Abstract
A novel mathematical model is reported for end-point control during displacement kraft pulping. The model was based on an on-line process that measured the dissolved lignin content in cooking liquor using an attenuated total reflection ultraviolet spectroscopy method that had been developed previously, from which a relationship between the pulp kappa number and integrated dissolved lignin content was established. The results showed that there was good agreement between the pulp kappa numbers measured by the presented model and TAPPI standard method. The presented method is straightforward and accurate and has the potential for on-line process control in mill operation.
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A Dissolved Lignin Monitoring-based Model for End-point Control during Displacement Kraft Pulping
Li-Ping Xin,a,b,* Bo Yu,a and Yuguo Zhou a
A novel mathematical model is reported for end-point control during displacement kraft pulping. The model was based on an on-line process that measured the dissolved lignin content in cooking liquor using an attenuated total reflection ultraviolet spectroscopy method that had been developed previously, from which a relationship between the pulp kappa number and integrated dissolved lignin content was established. The results showed that there was good agreement between the pulp kappa numbers measured by the presented model and TAPPI standard method. The presented method is straightforward and accurate and has the potential for on-line process control in mill operation.
Keywords: Dissolved lignin; Cooking liquor; Kappa number; Displacement kraft pulping; Yellow bamboo; End-point control
Contact information: a: School of Information and Control Engineering, Qingdao University of Technology, Qingdao, Shandong, China; b: State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou, China; *Corresponding author: lpxin@qut.edu.cn
INTRODUCTION
Presently, kraft pulping (using NaOH and Na2S as the cooking agents) is the dominant process worldwide for the production of chemical pulps (Brown 2014). Among the kraft pulping methods, displacement cooking (i.e. SuperBatch, Enerbatch, and Rapid Displacement Heating) has a number of advantages over conventional batch cooking, which is accomplished with a batch digester connected to multiple intermediate liquor holding tanks. The biggest advantage is that such cooking process options can avoid the extensive degradation of hemicelluloses/cellulose during the initial cooking phase caused by high alkalinity and the condensation of dissolved lignin on the pulps at the end of cooking caused by low alkalinity (Sixta 2006). In kraft pulping, the pulp kappa number represents the degree of delignification and is an important parameter for determining the cooking end-point (Pelzer et al. 2013). But there is difficulty in realizing a real-time determination of the pulp kappa number. Because of the pulping process with high temperature and high pressure, it is almost impossible to sample from the pressure-tight digester. Therefore, an effective model for determining the end-point during displacement kraft pulping is highly desired.
Currently, there are many models available for the prediction of pulp kappa numbers during conventional batch cooking processes (Vroom 1957; Chari 1973; Hatton 1973; Tasman 1981; Christensen 1982; Gustafson et al. 1983; Kesavan et al. 2000; Lee and Bennington 2007). Because of the complexity of the fundamental models (Tasman 1981; Christensen 1982; Gustafson et al. 1983), empirical or semi-empirical models (Vroom 1957; Chari 1973; Hatton 1973; Kesavan et al. 2000) based on the initial chemical charges (i.e., concentration of hydroxide and sulfide), H-factors (time and energy integrated parameter), and pulping raw material are typically adopted in mill applications. However, the major problem of these models is their feasibility because the raw pulping material uniformity (e.g. the diversity of wood species and tree-age) has a notable impact on the accuracy of the pulp kappa number prediction (Santos et al. 2015). Therefore, models based on the on-line monitoring of the concentrations of chemical parameters, such as residual alkali, sulfide, and dissolved lignin in the cooking liquor, have been developed (Kerr 1976; Michell 1990; Venkateswarlu and Gangiah 1992; Vanchinathan and Krishnagopalan 1995; Masura 1999; Saucedo and Krishnagopalan 2000). These models provide more reliable pulping control because the changes in these chemical parameters have direct connections to delignification. Unfortunately, there are currently no chemical monitoring-based models available for displacement batch pulping because such cooking systems are more complicated than conventional batch cooking systems. Instead, pulping control in displacement batch cooking systems is mainly based on measuring the pulp kappa number by either on-line sensors (Faix et al. 1988; Chai et al. 2000; Trung et al. 2009) or an off-line titration method (T 236 om-99 1999) at the washing stage after the termination of pulping. As such, the kappa number information obtained from these methods has such a major time-tag that it is usually measured too late for use in controlling the pulping process. Moreover, although the kappa number information might be helpful for a feedback control mode, these methods fail to determine where the raw materials (wood species and compositions) vary remarkably (Faix et al. 1988; Chai et al. 2000; Trung et al. 2009; T 236 om-99 1999). Therefore, the development of a real-time model for end-point control in a displacement kraft pulping system is highly desired.
In this study, a new model was developed for end-point control during the batch displacement kraft pulping process with yellow bamboo. The model was based on on-line monitoring of dissolved lignin in the cooking liquor from three different stages: impregnation, hot displacement, and heating/cooking. The main focuses were to find the relationship between the pulp kappa number and integrated dissolved lignin content in the cooking liquor, the establishment of a dissolved lignin-based model for predicting the pulp kappa number, and application of the model in a lab-scale displacement kraft pulping process. The present model is straightforward and accurate and has great potential to be adopted for on-line process control in mill operations.
