Chapter 3

Su4al' alld
Slal'cll Illdusll'iES
Carbohydrates, sugars and starches, are major foods for humans that are synthesized by plants
using carbon dioxide and water from the atmosphere. These serve as the principal foodstuffs
for animals, including humans, and have considerable promise as major chemical raw m'ate-
rials. There is much political demand to convert agricultural surpluses into materials, such as
motor fuels, in which the coufltry is deficient, but experimentation ovcr a 50-year period has
failed to find an economical approach. Hising petroleum prices make the goal seem nearer.
As foods, their use remains extremely important.

SUGAR

Humans desire sweetness in their diet and nature provides it from several sources. The aver-
age person in the United States consumes 32 kg of sugar per year, but this amount has been
slowly diminishing. The world average is only one-third of this but is increasing. Sugar is not
prized for its sweet taste alone, for it supplies about 1,'3 percent of the energy required for
existence. As a result, sugar production and refining is a huge industry. consuming 8.3 X 106
t of sugar in the United States alone in 1982. The total world sugar production is estimated 1
at 95.8 X 106 t. la

HISTORICAL. It is difficult to determine just when sugar nrst became known to humankind
but it probably tra\'eled from i\e\\' GUill(',l to Inelia many cellturies before Christ. \1ethods
for extracting and purifying the sugar from the cane wert' \'ery slo\\ ill bcing developed, but
\\'e find a record of crude methods having been brought from the east to Europe about 1400.
The sugar trade between Asia and Europe was one of the most important commercial items
in the early centuries. Sugar was first extracted in North America in 1689, using cane from
the West Indies, and in 1751 cane was grown on the continent. From that time on, the indus-
try increased steadily, both in size and in quality of product. Steam-driven crushing and
grinding roller mills were introduced in the latter part of the eighteenth century: the vacuum
pan was invented by Howard about 1824; bone-char decolorization was employed for the
first time in 1812. \1ultieffect evaporation was proposed about 18:34, and the first suspended
centrifuge was developed by Weston in 1852. The use of granular activated carbon and ion-
exchange processes to remove color and ash has become common. Evaporation,'adsorption,
centrifugation, and f:iltration were from the beginning the important and necessary steps in

lSugar}. 44 (9) 8 (1982).

,lat = 1000 kg.
 the manufacturing sequences, and much of our knowledge of these methods carne from their
application in the sugar industry. This study of the functioning of evaporation, adsorption,
centrifugation, and filtration as used in sugarmaking helped to establish the generalized con-
cept of unit operations.
In 1747 beet sugar was discovered, but it was not introduced into the United States until
1830, and no sucr:essful plants were operated until 1870. A great deal of time, effort, and
mOl ley were expen(~l?d in bringing the more complicated beet-sugar industry to the !JOint
where it could compete with the cane-sugar industry. The various tariffs imposed on raw
cane-sugar imports, among other things, are responsible for the continuance of both the beet-
sugar and the domestic ca;1e-sugar :ndustries.
The first preparation of dextrose in 1811 led to the development of the corn-sugar industry
in this country. The first manufacturing began about 1872, the product being liquid glucose
It was not until 1918, however, that appreciable quantities of pure, crystalline dextrose were
produced. The most recent major change in the industry was the introduction of high-fructose
corn-der·ived sweetener (HFCS) which became commercial1bout 1970. This made available
a high-quality sweetening material which made corn competitive with cane and sugar beets
as a major source of sweetener.
. At the start of the present century: the Bergius process for the production of sugar b)
saccharification, or hydrolysis, of wood received its first industrial trial. As far as the United
States is concerned, these acid hydrolysis processes, although chemically feasible, have gen-
erally proved economically unsound, because of the abundance and low price of starch and
sugar; however, they seem to be increaSingly promising. Studies with cellulase enzyme con-
versions to convert wood wastes to glucose to be fermented to give alcohol for use as motor
fuel also appear promising. The changing pattern of nutritive sweetener deliveries is shown
in Table 30.1.

USES AND ECONOMICS. In 1982, about 8.3 X 106 t of sugar was consumed in the United
6
States. Total nutritive sweeteners, however, totaled 12.8 X 10 t. Of this total. ,'36 percent
2
came from corn, 33 percent from beets, and 31 percent from cane Renned sugar sold in the

'2Stalistica! Abstract of the United States, 102nd ed., 1982, and US. Agricultural Outlook
Conference, 1980; Food Eng., 54 (7) 77 (1982).

Table 30.1 Nutritive Sweetcner Deliverics in the United States

(in thousands of nwtric tons of dry substance)

( :orn % SWE'E'tner
Year Sucrose Syrup Dextrose HFCS from Corn

1970 9484 1:)(1.') 427 68 16

1975 ,')75,'3 lilS 495 -183 2-1
1977 91,'30 17(j,j 41·) 944 2.'5
1979 q]88 1,')2,') 391 15-16 29
1smo .')7/3 I ';.<-;f, 39q 195.') '3.'3
1981 1)422 1924 407 :2432 36
1982 H273 IQ09 363 2273 36
1985" 7727 2000 409 3182 4,'3

"Estimated.
SOURCES: Sugar]. 43 (8) 13 (1981); Food Eng 54 (7) 77 (1982)
 enited $ta.tes is utilized as follows;') bakery products, 12 ..5 percent; beverages, 23.7 percent;
c::onfec.1:ionery, 8.9 percent; hotel and restaurant use, 1 percent; ice cream and dairy products,
4.6 percent; jams, jellies, and preserves, 6 ..5 percent; other food uses, 4.7 percent; nonfood
uses, 1.2 percent; sold by retail grocers, 12.2 percent; and sold by sugar jobbers, 19.9 percent.
HFCS pas made inroads into all these markets except confections as a major replacement for
sucrose. Both sucrose and HFCS are sold in large quantities in bulk and as syrups .
.Yonfood uses of sugar are very few and constitute only a small amount of the total output.
They include the use of sugar as a sucrose octaacetate, a denaturant in ethyl alcohol; as sucrose
diacetate hexaisobutyrate and octabenzoate, plasticizers; as mono- and difatty acid esters for
surfactants, allyl sucrose; and as a raw material for the manufacture of glycerol and mannitol.
Dextran, a polysaccharide produced from sucrose by certain bacteria, is a very effective
plasma volume expander. Administered by intravenous infusion, it relieves shock and pre-
vents ioss of body fluids after extensive burns or other wounds. Other uses for sucrose deriv-
atives are under investigation.
No other crystalline organic product of comparable purity (99.86S'"c anhydrous basis) has
been offered on the market for so Iowa price as sugar and in such large volume. This, ho\\'-
ever, is merely a reflection of the progress and growth in refining methods due to applied
chemical engineering within the industry, which has succeeded in reducing the price from
the $8.80 per kilogram in 1796 to its present level of about 81 cents per kilogram. With corn
at $12.80 per 100 kg, corn sweetener costs under 33 cents per kilogram to produce.

