Adsorbent materials from paper industry waste materials and their use in Cu(II) removal from water

doi:10.1016/j.jhazmat.2008.10.055

Journal of Hazardous Materials

Volume 165, Issues 1–3, 15 June 2009, Pages 736-743

https://doi.org/10.1016/j.jhazmat.2008.10.055 Get rights and content

Abstract

This paper deals with the removal of Cu²⁺ from water using adsorbent materials prepared from paper industry waste materials (one de-inking paper sludge and other sludge from virgin pulp mill). Experimental results showed that de-inking paper sludge leads to mesoporous materials (V_mic/V_T = 0.13 and 0.14), whereas the sludge from virgin pulp mill produces high microporous adsorbents (V_mic/V_T = 0.39 and 0.41). Adsorbent materials were then used for Cu²⁺ removal from water at acid pH. During water treatment, heavy metals lixiviation from adsorbent materials was not produced. However, important Ca and Mg leaching was observed. Final pH significantly increases after treatment of water with adsorbent materials probably due to their elevated CaCO₃ content. In general, highest Cu²⁺ removal was obtained using adsorbent materials from de-inking paper sludge. This result could be due to their higher content in oxygenated surface groups, high average pore diameter, elevated superficial charge density, high CaCO₃ amount and high Ca and Mg exchange content.

Introduction

Paper pulp manufacturing separates cellulose fibres using both, mechanical and chemical process and generates important amount of waste materials. Currently, they are disposed through combustion or landfilling. So, the reuse of these organic wastes in any industrial process is a high priority today.

In recent years, an increasing proportion of recycled fibres are used in paper industries due to their important environmental and economical benefits. A ton of pulp produced from recycled paper requires 60% less energy to manufacture than a ton of bleached virgin kraft pulp [1]. However, removing the ink, clay, coatings and contaminants from waste paper in order to produce recycled paper creates large amounts of de-inking paper sludge (DPS). In Spain, more than 200,000 t of DPS were produced during 2006 [2].

Due to their high organic matter content, DPS could be used as amendment to improve or restore soil fertility and biological functioning [3], [4]. Used in agriculture and in restoration, DPS amendments increase yield and plant growth and improve soil properties such as: organic matter content, water holding capacity and cation exchange capacity [5]. So, DPS provide materials serving as a long-term source of organic matter [4]. However, since DPS are poor in phosphorus and nitrogen, supplemental P or N fertilizers have to be added to improve the growth of woody species [6].

Other possible alternative is composting. Nevertheless, the high C/N of DPS limits their used and some studies are focused on their composting mixed with some organic waste materials such as poultry manure [7] or wastewater sludge [8].

In recent years, large volume of heavy metals has been disposed on the environment. Due to their toxicity, numerous treatments have been developed for the metal removal from contaminated waters. Conventional methods like precipitation are unfavourable especially when dealing with large volumes of water which contain metal ions in low concentration. Frequently, after precipitation and following filtration, concentration of metal ions still remains on the level of few mg L⁻¹ and a great amount of waste precipitated was produced. Other methods like ion-exchange or adsorption with commercial activated carbon are expensive and the high cost could limit their use. In the last years, many efforts have been focused on low cost adsorbent materials from pyrolysis of waste materials such as sewage sludges [9], [10], agricultural by-products [11], [12], biomass residues [13], [14] or recycled plastics [15]. DPS and other organic waste materials from paper industry could be interesting precursors of these carbon materials due to their high carbon content and specially, cellulose fibres proportion.

The main objective of this work is to study the use of adsorbent materials obtained from pyrolysis of paper industry waste materials in the Cu²⁺ removal from water.

Section snippets

Raw material

Two paper industry waste materials were used as adsorbent precursors: one de-inking paper sludge from recycled paper-press manufacturing (HP) and other organic sludge from eucalyptus virgin pulp mill (RT). Samples were air-dried, crushed and sieved through 2 mm mesh.

Raw materials characterisation

Both samples were characterised as follows:

pH and electrical conductivity (EC) were measured in a Crison micro-pH 2000 and a Crison 222 conductivimeter, respectively, after stirring a mixture of each sample and distilled water (4 g L⁻¹

Raw material characterisation

Table 1 summarises main properties of paper industry waste materials used in this work. HP and RT show similar pH and EC values. Both were lightly basic with low EC values. Main differences between both materials were found in the TOM, CEC and CaCO₃ content. CEC and CaCO₃ content of HP were significantly elevated (25.37 cmol_(c) kg⁻¹ and 24.4 wt%, respectively) while RT shows higher organic matter content (88.7 wt%). During de-inking process of paper-press, removal of inorganic additives of paper,

Conclusions

1.
Waste materials from paper industry seem to be adequate adsorbent materials precursors. De-inking paper sludge leads to interesting mesoporous materials, whereas organic sludge from eucalyptus pulp mill produces high microporous adsorbents.
2.
During water treatment with adsorbent materials obtained from paper industry waste materials, lixiviation of metals was not observed. However, important Ca²⁺ and Mg²⁺ leaching were produced as a result of cation exchange reactions.
3.
pH significantly increases

Acknowledgements

Authors wish to thank Spanish Environment Ministry for the support of this work (ref. A108/2007/3-11.1).

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Adsorbent materials from paper industry waste materials and their use in Cu(II) removal from water

Abstract

Introduction

Section snippets

Raw material

Raw materials characterisation

Raw material characterisation

Conclusions

Acknowledgements

Soil Biology and Biochemistry

Conservation and Recycling

Bioresource Technology

Bioresource Technology

Chemical Engineering Journal

Chemosphere

Chemical Engineering Journal

Applied Surface Science

Chemosphere

Applied Clay Science

Powder Technology

Journal of Analytical and Applied Pyrolysis

Journal of Hazardous Materials

Journal of Colloid and Interface Science