CA1092161A

CA1092161A - Promoting the catalytic process for making polyhydric alcohols

Info

Publication number: CA1092161A
Application number: CA262,265A
Authority: CA
Inventors: Leonard Kaplan
Original assignee: Union Carbide Corp
Current assignee: Union Carbide Corp
Priority date: 1975-09-30
Filing date: 1976-09-29
Publication date: 1980-12-23
Also published as: FR2326399B1; GB1565978A; NL7610773A; DE2643913C2; BE846708A; JPS5242810A; FR2326399A1; DE2643913A1

Abstract

PROMOTING THE 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 deri-vatives by reacting hydrogen and oxides of carbon in the presence of a rhodium carbonyl complex in combination with optimum amounts of amine promoters.

S P E C I F I C A T I O N

Description

~ 6 ~ 10,556 This invention is concerned with the manufacture of polyhydric alcohols, their ether and ester derivatives, and oligomers of such alcohols. This invention also produces monohydric alcohols such as methanol, and their ether and ester derivatives.
It is known that monofunctîonal 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 témperatures ranging from 250C to 500C, using mixtures of copper9 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, a~d hydrogen in the presence of hydrogenation catalysts. It h~s-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 ~ailed 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 com-pletely inoperative or else give rise to insignificantly small quantities o~ formaldehyde.

~ 9 z ~ ~ ~ ' 10,556 In British 655,237, publi,shed July 11, 1951, there is disclosed the reaction between carbon monoxide and hydrogen at elevated pre~ures and temperatures, e.g., above 1500 atmospher~ at temperatures up t~ 400C., using certain hydrogenation catalysts as exemplified by cobalt-containing compounds. U. S. Patents No. 2,534,018,

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 ~.S. 2,636,046 are those which contain cobalt.
l It is also well-known that nickel is predomin-antly a catalyst for synthesis and for reforming,methane ~ccording to the reaction C0 + 3H2 4 2 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~ ~olume 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 9 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.

, '' ' 3.

~ 9 Z 1 ~ 10,556 The consequence of this has been the recognition of the need for a new lo~ 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 J containing 2, 3 or 4 carbon atoms, and derivatives such as their esters. Key products of the process of this invention are ethylene glycol and its ester derivatives. Byproducts of this invention are the lesser valuable, but valuable never-theless, monohydric alkanols such as methanol, ethanoland propa~ols, and their ether and ester derivatives.
The products o~ the process of this invention contain carbon, hydrogen and oxygen.
There is described in U.S. Patent 3,833,634, issu~d September 3, 1974, a process for reacting hydro-gen and oxides of carbon in the presence of rhodium carbonyl complex catalysts. The conditions, broadly speaking, employed in that process involve reacting a mixtur~ of an oxide of carbon and hydrogen wi~h a catalytic amount o~ rhodium in complex combination with carbon monoxide, 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. Illustrative of such "ligands" are oxygen and/or nitrogen organic compounds.
similar description can be found in U.S. Patent

3,g57,857, issued May 18, 1976, which is commonly assigned. Both patents speak about the use of such

4.
L

10,556 ~ ~ 2~

"ligands" as well as a number of amines which can ~e 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 actîvity of the catalyst. Since the filing of the applications which issued to U.S. Patent 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-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 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 concentrations the productivity of such polyols would be materially and unexpectedly enhanced. It has now . 5.

~ 9 Z ~6 ~ 10,556 been found that there is a specific concentration for each such promoter which will provide the optimum yield of alkane polyol that is ob~ainable under each selected condition of reaction and catalyst concentration.
It follows from ~his that there now exists a recogni-tion of a specific concentration of such promoter which creates the most favorable balance between the promoting and inhibiting effects of such promoters.
The process of this invention, as stated previously, involves the production of alkane polyols of two to four carbon atoms. The primary product of the process is ethylene glycol mainly in terms of cpmmercial value and secondly in terms of product efficiency. The process involves providing oxides of carbon, particula~ly carbon monoxide, and hydrogen in a homogeneous liquid phase reaction mixture containing a rhodium carbonyl complex in combination with a nitrogen Lewis base promotèr. The catalyst concentration, the . temperature and the pressure during the reaction are correlated so as to result in the production of alkane polyol, The promoter provided;to the mixture is present in an amount determined from the promoter's basicity to achieve the optimum rate of formation of said alkane polyol at said correlated catalyst concentration, temperature 8nd pressure of such reaction mixture.
Suitable nitrogen Lewis bases used as promot-ers generally contain hydrogen and nitrogen atoms. They may also contaln carbon and/or oxygen a~oms. They may be organic or-~norganic compounds. With respect to the 6, ;~

~L~9Zl~ lo, 5s6 i ~' organic compounds, the carbon atoms can be part of an acyclic and/or cyclic radical such as aliphatic, cyclo-aliphatic, 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 (N-), etc.
Desirably, the Lewis base nitrogen atoms are in the form of imino nitrogen and/or amino nitrogen. The oxy~en atoms can be in the form of groups such as hydro~yl (aliphatic or phenolic), carboxyl (-COH), O
carbonyloxy (-bo-) oxy (-o-) carbonyl (-C-~, e~c., all of said groups containing Lewis base oxygen atoms.
In,this respect, it is the "hydroxyl" oxygen in the O O

-COH group and the "oxy" oxygen in the -CO- ~roup that are acting as the Lewis base ~toms. The organic Lewis bases may also contain other atoms and/or groups, as ~- substituents of the aforementioned radicals, such as alkyl, cycloalkyl, aryl, chloro, trialkylsilyl sub-stitue`nts.

