January, 1945

INDUSTRIAL AND ENGINEERING CHEMISTRY

MRATURE CITED

43

A series of three-cycle hydrolyses was made: rune 183, 184, and 185 at 1 8 5 O C., and 186 and 188 at 190'. The yield varied from 37.7 to 40.4 gallons per ton. I n rune 187 and 189 four 3minute cycles were used at 190 and 185' C., respectively. 4 . 0 gallons per ton were obtained, Yields of 41.5 and 4
SUMMARY

Studies on the hydrolysis of wood in the rotary digester have resulted in several alternative methods of operation for the singlestage, multistage, and limited multistage hydrolysis of yields obtained' depending On technique Of in lo minutas to 6o vmfrom aPPro*kly 8o muons per gallons in 3 hours.

(1) Demuth, R, von, 2. angsro. C h m . , 26, Aufndrt., 786-92 (1913). (2) Foth, G., C h . - Z t g . , 37, 1221-2, 1297-8 (1913). (3) Harrk, E . E., Forest Products Lab., M i m w r u p h 81446, 1-68 ( 1 Q W . (4) Kresemen, F.W., U.8 .bept. Agr., BUU. 983, 1-100 (1922). (S) Neuman, J., diseertation, Polytech. Inat., Dresden, 1910. ( 6 ) Saeman, J. F,, IND.ENO.CRBIY., 37, 48 (1946). a r r i s ,E. E., IND.ENG. CHZDK., (7) Bsemm, J. F., Bubl, J. L.,and H

(8) Saeman, J. F . , Harris, E .E . ,Kline, A. A., Zbid., 1044. CHBIM., 10,869 (1918). (9) Tomlimn, C. H., J. IND.ENO.
B A l l l D on rtudiea of the 0 .8. Forest Products Laboratory in cooperation with the 0 5 0 s of Production Rbaearch and Development, War Production Board.

ANAL.ED.,to b published.

KINETICS of WOOD SACCHARIFICA TION

Hydrolysis of Cellulose and Decomposition o f Sugars in Dilute Acid at High Temperature
JEROME F. SAEMAN
U. S.
F o r d Products Laboratory, Madison, Wir.
APPARATUS AND ANALYSES

acid at low temperature. Most of this work was done with fuming hydrochloric acid or 60% or stronger sulfuric acid a t room temperature or below. The research of Freudenberg has been especially noteworthy in this field (1-4). Sherrard and Froehlke (16)studied the rate a t which dflerent cellulose preparations are hydrolyzed in fuming hydrochloric acid and found marked merenaes, depending on the cellulose used. Wolfrom and co-workers studied the depolymerization of cellulose in concentrated hydrochloric acid by a simultaneous hydrolysis-mercaptalation method. They used the increase in the sulfur content of the product as a measure of the free aldehyde group8 and, hence, of the amount of hydrolytic cleavage (17,18). I n 1922 and 1923 Meiler (8) and Scholler (13)working in the laboratory of Lflers a t Munich, studied the hydrolysis of a cellulose dextrin. On the basis of these findings the Scholler proceas (2.6) for wood hydrolysis was developed. After some plant-scale reported on experimental work had been completed, Lflers (6,8) the kinetics of the hydrolysis of cellulose dextrin. He stated that both the hydrolysis of the dextrin in dilute acid and the degradation of the resulting sugara are unimolecular reactions. He further reported that the speed of both reactions WES proportional to the acid concentrations and that both reactions were equally affected by temperature. He gave no experimental data to support such claims. There is much information in the literature on the hydrolysis of cellulose in strong acid a t low temperatures; but there is little quantitative work describing the hydrolysis of cellulose in dilute acid at high temperature-that is, hydrolyses using acid concentrations below 3% and temperatures above 150' C. This paper will describe recent research on the kinetics of the saccharification of wood in dilute acid a t high temperature. The work was a part of the program authorized by the War Production Board to develop a commercially practical method for the conversion of wood t o sugar and the subsequent fermentation of the sugar t o alcohol.

NUMBER of inveeti tors have made valusble contributions to the study of l r netics of cellulose hydrolysisin strong

The experiments on the hydrolysis of wood and the decomosition of sugars were carried out in sealed lass bombs heated gy direct steam in a rotating digester. A hoyder for the bombs was made by brazing together a number of length of &-inch streamline copper pi into a nest of such size as to t convenientl in a cylind%al sheet-iron container fitted with a lid held on i y win nuts. The assembly is shown in Fi Soft glaaa cukure tubes (10 X 150 mm.) were s e a E i k a blast lam in such a way as to give a smoothly rounded end, as shown in &gwe 1. The tubes could be opened by a hot wwe cutter. Breakage of these tubes in the di ester was rare. When tubes of 8 lsrger diameter and thinner waql (I9 X 150 mm. standard soft glass teat tubes) were used,breakage was more fre uent. When emere cooks were made, using sugar s&tions of high concentration, a significant amount of gas was formed, but at no time under the conditions of these experimenta was enough gas formed to be dangerous. About 1.5 minutes were required to reach the desired steam pressure in the digester and an equal time was required to drop it t o atmospheric pressure. If these operatiom had been carried out more rapidly, it is possible that breakage of the bombs would have been more frequent. Sugar anal ses were made by the Shaffer and Somogyi method (16), using tgeir reagent No. 50 and a 30-minute boiling time. Unhydrolyzed carbohydrate material was determined b sub'ecting the residue to a quantitative saccharification, followed by sugar analysis. This saccharification causes a small amount pf decomposition but the reducing-sugar yield from cellulose is i n excess of 95% of the theoretical amount. The values are reproducible and can be corrected for the loss in sugar by an experimentally determined factor. I n this work, however, because the constant factor involved would have no effect on the determination of the rate constante, the values were used without correction. The fermentability of the su ars was determined by measuring the sugars sorbed by east in %igh concentration from the &luted sugar solutions. getailed descriptions of these methods are given in other reports (11, I d ) .

