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JOURNAL OF THE
REVIEWS AND NEWS-
Developmentand Commercializationof the Monsanto
ElectrochemicalAdiponitrileProcess1
Monsanto Fibers and Intermediates Company, Pensacola, Florida 32575
Mr. President, I would like to begin this Vittorio de
Nora-Diamond Shamrock Award address by expressing
m y sincere appreciation to the m e m b e r s of the Board of
Directors of The Electrochemical Society for naming me
the award recipient. When I learned several months ago
that I had been selected for this honor, I was i m men sel y
pleased, but also surprised; I really consider m y s e l f more
a conventional chemical engineer than an electrochemical
technologist. My assignment with Monsanto over the past
26 years has been to seek cost-effective processes for syn-
thetic fiber intermediates, employing whatever type of
technology best gets the job done. Fortunately, as a result
of Manual Baizer's 1960 discovery of an efficient electro-
chemical method for reductively coupling acrylonitrile to
form adiponitrile (which is an important nylon intermedi-
ate), I have been able to spend much of the past 20-plus
years in the area of technology of primary interest to this
Society.
Before I get into the description of the d e v e l o p m en t
and commercialization of the Monsanto electrochemical
adiponitrile process, I must say that I could not possibly
accept this award without making it very clear that I had
a tremendous amount of able help in this successful ven-
ture. The team responsible for the laboratory and pilot
plant d ev el o p m en t of our electrohydrodimerization pro-
cess (or, as we called it, EHD) consisted of about 20 chem-
ists and engineers working in our technical center at
Pensacola, Florida. Many others in our Engineering and
Manufacturing organization also made significant contri-
butions as we moved from laboratory to pilot plant to an
operating commercial facility. So as I stand before you
this afternoon, please consider that, in a very real sense, I
am acting rather as the captain of a ball club representing
his team.
The story of the Monsanto EHD process begins in our
St. Louis research labs, where D~. Baizer had been asked
to investigate the possibility of converting acrylonitrile
(AN) to adiponitrile (ADN). The impetus for this work
stemmed from Monsanto's projections at that time of
high growth rates for nylon and acrylic fibers, which
translated into a need for additional ADN and AN pro-
duction capability. If adiponitrile could be made from
acrylonitrile, the size of the new AN plant ~ould be in-
creased, improving plant economics, and adipic acid ca-
pacity formerly required to provide feed for the existing
ADN process would be freed up for use in producing ad-
ditional nylon 66 salt.
The reductive coupling of AN had been examined by a
number of prior investigators, but only with modest suc-
cess. The highest selectivity to ADN was about 60% for a
reaction system using potassium amalgam, as reported by
Knunyants and Vyanzankin in the USSR. While falling
far short of acceptable yields, this work did lead Baizer to
*Electrochemical Society Active M e m b e r .
~Vittorio de N o r a - D i a m o n d S h a m r o c k A w a r d a d d r e s s deliv-
ered M a y 8, 1984 at t h e Cincinnati, Ohio, M e e t i n g of t h e Society.
ELECTRDCHEMICAL E~DCIETY
OCTOBER
@ 1984
D. E. Danly*
think in terms of an electrochemical approach, and he be-
gan to experiment with various electrolyte/electrode sys-
tems. I do not plan to relate the details of this research ef-
fort, although it is a fascinating story in itself. Let me
simply summarize the very significant discovery stem-
ming from Baizer's study - - namely, that electrolysis of
AN in relatively concentrated aqueous solutions of cer-
tain quaternary a m m o n i u m salts gave nearly quantitative
yields of ADN. Cathodes of mercury or lead gave the best
q
results.
Once the feasibility of the EHD chemistry had been
demonstrated in Baizer's 500 ml lab cell, the question was
addressed of how to best proceed with the process devel-
opment. After m u c h discussion and debate at headquar-
ters in St. Louis, it was decided (and I firmly believe cor-
rectly so) that the operating division expected to
commercialize the process should carry out the scale-up
studies. Thus, the task fell to the Chemstrand Division
(now Monsanto Fibers and Intermediates Company),
which had in-place at Pensacola, Florida, a chemical pro-
cess development group under Dr. Frank Riordan. I had
joined this organization three years previously, following
completion of m y graduate work in chemical engineering
at the University of Florida. None of the group had any
real experience in electrochemistry. I was probably the
only one who had ever been to a national Electrochemical
Society meeting, that a single event as a result of a part-
time job at the University in battery research. Being per-
fectly frank, my background in electrochemistry went lit-
tle beyond familiarity with the Nernst equation, and I
actually found little opportunity to use it in the following
days. Since I was eager to be involved in d ev el o p m e nt of
this unique process, I may have been guilty of overselling
my expertise, but for whatever reason, I found myself ap-
pointed project leader for the pilot plant EHD studies.
This was late 1961, and since our forecasts indicated we
needed additional A D N capacity by early 1965, we deter-
mined that we only had a little over a year to prove out
the process. Thus, I need not have worried about getting
on the project, since before long the entire research and
d ev el o p m en t group was working on one aspect or
another of the process. The chemists began screening
electrode materials, diaphragms, alternate electrolytes,
and operating conditions, while the mechanical engineers
began to consider the cell design. Baizer's lab cell was a
glass resin flask containing a platinum wire anode and a
mercury pool as cathode, with an alundum cup serving to
separate the anolyte and catholyte. Having calculated that
it would take 350,000 of these cells to give the targeted
