HYDROLYSIS OF CELLULOSE

Cellulose acid hydrolysis is an entry point for a biorefinery [139]. Recently, heterogeneous catalytic depolymerization of cellulose has received much attention [10, 140, 141). Solid materials modified with sulfonic acid groups have been widely attempted for cellulose hydrolysis. SuUbnated mesoporous sihcas [142], suUbnated carbon materials [69, 143-145], suUbnated carbon-siUca nanocomposites [146], and styrene-based sulfonic acid resins [147] have all been reported for sugar hydrolysis. 

Sulfonated silica/carbon nanocomposites are also known to be an effective catalyst for cellulose hydrolysis [147], with their hybrid structure influencing catalytic activity. Increasing the silicaicarbon ratio enhanced the turnover frequency, suggesting that hydrophilic silica groups fadlitate substrate adsorption. 

As mentioned earlier, the most important issue in cellulose hydrolysis is sohd acid operation in water. Cellulose is insoluble in water, but soluble in some ionic Hquids such as l-butyl-3-methyHmidazolium chloride (BMIMCl). The use of ionic hquids thus affords a good accessibihty to dissolved cehulose for conversion at active sites of sohd add catalysts. Amberlyst resins in ionic hquids could effectively depolymerize cellulose (microcrystaUine cehulose and a-cehulose) into ceUo-ohgomers under mild reaction conditions (373 K, 5 h) [147]. 

In contrast to sulfonated materials, novel metal oxide catalysts are also apphcable for sugar hydrolysis. Water-tolerant sohd adds, such as layered HNbMoOg [55, 151], HTaMoOg [54], mesoporous Nb-W oxides [61], andTa-W oxides [62], showed high activity for ceUobiose hydrolysis, a unit of cellulose. The high performance of layered oxides is attributed to facile intercalation of ceUobiose into the interlayer 

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Maltose obtained by the hydrolysis of starch and cellobiose by the hydrolysis of cellulose are isomenc disaccharides In both maltose and cellobiose two d glucopyra nose units are joined by a glycosidic bond between C 1 of one unit and C 4 of the other The two are diastereomers differing only m the stereochemistry at the anomeric carbon of the glycoside bond maltose is an a glycoside cellobiose is a (3 glycoside... 

Animals lack fhe enzymes necessary fo cafalyze fhe hydrolysis of cellulose and so can 1 digesf if Caffle and ofher rummanfs use cellulose as a food source mdirecfly... 

Cation (Section 1 2) Positively charged ion Cellobiose (Section 25 14) A disacchande in which two glu cose units are joined by a 3(1 4) linkage Cellobiose is oh tamed by the hydrolysis of cellulose Cellulose (Section 25 15) A polysaccharide in which thou sands of glucose units are joined by 3(1 4) linkages Center of symmetry (Section 7 3) A point in the center of a structure located so that a line drawn from it to any element of the structure when extended an equal distance in the op posite direction encounters an identical element Benzene for example has a center of symmetry Cham reaction (Section 4 17) Reaction mechanism m which a sequence of individual steps repeats itself many times usu ally because a reactive intermediate consumed m one step is regenerated m a subsequent step The halogenation of alkanes is a chain reaction proceeding via free radical intermediates... 

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

By-product acetic acid is obtained chiefly from partial hydrolysis of cellulose acetate [9004-35-7]. Lesser amounts are obtained through the reaction of acetic anhydride and cellulose. Acetylation of saHcyHc acid [69-72-7] produces one mole of acetic acid per mole of product and the oxidation of allyl alcohol using peracetic acid to yield glycerol furnishes by-product acid, but the net yield is low. 

Emymatic Hydrolysis of Cellulose to Glucose—A Report on the Natick Program, U.S. Army, Natick Research and Development Command, Natick, Mass., Sept. 1981. 

The rate of hydrolysis of cellulose acetate can be monitored by removing samples at intervals during hydrolysis and determining the solubiUty of the hydrolyzed acetate. When the desired DS is reached, the hydrolysis is stopped by neutralizing the catalyst with magnesium, calcium, or sodium salts dissolved in aqueous acetic acid. 

Increasingly, biochemical transformations are used to modify renewable resources into useful materials (see Microbial transformations). Fermentation (qv) to ethanol is the oldest of such conversions. Another example is the ceU-free enzyme catalyzed isomerization of glucose to fmctose for use as sweeteners (qv). The enzymatic hydrolysis of cellulose is a biochemical competitor for the acid catalyzed reaction. 

Grain that is usable as food or feed is an expensive substrate for this fermentation process. A cheaper substrate might be some source of cellulose such as wood or agricultural waste. This, however, requires hydrolysis of cellulose to yield glucose. Such a process was used in Germany during World War II to produce yeast as a protein substitute. Another process for the hydrolysis of wood, developed by the U.S. Forest Products Laboratory, Madison, Wisconsin, uses mineral acid as a catalyst. This hydrolysis industry is very large in the former Soviet Union but it is not commercial elsewhere. 

