ENVIRONMENTAL ENGINEERING SCIENCE Volume 24, Number 3, 2007 Mary Ann Liebert, Inc. DOI: 10.1089/ees.2005.

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Aerobic vs. Anaerobic-Aerobic Biotreatment: Paper Mill Wastewater

M. Lerner,1 N. Stahl,2 and N. Galil1
1Department

of Civil and Environmental Engineering TechnionIsrael Institute of Technology Haifa 32000, Israel 2American-Israeli Paper Mills (AIPM) Hedera 38101, Israel

ABSTRACT The operation of existing activated sludge treatment plants at paper mills in the world is often characterized by disturbances, caused by bad biosolids settling, sludge bulking, and reduction of biomass activity. This paper presents a comparison between the results obtained in a case study based on a full-scale activated sludge treatment (AST) system working as the only biotreatment and the AST working with anaerobic pretreatment by upflow anaerobic sludge blanket (UASB). The study was performed at paper mills in Hedera, Israel. The data was collected during 8 years. The anaerobic/aerobic system (20022004) provided steady operation performance, while the AST system without anaerobic pretreatment (19972001) produced effluent characterized by oscillatory values. The results indicate much lower levels of total suspended solids in the anaerobic/aerobic treatment system effluent, 510 mg/L, compared to 5085 mg/L in the AST system only. Similar improvement was observed in terms of the organic matter removal: 220250 mg/L vs. 80120 mg/L as CODt, and 2040 mg/L vs. 47 mg/L as BODt with low corresponding fluctuations. After the operation of the anaerobic pretreatment, the sludge age increased from 810 days to 3040 days and the activated sludge performance substantially improved: the sludge volume index decreased from 200 to 80 mL/g with significant reduction of the excess sludge amount. The data collected during the operation monitoring clearly indicates that the anaerobic process followed by AST considerably reduced electrical and chemicals consumption in the biological treatment plant and provided low operational cost. Key words: activated sludge; anaerobic pretreatment; UASB; paper mill INTRODUCTION
thorities, local regulations, consumers, and economic issues has forced the papermaking industry to apply technologies for wastewater minimization and proper wastewater treatment. Water recycle/reuse (closing the loops) is the most common technique used for fresh water and

is one of the biggest users of water and generates large quantities of highly polluted wastewater. Great pressure from environmental auHE PAPERMAKING INDUSTRY

*Corresponding author: Department of Civil and Environmental Engineering, TechnionIsrael Institute of Technology, Haifa 32000, Israel. Phone: 972-4-8292645; Fax: 972-4-8293629; E-mail: galilno@tx.technion.ac.il

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278 wastewater reduction in paper industry. However, water system closure without appropriate treatment is associated with an increase in organic and inorganic contaminant concentration in mill process water streams. It may have a negative impact on product quality, and could result in accelerated scaling and corrosion problems of papermaking equipment, odors in water and paper, deposits of sticky material, increase in biological activity in the mill process water (slime growth), and influence on efficiency of paper making chemicals (Malmqvist et al., 1999; Berard, 2000). On the other hand, the increasing reuse of water and the reduction in fresh water consumption by paper mills are causing extensive problems in the biological wastewater treatment, especially in the activated sludge process. Therefore, an important part of the paper mill water closure strategy is the upgrading of existing biological wastewater treatment units and/or applying additional technologies. Biological wastewater treatment has been traditionally widely utilized in paper industry in order to purify their wastewater containing lost cellulose fibers, resin acids, plant sterols, lignin, starch, chlorinated organic compounds, fatty acids, sulphur compounds, dyes, and others. This wastewater is characterized by relatively high chemical and biochemical oxygen demand (COD, BOD) and suspended solids (mainly fibers). During the past 2 decades, activated sludge treatment (AST) has become more popular for pulp and paper mill wastewater purification showing high organic matter removal efficiency. However, AST is highly sensitive to external disturbances (both physical and chemical nature) created during the purification (Hynninen, 1998). In case of paper
Table 1.

