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The Purification of ,Glycerin by Ion-Exchange 1

G. W. BUSBY Qnd D. E. GROSVENOR, Lever Brothers Compony, Combridge, MossQchusetts

N May, 1951, the first commercial ion-exchange unit making a total of seven vessels which are arranged in
I for the purification of soap-lye crude glycerin was
put into successful o p e r a t i o n at the new Lever
series. Each of the primary exchangers has 4,460
gallons capacity and contains approximately 330 cu-
Brothers Company plant in Los Angeles, Calif. This bic feet of resin. Each of the secondary vessels has
unit was designed by the Illinois Water Treatment 920 gallons capacity and contains 66 cubic feet of
Company of Rockford, Illinois, and was fabricated resin. Each of the t e r t i a r y uni t s has 206 gallons
and installed under their supervision. The purifica- capacity and contains 12 cubic feet of resin. The
tion capacity of the plant is 26,600 lbs. of crude glyc- mixed-bed has a capacity of 350 gallons and con-
erin per day. tains 8 cubic feet of cation-exchange resin and 16
Because of the fact that sodium chloride comprises cubic feet of anion-exchange resin. In each of the
the bulk of the impurity which must be removed from first six exchangers the resin is supported by a bed
crude glycerin in the purification process, ion-exchange of graded gravel.
has for some years been recognized as a means of ac- All the exchanger vessels are of rubber-lined steel
complishing this end. Low capacity ion-exchange res- construction and were built to withstand pressure.
ins and high o p e r a t i n g costs have heretofore made They are cylindrical in shape and sized in such a
such a process economically inferior to conventional manner that all will become exhausted and require
distillation methods. This was especially true in the regeneration at approximately the same time. Each
purification of soap-lye crudes which are high in salt exchanger vessel is equipped with two glass observa-
content. The development of high capacity synthetic tion ports located near the center of the side wall.
resins during the past few years has changed this pic- These permit visual inspection of the resin surface
ture however, and a point has been reached where it and are used in connection with liquid-level control.
appears economically sound to install ion-exchangers Influent lines to the cation exchangers are for di-
in a new plant instead of stills. lute glycerin, raw water, dilute sulfuric acid regen-
Preliminary investigational work on the purifica- erant, and compressed air. Effluent lines are for the
tion of soap-lye crude glycerin by ion-exchange was dilute product, clean and dirty water recovery, and
an outgrowth of experiments made on saponification waste to the sump. The anion exchangers are simi-
crude. Experiments were carried out on both labora- larly equipped, except that treated or softened water
tory and pilot plant scale during 1949 and 1950 at is used in place of raw water, and dilute sodium hy-
the Illco Laboratories in Rockford, Illinois. In spite droxide is used for regeneration instead of acid.
of the fact that the deionization of crude glycerin re-
Radial-type distributors are located at the top, cen-
quired dilution of the crude and reconcentration of
ter, and bottom of each vessel. These handle the flow
the product, pilot plant findings indicated that the
of liquid into and out of the tanks and are for the
process possessed a number of advantages over the
purpose of reducing turbulence and channeling.
conventional distillation method. Most important of
these were: low capital investment, economy of oper- All lines carrying partially deionized glycerin, acid,
ation, and exceptionally high product quality. or alkali are rubber lined, and all valves in the system
Crude glycerin, as produced from soap lyes, is a are of the Saunders patent type. Flow is controlled
viscous, amber-colored liquid which normally contains by Rotameters and disc-type fluid meters.
82% glycerin and 20% ash;~ the balance consists of The crude glycerin dilution tank has a capacity of
moisture and other impurities. It is produced by the 12,000 gallons and is fabricated of steel. The dilute
evaporation and desalting of treated soap lyes. The product tank, which serves only as a relay vessel, is
purification of crude glycerin is usually carried out fabricated of stainless-clad steel.
batchwise in large stills under vacuum. The glycerol Waste from the plant, which includes spent regen-
is steam distilled, and the vapors are condensed in erant solutions containing sodium sulphate, sodium
fractions which represent C.P. (Chemically Pure) and chloride, sulphuric acid, sodium hydroxide, and or-
H.G. (High Gravity)products. The C.P. glycerin is a ganic color and odor bodies, is run into a 12,000-gal-
colorless liquid which is concentrated under vacuum lon sump. Dirty water, obtained from backwashing
to the desired specific gravity, and finally bleached the resin beds, and rinse waters containing sulphuric
and filtered. Some of the extra quality grades of C.P. acid and sodium hydroxide, are also run into this
glycerin marketed today are double-distilled in order sump. Since more acid than alkali is used for regen-
to meet the exacting color and odor specifications of eration, the waste regenerants do not neutralize one
buyers. The H.G. fraction contains more impurities another in the sump and it is necessary to add soda
than the C.P. fraction and is concentrated and mar- ash before discharging the waste to the sewer.
keted as a lower grade product. Five different synthetic resins are employed in the
unit; the choice and location of each in the system
Description of Plant and Process are based upon particular exchange and adsorption
characteristics. For example, the primary cation ex-
Plant. The ion-exchanger, which was installed at changer, into which is first introduced the dilute crude
Los Angeles, is a four-stage unit, consisting of three glycerin, contains a high capacity resin of the sul-
pairs of cation-anion exchangers and a mixed-bed, fonic-acid type. The primary anion exchanger con-
9 Presented a t the Tall Meeting of the American Oil Chemists' Society tains a weak base, phenol formaldehyde resin, which
at Ohicago, Ill., OefL 8-10, 1951.
2The NaG1 content of the ash is approximately 6%. has excellent color adsorption characteristics.
318
T~E JOURNAL OF THE A~ZE~ICAN Om CI=[EMIST$' SOCIETY,AUGUST, 1952 319

