Remediation of lignin and its derivatives from pulp and paper industry wastewater by the combination of chemical precipitation and ozonation

https://doi.org/10.1016/j.jhazmat.2009.03.152Get rights and content

Abstract

In the present work the degradation of the lignin and its derivatives in the residual water of a paper industry by simple ozonation was investigated. The remediation of lignin was realized using the combination of the pre-treatment with chemical precipitation, using concentrated sulfuric acid (97.1%) at the pH 1 and 3, and of the simple ozonation of the filtered residual water at the pH 1, 3, 8 and 12. Since the high residues content (the initial chemical oxygen demand (COD) is 70,000 mg/L) in the experiments the diluted samples (1:10) were used. The previous precipitation has showed a significant effect on the reduction of the COD (77%) and color (96.1%). The sludge precipitated contents sulfolignin, which in the reaction with sulfuric acid was formed. In ozonation of the filtered residual water during 25 min at the pH 1, 3, 8 and 12 the follows by-products were formed: fumaric, maleic, malonic and formic acids. The biodegradability of the treated water in ozonation increases up 0.067–0.29. The effect of the precipitation and the ozonation conditions on the decolorization kinetics was evaluated.

Introduction

The pulp and paper industry has been considered as one of the biggest consumers of natural resources (wood, water) and energy (fossil fuels and electricity) and as a significant taxpayer of discharge of pollutants to the environment [1], [2], [3], [4]. The wood pulping and production of the paper products generate a considerable amount of pollutants characterized by biochemical oxygen demand (BOD), chemical oxygen demand (COD), suspended solids (SS), toxicity, and color when untreated or poorly treated effluents are discharged to receiving water. Pulp and paper mills generate varieties of pollutants depending upon the type of the pulping process [5]. This is made from cellulose fibers, carbohydrates as sugar and lignin, and is adhesive substance for the cellulose fibers [4]. The current environmental limitations have caused the decrease of the consumption of the natural resources for this industrial use. So, in this industry the recycling of fibrous raw materials and/or alternative is [6], [7]. The high water usage, between 20,000 and 60,000 gallons/t of products [8], results in large amounts of wastewater generation. The water consumption dependents on the technology and the product obtained [9], [10]:

  • Carton: 3–8 m3/t of product.

  • Newspaper: 10–15 m3/t of product.

  • Papel tisú: 15–20 m3/t of product.

  • Writing paper: 10–20 m3/t of product.

The sources of the contamination of the circuits of water in the production of the paper and cardboard are as follows: the fibrous raw materials, the additives and the feeding water, which provide a lot of pollutants such as resinic acids, wax, as well as lignin and their derivates, organic chlorides, dioxins, benzophenils, etc. It is well known that the process of paper production generates a high grade of contamination on the environment [1], [2], [3], [4], [11], so much for the discharge volumes like for its content. This process has limited ability to provide effluents of high-quality conforming to stringent regulations, since large amounts of lignin and lignin-derived compounds remain in the wastewater. These effluents are characterized of high coloration, suspended solids, unstable pH, high COD and DBO5, besides chlorides, sulfate, etc. [11], [12], [13], [14], [15]. On the other hand, these pollutants can be carcinogenic, due to the chlorine lignin and chlorine phenols that are formed along the process [15], [16], [17]. The chemical structure of lignin as the principle residue is not defined. It is known that it is a natural irregular biopolymer, which consists of phenyl propane units with various substitutes (single bondOCH3, single bondOH, single bondCOOH) combined with bonds of different types [18], [19]. An important group of compounds is responsible for the toxicity of this residual water and may adversely affect the microbial systems in the bioreactors [14], [15], [20], [21], [22]. These compounds are resistant to the biodegradation, because generally they are toxic products with the most complex structures [7], [18], [23]. Makris and Banerjee [24] studied the fate of the resinic acids in the secondary treatment system. The resinic acids are toxic components with securities of 0.4–1.1 mg/L [15]. Many authors reported the presence of toxic species in fish or toxic effects on fish such as respiratory stress, mixed function oxygenase activity, toxicity and mutagenicity, liver damage, or genotoxic effects, and lethal effects on the fishes exposed to pulp and paper mill wastewaters [25], [26], [27]. Since described before, in certain cases novel treatment technologies or the combination of different alternative methods for the remediation of contaminated water are necessary [18], [19], [21], [23]. Exist alternatives methods to treat the waste water of paper industry like catalytic process, bio-catalysis, membranes, water treatment with high temperatures and pressures [1], [2], [3], [4], [9], but these processes are not very efficient and its operations is very costly. Ozonation [6], [14], [27], [28] and advanced oxidation processes (AOPs) including photocatalitic oxidation and catalytic ozonation [29], [30], [31], [32], [33] are the alternative to degrade lignin and their derivatives in water, but the efficiency of the treatment depends on the real practice of the operation process and the quality of the treated water. The very interest aspect has the combination of two or more processes. So, a combination of coagulation and wet oxidation [34], [35], of ozonation and biofilm reactor [36] and biodegradation [37], etc., have shown high removals of COD and total organic carbon (TOC) and the acute toxicity reduction.

The objective of this work was to improve the treatment performance of pulp and paper mill effluents by the combination of the chemical precipitation and the simple ozonation. The wastewater, which contains considerable amounts of high-molecular-weight pollutants, was pre-treated separately by precipitation with sulfuric acid at the initial pH 1 and 3, then by the simple ozonation at the pH 1, 3, 8 and 12 in order to reduce color, decompose dissolved contaminants and increase the biodegradability (BOD5/COD) of the final compounds composition. The effect of the precipitation conditions and of the ozonation time on the decolorization kinetics and on the composition of the ozonation products has been evaluated.

Section snippets

Chemical precipitation of lignin by sulfuric acid

In all experiments the samples of original wastewater from the paper plant “Kimberly Clark” of Orizaba City, Veracruz, Mexico were used. Table 1 depicts some characteristics of this wastewater that coincides with the reported in the references [38], [39]. The lignin precipitation in the diluted samples (1:10) was carried out using the concentrated sulfuric acid (97.1%, FERMONT) with the magnetic agitation. The acid concentration varies from 1.025 to 2.25 vol% at the initial pH 3 and 1,

Effect of the sulfuric acid dose on the lignin precipitation efficiency

In the preliminary study [41] a ferric sulfate as the coagulant has been utilized, which demonstrated good results in the color remove and in the ozonation time reduction, but the sludge formed in coagulation is also toxic and provokes an environment impact. In the present study sulfuric acid was used in the lignin precipitation for the possible sulfolignin formation, since the sulfolignin has an application in the additives and cement production [42]. Based on the obtained results presented in

Conclusions

The following conclusions may be done based of the results of this study:

  • 1.

    The previous precipitation of the diluted samples with sulfuric acid decreases the initial color in 96% and the formed sludge in 90%.

  • 2.

    The coagulated sludge contains sulfolignin complex, which may be obtained during the precipitation in the presence of sulfuric acid.

  • 3.

    In the decomposition of the lignin derivatives dissolved in the filtered water after the precipitation with ozone during 25 min are formatted the simple acids

Acknowledgements

The authors thank the Department of Graduate Study and Investigation of the National Polytechnic Institute of Mexico (Project #20070444) and the National Counsel of Science and Technology of Mexico-CONACyT (Project #49367) for the supporting of this investigation. Additionally, Department of Biotechnology and Bioengineering of CINVESTAV-IPN, particularly, to Dr. Refugio Rodríguez-Vázquez for providing the wastewater samples.

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