This invention relates to a process for separating one or more phosphorus acidic compounds from a hydroformylation reaction product fluid containing said one or more phosphorus acidic compounds, a metal-organophosphite ligand complex catalyst and optionally free organophosphite ligand which process comprises treating said hydroformylation reaction product fluid with water sufficient to remove at least some amount of said one or more phosphorus acidic compounds from said hydroformylation reaction product fluid.

This application claims the benefit of provisional U.S. patent application 
Ser. Nos. 60/008289, 60/008763, 60/008284 and 60/008286, all filed Dec. 6, 
1995, and all of which are incorporated herein by reference. 
BRIEF SUMMARY OF THE INVENTION 
1. Technical Field 
This invention relates to an improved metal-organophosphite ligand complex 
catalyzed hydroformylation process directed to producing aldehydes. More 
particularly this invention relates to the use of water to prevent and/or 
lessen hydrolytic degradation of the organophosphite ligand and 
deactivation of the metal-organophosphite ligand complex catalyst of such 
hydroformylation processes. 
2. Background of the Invention 
It is well known in the art that aldehydes may be readily produced by 
reacting an olefinically unsaturated compound with carbon monoxide and 
hydrogen in the presence of a rhodium-organophosphite ligand complex 
catalyst and that preferred processes involve continuous hydroformylation 
and recycling of the catalyst solution such as disclosed, for example, in 
U.S. Pat. Nos. 4,148,830; 4,717,775 and 4,769,498. Such aldehydes have a 
wide range of known utility and are useful, for example, as intermediates 
for hydrogenation to aliphatic alcohols, for aldol condensation to produce 
plasticizers, and for oxidation to produce aliphatic acids. 
However, notwithstanding the benefits attendant with such 
rhodium-organophosphite ligand complex catalyzed liquid recycle 
hydroformylation processes, stabilization of the catalyst and 
organophosphite ligand remains a primary concern of the art. Obviously 
catalyst stability is a key issue in the employment of any catalyst. Loss 
of catalyst or catalytic activity due to undesirable reactions of the 
highly expensive rhodium catalysts can be detrimental to the production of 
the desired aldehyde. Likewise degradation of the organophosphite ligand 
employed during the hydroformylation process can lead to poisoning 
organophosphite compounds or inhibitors or acidic byproducts that can 
lower the catalytic activity of the rhodium catalyst. Moreover, production 
costs of the aldehyde product obviously increase when productivity of the 
catalyst decreases. 
Numerous methods have been proposed to maintain catalyst and/or 
organophosphite ligand stability. For instance, U.S. Pat. No. 5,288,918 
suggests employing a catalytic activity enhancing additive such as water 
and/or a weakly acidic compound; U.S. Pat. No. 5,364,950 suggests adding 
an epoxide to stabilize the organophosphite ligand; and U.S. Pat. No. 
4,774,361 suggests carrying out the vaporization separation employed to 
recover the aldehyde product from the catalyst in the presence of an 
organic polymer containing polar functional groups selected from the class 
consisting of amide, ketone, carbamate, urea, and carbonate radicals in 
order to prevent and/or lessen rhodium precipitation from solution as 
rhodium metal or in the form of clusters of rhodium. Notwithstanding the 
value of the teachings of said references, the search for alternative 
methods and hopefully an even better and more efficient means for 
stabilizing the rhodium catalyst and organophosphite ligand employed 
remains an ongoing activity in the art. 
For instance, a major cause of organophosphite ligand degradation and 
catalyst deactivation of rhodium-organophosphite ligand complex catalyzed 
hydroformylation processes is due to the hydrolytic instability of the 
organophosphite ligands. All organophosphites are susceptible to 
hydrolysis in one degree or another, the rate of hydrolysis of 
organophosphites in general being dependent on the stereochemical nature 
of the organophosphite. In general, the bulkier the steric environment 
around the phosphorus atom, the slower the hydrolysis rate. For example, 
tertiary triorganophosphites such as triphenylphosphite are more 
susceptible to hydrolysis than diorganophosphites, such as disclosed in 
U.S. Pat. No. 4,737,588, and organopolyphosphites such as disclosed in 
U.S. Pat. Nos. 4,748,261 and 4,769,498. Moreover, all such hydrolysis 
reactions invariably produce phosphorus acidic compounds which catalyze 
the hydrolysis reactions. For example, the hydrolysis of a tertiary 
organophosphite produces a phosphonic acid diester, which is hydrolyzable 
to a phosphonic acid monoester, which in turn is hydrolyzable to H.sub.3 
PO.sub.3 acid. Moreover, hydrolysis of the ancillary products of side 
reactions, such as between a phosphonic acid diester and the aldehyde or 
between certain organophosphite ligands and an aldehyde, can lead to 
production of undesirable strong aldehyde acids, e.g., n-C.sub.3 H.sub.7 
CH(OH)P(O)(OH).sub.2. 
Indeed even highly desirable sterically-hindered organobisphosphites which 
are not very hydrolyzable can react with the aldehyde product to form 
poisoning organophosphites, e.g., organomonophosphites, which are not only 
catalytic inhibitors, but far more susceptible to hydrolysis and the 
formation of such aldehyde acid byproducts, e.g., hydroxy alkyl phosphonic 
acids, as shown, for example, in U.S. Pat. Nos. 5,288,918 and 5,364,950. 
Further, the hydrolysis of organophosphite ligands may be considered as 
being autocatalytic in view of the production of such phosphorus acidic 
compounds, e.g., H.sub.3 PO.sub.3, aldehyde acids such as hydroxy alkyl 
phosphonic acids, H.sub.3 PO.sub.4 and the like, and if left unchecked the 
catalyst system of the continuous liquid recycle hydroformylation process 
will become more and more acidic in time. Thus in time the eventual 
build-up of an unacceptable amount of such phosphorus acidic materials can 
cause the total destruction of the organophosphite present, thereby 
rendering the hydroformylation catalyst totally ineffective (deactivated) 
and the valuable rhodium metal susceptible to loss, e.g., due to 
precipitation and/or depositing on the walls of the reactor. Accordingly, 
a successful method for preventing and/or lessening such hydrolytic 
degradation of the organophosphite ligand and deactivation of the catalyst 
would be highly desirable to the art. 
DISCLOSURE OF THE INVENTION 
It has now been discovered that water may be employed to effectively remove 
such phosphorus acidic compounds and thus prevent and/or lessen hydrolytic 
degradation of organophosphite ligands and deactivation of 
metal-organophosphite ligand complex catalysts that may occur over the 
course of time during a hydroformylation process directed to producing 
aldehydes. Although both water and acid are factors in the hydrolysis of 
organophosphite ligands, it has been surprisingly discovered that 
hydroformylation reaction systems are more tolerant of higher levels of 
water than higher levels of acid. Thus, the water can be used to remove 
acid and decrease the rate of loss of organophosphite ligand by 
hydrolysis. It has also been surprisingly discovered that minimum loss of 
organophosphite ligand occurs when a hydroformylation reaction product 
fluid containing a metal-organophosphite ligand complex catalyst is 
contacted with water even at elevated temperatures. 
This invention relates in part to a process for separating one or more 
phosphorus acidic compounds from a hydroformylation reaction product fluid 
containing said one or more phosphorus acidic compounds, a 
metal-organophosphite ligand complex catalyst and optionally free 
organophosphite ligand which process comprises treating said 
hydroformylation reaction product fluid with water sufficient to remove at 
least some amount of said one or more phosphorus acidic compounds from 
said hydroformylation reaction product fluid. 
This invention also relates in part to a process for stabilizing an 
organophosphite ligand against hydrolytic degradation and/or a 
metal-organophosphite ligand complex catalyst against deactivation which 
process comprises treating a hydroformylation reaction product fluid 
containing a metal-organophosphite ligand complex catalyst and optionally 
free organophosphite ligand and which also contains one or more phosphorus 
acidic compounds, with water sufficient to remove at least some amount of 
said one or more phosphorus acidic compounds from said hydroformylation 
reaction product fluid. 
This invention further relates in part to a process for preventing and/or 
lessening hydrolytic degradation of an organophosphite ligand and/or 
deactivation of a metal-organophosphite ligand complex catalyst which 
process comprises treating a hydroformylation reaction product fluid 
containing a metal-organophosphite ligand complex catalyst and optionally 
free organophosphite ligand and which also contains one or more phosphorus 
acidic compounds, with water sufficient to remove at least some amount of 
said one or more phosphorus acidic compounds from said hydroformylation 
reaction product fluid. 
This invention yet further relates in part to an improved hydroformylation 
process which comprises reacting one or more olefinic unsaturated 
compounds with carbon monoxide and hydrogen in the presence of a 
metal-organophosphite ligand complex catalyst and optionally free 
organophosphite ligand to produce a reaction product fluid comprising one 
or more aldehydes, the improvement comprising preventing and/or lessening 
hydrolytic degradation of any said organophosphite ligand and deactivation 
of said metal-organophosphite ligand complex catalyst by treating at least 
a portion of said reaction product fluid derived from said 
hydroformylation process and which also contains phosphorus acidic 
compounds formed during said hydroformylation process with water 
sufficient to remove at least some amount of the phosphorus acidic 
compounds from said reaction product fluid. 
This invention also relates in part to an improved hydroformylation process 
for producing aldehydes which comprises (i) reacting in at least one 
reaction zone one or more olefinic unsaturated compounds with carbon 
monoxide and hydrogen in the presence of a metal-organophosphite ligand 
complex catalyst and optionally free organophosphite ligand to produce a 
reaction product fluid comprising one or more aldehydes and (ii) 
separating in at least one separation zone or in said at least one 
reaction zone the one or more aldehydes from said reaction product fluid, 
the improvement comprising preventing and/or lessening hydrolytic 
degradation of any said organophosphite ligand and deactivation of said 
metal-organophosphite ligand complex catalyst by (a) withdrawing from said 
at least one reaction zone or said at least one separation zone at least a 
portion of a reaction product fluid derived from said hydroformylation 
process and which also contains phosphorus acidic compounds formed during 
said hydroformylation process, (b) treating in at least one scrubber zone 
at least a portion of the withdrawn reaction product fluid derived from 
said hydroformylation process and which also contains phosphorus acidic 
compounds formed during said hydroformylation process with water 
sufficient to remove at least some amount of the phosphorus acidic 
compounds from said reaction product fluid, and (c) returning the treated 
reaction product fluid to said at least one reaction zone or said at least 
one separation zone. 
This invention further relates in part to an improved hydroformylation 
process for producing aldehydes which comprises (i) reacting in at least 
one reaction zone one or more olefinic unsaturated compounds with carbon 
monoxide and hydrogen in the presence of a metal-organophosphite ligand 
complex catalyst and optionally free organophosphite ligand to produce a 
reaction product fluid comprising one or more aldehydes and (ii) 
separating in at least one separation zone or in said at least one 
reaction zone the one or more aldehydes from said reaction product fluid, 
the improvement comprising preventing and/or lessening hydrolytic 
degradation of any said organophosphite ligand and deactivation of said 
metal-organophosphite ligand complex catalyst by treating at least a 
portion of said reaction product fluid derived from said hydroformylation 
process and which also contains phosphorus acidic compounds formed during 
said hydroformylation process by introducing water into said at least one 
reaction zone and/or said at least one separation zone sufficient to 
remove at least some amount of the phosphorus acidic compounds from said 
reaction product fluid.

DETAILED DESCRIPTION 
The hydroformylation processes of this invention may be asymmetric or 
non-asymmetric, the preferred processes being non-asymmetric, and may be 
conducted in any continuous or semi-continuous fashion and may involve any 
catalyst liquid and/or gas recycle operation desired. Thus it should be 
clear that the particular hydroformylation process for producing such 
aldehydes from an olefinic unsaturated compound, as well as the reaction 
conditions and ingredients of the hydroformylation process are not 
critical features of this invention. As used herein, the term 
"hydroformylation" is contemplated to include, but not limited to, all 
permissible asymmetric and non-asymmetric hydroformylation processes which 
involve converting one or more substituted or unsubstituted olefinic 
compounds or a reaction mixture comprising one or more substituted or 
unsubstituted olefinic compounds to one or more substituted or 
unsubstituted aldehydes or a reaction mixture comprising one or more 
substituted or unsubstituted aldehydes. As used herein, the term "reaction 
product fluid" is contemplated to include, but not limited to, a reaction 
mixture containing an amount of any one or more of the following: (a) a 
metal-organophosphite ligand complex catalyst, (b) free organophosphite 
ligand, (c) one or more phosphorus acidic compounds formed in the 
reaction, (d) aldehyde product formed in the reaction, (e) unreacted 
reactants, and (f) an organic solubilizing agent for said 
metal-organophosphite ligand complex catalyst and said free 
organophosphite ligand. The reaction product fluid encompasses, but is not 
limited to, (a) the reaction medium in the reaction zone, (b) the reaction 
medium stream on its way to the separation zone, (c) the reaction medium 
in the separation zone, (d) the recycle stream between the separation zone 
and the reaction zone, (e) the reaction medium withdrawn from the reaction 
zone or separation zone for treatment with the water, (f) the withdrawn 
reaction medium treated with the water, (g) the treated reaction medium 
returned to the reaction zone or separation zone, and (h) reaction medium 
in external cooler. 
Illustrative metal-organophosphite ligand complex catalyzed 
hydroformylation processes which may experience such hydrolytic 
degradation of the organophosphite ligand and catalytic deactivation 
include such processes as described, for example, in U.S. Pat. Nos. 
