Process Biochemistry 38 (2003) 1063 /1067 www.elsevier.

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Enzymic deinking of old newspapers with cellulase

M.A. Pelach a, F.J. Pastor b, J. Puig a,*, F. Vilaseca a, P. Mutje a `
a

` ` ` Laboratori dEnginyeria Paperera i Materials Polmers, Departament dEnginyeria Qumica, Agraria i Tecnologia Agroalimentaria, Escola Politecnica Superior, Universitat de Girona, Girona 17071, Spain b Departament de Microbiologia, Universitat de Barcelona, Barcelona, Spain Received 18 May 2001; received in revised form 2 August 2002; accepted 12 August 2002

Abstract Paper recycling industries are oriented towards re-use and sustainability. These effects are combined in different ways to achieve the requirements on printing and writing papers. Biodeinking is an alternative analysed in this study. Cellulase uses improve ink detachment from old newspapers giving similar or better results when cellulase is used in place of classical chemicals. Cellulase needs an optimal contact time with the pulp suspension. Ink detachment can also be optimised by means of defibering efficiency and specific energy consumption. Increasing the consistency and decreasing the repulping time enhance savings and therefore sustainability. These two parameters are analysed in terms of shear factor l . # 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Biodeinking; Repulping; Ink detachment; Cellulase; Old newspaper; Shear factor

1. Introduction Sustainability requires proper management of both natural resources and energy, as well as feasible recycling of wastes and methods for increasing production without environmental concern. Paper recycling represents a subsection of the paper industry that is being oriented towards re-use and sustainability. The main implications of this process are the preservation of important woodland resources and energy saving. Moreover, with the recycling of this kind of waste, two significant purposes are attained: (i) the elimination of large quantities of residual materials and (ii) the added value of the pulp. In the paper recycling industry, deinking is necessary to achieve minimum brightness values required for printing and writing papers. A typical deinking process starts with disintegration of recycled paper. This step is generally carried out by the addition of chemicals in a strong alkaline medium in order to promote defibering and ink particle detachment. Subsequently, washing or

* Corresponding author. Fax: '/34-972418399 E-mail address: josep.puig@udg.es (J. Puig).

flotation technologies, generally in mild alkaline media, allow ink removal from the suspension. Biodeinking is proposed as an alternative to the use of chemical products at the disintegration stage. The proposed methodology uses a neutral medium, which allows the reduction of the contaminant charge and is comparatively more suitable for the maintenance of the environment. Different kinds of cellulase enzymes are used to facilitate ink detachment, essential in the deinking process for the removal of the ink later [1,2]. The application of cellulase in deinking is a recent methodology and contradictory results have been published. In addition, the proposed mechanisms of cellulase functioning in deinking are different. According to Wodward et al. [3], cellulase binding on pulp fiber may result in surface fiber alteration, sufficient to favour detachment during repulping. Nevertheless, other authors reported that the main effect is the hydrolysis and superficial degradation of cellulose that implies ink removal from fibers [4 /6]. It has also been reported that enzymic and mechanical actions are basic in the process [7]. Enzymic deinking increases in effectiveness on increasing the disintegration consistency caused by a higher friction between fibers. Conversely, Putz et al. [8] minimise the importance of the mechanical action in the enzymic process.

0032-9592/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 0 3 2 - 9 5 9 2 ( 0 2 ) 0 0 2 3 7 - 6

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This study evaluates the use of industrial enzymes (cellulases) as an alternative to classical disintegration process of recycled papers. Defibering and ink detachment are analysed as quality parameters of the process [9]. A possible choice is also analysed for the optimisation of mechanical disintegration conditions to promote considerable energy saving.

with a maximum diameter of 26.6 cm. Pulcell is equipped with a measuring power and energy system. This pulper was characterised reologically according to Metzner and Otto [12] expressed by Eqs. (1) and (2). This allows the calculation of the shear factor l (Pa s) of the suspension from the net power measured during repulping: Np 0 7:76Re(0:232 Fr(0:597 ; (1) (2)