DECOMPOSITION OF SUGARS

Early workers (9) on wood hydrolysis recognized that the sugars produced from cellulose were subject t o decomposition on continued exposure t o hot dilute acid, All sugara subjected to this treatment yield humic substances of indefinite composition.

INDUSTRfAL AND ENGINEERING CHEMISTRY

V d 37. No. 1

Data arc presented to &city the ,<aitionr occurring in wood rdcchsrification. Hydrolysis of hemicellulose occurs easily and requires en insignificant time, in comparison with that required for hydrolysis o f the resistent portion o f the ccllulore. Saccharification ot celluloie involves two reactions: hydrolysis to reducing sugar and coniecutive decomposition of sugar formed. The decomposition of the ruger and the hydrolyrit o f the resistant portion of the celluloie &re both first-order reactions and P O I I ~ S Prates of similar magnitude. Conrtantr are determined to show the dependence of reaction rete on acid concentration and temperature. O n the barir of there kinetic studies, it is determined that the efficiencyo f the conversion o f cellulose to rcducing I U S incremes ~ with increasing temperature and increasing acid concentrations. Thecomparative hydrolyrirrsterof five different species of woods are determined.

Figure 1,

Bomb Tube Holder and GIwr Bomb

Pentoses form furfural in high yield; but if the furfural is not removed as formed, it partially condenses into high-molecularweight matcrisl8. By an analogous proccss hexoses yield hydroxymethylfurfurd which, on continued heating, yields levul i N c acid arid formic acid. I n this paper no study is made of sugar decomposition produeta, attention being confined to the faetom affecting the disappearance of the sugtr. DECOMPOSrTlON RATE OF GLUCOSE. When SOiUtions are sealed in bombs of tho &e wed for this work, at lenst an equal volume of air is present. The effect of this sir on the rate of deeompwition of sugar in acid solution was an unknown factor, no an experiment was performed to determine the effecto f vmious atmosphere8 in contact with tho miution. Five milliliters of a solution, mado up o f 4.88grams glucose in 100 ml. of 0.5% sulfuric acid, were put into 16 X 150 ml. culture tubes; the nerks were drawn down to a mrmw opening. Carbon dioxide or oxygen was admitted through a cepillary tube and bubbled through the eolution long enough to displace sll the sir from the tube. The constricted mouth of the tube was quickly wied. A set o f similar tubes wm prepred with m atmosphere of air. The tubes we10 heated at 185* C . for 5, 10,20, and 40 minutes. The concentration of the mgar remaining at eneh time is shown in Table I. The decomposition of glucose proceeds st similar rates in the presence of the three gsses tested. Since even pure oxygen daw not cause a large e h g e in the rate of decomposition, it WBS conadered that sir (20% oxygen) would not affect the resulk? si& Besntly. RELATIVE DECOMPOSITION Rums OP Suomr. To determine the rohtive rates of decomposition of various sugars, solutions o f 5 grams of xylave, arabinose, msnnwe, galactose, and glucose were made in 1 W ml. of 0.8% sulfuric scid. Five-milliliter samples of these sugars were placed in sealed bombs and heated simultaneously at 180' C. for various times with direct steam in B rotary digester and then analyzed. The amount of residual sugar w m expremd in terms of percentage of snalyzed initial ooneentration. The results sre shown graphicslly in Figure 2. The data indicate that, in all the sugars tested, straight lines are produced when the logarithm of the residual sugar concentration is plotted 89 B function of time. This is the criterion of a firat-order reaction. In such a reaction the rate is directly proportional to the concentration of the rencting substances. Where the logarithm of the reaidual eoneentration is plotted 8s 8 fuoction of time, the wristant may be readily

evaluated by multiplying the aiope of the line by -2,303. Ail constants were determined in this manner. Figure 2 shows that none of the decomposition curves reaches the initial concentration when extrapolated to zero time. This is due, in p & , to the fnot that ahout 1.5 minutes were required to raise the temperature to the desired level, and approximately the same time was required to lower it. At temperatures 309 or more below the desired level, however, the rate of resction is so slow that it has little effect on the net result. In addition to the timing error, there seems to be same other factor that results in a rapid initial lass in sugar. To study this factor, however, it will be neeeuery to devise equipment that will dlow more rapid and positive raising snd Lowering of the temperature snd permit better oontrol of time. The &&order resetion comtants and half-life periods determined from the data in Figure 2 follow:

D E C O M P ~ S OF I~O GLOOOSE N AS FUNCZYON OF ACIDCONCENM D TEMPERATOBE. Since glueose is the sugar of chief intereat in wood hydrolysstes, 8n extemive study W88 made of its decompoeition st vsrious temperaturea and in acid ofmriow concentrations. In this study 5 pama per 100 ml. solutions of ~ I U C O Sin ~ 0.4, 0.8, and 1.6% sulfuric acid were heated at 170", 180", and 190' C. for vmioua periods. The results are shown in Figure 3. Glucose solutions we initially 100% fermentable. After they m hested, however, the fermentable sugar content is less than the analyzed reducing sugar content. This ie due to the presence of unfermentable reducing substances. Therefore both the ferTBATION

Table 1 .