Illustrative of organic aza-oxa Lewis bases are, for example, the alkanolamines, such as ethanol-amine, diethanolamine, isopropanolamine, di-n-propanol-amine, and the like; N,N-dimethylglycine, N,N-diethyl-~lycine; iminodiacetic acid, N-methyliminodiacetic acid; N-methyldiethanolamine; 2-hydroxypyridine, _ ~92~ o, ss6 2,4-dihydroxypyridine, 2-methoxypyridine, 2,6-dimethoxy-pyridine, 2-ethoxypyridine; lower allcyl substituted hydroxypyridines, such as 4-methyl-2-hydroxypyridine, 4-methyl-2-6-dihydroxypyridine, and the like; morpho-line, substituted morpholines, such as 4-methylmorpho-line, 4-phenylmorpholine; picolinic acid, methyl-substituted picolinLc acid; nitrilotriacetic acid, 215-dicarboxypiperazine, N-(2-hydroxyethyl)-imino-diacetLc acid, ethylenediaminetetraacetic acid;
10 2,6-d~carboxypyridine; 8-hydroxyquinoline, 2-carboxy-quinoline, cyclohexane-1,2-diamine-N,N,N',N'-tetra-acetic acid, the tetramethyl ester of ethylenediamine-tetraacetic acid, and the likeO
Illustrative of suitable inorganic amine pro-moters are, e.g., ammonia, hydroxylamine, and hydrazine.
Any primary, secondary, or tertiary organic amine is suitable as a promoter in the practice of the present - invention. This includes the m~no- and polyamines (such as di-, tri-, tetraamines, etc.) and those com-20 pounds in which the Lewis base nitrogen fonms part of a ring structure as in pyridine, quinoline, pyrimidine, - morpholine, hexamethylenetetraamine, and the like. In additlon any compound capable of yielding an amino nitrogen under the reaction conditions of the present invention is suitable, as in the case of an amide, ~uch as formamide, cyanamide, and urea, . _ . . . _ ~0~ 6~ lo, 556 or an oxime. Further illustrative of these Lcwis base nitrogen compounds are alipha~ic amines such as methyl-amine, ethylamine, n-propylamine, isopropylamine, octyl-amine, dimethylamine, diethylamine, diisoamylamine, methylethylamine, diisobutylamine, trimethylamine, methyldiethylamine, triisobutylamine, tridecylamine, and the like; aliphatic and aromatic di- and polyamines such as 1,2-ethanediamine, 1,3-propanediamine, N,N,N',N'-tetramethylenediamine, N,N,N',N'-tetraethylethylene-diamine, N,N,N',N'-te~ra-n-propylethylenediamine, N,N,N',N'-tetrabutylethylenediamine, o-phenylene-diamine, m-phenylenediamine, ~-phenylenediamine, ~-tolylenediamine, o-tolidene, N,N,N',N'-tetra-methyl-l-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-(1,8)-dimethylamino-~0 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; 6ubstituted pyridines such as 2-methyl-pyridine, 2-phenylpyridine, 2-methyl-4-ethylpyridine, 2,4,~- trimethylpyridine, 2-dodecylpyridine, 2-chloropyridinç, and 2-(dimethylamino)pyridine;
quinoline; substituted quinolines, such as` 2-(dimethyl-_.. . ... . .

10 ~ 556 amino)-6-methoxyquinoline; 4,5-phenanthroline; 1,8-phenanthroline; 1,5-phenanthL-oline, piperazine; sub-stituted piperazines such as N-methylpiperazine, N-ethylpiperazine, 2-methyl-N-methylpiFe~zine; 2,2'-dipyridyl, methyl-substituted 2,2'-dipyridyl; ethyl-substituted 2,2'-dipyridyl; 4-triethylsilyl-2,2'-dipyridyl; l,~-diazabicyclo[2O2.2]octane, methyl substituted 1,4-diazabicyclo[2.2.2]octane, purine and the like.

As stated previously, the promoter is pro-vided in the homogeneous reaction mixture in an amount determined from its basicity to achieve the maximum yield of the alkane polyols, such as ethylene glycol.
For the purposes of discussion o 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 import-ant 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 acation in the homogeneous mixture as noted in the pre-vious discussion relative to the so-called "ligands"

and amines, and their function in the catalyticreaction.
It has been ~ound that the optimum concen-tration of a strongly basic nitrogen Lewis base promoter in the process of this invention is a minimum concentration that provides the optimum results.
This means th~t a relat~v~ly small amount of - such promo~er achieves the Qptimum yield obtainable 10.

~ 10,556 with that promoter. On the other hand, it has bcen found that as the base becomes progressively wealcer, a ~reater and greater amount of the base is needed to achieve the maximum yield of the allcane polyol.
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 thè 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 concèntration increases.
Postulate a. can be illustrated by the followin~ reaction scheme:
_ 20 (n-m)amine (I) Rh ~ m(amine) ~ Rh(amine)m ' ~ Rh(amine)n ? *
alkane polyol Promoter Function ' Inhibitor Fun~tion * The looped arrow employed herein denotes several undefined process steps.

;
.

2~
~?' ... ....
10,556 [Note: In the above reaction scheme the charge of the rhodium carbonyl complex is n~t shown;
n and _ represent integers; Rh denotes a species with a fixed number of rh~diums with the option of a chan~in~ number of ~,O's anA
H's; the rate and equllibrium constants implicitly contain any appropriate C0 and H2 concentrations.]
- In the above scheme, the amine aids produc-tion 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 conse-quence 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 ~he active catalyst.l Since K would be expected to be larger for weaker bases, this scheme is consist-ent with the aforementioned observed results.
A complementary or supplementary reaction scheme may be characteri~ed as follows:

.

