which data are available in Table II or III are N~3 CEt3Nr~ 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 counteriGm than are aryl carboxylates, small differences in pKdissocn are of greater significance for picrate, the conjugate acids ion pairing ability is ordered as NH4+ Et3NH~ ~ BU2NH2+ <pyH~
This ranking must be considered along with the relative basicities of the amines (see above). Based on 1) basicity date (Table V below) in water and in the two solvents in which the ion pairing abilities were deter-mined and 2) the Ho function in sulfolane ~See R.W. Alder et alO, Chemical Communications, p. 405 (1966)], the pK's in sulfolane are ordered as Et3NH ~ Bu2NH2 ~ NH4 ~ PY
Thus, the observed inhibitory abilities of the amines may be explained in terms of 1) the conjugate acids of Et3N
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 Et3Nand Bu2NH but ammonia being less basic. Note that the effective ion pairing ability in sulfolane may, in the 26.
10~ 555 2 12 ~ RNH3, and especially NH ~ be decreased by H-bonding to each of the sulEone oxygens .
O' ~L~ ;7 10 ~ 5 5 S
T~BLE V
Acidity of Ammonium Ions, PKa (25) ....
H20 Acetonitrilea'b NitrobenzeneC
NH4~ 9.3 16.5 EtNH3 10.6 18.4 7 1 BuNH~+ 10.6 18.3 Et2NH2+11.0 18.8 7.1 ~l~2NH2+11.3 7.1d Et3NH+ 10.7 18.5 7.3 Bu3NH+ 11.0 18.1 7.3d pyH+ 5.2 12.3 2.1 a J.F. Coetzee and GoRo Padmanabhan, J. Am. Chem. Soc., 87, 5005 (1965).
bI.M. Kolthoff, M.K. Chantooni, Jr., and S. Bhowmik, ibid. 90, 23 (1968).
c D. Feakins, W.A. Last and R.A. Shaw, J. Chem. Soc., 2387 (1964).
dBased on 1) results for EtNH3+ vs. BuNH3+ in H20 and MeCN, Et2NH2 vs. Bu2NH2 in water, and Et3NH~ vs. Bu3NH+ in H20 and MeCN and 2) the constancy of t~e effects of solvent on pK, we estimate pK (Et2NH2+)~ pK ~Bu2NH2+) in MeCN and PhN02 and pK(Et3NH~) ~ pK(Bu3NH+) in PhN02.
28.
' 10,555 ~ '7 Relationships apparent rom the data referred to in Table IV are explained in Table VI. In order to minimiæe inhibition by the amine and obtain thereby, withDut 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 c~njugate acid's positive charge is not substantially localized on only one atom is particularly good.
29.
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10,555 ~ 3~
The following examples are merely illustrative and are not presented as a definition of the limits of this invention.
Procedure employed in examples:
A 150 ml. capacity stainless steel reactor capable of withstanding pressures up ~o 7,000 atmo-spheres was charged with a premix of 75 cubic centi-meters (cc) o~ 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 190C, as measured by a suitably placed thermocouple, an additional adjust-ment of carbon monoxide and hydrogen (H2:C0=1:1 mole ratio) was made to bring the pressure back to 8000 psig.
The temperature (in C.) was maintained at the desired value for 4 hoursO 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 + 4G0 psig over the entire 4 hour period.
10,555 After the 4 hour period, the vessel and its contents were cooled ~o ro~m 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 TM 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 reac~or con-sisted of charging to the reactor 100 cc of the solvent used for that experLment, and bringing the reactor and it contents to a temperature of 160C.
and a pressure of 14,000 to 15,000 psig and main-taining these conditions for a period o~ 30 minutes.
The reactor was then cooled and the unreacted gases .
vented and an at~mic absorption analysis for rhodium was run Dn the reactor's contents. ~le rhodium recovery values recited beIow 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 t~me The same equipment and procedure were used i~ all the examples in Tables A-S except for the reactants and conditions specified The product weights in ~he Tables are reported in grams.
