process optimization for treatment of pulp an paper mill industry

ppt of slu

1. Process Optimization For Treatment of Pulp & Paper Mill Industry Effluent Using Iron Nanoparticles Abhishek Kumar, Kirti Srivastava, Roli Verma, R.S.Jagadish 1 Department of Chemistry, JSS Academy of Technical Education, Sector 62, Noida

2. ABSTRACT Because of its dark hue, unpleasant odour, elevated organic content, and significant levels of COD, BOD, and chlorinated compounds, wastewater from pulp and paper mills is highly polluted. Iron nanoparticles and ferrous sulphate heptahydrate are employed in varying quantities to chemically precipitate these harmful contaminants from the solution. KEYWORDS: Iron nanoparticle, pulp & Paper mill effluent, chemical treatment, chlorinated organic compounds

3. Content INTRODUCTION . MATERIALS AND METHODS. RESULTS AND DISCUSSION. CONCLUSION. REFERENCES.

4. Introduction The pulp and paper mill (P&P) industry is one of the largest industrial sectors in India and the world. Throughout the manufacturing process , a sizable amount of lignocellulosic materials and water are used (Singh et al 2006). The aquatic bodies that absorb the effluents have negative changes in temperature, dissolved oxygen levels, color, turbidity, and solids content. High levels of alkalinity, biochemical oxygen demand (BOD), chemical oxygen demand (COD), total suspended solids (TSS), and other parameters are produced in the effluent (Nagarathnamma et al 1999).

5. Investigations on the hazardous effects of effluent on agricultural fields have revealed that there was a radical alteration in the soil's chemistry, which ultimately hindered plant development and increased dangers to public health such diarrhea, vomiting, headaches, nausea, and eye irritation (Gupta, 1997; Dutta, 1999, Mandeep et al 2019). Due to its low cost and environmental friendliness, nanotechnology can help waste water remediation technologies overcome their constraints. It is now among the most actively researched technologies of the twenty-first century. Small size, high surface to volume ratio, well-organized structure, and capability of filtration, electrostatic, hydrophilic, and hydrophobic interactions are all distinctive characteristics of nanomaterials that are beneficial for adsorption, catalysis, sensoring, and optoelectronics. (Das et al., 2012). The main aim of the current work is to use iron nanoparticles for the synthesis, characterization, and treatment of PULP & PAPER effluent waste water.

6. MATERIALS AND METHODS Location & Sampling of Effluent The effluent samples of wastewater sample were collected from Suchi paper mill, Ghaziabad (28.6169° N, 77.4777° E), India. Collection of effluent was done in PET bottles which were then kept at 4°C in refrigerator till used. Reagent and chemicals Iron (II) sulphate heptahydrate (FeSO 4 .7H 2 O) and sodium borohydride (NaBH 4 ) were obtained from Sigma Aldrich and all reagents used were of analytical grade.

7. In synthesis of iron nanoparticles ,we have mixed 0.05M ferrous sulphate heptahydrate Iron crystals ( FeSO 4 .7H 2 O) and 0.2M Sodium borohydride (NaBH 4 ) in different volumertic ratios like 20:1, 15:1, 10:1, 5:1 and obtained Zero valent iron nanoparticles as results.  

8. Characterization of n-ZVI The synthesized nanoparticles were characterized with the help of various instrumental techniques such as Ultraviolet-Visible spectroscopy, FTIR spectroscopy, XRD (X-Ray Diffraction), SEM (Scanning Electron Microscopy).

9. Treatment of pulp and paper mill effluent with Iron (II) sulphate heptahydrate and n-ZVI in different ratios In the first set of conical flasks (250 ml) Erlenmeyer flasks , 50 ml of P&P effluent and 50 ml Iron (II) sulphate heptahydrate (1g/L) was taken. In the other four sets of the flasks, effluent was mixed with n-ZVI (prepared via 4 volume ratios of 20:1, 15:1, 10:1, 5:1 of Iron (II) sulphate heptahydrate and n-ZVI). All the flasks were firstly centrifuged at 200 rpm for 2 hrs and later at 5000 rpm for 10 minutes. Finally TSS, BOD, COD and color were measured.

