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Scholarly Research Journal for Interdisciplinary Studies, Online ISSN 2278-8808, SJIF 2019 = 6.380, www.srjis.com PEER REVIEWED & REFEREED JOURNAL, MAR-APR, 2020, VOL- 7/58 TSS, TDS AND TS OF EFFLUENTS FROM POTASSIUM HYDROXIDE AND CALCIUM HYPOCHLORITE BLEACHING Chukwudebelu, J.A.1 & Agunwamba, J.C.2 1 Chief Research Officer, Department of Chemical, Fibre& Environmental Technology, Federal Institute of Industrial Research, Oshodi, Lagos- Nigeria 2 Professor, Department of Civil Engineering, University of Nigeria Nsukka, Enugu-Nigeria Abstract The use of different raw materials and chemicals by pulp and paper industries during pulp and paper production has contributed immensely to the pollution load on the environment. This research used TCF (KOH) and Hypochlorite (CaCIO)2 to bleach pulped agricultural residue (kenaf stem) to determine one with better environmental parameters. The dewatered kenaf was pulped with different concentrations of sodium hydroxide and formic acid at different time intervals. At the end, the pulp from each cooking was bleached with 20%, 60% and 90% concentrations of potassium hydroxide and calcium hypochlorite and the bleaching time were varied from 1hr, 2 hrs and 3 hrs at room temperature and TSS, TDS and TS of the bleaching effluents were compare for environmental quality. From physical pulp quality, 60% concentration and 2 hrs bleaching was selected and the effluent from that gave TSS 507.5 mg/L, TDS 2341.5 mg/l and TS 2849 mg/L for KOH and TSS 4492.5 mg/L, TDS 3707.5 mg/L and TS 8200 mg/L for Ca(CIO)2. This result showed that the effluent from KOH bleaching has lower pollution load. Keywords: Total dissolved solid, Calcium hypochlorite, Bleaching, Kenaf pulp, Environmental quality.

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INTRODUCTION Water is one of the essential requirements for life. Our water resources are depleting at an alarming rate due to increasing population. Industries play a major role in water pollution, Pulp and paper industry is considered as one of the most polluting industry due to the compounds they release into the environment (Baharet al,. 2015). These compounds increase the toxicity of effluent substances as well as Chemical Oxygen Demand (COD), Biological Oxygen Demand (BOD) and Total Dissolved Solids (TDS) of the receiving aquatic resources, which consequently imbalances the aquatic life (Singh and Chandra, 2019). The most significant sources of pollution among various processing stages are wood preparation, pulping, pulp washing, screening and bleaching (Akan,2008). Among various processes, chemical pulping generates high amount of waste water.

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Nowadays, bleaching of chemical pulps is achieved by two processes, i.e., the elemental chlorine-free (ECF) process and/or the total chlorine-free (TCF) one, in which bleaching is carried out essentially by using oxygen compounds (El-Sakhawy et al,. 1996). Which concept is preferred depends mainly on the desired final brightness of the pulp to be bleached, its properties, capital costs of bleaching chemicals, and concentration of chlorine-containing components in the effluent (Otůček and Říhová, 2016). In countries with limited forest resources, the use of agricultural residues for pulp manufacturing offers a possibility to solve the lack of wood and also using totally chlorinefree bleaching will be a win-win for the environment (El-Sakhawy et al,. 1996). Bleaching is engaged on the brown pulp obtained after pulping in order to meet the desired colour dictated by product standards(Parker et al,. 1990). Bleaching is a sequence of chemical treatments and washes of the pulp. The bleaching of pulp generates wastes. A substantial part of the waste is in liquid form. This effluent arises from the washing of pulp between some bleaching stages. It contains spent bleaching chemicals, degraded lignin, and other substances (Parker et al,. 1990). The particular sequence used mainly depends on the nature of the fibre (for example, softwood, hardwood, or non-wood), the type of pulping process applied, and the end use of the fibre. Regardless of the method of bleaching, the effluent may have certain characteristics which can damage the environment, such as suspended and dissolved solids and the capacity to deplete oxygen from the receiving waters (Parker et al,. 1990). Pulp and paper mills can take measures to reduce the formation of organochlorines, organic materials, heavy metals, suspended solids, and other potential pollutants in their bleaching wastes by modifying bleaching processes as well as the use of total chlorine free chemicals (Parker et al,. 1990. Several bleaching agents, including chlorine, chlorine dioxide, hydrogen peroxide, oxygen, ozone, etc. may be used either singly or in combination. It is in this step that lignin, phenols, resin acids, etc. get chlorinated and transformed into highly toxic xenobiotics(Kaizar and Norli,2015). Bleaching of pulp using conventional methods releases a range of pollutants, including organic products that have affected the water bodies and also the aquatic fauna as well as livelihood of the surrounding communities.Up to 85% of the total effluent volume is generated in the bleaching stage. The degree of delignification of the unbleached pulp, the Copyright © 2020, Scholarly Research Journal for Interdisciplinary Studies