4,148,830; 4,593,127; 4,769,498; 4,717,775; 4,774,361; 4,885,401; 
5,264,616; 5,288,918; 5,360,938; 5,364,950; and 5,491,266; the disclosures 
of which are incorporated herein by reference. Accordingly, the 
hydroformylation processing techniques of this invention may correspond to 
any known processing techniques. Preferred processes are those involving 
catalyst liquid recycle hydroformylation processes. 
In general, such catalyst liquid recycle hydroformylation processes involve 
the production of aldehydes by reacting an olefinic unsaturated compound 
with carbon monoxide and hydrogen in the presence of a 
metal-organophosphite ligand complex catalyst in a liquid medium that also 
contains an organic solvent for the catalyst and ligand. Preferably free 
organophosphite ligand is also present in the liquid hydroformylation 
reaction medium. By "free organophosphite ligand" is meant organophosphite 
ligand that is not complexed with (tied to or bound to) the metal, e.g., 
metal atom, of the complex catalyst. The recycle procedure generally 
involves withdrawing a portion of the liquid reaction medium containing 
the catalyst and aldehyde product from the hydroformylation reactor (i.e., 
reaction zone), either continuously or intermittently, and recovering the 
aldehyde product therefrom by use of a composite membrane such as 
disclosed in U.S. Pat. No. 5,430,194 and copending U.S. patent application 
Ser. No. 08/430,790, filed May 5, 1995, the disclosures of which are 
incorporated herein by reference, or by the more conventional and 
preferred method of distilling it (i.e., vaporization separation) in one 
or more stages under normal, reduced or elevated pressure, as appropriate, 
in a separate distillation zone, the non-volatilized metal catalyst 
containing residue being recycled to the reaction zone as disclosed, for 
example, in U.S. Pat. No. 5,288,918. Condensation of the volatilized 
materials, and separation and further recovery thereof, e.g., by further 
distillation, can be carried out in any conventional manner, the crude 
aldehyde product can be passed on for further purification and isomer 
separation, if desired, and any recovered reactants, e.g., olefinic 
starting material and syn gas, can be recycled in any desired manner to 
the hydroformylation zone (reactor). The recovered metal catalyst 
containing raffinate of such membrane separation or recovered 
non-volatilized metal catalyst containing residue of such vaporization 
separation can be recycled, to the hydroformylation zone (reactor) in any 
conventional manner desired. 
In a preferred embodiment, the hydroformylation reaction product fluids 
employable herein includes any fluid derived from any corresponding 
hydroformylation process that contains at least some amount of four 
different main ingredients or components, i.e., the aldehyde product, a 
metal-organophosphite ligand complex catalyst, free organophosphite ligand 
and an organic solubilizing agent for said catalyst and said free ligand, 
said ingredients corresponding to those employed and/or produced by the 
hydroformylation process from whence the hydroformylation reaction mixture 
starting material may be derived. It is to be understood that the 
hydroformylation reaction mixture compositions employable herein can and 
normally will contain minor amounts of additional ingredients such as 
those which have either been deliberately employed in the hydroformylation 
process or formed in situ during said process. Examples of such ingredients 
that can also be present include unreacted olefin starting material, carbon 
monoxide and hydrogen gases, and in situ formed type products, such as 
saturated hydrocarbons and/or unreacted isomerized olefins corresponding 
to the olefin starting materials, and high boiling liquid aldehyde 
condensation byproducts, as well as other inert co-solvent type materials 
or hydrocarbon additives, if employed. 
Illustrative metal-organophosphite ligand complex catalysts employable in 
such hydroformylation reactions encompassed by this invention as well as 
methods for their preparation are well known in the art and include those 
disclosed in the above mentioned patents. In general such catalysts may be 
preformed or formed in situ as described in such references and consist 
essentially of metal in complex combination with an organophosphite 
ligand. It is believed that carbon monoxide is also present and complexed 
with the metal in the active species. The active species may also contain 
hydrogen directly bonded to the metal. 
The catalyst useful in the hydroformylation process includes a 
metal-organophosphite ligand complex catalyst which can be optically 
active or non-optically active. The permissible metals which make up the 
metal-organophosphite ligand complexes include Group 8, 9 and 10 metals 
selected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), 
iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and 
mixtures thereof, with the preferred metals being rhodium, cobalt, iridium 
and ruthenium, more preferably rhodium, cobalt and ruthenium, especially 
rhodium. Mixtures of metals from Groups 8, 9 and 10 may also be used in 
this invention. The permissible organophosphite ligands which make up the 
metal-organophosphite ligand complexes and free organophosphite ligand 
include mono-, di-, tri- and higher polyorganophosphites. Mixtures of such 
ligands may be employed if desired in the metal-organophosphite ligand 
complex catalyst and/or free ligand and such mixtures may be the same or 
different. This invention is not intended to be limited in any manner by 
the permissible organophosphite ligands or mixtures thereof. It is to be 
noted that the successful practice of this invention does not depend and 
is not predicated on the exact structure of the metal-organophosphite 
ligand complex species, which may be present in their mononuclear, 
dinuclear and/or higher nuclearity forms. Indeed, the exact structure is 
not known. Although it is not intended herein to be bound to any theory or 
mechanistic discourse, it appears that the catalytic species may in its 
simplest form consist essentially of the metal in complex combination with 
the organophosphite ligand and carbon monoxide and/or hydrogen when used. 
The term "complex" as used herein and in the claims means a coordination 
compound formed by the union of one or more electronically rich molecules 
or atoms capable of independent existence with one or more electronically 
poor molecules or atoms, each of which is also capable of independent 
existence. For example, the organophosphite ligands employable herein may 
possess one or more phosphorus donor atoms, each having one available or 
unshared pair of electrons which are each capable of forming a coordinate 
covalent bond independently or possibly in concert (e.g., via chelation) 
with the metal. Carbon monoxide (which is also properly classified as a 
ligand) can also be present and complexed with the metal. The ultimate 
composition of the complex catalyst may also contain an additional ligand, 
e.g., hydrogen or an anion satisfying the coordination sites or nuclear 
charge of the metal. Illustrative additional ligands include, for example, 
halogen (Cl, Br, I), alkyl, aryl, substituted aryl, acyl, CF.sub.3, C.sub.2 
F.sub.5, CN, (R).sub.2 PO and RP(O)(OH)O (wherein each R is the same or 
different and is a substituted or unsubstituted hydrocarbon radical, e.g., 
the alkyl or aryl), acetate, acetylacetonate, SO.sub.4, PF.sub.4, PF.sub.6, 
NO.sub.2, NO.sub.3, CH.sub.3 O, CH.sub.2 .dbd.CHCH.sub.2, CH.sub.3 
CH.dbd.CHCH.sub.2, C.sub.6 H.sub.5 CN, CH.sub.3 CN, NH.sub.3, pyridine, 
(C.sub.2 H.sub.5).sub.3 N, mono-olefins, diolefins and triolefins, 
tetrahydrofuran, and the like. It is of course to be understood that the 
complex species are preferably free of any additional organic ligand or 
anion that might poison the catalyst or have an undue adverse effect on 
catalyst performance. It is preferred in the metal-organophosphite ligand 
complex catalyzed hydroformylation reactions that the active catalysts be 
free of halogen and sulfur directly bonded to the metal, although such may 
not be absolutely necessary. 
The number of available coordination sites on such metals is well known in 
the art. Thus the catalytic species may comprise a complex catalyst 
mixture, in their monomeric, dimeric or higher nuclearity forms, which are 
preferably characterized by at least one organophosphite-containing 
molecule complexed per one molecule of metal, e.g., rhodium. For instance, 
it is considered that the catalytic species of the preferred catalyst 
employed in a hydroformylation reaction may be complexed with carbon 
monoxide and hydrogen in addition to the organophosphite ligands in view 
of the carbon monoxide and hydrogen gas employed by the hydroformylation 
reaction. 
The organophosphites that may serve as the ligand of the 
metal-organophosphite ligand complex catalyst and/or free ligand of the 
hydroformylation processes and reaction product fluids of this invention 
may be of the achiral (optically inactive) or chiral (optically active) 
type and are well known in the art. Achiral organophosphites are 
preferred. 
Among the organophosphites that may serve as the ligand of the 
metal-organophosphite ligand complex catalyst containing reaction product 
fluids of this invention and/or any free organophosphite ligand of the 
hydroformylation process that might also be present in said reaction 
product fluids are monoorganophosphite, diorganophosphite, 
triorganophosphite and organopolyphosphite compounds. Such organophosphite 
ligands employable in this invention and/or methods for their preparation 
are well known in the art. 
Representative monoorganophosphites may include those having the formula: 
##STR1## 
wherein R.sup.1 represents a substituted or unsubstituted trivalent 
hydrocarbon radical containing from 4 to 40 carbon atoms or greater, such 
as trivalent acyclic and trivalent cyclic radicals, e.g., trivalent 
alkylene radicals such as those derived from 1,2,2-trimethylolpropane and 
the like, or trivalent cycloalkylene radicals such as those derived from 
1,3,5-trihydroxycyclohexane, and the like. Such monoorganophosphites may 
be found described in greater detail, for example, in U.S. Pat. No. 
4,567,306, the disclosure of which is incorporated herein by reference 
thereto. 
Representative diorganophosphites may include those having the formula: 
##STR2## 
wherein R.sup.2 represents a substituted or unsubstituted divalent 
hydrocarbon radical containing from 4 to 40 carbon atoms or greater and W 
represents a substituted or unsubstituted monovalent hydrocarbon radical 
containing from 1 to 18 carbon atoms or greater. 
Representative substituted and unsubstituted monovalent hydrocarbon 
radicals represented by W in the above Formula (II) include alkyl and aryl 
radicals, while representative substituted and unsubstituted divalent 
hydrocarbon radicals represented by R.sup.2 include divalent acyclic 
radicals and divalent aromatic radicals. Illustrative divalent acyclic 
radicals include, for example, alkylene, alkylene-oxy-alkylene, 
alkylene-NR.sup.4 -alkylene wherein R.sup.4 is hydrogen or a substituted 
or unsubstituted monovalent hydrocarbon radical, e.g., an alkyl radical 
having 1 to 4 carbon atoms; alkylene-S-alkylene, and cycloalkylene 
radicals, and the like. The more preferred divalent acyclic radicals are 
the divalent alkylene radicals such as disclosed more fully, for example, 
in U.S. Pat. Nos. 3,415,906 and 4,567,302 and the like, the disclosures of 
which are incorporated herein by reference. Illustrative divalent aromatic 
radicals include, for example, arylene, bisarylene, arylene-alkylene, 
arylene-alkylene-arylene, arylene-oxy-arylene, arylene-NR.sup.4 -arylene 
wherein R.sup.4 is as defined above, arylene-S-arylene, and 
arylene-S-alkylene, and the like. More preferably R.sup.2 is a divalent 
aromatic radical such as disclosed more fully, for example, in U.S. Pat. 
Nos. 4,599,206, 4,717,775, 4,835,299, and the like, the disclosures of 
which are incorporated herein by reference. 
Representative of a more preferred class of diorganophosphites are those of 
the formula: 
##STR3## 
wherein W is as defined above, each Ar is the same or different and 
represents a substituted or unsubstituted aryl radical, each y is the same 
or different and is a value of 0 or 1, Q represents a divalent bridging 
group selected from --C(R.sup.3).sub.2 --, --O--, --S--, --NR.sup.4 --, 
Si(R.sup.5).sub.2 -- and --CO--, wherein each R.sup.3 is the same or 
different and represents hydrogen, an alkyl radical having from 1 to 12 
carbon atoms, phenyl, tolyl, and anisyl, R.sup.4 is as defined above, each 
R.sup.5 is the same or different and represents hydrogen or a methyl 
radical, and m is a value of 0 or 1. Such diorganophosphites are described 
in greater detail, for example, in U.S. Pat. Nos. 4,599,206, 4,717,775, and 
4,835,299 the disclosures of which are incorporated herein by reference. 
Representative triorganophosphites may include those having the formula: 
##STR4## 
wherein each R.sup.6 is the same or different and is a substituted or 
unsubstituted monovalent hydrocarbon radical e.g., an alkyl, cycloalkyl, 
aryl, alkaryl and aralkyl radicals which may contain from 1 to 24 carbon 
atoms. Illustrative triorganophosphites include, for example, trialkyl 
phosphites, dialkylaryl phosphites, alkyldiaryl phosphites, triaryl 
phosphites, and the like, such as, for example, trimethyl phosphite, 
triethyl phosphite, butyldiethyl phosphite, tri-n-propyl phosphite, 
tri-n-butyl phosphite, tri-2-ethylhexyl phosphite, tri-n-octyl phosphite, 
tri-n-dodecyl phosphite, dimethylphenyl phosphite, diethylphenyl 
phosphite, methyldiphenyl phosphite, ethyldiphenyl phosphite, triphenyl 
phosphite, trinaphthyl phosphite, 
bis(3,6,8-tri-t-butyl-2-naphthyl)methylphosphite, 
bis(3,6,8-tri-t-butyl-2-naphthyl)cyclohexylphosphite, 
tris(3,6-di-t-butyl-2-naphthyl)phosphite, 
bis(3,6,8-tri-t-butyl-2-naphthyl)(4-biphenyl)phosphite, 
bis(3,6,8-tri-t-butyl-2-naphthyl)phenylphosphite, 
bis(3,6,8-tri-t-butyl-2-naphthyl)(4-benzoylphenyl)phosphite, 
bis(3,6,8-tri-t-butyl-2-naphthyl)(4-sulfonylphenyl)phosphite, and the 
like. The most preferred triorganophosphite is triphenylphosphite. Such 
triorganophosphites are described in greater detail, for example, in U.S. 
Pat. Nos. 3,527,809 and 5,277,532, the disclosures of which are 
incorporated herein by reference. 