10. RESULTS AND DISCUSSION The UV-visible absorption spectrum of n-ZVI (synthesized by using Iron (II) sulphate heptahydrate and NaBH 4 ) is scanned in the wavelength range of 400–800 nm . It showed the absorption maxima at the λ max of 278 nm which is characteristic of zero-valent iron nanoparticles and clearly suggests its formation (Fig 2).

11. In the IR spectrum of n-ZVI (Fig. 3), absorption bands at 3342 cm -1 and 1604 cm -1 were credited to -OH str and -OH bending respectively. This could probably be due the formation of ferric-oxo-hydroxide by the adsorption of water on the surface of n-ZVI.

12. The XRD pattern of synthesized n-ZVI under ambient conditions is shown in Fig. 4. The distinguishing broad peak 45.2º (2θ) indicates that the zero valent iron (Fe ) mainly present in the sample. The mean crystallite size (d) is found to be 2.003 nm and size of one crystal particle is approximately 29.44 nm. Traces of iron oxides could also be seen. The crystallite size of amorphous iron was determined by using the Scherer’s equation . Fig. 4: XRD pattern of nanoscale zero valent iron (a) before the reaction (b) after the reaction

13. SEM images displayed that synthesized n-ZVI existed as nanospheres and also exhibit chain-like morphology . More than 85% of n-ZVI have the size < 100 nm. Occurrence of iron oxide (5-10%) is also established in the sample by the presence of few scaly and chipped forms. Fig 5: (a) ZVI before the reaction (b) ZVI after the reaction

14. Treatment of Pulp and paper mill effluent with Iron nanoparticles (n-ZVI ) Physicochemical characteristics of the effluent before and after the experiment are summarized in Table 1. All the values are in ppm means (n=3) ± standard error. Parameters Spent wash Before treatment Spent wash After treatment pH 8.2 7.4 Colour 6287 137 Odour Unpleasant No odour TSS 9,566.66 (±88.19) 670 COD 44,983 (±967.34) 7869 BOD 32508(±20.91) 3546

15. Comparative percentage reduction in Color and COD- There was a remarkable decrease in color by 97.82% and COD by 82.5%.

16. Comparative percentage reduction in BOD and TSS- There was a remarkable decrease in BOD by 80.09% and TSS by 90.4%.

17. All the values are in ppm mean (n=3) ± standard error of the P&P effluent with Iron (II) sulphate heptahydrate and Zerovalent Iron Nanoparticles (5:1 volumetric ratio) is presented in it this figure.

18. CONCLUSION The P&P effluent has high proportion of different organic & inorganic impurities having varied degree of toxicity which depends upon the sources of origin. The characterization of synthesized n-ZVI by various techniques such as UV- vis , IR spectra, X-ray and SEM data clearly proves the formation of the same. Treatment of pulp and paper mill P&P effluent was carried out with by Iron (II) sulphate heptahydrate and n-ZVI separately. From the results reported in the paper, it is concluded that the use of n-ZVI particles as a sorbent has a great potential in decreasing the BOD, COD and color as compared to application of sole Iron (II) sulphate heptahydrate for the remediation of pulp and paper mill effluent. Efforts have to be made to improve the stability of these nanoparticles by increasing their oxidation resistance in air.