Decomposition d Glucose in Prerner 01 Air, Grbcn Dioxide, and Ory3rn

5 r 3 9u 409

Atrnoaohms

% Of sugsr Remaining after: - 10 mi". 20 mi& 40 min.

3 67 3 73

As

OiYBell

cor

ua

3 66

z n7

2 91 3 00

2 00 1 99

nu

January, 1945

INDUSTRIAL AND ENGINEERING CHEMISTRY

4s

mentable and reducing sugar contents of the heated solutions were determined. The straight lines of Figure 3 indicate that a t the temperatures and acid concentrations tested, when following either fermentable sugar or reducing sugar, the reaction is first order. After more than 80% of the initial sugar has been decomposed, the data become more erratic, presumably because of the accumulation of various decomposition products. This is of tittle importance, however, since conditions under which this occurs are of no practical interest. Table I1 gives reaction constants and half-life values of glucoae exposed to various temperatures and acid concentrations; both factors have a large effect on the rate of decomposition. When the logarithms of the reaction rates in Table I1 are plotted as a function of the logarithm of acid concentration, straight lines (Figure 4) are obtained. Figure 4 shows that the reaction rate increases by a constant multiple when the arid concentration is increased by a constant multiple. Table I11 gives values for the slope, M ,of the lines in Figure 4. The average slope of the lines over the temperature range . 0 2 whether obtained by following thc loss tested has a value of 1 in reducing power or the loss in fermentable sugar. The formula rehting acid concentrations and the corresponding reaction constants a t a certain temperature is
log k2 log c,

- lop kl

- log 4

(1)

where M has the value 1.02 over the range 170" to 190' C. This corresponds to an increase of 103% in the rate of decomposition with a 100% increase in acid concentration. When the logarithms of the reaction constants in Table I1 are plotted against th8reciprocal of the absolute temperature, straight lines are obtained (Figure 5); therefore this reaction follows the general law of Arrhenius relating the speed of a chemical reaction to the temperature:

log k = . j j R T

- AH, + constant

(3)

where s = a constant AHa = heat of activation The activation energy can be conveniently evaluated by multiplying the slope of the lines in Figure 5 by -4.576-that is, -2.303 R. Table IVgives the activation energy of the reaction for various acid concentrations as determined by following both the loss in reducing power and the loss in fermentable sugar.

Figure 3.

Decomposition of Glucose in Dilute Sulfuric Acid dt 170, 180, dnd 190* c.

46

INDUSTRIAL A N D ENGINEERING CHEMISTRY

Vol. 37, No. 1

Table II. Decomposition ol Glucose in 0.4, 0.8, and 1.6% Sdfuric A c i d at 170, 180", and 190" C.

TzzfT gz?:,, C. %
0

170

E:$ I:xy$+ t:{$ig '!:e"

1.6

180 190

0 .. 4 0 8
1.6

0.4

o.' 1.6

mill; samples were separated of such particle size as to pms a 2Gmesh and be retained on a 4&m& screen, paas a 40-mesh and be retained on an 80-meah of Reducing PowerBaaedon Loas of Fermentable Sugar screen, and pass an 80-mesh and be retained on a Based on P 1st-order reaction 200-mesh screen. Samples (0.5 gram) of each particonatant, k (rnh-1) constant, k (rnh-8) life, cle size were subjected to hydrolysis in sealed bombs Obavd. Calcd. Min. Obsvd. Calod. mln. with a 10 to 1 1iquid;solid ratio, using 0.8% sulfuric ~ : $ ) ~ ~ 5 acidat 180' C, After they were heated for various 0.0225 0,0221 31.1 0.0234 0.0235 29.6 times, the samples were filtered and washed on a 0.0123 0.0123 68.3 0.0129 0.0130 53.8 Gooch crucible. The filtrate was made up to 250 0.0242 0.0248 28.6 0.0259 0.0264 2 8.8 o.0606 0,0504 13.7 0.06p1 0.063s 13. o ml. in a volumetric flask and analyzed for sugar by 0.0270 o 0268 28.6 0.0292 0.0288 23.8 the Shaffer and Somogyi method (f2). The re0.0536 0.0546 "*O 0.0579 0.05*0 sidual cellulosic material, together with the asbestos 0.109 0.110 6.4 0.119 0.118 pad, waa subjected to a quantitative saccharification and the potential sugar content of the material w a s determined (f I). It has been customary in work on wood saccharification to express sugar yields in terms of grams of sugar obtained from 100 grams of cellulosic material rather than on the basis of stoichiometric yield. I n this report, too, net sugar yields are given on the basis of weight of starting material, Unhydrolyaed polysaccharide is expressed as grams of sugar potentially obtainable per 100 grams of starting material. This is convenient for two reasons: It simplifies calculations, and the value is obtained directly by an analytical method which, for its purpose, is superior to any available cellulose analysis. I n a residue remaining after an hydrolysis, the percentage of potential sugar is based on the weight of original wood subjected to hydrolysis rather than on the weight of residual wood.

o&t*

00:1y:2"g

'82:;

';::

Table 111.