plant capacity of 15,000 metric tons per year, we began to
appreciate the magnitude of the scale-up challenge facing
US.
Electrode Selection
The selection of a cathode material was relatively easy.
Baizer had shown that either lead or mercury was suit-
able, and we were so horrified by the anticipated envi-
435C
436C J. Electrochem. Soc.: R E V I E W S A N D N E W S
Old Process
9 Oxidation
HOOC(CH2)4COOH
Cycl ohe~ane Adipic Acid
'~NH3
~
Desired Process
air, N~3
CH2=CHCH3 ~ CH2=CHCN
Propylene Acrylonitrile
Fig. 1. Routesto adiponitrile
ronmental and cell design problems with mercury that we
quickly settled on lead. We tested a long list of other ma-
terials reported to give high hydrogen overvoltages, but
none was found superior to lead.
An o d e selection proved to be considerably more diffi-
cult. We began our studies using platinized titanium, but
the platinum loss was clearly intolerable. With a switch
from Baizer's anolyte of toluene sulfonic acid to dilute
sulfuric acid, the use of lead alloys was made possible.
Tainton's alloy of 1% Ag in lead had been used success-
fully in aqueous }-I2SO4for the manufacture of electrolytic
zinc, and this was our early choice, although we tested a
n u m b e r of other lead alloys reported in the literature to
have greater stability.
The real surprise in anode development came during
the first attempts to operate a pilot-scale cell. While an-
ode corrosion rates as low as 3 mm/yr were measured in
short lab tests, we found that in extended pilot-plant runs
the corrosion rate would increase by 20-fold over a 24h
operating period. Our analytical folks were able to place
the blame on a buildup of nitrates and various chlorine
containing anions in the anolyte. The nitrate anions were
evidently being formed by oxidation of AN diffusing
through the m e m b r a n e into the anolyte compartment,
while the chlorine was entering the system in small
amounts in the sulfuric acid and quaternary a m m o n i u m
salt. The problem was solved by putting tight chloride
specifications on the raw materials and instituting a con-
tinuous purge and makeup of anoiyte to hold the nitrate
concentration below a critical level.
Selection of Supporting Electrolyte
Baizer's r e c o m m e n d e d catholyte was a 40% aqueous so-
lution of tetraethylammonium p-toluenesulfonate. This
electrolyte possessed two properties which at that time
were believed to be necessary for high A D N selectivity:
(i) the cation was not reduced at the cathode, and (ii) the
salt greatly enhanced the solubility of AN in the solution.
Other factors considered important for a commercial pro-
cess were the electrolyte cost, electrical conductivity, and
ease of removal of ADN from the electrolyte. More than
30 quaternary a m m o n i u m salts were prepared for mea-
surement of these properties. Four of these were selected
for extensive benchscale and pilot plant testing, from
which it was determined that the yield of electrolysis by-
products (propionitrile and high-boiling AN oligomers)
decreased with increasing size Qf the quaternary ammo-
n i u m cation. Salts with cations larger than tetraethylam-
m o n i u m were not felt to be practical because their aque-
ous solutions exhibited poor electrical conductivities and
very high AN and A D N solubilities, making extraction of
product difficult. Tetraethylammonium ethylsulfate was
a clear choice, since it not only gave the best A D N selec-
tivity, but also could be simply prepared by combination
October 1984
NC(CHz)4CN I~ HzN(CH2)6NH2 ~r Nylon 66
Adiponitrile Hexamethylenediamine
of two low-cost intermediates, triethylamine and diethyl-
sulfate.
In attempting briefly to outline our research and devel-
opment studies, I am greatly oversimplifying the story. I
have made it sound as though we tested cathodes, . . .
picked one, . . . tested anodes, . . . picked one, . . . tested
e l e c t r o l y t e s , . . , picked one, and so forth. It really was not
that straightforward. For example, we solved the problem
of poor stability of pure lead as an anode by adding a
small amount of silver, only to discover the Ag cation in-
troduced into the anolyte by corrosion of the anode
passed through the membrane, deposited on the cathode,
and sharply depressed the ADN selectivity. This particu-
lar problem was ultimately resolved by electrodeposition
of the silver ions contained in the recycled quaternary
a m m o n i u m salt on a lead-shot cathode of a packed-bed
electrolyzer. We also found that the best anode alloy when
using a p-toluene sulfonate anion in the catholyte was not
the best one w h e n we switched to ethylsulfate anion.
Small amounts of these anions migrating from the
catholyte into the anolyte had a significant impact on an-
ode stability.
Membrane Development
The selection of a diaphragm for separation of anolyte
and catholyte required something more than the cut-and-
try approach used with electrodes and supporting electro-
lyte. We did begin our search by testing samples of all of
the commercial cation-permselective membranes, but the
majority of these failed in less than a day. Unfortunately,
the perfluorinated m e m b r a n e s now proving so success-
ful in chloralkali cells were not around in 1962. Of the ma-
terials available, the most encouraging results were with a
m e m b r a n e made by Ionics, Incorporated, composed of
sulfonated polystyrene/divinylbenzene polymer and a
glass fiber reinforcing cloth. With these, benchscale runs
of a week or so were possible. Since considerable im-
p r o v e m e n t in durability was needed to achieve the tar-
geted 1000h service life, we entered into a joint m e m b r a n e
d ev el o p m en t program with Ionics. They provided numer-
ous test samples, varying such parameters as degree of
Table I. Pilot-plant electrolyte evaluations (50 A/dm2, 50~
Electrolyte Selectivities (%)
Cation Anion EHD by-products ADN'
Me4N p-Toluenesulfonate 9.0 89.8
MeEt3N p-Toluenesulfonate 7.1 89.2
Et4N Benzenesulfonate 7.2 90.9
Et4N Ethyl sulfate 4.9 93.4
' ADN selectivity corrected for AN recoverable from
cyanoethylation by-products.
Vol. 131,No. 10 V I T T O R I O de N O R A - D I A M O N D S H A M R O C K AWARD 437C