Representative organopolyphosphites contain two or more tertiary 
(trivalent) phosphorus atoms and may include those having the formula: 
##STR5## 
wherein X represents a substituted or unsubstituted n-valent organic 
bridging radical containing from 2 to 40 carbon atoms, each R.sup.7 is the 
same or different and represents a divalent organic radical containing from 
4 to 40 carbon atoms, each R.sup.8 is the same or different and represents 
a substituted or unsubstituted monovalent hydrocarbon radical containing 
from 1 to 24 carbon atoms, a and b can be the same or different and each 
have a value of 0 to 6, with the proviso that the sum of a+b is 2 to 6 and 
n equals a+b. Of course it is to be understood that when a has a value of 2 
or more, each R.sup.7 radical may be the same or different. Each R.sup.8 
radical may also be the same or different any given compound. 
Representative n-valent (preferably divalent) organic bridging radicals 
represented by X and representative divalent organic radicals represented 
by R.sup.7 above, include both acyclic radicals and aromatic radicals, 
such as alkylene, alkylene-Q.sub.m -alkylene, cycloalkylene, arylene, 
bisarylene, arylene-alkylene, and arylene-(CH.sub.2).sub.y --Q.sub.m 
--(CH.sub.2).sub.y -arylene radicals, and the like, wherein each Q, y and 
m are as defined above in Formula (III). The more preferred acyclic 
radicals represented by X and R.sup.7 above are divalent alkylene 
radicals, while the more preferred aromatic radicals represented by X and 
R.sup.7 above are divalent arylene and bisarylene radicals, such as 
disclosed more fully, for example, in U.S. Pat. Nos. 4,769,498; 4,774,361: 
4,885,401; 5,179,055; 5,113,022; 5,202,297; 5,235,113; 5,264,616 and 
5,364,950, and European Patent Application Publication No. 662,468, and 
the like, the disclosures of which are incorporated herein by reference. 
Representative preferred monovalent hydrocarbon radicals represented by 
each R.sup.8 radical above include alkyl and aromatic radicals. 
Illustrative preferred organopolyphosphites may include bisphosphites such 
as those of Formulas (VI) to (VIII) below: 
##STR6## 
wherein each R.sup.7, R.sup.8 and X of Formulas (VI) to (VIII) are the same 
as defined above for Formula (V). Preferably each R.sup.7 and X represents 
a divalent hydrocarbon radical selected from alkylene, arylene, 
arylene-alkylene-arylene, and bisarylene, while each R.sup.8 radical 
represents a monovalent hydrocarbon radical selected from alkyl and aryl 
radicals. Organophosphite ligands of such Formulas (V) to (VIII) may be 
found disclosed, for example, in U.S. Pat. Nos. 4,668,651; 4,748,261; 
4,769,498; 4,774,361; 4,885,401; 5,113,022; 5,179,055; 5,202,297; 
5,235,113; 5,254,741; 5,264,616; 5,312,996; 5,364,950; and 5,391,801; the 
disclosures of all of which are incorporated herein by reference. 
Representative of more preferred classes of organobisphosphites are those 
of the following Formulas (IX) to (XI) 
##STR7## 
wherein Ar, Q, R.sup.7, R.sup.8, X , m, and y are as defined above. Most 
preferably X represents a divalent aryl-(CH.sub.2).sub.y --(Q).sub.m 
--(CH.sub.2).sub.y -aryl radical wherein each y individually has a value 
of 0 or 1; m has a value of 0 or 1 and Q is --O--, --S-- or 
--C(R.sup.3).sub.2 where each R.sup.3 is the same or different and 
represents hydrogen or a methyl radical. More preferably each alkyl 
radical of the above defined R.sup.8 groups may contain from 1 to 24 
carbon atoms and each aryl radical of the above-defined Ar, X, R.sup.7 and 
R.sup.8 groups of the above Formulas (IX) to (XI) may contain from 6 to 18 
carbon atoms and said radicals may be the same or different, while the 
preferred alkylene radicals of X may contain from 2 to 18 carbon atoms and 
the preferred alkylene radicals of R.sup.7 may contain from 5 to 18 carbon 
atoms. In addition, preferably the divalent Ar radicals and divalent aryl 
radicals of X of the above formulas are phenylene radicals in which the 
bridging group represented by --(CH.sub.2).sub.y --(Q).sub.m 
--(CH.sub.2).sub.y -- is bonded to said phenylene radicals in positions 
that are ortho to the oxygen atoms of the formulas that connect the 
phenylene radicals to their phosphorus atom of the formulae. It is also 
preferred that any substituent radical when present on such phenylene 
radicals be bonded in the para and/or ortho position of the phenylene 
radicals in relation to the oxygen atom that bonds the given substituted 
phenylene radical to its phosphorus atom. 
Of course any of the R.sup.1, R.sup.2, R.sup.6, R.sup.7, R.sup.8, W, X, Q 
and Ar radicals of such organophosphites of Formulas (I) to (XI) above may 
be substituted if desired, with any suitable substituent containing from 1 
to 30 carbon atoms that does not unduly adversely affect the desired 
result of the process of this invention. Substituents that may be on said 
radicals in addition of course to corresponding hydrocarbon radicals such 
as alkyl, aryl, aralkyl, alkaryl and cyclohexyl substituents, may include 
for example silyl radicals such as --Si(R.sup.10).sub.3 ; amino radicals 
such as --N(R.sup.10).sub.2 ; phosphine radicals such as 
-aryl-P(R.sup.10).sub.2; acyl radicals such as --C(O)R.sup.10 acyloxy 
radicals such as --OC(O)R.sup.10 ; amido radicals such as 
--CON(R.sup.10).sub.2 and --N(R.sup.10)COR.sup.10 ; sulfonyl radicals such 
as --SO.sub.2 R.sup.10, alkoxy radicals such as --OR.sup.10 ; sulfinyl 
radicals such as --SOR.sup.10, sulfenyl radicals such as --SR.sup.10, 
phosphonyl radicals such as --P(O)(R.sup.10).sub.2, as well as halogen, 
nitro, cyano, trifluoromethyl, hydroxy radicals, and the like, wherein 
each R.sup.10 radical individually represents the same or different 
monovalent hydrocarbon radical having from 1 to 18 carbon atoms (e.g., 
alkyl, aryl, aralkyl, alkaryl and cyclohexyl radicals), with the proviso 
that in amino substituents such as --N(R.sup.10).sub.2 each R.sup.10 taken 
together can also represent a divalent bridging group that forms a 
heterocyclic radical with the nitrogen atom, and in amido substituents 
such as --C(O)N(R.sup.10).sub.2 and --N(R.sup.10)COR.sup.10 each R.sup.10 
bonded to N can also be hydrogen. Of course it is to be understood that 
any of the substituted or unsubstituted hydrocarbon radicals groups that 
make up a particular given organophosphite may be the same or different. 
More specifically illustrative substituents include primary, secondary and 
tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, 
sec-butyl, t-butyl, neo-pentyl, n-hexyl, amyl, sec-amyl, t-amyl, iso-octyl, 
decyl, octadecyl, and the like; aryl radicals such as phenyl, naphthyl and 
the like; aralkyl radicals such as benzyl, phenylethyl, triphenylmethyl, 
and the like; alkaryl radicals such as tolyl, xylyl, and the like; 
alicyclic radicals such as cyclopentyl, cyclohexyl, 1-methylcyclohexyl, 
cyclooctyl, cyclohexylethyl, and the like; alkoxy radicals such as 
methoxy, ethoxy, propoxy, t-butoxy, --OCH.sub.2 CH.sub.2 OCH.sub.3, 
--O(CH.sub.2 CH.sub.2).sub.2 OCH.sub.3, --O(CH.sub.2 CH.sub.2).sub.3 
OCH.sub.3, and the like; aryloxy radicals such as phenoxy and the like; as 
well as silyl radicals such as --Si(CH.sub.3).sub.3, --Si(OCH.sub.3).sub.3, 
--Si(C.sub.3 H.sub.7).sub.3, and the like; amino radicals such as 
--NH.sub.2, --N(CH.sub.3).sub.2, --NHCH.sub.3, --NH(C.sub.2 H.sub.5), and 
the like; arylphosphine radicals such as --P(C.sub.6 H.sub.5).sub.2, and 
the like; acyl radicals such as --C(O)CH.sub.3, --C(O)C.sub.2 H.sub.5, 
--C(O)C.sub.6 H.sub.5, and the like; carbonyloxy radicals such as 
--C(O)OCH.sub.3 and the like; oxycarbonyl radicals such as --O(CO)C.sub.6 
H.sub.5, and the like; amido radicals such as --CONH.sub.2, 
--CON(CH.sub.3).sub.2, --NHC(O)CH.sub.3, and the like; sulfonyl radicals 
such as --S(O).sub.2 C.sub.2 H.sub.5 and the like; sulfinyl radicals such 
as --S(O)CH.sub.3 and the like; sulfenyl radicals such as --SCH.sub.3, 
--SC.sub.2 H.sub.5, --SC.sub.6 H.sub.5, and the like; phosphonyl radicals 
such as --P(O)(C.sub.6 H.sub.5).sub.2, --P(O)(CH.sub.3).sub.2, 
--P(O)(C.sub.2 H.sub.5).sub.2, --P(O)(C.sub.3 H.sub.7).sub.2, 
--P(O)(C.sub.4 H.sub.9).sub.2, --P(O)(C.sub.6 H.sub.13).sub.2, 
--P(O)CH.sub.3 (C.sub.6 H.sub.5), --P(O)(H)(C.sub.6 H.sub.5), and the 
like. 
Specific illustrative examples of such organophosphite ligands include the 
following: 
2-t-butyl-4-methoxyphenyl(3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2' 
-diyl)phosphite having the formula: 
##STR8## 
methyl(3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)phosphite 
having the formula: 
##STR9## 
6,6'-4,4'-bis(1,1-dimethylethyl)-1,1'-binaphthyl!-2,2'-diyl!bis(oxy)!bis 
- 
dibenzod,f!1,3,2!-dioxaphosphepin having the formula: 
##STR10## 
6,6'-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy-1,1'-biphenyl!-2,2'-diyl 
! 
bis(oxy)!bis-dibenzod,f!1,3,2!dioxaphosphepin having the formula: 
##STR11## 
6,6'-3,3',5,5'-tetrakis(1,1-dimethylpropyl)-1,1'-biphenyl!-2,2'-diyl!bis 
( 
oxy)!bis-dibenzo d,f!1,3,2!dioxaphosphepin having the formula: 
##STR12## 
6,6'-3,3',5,5'-tetrakis(1,1-dimethylethyl)-1,1'-biphenyl!-2,2'-diyl!bis(o 
x 
y)!bis-dibenzod,f!1,3,2!-dioxaphosphepin having the formula: 
##STR13## 
(2R,4R)-di2,2'-(3,3',5,5'-tetrakis-tert-amyl-1,1'-biphenyl)!-2,4-pentyldip 
h 
osphite having the formula: 
##STR14## 
(2R,4R)-di2,2'-(3,3',5,5'-tetrakis-tert-butyl-1,1'-biphenyl)!-2,4-pentyldi 
p 
hosphite having the formula: 
##STR15## 
(2R,4R)-di2,2'-(3,3'-di-amyl-5,5'-dimethoxy-1,1'-biphenyl)!-2,4-pentyldiph 
o 
sphite having the formula: 
##STR16## 
(2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-dimethyl-1,1'-biphenyl)!-2,4-penty 
l 
diphosphite having the formula: 
##STR17## 
(2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-diethoxy-1,1'-biphenyl)!-2,4-penty 
l 
diphosphite having the formula: 
##STR18## 
(2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-diethyl-1,1'-biphenyl)!-2,4-pentyl 
d 
iphosphite having the formula: 
##STR19## 
(2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl)!-2,4-pent 
y 
ldiphosphite having the formula: 
##STR20## 
6-2'-(4,6-bis(1,1-dimethylethyl)-1,3,2-benzodioxaphosphol-2-yl)oxy!-3,3' 
- 
bis(1,1-dimethylethyl)-5,5'-dimethoxy1,1'-biphenyl!-2-yl!oxy!-4,8-bis(1,1- 
dimethylethyl)-2,10-dimethoxydibenzod,f!1,3,2!dioxaphosphepin having the 
formula: 
##STR21## 
6-2'-1,3,2-benzodioxaphosphol-2-yl)oxy!-3,3'-bis(1,1-dimethylethyl)-5,5' 
- 
dimethoxy1,1'-biphenyl!-2-yl!oxy!-4,8-bis(1,1-dimethylethyl)-2,10-dimethox 
ydibenzod,f!1,3,2!dioxaphosphepin having the formula: 
##STR22## 
6-2'-(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl)oxy!-3,3'-bis(1,1-dimeth 
y 
lethyl)-5,5'-dimethoxy1,1'-biphenyl!-2-yl!oxy!-4,8-bis(1,1-dimethylethyl)- 
2,10-dimethoxydibenzod,f!1,3,2!dioxaphosphepin having the formula: 
##STR23## 
2'-4,8-bis(1,1-dimethylethyl)-2,10-dimethoxydibenzod,f!1,3,2!-dioxaphos 
p 
hepin-6-yl!oxy!-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy1,1'-biphenyl!-2 
-yl bis(4-hexylphenyl)ester of phosphorous acid having the formula: 
##STR24## 
2-2-4,8,-bis(1,1-dimethylethyl),2,10-dimethoxydibenzo-d,f!1,3,2!dioxo 
p 
hosphepin-6-yl!oxy!-3-(1,1-dimethylethyl)-5-methoxyphenyl!methyl!-4-methoxy 
,6-(1,1-dimethylethyl)phenyl diphenyl ester of phosphorous acid having the 
formula: 
##STR25## 
3-methoxy-1,3-cyclohexamethylene 
tetrakis3,6-bis(1,1-dimethylethyl)-2-naphthalenyl!ester of phosphorous 
acid having the formula: 
##STR26## 
2,5-bis(1,1-dimethylethyl)-1,4-phenylene 
tetrakis2,4-bis(1,1-dimethylethyl)phenyl!ester of phosphorous acid having 
the formula: 
##STR27## 
methylenedi-2,1-phenylene tetrakis2,4-bis(1,1-dimethylethyl)phenyl!ester 
of phosphorous acid having the formula: 
##STR28## 
1,1'-biphenyl!-2,2'-diyl 
tetrakis2-(1,1-dimethylethyl)-4-methoxyphenyl!ester of phosphorous acid 
having the formula: 
##STR29## 
As noted above, the metal-organophosphite ligand complex catalysts 
employable in this invention may be formed by methods known in the art. 