Afanufacture of Sugar

The major processing methods used for refining cane sugar today have been \vorked out for
many years and are unlikely to change drastically soon. Alterations to conserve energy and
perhaps reduce the use of some reagents are to be expected, but major process changes seem
unlikely.

CANE. Sugarcane is a member of the grass family. It has a bamboolike stalk, grows to a
height of from 3 to 5 m, and contains 11 to 15% sucrose by weight. The sources of the raw
cane refined in the United States are shown in Table 30.2. The cane is usually planted with
cuttings from the mature stalks, which sprout and produce a number of ne\v stalks. As many
as seven successive crops, or ratoons, may be obtained from a single planting, provided con-
ditions are favorable. The approximate period of gro\vth of the cane in Cub", is 12 to 1.5
months, and nearly twice this in Hawaii and Peru. In Louisiana and Florida the growing
season is 6 to 9 months. Harvesting is done by hand with machetes or bv mechanical cutters
follov,:ing burning to remove the leaves. The workers cut off the stalks' close to the ground
and top the cane. The cane is loaded on tracto;--pulled cane carriers and hauled to the ra\\'-
sugar plants, or centrales. There can be no delay in transporting the freshly cut cane to the
factory, because failure to process it within less than 2.4 h after cutting causes loss by inversion
to glucose and fructose.
The production of raw cane sugar at the facton' is illustrated in Fig. 30.1 and may be
divided into the following unit operations and chemical c:onversions 4

3Commodlty Yearbook, COIlllIl()dity Hescarch Bureau. \.;;0\\ York. 1981: :\gricultural Out-
look Conference, 1980. . ~
~Birch and Parker, ':iugar. ':ielence and Technology, App\. Sci. Pub\. Londo!!, 1979; also
ECT, 2d ed., vol. 10, 1969, IJ, 166.
Table 30.2 Raw Sugar Suppliers to the United
States (in thousands of metric tons)

Supply Area 195fl 1978 1979 1980

U.S. beet 2013 2907 2901 2701

U.S. cane (mainland) 522 1179 1120 1918
Hawaii 572 917 859 912
Puerto Rico 748 47 43 162
Philippines 891 757 375 372
Dominican Republic 80 667 742 559
Peru 80 204 172 47
Mexico 61 48 55
Brazil 546 1147 769
All other countries 3134 2037 2061 2.339
Total SlOl 9:309 Q·fi5 977~

SOURCE: Agricultural Statistics 1981, United States Department of

Agriculture.

The cane is first washed to remove mud and debris.

The cane is chopped and shredded by crushers in preparation for remo .... ing the juice.
The iuice is extracted by passing the crushed cane through a series of mills, tCich of which
consists of three grooved rolls that exert heavy pn:S5ure Water and y,:eak juices rnay be added
to help macerate the cane and aid in the extraction.) ;\bout percent of the juiu: IS f:xtracted en
.'; As with sugar beets, sugar is beillg extracted from the chopped b\ continuous coun· (',Ult

tercurrent extraction with hot water in diffuser:" Chern. Eng. ·S:2 ('3/'32 i 1Cj-;-.SJ

,
----.
( (Jill'

o
u

,
WfI/l'f'
\ lill I1:J\'I),\
',:![' " .. :c.'::
:.,

O[}
.::. ,""

.II d In III ... -... ~

, tf ''-..j ...... ~
1111( t' tank

Bogosse to i
BOiler Or lUx
byprodu( t tt>
4th mill I _-r
juice tank/--L
I
I T\ (/(}U;Jy
(If/rolt'
_-
-H-~ Hign s;::e
'----- ro'f' Si.....;.: ..
- Primary
clarrfier Molasses storage

Fig. 30.1. Flowchart for the manufacture of raw cane sugar

 from the cane. The spent cane (bagasse) is either burned for fuel or used to manufacture
paper, hardboard, or insulating materiaL
The juice is screened to rf:move floating impurities ancl tre8ted with lime to coagulate part
of the colloidal matter, precipitate some of the impurities, and challge the pH. Phosphoric
acid may be added because juices that do not contain a small amount of phosphates do not
clarify well. Lime in slight excess over that theoretically required to precipitate all the phos-
phate is then added.
The mixture is heated with high-pressure steam and settled in large tanks called clarifiers
'or in continuous settlers or thickeners.
To recover the sugar from the settled-out muds, continuous rotary-drum vacuum filters are
generally used. The cake constitutes 1 to 4% of the weight of cane charged and is used as
manure.
The filtrate, a clarified juice of high lime content, contains about 855c water. It is evapo-
rated to approximately 40% water in triple- or quadruple-effect evaporators b to ~l thick, pale-
yellow juice.
The resulting thick juice goes to the first of three Single-effect vacuum pans. where it is
evaporated to a predetermined degree of supersaturation. Sugar-crystal nuclei are added
(shock seeding) and, by the addition of thick juice ancl controlled e\·aporation. the crvstals
are grown to the desired size in these "strike" pans. At this optimum point, tIle pan is mostly
filled with sugar crystals with about 10% water. The mixture of syrup and crystals (masse-
cuite) is dumped into a crystallizer, which is a horizontal agitated tank equipped with cooling
coils. Here additional sucrose deposits on the crystals already formed, and crystallization is
completed.
The massecuite is then centrifuged to remove the syrup. Thl.:' crystals ;.ne qualit> high-grade
raw sugar, and the syrup is re-treated to obtain one or t\,. ,o more crops of crystais. The final
liquid after reworking is known as blackstrap molasses.
The raw sugar (light brown in color), containing approximately 97.85:( sucrose, is shipped
in bulk to the refinery, freq uently outside the country of origin.
The molasses is shipped to the United States and other countries in full-tank steamers and
is used as a source of carbohydrates (a decreasing use) for catile feed and for . . . itric acid and
other fermentations i Chap. 31).

