‘
`
`‘_C§atél§st‘ syétém for
`-_ox_i _afi.pn otammonia
`=_.to niifi ‘acid
`'
`
`-
`
`~
`
`'_
`
`.»._
`:'
`
`-
`
`—'
`
`,‘
`
`R2015-001'7':1,j”:
`IPR2015-00171
`Exhibit 1061
`EX|"1ibit1Q61
`
`
`000001
`
`000001
`
`

`
`View from the Top, continued
`
`-Desirability of the project, based on
`the anticipated number of customers,
`the competitive situation, and whether
`the product can be patented or other-
`wise protected
`The last parameter varies widely from
`company to company and with time
`because it is here that specific corporate
`objectives are injected into the evaluation
`process.
`
`How should these control procedures be
`used? First,
`they must
`be
`flexible.
`Active R&D projects should be reviewed
`monthly, at least quarterly, or every time
`dollar expenditure has reached a pre-set
`level or rate. Projects that have been
`abandoned should also be periodically
`reexamined because any change in the
`parameters changes the feasibility of the
`project.
`Rating research projects channels R&D
`spending into areas with the best proh-
`ahili/y ofpayout. Further, it strengthens
`the relationship between the scientist
`and management. Researchers, by sup-
`plying data for project evaluation and
`otherwise participating in the evaluative
`procedure, are closely involved in the
`decision-making process. This involve-
`ment gives them a new understanding of
`the desirability and practicality of the
`project and of its constraints, some of
`
`which they can attack and some of which,
`often crucial ones,
`they cannot. The
`researchers may consciously, or subcon-
`sciously,
`fail
`to realize that the project
`on which he is working has become so
`complicated and expensive that even if
`the synthesis is successful, the costs will
`prevent commercialization. Or, maybe
`the market has dried up. Or, capital is
`not available in the foreseeable future.
`This is why we use factors: When any
`factor reaches zero,
`the whole project
`becomes zero no matter how good other
`factors are.
`Scientists understand numbers. Our
`methods of rating projects is expressed
`in numerical
`terms.
`It is
`impersonal.
`It
`is not “prejudiced"
`The seienlist
`has participated in its determination and
`supplied other
`inputs.
`This can help
`keep him out of the growing army of
`disenchanted chemists who complain that
`“management did not understand me”
`or “failed to support research” when his
`project
`is deactivated because it
`is no
`longer attractive.
`It would thus seem
`to the researcher’s advantage to famil-
`iarize himself with his firm’s evaluation
`techniques. And,
`if there are none, or
`he sees them as deficient, then he should
`champion their introduction or improve-
`ment.
`
`CHEM TECH
`
`“'
`
`October 1971
`
`/
`
`CHM Bl. 1(10) 577-640 (1971)
`
`EDITOR: B. J. Luberoff
`
`DIRECTOR or DESIGN:
`Joseph Jacobs
`PRODUCTION MA NAG ER:
`Bacil Guiley
`ART DIRECTOR:
`Norman W. Favin
`ASSOCIATE‘. PRODUCTION MANAGERS:
`Leroy L. Corcoran, Charlotte C. Sayre
`COPY EDITOR:
`Gloria L. Dinote
`
`ADVISORY PANEL: Division represented
`Leo Friend (Chairman), Industrial and Engi-
`neering C/zemis/‘7;y
`A. L. Alexander, Organic Coatings and Plastics
`Chemisiry
`G. A. Mills, Petroleum
`David Bixby, Fertilizer and Soil Chemislry
`Robert Blanks, Polymer Chemistry
`Bernard D. Blaustein, Fuel Chemistry
`E. M. Buras, Cellulose, Wood, and Fiher
`Chemistry
`N. H. Giragosian, Chemical
`Eeonomies
`
`lliarlceting and
`
`Peter Hosler, Mierohial Chemislry and
`Technology
`
`J. P. Lodge, Water, Air, and Waste C/zemis/ry
`L. E. Straka, Ruhher Chemistry
`J. K. Taylor, A/nabitieal Chemistry
`EXECUTIVE BOARD:
`
`L. T. Chavkin, Bristol Myers Co.
`H. A. Hill, Riverside Research Lahoralories, Ino.
`J. J. Menn, Siaufler Chemical Co.
`G. L. Nelson, General Eleetrie Co.
`N. Platzer, Monsanto Co.