Process. The ion-exchange plant was designed to pur-


DILUTE CRUDE:
ify 26,000 lbs. of crude glycerin (82% glycerol) per GLYCERINE
day in two 12-hour cycles, using 13,300 lbs. of crude
per cycle. A cycle includes dilution and purification
of a batch of glycerin and the regeneration and prep- i
,
,METs

P R I M A R Y STAGE
aration of the resins for further use. The impurities caraoN ANION SECONDARY STAGE MIXtrO Bs

to be removed from crude glycerin are: sodium chlo-


ride, sodium sulphate, small amounts of calcium and
magnesium from the water, traces of fatty acids, and
nonionized color and odor bodies.
Because of the fact that all resin beds are kept
covered with water between cycles, some additional
dilution of the crude material takes place as the glyc-
erin solution passes through each vessel. This dilu- coNo~'n Vl~ Y
tion is kept at a minimum however and is referred to CELL

as "sweetening o n " when the dilute crude is being TO EVAPORATOR

run into the system displacing the water in the resin FIG. 1. Ion-exchange unit for the purification of soap-lye
voids. "Dilution at the end of a purification run, when crude glycerine.
glycerin solution is being displaced from the resin
voids by water, is referred to as "sweetening off."
The terms "sweetening o n " and "sweetening off" ciency and permits the purification of solutions con-
were borrowed from the sugar industry. taining up to 30% glycerin.
Each 13,300-pound batch of crude is diluted to ap- After the unit has been "sweetened off," all resin
proximately 25% glycerin in the dilution tank and beds are backwashed to remove dirt and resin fines.
pumped through a Hercules leaf-type filter into the Each vessel is backwashed at a preset rate, this rate
primary unit at a rate of 150 g.p.m. The capacity of being determined by the size of the particular vessel
the two primary vessels, including the space above in question and the characteristics of the resin in-
the resin beds, is greater than the volume of a single volved. The backwash effluent from each bessel is run
batch of dilute crude, and it is therefore possible to to the waste sump for several minutes and then, to
transfer an entire batch from the dilution tank to the conserve water, to the cooling tower system.
primary unit at the high rate of 150 g.p.m. Regeneration. After the backwash the liquid level
As soon as a batch of dilute crude has been pumped in each tank is lowered to within a few inches of the
into the unit, liquid levels in the primary vessels are resin bed, and regeneration is begun. Except for the
adjusted by means of compressed air until normal mixed-bed, which requires special handling, regener-
operating levels are attained. During this adjustment ation is carried out downflow.
period the following vessels are "sweetened on," and Regenerant solutions, 12% sulphuric acid for the
the effluent flow from the mixed-bed is controlled at cation exchange resins and 5% sodium hydroxide for
a rate of 20 g.p.m. This rate is continued throughout the anion exchange resins, are run into the vessels at
the run and the subsequent "sweetening off" period. controlled rates. In practice, a quantity of reclaimed
In passing through the primary cation exchanger, sulphurie acid is run through Primary Cation Ex-