LERNER ET AL. industry wastewaters, these disturbances may vary from sudden changes in pH or organic loading rate (because of chemical spills, for example) to toxicity caused by resins acids or chlorinated organic compounds. Sarlin et al. (1999) reported that unusual changes in the paper mill wastewater characteristics (because of spillage of biocides, oils, dyes, acids, and others) can reduce biomass activity and have a negative effect on biosolids settleability. The surface active material accumulation and/or certain species of bacteria could encourage foaming in the aerated basin of the biological plant and affect both AST performances and effluent quality (Richard, 2003). Another typical problem of the AST plant that deteriorates effluent quality is sludge bulking caused by excessive growth of filamentous bacteria, especially Microthrix parvicella (Richard, 2003). Webb (1994) reported that bulking in AST plant of paper mills is often connected with wastewater composition containing easily biodegradable materials such as sugars and starches. In addition to the low organic load (i.e., low F/M ratio), a limited supply of nutrients (phosphorous and/or nitrogen) and some essential metals is typical for paper wastewater. These limitations could also be the reason for sludge bulking and loss of light biosolids with the effluent (Hynninen and Ingman, 1998). In the 1990s, the anaerobic biological treatment processes became very popular for purification of paper mills wastewater. Webb (2002) and Stahl et al. (2004) reported that combination of anaerobic pretreatment with aerobic biotreatment provided excellent results in the removal of organic matter and other problematic substances present in paper mill effluent. Kortikaas et al. (1994) and Eroglu

AIPM wastewater composition and UASB effluent quality. Parameter Wastewater 6.73 2300 1950 1180 990 160 540 170 22.9 5.7 6.5 1.3 140 410 34.8 0.58 590 530 270 260 110 140 110 6.9 2.5 5.1 1.3 52 207 3.1 UASB effluent 6.59 760 575 410 300 170 490 940 22.4 9.1 13.7 6.2 65 6 35.5 0.17 360 230 280 240 140 80 150 6.8 4.3 10.9 3.7 30 5 2.9

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

pH Total COD, mg/L Soluble COD, mg/L Total BOD, mg/L Soluble BOD, mg/L TSS, mg/L Ca Hardness, mg/l as CaCO3 Alkalinity, mg/l as CaCO3 TKN, mg/L NH4-N, mg/L Total P, mg/L PO4-P, mg/L SO4, mg/L VFA, mg/L Temperature, C

Abbreviations: BOD, biochemical oxygen demand; COD, chemical oxygen demand; TKN, total Kjeldohl nitrogen; TSS, total suspended solids.

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Figure 1.

Schematic description of the full-scale wastewater treatment plant, before and after 2002.

et al. (1994) have found that anaerobic-aerobic treatment systems produced effluent of much better final quality at lower capital and operational cost than anaerobic or aerobic processes separately. It should be noted that most of the anaerobic-aerobic treatment studies and reports based on full-scale installations have been carried out for wastewater purification originating from one specific (single) paper mill producing one type of paper. These wastewaters might be characterized by a relatively uniform composition, regarding organic and hydraulic loads, and this could enable good biomass acclimation. However, there are some papermaking mills operating several lines for producing different kinds of paper on the same site. The general wastewater stream of such mills is characterized by unstable

complicated chemical composition and by fluctuating hydraulic load during short time periods. The aim of the work was to study technological, environmental, and economic issues connected with the operation of an anaerobic system as pretreatment for an aerobic process both involved in the treatment of wastewater from a paper mill complex producing three different types of paper.

EXPERIMENTAL PROTOCOLS
All of the tests and measurements were carried out at the American Israel Paper Mills (AIPM group) full-scale wastewater treatment plant (WWTP) in Hedera, Israel. The mills produce approximately 300,000-ton tissue, fine

Table 2.