CAlVE-SUGAR REFINING. R8 W sug'~;- i:, delivered to dw rebnenes in bulk. Figure 30.2 illus-
trates the following sequences in the refining of calle sugar.-

The first step in refining is called affination, wherein tlw raw-sugar crystals are treated with
a heavy syrup (60 to 80° Brix)8 in order to remove the film of adhering molasses. This strong
syrup dissolves little or none of the sugar but does soften or cltssolve the coating of impuritie~
This operation i~ performed in lllinglers, which are heav) scroll L'()r1\e\()r~ Litted \\lth strong
mixing flights.

6For vacuum evaporatioIl equipment and accessoril's. hCll-tramft'f" data. ~llld C'onden5cr
water data, see Perry, pp. 1 J -2H to 11-3H
7Birch and Parker, op. cit.; Labille, l'.1elt House Redesigned for Automatic Flo\\. Chem.
Eng. 67 (9) 94 (1960); EeT, 2d eel, voL 19, H)()7, p. 185.
B-rhe degree Brix is the percentage. b\ welght. ()f SI1(T()St"' ill a pure sugar solution: com-
mercially it is taken as the approximate percentage of solid matter dissolved in a liquid
 _. _ •• <p-- --

.--=...".,

Clean Soft
bags sugars
.' .'. Concentmtedsweef ~ fers !'ockC1g'
shipme77'
Con" Multiple effects -

I
Mudouf-----Pres5ure filters

In order to produce 100 kg of refined sugar (about 400 kg residual syrup is also produced). the following
materials and utilities are required:

Raw sugar (97°pol.) 106 kg Condensing water 2000~3500 kg

Hydrated lime 0.05 kg Pure water 600 kg
Kieselguhr 0.25 kg Po\ver process steam 17S kg
Bone char (in 10,5-250 kg Power steam
process)
Bone char (revivified) 35-75 kg Char kiln fuel 58 MJ
Bone char (new) 0.25-03 kg Direct labor 0.66 work-h

Fig. 30.2. Flowchart for rdined cane-sugar manufacture. KEY: ~1n. mingkr; ~1, mixer; Con. condenser:
C. centrifugal: .

The resulting syrup is removed by a centrifuge, and the sugar cake is sprayed with water.
The crystals are dumped into the melter, where they are dissolved in about half their
weight of hot water, part of which is sweet water from the filter presses. The syrup from the
centrifugals is divided. part being diluted and reused as mingIer syrup and the remainder
diluted to about 54° Brix and sent either to the char house for claribcation and refiltration or
to the pans to ]w boiled with remelt.
The melted and washed raw sugar (in refineries, melted means dissolved) is then treated
by a process known as clarificatiun or defecation. Either mechanical or chemical processes
can be used. Mechanical clarification requires the addition of diatomaceolls earth or a similar
illert material; the pH is thcll acljllStcd and tIll' mixture fJltereJ in a press. This system gives
an absolutely clear solutiuII of slightly improved color and is inherently a batch process.
The chemical system mcs either a frothing clariner or a carbonation system. Liquor treated
for frothing, containing entrapped air hubbIes, enters the clariner at aoout 65°C. In the clar-
ifier it ;s heated, callsinl!; a trutL to form which rises to the surface carrying gelatinous trical-
cium phosphate and entrapped impurities. The clarified liquor is filtered and sent to
decolorization. This process reduces the coloring matter present by 2..S to 45 percent, which
greatly reduces the size of the subs(,(:~lCnt decolorizers.
The carbonation system adds carbon dioxide from scrubbed flue gas to the melted sugar,
which precipitates calcium carbonate. The precipitate carries down with it over 60 percent
of the coloring matter present and is removed by filtration.
DECOLORIZATION-CHAR FILTRATION. The clarified effluent liquor, now free of insoluble'
material, still retains a large amount of dissolved impurities. These impurities are removed
by percolation through bone char. 9 (Activated carbon is also used.) The char tanks are about
3 m in diameter and 6 m deep. From 20 to 80 char filters are req uired per 1 X 106 kg of
melt. The percolation is carried out at about 82°C, and the. initial product is a clear, water-
white syrup. Experience teaches the operator when to shift the char-filter eff]uent to a lower
grade of syru p.
After a certain amount of use, the char loses its decolorizing ability and must be revivified.
This is done approximately every hour by first washing it free of sugar. remo\'ing it. and
roasting it. A continuous decolorizing process is also used.
The syrups from the bone-char filters are piped to the liquor gallery, where they are graded
according to purity and strength: 99- to 99.7-deg purity, 90- to 93-deg purity, 84- to 87-deg
purity, and 75- to 80-deg purity.
Darker-colored liquors are treated with either bone char, synthetic bone char (Synthad),
activated carbon, ion-exchange resins, or some combination to form what are known as "soft
brown sugars." When the bone char loses its decolorizing pov,:er, it can be revivified by heat-
ing it to 400 to 500°C in vertical pipe or Herreschoff kilns. Careful heating ensures that the
active surface is not oxidized away.
Activated carbon is superior to bone char as a decolorizer because its adsorption cycle is
longer, but it does not remove inorganics. Coarse carbon granules can be used in beds like
bone char and revivified by roaiting at a higher temperature (lOOO°C). For small installations
or seasonal batches, once-through decolorization employspO\vdered carbon, which is dis-
carded after a single use. A recent cleveloprrl~nt makes llse of a decolorizing chemical addi-
tive, dioctadecyl dimethylammonium chloride (Talofloc) and a proprietary flocculating agent
of polyacrylamide (TaloOote). It has been reported 9 that clarity and capacity can be increased
by 75 percent by such a system. Where inorganic salts are a problem, ion exchange can be
used to remove them A cation exchanger absorbs cations from solution leaving it very acid.
An anion exchanger (usually mixed with the cation exchanger) then removes the free acid.
The combination does an excellent polishing job. Ion exchange has been extensively tested lO
as a complete replacement for char/activated carbon treatment but has cost too much. The
major problems are fouling of the resin and handling the wash waters used during the regen-
eration for reuse.
Figure 30.3 shov,'s a cross section of the crystallizing, or "strike," vacuum pan. Here the
sugar syrup is concentrated to a'predetermined degree of"supersaturation; when it is seeded
with a measured amount of fine sugar These small crystals :ue grown to a marketable size
by a properly regulated rate of boiling or evaporation, as well as of agitation and syrup inflow.
The rate should not be too rapid, or new crystals (false grains) will be formed and not have
time to grow, with consequent loss through the screen of the centrifuge.