More recently, interest has developed in the use of enzymes to catalyze the hydrolysis of cellulose to glucose (25—27). Domestic or forest product wastes can be used to produce the fermentation substrate. Whereas there has been much research on alcohol fermentation, whether from cereal grains, molasses, or wood hydrolysis, the commercial practice of this technology is primarily for the industrial alcohol and beverage alcohol industries. About 100 plants have been built for fuel ethanol from com, but only a few continue to operate (28). 

Fermentation can be combined with other operations. For example, feedback inhibition of enzymatic hydrolysis of cellulose can be relieved by removal of the product glucose by fermentation as it forms. This is teni ed. simultaneou.s-saccharification-fermentation (SSF). 

Hydrolysis of cellulose acetate membranes is another operational problem and occurs whenever the feed is too acid or alkaline that is, the pH deviates beyond designed range limits. As may readily happen, whenever C02 passes through the... 

Cellobiose (Section 25.14) A disaccharide in which two glucose units are joined by a (3(1,4) linkage. Cellobiose is obtained by the hydrolysis of cellulose. 

The glycosidic bond to an anomeric carbon can be either a or (3. Maltose, the disaccharide obtained by enzyme-catalyzed hydrolysis of starch, consists of two cv-D-glucopyranose units joined by a 1->4-o-glycoside bond. Cellobiose, the disaccharide obtained by partial hydrolysis of cellulose, consists of two /3-o-glucopyranose units joined by a 1—>4-/3-glycoside bond. 

Table VIII.—Rates of Hydrolysis of Cellulose and Its Lower Molecular Homologs in 51 Percent Sulfuric Acid at...

A. Onda, T. Ochi, and K. Yanagisawa, Selective hydrolysis of cellulose into glucose over solid acid catalysts, Green Chem., 10 (2008) 1033-1037. 

The acid-oxidant method is based on the idea that the hydrolysis of cellulose might be continuously determined from the rate of carbon dioxide evolution. Since, under controlled conditions, the rate of evolution of carbon dioxide is proportional to glucose concentration, it should be possible to follow the course of cellulose hydrolysis by means of the rate of carbon dioxide evolution provided that the sole final product of hydrolysis of cellulose is glucose. The latter assumption appears to be justified where the sample is reasonably pure. 

Simultaneous saccharification and co-fermentation (SSCF) one-stage enzymatic hydrolysis of cellulose and fermentation of pentoses and hexoses all in one process step. The upstream hydrolysis of the hemicellulose takes place in a separate process step. 

Levulinic acid is obtained by hydrolysis of cellulose-containing biomass. R D is actively conducted at DuPont Co. to employ levulinic acid for the synthesis of pyr-rolidones (solvents and surfactants), a-methylene-y-valerolactone [monomer for the preparation of polymers similar to poly(methyl methacrylate)], and levulinic acid esters (fuel additives) [26]. 

A new generation of cheap enzymes for hydrolysis of cellulose and lignocellu-lose to fermentable sugars (able to complete the biomass hydrolysis during fermentation). 

Further research is also needed in this area. Particularly, (a) to create a new generation of cheap enzymes for hydrolysis of cellulose and lignocellulose to fermentable sugars (able to complete the biomass hydrolysis during fermentation) (b) to develop improved biocatalysts that allow us to simplify the process and reduce energy input and (c) to improve separation and recovery. 

Scheme 11.—Mechanisms for the Acid-catalyzed Hydrolysis of Cellulose.

The mechanism of the acid-catalyzed hydrolysis of cellulose is based on that normally expected for an acetal (see Scheme 11). This involves formation of a conjugate acid by protonation of either of the acetal oxygen atoms at C-1, and formation of a carbonium ion, followed by stabilization of the product by heterolysis of a participating water molecule. The car-... 

Acid hydrolysis of cellulosic materials that include some hemicellulose, produces D-xylose, D-glucose, and cellobiose, as well as 11, 2-furalde-hyde (5), levulinic acid, formic acid, and acetic acid. In order to lessen the contamination due to hemicellulose, acid hydrolysis is generally performed in two steps dilute sulfuric acid (1%) at 80-120° followed by 5-20% sulfuric acid at 180°. The initial stage removes most of the pentogly-cans (pentosans). 

The effective pretreatments for enzymatic hydrolysis of cellulose in hardwoods and agricultural residues have been developed over the past 90 years and new or improved ones are still being developed. The initial impetus for pretreatment research was the expansion of a feed base for ruminants (i.e., cattle and sheep). The concentration of pretreatment research on animal feed preparation placed an additional burden on researchers, because the product must be not only fully convertible to animal live-weight, but also nontoxic and palatable. Early feeding trials of pretreated fine sawdust to cattle produced very dismal results (55). This may be the reason, besides the... 

Both digester systems exhibit extremely low levels of detectable cellulase activities (exoglucanase, endoglucanase, and -glucosidase) when compared to industrial saccharifying processes (See Table III) in which the hydrolysis of cellulose in the feedstock is optimized with respect to enzyme loading. Therefore, the data indicate the level of improvement that may be made to attain maximum rates for cellulose hydrolysis in the anaerobic reactor system. 

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