Average activated sludge treatment (AST) performances. Parameter AST before anaerobic system installation 5800 4500 1.8 0.14 23 5.2 8 30 196 1300 1000 0.8 0.06 11 2.4 2 4.1 122 AST after anaerobic system installation 6200 4200 2.5 0.06 16 3.9 31 30 80 1400 1000 1.5 0.03 6 1.4 5 1.9 19

1 2 3 4 5 6 7 8 9

MLSS, mg/L MLVSS, mg/L DO in aeration basin, mg O2/L F/M, kg BOD5/kgMLVSS* day OUR, mg O2/L*h SOUR, mgO2/gr MLVSS*h SRT, days HRT, h SVI, mL/g

Abbreviations: DO, dissolved oxygen; MLSS, mixed liquor suspended solids; HRT, hydraulic retention times; SRT, sludge retention time; SVI, sludge volume index.

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280 and packaging paper per year and require about 2,600,000 m3 of fresh water per year. The wastewater average flow is 250 m3/h, and its composition is shown in Table 1. WWTP consists of an anaerobic pretreatment stage accomplished and operated since April 2002, and an activated sludge system, operated since 1980 (Fig. 1). The aerobic plant includes a rectangular completely mixed aeration basin (8,500 m3) equipped with surface aerators and followed by four circular clarifiers for biosolids separation. The anaerobic system is an upflow anaerobic sludge blanket [UASB, Paques internal circulation (IC) reactor] with a 24-meter cylindrical, slim design reactor (1,200 m3). The average hydraulic retention time in the UASB system is 4.2 h. The overall amount of anaerobic bacteria in the IC reactor is about 32 ton, expressed as volitile suspended solids (VSS). In the

LERNER ET AL. anaerobic reactor the organic matter is converted into biogas (methane and carbon dioxide) producing a gas lift. Through gas-lift riser pipes the sludge/gas mixture upward to a sludge/gas separator on the reactor top. The biogas leaves the reactor through this separator and the anaerobic granules return to the reactor bottom via a downer pipe. The biogas production varies from 3,300 to 6,200 m3/day depending on the influent organic matter concentration. Nitrogen and phosphorous deficiency in raw mill wastewater created the need for controlled addition of H3PO4 and CO(NH2)2 to the inlet of the UASB system in order to keep the ratio of COD:N:P in level of 350:5:1, required for proper anaerobic treatment of the paper mill wastewater according to the Paques experience. It should be noted that the operation of the UASB allowed decreasing the organic load on the AST by about

(a)

(b)

Figure 2.

COD (a) and BOD (b) in effluent and removal efficiency (until June 2005).

AEROBIC VS. ANAEROBIC-AEROBIC BIOTREATMENT 65% as COD (see Table 1). The average performances of the AST plant before and after the operation of the anaerobic system are given in Table 2. All the analyses were performed in accordance with Standard Methods (1997). The AST performance was monitored during 8 years (from 1997 to 2005). During this period approximately 1,100 and 2,700 samples were collected for COD and BOD analysis accordingly. Soluble concentrations of COD and BOD have been performed by filtration through the standard glass microfiber GF/C filter with a 1.2-micron pore size.

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RESULTS AND DISCUSSIONS Organic matter removal

The results of organic matter removal expressed as COD and BOD (both total and soluble) are summarized

in Fig. 2. These parameters were measured two to three times per week and from 2001, the COD concentrations were daily determined. Total COD concentrations in the AST effluent during 1997 to 2001 (before UASB operation) were significantly higher (220 to 250 ppm) in comparison with 20022004, after UASB operation (80 to 120 ppm). Similar results were obtained also in terms of BOD removal: effluent total BOD concentrations before and after UASB operation were 20 to 40 and 4 to 7 ppm, accordingly. Additionally, the period from 1997 to 2001 was characterized by high effluent COD and BOD fluctuations which were caused by high sensitivity of the AST to changes in hydraulic and organic loading connected with the wastewater composition. A significant part of the time the AST was operated under strong bulking sludge conditions, low dissolved oxygen (DO) concentration, low F/M ratio and nutrient (P and N) deficiency. Moreover,

Figure 3.