2. Materials and methods The materials used in the experiments consisted of old newspaper (ONP) with a basis weight of 40 g/m2. This paper was composed of 90% thermo-mechanic pulp bleached with magnesium bisulphide (59% ISO) and 10% of filler. The paper was printed by the offset method. Cromogenia S.A. (Spain) supplied the enzymes used, called E1 and E2, from Novozymes. Enzyme E1 is a monocomponent produced by means of genetic selection. Enzyme E2 is a multicomponent product. These enzymes were well characterised on different substrates using the methods of Nelson and Somogyi [10] and Mandels et al. [11]. Table 1 shows the results, expressed in international units (IU), obtained during this characterisation. One International Unit (IU) is defined as the amount of enzyme necessary to produce 1 mmol of reducing sugar per minute under specified conditions of substrate concentration, pH and temperature. A higher activity was found in enzyme E2 with respect to E1 in the studied substrates. Despite that the results obtained in the assay on the non-printed newspaper were quantitatively similar. The old newspaper to deink was soaked with enzymes E1 and E2 both at 0.75 and 2.25% consistency, based on dry matter. The total volume was 20 l and the soaking time was 0.5 and 2 h for each formulation. Two paper consistencies were used: 6 and 10% over fiber-dried weight. The pH of the suspension was 6.5 and the temperature 60 8C in agreement with the specification of the enzymes. Repulping was carried out in a Pulcell cell from Metrotec S.A. (Spain), based on a Voith cell. Its total volume is 50 l and it was equipped with a helical rotor
Table 1 Enzymic activity (UI/mg enzyme) of E1 and E2 on CMC, avicel, xylan, and non-printed newspaper Enzyme Enzymic activity (UI/mg enzyme) CMCa E1 E2
a b

l0 6:085P4:31 r(3:31 n(6:78 ; n

where Np is the Newton number, Re the Reynolds number, Fr the Froude number, Pn the net power consumption (W), r the suspension density (kg/m3), n the rotor frequency (s (1). The conditions applied to characterise the pulper were temperature (50 8C), consistency (6 and 10%), and agitation rate (26.16 s (1). Repulping time (tD) was determined by means of Sommerville index (ISV), considering that pulp quality was correct when ISV B/0.1%. The Sommerville index measurement was performed with an apparatus equipped with a metallic sieve of 765 gaps, 45 mm long )/0.075 mm wide. The experiment was carried out according to Tappi method UM242. The measure of the ink amount present in the paper and its agglomeration degree was performed using the effective residual ink concentration (ERIC). This parameter is measured with Technibrite Micro TB-1C from Technidyne Corporation according to Tappi method T567. ERIC is the ratio of the absorption coefficient of pulp or paper, which contains ink, to the absorption coefficient of the ink itself as determined at 950 wavelength. ERIC units may be expressed as unitless or as parts per million (ppm). The ERIC method employs reflectance measurements in the infrared region of the spectrum where the absorption coefficient for the ink is several orders of magnitude greater than the absorption coefficient of the fiber and other components. Disintegrated pulp was submitted to a hyperwashing step to analyse the amount of non-detached or redeposited ink. The hyperwashing step consisted of washing the suspension on a 60-mesh screen with abundant tap water for 10 min [13]. An ink detachment parameter (InkD) was included to quantify the amount of ink that can be eliminated by flotation or washing operations. This parameter is defined as InkD 0 ERICD ( ERICHW ERICD )100; (3)

Avicela 0.003 0.022

Xylana 0.002 0.739

Non-printed newspaperb 0.035 0.039

0.055 0.327

Nelson /Somogyi method. Mandels method.

where ERICD is ERIC of disintegration handsheets (ppm), ERICHW, ERIC of hyperwashing handsheets (ppm).