a large percentage (approximately 80%) of the sodi- changer before the introduction of the fresh ]2% sul-
um ions is removed and replaced by hydrogen ions. phuric acid solution. This reclaimed acid is from the
The hydrochloric acid formed by the exchange reac- prior regeneration of the Primary Cation Exchanger
tion is removed in the primary anion exchanger as is and represents a substantial amount of the fresh acid
the bulk of the color and odor bodies. which was used for that regeneration.
As soon as a batch has been put into the system and In actual operation the reclaimed acid is pumped
run until the liquid level in each exchanger is in ad- by means of a Duriron pump into the Primary Cation
justment, a few inches above the resin bed, the unit
is "sweetened off" by introducing raw water into the
Primary Cation Exchanger at a rate of 20 g.p.m. This 25
tO7
hydraulically pushes the dilute glycerin solution out
of the resin bed and through each of the following 1.06 24
ion-exchange vessels.
In "sweetening o n " the mixed-bed, the effluent is L05_ .20
discharged into the crude dilution tank for several
minutes before glycerin appears in the product line. ~< L04. .16 ~-

Dilute deionized glycerin is run into this tank until


12 @
it reaches a concentration of approximately 15%, at u 1.03.

which point it is run into the product storage tank. $


8
As the unit is "sweetened off," all solution contain- ~ L02.

ing less than 15% glycerin is also run into the crude 4
1.01.
dilution tank. This glycerin solution is employed for
diluting the next batch of crude. [00 0
By adjusting the quantity of glycerin solution re- I000 2000 3000 4000 5000 7OOO
turned to the crude dilution tank during "sweetening GALLONS

o n " and "sweetening off," it is possible to eliminate FIG. '2. Typical deionization cycle for dilute soap-lye crude
the use of raw water for dilution. This improves eft- glycerine.
320 THE JOURNAL OF THE AMEErCAN OIb CHEMISTS' SOCIETY,AUGUST,1952
Exchanger. When the reclaimed acid tank is empty, the effluent f r o m the anion exchangers reaches speci-
the p u m p automatically switches over to the fresh fied limits. A considerable amount of the water used
acid regenerant tank and p u m p s 12% sulphuric acid for the rinse operation is reclaimed and sent to the
into the P r i m a r y Cation Exchanger. At the same time cooling tower system.
acid regenerant solution f r o m the fresh acid t a n k is The mixed-bed is handled separately, with the an-
p u m p e d to three gauge tanks which are located on an ion resin being rinsed downflow with treated water
u p p e r level. These are shut off automatically when and the cation resin being rinsed upflow with raw
filled and are for regeneration of the secondary, ter- water. A f t e r rinsing, the mixed-bed resins are agi-
tiary, and mixed-bed cation exchange resins. tated and mixed b y introducing air at the bottom of
Regeneration of all the anion resins is carried out the vessel.
simultaneously. A single p u m p supplies the feed for The i o n - e x c h a n g e cycle m a y be broken down to
all anion exchangers, and the regenerant solution sup- show the a p p r o x i m a t e time required for the various
plied to each is measured b y disc-type fluid meters steps as follows:
a n d controlled b y impulse counters on panel board. t~ o ~ rs