The purest syrups are reserved for liquid sugar (water-white), the next purest for tablets
and granulated sugar, ancl the remainder goes tu canners and bottlers, confectioners, and soft
sugars (brown).
The pan is discharged illtu a mixer, which keeps the whole Illass from sticking together,
and is then sent to centrifuges, where the crystals are separated from the syrup, washed, and
dropped to the wet-sugar storage bin.
The syrup is returned to the process for further recovery of sugar.

gJones and Lopez, Sugar, Ind. Technol. :3522 (1976).

IOECT, 3d eel., vol. 1.'3, 1980, p. 70,'3.
 Motor

---1r---- Va par outlet

Straightening vanes

/----.- Rotor

Conloct-moKln<;;
YvG~tme~er

Recording
wottmeter

Control
board

"'" ' - Thermometer

- Proof stick

Steam
in let

1-- Vacuum connection

drain
\ ··~·o
.- ... ---.... --- .- Discharge valve
~~~~~~~~--~r
" "'
Fig. 30.:3. Cross sectioll of vaCUUIll pall with IIlechanicalcirculatl1r The syrup
is heated by passage upward through the tubes of the steam chest. or enlan-
dria, near the bottom. The liquid boils at the upper surface, and vapor is
drawn (l'lt through the large central pipe t\ set of sere\,' impellers forces the
liquid hack through tIll' cen t ra I d()wn ta ke pipe. The st i rrer is rnotor-d ri \en
and has recording and controlling watt meters in its CIrCUIt (Esterline-Angus
Co.)

When the purity of the syrllp becomes too low, it is used for blended table S~TUpS. the
poorer lots going for animal ft'eel This syrup is commonl:- called molasses or blackstrap.
The wet sllgar is dried in a granulator, which is 8. horizontal rotating drum about :2 m in
diameter and ,~ rn long having a series of narrow shc:lves (flights) attached to its inner surface.
These flights lift th{" sugar alld allow it to fall thr(1I1gh the stream of hot air f}o\ving counter-
current to it.
Tl:e dried ('1"\,<;1;11, P'\\< ()\'("r :1 <;f'ril" ()f <;('r('t-'I1~. \dw[{~ the'\ die grdd'-'d dc(:ordln~ lU size
Various automatic packing <lnd weighing machines put IIp the sugar In bags and b{).Y.es WIth
a growing percentage in f)IJlk.
Powdered sugars arl' made l)y grinding grarllJiatcd sugar In mills but are so hy'gmsuJpic
that mixing with 3% corn stard) is practiced to make confectionery grades. Cube and tablet
slIgars are prepared by mixing certain types of granulated sugar with a hea\\ white S~TUp to
form a moist mass, which is then molded and dried
 54

The;. ldd of re(Jrlt,d Sllgdf ohtailwd, ha~ed OIl ra\\ ~lIg<1r ut ()Ii" poiarlzatl(JII. 1<; usuall~ y:)
to 94 percent, syrup 5 percent, and mechanical and \\<i,>h I()~st's 0.1 pt'rcent
In handling sugar. SUlIlc' imcrsiorl takes pla<.T <1ccurdlIlg tu the folkl\\ing reaction

Sucrose d-Clu('o,e d-Frllct(N:

Po!ari::.ation + 66.6° +,'):2 SO

The product is callf'd incert sugor. hIlt tlw polarization Id tht, pUfe sucrose of -fir) f;O - t(
the> right) 1)(1\\ recids -:20 ()O: I - to the left) for tllt' r(,~lIltllle: llli\tlHt'

+.52.8° - 928 0
2

The continu()us adsorption process used In The :\IIH'ricdii Sligar l\dl11ing C, i' elt It'
Bunker Hill refiner:. using h071P char ('onlilllw/ls/y, i<; a flllld<JIIJ('llt~11 impr,)\ elJ1t'llt ill thr'
purification pr()cE'~s 1lSed for decades. Here, in dec()l()rtzilig c()lumns 4 m III diameter. \\Ith
12-m beds of bone-char adsorbent. the sugar liqllor Tll()\('S upward at a uniform rate con-
trolled b\· the results desired_ and the bone char move~ dm\'fl\\ard_ though at a slower rate
than th~lt of the syrup The particles of bone char arC' ~Iightl: separated, or "expanded_"
resulting in maximum and uniform adsorption of impuritit-'~ from the sugar liquor in a truh
cr)untercurrent contilluom now; the bone char of the higlwst adsorptive capacity is automat-
ically in cont;lct with the ,>ugar liquor of the lowest levcl ()f impmitic'>. Thi~ results in a murt'>
f,fficient use (,f the h(Ine char, \\·itll IIi) sligar 11<1111<1 hlcllriiflg ~Hld II() liquor gall!·r: .-\151). till'
color uf tliE' pmcluct liquor can lw acljustt'clll\ mllph adjmtIllg the' ked rdtt- ,ll the bUlle-did!
in relation t(l that (1f tht-' sligar liq\lor High-qualit\ gralliliatt,cl sugar lias iJf'ell produced llSlIlg
·-IlO more thall 10 ttl 15 kg of hml(' char pt-'r 1()(J kg llIelt"'-lllllCh less thall ll(lrIlldll: used

Tht' bone' clur is degraeled in only ,1 minor \ \ , l \ , if at all. Fill~dl\, it i~ claimed that tilt' capital
ft'quirecl for this step ha~ heen hah'eel and tIll' lahor ree!II('('d qO perct'nt togetlil'f \\lth other
~,\\ ings TIlt' 'lwnt l k l f i~ deswed('n('d, deasllt'cl ill l'()llIlllll~, d(,\\ akn,e! t() 2(r-; Illui,turc <>r
les<;. Jnd rt'adi\at('d in d lnw-o\\c:('n (J-2C:; ()~) atl11(l"plH'lt, C(llltillII()lIsl:, ill a multiple-
IWdrth kiln

fi 1(; !'';'"l -:-1., ·,1:'1 :'.:.' ,d .!I""II -(lI)(,I("liI ,11 1.1" i),!~.t"" l'l"dll'·",i fllllli,d"" (,II!III-SL 'k,(!::
I, ,r P(l\\ t·r ll,"il til filII Ih(, mill I klll't' :3(1 [wlr't'lll i~ ~l\ ,lll~d>it' In lllakt, .III illSlIiatillg .IIld
\,uIicling \JI)~lfd like (·(,I(llt'\ or III digt'~t tilt' ha\~as~(' wIth cllt'micals \"~lOH_ dc ) to J pulp
fur pd!Wr Illallllfacture ()!I Fourdrinier m,l(\lillt's F:lrthernl()rt'. of tell much more than the :311