The metal-organophosphite ligand complex catalysts may be in homogeneous 
or heterogeneous form. For instance, preformed rhodium 
hydrido-carbonyl-organophosphite ligand catalysts may be prepared and 
introduced into the reaction mixture of a hydroformylation process. More 
preferably, the rhodium-organophosphite ligand complex catalysts can be 
derived from a rhodium catalyst precursor which may be introduced into the 
reaction medium for in situ formation of the active catalyst. For example, 
rhodium catalyst precursors such as rhodium dicarbonyl acetylacetonate, 
Rh.sub.2 O.sub.3, Rh.sub.4 (CO).sub.12, Rh.sub.6 (CO).sub.16, 
Rh(NO.sub.3).sub.3 and the like may be introduced into the reaction 
mixture along with the organophosphite ligand for the in situ formation of 
the active catalyst. In a preferred embodiment of this invention, rhodium 
dicarbonyl acetylacetonate is employed as a rhodium precursor and reacted 
in the presence of a solvent with the organophosphite ligand to form a 
catalytic rhodium-organophosphite ligand complex precursor which is 
introduced into the reactor along with excess (free) organophosphite 
ligand for the in situ formation of the active catalyst. In any event, it 
is sufficient for the purpose of this invention that carbon monoxide, 
hydrogen and organophosphite compound are all ligands that are capable of 
being complexed with the metal and that an active metal-organophosphite 
ligand catalyst is present in the reaction mixture under the conditions 
used in the hydroformylation reaction. 
More particularly, a catalyst precursor composition can be formed 
consisting essentially of a solubilized metal-organophosphite ligand 
complex precursor catalyst, an organic solvent and free organophosphite 
ligand. Such precursor compositions may be prepared by forming a solution 
of a rhodium starting material, such as a rhodium oxide, hydride, carbonyl 
or salt, e.g. a nitrate, which may or may not be in complex combination 
with a organophosphite ligand as defined herein. Any suitable rhodium 
starting material may be employed, e.g. rhodium dicarbonyl 
acetylacetonate, Rh.sub.2 O.sub.3, Rh.sub.4 (CO).sub.12, Rh.sub.6 
(CO).sub.16, Rh(NO.sub.3).sub.3, and organophosphite ligand rhodium 
carbonyl hydrides. Carbonyl and organophosphite ligands, if not already 
complexed with the initial rhodium, may be complexed to the rhodium either 
prior to or in situ during the hydroformylation process. 
By way of illustration, the preferred catalyst precursor composition of 
this invention consists essentially of a solubilized rhodium carbonyl 
organophosphite ligand complex precursor catalyst, a solvent and 
optionally free organophosphite ligand prepared by forming a solution of 
rhodium dicarbonyl acetylacetonate, an organic solvent and a 
organophosphite ligand as defined herein. The organophosphite ligand 
readily replaces one of the carbonyl ligands of the rhodium 
acetylacetonate complex precursor at room temperature as witnessed by the 
evolution of carbon monoxide gas. This substitution reaction may be 
facilitated by heating the solution if desired. Any suitable organic 
solvent in which both the rhodium dicarbonyl acetylacetonate complex 
precursor and rhodium organophosphite ligand complex precursor are soluble 
can be employed. The amounts of rhodium complex catalyst precursor, organic 
solvent and organophosphite ligand, as well as their preferred embodiments 
present in such catalyst precursor compositions may obviously correspond 
to those amounts employable in the hydroformylation process of this 
invention. Experience has shown that the acetylacetonate ligand of the 
precursor catalyst is replaced after the hydroformylation process has 
begun with a different ligand, e.g., hydrogen, carbon monoxide or 
organophosphite ligand, to form the active complex catalyst as explained 
above. The acetylacetone which is freed from the precursor catalyst under 
hydroformylation conditions is removed from the reaction medium with the 
product aldehyde and thus is in no way detrimental to the hydroformylation 
process. The use of such preferred rhodium complex catalytic precursor 
compositions provides a simple economical and efficient method for 
handling the rhodium precursor and hydroformylation start-up. 
Accordingly, the metal-organophosphite ligand complex catalysts used in the 
process of this invention consists essentially of the metal complexed with 
carbon monoxide and a organophosphite ligand, said ligand being bonded 
(complexed) to the metal in a chelated and/or non-chelated fashion. 
Moreover, the terminology "consists essentially of", as used herein, does 
not exclude, but rather includes, hydrogen complexed with the metal, in 
addition to carbon monoxide and the organophosphite ligand. Further, such 
terminology does not exclude the possibility of other organic ligands 
and/or anions that might also be complexed with the metal. Materials in 
amounts which unduly adversely poison or unduly deactivate the catalyst 
are not desirable and so the catalyst most desirably is free of 
contaminants such as metal-bound halogen (e.g., chlorine, and the like) 
although such may not be absolutely necessary. The hydrogen and/or 
carbonyl ligands of an active metal-organophosphite ligand complex 
catalyst may be present as a result of being ligands bound to a precursor 
catalyst and/or as a result of in situ formation, e.g., due to the 
hydrogen and carbon monoxide gases employed in hydroformylation process of 
this invention. 
As noted the hydroformylation processes of this invention involve the use 
of a metal-organophosphite ligand complex catalyst as described herein. Of 
course mixtures of such catalysts can also be employed if desired. The 
amount of metal-organophosphite ligand complex catalyst present in the 
reaction medium of a given hydroformylation process encompassed by this 
invention need only be that minimum amount necessary to provide the given 
metal concentration desired to be employed and which will furnish the 
basis for at least the catalytic amount of metal necessary to catalyze the 
particular hydroformylation process involved such as disclosed, for 
example, in the above-mentioned patents. In general, metal, e.g., rhodium, 
concentrations in the range of from about 10 parts per million to about 
1000 parts per million, calculated as free rhodium, in the 
hydroformylation reaction medium should be sufficient for most processes, 
while it is generally preferred to employ from about 10 to 500 parts per 
million of metal, e.g., rhodium, and more preferably from 25 to 350 parts 
per million of metal, e.g., rhodium. 
In addition to the metal-organophosphite ligand complex catalyst, free 
organophosphite ligand (i.e., ligand that is not complexed with the metal) 
may also be present in the hydroformylation reaction medium. The free 
organophosphite ligand may correspond to any of the above-defined 
organophosphite ligands discussed above as employable herein. It is 
preferred that the free organophosphite ligand be the same as the 
organophosphite ligand of the metal-organophosphite ligand complex 
catalyst employed. However, such ligands need not be the same in any given 
process. The hydroformylation process of this invention may involve from 
about 0.1 moles or less to about 100 moles or higher, of free 
organophosphite ligand per mole of metal in the hydroformylation reaction 
medium. Preferably the hydroformylation process of this invention is 
carried out in the presence of from about 1 to about 50 moles of 
organophosphite ligand, and more preferably for organopolyphosphites from 
about 1.1 to about 4 moles of organopolyphosphite ligand, per mole of 
metal present in the reaction medium; said amounts of organophosphite 
ligand being the sum of both the amount of organophosphite ligand that is 
bound (complexed) to the metal present and the amount of free 
(non-complexed) organophosphite ligand present. Since it is more preferred 
to produce non-optically active aldehydes by hydroformylating achiral 
olefins, the more preferred organophosphite ligands are achiral type 
organophosphite ligands, especially those encompassed by Formula (V) 
above, and more preferably those of Formulas (VI) and (IX) above. Of 
course, if desired, make-up or additional organophosphite ligand can be 
supplied to the reaction medium of the hydroformylation process at any 
time and in any suitable manner, e.g. to maintain a predetermined level of 
free ligand in the reaction medium. 
As indicated above, the hydroformylation catalyst may be in heterogeneous 
form during the reaction and/or during the product separation. Such 
catalysts are particularly advantageous in the hydroformylation of olefins 
to produce high boiling or thermally sensitive aldehydes, so that the 
catalyst may be separated from the products by filtration or decantation 
at low temperatures. For example, the rhodium catalyst may be attached to 
a support so that the catalyst retains its solid form during both the 
hydroformylation and separation stages, or is soluble in a liquid reaction 
medium at high temperatures and then is precipitated on cooling. 
As an illustration, the rhodium catalyst may be impregnated onto any solid 
support, such as inorganic oxides, (i.e. alumina, silica, titania, or 
zirconia) carbon, or ion exchange resins. The catalyst may be supported 
on, or intercalated inside the pores of, a zeolite, glass or clay; the 
catalyst may also be dissolved in a liquid film coating the pores of said 
zeolite or glass. Such zeolite-supported catalysts are particularly 
advantageous for producing one or more regioisomeric aldehydes in high 
selectivity, as determined by the pore size of the zeolite. The techniques 
for supporting catalysts on solids, such as incipient wetness, which will 
be known to those skilled in the art. The solid catalyst thus formed may 
still be complexed with one or more of the ligands defined above. 
Descriptions of such solid catalysts may be found in for example: J. Mol. 
Cat. 1991, 70, 363-368; Catal. Lett. 1991, 8, 209-214; J. Organomet. Chem, 
1991, 403, 221-227; Nature, 1989, 339, 454-455; J. Catal. 1985, 96, 
563-573; J. Mol. Cat. 1987, 39, 243-259. 
The metal, e.g., rhodium, catalyst may be attached to a thin film or 
membrane support, such as cellulose acetate or polyphenylenesulfone, as 
described in for example J. Mol. Cat. 1990, 63, 213-221. 
The metal, e.g., rhodium, catalyst may be attached to an insoluble 
polymeric support through an organophosphorus-containing ligand, such as a 
phosphite, incorporated into the polymer. The supported catalyst is not 
limited by the choice of polymer or phosphorus-containing species 
incorporated into it. Descriptions of polymer-supported catalysts may be 
found in for example: J. Mol. Cat. 1993, 83, 17-35; Chemtech 1983, 46; J. 
Am. Chem. Soc. 1987, 109, 7122-7127. 
In the heterogeneous catalysts described above, the catalyst may remain in 
its heterogeneous form during the entire hydroformylation and catalyst 
separation process. In another embodiment of the invention, the catalyst 
may be supported on a polymer which, by the nature of its molecular 
weight, is soluble in the reaction medium at elevated temperatures, but 
precipitates upon cooling, thus facilitating catalyst separation from the 
reaction mixture. Such "soluble" polymer-supported catalysts are described 
in for example: Polymer, 1992, 33, 161; J. Org. Chem. 1989, 54, 2726-2730. 
More preferably, the reaction is carried out in the slurry phase due to the 
high boiling points of the products, and to avoid decomposition of the 
product aldehydes. The catalyst may then be separated from the product 
mixture, for example, by filtration or decantation. The reaction product 
fluid may contain a heterogeneous metal-organophosphite ligand complex 
catalyst, e.g., slurry, or at least a portion of the reaction product 
fluid may contact a fixed heterogeneous metal-organophosphite ligand 
complex catalyst during the hydroformylation process. In an embodiment of 
this invention, the metal-organophosphite ligand complex catalyst may be 
slurried in the reaction product fluid. 
The substituted or unsubstituted olefinic unsaturated starting material 
reactants that may be employed in the hydroformylation processes of this 
invention include both optically active (prochiral and chiral) and 
non-optically active (achiral) olefinic unsaturated compounds containing 
from 2 to 40, preferably 4 to 20, carbon atoms. Such olefinic unsaturated 
compounds can be terminally or internally unsaturated and be of 
straight-chain, branched chain or cyclic structures, as well as olefin 
mixtures, such as obtained from the oligomerization of propene, butene, 
isobutene, etc. (such as so called dimeric, trimeric or tetrameric 
propylene and the like, as disclosed, for example, in U.S. Pat. Nos. 
4,518,809 and 4,528,403). Moreover, such olefin compounds may further 
contain one or more ethylenic unsaturated groups, and of course, mixtures 
of two or more different olefinic unsaturated compounds may be employed as 
the starting hydroformylation material if desired. For example, commercial 
alpha olefins containing four or more carbon atoms may contain minor 
amounts of corresponding internal olefins and/or their corresponding 
saturated hydrocarbon and that such commercial olefins need not 
necessarily be purified from same prior to being hydroformylated. 
Illustrative mixtures of olefinic starting materials that can be employed 
in the hydroformylation reactions include, for example, mixed butenes, 
e.g., Raffinate I and II. Further such olefinic unsaturated compounds and 
the corresponding aldehyde products derived therefrom may also contain one 
or more groups or substituents which do not unduly adversely affect the 
hydroformylation process or the process of this invention such as 
described, for example, in U.S. Pat. Nos. 3,527,809, 4,769,498 and the 
like. 
Most preferably the subject invention is especially useful for the 
production of non-optically active aldehydes, by hydroformylating achiral 
alpha-olefins containing from 2 to 30, preferably 4 to 20, carbon atoms, 
and achiral internal olefins containing from 4 to 20 carbon atoms as well 
as starting material mixtures of such alpha olefins and internal olefins. 