`S. Reines, student Columhia University
`A. R. Rescorla, American Pe/roleztm Insfilute
`James Wei, University of Delaware
`R. W. Young, Polaroid Corp.
`PUBLISHED BY
`AMERICAN CHEMICAL SOCIETY
`1155 16th Street, N.W.
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`Frederick T. Wall
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`
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`
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`Please send manuscripts and correspondence concern 9
`Copyright
`I97I
`by the American Chemical Socieiy
`editorial matters to:
`
`Dr. B. J. Luberoff, Editor
`_
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`580 CHEM TECH OCTOBER 1971
`
`
`000002
`
`000002
`
`

`
`Low pressure process for
`acetic acid via carbonylation
`
`James F. Roth, John H. Craddock, Arnold Hershman, and Frank E. Paulik
`
`This paper describes the chemistry that underlies the new
`300»million pound per year acetic acid plant put on
`stream in 1970 by Monsanto (1).
`Reactions of carbon monoxide with organic molecules
`have been of interest both industrially and scientifically
`for over 30 years (2, 3). Their distinguishing feature is
`that carbon monoxide, a normally rather inert material,
`isoelectronic with N2,
`is activated catalytically.
`It adds
`to organic molecules initially as a carbonyl group. Such
`carbonylation reactions lead to a wide variety of oxygen-
`ates such as aldehydes (alcohols), ketones, carboxylic
`acids, etc.
`.The best known carbonylation is the reaction
`of carbon monoxide, hydrogen, and an olefin to form alde-
`hydes and alcohols. This is the Oxo reaction (15).
`
`RCH=CH2 + co + H. ——>“‘:‘”‘
`O
`
`RCH2CH2—iClII-I and/or R’CHgCHgOI-I
`isdii11(ci.rs
`isdmcelzrs
`
`(1)
`
`
`
`Left to right: Craddoc/e, Rotlz, Her:/zmtm, aria’ Prm/ik
`
`A less well—known carbonylation is the reaction of carbon
`monoxide with methanol to yield acetic acid (5)
`
`O
`H
`7'°°°;:.‘3;.‘§.‘:“.
`CH3OH + CO Ma CH;.COH
`‘.Z50°—350° C
`
`(2)
`
`The earliest catalysts for carbonylation of methanol to
`acetic acid consisted of acidic compounds such as boron
`trifluoride, and phosphoric acid alone and in conjunction
`with metal salts. These catalysts were used either in the
`liquid phase or on supports, but their use was characterized
`by drastic reaction conditions: Carbon monoxide pres-
`sure in the range of 10,000 psi and reaction temperatures
`greater than 300°C were frequently used. Such severe
`reaction conditions caused corrosion problems and low
`selectivity (6).
`In 1941, Reppe and his coworkers applied the knowl-
`edge obtained from their studies on the 0x0 reaction to the
`carbonylation of alcohols (24). They demonstrated that
`metal carbonyls, especially those of iron, cobalt, and
`nickel, were efiective catalysts for the carbonylation of
`
`Dr. Craddock is a Research Group Leader in the Homogeneous Catalysis
`Section of Monsanto’s Central Research Department. A native of
`Memphis, Tennessee, he received a B.S. from Memphis State University
`and Ph.D. in Inorganic Chemistry from Vanderbilt University in 1961.
`Prior to joining Monsanto in 1965 Dr. Craddock was at the Research
`Laboratories of the M. W. Kellogg Co. He has 15 publications and US.
`patents in homogeneous catalysis and coordination chemistry.
`
`Dr. Hershman is an engineering Group Leader in the Catalysis Section of
`Monsanto’s Central Research Department. Currently, his activities
`involve research on homogeneous catalyst systems. Hejoined Monsanto
`in 1960 upon completion of his Ph.D. in Chemical Engineering at th€
`University of Illinois. He has published on hydroformylation reactions,
`and during the past 5 years has worked primarily on carbon monoxide
`reactions. His major areas ofinterest are reaction kinetics and chemical
`reaction engineering.
`
`Dr. Roth is Manager of Catalysis Research in Monsanto’s Central Re-
`search Department, St. Louis, Missouri. His activities cover basic and
`applied research in catalysis directed toward new processes. He has
`authored 20 publications and numerous patents
`in both homo-
`geneous and heterogeneous catalysis. His discoveries led to two major
`commercial processes.. He received his Ph.D.