Z~ 0,556 a~ ~
~. o ~O
a~
J~
.,~ ..

.~ ~ U

~ a.~ ~1 ._ ' ' ' ~ U~' ' ~d Q~

h ,~
..

`
.- . ~J .

~J~.aL~3 ~L 10 ~ 556 In this scheme the aminc functions both as a rhodium-and as a proton base. It aids production of alkane polyol by forming a more active catalyst and hinders it by deprotonating the active catalyst.
- The resulting kinetic equation for reaction scheme (II) is -(III)rate is proportional to (Rh) (amine) m m Kb(amine) T~
l + (amineH+) ~¦ Kai - i=l where the Kai's are successive acid dissociation con-stants of the active catalyst, Kb is the proton affinity of the amine.
Equation (III) supports the previously observed result by showing that if the reaction is treated as being specific base catalyzed [see: A. A. Frost & ~. G.
Pearson, "Rinetics ~ Mechanism", 2d Ed., John Wiley & Sons ; . (1961)], addition of increasing amounts of amine could eventually become counter-productive. The equation (III) predicts that if the nature of the amine affects Kb more than it does the Kai's, and this is submitted to be a plausible assumption, the amine concentration corres-ponding to any maximum in yield of alkane polyol would be greater the less basic the amine.
A third reaction scheme, illustrative of postulate b., is characterized as follows:
.

14 .

. .

. 10,556 (IV) ~1 + amine ~ [~l~amine~l~ ~ Rh- ~ aminé~l~]

alkane pol~ol ~Note: Rh is defined as above in the note to equation ; (I).]
- In equation (IV) 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 p,recursor of,the acti~e catalyst.
In terms of reaction scheme (I~), with the use of a less basic amine, more amine would be necessary to.
insure that the first step of the equation'is guantitative.
After enough of such an amine is provided, any further amine additions can have on'ly negative effects in 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 (IV) 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 l~miting value co~responding to stoichiometric destructio of Rh, _ .

il~0~2~ P~L 10, 556 Consistent ~ith reaction scheme (IV) is the fact that the optimum concentration of an amine as sole promoter for Rh is less when the solvent employed has a high dielectric constant. For example, the optimum concentration of an amine as the sole promoter in sulfolane* [~ =43] is less than that in tetraglyme*
=7.5]-The concentration of the nitrogen Lewis basepromoter in the homogeneous liquid phase mixture of the process of this invention has not been found to be critic-ally dependent upon the temperature and pressure^of-the reaction, the rhodium concentration or the solvent employed.#
Of these factors, the rhodium concentration will have the more significant impact upon the optimum promoter concen-tration while ~emperature, pressure and solvent choice have minimum effect. However, the effect of rhodium concentration on promoter concentration is considered to be small and is hereafter discounted except for the purposes o~ giving numerical values to the selection of an amoun~
of promoter for practicing this invention.

*For a description of the use of sulfolane, see British Patent Specification No. 1,537,850, published January 10, 1979, and for a description of tetraglyme, see U.S. Patent No. 3,957,857, issued May 18, 1976.

#This statement refers to normal operation, which in tetraglyme involves the use of a salt (see below3 in addition to an amine as promoter, while the previous paragraph refers to use of amine as sole promoter in both solvents.

16.

, , .

~3 ~ 10,556 The ~erms strong or weak base are relative, and in view of the precedin~ discussion, sucll relative values are considered appropriate in defining this invention.
However, for convenience and to provide a numerical base rom which it may be considered desirable to discuss this invention, one may characterize a strong base as having a pK greater than about S and a weak base as having a pK
less than 5, with the assu~ption 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 characteri~ations by stating that a strong base has a pK o 5 to about 15 and a weak base has a pK of 0 to aboùt 5. pK refers to the acid dissociation constant of the conjugate acid of the nitrogen ~ewis base in water at 25C.
The optimum concentration of an untried promoter is determinable on a relative scale by comparing the pK
of that promoter to those set forth in Table I below and selecting a concèntration according to the pK relation-- ships and trends indicated. Overall,the 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.

. 170 _ . . . .

- 10~556 TABL~ I
Optimum* Concentration of Amine Promo~er REACTION SYSTL~-See Examples (below) Optimum*
Other moles promoter amine/
~minepK~ Solvent Temp. present mole Rh 1,8 bis(dimethyl- 12.3 Sulfolane 240 - ~ 0.1 amino)-naphthalene Sparteine 12.0 " " - 0.2-0.3 " " " 260 - ~0.4-~.7 Dibutylamine 11.3 " 240 - 0,3-0.5 Piperidine 11.1 " 220 - -0.3-0.5 Triethylamine10.7 " 240 - 0,3 N-methyl-pipPridine 1004 " " - 0.~-0.5 Piperazine 9,7 " 240 - 0.3-0,5 4-dimethylamino-pyridine 9.6 " 220 - ^~ 0.2 Ammonia 9.3 " 240 -- 0.3 AmberliteTM
IRA-93 9,o ~ _ 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-morpholine 7.3 " 260 - 0.5 .Pyridine 5.2 " 220 - 0.2-~.3 " " " 240 - ~ 0.1 " " " " (Ph~P)2NO Ac ~ 0.1 " " ~etraglyme 220 ~ 0.2-0.6 " " " " HC02CS 0,2-0.4 " '~ " 230 PhC02CS 0.3-0.6 l,10-phenanthro-line 4.8 sulfolane240 - 1.6 Aniline 4.6 " " - 2-3 2-hydroxypyridine 0.8 tetraglyme 220 Cs2-pyri~
dinolate pK of benzyldimPthylamine; 1RA-93 is an arylnlethyl dimethyl amine ion exchange resin sold by Rohm ~ Haas Co., Phila., Pa.
* The smallest which maximizes the yield o glycol.
~ H20, 25.