percent is lIsed for such t)\-products whcll other fllt'l is a\~lihhl(' at a cheaper price thall tilt'
SS pn till] tr,llliti(lII,dh a~("l(llt·e! t() hagasse TIlt' dlll(lUIlt (\1 LagClsst' lJ~lJall\ Cl\ aibble is ('qu,d
tel tfw ,1Ig,l r \ H,ld
The bdgas<'l' is Ct)II\(,\('d IJ\ all ('ndless Iwlt tt) dl(' rtltan digfsters, \\hich are 4,:3 m in
didtll('t(~r. arid IS «(,(Ikt·d 111Hlcr pH'S"lr!' III ()rd('r t() rt'lHln tl)(' libers pliatllt:_ 100Stl) the
('IIUlj)tillg Irult'ri,d. dl~s()"(' tJlgalll( lllatClidl. alld stcrill/(' th(' tiLer The resulting pulp_ ill:1
:2 t(1 ·3;~ SUSperlWHI. IS plllll peel to s\\ing-halnrnt'f shr('ddt'f~ aIle! \\ashed in Sp('ci~dk clc'siglll'd
rr;tan· \\~lshn) ill orcin to remov(, c1irt, 5CllulJl(' C()llljl()unds, and son1t' pIth Fr()m thl: \.. asl1t'r~.
thE: pulp ellters half stock lhesLs, where tht' SIZIIlg, 11SII<t1h papcrlllakt°rs' rusill alld alum. i~

11 LS. Pat(·!It 2,.5CJ4,:](J,S :--iepklnher :27. IlJf)O: \!arc\ i :\nll'flCdll SlIg:ar Ht'fining CU)
":\C1s(lrptwII 11\ Bllllt' Char L SIllg (:tllltlIIII(IU, :\t):,()rpll(J[1 t'rl)~n~, 2Uth :\lJllllai -'leetlng 1)1
Sug:8r Inclustn TechlllCi,Il\S, ~e\\ York, ~v!a\' l~i:)l.
 added and the mass stirred with powerful agitators to remove any irregularities. The fibers
are refined in conical refiners to give optimum fiber size. The refined fiber goes to stock chests,
from whidl it is fed, as' an approximately 2% suspension, to the head box of the board
machine. In the head box it is diluted to about 0.5%. The board machines, although of special
desigr:, are similar to Pourdrinier machines. The stock is fed onto forming screens and led to
drying felts and finally to press rolls. The sheets do not appear laminated but are felted
together to give the required thickness. The board from these machines is 4 m \vide, contains
50 to 55% water, and is proJuced at the rate of 60 m/min. It is dried in a continuous sheet,
at 150 to 230°C in a gas- or steam-heated dryer 250 to 300 m long. The product must be
sprayed with water as it leaves the dryer in order to bring it up to its normal water content
of approximately 8%. The board is then cut and fabricated.
Acoustical and structural wallboard, agricultural mulch and litter, plastic filler, furfural.
paper and plastic reinforcing fihers have all been made from bagasse. A high-quality wax has
also been extracted.

BEET SUGAR. Cane grows well only in tropical and semitropical climates, but sugar beets
grow well in the temperate zones. Only a skilled chemist can tell whether a sample of refined
sugar originated from the cane or the beet. Sucrose content of both sugars is very high, over
99.9%. For all normal purposes, the sugars obtained are interchangeable. All plants produce
some sugar, but only beets and cane are major sources. Other minor sources are the maple
tree, certain palm trces, and hone\, Food value and swc.-etness (but not sucrose) are econom-
ically obtained from corn, which illcreasingly effectively competes with beets and cane. Corn
seems to be gradually diminishing the beet market in the United States.
The sugar beet differs from the ordinary table beet in that it is much larger and is not red.
Sugar beets are an important crop in many sections of the world because of their sugar value.
Beet houses begin operation in late September and run until January or February. the
farmer harvesting the crop with machines that uproot the beets and elevate them to trucks.
The tops, good for cattle feed, rnay also be removed mechanically. The beets, containing from
13 to 17% sucrose and 0.8% ash, enter the factory by way of flumes, small canals filled with
warm water, which not only transport them but wash them as well.
Figure :30.4 illtlstrates the essential steps in the making of h<:'et sligar. This manufacturp
may be divided illto the following scquenccs: 12

The beds are rewashed, weighed, and sliced into long narrow strips called cassettes.
The cosselll'~ arc dropped into a ~p('cially dc,<,ignccl continu()us countercurrent diffuser (Fig.
:3(H). 'I'll(' sligar is cxtraclnl coulltercurrentl; with water <It ,0 to soac The resulting ra\\
juice is a hltw-black J 0 to 12S:;, sucrose solution with a small amount of invert sugar and 2 to
:Fc. ash. The pIlip ICllwilling c())ltains O. J to 0:3% S\lgar (based ()fj the beets). The pulp is
dcwatcred ill pl{'SS(~\, dried ill a mtary dryer, aile! sold as cattlE' feed. The change in the beet
iIldustry t() aulOlllatic l'()\lflll'r,'IlITl'lIt continu()lls cliffml'r.<, elil1linates the sweet-water h8.f1-
clling costs and red\I('('\ tIll' Iahm ["l'quirf'c1 by the b~ltter>.11 The amount of energy consumt'd
is sharpl y rcd uccd

12See also pictured flowchart, Beet Sugar Production, Chcrn Met. Eng. 49 (6), 110 (1942);
McDill, Beet Sugar Inelustry; Industrial Wastes. Incl. Eng Chern, 396.57 (19-17); Birch and
Parker, op. cit.
13Havighorsl, Beet Sugar: A Hadical NeVi Look, Chern. Eng. 68 (20) 76 (1961); Spreckles'
New De~eloprnents in Beet Sugar, Part 1, Chem. Eng. 71 (,) (1964).
 56

Carbon dioxlde------,
Slaked lime >u>pen"on Con

~ 'cc_C:o:T
- - - .- - - - - -- -- - - - - j