33' ._.. . . .
10,555 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 240~ 0.20 ~.4 0.8 34 + 5 " " 0.31 2.9 6.0 78 ~ 3 " " 0.63 2.7 5.1 67 +
" ll 0.94 2.8 5O0 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. SE~rteine as Promoter Weight of Conditions mmoles Product and other of Amine Reactants Promoter Methanol Glycol Rh Recover~%
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 34, . . lO,S55 Table. C. Dibutylamine as Promoter Conditions ~moles Weight of and other` of Amine Product reactants_ Promoter MetbanDl Glycoï 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, ~/O
~ .. ..... ~ .
Sulfolane, 220 0 0.4 0.0 11 + 21 " " ~.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 Tr_ethylamine as Promoter Conditions mmolesWeight o~
and other of AmineProduct -_ reactants Promoter Methanol Glycol Rh Recovery~ ~10 .
Sulfolane, . 240 0.65 3.3 2.2 71 + 7 " " 0.8 2.8 5.5 80 + 7 " " . 1.~5 3.5 . 5.1 79 + 5 " " 2.5 5.0 4.0 81 + 8 " " 7.0 4.0 2.2 80 + 8 35.
.
93 jL~ 7 10,555 Table F. N-Methylpiperidine as Promoter ConditionsmmolesWeight of and otherof AmineProduc~
ReactantsPromoterMethanol _lycol Rh Recovery, V/o Sulfolane 2400.63 3.0 3.0 66 ~ 3 " " 0O94 2.6 5.0 ~ 65 " " 1.25 3.5 4.~ 69 + 7 " " 2.5 4.5 3.8 86 ~ 7 Table G. Pieerazine as Promoter Conditionsmmoles~eight of and otherof AmineProduct ReactantsPromoterMethanol Glycol Rh Recovery, %
Sulfolane 2400,65 2.5 4.6 60 + 14 " " 1025 3.8 6.1 71 + 6 " " 2.5 4.6 5.1 83 ~ 4 Table I. Ammonia as Promoter ConditionsmmolesWeight of and otherof AmineProduct ReactantsPromoterMethanol ~ 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 6.6,5.3,52 84+6,77+9, 83 255 2.7,3.33361 5.4,58.0,5.1 691+4,50+4, 84 " " 2.0 4.6 4 6 83 + 8 " " 2.5 4.6 4.8 78 + 5 " " 10. 2.3 1.6 84 + 5 36.
10~ 555 31. i3~ ~ fi r3 ~
Tabl~ I~. 1 4-Diazabicy~lo ~2.2.2~ octanc as Pr~moter _._ __. _ . . __ ___ _~ ~_ _ _____~_ , . _ _ _ . _ _ Conditions mmoles Weight of and other of Amine Product reactan~s Pr~moter Methanol Glycol Rh Recovery, %
_ Sulf~lane, 220 .0 0,~ 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 ~.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 omoter Methanol Glycol 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 7;7 ~ 4 : " " 5.0 4.9 ~.5 . 76 + 3 . _ ., Table M. N-Methylmorpholine as Promo~er .` Conditions mmoles Weight of . and other of Amine Product _ reactants Promoter Methanol Glycol Rh Recovery7 7O
_ _ .
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 +
Sulfolane, 250C 7.0 3.6 6.4 64 ~ 3 11.0 4.6 6.0 67 + 7 " " ~0. 5.4 ~.4 ~9 + 6 .
.
10 ,555 Table N. Trimethylenedimorpholine as Promoter ConditionsmmolesWeight of and otherof AmineProduct reactarlts Promoter Methanol Glycol 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 " ll 12.0 5.1 6.0 77+5 Table 0. ridine as Promoter Conditions ~noles Weight of and otherof Amine Product _ reactantsPromoter Methanol Glycol Rh Recovery, %
Sulfolane, 220 0 0.4 0.0 11 + 21 " " 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, 0.312.4, 2.6 2.1, 5.7 74 ~ 4, 82 + 2 " " 0.63 2.7 5.7 76+4 " " 0.94 3.0 502 73 + 6 " " 1.25 3.4 4.7 76 + 3 " " 2.5 3.5 3.4 79 + 2 " " 5.0 206 2.0 87 ~ 3 Table P. l,10-Phenanthroline as Promoter Conditions mmoles Weight of and otherof Amine _ Product re ctantsPromoter Methanol Glycol Rh Recovery, ~/O
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 38.