Effect of Acid Concentration on Decomposition of Glucote *Based on Loss of:

Reducing power 1.02
1.03

Temp., C. 170 180 180

1.01

Fermentable sugar 1.03 1.03 1.01

no021

a.2

I
04 08

I
/.6

Table
3.2

IV. Activation Ener

HtsOi

SUlfURIC AGIO CONCNTffAT/ON[ E Q C M )

y for Decomposition of Glucose in A c i d of Dilerent Concentrations

Activation, Energy Based on Deereaae in: Reducing power Fermentable augar 33 100 cal. 33,200 oal. 32'900 33,300 32:IOO 32,100

Figure 4. Relation of First-Order Reaction Constant k to Acid Concentration in Decomf Glucose at Various Temperatures position o

Concn., % 0.4 0.8 1.6

The difierences in activation energy at different acid concentrations are within experimental error. By the use of the Arrhenius equation it is possible to predict the reaction rate for a certain temperature if the reaction rate is known for some other temperature a t the same acid concentration. As an approximation it is found that from 1 7 0 ' to 190' C. the rate of decomposition of glucose increases 125y0 with an increme of 10'

02
?
L Z

$ $.&

c.

2; ; ; 0.04 B 003
2 . 5 2 "jj
002

E 2%

HYDROLYSIS O F CELLULOSE

A study of the hydrolysis of more than twenty different woods, cellulases, and aellulose preparations a t temperatures ranging from 170" to 1 9 3 ' C. with a fourfold change in liquid-solid ratio and a tenfold change in acid concentration, established that the hydrolysis of cellulose in dilute acid follows the laws of a firstorder reaction. This is in agreement with the report of Ltiers ( 6 ,6) on the hydrolysis of a cellulose dextrin.

Q O

aw7
OOOb

p
Q

0.005 0004 no03

u)

E m n OF PARTICLE SIZEON HYDROLYSIS RATEOF DOVQLM

FIR. A sample of Douglas fir sawdust waa ground in a Wiley

Figure 5. Relation of First-Order Reaction Constant k to Temperature in Decomposition of Glucose with Sulfuric A c i d of Various Strengths

J . n o y , 194S

I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
50

41

Because of the difficulty of uniformly wetting fine sawdust with small quanM tities o f liquid, the study was not carried t o liquid20 solid ratios lower than 5 to 1. I n all other work reported in this paper a IO liquid-solid ratio of 10 to 1 9 was used. 8 7 C O M P A R A T I V ~ 4 HYDROLYSIS RATESOP 5 VARIOUS SPECIES. Samples of red oak, Douglas u lU 20 40 80 fir, hard maple, - . southern Figure 6. Hydrolyric of Douglas Fir of Figure 7. Hydrolysis of Douglas Fir at yellow pine, and aspen Various Liquid-Solid Ratios Various Particle Sizes were ground in a Wiley mill until each passed a 30-mesh sieve, Samples of these woods were then Table V. Hydrolysis of Various Species of Wood at 185" C. with 0.75% Sulfuric A c i d hydrolyzed at 185' C. with Half Fermentea 10 to 1 liquid-solid ratio L i f e bility of Potential Potential of csl% Net Reduoing Sugar in: and0.75%sulfuricacid for Reduoin Reduoin lulose Aah, % Min.' 6 M i n . 10 Min. 20 Min. 40 Min. 60 Min. various times. The data Speoiea Sugar, Sugar, Red oak 63.0 63.0 0.21 17.7 24.6 22.1 20.2 17.9 10.3 were plotted t o give the 00.6 86.2 0.08 17.9 28.9 28.9 23.9 20.a 10.4 D o laatlr lines shown in Figure 8. E a 3 maple 68.2 71.0 0.48 21.0 24.1 22.0 22.2 20.2 12.6 76.1 76.3 0.39 21.3 23.6 23.1 24.8 22.9 14.4 Anpen The hydrolysis of all amSouthern yellow pine 64.8 82.0 0.30 28.1 28.4 22.8 21.9 19.6 12.1 plea followed the laws of a f i r st - o r d e r reaction. There is a relatively large. vertical separation of the lines, and R small but significant differWhen the logarithm of the residual potential sugar is plotted ence in the slopea of the linea. The vertical separation is due t o the as a function of time of hydrolysis, the straight lines of Figure 6 different potential reducing-sugar contents of the various wdods are obtained. The three particle sizes give lines of equal slope Only the elope of the lines serves t o determine the rate of hybut are displaced vertically with respect t o one another. This drolysis of the resistant portion of the cellulose. displacement is due t o the fact that, after grinding and sieving, the more friable noncellulosic portions of wood are concentrated in the finer particle sizes; and although the three samples came from the same source, they contain different amounts of potenHydrobit Of Dou81as Fir In0*4 Om8 and lS6% Sulfuric Table tial reducing sugar. The fact that the lines are pardlel shows Acid at 170, 180, and . t h e C. that the resistant portion of the cellulose hydrolyzes a t a rate inObsvd. Half
M