Table I[. Benchscale membrane screening tests of a plate-and-frame design for the commercial cell from
the outset. This decision was reinforced when, in the
Supplier/Designation Service life (h) early days of process development, we called in the re-
nowned consultant, Dr. Robert B. MacMullin. Bob, as
AMF C-60 76* many of you know, was the second recipient of the Socie-
C-110 5 ty's Electrochemical Engineering and Technology Award.
C-313 2 He was asked to provide a design for a 250A lab cell and
Asahi Glass GSG-10 <24 then to make a preliminary design and cost estimate for
GMG-10 <24 the electrolysis portion of a commercial EHD plant, Al-
CMV-10 <24 though we never constructed the MacMullin cell, his de-
Asahi Chemical DK-1 <24 tailed design calculations were extremely valuable in
Tokuyama CHR-4 190' educating us in the techniques of voltage balances, elec-
Soda CL-2.5T 133" trolysis system heat balances, cellhouse layout, and a
Ionac Chemical MC3142 2 multitude of other electrochemical engineering consider-
Permutit/U.K. C-20 15 ations.
Radiation 320 2 The other distinguished advisor we enlisted was Dr.
Applications 1010 (paired) 115 Vittorio de Nora. Following discussions with us in Pensa-
Ionics AZG 255* cola during one of his frequent trips to the U.S., it was
agreed that the de Nora firm in Milan would design and
build us a prototype cell. I was immediately dispatched to
* Using Ionics AZG membrane for support. Italy to provide the de Nora engineers with what little
process information we had.
polymer cross-linkage, type of reinforcing fabric, and At the time of Dr. de Nora's visit, the d e v e l o p m e n t team
m e m b r a n e thickness. We geared up for performance at Pensacola had already moved well into the design of
testing, setting up six 1 dm 2 flow cells, which we oper- the first pilot-plant cell. We decided early-on that this cell
ated around the clock at typical EHD operating condi- should be the same size as visualized for the full-scale fa-
tions. cility. Surely if we could make a bank of 3-5 cells work in
When we began pilot plant operation with an 80-fold the pilot plant, operation of a plant using several hundred
scale-up in m e m b r a n e area, we found, to our dismay, that identical units should pose no problem. The size of the
the formulation that haa given several hundred hours ser- cell was set by the dimensions of the largest m e m b r a n e
v i c e life in the 1 dm 2 benchscale cells did not even last for then offered by Ionics: roughly 90 x 100 cm. Since we
a day. In pilot operation, the ion-exchange resin was ran- were trying to develop all the required plant design data
domly spalling off, forming small windows for m o v e m e n t in the space of 12 months, we pushed forward simulta-
of anolyte into the catholyte. As an expedient solution, we neously with both the Monsanto and de Nora cell designs.
simply installed dual membranes, banking on the odds The first Monsanto design was a single cell unit with
against the windows' lining up, and this allowed run the electrodes mounted on polyethylene plates, into
lengths of a week or two.
which were machined cavities for electrolyte distribution
This rather brute-force solution was not very elegant, (Fig. 2). Anolyte flow was vertically upward, while
but at least allowed us to stay on line with our pilot plant catholyte was introduced through a central vertical ple-
cell to try to answer other unresolved process and cell de- num, where it split and flowed horizontally to the two
sign questions. S o m e months later, our friends at Ionics sides. Dividing of the catholyte flow was aimed at
developed a m e m b r a n e incorporating two layers of glass
reducing the length of the catholyte flow path in order to
cloth in the same resin matrix. These exhibited operating
minimize the pressure differential across the membrane.
lives of up to 2000h in lab cells and were adopted as the
This cell was used briefly in the initial pilot-plant opera-
standard.
tion, but problems in sealing of the m e m b r a n e gaskets
Cell Design and evidence of u n e v e n distribution of electrolyte across
Since the process as we knew it at that time required the cathode led us to install the de Nora cell unit as soon
separation of anolyte and catholyte, we thought in terms as it arrived by air from Italy.