CODt in effluent vs. cumulative probability.

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282 occasionally spillage of oils and some other chemicals (especially starches in the year 2000) resulted in temporary biomass activity inhibition, foaming over the aeration basin and development of filamentous bacteria. All the above-mentioned abnormal conditions lead to instability of the AST performances and relative low average organic matter removal (Fig. 2). The situation drastically changed in 2002 with the installation and operation of the UASB. Both total and soluble average COD and BOD levels in the effluent considerably dropped off (90 and 7 ppm for total COD and BOD, respectively) in comparison with previous years. Effluent organic matter concentrations became more uniform (see Fig. 3) and the overall organic compounds removal efficiency increased (95.8% for total COD and 99.5% for total BOD). The organic removal improvement was associated with the reduction of the total organic loading on AST after UASB operating at about 65% as COD. It should be noted that after the operation of the anaerobic pretreatment, events of sludge bulking, and foaming have never been observed.

LERNER ET AL. However, with the operation of UASB, since 2002, the TSS removal improved (95%) with effluent average of 8 ppm and relatively low variation (Fig. 5). The results demonstrate that the application of the anaerobic pretreatment for paper mill wastewater purification improved the activated sludge settling characteristics and eliminated sludge bulking problems.

Activated sludge properties

Since the separation between final effluent and biomass is performed in the secondary clarifier of the AST plant, the settling characteristics of the mixed liquor suspended solids (MLSS) is one of the most important parameters. The average activated sludge performances (Fig. 6) indicate that after the operation of the UASB process, the settling characteristics of activated sludge improved from 200 to 80 mL/g, based on average values of sludge volume index (SVI). The improved MLSS settling ability not only improved the AST effluent quality, but also influenced the sludge age (sludge retention temperature: SRT). SRT increased from 810 days (before UASB running) to 3040 days. It is well known that the longer the sludge age, the amount of biosolids will be lower and more stable. During 19972001 the average quantity of excess sludge was 47 ton/day with ash content of 20%. After the operation of the anaerobic system (20022004), the average daily excess sludge amount decreased to 12 ton and contained about 35% ash, indicating stable sludge.

Suspended solids removal

During 19972001 the average effluent total suspended solids (TSS) concentration varied from 50 to 85 ppm (Fig. 4) corresponding to average TSS removal efficiency of 85%. It should be noted that during this period the daily effluent TSS concentration fluctuated within 8090%.

Figure 4.

TSS in effluent and removal efficiency (until June 2005).

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Figure 5.

Cumulative probability vs. TSS in effluent.

It should be noted that after UASB operation the biomass in the aeration basin changed color from a yellow to dark brown and odor problems disappeared.

Chemical consumption and cost comparison

Table 3 presents average daily electricity and chemicals consumption as well as annual costs for the biological treatment plant during the period 19992004. The data in Table 3 demonstrate that the anaerobic pretreatment improved AST performances, and final effluent quality lowered electricity requirements by 30% and substantially reduced the chemicals consumption. Polymer consumption was reduced by 50% due to lower production of waste biosolids. The nutrient (N and P) demand in the biological systems is correlated with

the organic load. The nutrient demand of the anaerobic treatment was about 60% of the AST plant, as shown in Table 3. Caustic soda is essential for controlling the pH level of the anaerobic process, and therefore, the UASB operation is connected with relatively large amounts of it (3.6 ton/day). When the pH in the reactor drops below 6, the methanogenic bacteria stop their activity (methane production) resulting in VFA accumulation and acidification of the reactor. Therefore, it is very important to keep the pH in the reactor always above 6 (in fact, set point of pH is 6.7) and for this purpose the caustic soda has to be added. Lately the facilities to strip the CO2 were added to the anaerobic reactor, and since then the caustic soda consumption has been quite lowered (1 ton/day).

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LERNER ET AL.

