Cellulose acid treatment

Cellulose is a high molecular weight polymer of D-glucose with fi( 1 -4)-glycosidic bonds, found in plant fibres it is the major component of most plant tissues. Starch is another common polysaccharide, containing two polymers of glucose, amylose and amylopectin. It was used in some paint preparations and in the production of paper. Acid treatment of starch produces dextrins, which are used as adhesives and additives in water colour paintings. 

The final product was subjected to ferric chloride-hydrochloric acid treatment in the same manner as commercial glucose and starch. A linear carbon dioxide-time relationship was observed which was practically identical with that for starch. In other words purified cotton cellulose, on relatively complete hydrolysis, appeared to give glucose in a... 

Relatively pure xylan isolated from the holocellulose of aspen (Populus) wood is said to contain 85% of xylose residues.78 One of the characteristic properties of xylan is its ease of hydrolysis. Because it hydrolyzes much more readily than cellulose, mild acid treatment may be employed to bring about preferential hydrolysis of xylan from plant material. Xylose is ordinarily prepared in the laboratory by direct sulfuric acid hydrolysis of the native xylan in ground corn cobs.74 Hydrolysis in hydrochloric acid proceeds rapidly, but decomposition to furfural also occurs to some extent.76 A commercial method for the production of D-xylose from cottonseed hulls76 and straw77 and from corn cobs17 78 has been described. 

Chromium and cobalt are the metals most commonly used in dyestuffs for polyamide fibres and leather because of their kinetic inertness and the stability of their complexes towards acid. Since the advent of fibre-reactive dyestuffs, chromium and cobalt complexes have also found application as dyestuffs for cellulosic fibres, particularly as black shades of high light-fastness. Copper complexes are of more importance as dyes for cellulosic fibres and are unsuitable for polyamide fibres because of their rather low stability towards acid treatments. 

These treatments convert to ionic substances, and remove, nearly all constituents of natural materials the acid treatments release any inositol present as phosphate, or combined in phospholipids, glycosides, etc. Glycerol remains in the deionized sample, but it can be oxidized separately, or be removed by heat decomposition or by repeatedly evaporating the solution to dryness. Such polyhydric alcohols of greater chain length as erythritol and mannitol, when present, would still interfere. However, corrections can be made for these compounds by determining the formaldehyde which they form on periodate oxidation, or they may be removed by chromatography on filter paper. The micro-periodate method is well suited to the analysis of samples eluted from filter paper, provided that care is exercised to remove the tiny particles of cellulose which are usually found in such eluates. 

Microcrystalline cellulose (MCC) is obtained by a controlled acid treatment intended to destroy the molecular bonding in the amorphous zones of cellulose. Usually HC1 or H2SO4 are used at 110°C for 15 min over native cellulose or regenerated cellulose. Colloidal gels are thus obtained showing thixotropy. MCC is used in the preparation of pharmaceutical compressed tablets due to its binding and disintegration properties. 

In natural cellulose, the microcrystals are packed tightly in the fiber direction in a compact structure resembling bundles of wooden match sticks placed side by side. Unhinging the interconnecting chains by acid treatment does not destroy this structure. However, the unhinged crystals are now free to be dispersed by mechanical disintegration.. . . We immediately set out to explore this new avenue, developing uses for colloidal dispersions of microcrystalline celluloses, known commercially as Avicel. 

At high concentrations, corrosion-resistant reactors and an effective acid recovery process are needed, raising the cost of the intermediate glucose. Dilute acid treatments minimize these problems, but a number of kinetic models indicate that the maximum conversion of cellulose to glucose under these conditions is 65 to 70 percent because subsequent degradation reactions of the glucose to HMF and lev-ulinic acid take place. The modem biorefinery is learning to exploit this reaction manifold, because these decomposition products can be manufactured as the primary product of polysaccharide hydrolysis (see below). 

Solid-state cellulose can also be noncrystalline, sometimes called amorphous. Intermediate situations are also likely to be important but not well characterized. One example, nematic ordered cellulose has been described [230]. In most treatments that produce amorphous cellulose, the whole fiber is severely degraded. For example, decrystallization can be effected by ball milling, which leaves the cellulose as a fine dust. In this case, some crystalline structure can be recreated by placing the sample in a humid environment. Another approach uses phosphoric acid, which can dissolve the cellulose. Precipitation by dilution with water results in a material with very little crystallinity. There is some chance that the chain may adopt a different shape (a collapsed, sixfold helix) after phosphoric acid treatment. This was concluded because the cellulose stains blue with iodine (see Figure 5.12), similar to the sixfold amylose helix in the starch-iodine complex. 

Surface Activation. Acid Activation. Acid treatment of cellulose and hemicelluloses generally leads to hydrolysis to monosaccharides, which can subsequently dehydrate and condense to form furan-type compounds such as furfural and its 5-hydroxymethyl adduct. Further reactions lead to polymeric materials of dark color as well as to monomers such as levulinic acid, formic acid, and angelica lactones. Various condensation and solvolysis reactions also accompany the acid treatment of lignin 123). The hydrolysis, dehydration, and condensation reactions have been used to explain formation of covalent bonds between surfaces (85), increase in water resistance (85, 124), and weakening of wood (75) in nonconventional plywood or particle board production. However, very little factual information is available on how far, in terms of the consecutive reactions mentioned, and in what direction, in terms of the parallel reactions mentioned, does the surface of lignocellulosic materials actually change... 

Cellulose acetate is prepared from highly purified cellulose by treatment with acid catalysis and acetic anhydride. 

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