. I

dependent of the particle size over the range tested. Evidence was obtained that with particle sizes greater than 20 mesh, the rate of hydrolysis becomes somewhat slower. Studies on this phase o f the problem are not yet completed. I n addition to the resistant cellulose, whose rate of hydrolysis is indicated by Figure 6, wood also contains a n easily hydrolyzed fraction. Under the conditions of this experiment this fraction appears to be hydrolyzed as soon as the system comes t o temperature. The 40-80 mesh sample whose hydrolysis is shown in Figure 6 contained 66.6% potential reducing sugar. The amount of resistant cellulose in this sample extrapolated t o 44% at zero time. The difference between these two values represents the easily hydrolyzed carbohydrateg in the sample. I n subsequent studies on wood hydrolysis, d l woods or hydrolyzed wood residues were so ground that the total sample passed a 30-mesh screen. I n this way variations in rate of hydrolysis due t o particle size were eliminated, since the rate of hydrolysis is practically independent of particle size in wood meals finer than 30 mesh. EFFECC OF LIOUID-SOLID RATIO ON HYDROLYSIS F ~ T OF E WOOD, Samples of Douglas fir ground t o pass a 30-mesh screen were hydrolyzed at 180' C.with 0.80/, sulfuric acid with 6 to 1, 10 t o 1, and 20 t o 1 liquid-solid ratios for various periods (Figure 7). The liquid-solid ratio over the range tested had a small but definite effect on the speed of the reaction. The half-life Deriods for the three liquid-soid ratios were: 5 to 1, 28.2 minu&; 1 0 to 1, 26.8 minutes; and 20 t o 1,25.0 minutes.

Temp.,

* c.
170 180
190

HrSOr Conon.,

Iet-Order Reaction Constant,

IC ( M h - 1 ) Obsvd. Calod.

& & : Cellulwe,

Min.
198.0

0.4 0.8 1 . 6 0.4 0.8 1.6 0.4 0.8 1.0

0.00366
0.00888

0.0222

0.0268 0,0064 0.0299 0.0726 0.183

0.00996

0.00348 0.0880 0.0223 0.0102 0.0268 0,0866 0.0288 0.0730 0.18b

78.2 31.2 69.6 26.8 10.4 23.2 9.66 3.78

Figure 8.

Comparative Rates of Hydrolysis of Various Species' of Wood

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INDUSTRIAL A N D ENGINEERING CHEMISTRY

Vol. 37, No. 1

of less interference due to its acid-neutralizing capacity than would be found with many other woods. It is not necessarily true, however, that such a low ash content is characteristic of all samples of Douglas fir. Samples of the Douglas fir composite, ground to pass a 30-mesh screen, were hydrolyzed with 0.4,0.8, and 1.6% sulfuric acid with a 1 0 to 1 liquid-solid ratio at 170, M O D , and 190" C. for various times. Figure 9 shows logarithms of residual potential sugar plotted as a function of time. Table V I gives the first-order reaction constant, k , and the half-life values calculated from the slope of the lines in Figure 9 for the different temperatures and acid concentrations. Figure 10 shows the net sugar yields obtained from the hydrolyses corresponding t o those graphed in Figure 9. Logarithms of the first-order reaction constants for the hydrolysis .of Douglas fir were plotted as a function of the logarithm of the acid concentration (Figure 11). As in the decomposition of glucose, this relation proved to be a straight-line function, showing again that the reaction constant increases by a constant multiple when the acid concentration is increased b y a certain multiple. The slope of the lines waa asfollows: 170" C., 1.32; 180,1.38; 190" 1.31; average, 1.34. This corresponds to a n increase of 153% in the rate of hydrolysis with a 100% increase in acid concentration. When the logarithm of reaction rate is plotted against the reciprocal of absolute temperature for each acid concentration, the straight lines of Figure 12 are obtained. In the rate of hydrolysis of wood, aa in the decomposition of sugar, the effect of temperature follows the law of Arrhenius. The energy of activation in calories ( A H . ) , calculated from the slope of these lines, is as follows: 0.4%,43,100; 0.8%, 42,800; l.SyO, 42,700. The exact effect of temperature on the . As an approxireaction is given by Equation 2 mation, a 10' rise in temperature over the range 170' t o 190" C. increases the reaction rate 186%.
EMPIRICAL EQUATIONS

Table V and Figure 8 show that the hydrolysis of various species of woods, both as regards the disappearance of cellulose and the formation of sugar, proceeds in much the same fashion. There is a small difference in the rate of hydrolysis of the resistant portion of the cellulose in wood of different species. hlcLean (7) and others have shown that paper and other cellulosic materials possess a definite buffering capacity for both acids and bases. The buffering capacity for acids correlates with the ash contents of the material. The wood samples in Table V wcrc analyzed, for ash content in an effort t o determine whether the differences in hydrolysis rate of the various species were due t o the neutralization of acid by ash-forming constituents. It vias found that the two woods with the lower ash content had the higher rates of hydrolysis. IIYDROLYSI~ RATEOF DOUGLAS FIR AS FUNCTION OF ACID COXCENTRATION AND TEMPERATURE. A study was undertaken to determine the factors that affect the rate of hydrolysis of Douglus fir. This wood was chosen because of its economic importance; it is available in large quantities as a waste which could be converted to sugar. Because of the low ash content of the sampIe used (Table V), this wood also has the advantage

Equations 2 and 3 define the effect of temperature on cellulose hydrolysis and glucose decomposition when the acid concentration is held constant. The effect of acid concentration under conditions of constant temperature is given by: where W a constant C, = concentration of sulfuric acid, % M = slope of line obtained by plotting log k against log of acid concentration The equation which simultaneously describes the effect of temperature and acid concentration is:

k =

wc:

(4)

k
or log

HC/e-AHa/RT

(5)

= log H $: M log

-2

AHa

The equation describing the rate of hydrolysis of Douglas fir is:

(7)

January, 1945

I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY

49

I
50

I
100

I
I50

I
200

I
250

I
300

I
350

+or

J
450

O.PO/

0.2

3 . 2 SULFUR/C AC/D CONCNTRATiON fPLRCfNT)

