Fibre Chem#tt% VoL 32, No.

2, 2000

FABRICATION OF ALKALI CELLULOSE

A.T. Serkov

UDC 677.463.021.122.223

Sheet celhdose is melverized in two stages. In the first stage, 4-6-fold swelling o f the cellulose takes place f o r 30-60 sec, and the alkali peneo'ating the swollen sheet is depleted due to chemical binding o f NaOH. In the second stage, which lasts for 1-2 h, diffusion leveling o f the concentrations takes place, and the amount o f chemically bound NaOH increases by 10-15%. In the continuous method o f sheet melrerization, treatment with alkali lastsf o r 30-60 see, and to ensure the required amount o f chemically bound NaOH, its concentration in the working solution is increased by 10-20%. Bulk mercerization, where cellulose filaments with a cross section o f O.03 mm are accessible to the alkali, takes place in 1-5 see, since the diffusion stage is almost absent in this case. The continuous method o f mercerization o f cellulose in bulk includes the positive aspects o f the process conducted in a VA unit and in UNM-30 continuous mercerization units and is free o f their drawbacks.

Alkali cellulose is an intermediate product in production of viscose fibres and cellulose ethers: carboxymethylcellulose, ethyl- and methylcellulose. In production of cellulose xanthate in viscose plants, the initial cellulose in the form of sheets is treated with an 18-20% solution of NaOH, then the excess alkali is squeezed out so that the product contains 30-32% cellulose, 15-16% NaOH, and 52-55% water. It is hypothesized that half of the indicated amount of NaOH and approximately 1/5 of the H20 is solvate-bound with the cellulose. Treatment of cellulose with an alkali is necessary to break down the crystalline sections in the cellulose fibrils to obtain the readily soluble xanthate. The initial solid product - - cellulose, into which carbon disulfide can diffuse at a very low rate (diffusion coefficient of 10-8 cm2/sec), is essentially converted into a gel, where the diffusion coefficient is close to the value characteristic of aqueous solutions, equal to 10-5 cmZ/sec, which allows conducting the xanthation reaction for the practically acceptable time of 60-90 min. The problem of producing alkali cellulose on the scientific level has two aspects: determining the chemical and physical structure of the alkali cellulose and studying the kinetics of its formation. The first research direction was introduced at the All-Union Scientific-Research Institute of Fibres (SRIF) by its founder, the well-known organic chemist Academician P. P. Shorygin, and developed in the research of Professor Z. A. Rogovin. Many experimental studies were conducted and lively discussions were held on how sodium binds with cellulose - - in the form of alcoholate or an additive compound, and which cellulose hydroxyls - - secondary or primary - - participate in the formation of the alkaline compound. The answers to these questions were probably important for correctly constructing the production process. However, the studies of the kinetics of formation of alkali cellulose was of equal and in my opinion decisive importance. Aleksandr Bemardovich Pakshver, whose hundredth anniversary we are marking, was the founder of this direction. The kinetics of heterogeneous processes, including production of alkali cellulose, is usually complicated by phenomena of heat and mass transfer. The complex study of chemical and physical processes in time invariably requires solving engineering problems related to the correct selection and design of the equipment and construction o f the production process. A. B. Pakshver always called for this and demonstrated examples of the scientific-engineering approach to solving process problems in his works. A. B. Pakshver can be called the ideologue of engineering at SRIF with total justification. He unobtrusively and tactfully conveyed his approach to solving process problems to his students and followers. I wrote my candidate dissertation, in which I particularly investigated the kinetics of formation of alkali cellulose, under the direction of A. B. Pakshver [ 1]. Some of the results obtained are still pertinent even today. There are two methods of determining the amount of sodium hydroxide bound with cellulose: direct and indirect. In determination by the direct method, the excess unbound alkali is washed offthe alkali cellulose with ethyl alcohol, the remaining

All-Russian Scientific-Research Institute of Fibres, Mytishchi. Translated from Khimicheskie Volokna, No. 2, pp. 11-15, March--April, 2000. 0015-0541/00/3202-0095525.00 ~ 2000 Kluwer Academic/Plenum Publishers 95