`in Physical Chemistry
`from the University of Maryland, and joined Monsanto in 1960.
`000003
`_
`600 ‘CHEM TECH OCTOBER 1971
`
`
`Dr. Paulik received his B.S. from Illinois, his M.S. from Purdue, and his
`Ph.D. in Chemistry from the University of Cincinnati in 1964. He (lid
`postdoctoral work at Chicago andjoined Monsanto as a research chemist
`in 1965. During 1967-1969 he did process development work on acetic
`acid at Texas City. Currently he is research chemist with the Hydro-
`carbons and Polymer Division in St. Louis. His papers cover metal-
`organic chemistry and industrial catalysis, and he has recently written a
`review on hydroformylation catalysis.
`
`
`
`000003
`
`

`
`of methanol
`
`Monsuntds 300 million lb/yr plant
`for producing acetic acid
`from methanol via the low pressure
`carbonylafion process,
`located in Texas City, Texas
`
`methanol between 250°~270°C, and carbon monoxide
`pressures from 3,000—5,000 psi
`if halogens or halogen~
`containing promoters were present. These reactions
`proceeded rapidly and conditions were milder than any
`known up to that time. The order of catalytic reactivity
`of these metals of the iron group was Ni > C0 > Fe and
`the order of halogen promoter effectiveness was I > Br >
`Cl.
`
`Recently workers at Badische Aniline and Soda Fabrik
`(BASF) reported a commercial acetic acid process via
`methanol carbonylation (7).
`It utilizes a cobalt catalyst
`in the presence of an iodine—containing promoter. Like
`the original Reppe (4) work this process employs carbon
`monoxide pressures of about 7,500 psi at 210°C. The
`molar selectivity of methanol and carbon monoxide to
`acetic acid are each about 90%. The major by—product
`from carbon monoxide is carbon dioxide via the water gas
`shift reaction
`
`The hydrogen produced by the above reaction is consumed
`to produce by—products such as methane and acetaldehyde.
`Additional liquid by—products include ethanol, propionic
`acid, propionaldehyde, butyraldehyde, and butanol with
`propionic acid making up about 50% of the total by-
`product (6).
`We now wish to describe some of the chemistry of a
`homogeneous liquid phase catalyst, which is capable of
`bringing about methanol carbonylation at 1 atm in 99%
`selectivity (8). This catalyst system is now employed
`in 1VIonsanto’s new commercial process for
`the produc-
`tion of acetic acid. The soluble catalyst system consists
`of
`iodide—promoted rhodium. No significant amounts
`of by—products are formed during the reaction even in
`the presence of hydrogen.
`
`Experimental
`
`Experiments were conducted in 300 ml Magnedrive
`autoclaves (Autoclave Engineers,
`Inc.). Reactor
`tem—
`perature was maintained at 175°C for most runs. Con~
`stant pressure was maintained by a high—pressure gas
`
`000004
`
`

`
`
`
`regulator that fed carbon monoxide from a storage reser-
`voir. Pressure in the reservoir was recorded automati-
`cally as a function of time. A rhodium compound, iodide
`promoter, and solvent system were placed in the autoclave
`and heated to temperature under an initial pressure of
`about 50 psig of carbon monoxide. After reaction tem-
`perature had been reached,
`the reaction was started by
`injecting methanol
`into the reactor from a pressurized
`charging bomb. Addition of methanol represented time
`zero. Stirring was then initiated and the reactor pressure
`brought up to the desired value with additional carbon
`monoxide. The experiment normally was allowed to
`proceed for about 17 hours (overnight). After cooling
`the reactor, the solution was drained from the autoclave
`and analyzed by gas chromatography (GC). A number
`of vent gas samples were analyzed via a m ass spectrometer
`scan of mass numbers between 2 and 92. The carbonyla-
`tion catalysts used included rhodium introduced from a
`variety of different species (Table 1).
`
`Results and discussion
`
`Methanol carbonylation reaction. The net reaction
`for conversion ofmethanol to acetic acid is shown in Equa-
`tion 4,
`
`rhodium
`CI-LOH + CO __cata1yst CH3COH
`promoter
`I I
`0
`
`(4)
`
`During the course of the reaction, however, several other
`complex equilibrium reactions are involved
`
`2 CH3OH (T: CH3OCH3 -1- H20
`CH.-,OH + CH3fiOH I: CH3‘COCH3 + H20
`l
`O
`
`O
`
`CH3OH + HI(aq) Z’ CHsI + H20
`
`(5)
`(6)
`
`(7)
`
`Since these reactions are controlled by equilibria that in-
`volve methanol, all of the intermediates can ultimately be
`converted to acetic acid. These equilibria are established
`quite rapidly at the reaction conditions.