.
18.

~0 9 Z~ ~ ~ 10,556 The prec~se role of the rhodium carbonyl c~mplexes, such as the rhodium carbonyl clusters, in the reaction of hydrogen with oxides of carbon to produce polyhydric alcohols is not f~lly appreciated at present. Under the reaction conditions of the present process the carbonyl complexes are believed to be anionic in their active forms. Rhodium carbonyl anions are known to be involved in the following set of reactions as indicated by SO Martinengo and P. Chini, in Gazz. Chim~ Ital., 102, 344 (1972) and the references cited therein.
(V) [Rhl2(C0~4_3~ ~' LRh~2(CO ~] ~ ~h6(CO)~] + ~Rh6(CO) ~Rh(CO~
[Rh6(CO)~ ~h(CO~ + CO [Rh7(CO)1;33~Rh4(C0~2- + [Rh(CO)~-*electron c Infrared spectra under reaction conditions of the present process have shown both RhtC0)4 and ~Rhl2(C0)3~_36~ anions, and other rhodium c~usters to be prese~t at various concentra~ions at different times of the reaction. Therefore the set of reactions and equilibria shown in (V) above may represent the active rhodium carbonyl species responsible for polyhydric alcohol formation or may be merely symptomatic of some further intermediate transitory rhodium carbonyl struc-ture which serves to convert the carbon monoxide and hydrogen to the polyhydric alcohol.

19 .

Z16~
lo, 556 The novel process is suita~ly effccted over a wide superatmospheric pressure range of from about 800 psia to about 50,000 psia. Pressures as high as 50,000 psia, and higher can be employed but with no apparent advantages attendant thereto which offset the unattractive plant investment outlay required for such high pressure equipment. Therefore, ~he upper pressure limitation is desirably approximately 16,000 psia. Effecting the present process below about 16,000 psia, especially below about 13,0~0 psia, and preferably at pressures below about 8000 psia, results in cost advantages which are associated with low pressure equipment requirements. In attempting to foresee a commercial operation of this process, pressures between about 4,000 psia and 16,000 psia appear to represent most realistic values.
In a preferred embodiment o~ the present invent-ion the pressures referred to above represent the total pressures of hydrogen and oxides of carbon in the reactor.
The process of this invention can also be carried -20 out by providing salts in the homogeneous liquid phase reaction mixture. Suitable salts include any organic or inorganic salt which does not adversely affect the pro-duction of polyhydric alcohols. Experimental work suggest that any salt is beneficial as either a copromoter and/or in aiding in maintaining rhodium in solution during the react~on. Illustrative of the salts useful in the practice of the present-invention are the ammonium salts and the 20.

~ ~ Z ~ ~ 10,556 salts of the metals of Group I and Group II of tlle Periodic Table (Handbook of Cllemistry and Physics - 50th Edition) for instance the halide, hydroxide, allcoxide, phenoxide and carboxylate salts such as sodium fluoride, cesium fluoride, cesium pyridinolate, cesium formate, cesium acetate, cesium benzoate, cesium p-methylsulfonyl-benzo`ate (CH3S02C6H4COO)Cs, rubidium acetate, magnesium acetate, strontium acetate, ammonium formate, ammonium benzoate and the like. Preferred are the cesium and ammonium carboxylate salts, most preferably their formate, benzoate and para-lower alkyl sulfonyl benzoate salts.
. . Also useful in the practice of the present invention are organic salts of the following formula:

21.

- . .

10,~56 ~ ~ 2 1~ 1 II l R4 - N R2J Y

\ R3 quaternary ammonium salts : ~ R R

III ~5 -P=~N-~P- R2 J Y

\ 3 /
bis(triorgano phosphine)iminium salts wherein Rl through R6 in ormulas (II) and (III~
above are any organic radical6 which do not ad-ve,sely affect the product:ion of polyhydric : alcohols by reacting oxides of carbon with hydro-gen in the presence of the ~foredefined rhodium earbonyl complex, such as a str~ight or branched chain alkyl group, having from 1 to 20 carbon atoms in the alkyl chain, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, octyl, 2-~thylhexyl, dodecyl, and the like; or a eycloaliphatie group including the monocyclic and blcyclic groups eyelopentyl, cyclohexyl, and bicyclo~2.2.1] heptyl groups, and the like 22.

. . _ . . .

Lfi IL

or an aryl, alkylaryl, or aralkyl group such as phenyl, naphthyl, xylyl, tolyl, t-butylphenyl, benzyl, beta-phenylethyl, 3-phenylpropyl and the like; or a functionally substituted alkyl such as beta-hydroxy-ethyl, ethoxymethyl, ethoxyethyl, phenoxy~thyl, and the like; or a polyalkylene ether group of the formula ~CIlH2nO)X-OR wherein n has an average value from 1 to 4, x has an average value from 2 to about 150, and R
may be hydrogen or alkyl of 1 to about 12 carbon atoms. Illustrative of such polyalkylene ether groups are poly(oxyethylene~, poly(oxypropylene), poly(oxy-ethyleneoxypropylene), poly(oxyethyleneoxybutylene~, and the like. Y in formulas II and III above may be any anion which does not adversely affect the produc-tion of polyhydric alcohols in the practice of the present invention such as hydroxide; a halide, for instance fluoride, chloride, bromide and iodide; a carboxylate group, such as formate, acetate, propionate, and benzoate and the like; an alkoxide group such as methoxide, ethoxide, phenoxide, and the like; a functionally substituted alkoxide or phenoxide group such as methox~ethoxide, ethoxyethoxide, phenoxy-ethoxide and the like; a pyridinolate or quinolate group; and others. Pre~erably Y in formulas II and III, above, is a carboxylate, most preferably formate, acetate and benzoate~
A suitable method for preparing the bis(tri-organophosphine) iminium salts is disclosed in an article by Appel, R. and Hanas, A. appearing in Z. Anorg. u. Allg. Chem., 311, 290, (1961).