---- - - '- - -
"~
f : - ! ~ .: ~.:.'

- - - -,

-,

In order to produce 1 t of refined sugar, 400 kg molasses (.50'; sucrose), and -400 kg driect rulp. the
following materials and utilities are required:

Farm land 0.2 ha Coal (PO\\('I ,111(] heating) 0.66 t

Sugar beets 8 t Sulf l1f 0.') kg
Limestone 0.35 t \Vatl'r 9.0 t
Coke 0.03 t Direct lahur 22 work-h

Fig. 30.4. Flowchart for beet-sugar manufacture KEY: CarD, cariJoIlators; sulf, sulfitors; F, filters; W,
wash water; C, centrifugals; Con, condensers; D, dissolvers. :--:OTE: About half of all plants use sweet
water from filter washing for slaking lime; others use fresh watl'r

The juice is gi ven a rough screening to [('IIl()\',' Forl'iL:ll llwterials.

Milk of lime is added until the concentration IS equi\Cllent to about ;2 to :3;( The lime aid
in the precipitatioII of uIldcsirable impurities. /\rly cakill1fl saccharate is decomposed in car
bonators by passing carbon dioxide from the lime kiln tllrough the juice continuously. Tht
foaming that occurs at this stage is reduced by adding a ~mall quantity of antifoam.
The sludge produced by the lime is equal to 4 or ,) percent of the weight of the beet
charged. This is removed by thickening and filtering Of[ rotarv filters.
Lime is added again until the concentration i~ ('qlli\~dt'!1t to 0.5 percent and the juice agaiI
carbonatt::c1, this timl' hut.
It is then filtered Oil pressure filters.
The resulting filtrak is bleached with sulfur dioxide.
The precipitate of calcium sulfite is removed by press me of plate-and-frame filters.
The purified juice is concentrated from 10 t() J 2% slIgar to about 60% sugar in multiple
effect evaporators. This increases the c---ncentratiof1 of calcillm ions again. Some calcium pre
cipitatcs out.
A Sprccklf',c;' pLtllt 11.'l(,S ab() a counterCliITt'lit dt,(,ldl1riLing reacti\'ated carbon adsorptior
system t() pilrify dI1l1 dt,(·(dIlIi/c the thick juict, ill tll\\ ('r~. \\here the juice risC's against tht
fa I ling ca r bOll.
The resulting tliick jllicc i:, grained in Val'UlIIn pam.' I u'Iltrifuged, washed, dried in a gran
uJator, screened, ,lIlel packl'd in much the saml' lll<lnIlt'j ~lS described for cane sugar.'

14McGinnis et al, Low-Purity Beet Sugar Factor\ \Ltterials. Ind. E'0g. Chem. 34 r;-:
(1942).
 The juice from the first vac\lum pan is given further treatment to recover more sugar crys-
tals, but this is not pure en()ugh for market and is )t'Ill hack to the process for t urthtr
purification.

The syrup remainillg after the several crystallizatiuns. c;.dll,J beet molasses. 15 ",dd iur \..dttle
feed Jirectly or added to tlw waste beet pulp. It is also an IIllportant medium for ft'frIlc"llta-

tion, particularly for citric acid, where the high nitrogeIllUrilt'nt of beet molasse:; i~ Id\(ljdbie
Processes for recovery of tfie remaining sugar have been v,(Jrked out and are used \..I)mme[-
ciall}'. Initial recover v was obtained by the Steffen pr()u~"" \ . . ·!licn is used e.xttrl~I\I:h If! the
United State:;.
[)ililted Illolass('s y'i('ld.() up its sucrose by precipitation ~j~:t rrwtal "accharatf:. IrnpIJriti f :', dff:

removed from the precipitate by 6ltration; the S1lcruse is trwrJ regenerated C;t!cil1rn :;trr'rJ-
tillfll, or barium eat'll fmlll iflSolllhle saccharates with SUCf()Sf' hut the calcium prr)cC-'S I) gtn-
erally preferred. Th(' proc('ss \Ising C':a(OH)2 as the precipitdflt is krJ()\'..[1 as the Sttfferl pr')<:<"55
after its inventor. Hcg(;rwratioll of the calcium s~lc(h:lrdtf' r('~IIits from tredting the m2tE'rio.i
with CO 2 and approximately gO percent of the Sllcrmf' call t)f' reco\'ered b;: the Steffen~ pro-
cess. The CaCO'l precipitated can be roasted and recon\t'rkd to milk of lime
Ion cxclwngel.5 has heen tried or proposed fur the trl:,d rfl(:T1t of process liq Ij()r) at Sf:', '~ro.l
places in the sugar-rnanuLlCturillg procedure. Ion e.xcharlgc works well for cleaning up pro-
cess liquors, but total-output treatment is freq1lentl\' t(IO i'xpensive because of the COS( ri
disposal of sweet waters and spt-'nt reagents (from \'..8.shing I. Hcsin life is also short rJ{'cause of
irrf'versihlc ahs()rpti(lll \\'itll ('anl' sllgar invf'r~i()ll [11<1\' tab, place and cause In~,t:"5
III ('<lS('\ \\'11<'r(' ill\I'I\11111 I.' dl'\ilt'd, i()ll-t''\l'II~llll!Y "il('I'\ d ~11{)d. v(llltr(tllablt, rndi,,,d
I ,iqtlid-pll;l\t' ('hlllll];It()\~I;tph\ I" is being utili/.l'd III ~I l'(llllll1t'rciJl phnt t,) ~t"P~ILlk ~lIlr"'"
1111111 IWt'1 Ifltlhs\I" i"I! II", liI""I'" i~ tno llt'\\ Irr ('\,litLlt<- It, <lrllllllt'rl'l,d pl.)~sib;Lt;C'~

I.V'/-:Hl,T JIi':f)f nU"M I;; \,.,. •.; fll 1\"., (Iirer'( 1l\:1!II:t:Wtll"" ,I '1C211 theft" ,ITt" ft'w e'r ,,' "I~(';Tl,"
cklllge~ thai rt:qllll(' (>11('1)..(\ /\ Irllost all tlw ~kps lil llil' Illd!lufdcturiflg seqUelllt'S In\ r:rh C'

physical changes or 1lf1it ojwr:ltimls Thes(' C'On5UrTW Clwr\.!\ 111 ttl(' form of pc)\',C'r t(lr crushing
ptlrTIpi:lg, and ('('ntrH \ !~:d IIHI ;t!lel heat for solution. ('\all< :r:dll In. dnd d[\ing :\t the Cx)ttntn
of the Dowclwrts for I('litl('d (',\11(' sugar and for bed SIII:(df' ,hl,(~·30.2 anJ :3U-i; S"f1JC' d\ t'fdgt