10, 555 ... .
lfi~'~
Table S. Quln~lclidine as Promoter Conditions ~noles~Jeight of and other of Amine Produc t reac~cants omoter Methanol Glycol RecDvery~ %
Sulf olane, 220 0 0.4 0.0 11 + 21 " " 0.63 2,5 3.5 76 + 7 " " 1.25 4.1 1.7 90+9 , 39.
.. , " . . ._ .
Claims (6)
1. The process of producing alkane polyols by the reaction of oxides of carbon and hydrogen in a homogeneous liquid phase mixture containing a rhodium carbonyl complex catalyst in combination with a nitrogen Lewis base promoter; the catalyst concentration, the temperature of between about 100°C. to about 375°C. and the pressure of between about 800 psia to about 50,000 psia are correlated so as to produce such alkane polyol;
the promoter is 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, which amount of the promoter is greater than the minimum amount which is sufficient to produce such optimum rate of formation.
the promoter is 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, which amount of the promoter is greater than the minimum amount which is sufficient to produce such optimum rate of formation.
2. The process of claim 1 wherein the mixture contains a solvent.
3. The process of claim 2 wherein the solvent is tetraglyme.
4. The process of claim 2 wherein the solvent is sulfolane.
5. The process of claim 1 wherein the mixture contains a salt therein.
6. The process of claim 1 wherein the oxide of carbon is carbon monoxide.
40.
40.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61802375A | 1975-09-30 | 1975-09-30 | |
| US618,023 | 1975-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1091697A true CA1091697A (en) | 1980-12-16 |
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ID=24476020
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA262,263A Expired CA1091697A (en) | 1975-09-30 | 1976-09-29 | Enhancing the promoting of the catalytic process for making polyhydric alcohols |
Country Status (6)
| Country | Link |
|---|---|
| BE (1) | BE846709A (en) |
| CA (1) | CA1091697A (en) |
| DE (1) | DE2643897C2 (en) |
| FR (1) | FR2326398A1 (en) |
| GB (1) | GB1565979A (en) |
| NL (1) | NL7610785A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE846708A (en) * | 1975-09-30 | 1977-03-29 | 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 |
| 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 |
| DE3615835A1 (en) * | 1986-05-10 | 1987-11-12 | Basf Ag | METHOD FOR PRODUCING ETHYLENE GLYCOL |
Family Cites Families (3)
| 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 |
| BE846708A (en) * | 1975-09-30 | 1977-03-29 | PROCESS FOR THE PRODUCTION OF AN ALKANE-POLYOL |
-
1976
- 1976-09-29 CA CA262,263A patent/CA1091697A/en not_active Expired
- 1976-09-29 BE BE171045A patent/BE846709A/en unknown
- 1976-09-29 NL NL7610785A patent/NL7610785A/en not_active Application Discontinuation
- 1976-09-29 GB GB40356/76A patent/GB1565979A/en not_active Expired
- 1976-09-29 DE DE2643897A patent/DE2643897C2/en not_active Expired
- 1976-09-29 FR FR7629295A patent/FR2326398A1/en active Granted
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| Publication number | Publication date |
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| NL7610785A (en) | 1977-04-01 |
| DE2643897A1 (en) | 1977-03-31 |
| GB1565979A (en) | 1980-04-23 |
| BE846709A (en) | 1977-03-29 |
| FR2326398B1 (en) | 1980-10-24 |
| DE2643897C2 (en) | 1982-02-11 |
| FR2326398A1 (en) | 1977-04-29 |
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