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bleaching process, the washing loss, type of wood, final brightness desired, chemical and water consumption and the degree of plant closure are important indicators of wastewater characteristics (European Commission,2015 and Dalh,2008). The two main types of bleaching methods in use are elemental chlorine free (ECF), when no molecular or gaseous chlorine is dosed in the bleaching, and totally chlorine free (TCF) bleaching ( European Commission. 2015). Owing to the differences between both the bleaching technologies and chemical composition of the bleaching effluents, it is necessary to study in order to predict and understand the environmental impact associated, and consequently to develop the most suitable treatment that decreases effluent loads and toxicity(MarĂa,2017) Effluent quality is commonly judged on the basis of such aggregate characteristics as biochemical oxygen demand, chemical oxygen demand, total suspended solids (TSS), total solids (TS), total dissolved solids (TDS) turbidity, pH, color e.t.c. Total suspended solid (TSS) represents the solid particles mixed in water or effluent. Total dissolved solids (TDS) are measured as the mass of residue remaining when a measured volume of filtered water is evaporated. Total solids (TS) are the amount of solid present in dissolved and suspended form. A significant number of studies pertaining to the chemical composition of bleaching effluents have been published. Several authors have worked inidentifying the chemical compounds in filtrates. More than 500 organic compounds have beenidentified in bleaching effluents so far. Most compounds identified in bleaching effluents are derived from lignin or other wood components, such as extractives or carbohydrates (Kague and Carlberg, 1996). Lignin is an organic material. The lignin that remains after chemical pulping is oxidised in the case of chlorine bleaching process. The effluent from the process contains a range of organochlorines. Some organochlorines break down quickly; and some, including dioxins and furans, have long lives.Organochlorines may be largely removed by treatment of effluent at the pulp mill, but it is not currently feasible to avoid discharging some into the environment with the effluent. Some organochlorines can also remain embedded in the pulp and, ultimately, in the paper products (Parker et al,. 1990). The effects of organochlorine discharges on people and on natural ecological systems are not fully understood or quantified. In this paper, soda and formic acid cooked pulps fromkenaf stemwere subjected to single stage bleaching with potassium hydroxide and calcium hypochlorite under laboratory Copyright ÂŠ 2020, Scholarly Research Journal for Interdisciplinary Studies

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conditions to check the effects of chemicals, concentrations and time on the effluent quality with respect to solids. MATERIALS AND METHODS Kenaf stem was manually chopped into 1 to 4 cm long, washed with warm water to remove dirt and dust. The washed kenaf was dewatered to a solid content of 40% to 45%. The dewatered Kenaf was pulped with different concentrations of sodium hydroxide and formic acid at different time intervals. At the end, the pulp from each cooking was bleached with 20%, 60% and 90% concentrations of potassium hydroxide and calcium hypochlorite and the bleaching time were varied from 1hr, 2 hrs and 3 hrs at room temperature. At the end of each bleaching, the sample was filtered with a fine mesh sieve of size 0.027 to get the effluent used in the analyses. The tests were carried out in triplicate and each value is an average of three samples. The effluent was analysed using the Standard Method for Examination of Water and Wastewater (APHA, 2005). The parameters determined were TSS, TDS and TS.