Figure 6.

Activated sludge properties (until June 2005).

The total reduction of electricity and chemical consumption resulted in a reduction of the operating expenses by about 50%, despite of the addition of caustic soda.

SUMMARY
The obtained results have shown that anaerobic pretreatment, performed by UASB high-rate internal circulation reactor (Paques), allowed successful purification of complicated wastewater generated by mixing of streams from producing different kinds of paper. The op-

eration of the anaerobic process significantly improved the performance of the aerobic biomass. The paper mill anaerobic/aerobic effluent quality, in terms of COD, BOD, and TSS, as well as their fluctuation, dramatically improved compared to the single aerobic treatment. This was achieved due to improved settleability of the biosolids and higher SRT in the activated sludge process. The data collected on the full-scale system during a monitoring period of over 2 years demonstrated that anaerobic/aerobic wastewater treatment was more costeffective compared to AST only. Electrical and chemicals consumption as well as waste sludge production considerably reduced wastewater treatment costs.

Table 3.

The wastewater treatment plant (WWTP) main expenses. Aerobic treatment only Anaerobic aerobic treatment 2001 10,200 67 1,186 624 0.291 2002 9,800 34 679 3,600 607 0.289 2003 7,100 19 747 a 1,900. 308 0.143 2004 7,000 31 708 a 1,000. 421 0.177

Parameter Electricity Polymers Nutrients (PN) Caustic soda Annual cost Cost per m3
aAfter

Unit kWh/day kg/day kg/day kg/day k$/year $/m3

1999 10,800 74 783 752 0.284

2000 10,100 64 1,464 743 0.320

addition of CO2 stripping system to the anaerobic tank.

AEROBIC VS. ANAEROBIC-AEROBIC BIOTREATMENT Anaerobic/aerobic treatment can be used as an important component of wastewater preparation for further internal paper mill water reuse/recycle (closing water loops).

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HYNNINEN, P., and INGMAN, L.C. (1998). Improved control makes activated sludge treatment more viable. Available from http://www.paperloop.com/db_area/archive/p_p_mag/ 1998/9811/focus2.htm KORTIKAAS, S., DOMA, H.S., POTAPENKO, S.A., FIELD, J.A., and LETTINGA, G. (1994). Sequenced anaerobic-aerobic treatment of hemp black liquors. Water Sci. Technol. 29(56), 409. MALMQVIST, ., TERNSTROM, A., and WELANDER, T. (1999). In-mill biological treatment for paper mill closure. Water Sci. Technol. 40(1112), 43. RICHARD, M. (2003). Activated sludge microbiology problems and their control. Available from www.dec. state.ny.us/website/dow/bwcp/DrRichard.pdf SARLIN, T., HALTTUNEN, S., VUORIRANTA, P., and PUHAKKA, J. (1999). Effects of chemical spills on activated sludge treatment performance in pulp and paper mills. Water Sci. Technol. 40(1112), 319. STAHL, N., TENENBAUM, A., and HABETS, L. (2004). Finding a better way. PPI 11, 29. WEBB, L. (1994). Legislative pressure means more changes in the pipeline. PPI 2, 31. WEBB, L. (2002). Kidney technology brings success. PPI 4, 28.

ACKNOWLEDGMENTS
The project was carried out at the American Israeli Paper Mill (AIPM), Hedera, Israel. Mark Lerner is a Ph.D. student, Nathan Stahl is project engineer at AIPM, Noah I. Galil is Professor of civil and environmental engineering at the Technion.

REFERENCES
BERARD, P. (2000). Filling in the holes after closing the loop. PPI 4, 44. EROGLU, V., OZTURK, I., UBAY, G., DEMIR, I., and KORKURT, E.N. (1994). Feasibility of anaerobic pre-treatment for the effluents from haedboard and laminated board industry. Water Sci. Technol. 29(56), 391. HYNNINEN, P. (1998). Environmental Control, book 19. Finland: Fapet Oy.

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