`the only
`Product composition. Acetic acid was
`product observed by gas chromatographic analysis of the
`liquid solution.
`In a few runs, which proceeded slowly,
`the overnight solution still contained unreacted methanol,
`methyl acetate, and methyl iodide. None of the liquid
`by—products such as ethanol, acetaldehyde, propionic acid,
`propionaldehyde, butyraldehyde, and butanol previously
`reported (6)
`for the cobalt—catalyzed reaction were de-
`tected. This high selectivity to acetic acid was observed
`even when a carbon monoxide feed contained as much as
`50% hydrogen.
`(By—products from hydrogenation are
`serious contaminants in other acetic acid processes.)
`The by—products described could be detected in amounts
`as low as 0.1%. Mass-spec analyses of the reactor gases
`at the end of a run showed negligible quantities of gaseous000005
`602 CHEM TECH OCTOBER 1971
`
`by—products such as hydrogen, carbon dioxide, and meth-
`ane when pure carbon monoxide was used as the feed.
`Catalyst composition. The carbonylation catalyst is
`generated from two components, a rhodium moiety and a
`halogen promoter, preferably iodide. Both are dissolved
`in a suitable solvent to give a homogeneous liquid phase.
`The catalytic species is believed to be a coordination com-
`plex of rhodium with carbon monoxide and halogen ligands.
`All of the rhodium and promoter compounds in Table 1
`gave invariant (i 10%) reaction rates and product distri-
`butions under comparable operating conditions. These
`results suggest that the catalyst starting materials ulti-
`mately form the same active catalytic species.
`(In some
`cases, depending on the order of addition of reagents and/
`or solvent and reagent compatibility, induction periods of
`varying duration were observed.)
`Choice of solvent is primarily dependent on solubility
`and compatibility of the reactants, products, and catalyst.
`The solvent may be “inert” such as a low molecular hy-
`drocarbon, or may be one of the reactants such as the
`alcohol, ester, or ether. Lower carboxylic acids can also be
`used. For a given set of reactants reaction rate is some-
`what faster in more polar media. These results suggest
`that the active catalytic species may be ionic. Solvent
`systems studied are shown in Table 1.
`The rhodium
`Effects of reaction parameters.
`catalyst system was studied in terms of reaction rate and
`product distribution as a function of pressure, and con-
`
`Table 1. Reagents employed for preparation of catalyst system
`Source or reference
`
`Rhodium component
`
`RhCla~3H-_>O
`Rh2Os
`
`[Rh(CO)-_»CI]g
`
`Matthey-Bishop lnc., Malvern, Pa".
`Engelhard lnd., Newark, N.J.
`
`J. Chen and B. L. Shaw, J. Chem. Soc., A,
`1437 (1966).
`
`[<I>..As][Rh(CO)2C|g] B. R. James and G. L. Rempel, Chem. Com-
`mun., 158 (1967).
`
`[<I>..As][Rh(CO)-_»lr,»]
`
`Rh (P423)-_»(CO)C|
`
`Rh (As<I>;i);-(CO)C|
`
`B. R. James and G. L. Rempel, Chem. Com-
`mun., 158 (1967).
`
`J. Chatt and B. L. Shaw, J. Chem. 800., A,
`1437 (1966).
`
`J. Chan and B. L. Shaw, J. Chem. 800., A,
`1437 (1966).
`
`Rl'l(P’n‘BU:x)::(CO)Cl R. F. Heck, J. Amer. Chem. Soc., 86, 2796
`(1964).
`
`Promoter component
`Aqueous HI
`CH3!
`Cal:-3H-_.O
`|..
`
`Solvent
`Water
`Acetic acid
`Methanol
`Benzene
`Methyl acetate
`
`
`
`000005
`
`

`
`Since various
`and catalyst.