16 A~"~-- I

q~

O" ~ - -

~o

oY /
O

JO

60

90

T, min

Fig. 1. Amount of chemically bound NaOH ( m ) vs. duration of reaction (~) with direct (1) and indirect (2) methods.

bound hydroxide is titrated with an acid; the cellulose is washed again and then dried; the amount of bound sodium hydroxide is expressed in percentage of the weight of the cellulose. The method gives an approximate result which is a function of the temperature and concentration of water in the ethyl alcohol. In standardized conditions, it was shown that for an 18-20% concentration of NaOH during mercerization, alkali cellulose contains one molecule of sodium hydroxide per glucose residue, i.e., one out of three hydroxyls, hypothetically positioned on the second carbon atom (3'= 100), reacts with the alkali. Despite the observed imprecision, the direct method can be successfully used for kinetic studies when constant conditions are respected, since the reaction of the cellulose with the alkali can be interrupted almost instantaneously after placing the cellulose in ethyl alcohol, which is important in studying the kinetics of formation of alkali cellulose. The concentration of bound sodium hydroxide is determined by the indirect method based on the decrease in its concentration in the mercerization alkali. It has been hypothesized that the decrease in the concentration is due to chemical binding of NaOH by the cellulose. The indirect method also produces approximate results. In addition to binding sodium hydroxide, cellulose chemically (solvate) binds water which on the contrary increases the concentration of NaOH. In addition, the morphological and crystal structure of the cellulose affects the accessibility of hydroxyls for reacting with NaOH and H20. However, assuming that all of these factors are in the equilibrium state, the result is close to the result obtained by the direct method, i.e., one molecule of NaOH per glucose residue (3' = 100). The possibility of utilizing the indirect method for kinetic studies requires additional examination. The kinetics of chemical binding of sodium hydroxide in immersion of cellulose in a solution of NaOH investigated by the direct and indirect methods is shown in Fig. 1. The conditions of treatment and analysis in which ~ = i00 is attained were not observed in the experiment, but this did not affect the shape of the kinetic curves. According to the results obtained by the direct method, the amount of NaOH bound after 1-5 rain is close to the equilibrium amount attained after treatment for 2 h. In the indirect method, on the contrary, binding takes place slowly and a state close to equilibrium is only attained after 60-90 min. These data are typical and were obtained by many investigators. The analysis of these data and explanation of the causes of the different shapes of the kinetic curves obtained in studies by the direct and indirect methods will allow understanding the mechanism of formation of alkali cellulose and finding the optimum conditions for conducting the process. In addition to chemical binding of NaOH, production of alkali cellulose is accompanied by swelling of the cellulose, alteration of the geometric dimensions of the fibres, important release of heat, and destruction of the crystal lattice of the natural cellulose. It is important to note that all of these processes take place in 1-3 min for 80-90% in the equilibrium state and the equilibrium values are attained in 1.0-1.5 h. A comparison of this information with the kinetic data on chemical binding of NaOH leads to the conclusion that 80-90% of chemical binding takes place in the first 1-3 min, it is most correctly described with the direct method, while the indirect method reflects the kinetics of the diffusion process, which lags behind chemical binding. We propose the following mechanism of the reaction of cellulose with an aqueous solution of NaOH. When the cellulose sheet (pulp) is immersed in the solution of NaOH, rapid swelling takes place for 1-3 rain. The cellulose absorbs

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i~

2 8 0 g/iterNll0H

(+/11
2JO g/liter Nil [114

Fig. 2. Diagram of the unit for continuous mercerization of sheet cellulose: 1) cellulose roll; 2) rollers; 3) mercerization trough; 4) squeezer rollers. a 4-6-fold amount of NaOH with respect to the weight. The sodium hydroxide penetrates the cellulose as aresult of capillary wetting together with the medium (water) in which it is dissolved. This transport (together with the medium) is called convective diffusion. The solution of NaOH penetrating the fibre by a mechanism of convective diffusion is immediately depleted due to chemical binding of NaOH by cellulose hydroxyls. A difference in concentrations arises between the outer solution and the solution absorbed by the cellulose as a result of swelling, and it is leveled by slow molecular diffusion from the outer solution to the depleted solution in the swollen cellulose. Due to the low rate of molecular diffusion, leveling of the concentrations takes place slowly (1.0-1.5 h). By measuring the decrease in the concentration in the outer solution, as is done in determining the bound NaOH by the indirect method, we determine the rate of leveling of the concentrations between the outer solution and the solution penetrating the cellulose during its swelling. The indirect method thus reflects the amount of chemically bound NaOH only after leveling of the concentrations and attainment of a state of equilibrium. The correspondence with the well-known Crank diffusion equation is evidence of the diffusion character of curve 2 in Fig. 1:

me __4 (

where mr and m are the amount of bound NaOH at time ~ and on attaining equilibrium; D is the diffusion coefficient; 8 is the thickness of the swollen sheet of cellulose. The average value of the diffusion coefficient calculated with the Crank equation is equal to 0.93.10 -5 cm2/sec. It is constant within the limits of 0.82.10-5-1.1.10 -5 cm2/sec, which is close to the handbook value [2], equal to 1.49.10 -5 cm2/sec obtained for a less concentrated aqueous solution of NaOH. Based on this mechanism of the reaction of cellulose with aqueous solutions of NaOH, it was concluded that the duration of treatment can be reduced significantly if the diffusion part of the process is eliminated. This can be done either by increasing the concentration of NaOH in the working solution or by conducting alkali treatment in bulk. In the first case, the concentration of NaOH in the working solution increases by 10-15%. After swelling of the cellulose sheet in the alkali and chemical binding of some of the NaOH, its concentration in the sheet, despite the dilution, is sufficient to destroy the crystalline sections of the cellulose and obtain alkali cellulose of the given composition. The lengthy diffusion part of the process is superfluous. Alkali treatment is conducted in 30-60 sec. The experimental setup for continuous mercerization of sheet cellulose based on this process produced positive results in testing. Its diagram is shown in Fig. 2. Cellulose roll 1 is unwound with rollers 2 and continuously fed into trough 3 filled with the working solution of NaOH in the concentration of 270-280 g/liter. The residence time of the cellulose in the alkali is 30-60 see. After this time, swelling and chemical binding of NaOH take place. Its concentration inside the sheet decreases to 230-240 g/liter. The swollen sheet enters squeezer rollers where the excess alkali enriched in hemicellulose is squeezed to the given composition. Despite the fact that the experimental setup produced viscose solutions with good filterability, work on its creation did not continue further due to the poor economy of shipping roiled cellulose, since shipment did not allow efficiently utilizing the volume of the railway cars. However, this project could again become pressing if the question of creating a viscose plant in the same industrial installation with a cellulose plant arises. 97

280 g/liter NaOH

1t ----2

~3

Fig. 3. Diagram of the continuous mercerization and squeezing unit: 1) container; 2) jacket for tempering; 3) squeezer rollers; 4) clearance between squeezer rollers; 5) squeezed out alkali cellulose; 6) partitions; 7) serrated pulverizers; 8) cellulose.