Kenaf stem Bleached pulp Bleaching effluent Figure1. Samples of experimental materials RESULTS AND DISCUSSION Table 1: Effluent from-bleaching with 10g KOH-H2O2 and Ca (CIO)2 at 20% Time(Hrs) 1

Chemicals/Parameters

TDS(mg/L)

TSS(mg/L)

TS(mg/L)

KOH

8726.5

367.5

9094

Ca(CIO)2

4170.2

3832

8002.2

KOH

7477

360

7837

Ca(CIO) 2

6770

1105

7875

KOH

4608

330

4938

Ca(CIO) 2

5564.5

473

6037.5

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The pulps obtained from 1hr, 2hrs and 3hrs bleaching with 20%, 60% and 90% concentrationswere examined physically and the pulp bleached with 60% concentration for 2 hrs gave the best. Table 1 showed the values of TSS, TDS and TS of the effluent when the pulp was bleached with 20% concentration of potassium hydroxide and calcium hypochlorite at 1, 2 and 3 h intervals. The result showed that with potassium hydroxide (KOH-H202), TSS decreased from 367.5 mg/L to 330mg/L as the time of bleaching increased which was not so significantly. This suggests that solid in the KOH solution was not degraded much with time and concentration. With Hypochlorite (Ca(CIO)2), TSS values decreased significantly from 3832 g/L to 473 mg/L as the time of bleaching increased. From the study, TDS showed a decrease in value with increase in bleaching time in KOH bleaching effluent while TDS values increased with increase in bleaching time in Ca(CIO)2 bleached effluent. TS values reflected the outcome of TSS and TDS for the two chemicals with results that showed reduction in values as the bleaching time increased. This may be indicative that chemicals and raw materials react differently. Table 2: Effluent from bleaching with 10g KOH-H2O2 and Ca(CIO)2 at 60% Time(Hrs) Chemicals/Parameters TDS(mg/L) TSS(mg/L) TS(mg/L) 1

KOH

2768

820

3588

Ca(CIO) 2

5275

5090

10365

KOH

2341.5

507.5

2849

Ca(CIO) 2

3707.5

4492.5

8200

KOH

1553

490

2043

Ca(CIO) 2

291.5

3037.5

3329

In table 2, values of TSS, TDS and TS of effluent obtained from bleaching of kenaf pulp at 1h, 2hrs and 3hrs time interval at 60% concentration of KOH and (Ca(CIO)2) was provided. The result showed that the whole solids showed decrease in values as the time of bleaching increased, this suggest that more organic matter was degraded with time. Most reduction was observed in the values of TDS in Ca(CIO)2 bleaching that reduced from 5275 mg/L to 291.5 mg/L during the 3 hrs period. The highest values were obtained for TDS, TSS and TS from 1 hr bleaching with Ca(CIO)2 bleaching effluent having higher solid values than KOH effluent.

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Table 3:Effluent from bleaching with 10g KOH-H2O2 and Ca(CIO)2 at 90% Time(Hrs) Chemicals/Parameters TDS(mg/L) TSS(mg/L) TS(mg/L) 1