figures for energy rCCjuircmf'nts are given. The steacL irnprmement of the equipment nec-
essary to make tllt's(' \ Mioll' Illlit u[,erations fUrIC·tioli dfll II'litly has gradually rr_'due-td tht,
('rwrgy requircments to the reas()nable amounts given. flilt llltlch remains to be done
Although f)ag;!s\!' I.S Ilsi'd illl 1111'1 in mallY ra\\-s\lgar Ililli, It IS bt'l'orning d mill'" lf1lp"r:~I::
(';1\\' matt'ri;ti \I'arh 11)1 1',11'1'1 ,11Id hoard. hl'III'I' ()tlll'r fill" Ir: ,iii ,;j'~""
Illd\ l,t' employed
rn<lllldactlIrilig t'sLillii\IIIIII'IJl, tlJ('rt, is all eCOlI(lfllil'~ll 1111.1: 11'/' Ili ~kam [x,sSlhlt· '~>t' T,l[';t'
.j!)) \\'lie['('ill high-p('I'S'lIlI' ,11';Ifll from the boil,'r i, ".'.}idII,j"d through a turhirl!- tl:' fL,rnJs~.
[lImn and tfw 1,\lidllC,\ \t";IIII I' ('Ilndellsed tu ~l'UIrI' 11t',1l inr l'\,~,puro.ti()[j of the' JUlu::; CinG
S\'lllP\ TIl(' ('llll<i('lI\,lk w;t\('f [,",Idting is plHllfwd L:I(·k tl) ifJl' f,()ilus ur f:mpl(JYhllrl rTldk!flt;:
syrilpS Fm 1,1'I't-\\I'-':;11 11·lilllll~ I:I~ ,'3().4 inclir-:ill'\ () f)h I I,f ('(Ial for 1 t ()f rdirlf:d 'llj£2.f (J[

2:~:2 \1; 1)('1 kl!.l\~I,1111 ,,: II:'.,II'>'llll(' plaflh lill\\ 1,1"1:'1"

lill d (' r I,' 3 ~) \, II

1'i\1icherWI et al. IIITI 1',\I'fl;lllL:t' in Beet SUgdl l"dltorl'" Inri fnJ!. Chern. -1~ 'J-!) .j':!5CJ.
Malldru, Ion Exchallgt' in 1)('('1 '>llgar ManufactlJrt' Ind. Chern . L3 615 11':151
(n!.!.

liiHeikkila, S(:pal~dllig -;Il,-,:al, .tllcl Amino ,Acids \\Itli Chrl)ff1dt l)graph:, Chern fTl;; 902
50 (1983)
 - y
)
'-'

MISCELLANEOUS SUGARS. Lactose, or milk sugar, is made from wastE:' skim milk. Sorbitol is
manufactured by hydrogenation of dextrose under pressure, using a nickel catalyst, or by
reduction in an electrolytic cell. Mannitol, made by hydrogenating sucrose to yield a 3: 1
sorbitol/mannitol mixture difficult to separate, is used in pill manufacture and electrolytic
condensers_ Xylitol, a sugar alcohol made by reduction of xylose, is now produced on a large
scale. It can be assimilated by diabetics without use of insulin, is nonfermentable. and doe~
not promote dental caries, so it is used in high-priced dietetic candies, che\\·ing gum, tooth-
pastes, etc. Gluconic acid, made by oxidizing glucose' by fermentation or by electrolytic oxi-
dation, forms llseful calcium and iron salts used pharmaceutically.

CORN SWEETENERS. A major portion of nutritive ~\\ t~dt:ller.) JlOW COlJle~ tro!ll ::.tarch llllJlnl~
corn) conversion into fructose-containing syrups. CO!lversion of starch into glucose by treat-
ment with acid or with the enzyme a-amylase has been practiced for many year~) and the'
syrups thus obtained are nourishing but not very sweet tasting. The discovery that enzymes
could be immobilized on organic substrates SUdl as didhyl-aminoethyl cellulose or certain
ceramic materials made enzyme use ecollomic;,t/ly possible because a single charge could
serve for a comparatively long period (several hundred hours) and treat a considerable quan-
tity of material before requiring replacement. Glucosl' s\rup prepared from starch by treat-
ment with a-amylase can be treated with a different illllilubilized eIlzyme, gluC()se isomer,m-
(see Fig. 30.5), which can convert up to 42 pC'n'C'nt ()f tflt' glucose to fructo.'>e. \\hich has 1::;
times the sweetening power of sucrose. This syrup call bl' u~ed directly as a s\\eetenillg 5: rup
essentially equivalent to sucrose syrup or, by separ,ilillg fructose and reCirculating the syrup
over the enzyme, 55% fructose can be made. This material can be dried, but because the solid
formed is hygroscopic, it is IlOt very desirable for JIO!lll' use. In 1980,42% syrup :;uld for 6-1
cpnts ppr kilogram, 550,:; fnr 75 cents per kilogram, ,llid refined sugar for HI cents per kilo-
gram, ill comp,naille bulk quantities.
Another procedure call be used to make 95 to 100>0 f fuctose. This passes the glucose solu-
tion over a bed of immobilized glucose-2-oxiclasc, w!Jicll uxidizes the glucose to glucosone.
which can in turn be hydrogenated to fructose I~ The pmcess is not yet commercial.

l~Basta, ImmobilizatioTi Houtes, They're Not Standing Still, Chem. Eng 89 (17) 55 (1982:

Spent
Corban corban
f,H .L'\CJlJ~1rnen1

t
ct--Steom

Make-up ~~\
tonk ~zzzr-;~tSr:OIIOw HFCS
er.zyme beds

. .....!

Fig. 30.5. Fruct 05(';' gl tlC()S(' snll p from glucose SHU p

STARCHES AND RELATED PRODUCTS

Starch consists of a chain of o-glucopyranosyl units and has the general formula (C 6 H 100 S)n
with n = 250 to over 1000. Two major components are recognized as usual, a branched-
chain form, amylopectin (75 to 80% in common starches), and a linear form, amylose.

CH 2 0H
I
C--() C--(J
H //H
C
~
C
H H
C
/H ~.
(
H

~OH ~ ~OH ~
°
'" /
c-·---- c
H
H/
OH
°/
c--(
H
H//
OH
°
/

Amyl"",·' '''gment of a linfar ,haln

Starch is one' of the most common substances existing in nature and is the major basic con-
stituent of the aver:tg(' diet. IIldustrially, its applications ls :He numerous. and it is used in
more than 300 modern illdustrie's, including the manufacture of textiles, paper, adhesives.
insecticide's, paints, soaps, explosives, and such derivatiyes as dextrins, nitrostarch, and corn