46

I
0.4

I
0.8

Figure 11. Relation of First-Order Reaction Constant k to Acid Concentration in H y drolysis of Douglas Fir at Various Temperaturer

KINETICS O F CONSECUTIVE REACTIONS I N V O L V E D IN WOOD SACCHARIFICATION

The data presented previously show that the saccharification of wood involves two consecutive first-order reactions, the rates of which are of similar magnitude : Cellulose ICl reducing sugar k2 sugar decomposition + i products. Liiers (6) stated that the course of the reaction for cellulose dextrin is exclusively as indicated by t!-is relation. This report will also show that present findings indicate this to be true. The rate of the Figure 10. N e t Sugar Yields Obtained b y Hydrolysis of Douglas Fir at 170, 180, and 190' C. second reaction as determined by the loss of fermentable sugar or of reducing power can be measured with accuracy, but the products of this reaction are The rate of loss of reducing power of glucose is given by: only partly known. The concentration of the three materials in the reaction stated as 100 (8) k ,= 1.86 x 1014c:.o*e -Z&G previously is given by the following formulas: The rate of loss of fermentable sugar from glucose solutions is given by:

CA = residual potential sugar = a e - k :

CB

2.39 X 1014Cf.OZe -a.aOBRr

awro

(9)

(10)
[e-kie

net reducing sugar = a

1 -

kl

e-ka]

(11)

Tables I1 and VI show the observed reaction raw and the oslculated values obtained by these equations. The agreement between observed and calculated values was better than expected on the basis of the temperature and time control used. The experiments on the hydrolysis of wood and on the decomposition of glucose, requiring the same temperature and time, were run simultaneously to reduce error in comparison between the rates of sugar production and destruction.

CC = sugar decomposition products = (12)

where a = initial concentration

All concentrations in this paper are given in tenns of glucose equivalents per 100 grams of starting material. Thus the amount of ceUulose ~ r w e n tis expressed in terms of potential reducing

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 37, No. 1

0.05
0.04

0.03
0.02

-awz
0 . 0 0 3
LOOl
0.00215

0806 0005

0.0022ff

0 . 0 0 . ? 2 s

OOff30

RC/PROCAL O f ABSOLUTE TMPRATURE

Figure 12. Relation of First-Order Reaction Constant k to Temperature in Hydrolysis of Douglas Fir with Sulfuric A c i d of Various Strengths

sugar, and sugar decomposition products can be expressed in terms of grams of glucose destroyed per 100 grams of starting material. Equations 10,11, and 12 show that none of the reactions go to completion. The amount of cellulose present decreases constantly, the amount of decomposition products increases constantly, and the amount of net sugar produced Dasses through a xuxhum. The time at which net sugar proiuction reaches a maximum is given by:

(13)
The maximum net sugar yield is given by the approximate formula:

(14)
Formulas 10 to 14 (4A), inclusive, apply only to homogeneous materials. Probably no naturally occurring cellulose- fulfills this condition. All native celluloses tested showed a marked

difference between the rate of hydrolysis of the portions that were easy and that of the portions that were difficult to hydrolyze, The portions easily hydrolyzed were removed in a short time, and the rate of hydrolysis of only the portions difficult to hydrolyze was measured. From a kinetic standpoint, the resistant portion of the cellulose without exception has proved to be homogeneous. To determine how well Equation 11 serves to describe the yield of net sugar formed by the hydrolysis of cellulose in a closed system, two experiments were performed. In the first a sample of wood was hydrolyzed to remove all the hemicellulose, washed free of acid and sugar, and dried. The oven-dry residue so obtained contained 5 7 . 9 grams of potential reducing sugar per 100 grams. This material was subjected t o hydrolysis with 0.8% suUuric acid at 180" C. for various t i e s . The reaction rate for the conversion of this sample of cellulose to reducing sugars under these conditions was 0.0266. The first-order reaction rate for the decomposition of glucose under these same conditions is 0.0242. Substituting these values in Equations 10, 11, and 12 gives the curves of Figure 13. The indicated points are the observed net sugar.yields at 10, 20, 40,and 80 minutes. The observed .and calculated values are in good agreement, In a second experiment a sample of U.S.P.absorbent cotton 8 5 ' C. for 15 minutes with 0.5% sulfuric was hydrolyzed at 1 acid to remove the easily hydrolyzed portion, washed, dried, and 8 0 ' C. The rehydrolyzed in bombs with 0.8% sulfuric acid a t 1 rate of hydrolysis was substantially the same as that for the resistant portion of cotton given no preparation, kl = 0.0113. The rate of decomposition of glucose is the same as that used in the preceding experiment. Substituting these values in Equation 11, Figure 14 was obtained. The indicated points are the observed values a t 10,20, 40,and 80 minutes. This agreement between the observed and calculated yield of net sugar is the best evidence a t hand that the saccharification of cellulose proceeds through the steps cellulose --c reducing sugar + sugar decomposition products, and that the reaction cellulose -+ decomposition products, if it occurs a t all, is of minor importance. Because of the presence of hemicellulose, the hydrolysis of wood follows a more complex course than does that of homogeneous cellulosic materials. If a sample of Douglas fir is hydrolyzed with 0.8% sulfuric acid a t 180" C., and the curve of log residual potential sugar against time is extrapolated to zero time, a value of 44y0potential sugar is obtained. This represents the amount of cellulose that is difficult to hydrolyze (Figure QB). From the net sugar yield curve it appears that 24% sugar is obtained in what, for present purposes, may be considered zero time. A fermentability vs. time curve indicated that a t zero time