Fig. 2. Monsanto Mark I EHD

cell.
438C J. Electrochem. Soc.: R E V I E W S A N D N E W S
Fig. 3. de Nora cell
The de Nora unit (Fig. 3) contained five bipolar cells.
The electrolyte streams were introduced through tapered,
external distribution boxes, then passed through a series
of small holes into internal plenum chambers in the cell
plates. This design provided greatly improved uniformity
of electrolyte flow compared to the first Monsanto de-
sign. This cell was operated for several months to con-
duct studies of spacer design and the effects of catholyte
velocity, composition, and temperature. The chief prob-
lems with the cell were the integrity of the hydraulic seals
and recurring failures of the external distribution boxes,
which were made by welding together sections of poly-
propylene sheeting.
These problems were overcome in the third-generation
design (Fig. 4), which employed tapered electrolyte distri-
bution cavities machined into polypropylene plates be-
hind the electrodes. The membranes were held between
two mated polypropylene frames for convenience in ham
dling. The fluid leakage problem was solved by the use
of a beaded gasket, which markedly lowered the required
sealing force. This proved to be a reliable assembly, and
with minor modifications it was ultimately adopted for
use in the commercial plant.
Fig. 4. Mark II Monsanto cell
October 1984
Probably one of the most important electrochemical en-
gineering concerns we faced was that of achieving high
mass-transfer rates at the cathode surface. The transfer of
AN across the diffusion layer from bulk catholyte to the
cathode turned out to be less critical than neutralization
of the hydroxyl ions produced at the cathode (Fig. 5).
Acrylonitrlle reacts very rapidly with water u n d e r alka-
line conditions to form the cyanoethylation by-products
hydroxypropionitrile and bis-cyanoethylether. These side
reactions represented a very significant AN-yield loss in
early experiments at low catholyte flow velocities. Our
first approach was to employ turbulence promoters, such
as plastic webbing or baffles, similar to the types proven
effective in electrodialysis devices. While several of these
significantly lowered losses of AN due to cyanoethyla-
tion, buildup of AN polymer on the plastic spacers in
time gave rise to an intolerable pressure drop along the
catholyte flow path. Various means of in-place cleaning
were tested, but we finally concluded that only fully
open channels offered any chance for reasonable on-
stream time. After m a n y aborted efforts, we found the
most dependable way to form the open channels was to
attach narrow plastic ribs directly to the Pb cathode in
Vol. 131, No. 10 V I T T O R I O de N O R A - D I A M O N D S H A M R O C K AWARD 439C

OH-
CH2=CHCN + H~O b- HOCHzCHzCN 20 i : : : :

acryIonltr{le hydroxypropionltrfle
(AN) (HOPN) ......................... ; ......................... i .............. : ...... :....'._.....
9 9 :: ! ! ! i : !