Illustrative alpha and internal olefins include, for example, ethylene, 
propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 
1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 
1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 
2-butene, 2-methyl propene (isobutylene), 2-methylbutene, 2-pentene, 
2-hexene, 3-hexane, 2-heptene, 2-octene, cyclohexene, propylene dimers, 
propylene trimers, propylene tetramers, butadiene, piperylene, isoprene, 
2-ethyl-1-hexene, styrene, 4-methyl styrene, 4-isopropyl styrene, 
4-tert-butyl styrene, alphamethyl styrene, 4-tert-butyl-alpha-methyl 
styrene, 1,3-diisopropenylbenzene, 3-phenyl-1-propene, 1,4-hexadiene, 
1,7-octadiene, 3-cyclohexyl-1-butene, and the like, as well as, 
1,3-dienes, butadiene, alkyl alkenoates, e.g., methyl pentenoate, alkenyl 
alkanoates, alkenyl alkyl ethers, alkenols, e.g., pentenols, alkenals, 
e.g., pentenals, and the like, such as allyl alcohol, allyl butyrate, 
hex-1-en-4-ol, oct-1-en-4-ol, vinyl acetate, allyl acetate, 3-butenyl 
acetate, vinyl propionate, allyl propionate, methyl methacrylate, vinyl 
ethyl ether, vinyl methyl ether, allyl ethyl ether, n-propyl-7-octenoate, 
3-butenenitrile, 5-hexenamide, eugenol, iso-eugenol, safrole, iso-safrole, 
anethol, 4-allylanisole, indene, limonene, beta-pinene, dicyclopentadiene, 
cyclooctadiene, camphene, linalool, and the like. 
Prochiral and chiral olefins useful in the asymmetric hydroformylation that 
can be employed to produce enantiomeric aldehyde mixtures that may be 
encompassed by in this invention include those represented by the formula: 
##STR30## 
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are the same or different 
(provided R.sub.1 is different from R.sub.2 or R.sub.3 is different from 
R.sub.4) and are selected from hydrogen; alkyl; substituted alkyl, said 
substitution being selected from dialkylamino such as benzylamino and 
dibenzylamino, alkoxy such as methoxy and ethoxy, acyloxy such as acetoxy, 
halo, nitro, nitrile, thio, carbonyl, carboxamide, carboxaldehyde, 
carboxyl, carboxylic ester; aryl including phenyl; substituted aryl 
including phenyl, said substitution being selected from alkyl, amino 
including alkylamino and dialkylamino such as benzylamino and 
dibenzylamino, hydroxy, alkoxy such as methoxy and ethoxy, acyloxy such as 
acetoxy, halo, nitrile, nitro, carboxyl, carboxaldehyde, carboxylic ester, 
carbonyl, and thio; acyloxy such as acetoxy; alkoxy such as methoxy and 
ethoxy; amino including alkylamino and dialkylamino such as benzylamino 
and dibenzylamino; acylamino and diacylamino such as acetylbenzylamino and 
diacetylamino; nitro; carbonyl; nitrile; carboxyl; carboxamide; 
carboxaldehyde; carboxylic ester; and alkylmercapto such as 
methylmercapto. It is understood that the prochiral and chiral olefins of 
this definition also include molecules of the above general formula where 
the R groups are connected to form ring compounds, e.g., 
3-methyl-1-cyclohexene, and the like. 
Illustrative optically active or prochiral olefinic compounds useful in 
asymmetric hydroformylation include, for example, p-isobutylstyrene, 
2-vinyl-6-methoxy-2-naphthylene, 3-ethenylphenyl phenyl ketone, 
4-ethenylphenyl-2-thienylketone, 4-ethenyl-2-fluorobiphenyl, 
4-(1,3-dihydro-1-oxo-2H-isoindol-2-yl)styrene, 
2-ethenyl-5-benzoylthiophene, 3-ethenylphenyl phenyl ether, 
propenylbenzene, isobutyl-4-propenylbenzene, phenyl vinyl ether and the 
like. Other olefinic compounds include substituted aryl ethylenes as 
described, for example, in U.S. Pat. Nos. 4,329,507, 5,360,938 and 
5,491,266, the disclosures of which are incorporated herein by reference. 
Illustrative of suitable substituted and unsubstituted olefinic starting 
materials include those permissible substituted and unsubstituted olefinic 
compounds described in Kirk-Othmer, Encyclopedia of Chemical Technology, 
Fourth Edition, 1996, the pertinent portions of which are incorporated 
herein by reference. 
The reaction conditions of the hydroformylation processes encompassed by 
this invention may include any suitable type hydroformylation conditions 
heretofore employed for producing optically active and/or non-optically 
active aldehydes. For instance, the total gas pressure of hydrogen, carbon 
monoxide and olefin starting compound of the hydroformylation process may 
range from about 1 to about 10,000 psia. In general, however, it is 
preferred that the process be operated at a total gas pressure of 
hydrogen, carbon monoxide and olefin starting compound of less than about 
2000 psia and more preferably less than about 500 psia. The minimum total 
pressure is limited predominately by the amount of reactants necessary to 
obtain a desired rate of reaction. More specifically the carbon monoxide 
partial pressure of the hydroformylation process of this invention is 
preferable from about 1 to about 1000 psia, and more preferably from about 
3 to about 800 psia, while the hydrogen partial pressure is preferably 
about 5 to about 500 psia and more preferably from about 10 to about 300 
psia. In general H.sub.2 :CO molar ratio of gaseous hydrogen to carbon 
monoxide may range from about 1:10 to 100:1 or higher, the more preferred 
hydrogen to carbon monoxide molar ratio being from about 1:10 to about 
10:1. Further, the hydroformylation process may be conducted at a reaction 
temperature from about -25.degree. C. to about 200.degree. C. In general 
hydroformylation reaction temperatures of about 50.degree. C. to about 
120.degree. C. are preferred for all types of olefinic starting materials. 
Of course it is to be understood that when non-optically active aldehyde 
products are desired, achiral type olefin starting materials and 
organophosphite ligands are employed and when optically active aldehyde 
products are desired prochiral or chiral type olefin starting materials 
and organophosphite ligands are employed. Of course, it is to be also 
understood that the hydroformylation reaction conditions employed will be 
governed by the type of aldehyde product desired. 
The hydroformylation processes encompassed by this invention are also 
conducted in the presence of an organic solvent for the 
metal-organophosphite ligand complex catalyst and free organophosphite 
ligand. The solvent may also contain dissolved water up to the saturation 
limit. Depending on the particular catalyst and reactants employed, 
suitable organic solvents include, for example, alcohols, alkanes, 
alkenes, alkynes, ethers, aldehydes, higher boiling aldehyde condensation 
byproducts, ketones, esters, amides, tertiary amines, aromatics and the 
like. Any suitable solvent which does not unduly adversely interfere with 
the intended hydroformylation reaction can be employed and such solvents 
may include those disclosed heretofore commonly employed in known metal 
catalyzed hydroformylation reactions. Mixtures of one or more different 
solvents may be employed if desired. In general, with regard to the 
production of achiral (non-optically active) aldehydes, it is preferred to 
employ aldehyde compounds corresponding to the aldehyde products desired to 
be produced and/or higher boiling aldehyde liquid condensation byproducts 
as the main organic solvents as is common in the art. Such aldehyde 
condensation byproducts can also be preformed if desired and used 
accordingly. Illustrative preferred solvents employable in the production 
of aldehydes include ketones (e.g. acetone and methylethyl ketone), esters 
(e.g. ethyl acetate), hydrocarbons (e.g. toluene), nitrohydrocarbons (e.g. 
nitrobenzene), ethers (e.g. tetrahydrofuran (THF) and sulfolane. Suitable 
solvents are disclosed in U.S. Pat. No. 5,312,996. The amount of solvent 
employed is not critical to the subject invention and need only be that 
amount sufficient to solubilize the catalyst and free ligand of the 
hydroformylation reaction mixture to be treated. In general, the amount of 
solvent may range from about 5 percent by weight up to about 99 percent by 
weight or more based on the total weight of the hydroformylation reaction 
mixture starting material. 
Accordingly illustrative non-optically active aldehyde products include 
e.g., propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 
2-methyl 1-butyraldehyde, hexanal, hydroxyhexanal, 2-methyl valeraldehyde, 
heptanal, 2-methyl 1-hexanal, octanal, 2-methyl 1-heptanal, nonanal, 
2-methyl-1-octanal, 2-ethyl 1-heptanal, 3-propyl 1-hexanal, decanal, 
adipaldehyde, 2-methylglutaraldehyde, 2-methyladipaldehyde, 
3-methyladipaldehyde, 3-hydroxypropionaldehyde, 6-hydroxyhexanal, 
alkenals, e.g., 2-, 3- and 4-pentenal, alkyl 5-formylvalerate, 
2-methyl-1-nonanal, undecanal, 2-methyl 1-decanal, dodecanal, 2-methyl 
1-undecanal, tridecanal, 2-methyl 1-tridecanal, 2-ethyl, 1-dodecanal, 
3-propyl-1-undecanal, pentadecanal, 2-methyl-1-tetradecanal, hexadecanal, 
2-methyl-1-pentadecanal, heptadecanal, 2-methyl-1-hexadecanal, 
octadecanal, 2-methyl-1-heptadecanal, nonodecanal, 2-methyl-1-octadecanal, 
2-ethyl 1-heptadecanal, 3-propyl-1-hexadecanal, eicosanal, 
2-methyl-1-nonadecanal, heneicosanal, 2-methyl-1-eicosanal, tricosanal, 
2-methyl-1-docosanal, tetracosanal, 2-methyl-1-tricosanal, pentacosanal, 
2-methyl-1-tetracosanal, 2-ethyl 1-tricosanal, 3-propyl-1-docosanal, 
heptacosanal, 2-methyl-1-octacosanal, nonacosanal, 2-methyl-1-octacosanal, 
hentriacontanal, 2-methyl-1-triacontanal, and the like. 
Illustrative optically active aldehyde products include (enantiomeric) 
aldehyde compounds prepared by the asymmetric hydroformylation process of 
this invention such as, e.g. S-2-(p-isobutylphenyl)-propionaldehyde, 
S-2-(6-methoxy-2-naphthyl)propionaldehyde, 
S-2-(3-benzoylphenyl)-propionaldehyde, 
S-2-(p-thienoylphenyl)propionaldehyde, 
S-2-(3-fluoro-4-phenyl)phenylpropionaldehyde, 
S-2-4-(1,3-dihydro-1-oxo-2H-isoindol-2-yl)phenyl!propionaldehyde, 
S-2-(2-methylacetaldehyde)-5-benzoylthiophene and the like. 
Illustrative of suitable substituted and unsubstituted aldehyde products 
include those permissible substituted and unsubstituted aldehyde compounds 
described in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth 
Edition, 1996, the pertinent portions of which are incorporated herein by 
reference. 
As indicated above, it is generally preferred to carry out the 
hydroformylation processes of this invention in a continuous manner. In 
general, continuous hydroformylation processes are well known in the art 
and may involve: (a) hydroformylating the olefinic starting material(s) 
with carbon monoxide and hydrogen in a liquid homogeneous reaction mixture 
comprising a solvent, the metal-organophosphite ligand complex catalyst, 
and free organophosphite ligand; (b) maintaining reaction temperature and 
pressure conditions favorable to the hydroformylation of the olefinic 
starting material(s); (c) supplying make-up quantities of the olefinic 
starting material(s), carbon monoxide and hydrogen to the reaction medium 
as those reactants are used up; and (d) recovering the desired aldehyde 
hydroformylation product(s) in any manner desired. The continuous process 
can be carried out in a single pass mode, i.e., wherein a vaporous mixture 
comprising unreacted olefinic starting material(s) and vaporized aldehyde 
product is removed from the liquid reaction mixture from whence the 
aldehyde product is recovered and make-up olefinic starting material(s), 
carbon monoxide and hydrogen are supplied to the liquid reaction medium 
for the next single pass without recycling the unreacted olefinic starting 
material(s). Such types of recycle procedure are well known in the art and 
may involve the liquid recycling of the metal-organophosphite complex 
catalyst fluid separated from the desired aldehyde reaction product(s), 
such as disclosed, for example, in U.S. Pat. Nos. 4,148,830 or a gas 
recycle procedure such as disclosed, for example, in U.S. Pat. Nos. 
4,247,486, as well as a combination of both a liquid and gas recycle 
procedure if desired. The disclosures of said U.S. Pat. Nos. 4,148,830 and 
4,247,486 are incorporated herein by reference thereto. The most preferred 
hydroformylation process of this invention comprises a continuous liquid 
catalyst recycle process. Suitable liquid catalyst recycle procedures are 
disclosed, for example, in U.S. Pat. Nos. 4,668,651; 4,774,361; 5,102,505 
and 5,110,990. 
In an embodiment of this invention, the aldehyde product mixtures may be 
separated from the other components of the crude reaction mixtures in 
which the aldehyde mixtures are produced by any suitable method. Suitable 
separation methods include, for example, solvent extraction, 
crystallization, distillation, vaporization, wiped film evaporation, 
falling film evaporation, phase separation, filtration and the like. It 
may be desired to remove the aldehyde products from the crude reaction 
mixture as they are formed through the use of trapping agents as described 
in published Patent Cooperation Treaty Patent Application WO 88/08835. A 
preferred method for separating the aldehyde mixtures from the other 
components of the crude reaction mixtures is by membrane separation. Such 
membrane separation can be achieved as set out in U.S. Pat. No. 5,430,194 
and copending U.S. patent application Ser. No. 08/430,790, filed May 5, 
1995, referred to above. 