23.

~6 lO,556 Other organic salts u~eful in the practice of the present invention include the quaternized hetero-cyclic amine salts such as the pyridinium7 piperidinium, morpholinium, quinolinium saltc and the like, e.g., N
ethylpyridinium fluoride, N-methylmorpholinium benzoate, N-phenylpiperidinium hydroxide, N,N'-dimethyl-.2,2-bipyridinium acetate, and the like.
In addition, the anion of the above salt may be any of the rhodium carbonyl anions. Suitable rhodium .10 carbonyl anions include 1Rh6(CO)15] ; [Rh6(CO)15Y]
wherein Y may be halogen, such as chlorine, bromine, or iodine, [Rh6(C0)15(COOR"] wherein R" is lower alkyl or aryl such as methyl, ethyl, or phenyl; [Rh6(CO)14]
[ 7( )16] ; [Rhl2(c0~o~2 ; Rhl3(oo~4~ ;and Rh~(C0~4H22 Under reaction conditions where a salt is employed the salt is desirably added ~ith the intial charge of re-actants in amount~ of from about 0;5 to about 2.0 moles, preferably from about 0.8 to about 1.6 moles, and most preferably from about 0.9 to 1.4 moles of salt for every five atoms of rhodium present in the reaction mixture.
Illus~rative solvents which are generally suit-able in making the homogPneous mixture include, for example, ethers such as tetrahydrofuran, tetrahydropyran,.
diethyl ether, l,2 dimethoxybenzene, l,2-diethoxybenzene, the mono- and dialkyi ethers of ethylene glycol, of propylene glycol, of butylene glycol, of diethylene glycol, of dipropylene glycol, of triethylene glycol, of tetra-ethylene glycol, of dibutylene glycol, of oxyethylene-propylene glycol, etc; alkanols such as methanol, ethanol, .
- 24.

~ ~2 ~ 10,556 propanol, isobutanol, 2-ethylhexanol, etc.; ketones such as acetone, methyl ethyl keton~, cyclohexanone, cyclo-pentanone, etc.; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl butyrate, methyl laurate, etc.; wat~r; gamma-butyrolactone, delta-valerolactone; substituted and unsubstituted tetrahydrothiophene-l,l-dioxides (sulfolanes) as disclosed in British Patent Specification No. 1,537,850, published January 10, 1979; and others. The mono and dialkyl ethers of tetraethylene glycol, gamma-butyro-lactone, particularly sulfolane and 3,4-bis(2-methoxy-ethoxy)sulfolane, are the preferred solvents.
The temperature which may be employed can vary over a wide range of elevated temperatures. In general, the process can be conducted at a temperature in the range of from about 100C. and upwards to approximately 375C., and higher. Temperatures outside this stated range are not excluded from the scope of the invention. At the lower end of the temperature range, and lower, the rate of reaction to desired product becomes markedly slow. At the upper temperature range, and beyond, signs o~ some catalyst instability are noted. Notwithstanding this factor, reaction continues and alkane polyols and /or thèir derivatives are produced. Additionally, one should take notice of the equilibrium reaction for forming ethylene glycol 2 CO + 3H ~ HOCH CH OH
At relatively high temperatures thè~-equilibrium increasing-ly favors the left hand side of the equation. To drive the ~ 9 ~ 10,556 reaction to the formation of increased quantities o~
e~hylene glycol, higher partial pressures of carbon monoxide and hydrogen are required, Processes based on correspondingly higher pressures, however, do not represent preferred embodiments of the invention in view of the high investment rosts associated with erecting chemical plants which utilize high pressure utilit~es and the necessity of fabricating equipment capable of withstanding such enormous pressures. Suitable tempera-tures are between about 150C to about 320DC, and desirably from about 210C to about 300C.
The novel process is effected for a period oftime sufficient to produce the alkane polyols and/or der~vatives thereof. In general, the residence t~me can vary from minu~es to severa:L hours, e.g., ~rom a few minutes to approximately 24 hours, and longer. It is readily appreciated that the residence period will be -- ~nfluenced to a significant extent by the reaction tem-perature, the concentration and choice of the catalyst, the total gas pressure and the partial pressures exerted by its componentsg the concentration and choice of diluent, and other factors. The synthesis of the desired product(s) ~y the reaction o hydrogen with an oxide of carbon is suitably conducted under operative .conditions which give reasonable reaction rates and/or converslons. ~
The relative amounts of oxide of carbon - and hydro~cn which are initially present in the 26.

. . .

~3~16.~ lo, 556 reaction mixture can be varied over a wide range.
In general, the mole ratio of CO:H2 is in the range of from about 20:1 to about 1:20, suitably from about 10:1 to about 1:10, and preferably from about 5:1 to about 1:5.
It is to be understood, however, that molar ratios outside the aforestated broad range may be employed. Substances or reaction mixtures which give rise to the formation of carbon monoxide and hydrogen under the reaction conditions may be employed instead of mixtures comprising carbon monoxide and hydrogen which are used in preferred embodiments in the practice of the invention.
For instance, polyhydric alcohols are obtained by using mixtures containing carbon dioxide and hydrogen. Mixtures of carbon dioxide, carbon monoxide and hydrogen can also be employed. If desired, the reaction mixture can comprise stea~
and carbon monoxide.
The novel process can be executed in a batch, semi-continuous, or continuous fashion.
The reaction can be conducted in a single reaction zone or a plurality of reaction zones, in series or in parallel, or it may be conducted inter-mittently or continuously in an elongated tubular zone or series of such zones. The material of construction should be such that it is inert 27.

