Cellulosic materials hydrolysis

The most common material used is cellophane, which is a cellulose film, which acts as a membrane and is capable of resisting zinc penetration. The cycle life of cells utilizing this material is severely limited due to the hydrolysis of the cellophane in alkaline solution. Various methods have been tried to stabilize cellulose materials, such as chemical treatment and radiation grafting to other polymers, but none have, as of now proved economically feasible. The most successful zinc migration barrier material yet developed for the nickel—zinc battery is Celgard microporous polypropylene film. It is inherently hydrophobic so it is typically treated with a wetting agent for aqueous applications. 

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 advances made in enzymatic hydrolysis of cellulosic materials (14) are also of interest. This technology involves only moderate temperature processes in simple equipment which promises to be of significantly lower capital cost than the pressure equipment associated with conventional acid wood hydrolysis processes. All of these considerations combined to lead us to study processes for ethanol production from wood, especially in an effort to obtain data for material and energy balances, and possibly for the economics. 

Two broad areas of application for xylanolytic enzymes have been identified (1). The first involves the use of xylanases with other hydrolytic enzymes in the bioconversion of wastes such as those from the forest and agricultural industries, and in the clarification and liquification of juices, vegetables and fruits. For these purposes, the enzyme preparations need only to be filtered and concentrated as essentially no further purification is required. Several specific examples of applications involving crude xylanase preparations include bioconversion of cellulosic materials for subsequent fermentation (2) hydrolysis of pulp waste liquors and wood extractives to monomeric sugars for subsequent production of single cell protein (3-5). Xylose produced by the action of xylanases can be used for subsequent production of higher value compounds such as ethanol (6), xylulose (7) and xyIonic acid (8-9). 

Cornelius Steelink Perhaps plant cellulosic material, after hydrolysis, could be used by soil microorganisms to produce phenolic substances, which could then be incorporated into humic acids. I think it is significant that nonlignin-derived phenols occur in podzol humic acids. 

A few animals (especially ruminants and termites) are able to metabolize cellulose, but even these animals depend on appropriate microorganisms in their intestinal tracts to hydrolyze the -1,4 links other animals, including man, cannot utilize cellulose as food because they lack the necessary hydrolytic enzymes. However, such enzymes are distributed widely in nature. In fact, deterioration of cellulose materials —textiles, paper, and wood —by enzymatic degradation (such as by dry rot) is an economic problem that is not yet adequately solved. Efforts to turn this to advantage through enzymatic hydrolysis of cellulose to glucose for practical food production have not been very successful (see Section 25-12). 

While this reaction is substantially exothermic (6), it provides an intriguing approach to the production of fuels from renewable resources, as the required acids (including acetic acid, butyric acid, and a variety of other simple aliphatic carboxylic acids) can be produced in abundant yields by the enzymatic fermentation of simple sugars which are, in turn, available from the microbiological hydrolysis of cellulosic biomass materials ( ] ) These considerations have led us to suggest the concept of a "tandem" photoelectrolysis system, in which a solar photoelectrolysis device for the production of fuels via the photo-Kolbe reaction might derive its acid-rich aqueous feedstock from a biomass conversion plant for the hydrolysis and fermentation of crop wastes or other cellulosic materials (4). 

Acid hydrolysis of cellulosic materials has been studied for many years (13,33). Although it is a relatively straightforward process, it has the problems of requiring acid-resistant equipment and yielding a poor grade of sugar (because the product contains many reaction product impurities). However, in terms of practical application, acid hydrolysis of cellulosic material is by far the most commonly used hydrolysis system. 

Cellulosic materials are quite variable from source to source, not only in cellulose, hemicellulose, and lignin content but also in the crystallinity of the cellulose. As a consequence, each natural substrate would be expected to have its own unique set of process conditions to optimize glucose yield and minimize secondary product contamination. The next section on kinetics of acid hydrolysis will examine this point. 

A considerable amount of experimentation has been done on the kinetics of acid hydrolysis of pure cellulose substrates. Little experimentation has been done on natural cellulosic materials. Typical examples of kinetic studies of acid hydrolysis of cellulose can be found in the papers of Saeman (33) and Grethlein (13). These researchers depict the acid hydrolysis process as a pseudo-first-order sequential process, with the rate constants as a function of the acid concentration raised to a power, i.e.,... 

Table III. Acid Hydrolysis Constants for Various Cellulosic Materials...

Both pilot-plant and plant-scale processes for cellulose hydrolysis or digestion by acids, enzymes, and microorganisms have been built (I, 7,15,27). Acid and enzyme processes usually have as their objective the production of a sugar syrup, while the microbial process usually results in microbial protein for animal feed. Figure 10 is illustrative of a microbial process (29) that has been developed to convert the unused cellulosic material in manure to recycle feed. Similar processes have been developed... 

Influence of Fine Grinding on the Hydrolysis of Cellulosic Materials—Acid Vs. Enzymatic... 

The whole procedure normally takes about 1 hr. The acid is then evaporated, and the dry matter can be analyzed. This method can be applied to cellulose from wood, as a-cellulose or pulp, or to other celluloses (e.g., cotton) as well as to cellulosic materials with higher amounts of other polysaccharides (e.g., holocellulose). The chromatograms of the hydrolysates of a-cellulose from beechwood and of holocellulose from sprucewood (Figure 6) are examples of the application of this method. Compared with sulfuric acid hydrolysis, the total sugar yield from the spruce holocellulose is higher after the hydrolysis with concentrated TFA (Table II). Regarding the individual sugars, it can be seen that the... 

Some additional experiments have been conducted in which a direct analysis was employed.27 Cellulosic materials were boiled in 2.5 N sulfuric acid for varying times and the hydrolyzates were quantitatively examined for glucose. A modification of the glucose method of Hassid28 was employed. This approach was designed to give more accurate information on the early stages of the hydrolysis than could be obtained by other methods. 

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