As indicated above, at the conclusion of (or during) the process of this 
invention, the desired aldehydes may be recovered from the reaction 
mixtures used in the process of this invention. For example, the recovery 
techniques disclosed in U.S. Pat. Nos. 4,148,830 and 4,247,486 can be 
used. For instance, in a continuous liquid catalyst recycle process the 
portion of the liquid reaction mixture (containing aldehyde product, 
catalyst, etc.), i.e., reaction product fluid, removed from the reaction 
zone can be passed to a separation zone, e.g., vaporizer/separator, 
wherein the desired aldehyde product can be separated via distillation, in 
one or more stages, under normal, reduced or elevated pressure, from the 
liquid reaction fluid, condensed and collected in a product receiver, and 
further purified if desired. The remaining non-volatilized catalyst 
containing liquid reaction mixture may then be recycled back to the 
reactor as may if desired any other volatile materials, e.g., unreacted 
olefin, together with any hydrogen and carbon monoxide dissolved in the 
liquid reaction after separation thereof from the condensed aldehyde 
product, e.g., by distillation in any conventional manner. In general, it 
is preferred to separate the desired aldehydes from the 
catalyst-containing reaction mixture under reduced pressure and at low 
temperatures so as to avoid possible degradation of the organophosphite 
ligand and reaction products. When an alpha-mono-olefin reactant is also 
employed, the aldehyde derivative thereof can also be separated by the 
above methods. 
More particularly, distillation and separation of the desired aldehyde 
product from the metal-organophosphite complex catalyst containing 
reaction product fluid may take place at any suitable temperature desired. 
In general, it is recommended that such distillation take place at 
relatively low temperatures, such as below 150.degree. C., and more 
preferably at a temperature in the range of from about 50.degree. C. to 
about 140.degree. C. It is also generally recommended that such aldehyde 
distillation take place under reduced pressure, e.g., a total gas pressure 
that is substantially lower than the total gas pressure employed during 
hydroformylation when low boiling aldehydes (e.g., C.sub.4 to C.sub.6) are 
involved or under vacuum when high boiling aldehydes (e.g. C.sub.7 or 
greater) are involved. For instance, a common practice is to subject the 
liquid reaction product medium removed from the hydroformylation reactor 
to a pressure reduction so as to volatilize a substantial portion of the 
unreacted gases dissolved in the liquid medium which now contains a much 
lower synthesis gas concentration than was present in the hydroformylation 
reaction medium to the distillation zone, e.g. vaporizer/separator, wherein 
the desired aldehyde product is distilled. In general, distillation 
pressures ranging from vacuum pressures on up to total gas pressure of 
about 50 psig should be sufficient for most purposes. 
As stated above the subject invention resides in the discovery that 
hydrolytic decomposition and rhodium catalyst deactivation as discussed 
herein can be prevented or lessened by treating at least a portion of the 
reaction product fluid derived from the hydroformylation process and which 
also contains phosphorus acidic compounds formed during the 
hydroformylation process with water sufficient to remove at least some 
amount of the phosphorus acidic compounds from the reaction product fluid. 
Although both water and acid are factors in the hydrolysis of 
organophosphite ligands, it has been surprisingly discovered that 
hydroformylation reaction systems are more tolerant of higher levels of 
water than higher levels of acid. Thus, the water can surprisingly be used 
to remove acid and decrease the rate of loss of organophosphite ligand by 
hydrolysis. The use of water to prevent and/or lessen hydrolytic 
degradation of an organophosphite ligand and deactivation of a 
metal-organophosphite ligand complex catalyst is disclosed in copending 
U.S. patent application Ser. No. 08/756,786, filed on an even date 
herewith, the disclosure of which is incorporated herein by reference. 
The removal of at least some amount of the phosphorus acid compounds, for 
example, H.sub.3 PO.sub.3, aldehyde acids such as hydroxy alkyl phosphonic 
acids, H.sub.3 PO.sub.4 and the like, from the hydroformylation system 
allows one to control the acidity of the hydroformylation reaction medium, 
thereby stabilizing the useful organophosphite ligand by preventing or 
lessening its hydrolytic decomposition. The need to control the acidity in 
organophosphite promoted metal catalyzed hydroformylation was explained 
above. Thus the purpose of the subject invention is to remove or reduce 
excessive acidity from the catalyst system in order to maintain a proper 
acidity level in the reaction product fluid so that the consumption of the 
useful organophosphite ligands do not hydrolytically degrade at an 
unacceptable rate while keeping catalyst activity at a productive level. 
The subject invention submits that the best means for regulating such 
acidity is to extract (remove) such phosphorus acidic materials from the 
reaction product fluid using water. In this way the acidic materials are 
extracted into the water as disclosed herein as opposed to merely being 
scavenged and/or neutralized and allowed to remain in the reaction medium, 
thereby avoiding accumulation of such scavenged and/or neutralized 
byproducts, and preventing further possible necessary secondary chemistry 
or the buildup of salt deposits in the reaction zone, separation zone 
and/or scrubber zone. 
Said treatment of the metal-organophosphite ligand complex catalyst 
containing reaction product fluid with the water may be conducted in any 
suitable manner or fashion desired that does not unduly adversely affect 
the basic hydroformylation process from which said reaction product fluid 
was derived. For instance, the water treatment may be conducted on all or 
any portion of the desired reaction product fluid that is to be treated 
and which has been removed from the at least one reaction zone or the at 
least one separation zone into at least one scrubber zone. The treated 
reaction product fluid may then be returned to the at least one reaction 
zone or the at least one separation zone. Alternately, water may be 
sprayed into or otherwise added to the at least one reaction zone or the 
at least one separation zone to achieve acidity control. The water layer 
formed may then be separated, e.g., decanted, from the reaction product 
fluid. 
This invention involving the use of water is especially adaptable for use 
in continuous liquid catalyst recycle hydroformylation processes that 
employ the invention of U.S. Pat. No. 5,288,918, which comprises carrying 
out the process in the presence of a catalytically active enhancing 
additive, said additive being selected from the class consisting of added 
water, a weakly acidic compound (e.g., biphenol), or both added water and 
a weakly acidic compound. The enhancing additive is employed to help 
selectively hydrolyze and prevent the build-up of an undesirable 
monophosphite byproduct that can be formed during certain processes and 
which poisons the metal catalyst as explained therein. Nonetheless, it is 
to be understood that a preferred hydroformylation process of this 
invention, i.e., the embodiment comprising preventing and/or lessening 
hydrolytic degradation of the organophosphite ligand and deactivation of 
the metal-organophosphite ligand complex catalyst by (a) withdrawing from 
said at least one reaction zone or said at least one separation zone at 
least a portion of a reaction product fluid derived from said 
hydroformylation process and which also contains phosphorus acidic 
compounds formed during said hydroformylation process, (b) treating in at 
least one scrubber zone at least a portion of the withdrawn reaction 
product fluid derived from said hydroformylation process and which also 
contains phosphorus acidic compounds formed during said hydroformylation 
process with water sufficient to remove at least some amount of the 
phosphorus acidic compounds from said reaction product fluid, and (c) 
returning the treated reaction product fluid to said at least one reaction 
zone or said at least one separation zone, is still considered to be 
essentially a "non-aqueous" process, which is to say, any water present in 
the hydroformylation reaction medium is not present in an amount sufficient 
to cause either the hydroformylation reaction or said medium to be 
considered as encompassing a separate aqueous or water phase or layer in 
addition to an organic phase. 
Also, it is to be understood that another preferred hydroformylation 
process of this invention, i.e., the embodiment comprising preventing 
and/or lessening hydrolytic degradation of the organophosphite ligand and 
deactivation of the metal-organophosphite ligand complex catalyst by 
treating at least a portion of said reaction product fluid derived from 
said hydroformylation process and which also contains phosphorus acidic 
compounds formed during said hydroformylation process by introducing water 
into said at least one reaction zone and/or said at least one separation 
zone sufficient to remove at least some amount of the phosphorus acidic 
compounds from said reaction product fluid, is considered to be a separate 
aqueous or water phase or layer in addition to an organic phase. 
Thus, for example, water may be used to treat all or part of a reaction 
product fluid of a continuous liquid catalyst recycle hydroformylation 
process that has been removed from the reaction zone at any time prior to 
or after separation of the aldehyde product therefrom. More preferably 
said water treatment involves treating all or part of the reaction product 
fluid obtained after distillation of as much of the aldehyde product 
desired, for example, prior to or during the recycling of said reaction 
product fluid to the reaction zone. For instance, a preferred mode would 
be to continuously pass all or part (e.g. a slip stream) of the recycled 
reaction product fluid that is being recycled to the reaction zone through 
a liquid extractor containing the water just before said catalyst 
containing residue is to re-enter the reaction zone. 
Thus it is to be understood that the metal-organophosphite ligand complex 
catalyst containing reaction product fluid to be treated with water may 
contain in addition to the catalyst complex and its organic solvent, 
aldehyde product, free organophosphite ligand, unreacted olefin, and any 
other ingredient or additive consistent with the reaction medium of the 
hydroformylation process from which said reaction product fluids are 
derived. 
Moreover, removal of the desired aldehyde product can cause concentrations 
of the other ingredients of the reaction product fluids to be increased 
proportionately. Thus for example, the organophosphite ligand 
concentration in the metal-organophosphite ligand complex catalyst 
containing reaction product fluid to be treated by water in accordance 
with the process of this invention may range from between about 0.005 and 
15 weight percent based on the total weight of the reaction product fluid. 
Preferably the ligand concentration is between 0.01 and 10 weight percent, 
and more preferably is between about 0.05 and 5 weight percent on that 
basis. Similarly, the concentration of the metal in the 
metal-organophosphite ligand complex catalyst containing reaction product 
fluid to be treated by the water in accordance with the process of this 
invention may be as high as about 5000 parts per million by weight based 
on the weight of the reaction product fluid. Preferably the metal 
concentration is between about 50 and 2500 parts per million by weight 
based on the weight of the reaction product fluid, and more preferably is 
between about 70 and 2000 parts per million by weight based on the weight 
of the reaction product fluid. 
The manner in which the metal-organophosphite ligand complex catalyst 
containing reaction product fluid and water are contacted, as well as such 
treatment conditions, as the amount of water, temperature, pressure and 
contact time are not narrowly critical and obviously need only be 
sufficient to obtain the results desired. For instance, said treatment may 
be carried out in any suitable vessel or container, e.g. any conventional 
liquid extractor, which provides a suitable means for thorough contact 
between the organic reaction product fluid and water, may be employed 
herein. In general it is preferred to pass the organic reaction product 
fluid through the water in a sieve tray extractor column in a 
counter-current fashion. The amount of water employed by the subject 
invention and time of contact with the reaction product fluid need only be 
that which is sufficient to remove at least some amount of the phosphorus 
acidic compounds which cause hydrolytic degradation of the desirable 
organophosphite ligands. Preferably the amount of water is sufficient to 
at least maintain the concentration of such acidic compounds below the 
threshold level that causes rapid degradation of the organophosphite 
ligand. 
For instance, a preferred quantity of water is the quantity which ensures 
that any degradation of the organophosphite ligand proceeds by the 
"non-catalytic mechanism" as described in "The Kinetic Rate Law for 
Autocatalytic Reactions" by Mata-Perez et al., Journal of Chemical 
Education, Vol. 64, No. 11, November 1987, pages 925 to 927, rather than 
by the "catalytic mechanism" described in said article. Typically maximum 
water concentrations are only governed by practical considerations. As 
noted, treatment conditions such as temperature, pressure and contact time 
may also vary greatly and any suitable combination of such conditions may 
be employed herein. For instance, a decrease in one of such conditions may 
be compensated for by an increase in one or both of the other conditions, 
while the opposite correlation is also true. In general liquid 
temperatures ranging from about 10.degree. C. to about 120.degree. C., 
preferably from about 20.degree. C. to about 80.degree. C., and more 
preferably from about 25.degree. C. to about 60.degree. C. should be 
suitable for most instances, although lower or higher temperatures could 
be employed if desired. As noted above, it has been surprisingly 
discovered that minimum loss of organophosphite ligand occurs when a 
hydroformylation reaction product fluid containing a metal-organophosphite 
ligand complex catalyst is contacted with water even at elevated 
temperatures. Normally the treatment is carried out under pressures 
ranging from ambient to reaction pressures and the contact time may vary 
from a matter of seconds or minutes to a few hours or more. 
Moreover, success in removing phosphorus acidic compounds from the reaction 
product fluid according to the subject invention may be determined by 
measuring the rate degradation (consumption) of the organophosphite ligand 
present in the hydroformylation reaction medium. The consumption rate can 
vary over a wide range, e.g., from about.ltoreq.0.6 up to about 5 grams 
per liter per day, and will be governed by the best compromise between 
cost of ligand and treatment frequency to keep hydrolysis below 
autocatalytic levels. Preferably the water treatment of this invention is 
carried out in such a manner that the consumption of the desired 
organophosphite ligand present in the hydroformylation reaction medium of 
the hydroformylation process is maintained at an acceptable rate, 
e.g.,.ltoreq.0.5 grams of ligand per liter per day, and more 
preferably.ltoreq.0.1 grams of ligand per liter per day, and most 
preferably.ltoreq.0.06 grams of ligand per liter per day. As the 
extraction of phosphorus acidic compounds into the water proceeds, the pH 
of the water will decrease and become more and more acidic. When the water 
reaches an unacceptable acidity level it may simply be replaced with new 
water. 
The preferred method of operation of this invention is to pass all or a 
portion of the reaction product fluid before aldehyde removal or reaction 
product fluid concentration after removal of aldehyde through the water. 