`reactants
`centration of
`sources of the catalyst precursors (i.e., rhodium and iodide)
`had been demonstrated to give equivalent results,
`for
`convenience the commonly available forms RhCl-3-3H2O
`and aqueous hydrogen iodide were employed in a water-
`acetic acid solvent system for these studies. Neglecting
`such minor effects as liquid volume expansion (~15%)
`and displacement of the more volatile methanol component
`in the reactor vapor space as acetic acid is produced (with
`a corresponding increase in carbon monoxide partial pres-
`sure of about 50 psi), the reaction parameters remain es-
`sentially constant during any run.
`About 50 runs were conducted during this investigation,
`and in each of these runs the rate of carbon monoxide con-
`sumption was determined. Experimentally,
`the reactor
`was maintained at constant pressure by feeding carbon
`monoxide on demand from a high—pressure gas reservoir.
`The reservoir volume was kept small enough that a signifi-
`cant pressure drop occurred during an experiment.
`Since
`one mole of carbon monoxide is consumed per mole of
`acetic acid formed, the rate measured by recording pres—
`sure drop vs.
`time represents the rate of carbonylation.
`The pressure drop and the quantity of methanol reacted
`were found to be proportional. The reaction was allowed
`to run to >95% conversion of the methanol to acetic acid
`as indicated by amount of carbon monoxide consumed and
`verified by the GC analysis of the liquid product.
`The rate (kg) of carbon monoxide consumption was con-
`stant to within 10% during at least 90% of any reaction.
`The constant reaction rate as methanol concentration de-
`
`creased by a factor of 10 implies that the reaction is zero-
`order with respect to methanol.
`As another check of the independence of reaction rate on
`methanol concentration,
`the initial methanol concentra-
`tion was varied over 3.3—fold. The values for kg varied by
`less than 20% for this large change in initial methanol
`concentration.
`
`the reactor composition was moni-
`During two runs,
`tored by analysis of timed liquid samples removed during
`the course of the reaction. The data were reduced to a
`
`representation of product composition as a function of time.
`These results also provided a Verification, independent of
`the pressure drop data, that the reaction rate is constant
`over at least 90% of the methanol reaction and of the
`zero»order dependence of reaction rate on methanol con-
`centration. They showed that esterification of methanol
`and acetic acid occurs very rapidly and that both methanol
`and methyl acetate concentrations decrease during the
`reaction. These results also showed that methyl iodide
`reached a steady—state concentration very rapidly that
`remained essentially constant over most of the reaction
`while the methanol and methyl acetate were being con-
`verted to acetic acid.
`The effects of rhodium and iodide concentration on rate
`were also observed. Rhodium and iodide concentration
`
`were varied independently over a fourfold range. Rate
`was found to be directly proportional to both the rhodium
`
`Automated reactor system used in methanol carbonylation research
`
`and iodide concentrations to within :2 5%.
`The partial pressure of carbon monoxide (pCO) was
`varied between 200 and 1800 psia in 7 runs.
`In estimating
`pCO, allowance was made for the partial pressure of gas-
`eous components other than carbon monoxide. The rate
`computed at each of the carbon monoxide pressures was
`invariant (:l: 7%) over this 9X pressure range, establishing
`the lack of dependence of reaction rate on pCO.
`It was
`also ascertained that facile carbonylation even occurs at
`pCO of 1 atm and lower. As a further check that the re-
`action was zero-order in pCO,
`it was raised during the
`course of a run.
`In one case after about 25% of the reac-
`tion was completed, pCO was raised from 200 to 500 psi;
`in a second case from 200 to 800 psi.
`In neither case did
`the rate change by more than 10%, which is within the
`reproducibility limits for the experimental system.
`Addition of hydrogen did not eflfect
`reaction rate.
`Since, as discussed above, hydrogen exerted no ill effect on
`the product composition, it behaves as an inert diluent.
`00PQ0§ummary then, reaction rate was found to be inde-
`
`OCTOBER 1971 CHEM TECH 603
`
`000006
`
`

`
`
`
`The reaction is believed to proceed in a step—wise manner
`and to include the five steps shown below.
`Reaction steps in the carbonylation of methanol
`
`1. CH3OH + HI Z CH3I + H20
`
`CH3
`i
`S ()\V
`2. CH3I + [Rh complex] —1—> Rh complex
`
`II
`
`I
`Rh complex
`I
`1
`
`CH3
`I
`—I- CO —> Rh complex-CO
`I
`1
`
`4.