+AN ~IOH- . .................... ,.............................. i ....... i ........... fi . . . . . . . .

d
O(CH~CH2CN)z r |9 ................................................
................ i i
..... i .......
i : : !
blscyanoethylether
(BCE) 9 ,, i i ] !
0
Fig. 5. Cyanoethylotion reactions
9 :
m
m u c h the same way the chrome strip is fastened to one's 0
automobile fender. We tested different gauges, widths,
and thicknesses of the parallel strips, and most impor- 9 iii. i
tantly, the catholyte velocity needed to control the : i i i i
cyanoethylation side reaction (Fig. 6). A velocity of 2 m/s 4 ......................... :.......... 9 ..................... ::"...... i.....i....i....i...
was selected as giving the o p t im u m balance between AN- 0
yield loss and catholyte p u m p i n g cost.
While definition of the cell design and optimization of C9
the electrolysis conditions were paramount to the success
of the process development, a substantial effort was also
needed to define the product recovery and purification
systems. Processing downstream of the cells (Fig. 7) con-
2 : .... : : : :--
sisted of extraction of ADN from catholyte with AN, 3 2 5 10
stripping of the AN to produce a crude ADN, and final
Catholyte Velocity, m/see
clean up in a four-column distillation train. We felt it was
imperative to demonstrate the process in the pilot plant Fig. 6. Effect of catholyte velocity on cyanoethylation by-products
with all the recycle loops closed. Had we not done this,
the serious consequences of silver ion buildup in tt~e D ev el o p m en t team. Our first pass through the p r o j e c t e d
recycle QAS might never have been recognized. We also process economics was based on operation at a cathode
felt obliged to show that our refined A D N could be satis- current density of 20 A/dm ~, and we discovered the in-
factorily hydrogenated to h e x a m e th y l e n e diamine and vestment in cells would be enormous. We e x a m i n e d
converted into standard-quality nylon polymer. All of higher current densities on paper and found the o p t i m u m
these steps were demonstrated in the pilot plant. balance between electrolysis operating costs and capital
In scaling up a new process, one generally prefers to burden occurred in the current density range 40-60 A/dm =
complete laboratory demonstration and then prepare the (Fig. 8). Fortunately, lab studies showed no measurable
plant-design documents. Our tight timetable for commer- decline in electrolysis performance below 100 AJdm 2, pro-
cialization of the process did not allow us this luxury. A vided the catholyte flow was 2 m/s. This early concep-
very preliminary design of the full-scale facility was de- tualization and evaluation of the proposed commercial
veloped even before the first pilot-plant r u n by a m e m b e r process thus proved to be most valuable in guiding our
of the Engineering D e p a r t m e n t assigned to work with the d ev el o p m en t efforts.

Electrohydrodimerisation section Extractor AN strippmg

- .................................... T ~ ~-oE ..... ~a;~r e~oT~oT ' - -' .................
IPilot AN
r....... _ _ column make
~ Lextraction . _ _ lower layer ist r l p p m l g ~
I i ~ ~L. ~ .co~uron k J
--J~ "L ~ L J kz~/ [ I ~ ~Vent
~_\! ~ - - ~ s o , ! 1 I Hp,,otO, S i J I r
stoANrfr~ r - - - - - - . . . . ~ m ~ I w .... I t i i ....... ~on ~ l
, age It . .. r-~-~/ II1['1 Anolyte.~.L~(pure) I I II c~ iI I I
tank I bamolyte / tank I
L.~l I[ I EHDcellII l ~ {'~ I9 ~ ~ Feed
tankl J Feed [i" 1 ~ " ~ .... agd I
J--_-.J- ~L ~
Catholyte p u m ~ ] ~
~
A.oJyte pump
I Towater ~l
"rJLTowa'
L evaporator
~ pump I'.~J- I
3ump ~.
t ~l.eOo,ler
,tank[ J
............. - i ~, ' Transfer pump
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . = . . . . . . . . . . . . . . . . . . .