Alternately, water may be sprayed into or otherwise added to the at least 
one reaction zone or the at least one separation zone to achieve acidity 
control. The water layer formed may then be separated, e.g., decanted, 
from the reaction product fluid. An advantage of this scheme is that 
extraction capability is immediately available if acidity forms in the 
reaction product fluid. This invention is not intended to be limited in 
any manner by the permissible means for contacting a reaction product 
fluid with water (either inside or outside of the reaction zone or 
separation zone). 
For purposes of this invention, "non-contacted water" is contemplated to 
include water that has not been contacted with the reaction product fluid 
and "contacted water" is contemplated to include water that has been 
contacted with the reaction product fluid. 
Any means to prepare the non-contacted water for use with the process of 
this invention can be used so long as the water is substantially free of 
catalyst poisons, inhibitors, or compounds that would promote undesirable 
side reactions in the catalyst solution. A summary of water treatment 
techniques can be found in the Kirk Othmer, Encyclopedia of Chemical 
Technology, Fourth Edition, 1996. 
Water treatment should begin with an evaluation of the water quality needs 
for the process. For acid extraction from reaction product fluids 
containing metal-organophosphite ligand complex catalysts, the quality of 
water required is generally of boiler quality or better. Sources of water 
for purification can vary greatly in purity from river water containing 
logs, silt and other debris, to steam condensate that is relatively pure. 
If river water is to be used, purification starts with filtration of the 
largest pieces. Grates or screens may be used for this first filtration 
step. A number of techniques can be used to remove other solids that may 
be present in the water including; sedimentation, centrifugal separation, 
filtration, coagulation, flocculation, magnetic separation, of 
combinations of these. After clarified water is obtained, the remaining 
dissolved solids can also be treated in a number of ways. Distillation is 
still commonly practiced. Dissolved salts may be treated with other acids 
or bases to precipitate certain compounds. The acids or bases that are 
added are chosen based on the solubility of the compounds that will be 
produced. Ion exchange is another popular method for removing dissolved 
salts. The most common ion exchange method uses sodium as the cation. 
Other ion exchange techniques with protons or hydroxide ions may also be 
employed. Adsorption can be used to remove some metal salts and organic 
compounds that may be present. Activated carbon is used commonly as an 
adsorbent. Membranes are still another technique that may be used removed 
dissolved salts or other colloidal particles. 
Membranes separate based on size, electronic charge, hydrophobicity, or 
other physical-chemical property differences. Reverse osmosis is an 
example of using membranes to purify water. If dissolved gases such as 
oxygen are present, the water can be stripped with steam or nitrogen or 
subjected to vacuum to remove or replace the dissolved gas. 
A preferred process to purify non-contacted water necessary for the acid 
removal would be a combination of some of the aforementioned techniques. 
Internal techniques where additives are used to counteract the harmful 
effects of impurities can also be used to prepare non-contacted water for 
use in extraction, but the external techniques described in the preceding 
paragraph are more preferred. 
The contacted water employable in this invention may comprise any suitable 
water such that the pH of the contacted water may range from about 2 to 
about 7.5, preferably from about 2.5 to about 7 and more preferably from 
about 3 to about 6. The flowrate of water through the extractor and/or the 
addition of water to the at least one reaction zone and/or the at least one 
separation zone should be sufficient to control pH of the water at desired 
levels. An increased flowrate of water through the extractor may cause 
removal, i.e., through the water effluent, of certain amounts of one or 
more aldehyde products from the process. 
In a preferred embodiment of this invention, one or more aldehyde products 
removed by water extraction can be recovered and returned to the 
hydroformylation process as depicted in the process flow diagram of FIG. 
1. For example, the one or more aldehyde products may be returned to the 
hydroformylation process by steam stripping the water effluent from the 
extractor and returning the organic phase of the condensed stripper heads 
to the hydroformylation process. The aqueous phase of the stripper heads 
may be returned to the stripper feed. The tails of the stripper may 
contain the acidic decomposition products from the catalyst. 
In another embodiment, this invention relates to treating at least a 
portion of the contacted water which contains phosphorus acidic compounds 
formed during said hydroformylation process by introducing one or more 
strong bases into the at least one scrubber zone sufficient to neutralize 
at least some amount of the phosphorus acidic compounds contained in said 
water, provided the pH of the contacted water does not exceed 7.5. The 
strong base treated contacted water should have the following 
characteristics: (i) not reactive with the aldehyde product; (ii) not so 
basic as to promote aldol condensation; and (iii) basic salts are water 
soluble so as to facilitate removal from the reaction zone. Preferably, 
the contacted water can be recycled and the aldehyde product recovered if 
the phosphorus acidic compounds are neutralized. If the phosphorus acidic 
compounds are not neutralized, the contacted water may not be recycled and 
will most likely go to an effluent waste treatment facility. Illustrative 
suitable strong bases include, for example, alkali and alkaline earth 
metal hydroxides, e.g., sodium hydroxide, alkali metal phosphates, e.g., 
trisodium phosphate, disodium hydrogen phosphate and the like. The 
quantity of strong base relative to contacted water will depend upon the 
quantity of phosphorus acidic compounds in the contacted water. The 
quantity of strong base need only be sufficient to reduce the phosphorus 
acidic compound concentration to the desired value, provided the pH of the 
contacted water does not exceed 7.5. 
Optionally, an organic nitrogen compound may be added to the 
hydroformylation reaction product fluid to scavenge the acidic hydrolysis 
byproducts formed upon hydrolysis of the organophosphite ligand, as 
taught, for example, in U.S. Pat. No. 4,567,306. Such organic nitrogen 
compounds may be used to react with and to neutralize the acidic compounds 
by forming conversion product salts therewith, thereby preventing the 
rhodium from complexing with the acidic hydrolysis byproducts and thus 
helping to protect the activity of the metal, e.g., rhodium, catalyst 
while it is present in the reaction zone under hydroformylation 
conditions. The choice of the organic nitrogen compound for this function 
is, in part, dictated by the desirability of using a basic material that 
is soluble in the reaction medium and does not tend to catalyze the 
formation of aldols and other condensation products at a significant rate 
or to unduly react with the product aldehyde. 
Such organic nitrogen compounds may contain from 2 to 30 carbon atoms, and 
preferably from 2 to 24 carbon atoms. Primary amines should be excluded 
from use as said organic nitrogen compounds. Preferred organic nitrogen 
compounds should have a distribution coefficient that favors solubility in 
the organic phase. In general more preferred organic nitrogen compounds 
useful for scavenging the phosphorus acidic compounds present in the 
hydroformylation reaction product fluid of this invention include those 
having a pKa value within .+-.3 of the pH of the contacted water employed. 
Most preferably the pKa value of the organic nitrogen compound will be 
essentially about the same as the pH of the water employed. Of course it 
is to be understood that while it may be preferred to employ only one such 
organic nitrogen compound at a time in any given hydroformylation process, 
if desired, mixtures of two or more different organic nitrogen compounds 
may also be employed in any given processes. 
Illustrative organic nitrogen compounds include e.g., trialkylamines, such 
as triethylamine, tri-n-propylamine, tri-n-butylamine, tri-iso-butylamine, 
tri-iso-propylamine, tri-n-hexylamine, tri-n-octylamine, 
dimethyl-iso-propylamine, dimethyl-hexadecylamine, methyl-di-n-octylamine, 
and the like, as well as substituted derivatives thereof containing one or 
more noninterfering substituents such as hydroxy groups, for example 
triethanolamine, N-methyl-di-ethanolamine, tris-(3-hydroxypropyl)-amine, 
and the like. Heterocyclic amines can also be used such as pyridine, 
picolines, lutidines, collidines, N-methylpiperidine, N-methylmorpholine, 
N-2'-hydroxyethylmorpholine, quinoline, iso-quinoline, quinoxaline, 
acridien, quinuclidine, as well as, diazoles, triazole, diazine and 
triazine compounds, and the like. Also suitable for possible use are 
aromatic tertiary amines, such as N,N-dimethylaniline, N,N-diethylaniline, 
N,N-dimethyl-p-toluidine, N-methyldiphenylamine, N,N-dimethylbenzylamine, 
N,N-dimethyl-1-naphthylamine, and the like. Compounds containing two or 
more amino groups, such as N,N,N',N'-tetramethylethylene diamine and 
triethylene diamine (i.e. 1,4-diazabicyclo-2,2,2!-octane) can also be 
mentioned. 
Preferred organic nitrogen compounds useful for scavenging the phosphorus 
acidic compounds present in the hydroformylation reaction product fluids 
of the this invention are heterocyclic compounds selected from the group 
consisting of diazoles, triazoles, diazines and triazines, such as those 
disclosed and employed in copending U.S. patent application Ser. No. 
08/756,787, filed on an even date herewith, the disclosure of which is 
incorporated herein by reference. For example, benzimidazole and 
benztriazole are preferred candidates for such use. 
Illustrative of suitable organic nitrogen compounds include those 
permissible organic nitrogen compounds described in Kirk-Othmer, 
Encyclopedia of Chemical Technology, Fourth Edition, 1996, the pertinent 
portions of which are incorporated herein by reference. 
The amount of organic nitrogen compound that may be present in the reaction 
product fluid for scavenging the phosphorus acidic compounds present in the 
hydroformylation reaction product fluids of the this invention is typically 
sufficient to provide a concentration of at least about 0.0001 moles of 
free organic nitrogen compound per liter of reaction product fluid. In 
general the ratio of organic nitrogen compound to total organophosphite 
ligand (whether bound with rhodium or present as free organophosphite) is 
at least about 0.1:1 and even more preferably at least about 0.5:1. The 
upper limit on the amount of organic nitrogen compound employed is 
governed mainly only by economical considerations. Organic nitrogen 
compound: organophosphite molar ratios of at least about 1:1 up to about 
5:1 should be sufficient for most purpose. 
It is to be understood the organic nitrogen compound employed to scavenge 
said phosphorus acidic compounds need not be the same as the heterocyclic 
nitrogen compound employed to protect the metal catalyst under harsh 
conditions such as exist in the aldehyde vaporizer-separator, as taught in 
copending U.S. patent application Ser. No. 08/756,789, referred to above. 
However, if said organic nitrogen compound and said heterocyclic nitrogen 
compound are desired to be the same and perform both said functions in a 
given process, care should be taken to see that there will be a sufficient 
amount of the heterocyclic nitrogen compound present in the reaction medium 
to also provide that amount of free heterocyclic nitrogen compound in the 
hydroformylation process, e.g., vaporizer-separator, that will allow both 
desired functions to be achieved. 
Accordingly the water extraction of this invention will not only remove 
free phosphoric acidic compounds from the metal-organophosphite ligand 
complex catalyst containing reaction product fluids, the water also 
surprisingly removes the phosphorus acidic material of the conversion 
product salt formed by the use of the organic nitrogen compound scavenger 
when employed, i.e., the phosphorus acid of said conversion product salt 
remains behind in the water, while the treated reaction product fluid, 
along with the reactivated (free) organic nitrogen compound is returned to 
the hydroformylation reaction zone. 
Another problem that has been observed when organopolyphosphite ligand 
promoted metal catalysts are employed in hydroformylation processes, e.g., 
continuous liquid catalyst recycle hydroformylation processes, that involve 
harsh conditions such as recovery of the aldehyde via a 
vaporizer-separator, i.e., the slow loss in catalytic activity of the 
catalysts is believed due at least in part to the harsh conditions such as 
exist in a vaporizer employed in the separation and recovery of the 
aldehyde product from its reaction product fluid. For instance, it has 
been found that when an organopolyphosphite promoted rhodium catalyst is 
placed under harsh conditions such as high temperature and low carbon 
monoxide partial pressure, that the catalyst deactivates at an accelerated 
pace with time, due most likely to the formation of an inactive or less 
active rhodium species, which may also be susceptible to precipitation 
under prolonged exposure to such harsh conditions. Such evidence is also 
consistent with the view that the active catalyst which under 
hydroformylation conditions is believed to comprise a complex of rhodium, 
organopolyphosphite, carbon monoxide and hydrogen, loses at least some of 
its coordinated carbon monoxide ligand during exposure to such harsh 
conditions as encountered in vaporization, which provides a route for the 
formation of catalytically inactive or less active rhodium species. The 
means for preventing or minimizing such catalyst deactivation and/or 
precipitation involves carrying out the invention described and taught in 
copending U.S. patent application Ser. No. 08/756,789, referred to above, 
which comprises carrying out the hydroformylation process under conditions 
of low carbon monoxide partial pressure in the presence of a free 
heterocyclic nitrogen compound as disclosed therein. 
By way of further explanation it is believed the free heterocyclic nitrogen 
compound serves as a replacement ligand for the lost carbon monoxide ligand 
thereby forming a neutral intermediate metal species comprising a complex 
of the metal, organopolyphosphite, the heterocyclic nitrogen compound and 
hydrogen during such harsh conditions, e.g., vaporization separation, 
thereby preventing or minimizing the formation of any such above mentioned 
catalytic inactive or less active metal species. It is further theorized 
that the maintenance of catalytic activity, or the minimization of its 
deactivation, throughout the course of such continuous liquid recycle 
hydroformylation is due to regeneration of the active catalyst from said 
neutral intermediate metal species in the reactor (i.e. hydroformylation 
reaction zone) of the particular hydroformylation process involved. It is 
believed that under the higher syn gas pressure hydroformylation 
conditions in the reactor, the active catalyst complex comprising metal, 
e.g., rhodium, organopolyphosphite, carbon monoxide and hydrogen is 
regenerated as a result of some of the carbon monoxide in the reactant syn 
gas replacing the heterocyclic nitrogen ligand of the recycled neutral 
intermediate rhodium species. That is to say, carbon monoxide having a 
stronger ligand affinity for rhodium, replaces the more weakly bonded 
heterocyclic nitrogen ligand of the recycled neutral intermediate rhodium 
species that was formed during vaporization separation as mentioned above, 
thereby reforming the active catalyst in the hydroformylation reaction 
zone. 