KOH

2602

1970

4572

Ca(CIO) 2

14522.5

4162.5

18685

KOH

2163.5

837.5

3001

Ca(CIO) 2

13446

3961

17407

KOH

998.5

537.5

1536

Ca(CIO) 2

13092.5

1887.5

14980

*Each value is an average of three samples. From table 3 which recorded the values of 90% bleaching, the result showed reduction in values of the solids as the bleaching time increased. This followed the same pattern with 20% and 60% with the highest reduction being observed in the values of TSS that reduced from 1970 mg/L to 537.5 mg/L during the 3 hrtime of bleaching. This is similar with the result reported by Nagdhi et al (2013) in which a value of 1800mg/L was obtained for TSS. The TS of the three concentrations at the 3 hr periods followed the pattern of the TSS and TDS and decreased as the bleaching time increased. The highest TS (18685 mg/L) was reportedin the Ca(CIO)2 effluent after 1 hr bleaching with 90% concentration while KOH effluent from 3 hr bleaching at 90% gave the lowest value (1536 mg/L). This may be due to the reactions between the chemicals and the raw materials that determined the distribution of the solids.Nagdhi et al (2013) and Kesalkar et al, (2012) reported 3000mg/L and between 1365 â€“ 1798mg/L respectively for TS. All the concentrations with the two chemicals have their maximum TSS, TDS and TS after 1 hr and minimum after 3 hr bleaching which suggest that more organic matter was degraded with time.Higher values of TDS observed across the bleaching periods with different concentrations may be due to the high concentration of sodium and potassium which can cause increase in salinity of the wastewater (Chandra et al,. 2020). But generally, higher values of solids were reported from Ca(CIO)2 bleaching effluentthan that of KOH effluent in all the processes. This study investigated TSS, TDS and TS in the KOH and Ca(CIO)2 bleaching effluentto determine their environmental quality. Solids are contaminants in an effluent and their high Copyright ÂŠ 2020, Scholarly Research Journal for Interdisciplinary Studies

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value poses danger of pollution to the environment. In Nigeria, the standard set by the regulatory body (FEPA, 1991) put the maximum limit to be discharged to the environment for total dissolved solid is 2000 mg/L, total suspended solid is 30 mg/L while total solid is 2030 mg/L. Table 4: Mean and SE of TSS (mg/l) over the concentrations, time and chemicals for Bleaching Concentration Time 1 Hour a

20%

2 Hours

3 Hours

1 Hour b

60%

2 Hours

3 Hours

1 Hour ab

90%

2 Hours

3 Hours

Chemical

Mean + SE

Ca(CIO)2

3832 + 3430.88a

KOH

7837 + 3430.88a

Ca(CIO)2

1105 + 3430.88a

KOH

9094 + 3430.88b

Ca(CIO)2

473 + 3430.88a

KOH

936 + 3430.88a

Ca(CIO)2

14980 + 3430.88a

KOH

3588 + 3430.88b

Ca(CIO)2

17407 + 3430.88a

KOH

2849 + 3430.88b

Ca(CIO)2

10365 + 3430.88a

KOH

2043 + 3430.88b

Ca(CIO)2

18685 + 3430.88a

KOH

1221 + 3430.88b

Ca(CIO)2

8200 + 3430.88a

KOH

536 + 3430.88b

Ca(CIO)2

3329 + 3430.88a

KOH

4572 + 3430.88b

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Table 5: ANOVA Table Source Sum of Squares df Chemical 232054444.444 1 Time 137025850.889 2 Conc 130359500.222 2 Chemical * Time 55919537.556 2 Chemical * Conc 401358908.222 2 Time * Conc 48529081.778 4 Chemical * Time * Conc 166987577.778 4 Error 423753788.000 18 Corrected Total 1595988688.889 35 b. R Squared = .734 (Adjusted R Squared = .484)

Mean Square 232054444.444 68512925.444 65179750.111 27959768.778 200679454.111 12132270.444 41746894.444 23541877.111

F 9.857 2.910 2.769 1.188 8.524 .515 1.773

Sig. .006 .080 .089 .328 .002 .725 .178

The Anova table above shows that while all the factors are not significant, only chemical – concentration interaction is significant (p < 0.05). Table 6: Mean and SE of TS (mg/l) over the concentrations, time and chemicals for bleaching Concentration Time 1 Hour 20%a