- - L_JJ~JJ~

J - ~ ~ Pilot ADN refining

Crude ADN columns (4)
Pilot PN p storage ,
tank I Make Fig. 7. Complete pilot plant
Reboiler Tails drums return storage system.
to reduction area tank r

................. .Re~.~c,e.A2............ . . . . . . . . . . . . 2,.,3r,_u .~~ ..... /

Diamine synthesis I Diamine refining Salt strike ~"
Charge tank
, i ~ harg ~aeed C~ I Pilot4~ h~ uP~'lk Ad~pc TOr~oirYnme~
a~ e~io~
L ~ r~ V~ I diarnine} ff . I I~ ,Darco '
9 l~oedl I Z r~ I~ Sep...... refmmg H RHMD ~ L~J~ -q ISa, ...... ge tank

i I ta~ I LJ 'T ~ ~ I s~t~h EY.~oYY ~ - t?~ I%WZi i[~sol A P~"'~ :,

I "Y J/ / ~--~-~---~--"~-~ i k~"'er'C'lhb~ 4"-% il ~ ib~, I U ~

;. . . . . . . . ....................... _1 . . . . . . . . . . . . . . . . . . . . ~ .... ~u& ................ j

Transfer pump High boilers to To waste Transfer pump
waste drum disposaP
440C J. Electrochem. Soc.: R E V I E W S A N D N E W S October I984

year of operation by use of improved membranes from

K Ionics, installation of a supplemental QAS cleanup sys-
%
9-~ 4
.g
8 process. The divided-cell technology we had commercial-
Total Cost
c.~
N
d 2
§
3 plant startup, some Russian investigators (Tomilov, Var-
1
~o
.2 .4 .6
Current Density, A/em 2
Fig. 8. Current density optimization
The preliminary plant design was modified repeatedly
as we learned more about the process and cell require-
ments, and a final d o c u m e n t was approved almost ex-
actly one year from the initial pilot plant run. The first
EHD facility (Fig. 9) was constructed at our Decatur,
Alabama, plantsite and had a design capacity o f 14,500
MT/Y ADN. The electrolysis system consisted of 16 cell
presses, each housing 24 bipolar cells and operating at
about 3000A. Four independent catholyte circulating sys-
tems were employed to minimize the impact of a major
m e m b r a n e failure on total plant operations.
I wish I could tell you the plant was built, started up,
and ran like a Swiss watch from the outset. However, I
must confess that initial plant operation was plagued by
short membrane lives, deterioration in A D N selectivity
due to a buildup of previously unidentified impurities in
the recycle QAS, and several small fires stemming from
ruptured catholyte hoses supplying feed to the cells.
These problems were largely resolved during the first
1. . . . . . . . . . . . . . . .
tem, and a change-over to steel-reinforced hoses.
Meanwhile, back at the labs in Pensacola, we were busy
seeking ways to make a step-change i m p r o v e m e n t in the
/
ized had three serious drawbacks: the electrical power us-
age was high (7-8 kWh/kg), the cells were complicated and
expensive, and m e m b r a n e replacement still remained a
significant operating cost. Clearly, if we could devise a
workable undivided cell system, we would avoid or re-
duce all of these penalties. In 1965, the same year as our
shavskii, and Knunyants) reported ADN selectivites as
high as 90% in an undivided cell using an emulsion of AN
in an aqueous electrolyte of 1N sodium hydrogen phos-
phate containing about 1 weight percent tetraethylam-
.8
m o n i u m phosphate. Their cell employed a graphite cath-
ode and a magnetite anode, and was operated at 18~ to
minimize cyanoethylation side reactions. While the fragile
nonmetallic electrodes used in this work seemed ill-
Suited to a commercial cell, the high electrical conductiv-
ity of the aqueous alkali phosphate electrolyte seemed
most appealing. We initiated studies of alternate cathode
and anode materials, targeting an all-metal electrode sys-
tem capable of operation at higher temperatures, in order
to avoid refrigeration.
I will not go through the long laundry list of electrode
and electrolyte systems we examined, but will summarize
several years of testing by saying that carbon steel proved
to be a very satisfactory anode, provided small amounts
of Na4EDTA and Na2B407 were added to the phosphate
electrolyte as corrosion inhibitors. These additives re-
duced the anode corrosion rates from about 10 mm/yr in
uninhibited electrolyte to a quite acceptable level of 0.5
mm/yr.
Of all the solid metals tested as cathodes, cad m i u m was
found to give the best performance with respect to ADN
selectivity and electrode stability. Aided some by seren-
dipity, we discovered that the Na4EDTA added to en-
hance anode stability led to mild corrosion at the cad-
m i u m cathode, thus serving to keep it free from
3000
~ ~A- -' accumulation of anode corrosion products (Fig. 10). In the