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To compare enzyme application with traditional chemicals added in the disintegration stage, additional experiments using sodium hydroxide and hydrogen peroxide were carried out. Disintegration consistency was maintained constant and the ratio of sodium hydroxide to hydrogen peroxide was 1:1.

Table 3 Effect test of variables over InkD Variables Enzyme type Enzyme concentration Disintegration consistency Contact time D.F. Sum of squares 1 2 1 1 0.81 364.84 192.67 43.20 F -ratio P  F 0.11 24.09 25.44 5.70 0.75 0.00 0.00 0.03

3. Results and discussion The literature consulted on the topic of study reports that enzyme application to deinking is usually at a rate of 0.05 and 0.1%. In the first experiment, this was rather ineffective and did not show hopeful results. Consequently, the applied enzyme percentage was increased to 0.75 and 2.25%. Table 2 shows the results of ink detachment (InkD, %) as a function of concentration of enzyme, type of enzyme, disintegration consistency (cD) and contact time between enzymes and pulp suspension. The results indicate that there was a substantial improvement in ink detachment by enzyme application. Nevertheless, in addition to the enzyme percentage activity, two other variables may affect the interpretation of results such as repulping consistency and contact time. The significance of both variables was corroborated by statistical analysis (Table 3). Values obtained for the two disintegration consistencies without enzyme application indicate that increasing contact time produced better values of InkD. These findings indicate that previous contact of the old newspapers with hot water may favour the subsequent release of the ink from the paper. It is possible that soaking time either weakens the ink binding property on the old newspaper or favours its disruption thereby improving overall ink detachment. The magnitude of improvement was similar in 6 and 10% formulations. Values of detachment factor (InkD) in enzyme-less experiments increased considerably from 6 to 10% of consistency. This finding was attributed to the shear strength factor (l ) of the suspension under the operating
Table 2 Values of InkD (%) obtained as a function of concentration and type of enzyme, disintegration consistency (cD, %) and contact time (t , min) between enzymes and pulp suspension cD (%) t (min) InkD (%) E1 0% 6 10 30 120 30 120 65.2 67.7 74.2 80.4 0.75% 79.4 79.4 76.1 81.9 2.25% 76 78.4 81.8 84.5 E2 0% 65.2 67.7 74.2 80.4 0.75% 77.1 77.3 79.6 80.9 2.25% 80.2 79.6 82.1 85.1

Influence of enzyme type, enzyme concentration (%), disintegration consistency (%), and contact time (min).

conditions that shifts from 0.35 Pa s at 6% consistency to 2.44 Pa s at 10% consistency. The term l represents the global quantification of the strengths involved in a detachment process such as mechanical impact on the rotor, pulper baffles and walls, and both acceleration and viscosity [13,14]. The increase of InkD is therefore logical when the consistency also increased, because the higher shear strength between the fibers produced a higher detachment. It was also observed that InkD did not vary significantly with increasing soaking time when no enzyme was added to pulp suspension even at higher consistency. Referring to the enzyme activity, results obtained and statistical analysis applied have shown that it is not significant. ERICHW results obtained with different enzymes were compared with classical chemicals (Table 4). The detachment degree obtained with a mixture of 1% NaOH'/1% H2O2 was of the same order or smaller than that obtained with the application of E1 and E2 under the same operating conditions. This indicates that products such as enzymes considered more sustainable could substitute classical chemistry. Results of E1 and E2 trials did not allow decisive conclusions because the difference in activity was rather small as was shown in the preliminary trials on nonprinted newspaper. Moreover, values were considerably different from those obtained with other substrates (Table 1) where a marked difference between E1 and E2 was found. This may mean that the evaluation of enzymic activity or enzyme behaviour must be evaluated using similar substrates. On the other hand, very promising results of ERIC from hyperwashing were found (Table 5). By comparing InkD values with results obtained with conventional deinking (Table 4), a significant improvement in the
Table 4 Values of ERIC (ppm) of hyperwashing handsheets obtained with conventional disintegration stage ERICHW (ppm) 1%NaOH'1%H2O2 2%NaOH'2%H2O2 250 310

Disintegration consistency: 6%; contact time: 30 min.