~ 10,556 during the reaction and the fabrication of the equipment should be able to withstand the reaction tem~erature and pressure. The reaction zone can be fitted with internal and/or external heat exchanger(s) to thus control undue tempera-ture fluctuations, or to prevent any possible "run-away" reaction temperatures due to the exothermic nature of the reaction. In preferred embod-iments of the invention, agitation means to vary the degree of mixing of the reaction mixture can be suitably employed. Mixing induced by vibration, shaker, stirrer, rotatory, oscillation, ultrasonic, etc., are all illustrative of the types of agitation means which are contemplated.
Such means are available and well-known to the art.
The catalyst may be initially introduced into the reaction zone batchwise, or it may be continuously or intermittently introduced into such zone during the course of the synthesis reaction. Means to ~0 introduce and/or adjust the reactants, either intermittently or continuously, into the reaction ; zone during the course of the reaction can be conveniently utilized in the novel process e~pecially to maintain the desired molar ratios of and the partial pressures exerted by the reactants.

28.

~ 10,556 i~;

As intimatcd previously, thc operative conditions can be adjusted to optimize the conversion of the desired product and/or the economics o~ thc no~el process. In a continuous process, ~or instance, when it is preferred to operate at relatively low conversions, it is generally desirable to recirculate unreactedsynthesis gas with/with-out make-up carbon monoxide and hydrogen to the reaction.
Recovery of the desired product can be achieved by mcthods well-known in the art such as by distillation, fraction-ation, extraction, and the like. A fraction comprising rhodium catalyst, generally contained in byproducts and/or normally liquid organic diluent, can be recycled to the re~action zone, if desired. All or a portion of such fraction can be removed for recovery of the rhodium values or regeneration to the ~ctive catalyst and intermittently added to the recycLe stream or directly to the reaction zone.
The active forms of the rhodium carbonyl clusters _ may be prepared by various techniques. They can be preformed and then introduced into the reaction zone or they can be formed in situ.
The equipment arrangement and procedure which provides the capability for determining the existence of anionic rhodium carbonyl complexes or clusters having de-fined infrared spectrum characteristics, during the course of the manufacture of polyhydric alcohols from carbon monoxide and hydrogen, pursuant to this invention is 29~

~3~ 10,556 dîsclosed and schematically depicted in U.S. Patent 3,957,857, issued May 18, 1976.
A particularly desirable infrared cell construct-ion is described în U.S. Patent No. 3,886,364, issued May 27, 1975.
The "oxide of carbon" as covered by the claims and as used herein is intended to mean carbon monoxide and mixtures of carbon dioxide and carbon monoxide, either introduced as such or formed in the reaction.
Preferably, the oxide of carbon is carbon monoxide.
The following examples are merely illustrative and are not presented as a definition of the limits of the invention:
.

30.

10,556 Procedure employed in examples:
A 150 ml. capacity stainless steel reactvr capable of withstanding pressures up to 7,000 at-mospheres was charged with a premix oE 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 190C, as measured by a suitably placed thermocouple, an addi-tional adjustment of carbon monoxide and hydrogen (H2:C0=1:1 mole ratio) was made to bring the pressure back to 8000 psig. The temperature (in G.) was main-tained at the desired value for 4 hours. During this period of time additional carbon monoxide and hydrogen wa~ 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 v~nted and the reaction product mixture was removed.

~z~

Analysis of the rcaction product mlxture was made by gas chromatographic analysis using a Hewlett Packard FM TM model 810 Research Chromatograph.
Rhodium recovery was detenmined 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 oon-sisted 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 160C
and a pressure of 14,000 to 15,~00 psig and main-taining 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-V except for the - reactants and conditions specified. The product weights in the Tables are reported in grams.

.
;
32.

. . _ .

3~61 lo, ss6 lXAMPLlS

Table A. 1,8-Bis(dimcthylamino)-laphthalene as Promoter ~ miili~ Weight of Conditions moles Product and other of Amine Reactant~ Promoter Methanol Glycol Rh Recover~, %
Sulfolane, 24~ 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 milli~. .
Condi~ions moles Weight of .and other of Amine Product ~ reactants Promoter Methanol Glycol Rh Recovery %
20 Sulfolane, 240 0.31 2.9 0.3 65 + 6 " " O.G3 3.3 5.7 79 + 8 " " 1.25 3,9 4.8 80 + 8 " " 5.0 ~.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 .

33.

2 ~ 6 10,556 Table C, ~ib-ltylamine as Prom,oter.
. . ,~.
milli-Conditions, n~oles Weight of and other of Amine Product reactants Promoter Methanol Glycol _ Recovery, %
Sulfolane, 240 0.65 2.7 5.477 + 5 " " 1.25 3.5 6.277 + 6 " " 2.5 .4.3 4.986 + 5 " " '5.0 ' 4.7 4,077 + 6 ' 0 ' Table D. Piperidine as Promoter , milli-Conditions moles Weight of and other of Amine _ Product reactants Promoter Methanol Glycol Rh Recovery, %
Sulfolane, ' 22~ 0 0,4 0,011 ~ 21 " '" ' 0.63 1.2 1.574 + 7 " " 1.25 2.7 2.589 + 8 " " 2.5 3.4 2.294 + 6 .
Table E. Triethylamine as Promoter milli- ' 20 Condi tions moles Weight of and ather of Amine _ Product reactants Promoter Methanol Glycol ~ Recovery~_~
Sulfolane, 240 0.65 3.3 2.~71 ~ 7 " " 0.8 2.8 5.580 ~ 7 . " " 1.25 3,5 5.179 + 5 ' " " 2,5 5,0 . 4.0' 81 + 8 ." " 7.0 ~.~ 2,280 ~ 8 . 34.