%
I- absence of EDTA, hydrogen evolution at the cathode in-
creased over a day's operation to the point where it repre-
sented greater than 10% loss in cathodic current
efficiency. We ultimately found it desirable to introduce
sufficient E D T A to chelate all the Cd and Fe cations en-
tering the electrolyte via electrode corrosion.
The other absolutely essential electrolyte co m p o n e nt is

% i"
S- I
the quaternary a m m o n i u m salt. We screened a n u m b e r of
candidates and found the higher molecular weight
analogs to give better results than the tetraethylam-
m o n i u m compounds used in our divided-cell process 9
H ex am et h y l en e bis(ethyldibutylammonium) phosphate

30

5-] Run conditions;

12~ N a ~ O 4
Z n~ Bu,~
Cd cathode/CS anode
2~ A / d i n R

%
20

Without
O
3-1

8
With 0.3Y~wt.
Na4 EDTA

ADN Production Rote 14,500 MT/Y 0 I I I

Current Density 45 A/drn= 0 50 100 150 2OO
Total Celts 384 Run time, hr.
Fig. 9. Original EHD plant layout Fig. 10. Effect of EDTA as cathode stabilizer
Vol. 131, No. 10 V I T T O R I O de N O R A - D I A M O N D S H A M R O C K A W A R D 441C

Table III. Quaternary ammonium salt evaluation, undivided cell Table IV. Comparison of EHD cell voltages