sugar. In recent years s\lch derivatives as heat-resistant adhesives, esters comparable with
cellulose esters, carl)()wlic ;l('icl~ from the oxidation of dextrose, and wetting agents have been
produced.

IlISTORICAL W It i.~;\ \\'('ll-kll()wl1 fact that the ancients IJsed starch in manufacturing paper
(as an adhesive and sl iffcIlt'r) a.s early as 3500 fl.c:. The Egyptians of this period cemented
papyrus tOt',ell\(,i III tim Ilt;tIITWT Between A.I) I()U and l:'3Ur), most paper was heavily coated
with starch, but the pradlCt' \\d~ abandoned tuw,nd tllt' ('lid of the fourteenth century and
\Vas flot rc\'i\'(·d ullti!llJ(' 11J(ld(,lll era, The use of starch in kxtiles began during the ~1iddle

18The Corn lndustric~ l'\csearch Foundation, Inc., lOCH Connecticut Ave., Washington
D,C., publishes an important .'icries of pamphlets on the corn wet-grinding industries, which
are b.'pt up to date. Titles arc Corn in Industry, Corn Starch, Corn Gluten, Corn Act, Corn
Syrups and Sugars.
19Knight, The Starch 111rillstrlj, Pergamon, Oxford, 1gog.
 ()( \

Ages, when it was a common stiffening agent. By 1744 the English.wc:re using it in sizing and
warp glazing. Textile demands soon brought about the introduction of potato starch to sup-
plement the wheat starch solely available up to this time. In 1811 the discoveries of Kirchhoff
with respect to glucose and the thinning of starches by enzymic action gave great impetus to
starch manufacture through the increased fields of application created. The use of roasted
starch (dextrins) did not begin until 1821, its usefulness being discovered as the result of a
textile f:ire at Dublin, Ireland. It had, however, been prepareJ by LeGrange as early as 180-1.
The first starch produced in this country was white potato starch, made at Antrim, :-':.H., in
1831. In 1842, Kingsford began the production of cornstarch, which became increasingly
popular until, by 1885, it had risen to the position of the leading textile starch in the Beld. It
was in this period also that the manufacture of dextrins (roasted starches) began in the Lnited
States.

USES AND ECONOMICS. In 1981 about 6.7 X 109 kg of starch was produced in the Lnited
States for all purposes, including conversion into syrup and sugar. Of this total about 98 per-
cent was cornstarch. Imports are principally tapioca, sago, and arrowroot starches, and
exports are principally cornstarch. The largest Single use for cornstarch is as food, about 2.'5
percent being thus consumed. Industrial uses account for the remaining 75 percent. The
paper industry utilizes cornstarch as a Bller and a sizing material. Textile, laundry, foundry,
air flotation, oil-well drilling, and adhesives use much starch (Chap. 25). White potato starch
can be employed for almost everyone of the uses outlined for cornstarch; it has a more desir-
able phosphoric acid content but is more expensive.
Wheat, rice, arrowroot, and cassava (tapioca) starches also have many of the same appli-
cations as cornstarch. Rice starch is particularly preferred for laundry purposes Tapioca
starch is very common as a food. In addition to the starches themselves, many further reaction
products are made. These include the following products: dextrin, which is available in more
than 100 different blends and types varying from pure white to light yellow in color is used
to make a great number of different pastes, gums, and adhesives. Corn syrups are a hydrolysis
product of cornstarch, containing dextrose, maltose, higher saccharides, and water. Approx-
imately 95 percent is used for food, and varying types are offered to the trade: conventional
syrups, primarily dextrose made by acid or enzyme hydrolysis; syrup solids and crystalline
dextrose made by drying conventional syrup; and three grades of high-fructose corn syrup
(HFCS) made by conversion with a special enzyme and containing 42%, 55%, and 90S:C fruc-
tose. Nonfood and industrial applications are important, as in the textile, leather-tanning,
adhesive, pharmaceutical, paper, and tobacco industries. Corn sugar, or dextrose, is the sugar
found in the blood and is our primary energy food. Its many food uses are dependent upon
its lower rate of crystallization, lesser sweetness, and different crystal formation. Dextrose is
consumed in baking and has additional uses in preserved hods, soft drinks, candy, and ice
cream. It is widely employed by the medical profession for infant feeding and for prescrip-
tions in syrup form. Industrially, it is important as a constituent of the viscose-rayon spinning
bath, in leather tanning, in tobacco conditioning, and in fermentation. Important by-products
of the starch industry are corn gluten, feed and meal, corn-oil meal, and corn oil \'irtuall:
all gluten and meal are used as feed, but a specially prep~lred gluten, very high in protein. is
employed as a raw material in manufacturing plastics aIld lacquers. Concentrated steep water
is consumed in the growing of penicillin and streptomycill (Chap. 40). Inositol. or hexahy-
droxycyclohexane, a sugar substance and a member of the vitamin B complex, is made from
corn steep water.