T/M fM/NUTL-5)

Figure 13. Saccharification of Hemicellulose-Free Hydrolyzed Wood Residue et 180" C. in 0.8% Sulfuric A c i d

Figure 14. Caiculated end Observed N e t Su ar Yields from Cotton Hydrolyzed at 180' C. in 0.8% Sul%wic A c i d

January, 1945

INDUSTRIAL AND ENGINEERING CHEMISTRY

51

Equation 14 shows that the maximum yield of reducing sugar from cellulose in a closed system increases as the ratio kl/k increases. T h e data in Figures 4,6 , 11, and 12 show that k1 increases relative to k when either the acid concentration or the temperature is increased. The ratio between Icl and k (loss of reducing power of glucose) at various acid concentrations and temperatum follows:
Temp.,
170
180 190

C.

H & 0 4 ,%
0.4 0.8

kr/kr*
0.62 0.84 1.00 0.81 1.07 1.31 1.11 1.86 1.68

ki more.

1.6 0.4 0.8 1.6 0.4 0.8 1.6

rats d hydrolyaio o f aellulose; kr

rate of dsoomporition of glu-

Flgure 15

H drol sir of 30-Mesh Douglas Flr at 180' C. in 0.8% Sulkric A c i d with a 10 to 1 Liquid-Solid Ratio

the hydrolyzate is composed of about one third unfermentable and two thirds fermentable sugar. If it is assumed that the sugars formed on wood hydrolysis consist exclusively of glucose and xylose, the net sugar yield from wood hydrolyzed in a closed system may be described 6 . Curve A shows the amount graphically as shown in Figure 1 of xylose present aa a function of time. Curve B shows the amount of glucose derived from the hemicelldose aa a function of time. Curve C shows the net sugar yield from the resistant portion of the cellulose. The sum of these three is given in curve D. The observed values are given in curve E. The equations used to calculate the values for these curves are:

The reason that the ratio of IC1 t o ka changes with changing conditions is that k 1 increases approximately 190% with a 10" rise in temperature, and Icl increases only 130%. Although a 100% increase in acid concentration causa a n increase of 163% in k1, it increases k, only 103%. Figure 16 shows the variations with time in net sugar yield at certain acid from a hemicellulose-free sample of Douglas concentrations and temperatures. The equations used to compute the valueg for theee curves follow:

1 9 0 ' C. and 1 . 6 % sulfuric acid:

180" C . and 0.8% sulfuric acid:

170" C . and 0.4% sulfuric acid:

Reducing sugar =

A: xylose = Se-0.0720' B: glucose = 16e-0.0*4*'

C: glucose = 44 0.0242
0.0258

0.00534 - 0.00366

0.00355'

(e-o.mwt

- e-o.oosau)

- 0.0268

[e-O.OSMt

e--O.Olllt]

The maximum height of these curves is a function of the ratio of Icl to k , . The time in which this height is reached is a function

The constants are experimentally determined values given previously. The fact that the calculated values are higher than the observed may be due in part to the fact that, for purposes of simplification, it was assumed that wood hydrolyzate3 contain only glucose and xylose. Actually, other more w i l y decomposed sugars are present as minor constituents. Figure 16 shows that the hydrolysis of wood in a closed system yields a maximum amount of sugar in a short time. It a h shows that, on extending the time of hydrolysis, the yield decreases slowly at firat, then f a decreasing percentage of unfermore rapidly. Because o mentable pentoses, the maximum yield of fermentable sugar or of alcohol does not coincide with the maximum yield of reducing sugar. This matter is discussed in more detail ie another report (IO).
APPLICATION O F RESULTS

The chief aim in this study of the kinetics of saccharification was to choose conditions of hydrolysis that result in a maximum efficiency of conversion of cellulose t o sugar. The work has so far been confined t o the use of h e I y divided wood with a high liquid-solid ratio. The conclusions have already been successfully applied to the larger-scale, single-stage hydrolysia of chips' (IO),and there is reason to believe that the same principles shduld apply to multistage processes. The hydrolysis of larger-sizedwood particles, however, is oomplicated by diffusion problems, which seem to be of no significance when wood meal ie used.

Figure 16. Calculated Net Sugar Yields from HemicellulosoFree Wood at Certain A c i d Concentrations and Temperatures as a Function of Time

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INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 37, No. 1

of the magnitude of kl and k,. These results are not in agreement with the findings of Luers (6, 6) on cellulose dextrin. He stated that the rates of hydrolysis and decomposition are equally affected by temperature and acid Concentration. Hence, changing these factors would have no effect on the maximum net sugar yields. The data in Figure 16 are also in disagreement with other earlier workers (9) who, having determined the fact that a large increase in decomposition occurred with increasing temperature, came to the conclusion that 175' C. represented a critical point above which it was useless to investigate wood saccharification. They failed to recognize the fact that hydrolysis of cellulose incrgases at an even faster rate, and that the situation becomes more favorable above this temperature. As soon as equipment is made available for the purpose, this study of wood saccharification will be extended to much higher temperatures, since the indications are that this will result in improved yields, decreased time, and decreased acid consumption, important points in any proposed commercial utilization of the process of wood hydrolysis.
SUMMARY

