Cellulose acetate process

The basic cellulose unit contains three hydroxyl groups. The triester cellulose triacetate forms when cellulose is reacted with glacial acetic acid. Hydrolysis removes some of the acetate groups to form a secondary ester, which averages about 2.4 acetyl groups per unit rather than three. The secondary ester is then dissolved in acetone and the solution ejected through a spinneret to form fibers. Cellulose acetate processed in this manner is referred to as acetate rayon, but it may be more commonly known by its trade name Celanese. 

Cuprammonium, Nitrocellulose, and Cellulose Acetate Processes for Rayon... 

A schematic flowsheet for the cellulose acetate process is shown in Figure 11.1. The cellulose sheet is broken up or disintegrated in the shredder. The shredded cellulose is conveyed to the pretreater, where acetic acid is added to pretreat the cellulose. The pretreated cellulose is... 

Since most cellulose acetate processes are of the batch type, it is desirable to blend flakes from many batches. This is done by computer program to obtain a most uniform blended flake on a continuous basis. 

Solution color refers to the yellowness of the cellulose acetate solution. The most meaningful measurement is the yellowness index (YI) for an 18% solution of cellulose acetate in 9/1 methylene chloride methanol (by weight). Measurement is made by the Hunter colorimeter described above. Hemicelluloses in the pulp affect the color of the solution of cellulose acetate, but there are other factors that relate to solution color including brightness of the wood pulp and cellulose acetate processing conditions. 

Secondary Acetate Processes. There is no commercial process to directiy produce secondary cellulose acetate sufficientiy soluble in acetone to produce fiber. Hence, the cellulose is completely acetylated to the triacetate during the dissolution step and then hydrolyzed to the required acetyl value. 

Most cellulose acetate is manufactured by a solution process, ie, the cellulose acetate dissolves as it is produced. The cellulose is acetylated with acetic anhydride acetic acid is the solvent and sulfuric acid the catalyst. The latter can be present at 10—15 wt % based on cellulose (high catalyst process) or at ca 7 wt % (low catalyst process). In the second most common process, the solvent process, methylene chloride replaces the acetic acid as solvent, and perchloric acid is frequentiy the catalyst. There is also a seldom used heterogeneous process that employs an organic solvent as the medium, and the cellulose acetate produced never dissolves. More detailed information on these processes can be found in Reference 28. 

The solution process consists of four steps preparation of cellulose for acetylation, acetylation, hydrolysis, and recovery of cellulose acetate polymer and solvents. A schematic of the total acetate process is shown in Figure 9. 

The precipitated cellulose acetate is filtered from the dilute (25—36%) acetic acid. The acetic acid and salts remaining from the sulfuric acid neutrali2ation are removed by washing. The wet polymer is typically dried to a moisture content of 1—5%. The dilute acetic acid obtained from the washing and precipitation steps caimot be used in other stages of the process. Its efficient recovery and recycle are an economic necessity. 

Cellulose Acetate. The extmsion process has also been used to produce ceUular ceUulose acetate (96) ia the deasity range of 96—112 kg/m (6—7 lbs /fT). A hot mixture of polymer, blowiag ageat, and nucleating agent is forced through an orifice iato the atmosphere. It expands, cools, and is carried away on a moving belt. 

Reverse Osmosis. This was the first membrane-based separation process to be commercialized on a significant scale. The breakthrough discovery that made reverse osmosis (qv) possible was the development of the Loeb-Sourirajan asymmetric cellulose acetate membrane. This membrane made desalination by reverse osmosis practical within a few years commercial plants were installed. The total worldwide market for reverse osmosis membrane modules is about 200 million /yr, spHt approximately between 25% hoUow-ftber and 75% spiral-wound modules. The general trend of the industry is toward spiral-wound modules for this appHcation, and the market share of the hoUow-ftber products is gradually falling (72). 