2 Hours 3 Hours 1 Hour

60%b

2 Hours 3 Hours 1 Hour

90%b

2 Hours 3 Hours

Chemical Ca(CIO)2 KOH Ca(CIO)2 KOH Ca(CIO)2 KOH Ca(CIO)2 KOH Ca(CIO)2 KOH Ca(CIO)2 KOH Ca(CIO)2 KOH Ca(CIO)2 KOH Ca(CIO)2 KOH

Mean + SE 360 + 2269.93a 12875 + 2269.93b 367.5 + 2269.93a 16252.5 + 2269.93b 330 + 2269.93a 6037.5 + 2269.93b 490 + 2269.93a 5090 + 2269.93b 820 + 2269.93a 4492.5 + 2269.93a 507.5 + 2269.93a 2037.5 + 2269.93a 537.5 + 2269.93a 572.5 + 2269.93a 837.5 + 2269.93a 562.5 + 2269.93a 1970 + 2269.93a 550 + 2269.93a

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Table 7: ANOVA Table Source Sum of Squares df Mean Square F Sig. Chemical 198340277.778 1 198340277.778 19.247 .000 Time 25038179.167 2 12519089.583 1.215 .320 Conc 173646037.500 2 86823018.750 8.425 .003 Chemical * Time 34919926.389 2 17459963.194 1.694 .212 Chemical * Conc 222381776.389 2 111190888.194 10.790 .001 Time * Conc 36296145.833 4 9074036.458 .881 .495 Chemical * Time * Conc 24973431.944 4 6243357.986 .606 .663 Error 185493175.000 18 10305176.389 Corrected Total 901088950.000 35 R Squared = .794 (Adjusted R Squared = .600) The table above shows that chemical, concentration and chemical – concentration interaction were significant (p < 0.05) while the remainder were not. Table 8: Mean ± Standard error of TDS(mg/L) of effluents from bleaching at different percentage of chemicals/ parameters Parameters

20 %

60%

90%

KOH

6937.17 ± 1219.16

2220.83 ± 355.89

1921.33 ± 478.47

Ca(CIO)2

5501.57 ± 751.16

3091.33 ± 1471.23

13687 ± 430.03

Table 9: Mean ± Standard error of TDS (mg/L) of effluents from bleaching at different time of chemicals/ parameters Parameters

1 hour

2 hours

3 hours

KOH

4698.83 ± 2014.4

3994 ± 1742.26

2386.5 ± 1122.22

Ca(CIO)2

7989.23 ± 3282.17

7974.5 ± 2875.05

6316.17 ± 3714.39

Table 10: ANOVA table Source Corrected Model Intercept Concentration (%) Time Parameters Error Total Corrected Total

Type III Sum of Squares 159682457.503a 556419224.294 83422682.321 13533428.354 62726346.827 164148467.493 880250149.290 323830924.996

df 5 1 2 2 1 12 18 17

Mean Square 31936491.501 556419224.294 41711341.161 6766714.177 62726346.827 13679038.958