These impulse counters are set to permit the flow of Dilution of crude and filtration ........................... 11~
definite volumes of regenerant solution into each an- "Sweetenon" (0 to 15% glycerin) .................. 3~
ion vessel and automatically stop flow when the meters Run (above 15% glycerin) .................................. 4
"Sweeten off" (15 to 0% glycerin) .................. 3~.
count-out the volumes. Regeneration of resins .......................................... 5
Regeneration is carried out at low flow rates to Total ............................................................... 12
permit sufficient time for the reverse exchange reac-
tion to take place. Sodium sulfate f r o m the cation Control. D u r i n g the service p a r t of the cycle, flow
resins and sodium chloride f r o m the anion resins are control is handled m a n u a l l y b y the a d j u s t m e n t of
r u n to the waste sump together with the excess regen- throttle valves. Rotameters and disc-type fluid me-
erant solutions. One exception to this is the fact t h a t ters permit reasonably accurate control of flow rates
some of the used acid f r o m the P r i m a r y Cation Ex- through the system.
changer is recovered and r u n into a reclaimed acid Liquid levels within the tanks are controlled b y
t a n k for use during the next cycle. means of air pressure and m a n u a l l y operated valves.
The mixed bed is handled b y a special technique A pressure of a p p r o x i m a t e l y 40 p.s.i.g, is maintained
involving classification of the resins during backwash, on the dome of the P r i m a r y Cation Exchanger, and
followed b y - s i m u l t a n e o u s regeneration of the sepa- each of the following vessels carries a p p r o x i m a t e l y 5
rated resins with alkali a n d acid. Since the anion- p.s.i.g, less than the one preceding it. Electrodes in-
exchange resin is above the cation resin a f t e r separa- side the vessels indicate high, normal, and low liquid
tion, dilute caustic soda solution is r u n in at the top of levels b y means of lights on a centrally located panel
the vessel and acid is r u n in at the bottom. The used board.
regenerant solutions are removed through a drawoff I n spite of an imposing a r r a y of manually operated
line at the interface between the resins. valves in the system, the p l a n t is r u n b y a single
A f t e r regeneration each bed is rinsed in parallel operator. D u r i n g the service cycle the one item which
with fresh water, using raw water for the cation ex- requires the most attention is the control of liquid
changers and treated water for the anion exchang- levels b y means of air pressure.
ers. Washing is continued, downflow, at specific rates Panel Board. The panel b o a r d for the ion-exchange
until the effluent acidity or alkalinity falls to a pre- unit is equipped with a system for m a n u a l l y control-
determined m a x i m u m figure. Following the parallel ling liquid levels in each of the ion-exchange vessels,
rinse is a series rinse, in which each pair of cation- conductivity instruments for measuring the concentra-
anion exchangers is rinsed until the conductivity of tion and p u r i t y of solutions, recording specific g r a v i t y
and conductivity instruments, and an automatic sys-
tem for the p r e p a r a t i o n and dispensing of regenerant
FIGURE 3
solutions. The b o a r d is also equipped with automatic
Analytical Data Showing Typical Double-Distilled
Glycerin and Ion-Exchanged Glycerin timing and valve switching devices, and an a l a r m sys-
tem which has both w a r n i n g lights and an audible
DoubIe- Ion-
Distilled Exchanged horn.
Product. The deionized glycerin solution is evapo-
Per cent glycerol .......................................... 95.14 99.30 rated u n d e r vacuum to 95-99% glycerol. The final
Per cent residue ........................................... 0.0084 0.0070
Per cent ash .................................................. 0 . 0 0 3 4 0.0006 product is exceptionally high in quality and does not
Per cent !WaC1................................................ 0.0007 0.0005 require filtering or bleaching. I t compares f a v o r a b l y
Fatty acids and esters'. .............................. 4.50 4.90 with a high-grade distilled glycerin.
aThis is a back-titration figure. Sample is treated with 5.0 mL of
0.SN. NaOH, and back-titrated with 0.5N. HC1. The fatty acids and
esters are expressed in terms of ml. of 0.5 N. HCl. [Received November 16, 1951]