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Table 5 Results of effective residual ink concentration (ERICHW, ppm) of hyperwashing handsheets as a function of concentration and type of enzyme and contact time at constant disintegration consistency (10%) t (min) ERICHW E1 0.75% 30 120 218 147 2.25% 166 165 E2 0.75% 198 185 2.25% 174 145

repulping step was observed. This may be beneficial for the whole suspension in order to obtain a high-quality deinking either through washing or flotation. Ink detachment was strictly related to defibering efficiency and specific energy consumption. Optimisation of ink detachment and environmental protection could be analysed by these two concepts. The main purpose of defibering is the individualisation of the flakes so as to obtain a suitable suspension for subsequent paper production, and the overall objective was to produce at minimum cost with possibly low energy consumption. In addition, by controlling the defibering time (energy consumption) it is possible to avoid the excessively fragmented ink, which may reprecipitate into the fibers, a phenomenon that may make complete elimination impossible. The study of disintegration as a function of time provides the pulping kinetics. These show that the evolution of Sommerville index (ISV) fitted a first-order kinetic equation. The evolution of ISV as a function of time for 6 and 10% consistency with 18.33 s (1 rotor speed and 50 8C temperature was determined. Using this kinetics, it is possible to determine the repulping time corresponding to ISV 5/0.1% which in this case was 4 and 14 min for 6 and 10% consistency, respectively. Higher values of repulping time may be detrimental for complete ink removal, either due to an excessive fractionation that leads to lower-sized particles, or by redeposition into the lumen fibers.
Table 6 Total energy consumption (kJ) in function of time (t , min) at different disintegration conditions (cD, %) t (min) Total energy consumption (kJ) cD 0 0% 2 4 6 8 10 12 14 50 100 147 194 237 280 327 cD 0 6% 152 280 416 549 676 807 939 cD 0 10% 201 378 554 720 892 1054 1229

Table 6 shows the evolution of energy consumption of 6 and 10% suspensions and the energy consumption in empty conditions. With these results, it is possible to calculate the net power. Values achieved were 728.6 W for 6% and 1113.3 W for 10% consistency. Substituting these values in expression (2) together with the respective densities and the frequency of the rotor gives the following shear factor values: 0.35 Pa s for 6% and 2.44 Pa s for 10%. Specific energy consumption (kJ/ton) is calculated by considering the tD and the energy consumption values. Results corresponding to 6 and 10% consistency (tD, 14 and 4 min, respectively) were 782.5 and 189.0 MJ/ton. This shows the advantages when experiments were carried out with high consistencies during repulping where the defibering and energetic efficiency were higher as a consequence of l increase with consistency.

4. Conclusions The use of cellulase-type enzymes may represent an alternative to conventional chemicals in repulping of old newspaper. With low consistency (6%) and reasonable contact time (30 min), the enzyme efficacy was equivalent or higher to that obtained by means of conventional deinking. For this same consistency and 120 min of contact time, the efficacy did not improve. For a medium consistency (10%) and 30 min of contact time the efficacy decreased, although the absolute detachment values improved. This behaviour was similar for a contact time of 120 min. Despite the different activities of the two investigated enzymes on the diverse substrates, this difference was not observed in deinking. Nevertheless, these results coincide with the observed activity on the non-printed paper. As a final conclusion, it can be stated that the behaviour of the two enzymes in deinking was similar and that the results improved slightly on increasing both the contact time and the enzyme amount. From an energetic point of view, increasing the consistency because of the decrease in the repulping time enhanced savings. Moreover, the effect of a higher consistency on the ink detachment was very positive because of the shear forces increase. This effect was also observed without enzymes.

Acknowledgements The authors would thank G. Pardini and M. Font for their contribution and also to Cromogenia S.A.

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