L61 .
lo, 556 Table F. N-M~tllylpipcridine as Pr~moter m;~
Conditions moles Weight of and other of ~mine Product reactants ~romoter Methanol Glycol ~t 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 Promo~er milli- Weigkt of and other of Amine Product reactants Promoter Methanol G1YCO1 Rh Recovery, %
Sulfolane, 240 0.~5 2.5 4.6 60 + 14 " " 1.25 3,8 6.1 71 + 6 " " 2,5 4.6 5.1 83 ~ 4 Table H. 4-Dimethyiaminopyridine as Promoter milli-Conditions moles Weight of and other of Amine Product eactants Promoter Methanol Glycol Rh RecoverY, V/~
Sulfolane, ~ 220 ~ ~.4 0,O 11 + 21 " " 0.31 1.6 1.3 74 ~ 4 " " 0.63 2.6 2.3 90 + 9 " 1.25 3.3 1,6 92 + 8 .

. 35.

-10,~56 Table 1. Ammonia as Promo~er Conditions mmoles Wei~ht of Productand other of Amine reactants Promoter _ethanol ~y~ Rh Recovery, %
Sulfolane, `240 0.50 2.7 4.3 63 + 15 " " 0.65 2.2 4.7 79 ~ 5 " " 0.8~ 2.3, 2.4 4.9, 5.~ 81 + 6, 86 ~ 5 " " 1.0 3.2, 3.6, 2.8 6.6,5.3,5.2 84+6,77~,83+7 ~' 1 1.~5 ~7, 3.3, 3.1 5.2,5P,S.1 69+4,8~+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 J. AmberliteTM IRA- 93 as Promoter _ Conditions mmoles Weight of and other of Amine Product reactants Promoter* Methanol G1YCO1 Rh reCOVerY**~ %
.
Sulfolane, 240 0.62 1.8 3.9 51 " " 1.25 3~0 5.8 82 " " 2,5 3,0 5.0 63 " " 10. 2.7 3.2 64 mmoles of nitrogen.
** Wash not analyzed for rhodium, 36.

9~6~L
10, 5~6 Ta'ble K. 1,4DDiazab~cyclol2.2,2]octane ~s Promoter Conditions ~noles ~eight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery~ %
Sulfolane, 220 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 . 6 33 . 1 6 . 5 7 5 ~ 6 " " 1.25 4.4 6.1 76 + 4 " " 2.5 4.3 4.5 74 + 6 " " ~.0 4.4 3.7 75 + 7 Table L. 2.4,6-TrimethYlE~ridine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Meth~nol Glycol Rh Recovery, %
Sulfolane, 240 0.31 2.6 1.0 60 + 3 " " 0 63 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 37 .

Z~L6~
lo, 556 Table M. N-MeLIlylmorpholil-c as Promoter ~_ ... - . .
Conditions mmoles!~ Weigllt of and other of ~mine Product reactants Promoter Methanol Glycol Rh Recovery, %
_ Sulfolane, 2~0 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 ll '' 7.0 4.1 5.4 82 + 2 Tetraglyme, 240, 0.65 mmoles cesium benzoate 0 2.2 2.9 27 + 52 " " 5,0 2.4 4.1 46 ~ 32 " '~ 10.0 1.7 3.0 12 + 64 Sulfolane, 250C 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, V/o .
Sulfolane, 260 0.65 3.3 3,2 49 + 4 " " ~.25 4.~ 5.6 67 ~ 6 " " 7.0 4.9 6.1 78 ~ 6 " " 12.0 5.1 6.0 77 ~ 5 38, .

10,556 ~ ~ 2 1 6 Table O. Pyridine as Pr~moter Conditions mmoles Weight of and other of Amine Product Rh Recovery~ %
Reactants Promoter Methanol G~ycol 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, 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 " " 5O0 2.6 2.0 87 + 3 Sulfolane, 0.75 mmoles bis(triphenyl-phosphine) iminiun acetate, i.e.
(Ph P) NOAc 0 3.2 5.2 79 + 4 " 3" 2 l~ 0.15 3-9 5.6 80 + 2 " " " 0.30 4.1 5.9 91 + 7 " " " 0.60 4.7 5.2 84 + 5 " " " 1.25 ~.4 4.3 73 + 7 Tetraglyme, 0.63 mmoles (Ph P) NOAc0.63 1.4 5.3 91 + 7 " 3" 2 l ~.25 1.4 5.0 85 + 8 " " " 2.5 105 4.5 82 + 7 Tetraglyme, 0.5 mmoles HCO Cs 0 1.2 2.8 69 + 3 "2" ~ 0.63 2.0 3.1 7~ + 13 " " " 1 25 2.2 3.1 78 + 12 ~ " " " 2 5 2.8, 2.8 2.4, 2.5 74 + 9, 77+15 .. .. l 5.0 2.6 2.8 74 + 7 tt ~I ~1 10.0 3.2 2.2 78 + 6 "" " 20.0 3.1 1.6 72 + 7 39.