Thus the possibility of metal catalyst deactivation due to such harsh 
conditions is said to be minimized or prevented by carrying out such 
distillation of the desired aldehyde product from the 
metal-organopolyphosphite catalyst containing reaction product fluids in 
the added presence of a free heterocyclic nitrogen compound having a five 
or six membered heterocyclic ring consisting of 2 to 5 carbon atoms and 
from 2 to 3 nitrogen atoms, at least one of said nitrogen atoms containing 
a double bond. Such free heterocyclic nitrogen compounds may be selected 
from the class consisting of diazole, triazole, diazine, and triazine 
compounds, such as, e.g., benzimidazole or benzotriazole, and the like. 
The term "free" as it applies to said heterocyclic nitrogen compounds is 
employed therein to exclude any acid salts of such heterocyclic nitrogen 
compounds, i.e., salt compounds formed by the reaction of any phosphorus 
acidic compound present in the hydroformylation reaction product fluids 
with such free heterocyclic nitrogen compounds as discussed herein above. 
It is to be understood that while it may be preferred to employ only one 
free heterocyclic nitrogen compound at a time in any given 
hydroformylation process, if desired, mixtures of two or more different 
free heterocyclic nitrogen compounds may also be employed in any given 
process. Moreover the amount of such free heterocyclic nitrogen compounds 
present during harsh conditions, e.g., the vaporization procedure, need 
only be that minimum amount necessary to furnish the basis for at least 
some minimization of such catalyst deactivation as might be found to occur 
as a result of carrying out an identical metal catalyzed liquid recycle 
hydroformylation process under essentially the same conditions, in the 
absence of any free heterocyclic nitrogen compound during vaporization 
separation of the aldehyde product. Amounts of such free heterocyclic 
nitrogen compounds ranging from about 0.01 up to about 10 weight percent, 
or higher if desired, based on the total weight of the hydroformylation 
reaction product fluid to be distilled should be sufficient for most 
purposes. 
An alternate method of transferring acidity from the hydroformylation 
reaction product fluid to an aqueous fraction is through the intermediate 
use of a heterocyclic amine which has a fluorocarbon or silicone side 
chain of sufficient size that it is immiscible in both the 
hydroformylation reaction product fluid and in the aqueous fraction. The 
heterocyclic amine may first be contacted with the hydroformylation 
reaction product fluid where the acidity present in the reaction product 
fluid will be transferred to the nitrogen of the heterocyclic amine. This 
heterocyclic amine layer may then be decanted or otherwise separated from 
the reaction product fluid before contacting it with the aqueous fraction 
where it again would exist as a separate phase. The heterocyclic amine 
layer may then be returned to contact the hydroformylation reaction 
product fluid. 
The hydroformylation processes of this invention may be carried out using, 
for example, a fixed bed reactor, a fluid bed reactor, a continuous 
stirred tank reactor (CSTR), or a slurry reactor. The optimum size and 
shape of the catalysts will depend on the type of reactor used. In 
general, for fluid bed reactors, a small, spherical catalyst particle is 
preferred for easy fluidization. With fixed bed reactors, larger catalyst 
particles are preferred so the back pressure within the reactor is kept 
reasonably low. The at least one reaction zone employed in this invention 
may be a single vessel or may comprise two or more discrete vessels. The 
at least one separation zone employed in this invention may be a single 
vessel or may comprise two or more discrete vessels. The at least one 
scrubber zone employed in this invention may be a single vessel or may 
comprise two or more discrete vessels. It should be understood that the 
reaction zone(s) and separation zone(s) employed herein may exist in the 
same vessel or in different vessels. For example, reactive separation 
techniques such as reactive distillation, reactive membrane separation and 
the like may occur in the reaction zone(s). 
The hydroformylation processes of this invention can be conducted in a 
batch or continuous fashion, with recycle of unconsumed starting materials 
if required. The reaction can be conducted in a single reaction zone or in 
a plurality of reaction zones, in series or in parallel or it may be 
conducted batchwise or continuously in an elongated tubular zone or series 
of such zones. The materials of construction employed should be inert to 
the starting materials during the reaction and the fabrication of the 
equipment should be able to withstand the reaction temperatures and 
pressures. Means to introduce and/or adjust the quantity of starting 
materials or ingredients introduced batchwise or continuously into the 
reaction zone during the course of the reaction can be conveniently 
utilized in the processes especially to maintain the desired molar ratio 
of the starting materials. The reaction steps may be effected by the 
incremental addition of one of the starting materials to the other. Also, 
the reaction steps can be combined by the joint addition of the starting 
materials. When complete conversion is not desired or not obtainable, the 
starting materials can be separated from the product, for example by 
distillation, and the starting materials then recycled back into the 
reaction zone. 
The hydroformylation processes may be conducted in either glass lined, 
stainless steel or similar type reaction equipment. The reaction zone may 
be fitted with one or more internal and/or external heat exchanger(s) in 
order to control undue temperature fluctuations, or to prevent any 
possible "runaway" reaction temperatures. 
The hydroformylation processes of this invention may be conducted in one or 
more steps or stages. The exact number of reaction steps or stages will be 
governed by the best compromise between capital costs and achieving high 
catalyst selectivity, activity, lifetime and ease of operability, as well 
as the intrinsic reactivity of the starting materials in question and the 
stability of the starting materials and the desired reaction product to 
the reaction conditions. 
In an embodiment, the hydroformylation processes useful in this invention 
may be carried out in a multistaged reactor such as described, for 
example, in copending U.S. patent application Ser. No. 08/757,743, filed 
on an even date herewith, the disclosure of which is incorporated herein 
by reference. Such multistaged reactors can be designed with internal, 
physical barriers that create more than one theoretical reactive stage per 
vessel. In effect, it is like having a number of reactors inside a single 
continuous stirred tank reactor vessel. Multiple reactive stages within a 
single vessel is a cost effective way of using the reactor vessel volume. 
It significantly reduces the number of vessels that otherwise would be 
required to achieve the same results. Fewer vessels reduces the overall 
capital required and maintenance concerns with separate vessels and 
agitators. 
For purposes of this invention, the term "hydrocarbon" is contemplated to 
include all permissible compounds having at least one hydrogen and one 
carbon atom. Such permissible compounds may also have one or more 
heteroatoms. In a broad aspect, the permissible hydrocarbons include 
acyclic (with or without heteroatoms) and cyclic, branched and unbranched, 
carbocyclic and heterocyclic, aromatic and nonaromatic organic compounds 
which can be substituted or unsubstituted. 
As used herein, the term "substituted" is contemplated to include all 
permissible substituents of organic compounds unless otherwise indicated. 
In a broad aspect, the permissible substituents include acyclic and 
cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic 
and nonaromatic substituents of organic compounds. Illustrative 
substituents include, for example, alkyl, alkyloxy, aryl, aryloxy, 
hydroxy, hydroxyalkyl, amino, aminoalkyl, halogen and the like in which 
the number of carbons can range from 1 to about 20 or more, preferably 
from 1 to about 12. The permissible substituents can be one or more and 
the same or different for appropriate organic compounds. This invention is 
not intended to be limited in any manner by the permissible substituents of 
organic compounds. 
Certain of the following examples are provided to further illustrate this 
invention. 
Example 1 
Into a glass vessel was added a stock solution of 536 parts per million of 
hydroxy butyl phosphonic acid in butyraldehyde. This solution was 
contacted with water in a weight ratio of 1.18:1 grams water to grams 
aldehyde/acid stock solution. The aldehyde and water phase were contacted 
thoroughly to allow the separation of acid between the organic and the 
aqueous layer to reach equilibrium. The aldehyde phase was analyzed for 
hydroxy butyl phosphonic acid by ion chromatography after contact with the 
water giving 52.3 parts per million of hydroxy butyl phosphonic acid. The 
water phase was also analyzed by ion chromatography for the acid. The 
water phase contained 414 parts per million of hydroxy butyl phosphonic 
acid. The partition coefficient between the water and the butyraldehyde 
phase was 414/52.3 or 7.92. 
Example 2 
This control example illustrates the stability of Ligand F (as identified 
herein) in a solution containing 200 parts per million of rhodium, and 
0.39 percent by weight of Ligand F in butyraldehyde containing aldehyde 
dimer and trimer in the absence of added acid or benzimidazole. 
To a clean, dry 25 milliliter vial was added 12 grams of the butyraldehyde 
solution mentioned above. Samples were analyzed for Ligand F using High 
Performance Liquid Chromatography after 24 and 72 hours. The weight 
percent of Ligand F was determined by High Performance Liquid 
Chromatography relative to a calibration curve. No change in the 
concentration of Ligand F was observed after either 24 or 72 hours. 
Example 3 
This Example is similar to Example 2 except that phosphorus acid was added 
to simulate the type of acid that might be formed during hydrolysis of an 
organophosphite. 
The procedure for Example 2 was repeated with the modification of adding 
0.017grams of phosphorous acid (H.sub.3 PO.sub.3) to the 12 gram solution. 
After 24 hours the concentration of Ligand F had decreased from 0.39 to 
0.12 percent by weight; after 72 hours the concentration of Ligand F had 
decreased to 0.04 percent by weight. This data shows that strong acids 
catalyze the decomposition of Ligand F. 
Example 4 
This Example is similar to Example 2 except that both phosphorus acid and 
benzimidazole were added. 
The procedure for Example 2 was repeated with the modification of adding 
0.018 grams of phosphorous acid and 0.0337 grams of benzimidazole to the 
solution. No decomposition of Ligand F was observed after either 24 or 72 
hours. This shows that the addition of benzimidazole effectively buffers 
the effect of the strong acid and thereby prevents the rapid decomposition 
of Ligand F. 
Example 5 
The following series of experiments were performed in order to determine 
the relationship of the pKa of a base to the effectiveness of the base to 
remain in the organic phase upon contact with an equimolar aqueous acid 
solution. In all cases the experiments were performed under nitrogen, 
unless otherwise specified. 
Solutions were prepared by dissolving a quantity of acid or base in solvent 
so that the final concentration was equal to 0.1 moles/liter. The 
1.times.10.sup.-3 moles/liter solutions were prepared by taking an aliquot 
of the 0.1 moles/liter solution and diluting to the specified 
concentration. The 1.times.10.sup.-5 moles/liter solutions were prepared 
in the same manner as the 1.times.10.sup.3 moles/liter solution with the 
modification of using an aliquot of the 1.times.10.sup.-3 moles/liter 
solution in place of the 0.1 moles/liter solution. 
In each extraction experiment, 5 milliliters of base solution in 
butyraldehyde was added to a clean, dry vial. To this vial was added 5 
milliliters of equimolar H.sub.3 PO.sub.3 solution. The resulting mixture 
was rapidly shaken for several minutes and then allowed to phase separate. 
A 1 milliliter aliquot of the aqueous layer was then transferred to a 
clean, dry vial. To this vial was added 1 milliliter of pH 7 
sodium/potassium phosphate buffer and 0.1 milliliter of Tergitole 15-S-9 
surfactant. The solution was shaken vigorously, and an aliquot was 
analyzed by high performance liquid chromatography for base content. The 
amount of base was then compared with a dichloromethane solution at the 
initial concentration. The partition coefficients calculated are for 
partitioning of the base from the organic phase to the water phase and is 
defined as K=amount of base in the water phase/amount of base in the 
organic phase. The results of the extraction experiment are summarized in 
Table A. 
TABLE A 
______________________________________ 
Concen- Concen- 
pKa trati on trati on 
of (moles/ (moles/ 
Run Base base liter) Acid liter) K 
______________________________________ 
1 2-benzylpyridine 
5.1 1 .times. 10.sup.-3 
H.sub.3 PO.sub.3 
1 .times. 10.sup.-3 
0.22 
2 2-benzylpyridine 
5.1 1 .times. 10.sup.-5 
H.sub.3 PO.sub.3 
1 .times. 10.sup.-5 
0.30 
3 quinoline 4.8 1 .times. 10.sup.-3 
H.sub.3 PO.sub.3 
1 .times. 10.sup.-3 
0.43 
4 quinoline 4.8 1 .times. 10.sup.-5 
H.sub.3 PO.sub.3 
1 .times. 10.sup.-5 
1.20 
5 3-acetylpyridine 
3.3 1 .times. 10.sup.-3 
H.sub.3 PO.sub.3 
1 .times. 10.sup.-3 
0.93 
6 3-acetylpyridine 
3.3 1 .times. 10.sup.-5 
H.sub.3 PO.sub.3 
1 .times. 10.sup.-5 
0.00 
7 benzotriazole 
1.6 1 .times. 10.sup.-3 
H.sub.3 PO.sub.3 
1 .times. 10.sup.-3 
0.08 
8 benzotriazole 
1.6 1 .times. 10.sup.-5 
H.sub.3 PO.sub.3 
1 .times. 10.sup.-5 
0.00 
9 1-benzyl-2- -0.7 1 .times. 10.sup.-3 
H.sub.3 PO.sub.3 
1 .times. 10.sup.-3 
0.02 
pyrrolidinone 
10 1-benzyl-2- -0.7 1 .times. 10.sup.-5 
H.sub.3 PO.sub.3 
1 .times. 10.sup.-5 
0.00 
pyrrolidinone 
______________________________________ 
The results show that the smaller the pKa of the base, the more remains in 
the organic phase. 
Although the invention has been illustrated by certain of the preceding 
examples, it is not to be construed as being limited thereby; but rather, 
the invention encompasses the generic area as hereinbefore disclosed. 
Various modifications and embodiments can be made without departing from 
the spirit and scope thereof.