The diffusion stage in bulk mercerization is also eliminated by breaking down the cellulose sheets during mixing so that the individual cellulose fibres become accessible to treatment. Their cross section is no greater than 30 ~tm, and diffusion of NaOH in them ends after 1-5 sec. Actually, mercerization is conducted for 15-30 rain, due to incomplete breakdown of the cellulose sheets and caking. The viscose usually used for production of staple fibre contains 9-10% cellulose and 5.5-6.0% NaOH, i.e., approximately 0.6 kg NaOH per 1 kg cellulose. The concentration of NaOH in alkali cellulose does not exceed 0.47 kg/kg (15/32%). The missing 0.13 kg/kg is usually introduced with the solvent alkali. The method of manufacturing alkali cellulose in which alkali cellulose containing the entire amount of NaOH necessary for the future viscose is obtained immediately is also interesting. In this case, mercerization with a calculated modulus or calculated amount of alkali is concerned. This process is conducted in VA units. The alkali cellulose obtained contains 26.5% cellulose and 16.0% NaOH. This method is characterized by great economy, but it has not been widely used due to the periodicity of the process and the inadequate filterability of the viscoses. The output of filtered viscose obtained in VA units does not exceed 1.2 m 3 from 1 m 2 of filtering area, while it attains 2.0-2.5 m3/m2 in the usual process. The impossibility of removing hemicellulose due to the lack of squeezing alkali and the high consumption of carbon disulfide in by-products due to the high concentration of free NaOH in the alkali cellulose were also considered drawbacks of this process. Industrial experience has shown that the last two drawbacks have lost their importance. Hemicellulose is not removed from the squeezed out alkali at almost all viscose plants to increase the profitability. To attain better filterability of the viscose, some plants have switched to use of "wet xanthation," where almost all of the squeezed out alkali is added to the alkali cellulose before xanthation and the composition of the alkali cellulose approaches the composition obtained in VA units. The small increase in CS 2 consumption in by-products is compensated in this case by the decrease in the xanthation temperature to 20-25~ and the related decrease in carbon disulfide losses, as well as the better solubility of the cellulose xanthate. However, the mercerization process with a calculated amount of NaOH is of great interest on the whole due to its simplicity and economy. Letus consider the possibility of overcoming the two remaining drawbacks of production of alkali cellulose in VA units - - the reduced filterability and the periodicity of the process. Mercerization of cellulose with a calculated amount of NaOH solution per 1 kg of cellulose gives a total of 2.1 liters of NaOH solution with a concentration of 280 g/liter, while the cellulose absorbs 4.0-4.5 liter/kg in swelling in alkali of the same concentration. Due to the deficiency of the alkali solution, impregnation of the cellulose is not uniform and even after mixing for 1.5-2-h, unmercerized fibres remain in the reaction mass. Their

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presence in the viscose is the basic cause of the reduced filterability. For uniform impregnation of the cellulose, no less than 4.0-4.5 liters of alkali per 1 kg of cellulose are required, with subsequent squeezing out of the excess solution so that the calculated amount of NaOH would remain in the squeezed out alkali cellulose. Conducting the described production process on existing continuous mercerization equipment will require increasing the ratio of the alkali pulp to 15 liters per 1 kg of cellulose. Technical complications with utilization of the drainage system arise again in using the squeezed out alkali solution, associated with existing continuous mercerization units. At the end of the '80s, we demonstrated the major possibility of production of alkali cellulose with the calculated amount of NaOH in a continuous unit in combining the stages of mercerization and squeezing in one unit in a 1-kg experimental laboratory unit. A diagram of the tested unit is shown in Fig. 3. The unit consisted of container 1 with tempering jacket 2. Squeezer rollers 3 with clearance 4 adjustable from 1 to 5 mm are installed in the lower part. The ends and shafts of the rollers are sealed with gaskets and teflon plates. The rollers rotate with a linear velocity of 1-5 mJmin. The space above the rollers is filled with alkali cellulose pulp formed when cellulose 8 is ground by serrated pulverizers 7 in alkali medium. Partitions 6, which separate the reaction space into three zones - - two outer where the pulp goes to the squeezer rollers, and one inner, through which the squeezed alkali goes up to the serrated pulverizers and is strengthened with a solution of NaOH with a concentration of 270-280 g/liter, are installed above the squeezer rollers. The rotating rollers take up the pulp and squeeze out the excess alkali and the squeezed alkali cellulose in the form of ribbon 5 is delivered for grinding. The rotation rate of the rollers, size of the clearance, temperature of the pulp, and concentration of the strengthening alkali are adjusted so that the concentration of cellulose and NaOH in the alkali cellulose is within the limits of 26-28 and 15-16%, respectively. The described unit combines the positive aspects of VA units and the UNM-30 continuous mercerization unit, while the drawbacks of both of these types of equipment are eliminated. In comparison to the process that takes place in VA units, complete impregnation of the cellulose and continuity of the process are obtained here. With respect to UNM-30 units, the drainage system for removing the squeezed-out alkali is eliminated from the process and it is no longer necessary to filter the squeezed-out alkali solution in transport operations. In addition, the process is not conducted in two units, but in only one. The elimination of the frequently clogged drainage system is especially important in processing cellulose obtained from deciduous species of wood and cellulose containing a large amount of short fibres.

REFERENCES
1.

2.

A. T. Serkov, A. B. Pakshver, and E. M. Mogilevskii, Zh. Prikl. Khim., 30, 303 (1975). Chemical Encyclopedia [in Russian], Vol. 2, Sov. Entsikl., Moscow (1990), p. 199.

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