`
`CH3
`I
`c=o
`CH3
`I
`I
`Rh complex-CO —> Rh complex
`I
`I
`I
`I
`
`CH3
`
`5.
`
`C=O
`
`IR
`
`I
`1
`
`h complex 53 CH3COH + [Rh complex] + HI
`II
`0
`
`pendent of both carbon monoxide pressure and methanol
`concentration, but directly proportional to concentrations
`of rhodium and iodide promoter.
`Mechanistic interpretation. The literature con-
`tains numerous references to various soluble rhodium com-
`plexes that may be related to, or postulated as,
`the
`catalytic intermediates in this methanol carbonylation
`system. Spectroscopic studies of the nature of reactive
`intermediates involved in the catalytic cycle have been
`performed by Dr. D. Forster of these laboratories and will
`be reported separately. For the purposes of discussing
`the reaction mechanism in terms of the kinetics results de-
`scribed herein, the catalyst can be considered to be com«
`prised of a soluble rhodium complex and an iodide
`promoter.
`
`
`
`
`To begin with, methanol is rapidly converted to methyl
`iodide. Then an oxidative addition reaction occurs be-
`tween methyl
`iodide and a Rh(I) complex (d3 square
`planar) to form a six—coordinate alkyl—rhodium(III) species
`(d6). Rapid insertion of carbon monoxide into the rho-
`dium—alkyl bond occurs, accompanied by subsequent or
`simultaneous replacement of CO in the rhodium coordina-
`tion sphere,
`to yield an acyl—rhodium(III)
`complex.
`Finally, reaction is completed by reaction of the acyl-
`rhodium(III) complex with water to yield acetic acid and
`the original rhodium(I) complex.
`Oxidative addition of covalent molecules, e.g., CHsI, to
`square planar d8 complexes to yield six—coordinatc d6 com-
`plexes are well known and have been discussed in detail
`(9). Furthermore,
`insertions of carbon monoxide into
`metal—carbon or metal—hydride bonds, as postulated in our
`reaction scheme, have been suggested for other systems,
`e.g., carbon monoxide insertion into CH3Mn(CO)5 or in
`olefin hydroformylation reactions employing catalysts
`such as HCo(CO)4 (2).
`The postulated reaction mechanism is consistent with
`000007 the present kinetic results and conclusions if one assumes
`
`Table 2. Comparison of cobaIi- and rhodium-catalyzed reaction
`Effect upon reaction rate
`Cobalt catalyst system
`Rhodium catalyst system
`First-order
`Zero-order
`Second-order
`Zero-order
`First—order
`First-order
`Variable
`First-order
`
`Reaction variable
`[CHsOH]
`pCO
`[|‘]
`[Co or Rh]
`
`604 FCHEM TECH‘ OCTOBER 1971
`
`000007
`
`

`
`is
`involving the oxidative addition of CH3I,
`that step 2,
`the rate—determining step, and that all preceding and sub-
`sequent steps occur very rapidly. The experimentally
`observed constancy of CH3I concentration over most of
`the reaction is consistent with the constant reaction rate
`
`It is also consistent
`observed during the same period.
`with the observed dependency on methanol, carbon monox-
`ide, rhodium, and iodide concentrations.
`The final step in the catalytic cycle involves reaction of
`the d“ acyl—rhodium(III) complex to yield acetic acid and
`regenerate the original d3 rhodium(I) complex.
`Several
`different types of reaction paths may be invoked to de-
`scribe this step. These include a direct hydrolysis of the
`acyl—rhodium(I) complex by water, a specific methanol-
`assisted solvolysis of this complex, or reductive elimination
`of acetyl
`iodide from the complex accompanied by im-
`mediate hydrolysis of the acetyl iodide to produce acetic
`acid and regenerate the original rhodium(I) complex. Of
`these possibilities, we favor the last involving reductive
`elimination of acetyl iodide.
`Comparison of rhodium vs. cobalt catalyst sys-
`tems. A study of the catalytic carbonylation ofmethanol
`to acetic acid by cobalt complexes was reported by Milo-
`roki et al. (10) in 1962. They employed a cobalt acetate
`and potassium iodide catalyst system. The operating
`conditions were severe (200°~260°C and 4,000—7,000 psi),
`presumably because of the lower reactivity of the cobalt
`catalyst system. Nevertheless, a comparison of rhodium-
`iodide vs. cobalt—iodide systems can be made (Table 2).