Many phases of wood hydrolysis can be conveniently studied on a small scale. A method has been described for hydrolyzing small samples of cellulosic materials in glass bombs by heating with direct steam in a rotating autoclave. Much of the convenience and success of the method depends on the fact that the small quantities used made sampling of the products unnecessary; all the hydrolyzate and all the residue were used for the analysis. The work described in this paper was confined to the use of finely divided wood with high liquid-solid ratios. The general principles derived, however, appear to be confirmed by larger-scale operation. Because of its fundamental importance in wood saccharification, the decomposition rates of glucose and other sugars in dilute acid were investigated. The decomposition of all sugars tested followed the laws of a first-order reaction. The energy of ac'tivation of the decomposition of glucose appeared to be independent of the acid concentration over the range 0.4 to L6Y0 sulfuric acid, and averaged 32,800 calories. As an approxima0 ' rise in tion, the rate of reaction increased 125'% with a 1 temperature over the range 170' to 190" C. A 100% increase in acid concentration resulted in a 102% increase in speed. The hydrolysis of a number of different cellulosic materials was investigated. All samples tested showed the presence of an easily hydrolyzed portion. The rate of hydrolysis of this portion was not investigated. The hydrolysis of the resistant portion of all celluloses tested was found to be a first-order reaction. There

was a large difference in the rate of hydrolysis of cotton and of wood cellulose. The samples of wood tested appeared to hydrolyze at rates differing from one another by not more then 20%. The rate of hydrolysis of finely divided wood (finer than 20 mesh) was found t o be independent of the particle size over a wide range. The hydrolysis of Douglas fir was investigated under conditions ranging from 170" to 190" C. and 0.4 to 1.6% sulfuric acid. A 100% increase in acid concentration resulted in a 153% increase in hydrolysis rate. The energy of activation of the reaction was independent of the acid concentration and averaged 42,900 calories. As an approximation it may be considered that a 10" C. rise in temperature results in a 186y0 increase in reaction rate. An investigation of the theory of consecutive reactions makes i t apparent that the efficiency of conversion of cellulose to reducing sugar increases with the ratio of the reaction rates for production and destruction of sugar. From the data just summarized, it is apparent that a n increase in either acid concentration or temperature results in a greater increase in the rate of hydrolysis of cellulose than in the rate of destruction of glucose. Consequently, it may be concluded that increasing acid conrentration and increasing temperature result in increasing efficiency of conversion of cellulose to reducing sugar.
LITERATURE CITED

(1) Freudenberg, K.,Trans. Faraday Soc., 32, 74-6 (1936). (2) Freudenberg, K., and Blomquist, G., Be?., 68B,2070-82 (1935). (3) Freudenberg, K.,Kuhn, W., Durr, W., Bolz, F., and Steinbrunn, G., Ibid., 63B, 1510-30 (1930). (4) Freudenberg, K., and Soff, K., Zbid., 66A,19-27 (1933). (4A) Glasstone, Samuel, "Textbook of Physical Chemistry", New York, D. Van Nostrand Co., 1940. (5) Lliers, H., 2. angew. Chem., 43,455 (1930). (6) Zbid., 45,369 (1932). (7) McLean, D.A.,IND. ENG.CHEM., 32, 209-13 (1940). (8) Meiier, L., dissertation, Teohn. Hoohschule, Munich, 1923. (9) Neuman, J., dissertation, Polytech. Inst., Dresden, 1910. (10) Plow, R.H., Saeman, J. F., Turner, H. D., and Sherrard, E. C., IND. ENC.CHEM., 37,36 (1945). (11) Saeman, J. F.,Bubl, J. L., and Harris, E. E., IND. ENQ. CHEM., ANAL.ED., t o be published. (12) Saeman, J. F., Harris, E. E., and Kline, A.,Zbid., 1944. (13) Scholler, H., dissertation, Teohn. Hochschule, Munich, 1923 (14) Scholler, H . , 2eZlsto.f Fasm, 32,65-74 (1935). , Somogyi, M., J. Biol. Chem., 100,695 (1923). (15) Shaffer, P a p . and (16) Sherrard, E. C.,and Froehlke, A. W., J . Am. Chem. Soc., 45, 1729 (1923). (17) Wolfrom, M. L., and Georges, L. W., Ibid., 59,282-6 (1937). (18) Wolfrom, M.L., and Snowden, J. C . , Ibid., 60, 3009-13 (1938).

BASED on studies of the U.S. Foreet Products Laboratory in cooperation with the O f f i c e of Production Research and Development, War Production Board.

By-Products of Wood Saccharification

R. LEONARD HASCHE, Tennessee Eastman Corporation, Kingsport, Tenn.
WOOD saccharification plant has been approved by the Government for the production of ethyl alcohol for war ' purposes. Soon after our entrance into the war the distilleries were converted to industrial alcohol production from grain due to the inadequate supply of blackstrap molasses to meet greatly increased requirements. I n turn, the wood saccharification unit has been approved as an insurance plant, in case a grain shortage should develop. Production costs on all of these emergency alcohol plants have been secondary considerations to wartime needs.

The enormous increase in ethyl alcohol requirements due to war is indicated by a 1944 production, estimated a t 650,000,000 gallons or four times prewar needs. Over half of the production has come from converted distilleries. The proposed wood sugar plant, is designed to produce 4,000,000 gallons of alcohol per year, or less than 1yoof the total. However, it should fulfill its purpose, that of a test plant. The survival of a wood saccharification industry in the United States in a postwar economy appears to be dependent upon byproduct credits of substantial value. I n making this statement