10% Na~HPO4 Divided cell Undivided cell

Cd cathode
0.002M QAS
QAS cation ADN selectivity (%)
Et4N§ 85
EtPr2N* 87
MeBu3N + 88
EtBu3N* 89
EtPe3N + 89
EtHx3N§ 87
PraN(CH~)4NPr3++ 88
EtBu2N(CH~)6NBu2Et§247 89
(Preferred QAS)
Me = CH3, Et = C2H5,Pr = C2H7,Bu = C4H~,Pe = CsH,,. Hx = C~H,,.
p e r f o r m e d best in t e r m s of A D N selectivity and ease of
e x t r a c t i o n from the organic products.
E l i m i n a t i o n of the m e m b r a n e vastly simplifies cell de-
sign (Fig. 11). B i p o l a r e l e c t r o d e s are p r e p a r e d f r o m 1.5
m m t h i c k sheets of c a r b o n steel by e l e c t r o p l a t i n g 50-100
~ m of Cd on one side. T h e s e are stacked t o g e t h e r using
plastic spacers to set the e l e c t r o d e distance. The total
t h i c k n e s s of an i n d i v i d u a l cell is only a b o u t 3 m m ; thus, a
100-cell bipolar stack has a t h i c k n e s s of only 30 cm. The
e l e c t r o d e stack is fitted w i t h a p o l y p r o p y l e n e h o u s i n g
and is c o n t a i n e d in a cylindrical vessel, w h i c h p r o v i d e s a
leak-free m e a n s o f circulating electrolyte t h r o u g h t h e
stack. Plastic e l e c t r o d e e x t e n s i o n s at t h e inlet a n d outlet
e n d s of the cell serve to limit c u r r e n t b y p a s s i n g t h r o u g h
t h e electrolyte in t h e v e s s e l heads. The cost p e r s q u a r e
m e t e r of c a t h o d e area for the u n d i v i d e d stack a s s e m b l y is
less t h a n o n e - t e n t h that of the earlier plate-and-frame cell.
Our M e c h a n i c a l E n g i n e e r i n g g r o u p at P e n s a c o l a d e s e r v e s
m o s t of the credit for t h i s a c c o m p l i s h m e n t .
A n o t h e r m a j o r a d v a n t a g e of the u n d i v i d e d cell is the
m a r k e d l y r e d u c e d cell v o l t a g e and p o w e r usage (Table
IV). The v o l t a g e r e d u c t i o n is due to t h e use of a
significantly m o r e c o n d u c t i v e catholyte and e l i m i n a t i o n
of the m e m b r a n e - and a n o l y t e - I R drops. I n addition, the
l o w cell cost shifts t h e e c o n o m i c o p t i m u m c u r r e n t den-
sity to l o w e r values, further r e d u c i n g the total voltage.
Cell power usage is cut by almost two-thirds.
However, we were not yet "home free," even though we
had a workable electrolyte system and cell design. In the
"--T
ER
Current density (A/din2) 45 20
Voltage drops
Reaction EMF 2.50 2.50
Overpotential 1.22 0.87
Catholyte IR drop 5.47 0.47
Anolyte IR drop 0.77 --
Membrane IR drop 1.69 ~_
Cell voltage 11.65 3.84
Power usage (kWh/kg) 6.6 2.4
u n d i v i d e d - c e l l E H D process, the offgas f r o m the cells is
an o x y g e n stream s a t u r a t e d w i t h acrylonitrile v a p o r and
m a y also contain 5%-10% H~. This r e p r e s e n t e d a serious
e x p l o s i o n hazard. We felt w e w e r e safe w i t h i n the cell it-
self, since the gas was p r e s e n t as small, discreet bubbles.
B u t s o m e w h e r e in the circulating s y s t e m w e had to face
up to h a n d l i n g large v o l u m e s of this e x p l o s i v e gas
mixture.
The p r o p o s e d solution (Fig. 12) i n v o l v e s t h e use of a
c o n e - c a p p e d e l e c t r o l y t e surge vessel, fitted w i t h a
s c r u b b i n g c o l u m n at t h e apex. T h e liquid level is main-
tained several m e t e r s up into the column, and the gas
b u b b l e s rising t h r o u g h the c o n e and into the c o l u m n cre-
ate an aerated zone, w h i c h acts as a s h o c k - a b s o r b e r in the
e v e n t of an e x p l o s i o n in the gas phase above. This small-
d i a m e t e r c o l u m n is d e s i g n e d to w i t h s t a n d a H2-O2 explo-
sion, w h i l e the rest of t h e s y s t e m is not. A N is s c r u b b e d
f r o m the offgas with A D N in the u p p e r section of the col-
u m n , w h i c h is p a c k e d w i t h plastic Pall rings. The c o n c e p t
of p r o t e c t i n g a large, thin-walled vessel f r o m an e x p l o s i o n
by a c o l u m n of aerated liquid was p r o v e n out in a small-
scale system, and it works.
The i m p r o v e d E H D p r o c e s s is capable of p r o d u c i n g
A D N at a significantly l o w e r cost t h a n t h e adipic-acid-
b a s e d r o u t e practiced by m a n y n y l o n m a n u f a c t u r e r s , and
we believe it is fully c o m p e t i t i v e w i t h t h e n e w e r technol-
ogy i n v o l v i n g direct h y d r o c y a n a t i o n of butadiene. Mon-
santo currently has installed E H D c a p a c i t y of about
180,000 MT/Y A D N , d i v i d e d r o u g h l y e q u a l l y b e t w e e n t h e
plant at Decatur, A l a b a m a , and a n e w e r facility at Seal
Sands, England, b r o u g h t on-stream in 1978. This is
d e a r l y the world's largest e x a m p l e of electro-organic pro-
cessing.
In conclusion, I w o u l d like to try to s u m m a r i z e w h a t I
believe to be the key to t h e success of the E H D process
d e v e l o p m e n t . Certainly, d e d i c a t i o n and i n n o v a t i o n w e r e

I YO
DILUT:AI~I~_~H DXYD
F~BE
GN
EN}

p
A
'ZT
OE
ND
ELIOUID
P L A S T I C F I LLER, YTE INLET

CELL
VESSEL

SECTION A A
C.~t.ER
Fig. 11. Undivided EHD cell Fig. 12. EHD offgas system
442C J. Electrochem. Soc.: R E V I E W S A N D N E W S October 1984

r e q u i r e d on the part of the entire technical team, but the
r e s o u r c e s surely w o u l d h a v e b e e n cut off at an early stage
h a d w e not c o m m i t t e d capital to that first c o m m e r c i a l in-
staIlation. It really was a g a m b l e on u n p r o v e n technology,
and there were t i m e s in t h o s e early years w h e n e v e n I had
s o m e doubts. But w i t h the plant sitting there, we had to
m a k e it w o r k and, as electricity and capital costs rose, w e
had to m a k e the p r o c e s s better. One s e l d o m can see all
the potential i m p r o v e m e n t s a t the outset, b u t as the ex-
p e r i e n c e - c u r v e p h i l o s o p h y tells us, w i t h w o r k t h e y will
come.
T h a n k you.