`
`The significant difference is that the cobalt—catalyzed re-
`action is strongly dependent on both carbon monoxide
`pressure and methanol concentration, while the rhodium-
`catalyzed reaction is not. This dissimilarity suggests that
`the cobalt and rhodium catalysts involve different rate-
`controlling steps, which in turn could imply completely
`different mechanisms.
`It also carries the important com-
`mercial implication of higher methanol conversion in the
`rhodium system as well as lower operating pressure.
`
`References
`
`(1) cf. Belgian Patent 713,296, October 7, 1968.
`(2) Bird, C. W., Chem. Rev., 61, 283 (1961); “Transition Metal Inter-
`mediates in Organic Synthesis,” Logos Press, London, 1967.
`(3) Eiclus, Ya. T., and Puzitskii, K. V., Rum. C/zcm. Rev. (Engl. transl.),
`33,438 (1954);
`
`(4) Reppe, J. W., “Acetylene Chemistry,” Charles A. Meyer and Co.,
`Boston, Mass., 1949.
`(5) Bhattacharyya, S. K., “Actes du Deuxieme Congress International
`de Catalyse,” Vol. II, Editions Technip, Paris, 1961, pp 2401-2427.
`(6) Von Kutepow, N., Himmele, W., Hohenschutz, H., C/zem.—Ing.-Tech,
`37, 383 (1965).
`
`(7) Hohenschutz, H., von Kutepow, N., Himmele, W., Hydrararéon
`P7'0C€5J., 45, 141 (1966).
`(8) Paulik, F. E., and Roth, F., Chem. Commun, 1578 (1968).
`(9) Collman, I. P., Accounts C/zem. Ran, 1, 136 (1968).
`(10) Mizoroki, T., Nakayama, M., Furumi, M., Kagyo Kagalcu Zasshi,
`65, 1054 (1962).
`
`Based on a presentation before the ISZEC Division of the National ACS
`Meeting, Washington, D.C., 1971.
`
`
`
`HEARD AT THE D. C. MEETING
`
`Holding the Petroleum Division banquet in
`the Smithsonian elicited comments
`like,
`“Wouldja believe Butch Hanford doing the
`Lindy-Hop in the Smithsonian Institute?”
`Or, “How come the Foucault Pendulum isn’t
`working?”
`“I guess they turned ofi the earth
`for lack of interest.’ ’
`
`Then, there was Alan Nixon's quip “During
`my years at Shell, I worked in 13 departments.
`I was so broad I was damn near flat.”
`
`Or, George Hammond’s response to a new
`plan, “I’m embarrassed to realize the extent to
`which I reserve unmitigated enthusiasm for
`my own suggestions and how traditional I am
`in my reactions to those made by others.”
`Or, “That shuttle bus took 40 minutes to do
`what a 75-cent cab does in 10.
`I guess my
`hourly rate is a buck and a half.”
`Or, “Preparing the sample turned out to be
`the tricky part.”
`Or, “Exotic Dancers aren’t
`erotic dancers.”
`
`the same as
`
`Or “The last paper in the symposium was the
`best and you heard that.”
`Or, “If you guys can figure out ‘The Fate of
`Naphthyl-1-“C-Carbaryl in Laying Chickens
`
`Under Continuous Feeding,’ why the devil
`can’t you make a bathing cap that doesn’t
`leak?”
`
`Or, “Didja ever hear of the Hass Rearrange-
`ment?"
`“You mean the Hass Shift;
`that’s
`wearing your name tag on the right lapel so it's
`visible when you're shaking hands.”
`Or, “CHEM TECH‘s T and E Section says the
`ACS cafeteria serves pheasant under glass.”
`“Yeh, gizzards under a beaker.”
`Or, “I got your old light scattering rig ‘cause
`nobody else wanted it and. . .”
`Or “We’re trying to develop a chemistry de-
`partment that our basketball team can be
`proud of.”
`Or, the sign that said
`
`“Computer Applications”
`THE FUTURE—PART II
`
`But, the one we reacted to most loudly (with
`apologies to Dr. Bens) was the badge that read:
`Dr. Bens Naval Weapons Center.
`Then, we got home to this classic sentence in
`Accounts: Typical nonnarcissistic automer-
`izations are antarafacial sigmatropic shifts of
`Ofiwml migrating centers.
`
`OCTOBER 1971 CHEM TECH 605
`
`000008