EXPERIMENTAL
Materials
The pulping chemicals, NaOH and Na2S, were purchased from commercial sources. The yellow bamboo chips (approximately 30 mm × 20 mm × 4 mm) were obtained from the Jinghong bamboo forest in Yunnan province, China, from bamboo approximately three years old. The chips were washed and then air-dried at room temperature.
Apparatus
A lab-scale digester (10 L, 2110-2, Greenwood, Kansas, USA) system with three custom-made 5-L pressurized tanks containing warm black liquor (WBL, Tank A), hot black liquor (HBL, Tank B), and hot white liquor (HWL, Tank C) was used during displacement pulping. The pressurized tanks had the capability for not only heating the cooking liquor to the desired temperatures, but also injecting the liquor into the digester by the metering pump to displace some portion of the cooking liquor in the digester at different cooking stages.
An ultraviolet (UV) spectrophotometer (UV-8453, Agilent, Palo Alto, USA) equipped with a peristaltic pump (RP-1, Rainin, Oakland, CA, USA), some tubing and connectors, and an attenuated total reflection (ATR) flow-cell (TNL-120H23-3, Axiom, New York, USA) was used to monitor the lignin in the cooking liquor at selected locations. The spectral data of the dissolved lignin was recorded by a computer.
Pulping Process
During the pulping process, 1.2 kg of yellow bamboo chips (oven-dried) were placed in the digester. The white liquors were prepared using NaOH and Na2S with de-ionized water.
Fig. 1. Schematic flow diagram of the simulated displacement pulping process
Table 1. Pulping Conditions
* The alkali ratios at the initial, middle, and final cooking stages were 10%, 30%, and 60%, respectively.
The effective alkali (EA) charge, i.e., EA = [NaOH] + 1/2 [Na2S], was maintained at 18%, 20%, and 23% of the oven-dry feedstock. The sulfidity ([Na2S]/([Na2S] + [NaOH])) was maintained at 15%, 20%, 25%, and 30%. The alkali ratios used in the initial, middle, and final cooking stages were 25%, 25%, and 50%, respectively. The liquor-to-feedstock ratio was 4.5 L/kg. The EA or sulfidity in the black liquor was adjusted by adding stock solutions of NaOH and/or Na2S. The preset maximum cooking temperatures were 140 °C, 150 °C, 160 °C, and 170 °C. The holding times at the maximum temperature were 90 min, 120 min, and 150 min. Table 1 shows a detailed description of the experimental conditions. Figure 1 is the schematic flow diagram of the simulated displacement pulping process.
Liquor and Pulp Analysis
The cooking liquors at the lower inlet, upper outlet, and middle circulation screen of the digester were sampled, and the dissolved lignin content in the liquors was determined using the ATR-UV spectroscopic method from the literature (Aulin-Erdtman and Sanden 1968; Chai et al. 2003a,b).
The kappa number of the final discharged pulp was measured by the TAPPI standard method T 236 om-99 (1999).
RESULTS AND DISCUSSION
Content Profile of the Dissolved Lignin in the Cooking Liquor during the Displacement Pulping Process
Figure 2 shows the content profiles of the dissolved lignin in the cooking liquors in the three stages during displacement pulping, i.e., the initial cooking stage with the WBL, the middle cooking stage with the HBL, and the final cooking stage with the HBL and HWL.
Fig. 2. Changes in the dissolved lignin content in the pulping liquor during the different cooking stages
It was found that the dissolved lignin content slightly decreased in the initial cooking stage, which was because the adjusted WBL was diluted by the moisture in the bamboo chips. The dissolved lignin content in the middle cooking stage slightly increased, which was because the temperature and EA charge were not sufficient for fast delignification. However, it was observed that major delignification took place during the first 50 min in the final cooking stage, where the EA charge was high (39.1 g/L to 25.2 g/L) and the temperature of the cooking liquor reached 160 °C. As a result, the net increase in the lignin content in the cooking liquor was approximately 34.7 g/L. After 200 min, the increase in the dissolved lignin in the cooking liquor was not major, which meant that pulping should be terminated during this period.
Relationship between the Pulp Kappa Number and Total Dissolved Lignin in the Pulping Liquor during the Batch Process
Figure 3 shows the relationship between the pulp kappa number (measured by TAPPI Method T 236 om-99 (1999)) and integrated dissolved lignin in the pulping liquors during the batch processes with different pulping conditions (such as high or low sulfidity, with or without pulp additives, and different temperatures) measured by the ATR-UV method (Chai et al. 2003a). It was observed that there was an inverse relationship between the pulp kappa number and integrated dissolved lignin. It was found that the R2 and the root mean square error (RMSE) were 0.95 and 1.07 respectively, using the inverse proportion function:
(1)
Therefore, the integrated dissolved lignin in the cooking liquor can be regarded as a reliable indicator of the degree of delignification during the batch pulping process.