. 10,556 Table 0 (continued)_ PyrLdi.ne ~s Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol ~1 Recovery, %
Tetraglyme, 23no ....... .Ø65 mmole cesium . benzoate 0 2.2 3.5 63 + 24 " " 1.25 2,2 4.6 50 + 31 " " 2.5 3.3 5.2 65 + 22 ll " 5.0 3.5 4.6 66 + 5 Tetraglyme, 240, 0.65 mmole cesium benzoate 0 2.2 2.9 27 + 52 " " 1.25 2.6 3~6 42 + 38 " ~ " 5.0 1.4 2.1 10 + 72 Sulfolane, 250 0.63 3.8 6.4 68 + 9 " " 2.5 6.3 5.5 93 + 11 Table P. l,10-Phenanthroline 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 " " 7.01.7, 2.~ 2.6 3.0,3.9,3.9 56+3,69+4,74+4 " " 10,03~0, 2.7 4.7,4.~ 77+3,77+~
" " 15, '3.2 4.9 74 ~ 5 " " 20. 2.5 4.3 77 ~ 5 _ 40 3Z~6.1~

o, 5s6 , .
Conditionsmmoles ~leight of and otllerof Amine Product reactants Promoter Methanol Glycol ~l Rccovery, %
Sulfolane, 2405.0 3.1 2,5 70 + 5 " " 10.0 2,9 3,3 64 + 10 " " 20, 2,2 3,1 61 + 9 Table R. 2-Hydroxypyridine as Pr~moter Conditionsmmoles Weight of ~nd otherof Amine Product reactants , Promoter Methanol Glycol Rh Recovery, %
Tetraglyme, 220, 0.5 mmole Cs 2-pyridino- .
late, 6mmoles Rh(CO)2 acetyl-acetonate 3.0 2,9 5,7 78 + 6 " " " 6.0 2,8 6.1 78 + 6 " " " l~.0 2,8 5.4 74 + 6 " " '' 20, 4.3 4.5 83 + 8 -_ Table S. Q_~nuclidine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recover~ %
Sulfolane, 2~0 0 0.4 0,0 11 + 21 " " ~.63 2.5 3.5 7~ ~ 7 3~ " " 1.25 4.1 1.7 90 + 9 41, .

9 2 ~ ~ ~
10,556 Table T. EthY~en~dim_rpholine as Promoter Cond~tlons mmole~ We~ght of and other Qf Amine Product reactants Promoter Methanol Glycol h RecoverY, %
Sulfolane, 240 0.65 3.0 6.3 89 ~ 5 " " 1.25 3.5 6.3 78 + 5 " " 7.0 .- 4,6 4.9 78 ~ 5 Table U. TetramethYlened~morPholine as Promoter Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh RecoverY. /~
Sulfolane, 260 0.65 3.~ 4.2 68 ~ 5 " " 1.25 4.5 5.3 73 + 5 ~ I' 7.0 3.6 3.2 72 + 3 Table V. Hydroxypyrid~nes 8S PrGmoter Conditions mmoles Weight of and other of Amine Product reactan~s Pr~moter Methanol G1YCO1 Recovery, %
DehydroxYPYridine (see Table O) (pK c 5.2) 2-Hvd~_r~ t (see also Table R) (pK = 0.8) Tetraglyme, 220, 0,75 mmole (Ph3P)2 NOAc 1.25 1.6 ~.7 82 + 6 Tetraglyme, 220 10.0 1.9 1.0 70 ~ 19 3~ Tetraglyme, 220, 0.5 mmole Cs 2-pyrid- ~
inolate 10.. ~ 1.7 4.3 82 + 15 42.

10,5s6 ~ t .
Table V (contin~led~ ~ydroxy~yridin .~; Pro~ot~
Conditions mmoles Weight of and other of Amine Product reactants Promoter Methanol Glycol Rh Recovery, %
3-Hydroxypyridine (pK = 4.8) Tetraglyme, 220 .10.0 . 3,2 0.4 99 ~ 15 Tetraglyme, : 10 0,5 mmole Cs 2-pyridin-olate 10.0 2.5 2.3 85 + 13 Tetraglyme, 220, 0.75 mmole (Ph3pl)2NoAc 1.25 ~ 5 2 ~ 8756 ++
4-Hydroxypyridine ~pK = 3.2) Tetraglyme, 220 10.0 2.4 0.6 88 ~ 17 Tetraglyme, 220, 0.5 mmole Cs 2-pyrid- -inolate 10.0 . 2.6 1.5 78 + 10 Tetraglyme, 0.75 mmole (Ph~P)2NOAc 3.0 1.3 4.6 87 ~ 9 " _ 1.5 2.9 76 + 11 - ` 43.
..

_ , 6 ~
10,556 Materials used in the examples possessed the follo~ing characteristics: cesium benæoate (recrystallized from H20, Analysis - Found: C, 32.62;
H, 1.90. Calcd. for C7H502Cs: C, 33.10; H, 1.98);
sparteine (bo 288-90); quinuclidine (sublimed, mp 161-2) trimethylenedimorpholine [bo 5 ~100, nmr(CDC13) :
~= 6.2-6.5 (m, 8.0H), 7.4-7.8 (m, 12H) 8.1-8.6 (m, 2.0H) tetramethylenedimorpholine [mp 51-4, nmr (CC14) :
~= 6.3-6.6 (m, 8.0H~, 7.5-7.9 (m, 12H), 8.4-8.7 (m, 4.0H).

44.

Claims

WHAT IS CLAIMED IS:

1. The process of producing alkane polyol 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; and the promoter provided in combination with the catalyst is present in an amount determined from the promoter's basicity to achieve the optimum rate of formation of the alkane polyol at said correlated catalyst concentration, temperature and pressure of said mixture, and the concentration of the promoter is the minimum concentration that provides the optimum rate of formation of the alkane polyol.

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.

45.