F 2.335 40.677 3.049 0.495 4.586

Sig. 0.106 0.000 0.085 0.622 0.053

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The ANOVA table showed no significant for the three factors but the interaction (intercept) was significant (p < 0.05). CONCLUSION These two chemical bleaching processes (KOH and Ca(CIO) 2) were compared for environmental quality with respect to solids. The method was bleaching with three different concentrations for 1hr, 2hrs and 3 hrs intervals. The pulp bleached with 60% concentrations of KOH and Ca(CIO)2 for 2 hrs gave better pulp on physical examination. The results of the solids obtained from the analyses of the effluents from the 60% concentration for 2 hrs bleaching showed that KOH process has fewer solids in its effluent. Though, the process did not meet the effluent standard of Nigeria, but it is closer to it. From the statistical analysis, mainly chemical-concentration interactions are significant (p > 0.05) while others are not. There is need for further research into other effluent parameters for a robust conclusion. Conflict of Interests The authors have not declared any conflict of interests. REFERENCES Akan, J. (2008). Physicochemical determination of pollutants in waste water and vegetable samples along the Jakara waste water channel in Kano Metropolis. European Journal Scientific Research. pp 122-23. Bahar, K.; Zeynep, C. and Etecioglu, O. (2015). Pollution prevention in the pulp and paper industries. Institute of Environmental Science and Environmental Engineering, Istanbul, Turkey. Chandra, R.; Tripathi, S. and Sharma, P. (2020). Environmental Impacts of Pulp Paper Mill Effluent: Potential Source of Chromosomal Aberration and Phytotoxicity. International Journal of Applied Environmental Sciences ISSN 0973-6077 15(2) 7792. Chukwudebelu, J.A. and Agunwamba, J.C. (2019).Characteristics of Effluent from Potassium Hydroxide and Calcium Hypochlorite Bleaching of Pulp from Kenaf Stem. SSRG International Journal of Agriculture & Environmental Science (SSRG-IJAES) 6, 6. ISSN: 2394 – 2568 Dahl, O. (2008). Process modifications to reduce effluent loads. In: Dahl O, editor. Environmental management and control. 1st Ed. PaperijaPuuOy; Helsinki pp. 70– 84. ISBN: 978-952- 5216-30-1. European Commission (2015). Joint Research Centre, Institute for Prospective Technological Studies. Integrated Pollution and Prevention Control. Best Available Techniques (BAT) reference document for the production of pulp, paper and board. http://eippcb.jrc.ec.europa.eu/reference/BREF/PP_revised_BREF_2015.pdf. Copyright © 2020, Scholarly Research Journal for Interdisciplinary Studies

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FEPA (1991). Guideline and Standard for Environmental Pollution Control in Federal Environmental Protection Agency Act (Cap 131 LFN), National Environmental Protection (Effluent Limitation) Regulation Official GazatteGovernment Publishing Service Canberra. Kague. M.; Carlberg, B. (1996). Effluent characteristics and composition. In: Dence C, Reeve D, editors. Pulp bleaching-principles and practices. TAPPI Press; AtlantaGA; 1996, pp.751–65. ISBN:0-89852-063-0. Kaizar, H. and Norli, I. (2015). Bioremediation and Detoxification of Pulp and Paper Mill Effluent: A Review. Research Journal of Environmental Toxicology, 9: 113-134. Kesalkar, V.; Khedikar, I.andSudame, A. (2012). Physico-chemical characteristics of wastewater from Paper Industry. International Journal of Engineering Research and Applications(IJERA).2(4)137-143. M. El-Sakhawy, B. Lönnberg, Y. Fahmy and A. A. Ibrahim, Cellulose Chem. Technol., 30, 483 (1996). María, N. (2017). Pulp Mill Wastewater: Characteristics and TreatmentUniversidad de la República, Engineering School, Chemical Engineering Institute, Forest. Naghdi, R. ;Karimi, A. ;Jahan, L.; Hamzeh. Y.; Mirshokraie. S andNadali, E. (2013). Biological removal of chloro-organic compounds from bagasse soda pulp bleaching effluent by Coriolusversicolor, Global NEST Journal, 15 (1) 29-36. Parker, M.; Mauldon, R.and Chapman, D. (1990). Pulp and Paper: Bleaching and the Environment. Overview and Findings Report No. 1 ISBN 0 644 12529 2 by Australian. Potůček, F. and Říhová, M. 2016 Elemental Chlorine-Free Bleaching of Soda Rapeseed Pulp Cellulose Chemistry and Technology Journal. Process Engineering, Montevideo, Uruguay.http://dx.doi.org/10.5772/67537. Singh, A. and Chandra, R. (2019). Pollutants released from the pulp paper industry: Aquatic toxicity and their health hazards. Aquatic Toxicology.pp.202-216.