19. REFERENCES Ali I (2012) New Generation Adsorbents for Water Treatment, Chem Rev 112(10): 5073-5091. Ali M, Sreekrishnan T R (2001), Aquatic toxicity from pulp and papermill effluents-A review, Adv Environ Res , 5(2):175-196. Amor C, Marchão L, Lucas M S, Peres J A (2019) Application of Advanced Oxidation Processes for the Treatment of Recalcitrant Agro-Industrial Wastewater: A Review, Water , 11:205. APHA.  Standard Methods for the Examination of Wastewater (SM) 2540 , 20th ed.; America Public Health Association: Washington, DC, USA, 2003. Central Pulp and Paper Research Institute, Annual Report, 2020-21. Chi Z, Wang Z, Liu Y, Yang G (2018) Preparation of organosolv lignin-stabilized nano zero- valent iron and its application as granular electrode in the tertiary treatment of pulp and paper wastewater, Chem Eng J , 331:317-325 . Das S K, Khan M M R, Guha A K, Das A R, Mandal A B (2012) Silver- nano biohybride material: Synthesis, characterization and application in water purification, Biores Technol 124:495-499. Dutta S K (1999) Study of the physicochemical properties of effluent of the paper mill that affected the paddy plants, J Environ Poll , 6 (2):181-188. Erisction G,  Larsson A (2000) DNA A dots in perch ( Perca fluviatillis ) in coastal water pollution with bleachen in pulp mill effluents, Ecotoxicol Environ Saf , 46:167-173. Gupta A (1997) Pollution load of paper mill effluent and its impact on biological environment, J Ecotoxicol . Environ. Monit , 7 (2):101-112. Iram M, Guo C, Guan Y, Ishfaq A, Liu H (2010) Adsorption and magnetic removal of neutral red dye from aqueous solution using Fe 3 O 4 hollow nanospheres . J Haz Mat , 181:1039-1050. Jukka A, Rintala JA, Puhakka D (1994) Anaerobic treatment in pulp and paper mill waste mamagement : A review, Biores Technol , 47:1-18 .

20. Kamali M, Khodaparast Z (2015) Review on recent developments on pulp and paper mill wastewater treatment.  Ecotoxicol . Environ. Saf .  114:326–342. Mandeep , Gupta G K, Liu H, Shukla P (2019) Pulp and paper industry–based pollutants, their health hazards and environmental risks, Current Opinion in Environmental Science & Health , 12:48-56. Nagarathnamma R, Bajpai P (1999) Decolorization and Detoxification of Extraction-Stage Effluent from Chlorine Bleaching of Kraft Pulp by  Rhizopus oryzae , Appl Environ Microbiol , 65(3):1078–1082. Pokhrel D, Viraraghavan T ( 2004 ) Treatment of Pulp and Paper Mill Wastewater—A Review. Science of the Total Environment , 333, 37-58. Ravikumar K V G, Dubey S, Pulimi M, Chandrasekaran N, Mukherjee A (2016) Scale-up synthesis of zero- valent iron nanoparticles and their applications for synergistic degradation of pollutants with sodium borohydride , J Mol Liq , 224:589-598.   Singh P, Jain P, Verma R, Jagadish RS (2016) Characterization of lignin peroxidase from Paecilomyces species for decolorisation of pulp and paper mill effluent, J Sci & Indus Res , 75:500-505. Singh P, Srivastava A, Srivastava N (2017) Electricity generation by microbial fuel cell using pulp and paper mill wastewater, vermicompost and Escherichia coli. Ind J Biotech 16:211-215. Singh P, Thakur IS (2006) Colour removal of anaerobically treated pulp and paper mill effluent by microorganisms in two steps bioreactor, Biores Tech , 97(2):218-223. Srivastava A, Srivastava K, Singh P, Singh P (2021) Application of Continuous Electrocoagulation Process for Distillery Wastewater Treatment, J Sci & Indus Res , 80, 486-490. Srivastava K, Srivastava A, Singh P, Sharma V, Singh P (2021) Remediation of Distillery Waste water Zero Valent iron Particles, Curr Res Green Sust Chem , 4:100072 Thompson G, Swain J, Kay M, Forster C F (2001), The treatment of pulp and paper mill effluent: a review, Bioresour Technol  77:275–286.  Uğurlu M, Karaoğlu M H (2009) Removal of AOX, total nitrogen and chlorinated lignin from bleached kraft mill effluents by UV oxidation in the presence of hydrogen peroxide utilizing TiO 2  as photocatalyst , Environ. Sci. Pollution Res.  16(3):265-273.

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