Membrane Sep r tion. The separation of components ofhquid milk products can be accompHshed with semipermeable membranes by either ultrafiltration (qv) or hyperfiltration, also called reverse osmosis (qv) (30). With ultrafiltration (UF) the membrane selectively prevents the passage of large molecules such as protein. In reverse osmosis (RO) different small, low molecular weight molecules are separated. Both procedures require that pressure be maintained and that the energy needed is a cost item. The materials from which the membranes are made are similar for both processes and include cellulose acetate, poly(vinyl chloride), poly(vinyHdene diduoride), nylon, and polyamide (see AFembrane technology). Membranes are commonly used for the concentration of whey and milk for cheesemaking (31). For example, membranes with 100 and 200 p.m are used to obtain a 4 1 reduction of skimmed milk. 

Plastics and Other Synthetic Products. Sulfur is used in the production of a wide range of synthetics, including cellulose acetate, cellophane, rayon, viscose products, fibers, and textiles. These uses may account for 2% of sulfur demand in developed countries. Sulfur intermediates for these manufacturing processes are equally divided between carbon disulfide and sulfuric acid. 

Other Cellulosics. Rayon is bleached similarly to cotton but under milder conditions since the fibers are more easily damaged and since there is less colored material to bleach. Cellulose acetate and triacetate are not usually bleached. They can be bleached like rayon, except a slightly lower pH is used to prevent hydrolysis. The above fibers are most commonly bleached with hydrogen peroxide. Linen, dax, and jute requite more bleaching and mil der conditions than cotton, so multiple steps are usually used. Commonly an acidic or neutral hypochlorite solution is followed by alkaline hypochlorite, peroxide, chlorite, or permanganate, or a chlorite step is done between two peroxide steps. A one-step process with sodium chlorite and hydrogen peroxide is also used. 

Cellulose Acetate. Almost all cellulose acetate, with the exception of fibrous triacetate, is prepared by a solution process employing sulfuric... 

Solution Process. With the exception of fibrous triacetate, practically all cellulose acetate is manufactured by a solution process using sulfuric acid catalyst with acetic anhydride in an acetic acid solvent. An excellent description of this process is given (85). In the process (Fig. 8), cellulose (ca 400 kg) is treated with ca 1200 kg acetic anhydride in 1600 kg acetic acid solvent and 28—40 kg sulfuric acid (7—10% based on cellulose) as catalyst. During the exothermic reaction, the temperature is controlled at 40—45°C to minimize cellulose degradation. After the reaction solution becomes clear and fiber-free and the desired viscosity has been achieved, sufficient aqueous acetic acid (60—70% acid) is added to destroy the excess anhydride and provide 10—15% free water for hydrolysis. At this point, the sulfuric acid catalyst may be partially neutralized with calcium, magnesium, or sodium salts for better control of product molecular weight. 

Recent Developments. A considerable amount of cellulose acetate is manufactured by the batch process, as described previously. In order to reduce production costs, efforts have been made to develop a continuous process that includes continuous activation, acetylation, hydrolysis, and precipitation. In this process, the reaction mixture, ie, cellulose, anhydride, catalyst, and solvent, pass continuously through a number of successive reaction zones, each of which is agitated (92,93). In a similar process, the reaction mass is passed through tubular zones in which the mixture is forced through screens of successively small openings to homogenize the mixture effectively (94). Other similar methods for continuous acetylation of cellulose have been described (95,96). 

Large quantities of secondary cellulose acetate are used worldwide in the manufacture of filter material for cigarettes. Because of its excellent clarity and ease of processing, cellulose acetate film is widely used in display packaging and extmded plastic film for decorative signs (see Packaging materials). Injection-molded plastics of cellulose acetate are used in toothbmsh handles, computer bmshes, and a large variety of other appHcations (7). 

Pentachloroethane is a good solvent for cellulose acetate, certain cellulose ethers, and for natural gums and resins, but its high toxicity has discouraged these uses. Pentachloroethane is still used as an intermediate in some tetrachloroethylene processes. 

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